TWI634160B - Organic-silicon metal composites, curable organopolysiloxane composition comprising thereof, and optical material comprising the composition - Google Patents
Organic-silicon metal composites, curable organopolysiloxane composition comprising thereof, and optical material comprising the composition Download PDFInfo
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- TWI634160B TWI634160B TW106112097A TW106112097A TWI634160B TW I634160 B TWI634160 B TW I634160B TW 106112097 A TW106112097 A TW 106112097A TW 106112097 A TW106112097 A TW 106112097A TW I634160 B TWI634160 B TW I634160B
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims description 14
- 229920001296 polysiloxane Polymers 0.000 title claims description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- -1 acryloyloxy, methacryloyloxy, mercapto, amino Chemical group 0.000 claims description 109
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003566 oxetanyl group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010953 base metal Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 5
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008393 encapsulating agent Substances 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004382 potting Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical group [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012788 optical film Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 230000004580 weight loss Effects 0.000 claims 1
- 239000002905 metal composite material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000012327 Ruthenium complex Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GSLTVFIVJMCNBH-UHFFFAOYSA-N 2-isocyanatopropane Chemical compound CC(C)N=C=O GSLTVFIVJMCNBH-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 101100043727 Caenorhabditis elegans syx-2 gene Proteins 0.000 description 2
- 101100422638 Caenorhabditis elegans syx-4 gene Proteins 0.000 description 2
- 101100422644 Caenorhabditis elegans syx-5 gene Proteins 0.000 description 2
- 101100535673 Drosophila melanogaster Syn gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FXNONNRUNQPNLF-UHFFFAOYSA-N cerium;2-ethylhexanoic acid Chemical compound [Ce].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O FXNONNRUNQPNLF-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FKKNTMLKOBOTGK-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C1(=CC=CC=C1)C(C)(C#C)O.C1(=CC=CC=C1)C(C)(C#C)O FKKNTMLKOBOTGK-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- QFUWHTBCUVMAMS-UHFFFAOYSA-N butan-1-olate cerium(3+) Chemical compound [Ce+3].CCCC[O-].CCCC[O-].CCCC[O-] QFUWHTBCUVMAMS-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- JITPFBSJZPOLGT-UHFFFAOYSA-N cerium(3+);propan-2-olate Chemical compound [Ce+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] JITPFBSJZPOLGT-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000000082 organogermanium group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
-
- 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
-
- 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
本發明提供一種有機-無機金屬複合物,以及包括其之可固化有機聚矽氧烷組成物。根據本發明之有機-矽金屬複合物及包括其之可固化有機聚矽氧烷組成物聚有良好的抗熱度以及低的膠黏特性,且可適於使用在光學元件中。 The present invention provides an organic-inorganic metal composite, and a curable organopolyoxane composition comprising the same. The organic-ruthenium metal composite according to the present invention and the curable organopolyoxane composition comprising the same have good heat resistance and low adhesive properties, and can be suitably used in an optical element.
Description
本發明是有關於一種有機矽金屬複合物以及包括其之可固化有機聚矽氧烷組合物。 This invention relates to an organic base metal composite and a curable organopolyoxyalkylene composition comprising the same.
發光二極體(LED)作為高效率及使用期限長之固態光源,且當相較於發光與使用期限折衷關係還未解決之傳統白熾電燈、日光燈(fluorescent light)、高光度放電燈(HID lamp)、或有機發光二極體(OLED)時更為廣泛使用。 A light-emitting diode (LED) is used as a solid-state light source with high efficiency and long life, and is a conventional incandescent lamp, fluorescent light, or high-intensity discharge lamp (HID lamp) that has not been resolved in comparison with the relationship between light emission and lifetime. ) or organic light-emitting diodes (OLEDs) are more widely used.
發光二極體元件的尺寸一般是幾毫米或更小。此類裝置係以單一或多個的形式安裝於不同的基板上,並使用用於保護及控制光線的封裝樹脂密封,以作為光源。 The size of the light emitting diode element is typically a few millimeters or less. Such devices are mounted on different substrates in single or multiple forms and sealed with a sealing resin for protecting and controlling light as a light source.
在發光二極體發展之初,係使用環氧樹脂(epoxy resin)作為封裝樹脂。近來,大部分在高輸出及可靠度的發光二極體中使用矽氧樹脂(silicon resin)作為封裝樹脂。 At the beginning of the development of light-emitting diodes, epoxy resin was used as the encapsulating resin. Recently, most of the high-output and reliability light-emitting diodes use a silicon resin as an encapsulating resin.
發光二極體之鏡片(lens)一般是藉由(例如是)灌封製程(potting process)所形成,發光二極體之封裝膠是使用低黏度的樹脂所形成,接著在分開的製程中所形成的鏡片是貼附於發光二極體。在這情況中,可使用底膠(primer)及黏著劑以改善鏡片與發光二極體之封裝膠之間的黏合性。然而,當輸出增加之發光二極體的光源中,光之釋出及熱度增加時,可能發生例如是鏡片剝落及黏著劑或底膠之顏色改變的缺陷。 The lens of the light-emitting diode is generally formed by, for example, a potting process, and the package of the light-emitting diode is formed using a low-viscosity resin, and then in a separate process. The formed lens is attached to the light emitting diode. In this case, a primer and an adhesive may be used to improve the adhesion between the lens and the encapsulant of the light-emitting diode. However, in the light source of the output of the light-emitting diode, when light is released and the heat is increased, defects such as lens peeling and color change of the adhesive or the primer may occur.
此外,在高溫狀態之下使用一長時間之後,發光二極體的封裝膠可能易於產生裂縫。為了減少裂縫的產生,可使用低硬度之有機聚矽氧烷(organopolysiloxane)之固化的產物。然而,使用低硬度之有機聚矽氧烷,在發光二極體封裝之製造過程期間,可能產生包括高度膠黏性所致之灰塵黏附的各種的缺陷。 In addition, after a long period of use under a high temperature state, the encapsulant of the light emitting diode may be prone to cracks. In order to reduce the generation of cracks, a cured product of a low hardness organopolysiloxane can be used. However, the use of low-hardness organopolyoxane may cause various defects including dust adhesion due to high adhesiveness during the manufacturing process of the light-emitting diode package.
本發明提供一有機矽金屬複合物及包括其之可固化有機聚矽氧烷組合物,可增加抗熱度並將物理特性的改變最小化。 The present invention provides an organogermanium metal composite and a curable organopolyoxane composition comprising the same that increases heat resistance and minimizes changes in physical properties.
根據本發明之一方面之有機矽金屬複合物包括一或多個下列式1或式2。 An organic base metal composite according to an aspect of the invention includes one or more of the following Formula 1 or Formula 2.
[式1][(R1R2R3SiO1/2)a(R4R5SiO2/2)b(R6SiO3/2)c(SiO4/2)d]XMY [(Formula 1][(R 1 R 2 R 3 SiO 1/2 ) a (R 4 R 5 SiO 2/2 ) b (R 6 SiO 3/2 ) c (SiO 4/2 ) d ] X M Y
在式1中,a、b、c及d各自獨立地大於或等於0且小於1,a+b+c+d=1,R1、R2、R3、R4、R5及R6各自獨立地為氫原子、烷 基(alkyl)、烯基(alkenyl)、芳香基(aryl)、環氧基(epoxy)、羥基(hydroxyl)、烷氧基(alkoxy)、氧雜環丁烷基(oxetanyl)、丙烯醯氧基(acryloyloxy)、甲基丙烯醯氧基(methacryloyloxy)、巰基(mercapto)、氨基(amino)或氰基(cyano),M為週期表中的金屬原子,且0<X/Y4。 In Formula 1, a, b, c, and d are each independently greater than or equal to 0 and less than 1, a+b+c+d=1, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Each independently is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetane group. (oxetanyl), acryloyloxy, methacryloyloxy, mercapto, amino or cyano, M is a metal atom in the periodic table, and 0< X/Y 4.
[式2][(R7R8R9Si-N-SiR10R11R12)e]xMy [Formula 2] [(R 7 R 8 R 9 Si-N-SiR 10 R 11 R 12 ) e ] x M y
在式2中,e是大於0且小於1,R7、R8、R9、R10、R11、及R12是各自獨立地為氫原子、烷基、烯基、芳香基、環氧基、羥基、烷氧基、氧雜環丁烷基、丙烯醯氧基、甲基丙烯醯氧基、巰基、氨基或氰基,M為週期表中的金屬原子,且0<X/Y4。 In Formula 2, e is more than 0 and less than 1, and R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aromatic group, or an epoxy group. a group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a fluorenyl group, an amino group or a cyano group, M is a metal atom in the periodic table, and 0<X/Y 4.
本發明之另一方面提供一可固化有機聚矽氧烷組成物,包括0.5至10重量份(part by weight)的有機矽金屬複合物、30至95重量份之有機聚矽氧烷、以及0.00005至0.003重量份之鉑族金屬催化劑(platinum group metal catalyst)。 Another aspect of the present invention provides a curable organopolyoxane composition comprising 0.5 to 10 parts by weight of an organoiridium metal complex, 30 to 95 parts by weight of an organopolyoxane, and 0.00005 To 0.003 parts by weight of a platinum group metal catalyst.
有機聚矽氧烷藉由下列式3表示:[式3](R13R14R15SiO1/2)M(R16R17SiO2/2)D(R18SiO3/2)T(SiO4/2)Q The organopolyoxane is represented by the following formula 3: [Formula 3] (R 13 R 14 R 15 SiO 1/2 ) M (R 16 R 17 SiO 2/2 ) D (R 18 SiO 3/2 ) T ( SiO 4/2 ) Q
在式3中,M、D、T及Q是大於或等於0且小於1的數值,M+D+T+Q=1,R13、R14、R15、R16、R17及R18是各自獨立地為氫原子,或者是一取代的或未取代的單價烴基(monovalent hydrocarbon group),具有相同或不同脂肪族飽和基(aliphatic saturated group), 至少其中一個烴基在分子之末端或側鏈具有1個、2個或大於2個的不飽和基,且烴基具有直的或分支狀的主鏈。 In Formula 3, M, D, T, and Q are values greater than or equal to 0 and less than 1, M + D + T + Q = 1, R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 Are each independently a hydrogen atom, or a monovalent or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups, at least one of which is at the end or side chain of the molecule There are 1, 2 or more than 2 unsaturated groups, and the hydrocarbon group has a straight or branched main chain.
有機含氫聚矽氧烷是藉由下列式4表示:[式4](R19R20R21SiO1/2)m(R22R23SiO2/2)d(R24SiO3/2)t(SiO4/2)q The organic hydrogen-containing polyoxyalkylene is represented by the following formula 4: [Formula 4] (R 19 R 20 R 21 SiO 1/2 ) m (R 22 R 23 SiO 2/2 ) d (R 24 SiO 3/2 ) t (SiO 4/2 ) q
在式4中,m、d、t及q是大於或等於0且小於1的數值,m+d+t+q=1,R19、R20、R21、R22、R23及R24是各自獨立地為氫原子,或者是一取代的或未取代的不具有相同或不同脂肪族不飽和鍵(aliphatic unsaturated bond)之單價烴基,。 In Formula 4, m, d, t, and q are values greater than or equal to 0 and less than 1, m + d + t + q = 1, R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 They are each independently a hydrogen atom, or a monovalent or unsubstituted monovalent hydrocarbon group which does not have the same or different aliphatic unsaturated bonds.
根據本發明之有機矽金屬複合物及可固化有機聚矽氧烷組成物具備良好的抗熱度以及低的膠黏特性,且較佳是可使用於光學元件中。 The organic base metal composite and the curable organopolyoxane composition according to the present invention have good heat resistance and low adhesive properties, and are preferably used in optical elements.
為了解決上述課題,本發明之一方面提供有機矽金屬複合物,有機矽金屬複合物可包括一或多個下列式1或式2。 In order to solve the above problems, an aspect of the present invention provides an organic base metal composite which may include one or more of the following Formula 1 or Formula 2.
[式1] [(R1R2R3SiO1/2)a(R4R5SiO2/2)b(R6SiO3/2)c(SiO4/2)d]XMY [(Formula 1] [(R 1 R 2 R 3 SiO 1/2 ) a (R 4 R 5 SiO 2/2 ) b (R 6 SiO 3/2 ) c (SiO 4/2 ) d ] X M Y
在式1中,a、b、c及d各自獨立地大於或等於0且小於1,a+b+c+d=1,R1、R2、R3、R4、R5及R6各自獨立地為氫原子、烷基(alkyl)、烯基(alkenyl)、芳香基(aryl)、環氧基(epoxy)、羥基(hydroxyl)、烷氧基(alkoxy)、氧雜環丁烷基(oxetanyl)、丙烯醯氧基(acryloyloxy)、甲基丙烯醯氧基(methacryloyloxy)、巰基(mercapto)、氨基(amino)或氰基(cyano),M為週期表中的金屬原子,且0<X/Y4。 In Formula 1, a, b, c, and d are each independently greater than or equal to 0 and less than 1, a+b+c+d=1, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Each independently is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetane group. (oxetanyl), acryloyloxy, methacryloyloxy, mercapto, amino or cyano, M is a metal atom in the periodic table, and 0< X/Y 4.
[式2][(R7R8R9Si-N-SiR10R11R12)e]xMy [Formula 2] [(R 7 R 8 R 9 Si-N-SiR 10 R 11 R 12 ) e ] x M y
在式2中,e是大於0且小於1,R7、R8、R9、R10、R11、及R12是各自獨立地為氫原子、烷基、烯基、芳香基、環氧基、羥基、烷氧基、氧雜環丁烷基、丙烯醯氧基、甲基丙烯醯氧基、巰基、氨基或氰基,M為週期表中的金屬原子,且0<X/Y4。 In Formula 2, e is more than 0 and less than 1, and R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aromatic group, or an epoxy group. a group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a fluorenyl group, an amino group or a cyano group, M is a metal atom in the periodic table, and 0<X/Y 4.
在根據本發明之一方面的「有機矽金屬複合物」中,「有機矽金屬複合物」可以是例如是式1的有機聚矽氧烷,或例如是式2的有機聚矽氮烷(organopolysilazane)。 In the "organo ruthenium metal complex" according to an aspect of the invention, the "organo ruthenium metal complex" may be, for example, an organopolyoxane of the formula 1, or an organopolysilazane of the formula 2, for example. ).
有機矽複合物中的金屬的包括不應為藉由物理或機械方法簡單混合金屬與有機矽複合物的包括,而是藉由有機矽複合物的化學鍵結的包括(即使未經確切驗證)。 The inclusion of the metal in the organic ruthenium complex should not be a simple addition of the metal to the organic ruthenium complex by physical or mechanical means, but rather by chemical bonding of the organic ruthenium complex (even if not exactly verified).
依常規而言,有時加入金屬添加物是為了在高溫之下穩固可固化有機聚矽氧烷組成物之物理特性。然而,在金屬成分是簡單 加入一組成物的情形中,最終固化之產物的穿透度(transmittance)(或霧度(haze))值可能顯著降低。 Conventionally, metal additions are sometimes added to stabilize the physical properties of the curable organopolyoxane composition at elevated temperatures. However, the metal composition is simple In the case of adding a composition, the transmittance (or haze) value of the final cured product may be significantly lowered.
藉由將金屬包括於有機矽複合物中,包括有機矽金屬複合物的可固化有機聚矽氧烷組成物之固化產物之抗熱度及穿透度可受到改善。 The heat resistance and penetration of the cured product of the curable organopolyoxane composition including the organic ruthenium metal complex can be improved by including the metal in the organic ruthenium complex.
金屬可包括週期表中的金屬元素,以改善高溫之下的物理特性,且可特別包括至少其中一種選自於由鑭(lanthanum,La)、鈰(cerium,Ce)、鐠(praseodymium,Pr)、釹(neodymium,Nd)、鉅(promethium,Pm)、釤(samarium,Sm)、銪(europium,Eu)、釓(gadolinium,Gd)、鋱(terbium,Tb)、鏑(dysprosium,Dy)、鈦(holmium,Ho)、鉺(erbium,Er)、銩(thulium,Tm)、鐿(ytterbium,Yb)、鎦(Lutetium,Lu)、鋯(zirconium,Zr)和鈦(titanium,Ti)所組成之群組。 The metal may include a metal element in the periodic table to improve physical properties under high temperature, and may specifically include at least one selected from the group consisting of lanthanum (La), cerium (Ce), and praseodymium (Pr). , neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), Titanium (Homium, Ho), erbium (Er), thurium (Tm), ytterbium (Yb), lanthanum (Lu), zirconium (Zr) and titanium (Ti) Group of.
在式1中,d可以是滿足於0<d<0.1之關係的範圍。由於與金屬之反應較佳是滿足上述範圍的式1之有機聚矽氧烷,含金屬之複合物的產物可增加,且同時在高溫之下需要抗熱度的可固化有機聚矽氧烷之已固化的產物可帶來高的抗熱度。 In Formula 1, d may be a range satisfying the relationship of 0 < d < 0.1. Since the reaction with the metal is preferably an organopolyoxane of the formula 1 which satisfies the above range, the product of the metal-containing composite may be increased, and at the same time, a heat-resistant curable organopolyoxane is required at a high temperature. The cured product provides high heat resistance.
式1及式2中特定之R1至R12可以是烷基(alkyl)以及具有1至18個碳原子的烷基(例如是甲基、乙基、丙基、異丙基和丁基),或者可以是芳香基(aryl)以及具有6至18個碳原子的芳香基(例如是苯基(phenyl)、氟苯基(fluorophenyl)、萘酚乙基(β-naphthyl)和β-蒽基(β-anthranyl))。 The specific R 1 to R 12 in the formulae 1 and 2 may be an alkyl group and an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group). Or may be an aryl group and an aromatic group having 6 to 18 carbon atoms (for example, phenyl, fluorophenyl, β-naphthyl, and β -fluorenyl) (β-anthranyl)).
在式1及式2中特定之R1至R12的情況是烯基(alkenyl)、具有2至6個碳原子的烯基,例如是可包括乙烯基、烯丙基、β-丁烯基和γ-丁烯基。 The specific R 1 to R 12 in the formulae 1 and 2 is an alkenyl group, an alkenyl group having 2 to 6 carbon atoms, and may, for example, include a vinyl group, an allyl group, and a β -butenyl group. And γ -butenyl.
此外,在式1及式2中特定之R1至R12的情況可適用於具有環氧基、氧雜環丁烷基、甲基丙烯醯氧基、丙烯醯氧基、巰基、氨基或氰基之取代基,具有1至6個碳原子的烷基,或具有3至12個碳原子的環烷基(cycloalkyl)。特別是,包括上述取代基之具有1至3個碳原子的烷基可能為合適的。 Further, the case of R 1 to R 12 specified in Formula 1 and Formula 2 can be applied to have an epoxy group, an oxetanyl group, a methacryloxy group, an acryloxy group, a decyl group, an amino group or a cyanide group. The substituent of the group, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. In particular, an alkyl group having 1 to 3 carbon atoms including the above substituent may be suitable.
環氧基可包括環氧丙基(glycidyl)、縮水甘油氧基乙基(glycidoxy ethyl)、α-縮水甘油氧基丙基(α-glycidoxy propyl)、β-縮水甘油氧基丙基(β-glycidoxy propyl)、γ-縮水甘油氧基丙基(γ-glycidoxy propyl)、α-縮水甘油氧基丁基(α-glycidoxy butyl)、β-縮水甘油氧基丁基(β-glycidoxy butyl)、γ-縮水甘油氧基丁基(γ-glycidoxy butyl)、δ縮水甘油氧基丁基(δ-glycidoxy butyl)、α-(3,4-環氧環己基)甲基(α-(3,4-epoxy cyclohexyl)methyl)、β-(3,4-環氧環己基)乙基(β-(3,4-epoxy cyclohexyl)ethyl)、γ-(3,4-環氧環己基)丙基(γ-(3,4-epoxy cyclohexyl)propyl)、δ-(3,4-環氧環己基)丁基(δ-(3,4-epoxy cyclohexyl)butyl)...等等。 An epoxy group may include glycidyl (glycidyl), glycidoxy ethyl (glycidoxy ethyl), α - glycidoxy propyl (α-glycidoxy propyl), β - glycidoxypropyl ([beta] glycidoxy propyl), γ - glycidoxypropyltrimethoxysilane (γ-glycidoxy propyl), α - glycidoxybutyl (α-glycidoxy butyl), β - glycidoxybutyl (β-glycidoxy butyl), γ - γ-glycidoxy butyl, δ -glycidoxy butyl, α- (3,4-epoxycyclohexyl)methyl (α-(3,4- Epoxy cyclohexyl)methyl), β- (3,4-epoxycyclohexyl)ethyl, γ- (3,4-epoxycyclohexyl)propyl (γ) - (3,4-epoxy cyclohexyl) propyl ), δ - (3,4- epoxycyclohexyl) butyl (δ- (3,4-epoxy cyclohexyl) butyl) ... and so on.
氧雜環丁烷基可包括(3-乙基氧雜環丁烷-3-基)丙基((3-ethyloxetane-3-yl)propyl)等等。丙烯醯氧基可包括丙烯醯氧基甲基(acryloyloxy methyl)、β-丙烯醯氧基乙基(β-acryloyloxy ethyl)、 β-丙烯醯氧基丙基(β-acryloyloxy propyl)、γ-丙烯醯氧基丙基(γ-acryloyloxy propyl)...等等。 The oxetane group may include (3-ethyloxetane-3-yl)propyl (3). The acryloxy group may include acryloyloxy methyl group, β -acryloyloxy ethyl group, β -acryloyloxy propyl group, γ -propylene group. Γ-acryloyloxy propyl... and so on.
此外,甲基丙烯醯氧基可包括甲基丙烯醯氧基甲基(methacryloyloxymethyl)、β-甲基丙烯醯氧基乙基(β-methacryloyloxyethyl)、β-甲基丙烯醯氧基丙基(β-methacryloyloxypropyl)、γ-甲基丙烯醯氧基丙基(γ-methacryloyloxypropyl)...等等。 Further, methyl group may include methyl Bingxi Xi Bing Xixi yloxymethyl (methacryloyloxymethyl), β - methyl Bing Xixi oxyethyl (β-methacryloyloxyethyl), β - methyl propyl Bingxi Xi (beta] -methacryloyloxypropyl), γ -methacryloyloxypropyl... and the like.
巰基可包括巰基甲基(mercapto methyl)、β-巰基乙基(β-mercapto ethyl)、β-巰基丙基(β-mercapto propyl)、γ-巰基丙基(γ-mercapto propyl)...等等。氨基可以包括氨基甲基(amino methyl)、β-氨基乙基(β-amino ethyl)、β-氨基丙基(β-amino propyl)、γ-氨基丙基(γ-amino propyl)、N-(β-(氨基乙基)(N-(β-(amino ethyl))、γ-氨基丙基(γ-amino propyl)...等等。氰基可以包括氰基甲基(cyanomethyl),β-氰基乙基(β-cyanoethyl)和β-氰基丙基(β-cyanopropyl)、γ-氰基丙基(γ-cyanopropyl)。異氰基(isocyano)可以包括異氰酸甲酯(isocyanomethyl)、β-異氰醯乙基(β-isocyanoethyl)、β-異氰酸丙酯(β-isocyanopropyl)、γ-異氰酸基丙酯(γ-isocyanopropyl)...等等。 Mercapto may include mercaptomethyl (mercapto methyl), β - mercapto ethyl (β-mercapto ethyl), β - mercaptopropyl (β-mercapto propyl), γ - mercaptopropyl (γ-mercapto propyl) ... etc. Wait. Amino group may include aminomethyl (amino methyl), β - aminoethyl (β-amino ethyl), β - aminopropyl (β-amino propyl), γ - aminopropyl (γ-amino propyl), N- ( β - (aminoethyl) (N- (β- (amino ethyl )), γ -. aminopropyl (γ-amino propyl) ... etc. cyano may include cyanomethyl (cyanomethyl), β - Cyanoethyl (β-cyanoethyl) and β -cyanopropyl (β-cyanopropyl), γ -cyanopropyl (γ-cyanopropyl). Isocyano can include isocyanatomethyl , β - acyl isocyanate ethyl (β-isocyanoethyl), β - propyl isocyanate (β-isocyanopropyl), γ - isocyanato ester (γ-isocyanopropyl) ... and so on.
根據本發明之另一方面,可提供包括一或多個式1或式2之使用有機矽金屬複合物的可固化有機聚矽氧烷。 According to another aspect of the present invention, a curable organopolyoxane comprising one or more of the organic ruthenium metal complexes of Formula 1 or Formula 2 can be provided.
特別是,可固化有機聚矽氧烷組成物可包括0.5至10重量份之包括1個或多個式1或是式2之作為抗熱度添加物的有機矽金屬 複合物。在有機矽金屬複合物小於0.5重量份的情況中,可能無法達到抗熱。在有機矽金屬複合物的量是大於10重量份的情況中,黃化程度(yellowing degree)可能增加,且光學特性可能惡化。 In particular, the curable organopolyoxane composition may comprise from 0.5 to 10 parts by weight of an organic base metal comprising one or more of Formula 1 or Formula 2 as a heat resistance additive. Complex. In the case where the organic base metal composite is less than 0.5 parts by weight, heat resistance may not be attained. In the case where the amount of the organic iridium metal complex is more than 10 parts by weight, the yellowing degree may increase, and the optical characteristics may be deteriorated.
根據本發明之實施例的可固化有機聚矽氧烷組成物在固化矽組成物之後之形成主鏈(backbone)中扮演著角色,且可包括30至95重量份之下列式3所式之有機聚矽氧烷。在有機聚矽氧烷的量小於30重量份的情況中,可固化組成物之已固化的產物係變軟,且已固化之產物可能被刮傷(scratched)或撕裂(torn)。在有機聚矽氧烷的量大於95重量份的情況中,組成物之液態黏度(viscosity)增加,且其可操作性(workability)可能惡化。 The curable organopolyoxane composition according to an embodiment of the present invention plays a role in forming a backbone after curing the ruthenium composition, and may include 30 to 95 parts by weight of the following formula 3 Polyoxane. In the case where the amount of the organopolysiloxane is less than 30 parts by weight, the cured product of the curable composition becomes soft, and the cured product may be scratched or torn. In the case where the amount of the organopolysiloxane is more than 95 parts by weight, the liquid viscosity of the composition increases, and the workability thereof may deteriorate.
[式3](R13R14R15SiO1/2)M(R16R17SiO2/2)D(R18SiO3/2)T(SiO4/2)Q [Formula 3] (R 13 R 14 R 15 SiO 1/2 ) M (R 16 R 17 SiO 2/2 ) D (R 18 SiO 3/2 ) T (SiO 4/2 ) Q
在式3中,M、D、T及Q是大於或等於0且小於1的數值,M+D+T+Q=1,R13、R14、R15、R16、R17及R18是各自獨立地為氫原子,或者是一取代的或未取代的具有相同或不同脂肪族飽和基(aliphatic saturated group)的單價烴基,至少其中一個烴基在分子之末端或側鏈具有1個、2個或大於2個的不飽和基,且烴基具有直的或分支狀的主鏈。 In Formula 3, M, D, T, and Q are values greater than or equal to 0 and less than 1, M + D + T + Q = 1, R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 They are each independently a hydrogen atom, or a monovalent or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups, at least one of which has one or two at the end or side chain of the molecule. One or more than 2 unsaturated groups, and the hydrocarbon group has a straight or branched main chain.
在式3中,M的數值可以是0.01至0.3。D的數值可以是0.3至0.6。T的數值可以是0至0.3。Q的數值可以是0.4至0.8。Q及D可以滿足Q/D等於0.3至0.9的關係。藉由控制式3之參數的數值於上述範 圍中,組成物的黏度及已固化產物之硬度可大大地受到控制,且組成物之已固化的產物可獲得高的透明度。此外,可獲得黏著劑之可靠度,且可確保關於光及熱的耐久度。 In Formula 3, the value of M may be from 0.01 to 0.3. The value of D can be from 0.3 to 0.6. The value of T can be from 0 to 0.3. The value of Q can be from 0.4 to 0.8. Q and D can satisfy the relationship that Q/D is equal to 0.3 to 0.9. By controlling the value of the parameter of Equation 3 to the above In the circumference, the viscosity of the composition and the hardness of the cured product can be greatly controlled, and the cured product of the composition can obtain high transparency. In addition, the reliability of the adhesive can be obtained, and durability against light and heat can be ensured.
根據本發明之實施例的可固化有機聚矽氧烷組成物可包括1至30重量份的下列式4所式之有機含氫聚矽氧烷(organohydro-polysiloxane),其中在分子之終端或側鏈包括氫原子,固化之後矽組成物形成主鏈,如此藉由共同使用有機含氫聚矽氧烷及有機聚矽氧烷來固化最終得到的可固化組成物所獲得之已固化的產物可達到良好的機械強度及硬度。 The curable organopolyoxane composition according to an embodiment of the present invention may include 1 to 30 parts by weight of an organohydro-polysiloxane of the formula 4 below, wherein the terminal or side of the molecule The chain includes a hydrogen atom, and after curing, the ruthenium composition forms a main chain, so that the cured product obtained by curing the finally obtained curable composition by using an organic hydrogen-containing polyoxyalkylene oxide and an organic polyoxyalkylene can be achieved. Good mechanical strength and hardness.
在有機含氫聚矽氧烷的量小於1重量份的情況中,可固化組成物之已固化產物可能變軟且可能容易被撕裂。在有機含氫聚矽氧烷的量大於30重量份的情況中,組成物之已固化的產物的黏著力可能會惡化。 In the case where the amount of the organic hydrogen-containing polysiloxane is less than 1 part by weight, the cured product of the curable composition may become soft and may be easily torn. In the case where the amount of the organic hydrogen-containing polysiloxane is more than 30 parts by weight, the adhesion of the cured product of the composition may be deteriorated.
[式4](R19R20R21SiO1/2)m(R22R23SiO2/2)d(R24SiO3/2)t(SiO4/2)q [Formula 4] (R 19 R 20 R 21 SiO 1/2) m (R 22 R 23 SiO 2/2) d (R 24 SiO 3/2) t (SiO 4/2) q
在式4中,m、d、t及q是大於或等於0且小於1的數值,m+d+t+q=1,R19、R20、R21、R22、R23及R24是各自獨立地為氫原子,或者是一取代的或未取代的單價烴基,不具有相同或不同脂肪族不飽和鍵(aliphatic unsaturated bond)。在式4中,m的數值可以是0.01至0.2,d的數值可以是0.3至0.9,t的數值可以是0至0.3,且q的數值可以是0.1至0.8。 In Formula 4, m, d, t, and q are values greater than or equal to 0 and less than 1, m + d + t + q = 1, R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 They are each independently a hydrogen atom, or a monosubstituted or unsubstituted monovalent hydrocarbon group, and do not have the same or different aliphatic unsaturated bonds. In Formula 4, the value of m may be 0.01 to 0.2, the value of d may be 0.3 to 0.9, the value of t may be 0 to 0.3, and the value of q may be 0.1 to 0.8.
式3或式4中R13至R24官能基的烴基可以是烷基以及具有1至18個碳原子的烷基(例如是甲基、乙基、丙基、異丙基和丁基),或者可以是芳香基以及具有6至18個碳原子的芳香基(例如是苯基、氟苯基、萘酚乙基和β-蒽基)。以式3及/或式4中包括的所有的有機基的總莫耳數為基準,可包括45莫耳百分比(mole%)或小於45莫耳百分比之芳香基。在包括45莫耳百分比或大於45莫耳百分比之芳香基的情況中,在高溫的抗熱度測試之下,由於芳香基之熱分解或氧化所造成的黃化(yellowing)可能會變嚴重,且穿透度可能顯著地惡化,因此可能無法應用於光學裝置。 The hydrocarbon group of the R 13 to R 24 functional group in the formula 3 or formula 4 may be an alkyl group and an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group). Or it may be an aromatic group and an aromatic group having 6 to 18 carbon atoms (for example, a phenyl group, a fluorophenyl group, a naphthol ethyl group, and a β -fluorenyl group). The aromatic group may be included in a molar percentage of 45 moles or less than 45 moles based on the total number of moles of all the organic groups included in Formula 3 and/or Formula 4. In the case of an aromatic group comprising 45 mole percent or more than 45 mole percent, under the high temperature heat resistance test, yellowing due to thermal decomposition or oxidation of the aromatic group may become severe, and The penetration may be significantly deteriorated and thus may not be applied to an optical device.
在烴基是烯基的情況中,可使用具有2至6個碳原子的烯基(例如是乙烯基、烯丙基、β-丁烯基和γ-丁烯基)。 In the case where the hydrocarbon group is an alkenyl group, an alkenyl group having 2 to 6 carbon atoms (for example, a vinyl group, an allyl group, a β -butenyl group, and a γ -butenyl group) can be used.
此外,在式3及式4中具有環氧基、氧雜環丁烷基、甲基丙烯醯氧基、丙烯醯氧基、巰基、氨基或氰基之取代基的情形中,具有1至6個碳原子的烴基,或具有3至12個碳原子的環烷基可能為合適的。特別是,包括上述取代基之具有1至3個碳原子的烴基可能為高度合適的。 Further, in the case of the substituent of the epoxy group, the oxetanyl group, the methacryloxy group, the acryloxy group, the fluorenyl group, the amino group or the cyano group in the formula 3 and the formula 4, it has 1 to 6 A hydrocarbon group of one carbon atom, or a cycloalkyl group having 3 to 12 carbon atoms may be suitable. In particular, a hydrocarbon group having 1 to 3 carbon atoms including the above substituent may be highly suitable.
環氧基可包括環氧丙基(glycidyl)、縮水甘油氧基乙基(glycidoxy ethyl)、α-縮水甘油氧基丙基(α-glycidoxy propyl)、β-縮水甘油氧基丙基(β-glycidoxy propyl)、γ-縮水甘油氧基丙基(γ-glycidoxy propyl)、α-縮水甘油氧基丁基(α-glycidoxy butyl)、β-縮水甘油氧基丁基(β-glycidoxy butyl)、γ-縮水甘油氧基丁基(γ-glycidoxy butyl)、δ縮水甘油氧基丁基(δ-glycidoxy butyl)、α -(3,4-環氧環己基)甲基(α-(3,4-epoxy cyclohexyl)methyl)、β-(3,4-環氧環己基)乙基(β-(3,4-epoxy cyclohexyl)ethyl)、γ-(3,4-環氧環己基)丙基(γ-(3,4-epoxy cyclohexyl)propyl)、δ-(3,4-環氧環己基)丁基(δ-(3,4-epoxy cyclohexyl)butyl)...等等。 An epoxy group may include glycidyl (glycidyl), glycidoxy ethyl (glycidoxy ethyl), α - glycidoxy propyl (α-glycidoxy propyl), β - glycidoxypropyl ([beta] glycidoxy propyl), γ - glycidoxypropyltrimethoxysilane (γ-glycidoxy propyl), α - glycidoxybutyl (α-glycidoxy butyl), β - glycidoxybutyl (β-glycidoxy butyl), γ - γ-glycidoxy butyl, δ -glycidoxy butyl, α- (3,4-epoxycyclohexyl)methyl (α-(3,4- Epoxy cyclohexyl)methyl), β- (3,4-epoxycyclohexyl)ethyl, γ- (3,4-epoxycyclohexyl)propyl (γ) - (3,4-epoxy cyclohexyl) propyl ), δ - (3,4- epoxycyclohexyl) butyl (δ- (3,4-epoxy cyclohexyl) butyl) ... and so on.
具有氧雜環丁烷基之取代基可包括(3-乙基氧雜環丁烷-3-基)丙基((3-ethyloxetane-3-yl)propyl)等等。具有丙烯醯氧基之取代基可包括丙烯醯氧基甲基(acryloyloxy methyl)、β-丙烯醯氧基乙基(β-acryloyloxy ethyl)、β-丙烯醯氧基丙基(β-acryloyloxy propyl)、γ-丙烯醯氧基丙基(γ-acryloyloxy propyl)...等等。 The substituent having an oxetane group may include (3-ethyloxetane-3-yl)propyl (3). The substituent having an acryloxy group may include acryloyloxy methyl group, β -acryloyloxy ethyl group, β -acryloyloxy propyl group. , γ -acryloyloxypropyl (...), and the like.
此外,甲基丙烯醯氧基可包括甲基丙烯醯氧基甲基(methacryloyloxymethyl)、β-甲基丙烯醯氧基乙基(β-methacryloyloxyethyl)、β-甲基丙烯醯氧基丙基(β-methacryloyloxypropyl)、γ-甲基丙烯醯氧基丙基(γ-methacryloyloxypropyl)...等等。 Further, methyl group may include methyl Bingxi Xi Bing Xixi yloxymethyl (methacryloyloxymethyl), β - methyl Bing Xixi oxyethyl (β-methacryloyloxyethyl), β - methyl propyl Bingxi Xi (beta] -methacryloyloxypropyl), γ -methacryloyloxypropyl... and the like.
具有巰基之取代基可包括巰基甲基(mercapto methyl)、β-巰基乙基(β-mercapto ethyl)、β-巰基丙基(β-mercapto propyl)、γ-巰基丙基(γ-mercapto propyl)...等等。具有氨基(amino)之取代基可以包括氨基甲基(amino methyl)、β-氨基乙基(β-amino ethyl)、β-氨基丙基(β-amino propyl)、γ-氨基丙基(γ-amino propyl)、N-(β-(氨基乙基)(N-(β-(amino ethyl))、γ-氨基丙基(γ-amino propyl)...等等。具有氰基(cyano)之取代基可以包括氰基甲基(cyanomethyl),β-氰基乙基(β-cyanoethyl)和β-氰基丙基 (β-cyanopropyl)、γ-氰基丙基(γ-cyanopropyl)...等等。具有異氰基之取代基可以包括異氰酸甲酯(isocyanomethyl)、β-異氰醯乙基(β-isocyanoethyl)、β-異氰酸丙酯(β-isocyanopropyl)、γ-異氰酸基丙酯(γ-isocyanopropyl)...等等。 Having a mercapto group of the substituents may include a mercaptomethyl (mercapto methyl), β - mercapto ethyl (β-mercapto ethyl), β - mercaptopropyl (β-mercapto propyl), γ - mercaptopropyl (γ-mercapto propyl) ...and many more. Having an amino group (Amino) the substituent may include aminomethyl (amino methyl), β - aminoethyl (β-amino ethyl), β - aminopropyl (β-amino propyl), γ - aminopropyl ([gamma] Amino propyl), N-( β- (aminoethyl)(N-(β-(amino ethyl)), γ -aminopropyl (γ-amino propyl), etc., having a cyano The substituent may include cyanomethyl, β -cyanoethyl and β -cyanopropyl, γ -cyanopropyl... isocyano the like having a substituent may include methyl isocyanate (isocyanomethyl), β -. acyl isocyanate ethyl (β-isocyanoethyl), β - propyl isocyanate (β-isocyanopropyl), γ - iso Γ-isocyanopropyl... and so on.
可固化有機聚矽氧烷組成物可包括0.00005至0.003重量份之鉑族金屬催化劑,作為用於促進固化之矽氫加成反應催化劑(hydrosilylation catalyst)。在鉑族金屬催化劑的量是小於0.00005重量份的情形中,交聯反應速率(cross-linking reaction rate)可能下降,而可能無法完成固化。在鉑族金屬催化劑的量是大於0.003重量份的情形中,固化速率可能太快,而可工作性(workability)可能不好,可能不經濟地大量使用昂貴的鉑,且可能產生例如是著色(coloring)之缺陷,而引發功能性之限制(functional limitation)。 The curable organopolyoxane composition may include 0.00005 to 0.003 parts by weight of a platinum group metal catalyst as a hydrosilylation catalyst for promoting solidification. In the case where the amount of the platinum group metal catalyst is less than 0.00005 parts by weight, the cross-linking reaction rate may be lowered, and curing may not be completed. In the case where the amount of the platinum group metal catalyst is more than 0.003 parts by weight, the curing rate may be too fast, workability may be poor, expensive platinum may be uneconomically used in large amounts, and coloring may occur, for example. The defect of coloring, which leads to functional limitation.
鉑族金屬催化劑可包括至少一個選自於由鉑微細粉(platinum micropowder)、鉑黑(platinum black)、氫氯鉑酸(chloroplatinic acid)、氫氯鉑酸之酒精修飾劑(alcohol modifier)、氫氯鉑酸/二烯複合物(hloroplatinic acid/diolefin complex)、鉑/烯烴複合物(platinum/olefin complex)、作為鉑-羰基複合物之雙(乙醯乙酸)鉑(platinum bis(acetoacetate))與雙(乙醯丙酮)鉑(platinum bis(acetylacetonate))、作為氫氯鉑酸/烯基矽氧烷複合物(chloroplatinic acid/alkenylsiloxane complex)之氫氯鉑酸/二乙烯基四甲基二矽氧烷複合物(chloroplatinic acid/divinyltetramethyldisiloxane complex)與氫氯鉑酸/四乙烯基四 甲基環四矽氧烷複合物(chloroplatinic acid/tetravinyltetramethylcyclotetrasiloxane complex)、由鉑/二乙烯基四甲基二矽氧烷複合物(platinum/divinyltetramethyldisiloxane complex)與鉑/四乙烯基四甲基環四矽氧烷複合物(platinum/tetravinyltetramethylcyclotetrasiloxane complex)組成之鉑/烯基矽氧烷複合物(platinum/alkenylsiloxane complex)、以及氫氯鉑酸與乙炔酒精(acetylene alcohol)之複合物所組成之群組。 The platinum group metal catalyst may include at least one selected from the group consisting of platinum micropowder, platinum black, chloroplatinic acid, chloroplatinic acid, alcohol modifier, hydrogen. Chloroplatinic acid/diolefin complex, platinum/olefin complex, platinum carbonyl (platinum bis (acetoacetate)) Platinum bis (acetylacetonate), chloroplatinic acid/alkenyl siloxane complex (chloroplatinic acid/alkenyl siloxane complex) chloroplatinic acid/divinyltetramethyl bismuth oxychloride Chloroplatinic acid/divinyltetramethyldisiloxane complex and chloroplatinic acid/tetravinyl four Chloroplatinic acid/tetravinyltetramethylcyclotetrasiloxane complex, platinum/divinyltetramethyldisiloxane complex and platinum/tetravinyltetramethylcyclotetrazepine A platinum/alkenyl siloxane complex composed of a platinum/tetravinyltetramethylcyclotetrasiloxane complex, and a complex of chloroplatinic acid and acetylene alcohol.
可固化有機聚矽氧烷組成物可依需求包括少量反應阻劑,反應阻劑可包括例如是2-苯基-3-丁炔-2-醇(2-phenyl-3-butyn-2-ol)。阻劑的量可較佳是以組成物之總重量為基準的0.0080重量份。阻劑的較低限制可以例如是0.00010重量份。特別是,在包括過量之反應阻劑的情況下,固化速率可能降低。 The curable organopolyoxane composition may include a small amount of a reaction resist as needed, and the reaction resist may include, for example, 2-phenyl-3-butyn-2-ol (2-phenyl-3-butyn-2-ol) ). The amount of the resist may preferably be 0.0080 parts by weight based on the total weight of the composition. The lower limit of the resist may be, for example, 0.00010 parts by weight. In particular, in the case of including an excessive amount of the reaction resist, the curing rate may be lowered.
此外,本發明之組成物可另外包括至少一選自於無機填充物(例如是矽石(silica)、玻璃、氧化鋁(alumina)、氧化鋅(zinc oxide)...等等)、矽橡膠粉末(silicon rubber powder)、樹脂粉末(例如矽氧樹脂(silicon resin)、聚甲基丙烯酸酯樹脂(polymethacrylate resin)...等等)、抗熱劑、抗氧化劑、自由基捕捉劑(radical scavenger)、光穩定劑、染劑、色素、阻焰添加劑(flame retardant additive)的選擇性成分,只要不破壞本發明之目的即可。 Further, the composition of the present invention may additionally include at least one selected from the group consisting of inorganic fillers (for example, silica, glass, alumina, zinc oxide, etc.), ruthenium rubber. Silicon rubber powder, resin powder (such as silicon resin, polymethacrylate resin, etc.), heat-resistant agent, antioxidant, radical scavenger (radical scavenger) An optional component of a light stabilizer, a dye, a pigment, or a flame retardant additive, as long as the object of the present invention is not impaired.
此外,根據本發明之可固化有機聚矽氧烷組成物可藉由使用本領域中已知的各種方法所製備。例如,事先在本發明之組成物 的成分中分別製備液體A及液體B,接著混合此2液體以得到最終組成物。 Further, the curable organopolyoxane composition according to the present invention can be prepared by using various methods known in the art. For example, the composition of the present invention in advance Liquid A and liquid B were separately prepared from the ingredients, and then the 2 liquids were mixed to obtain a final composition.
在已固化之產物是藉由固化根據本發明之一實施例的可固化有機聚矽氧烷組成物所形成的情況中,紫外可見光譜中260nm之波長下的穿透度是45%或小於45%,紫外可見光譜中450nm之波長下的穿透度是80%或大於80%。由於本發明之一實施例的可固化有機聚矽氧烷組成物之已固化的產物具有上述之物理特性,可在高溫之下達到高透明度及抗熱度。 In the case where the cured product is formed by curing a curable organopolyoxane composition according to an embodiment of the present invention, the transmittance at a wavelength of 260 nm in the ultraviolet visible spectrum is 45% or less. %, the transmittance at a wavelength of 450 nm in the ultraviolet visible spectrum is 80% or more. Since the cured product of the curable organopolyoxane composition of one embodiment of the present invention has the above physical properties, high transparency and heat resistance can be achieved at high temperatures.
根據本發明之另一方面,可提供包括可固化有機聚矽氧烷組成物的一光學材料,此光學材料可包括至少一選自於由發光二極體、光學半導體、黏著劑、光學塗佈材料、光學灌封劑(optical potting agent)、光學封裝膠、光學包覆層(optical cladding)及光學膜所組成之群組。 According to another aspect of the present invention, an optical material comprising a curable organopolyoxane composition may be provided, the optical material may include at least one selected from the group consisting of a light emitting diode, an optical semiconductor, an adhesive, and an optical coating. A group of materials, optical potting agents, optical encapsulants, optical cladding, and optical films.
下文中,本發明將參照下列實施例進行更詳細地說明,然本發明並不限於下列實施例。 Hereinafter, the present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to the following examples.
有機-無機金屬複合物之製備 Preparation of organic-inorganic metal composites
合成範例1 Synthesis example 1
將含有22%異辛酸鈰(cerium octoate)的120克之礦物油加入50克的二甲苯(xylene),接著進行混合。加入120克之六甲基二矽氮烷(hexamethyldisilazane),接著在80℃之下攪拌12小時。將20克之含有乙烯基的有機聚矽氧烷(ViMe2SiO(Me2SiO)70SiMe2Vi)加入,並充分攪拌。 120 g of mineral oil containing 22% cerium octoate was added to 50 g of xylene, followed by mixing. 120 g of hexamethyldisilazane was added, followed by stirring at 80 ° C for 12 hours. 20 g of a vinyl group-containing organic polyoxyalkylene (ViMe 2 SiO(Me 2 SiO) 70 SiMe 2 Vi) was added and stirred well.
接著,在5托耳(torr)的減壓之下於150℃蒸餾並移除低沸點之材料。過濾生成的沉澱物而獲得流狀黃色有機聚矽氧烷金屬複合物(fluidal yellow organopolysiloxane metal composite)(SYN-1)。 Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid yellow solid polysiloxane metal composite (SYN-1).
合成範例2 Synthesis example 2
將含有22%異辛酸鈰的120克之礦物油加入50克的二甲苯,並進行混合。加入180克之六甲基二矽氮烷,接著在80℃之下攪拌12小時。將20克之含有乙烯基的有機聚矽氧烷(ViMe2SiO(Me2SiO)70SiMe2Vi)加入,並充分攪拌。 120 grams of mineral oil containing 22% bismuth octoate was added to 50 grams of xylene and mixed. 180 g of hexamethyldioxane was added, followed by stirring at 80 ° C for 12 hours. 20 g of a vinyl group-containing organic polyoxyalkylene (ViMe 2 SiO(Me 2 SiO) 70 SiMe 2 Vi) was added and stirred well.
接著,在5torr的減壓之下於150℃蒸餾並移除低沸點之材料。過濾生成的沉澱物而獲得流狀棕色有機聚矽氧烷金屬複合物(SYN-2)。 Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a flowing brown organopolyoxane metal complex (SYN-2).
合成範例3 Synthesis example 3
將含有22%異辛酸鈰的100克之礦物油加入50克的二甲苯,並進行混合。加入107克之甘油基丙基三甲氧基矽烷(glycidoxypropyltrimethoxysilane),接著在70℃之下攪拌9小時。將40克之含有乙烯基的有機聚矽氧烷(ViMe2SiO(Me2SiO)70SiMe2Vi)加入,並充分攪拌。 100 grams of mineral oil containing 22% bismuth octoate was added to 50 grams of xylene and mixed. 107 g of glycidoxypropyltrimethoxysilane was added, followed by stirring at 70 ° C for 9 hours. 40 g of a vinyl group-containing organic polyoxyalkylene (ViMe 2 SiO(Me 2 SiO) 70 SiMe 2 Vi) was added and stirred well.
接著,在5torr的減壓之下於150℃蒸餾並移除低沸點之材料。過濾生成的沉澱物而獲得流狀棕色有機聚矽氧烷金屬複合物(SYN-3)。 Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a flowing brown organopolyoxane metal complex (SYN-3).
合成範例4 Synthesis example 4
將含有22%異辛酸鈰的100克之礦物油加入50克的二甲苯,並進行混合。加入125克之苯基三甲氧基矽烷(phenyltrimethoxysilane),接著在105℃之下攪拌12小時。 100 grams of mineral oil containing 22% bismuth octoate was added to 50 grams of xylene and mixed. 125 g of phenyltrimethoxysilane was added, followed by stirring at 105 ° C for 12 hours.
接著,在5torr的減壓之下於150℃蒸餾並移除低沸點之材料。過濾生成的沉澱物而獲得流狀暗黃色有機聚矽氧烷金屬複合物(SYN-4)。 Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid dark yellow organopolyoxane metal complex (SYN-4).
合成範例5 Synthesis example 5
將15克丁氧鈰(cerium butoxide)加入50克的二甲苯,並進行混合。加入550克之α,ω-氫氧聚矽氧烷(α,ω-hydroxypolysiloxane)(HOMe2SiO(Me2SiO)40SiMe2OH),接著在80℃之下攪拌9小時。 15 g of cerium butoxide was added to 50 g of xylene and mixed. 550 g of α,ω-hydroxypolysiloxane (HOMe 2 SiO(Me 2 SiO) 40 SiMe 2 OH) was added, followed by stirring at 80 ° C for 9 hours.
接著,在5torr的減壓之下於150℃蒸餾並移除低沸點之材料。過濾生成的沉澱物而獲得流狀淡黃色有機聚矽氧烷金屬複合物(SYN-5)。 Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid yellowish organopolyoxane metal complex (SYN-5).
合成範例6 Synthesis example 6
將18克異丙氧化鈰(cerium isopropoxide)加入50克的二甲苯,並進行混合。加入550克之氫氧聚矽氧烷(HOMe2SiO(Me2SiO)40SiMe2OH),接著在65℃之下攪拌12小時。 18 g of cerium isopropoxide was added to 50 g of xylene and mixed. 550 g of a hydroxide polyoxydeoxyoxane (HOMe 2 SiO(Me 2 SiO) 40 SiMe 2 OH) was added, followed by stirring at 65 ° C for 12 hours.
接著,在5torr的減壓之下於150℃蒸餾並移除低沸點之材料。過濾生成的沉澱物而獲得流狀淡黃色有機聚矽氧烷金屬複合物(SYN-6)。 Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid yellowish organopolyoxane metal complex (SYN-6).
範例1-8及比較例1-6 Example 1-8 and Comparative Example 1-6
範例1 Example 1
使用直立攪拌機(planetary mixer)混合100克含乙烯基之MQ樹脂(0.74mmol/g之乙烯基含量)及100克之兩終端皆被乙烯基所取代的線性二甲基聚有機矽氧烷(linear dimethylpolyorganosiloxane)(ViMe2SiO(Me2SiO)1300SiMe2Vi,下文中以VP表示),以製備母料(master batch)(下文中以MB1表示)。 100 g of vinyl-containing MQ resin (0.74 mmol/g vinyl content) and 100 g of linear dimethylpolyorganosiloxane substituted with vinyl at the end using a planetary mixer (ViMe 2 SiO(Me 2 SiO) 1300 SiMe 2 Vi, hereinafter denoted by VP) to prepare a master batch (hereinafter referred to as MB1).
(1)製備組成物A (1) Preparation of composition A
使用直立攪拌機在室溫下混合事先製備之25克MB1、28克之VP、0.03克之鉑複合物、及1.2克之合成範例1的「SYN-1」達1小時,以獲得可固化有機聚矽氧烷組成物A(下文中以「PTA」表示)。 25 g of MB1, 28 g of VP, 0.03 g of platinum complex, and 1.2 g of "SYN-1" of Synthesis Example 1 prepared in advance were mixed at room temperature for 1 hour using an upright mixer to obtain a curable organopolyoxyalkylene. Composition A (hereinafter referred to as "PTA").
(2)製備組成物B (2) Preparation of composition B
將5.4克之有機含氫聚矽氧烷(氫含量7.3mmol/g)、8.7克VP、作為阻劑之0.01克1-乙炔基-1-環己醇(1-ethynyl-1-cyclohexanol)及0.7克環氧丙醇三甲氧基矽烷加入玻璃容器中,並使用直立攪拌機在室溫下混合1小時,以獲得可固化有機聚矽氧烷組成物B(下文中以「PTB」表示)。 5.4 g of an organic hydrogen-containing polyoxyalkylene (hydrogen content: 7.3 mmol/g), 8.7 g of VP, 0.01 g of 1-ethynyl-1-cyclohexanol as a resist, and 0.7 Grafts of propylene glycol trimethoxy decane was placed in a glass vessel and mixed at room temperature for 1 hour using an upright mixer to obtain a curable organopolyoxane composition B (hereinafter referred to as "PTB").
(3)混合組成物A以及組成物B (3) Mixed composition A and composition B
在容器中秤重30重量份之組成物A及10重量份之組成物B,使用刮勺預先混合,再使用攪拌脫泡裝置(revolution-rotation mixer)(ARE-310:新基公司(THINKY corporation)所製造)在真空之下混合並去泡1分鐘,以獲得可固化有機聚矽氧烷組成物。組成物被固化以製造一已固化之薄片(sheet)。 30 parts by weight of the composition A and 10 parts by weight of the composition B were weighed in a container, and pre-mixed using a spatula, and then a resonance-rotation mixer (ARE-310: THINKY corporation) (manufactured) was mixed under vacuum and defoamed for 1 minute to obtain a curable organopolyoxane composition. The composition is cured to produce a cured sheet.
範例2 Example 2
除了將合成範例1之「SYN-1」改為合成範例2之「SYN-2」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by performing the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-2" of Synthesis Example 2. The composition is cured to produce a cured sheet.
範例3 Example 3
除了將合成範例1之「SYN-1」改為合成範例3之「SYN-3」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-3" of Synthesis Example 3. The composition is cured to produce a cured sheet.
範例4 Example 4
除了將合成範例1之「SYN-1」改為合成範例4之「SYN-4」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-4" of Synthesis Example 4. The composition is cured to produce a cured sheet.
範例5 Example 5
除了將合成範例1之「SYN-1」改為合成範例5之「SYN-5」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by performing the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-5" of Synthesis Example 5. The composition is cured to produce a cured sheet.
範例6 Example 6
除了將合成範例1之「SYN-1」改為合成範例6之「SYN-6」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-6" of Synthesis Example 6. The composition is cured to produce a cured sheet.
範例7 Example 7
除了將合成範例1之「SYN-1」的添加量改為3.0克之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that the addition amount of "SYN-1" of Synthesis Example 1 was changed to 3.0 g, and the composition was cured. A cured sheet is produced.
範例8 Example 8
除了將合成範例1之「SYN-1」的添加量改為7.2克之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that the addition amount of "SYN-1" of Synthesis Example 1 was changed to 7.2 g, and the composition was cured. A cured sheet is produced.
比較例1 Comparative example 1
除了改為不添加合成範例1之「SYN-1」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by performing the same process as described in Example 1 except that "SYN-1" of Synthesis Example 1 was not added, and the composition was cured to produce a Cured sheet.
比較例2 Comparative example 2
除了將合成範例1之「SYN-1」改為含有22%異辛酸鈰(cerium octoate)的0.5%之礦物油之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was described in Example 1 except that the "SYN-1" of Synthesis Example 1 was changed to a 0.5% mineral oil containing 22% cerium octoate. The same process is obtained and the composition is cured to produce a cured sheet.
比較例3 Comparative example 3
除了將合成範例1之「SYN-1」改為0.11%異辛酸鈰(純度99.8%)之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to 0.11% bismuth octoate (purity of 99.8%). And the composition is cured to make a cured sheet.
比較例4 Comparative example 4
除了將合成範例1之「SYN-1」改為0.01%丁氧鈰(純度99.8%)之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that the "SYN-1" of Synthesis Example 1 was changed to 0.01% butoxyxime (purity of 99.8%). And the composition is cured to make a cured sheet.
比較例5 Comparative Example 5
除了將合成範例1之「SYN-1」改為0.07%異丙氧化鈰(純度99.8%)之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to 0.07% isopropoxide (purity of 99.8%). And the composition is cured to make a cured sheet.
比較例6 Comparative Example 6
除了不添加合成範例1之「SYN-1」之外,可固化有機聚矽氧烷組成物是藉由進行描述於範例1之相同的過程所獲得,且組成物被固化以製造一已固化之薄片。 The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that "SYN-1" of Synthesis Example 1 was not added, and the composition was cured to produce a cured one. Sheet.
實驗範例 Experimental example
[實驗方法] [experimental method]
已固化之薄片的製造 Manufacture of cured sheets
可固化有機聚矽氧烷組成物主要是在120℃之下在用於成模為厚度2mm之一模具中固化30分鐘,接著在150℃之下於烘箱中後固化2小時,以形成已固化之薄片。 The curable organopolyoxane composition is mainly cured at 120 ° C for 30 minutes in a mold for molding to a thickness of 2 mm, followed by post-curing in an oven for 2 hours at 150 ° C to form a cured Thin sheet.
1)起始硬度 1) Initial hardness
重疊3層已固化的薄片,並在25℃之下使用蕭氏A型(shore A-type)或蕭氏D型硬度計測量硬度。 Three layers of cured sheets were overlapped and the hardness was measured using a Shore A-type or a Shore D durometer at 25 °C.
2)硬度變化 2) Hardness change
將用於起始硬度之量測所製造之薄片放置於250℃的烘箱中,藉由相同於起始硬度之量測的方法根據所經時間測量硬度。 The sheet for measurement of the initial hardness was placed in an oven at 250 ° C, and the hardness was measured according to the elapsed time by the same method as the measurement of the initial hardness.
3)穿透度 3) Penetration
使用紫外可見光譜(模式名稱:Lambda950,製造商:PERKIN ELMER)測量根據本發明之有機聚矽氧烷之已固化薄片(厚度2mm)的穿透度。 The transmittance of the cured sheet (thickness 2 mm) of the organopolysiloxane according to the present invention was measured using ultraviolet visible spectrum (pattern name: Lambda 950, manufacturer: PERKIN ELMER).
4)剩餘重量比例 4) Residual weight ratio
將有機聚矽氧烷之已固化產物豎放(stand)於250℃的烘箱中達168小時,並在收存(store)之前與之後測量其重量,以計算剩餘重量比例。剩餘重量比例愈高,則抗熱度愈佳。 The cured product of the organopolyoxyalkylene was stood in an oven at 250 ° C for 168 hours, and its weight was measured before and after the storage to calculate the remaining weight ratio. The higher the residual weight ratio, the better the heat resistance.
5)熱膨脹係數(coefficient of thermal expansion,CTE)的改變比例(%) 5) Change ratio of coefficient of thermal expansion (CTE) (%)
將有機聚矽氧烷之已固化產物存放於250℃的烘箱中達168小時,並在收存之前與之後使用動態熱特性分析儀(dynamic thermal characteristics analyzer)(模式名稱:DMA8000,製造商:PERKIN ELMER)測量其熱膨脹係數,並根據下列算式進行計算。熱膨脹係數的改變比例愈低,則抗熱度愈佳。 The cured product of the organopolyoxyalkylene was stored in an oven at 250 ° C for 168 hours, and a dynamic thermal characteristics analyzer was used before and after storage (mode name: DMA8000, manufacturer: PERKIN ELMER) measures its coefficient of thermal expansion and calculates it according to the following formula. The lower the ratio of change in the coefficient of thermal expansion, the better the heat resistance.
熱膨脹係數的改變比例(%)={(收存之前的CTE)-(收存之後的CTE)/(收存之前的CTE)}*100(%) The ratio of change in thermal expansion coefficient (%) = {(CTE before storage) - (CTE after storage) / (CTE before storage)} * 100 (%)
如表1及表2所示,當藉由紫外可見光譜測量時,根據本發明之高度可靠度及可固化的有機聚矽氧烷組成物(範例1至8)在260nm具有50%或小於50%之穿透度。然而,當藉由相同方法量測時,根據比較例1至6之抗熱度不佳的產物具有60%或大於60%之穿透度。 As shown in Tables 1 and 2, the highly reliable and curable organopolyoxane compositions (Examples 1 through 8) according to the present invention have 50% or less at 260 nm when measured by UV-visible spectroscopy. % penetration. However, when measured by the same method, the products having poor heat resistance according to Comparative Examples 1 to 6 had a transmittance of 60% or more.
在徹底檢視範例1至8及比較例1至6之後,藉由紫外可見光譜於260nm之有機聚矽氧烷已固化產物的起始穿透度整體而言是確保為與抗熱度成比例(剩餘的重量比例)。 After thoroughly examining Examples 1 to 8 and Comparative Examples 1 to 6, the initial penetration of the cured product of the organopolyoxane at 260 nm by UV-visible spectroscopy is generally ensured to be proportional to the heat resistance (remaining Weight ratio).
此外,熱膨脹係數一般是依據已固化產物之有機聚矽氧烷的硬度而有所不同。本發明之發明者確保,在250℃的抗熱度測試進行168小時之前及之後的熱膨脹係數改變比例,是隨著具有類似 的起始硬度(250℃,0小時)之樣本(範例1至6及比較例1至5)的起始穿透度之減少而降低。 Further, the coefficient of thermal expansion generally differs depending on the hardness of the organopolyoxane of the cured product. The inventors of the present invention ensured that the coefficient of thermal expansion change before and after 168 hours of the heat resistance test at 250 ° C is similar The initial hardness (250 ° C, 0 hours) of the samples (Examples 1 to 6 and Comparative Examples 1 to 5) decreased with a decrease in the initial penetration.
對於包括具有低硬度之薄片(範例1至6)及高硬度之薄片(範例7及8)的範例1至8而言,硬度並沒有在250℃、168小時之下增加,穿透度的降低很小,已固化薄片的熱分解很少,剩餘的重量比例為高,最大在2000小時之下薄片中沒有產生裂縫。 For Examples 1 to 8 including sheets having low hardness (Examples 1 to 6) and high hardness sheets (Examples 7 and 8), the hardness did not increase at 250 ° C, 168 hours, and the penetration was lowered. Very small, the cured sheets have little thermal decomposition, the remaining weight ratio is high, and no cracks are formed in the sheets up to 2000 hours.
即使未顯示於表中,蕭氏50A(範例1至6)之硬度的組成物中並沒有產生裂縫達2000小時。 Even though it is not shown in the table, no cracks were formed in the composition of the hardness of Xiao's 50A (Examples 1 to 6) for 2000 hours.
相對地,根據本發明之實施例之不包括有機-無機金屬複合物之比較例1至6,穿透度改變是小的,然由於熱分解,硬度增加率及重量降低率係相當大。 In contrast, in Comparative Examples 1 to 6 excluding the organic-inorganic metal composite according to the embodiment of the present invention, the change in the transmittance was small, but the rate of increase in hardness and the rate of weight reduction were considerably large due to thermal decomposition.
此外,根據本發明一實施例之包括抗熱添加劑(不同於有機-無機金屬複合物之抗熱添加劑之成分)的比較例2至5,當相較於不包括金屬原子之比較例1時,顯示顯著較差的穿透度,甚至表現出高的硬度改變及剩餘的重量比例。此外,當相較於範例1至8時,上列量測之所有的物理特性係顯著地惡化,特別是在250℃於700小時之內產生裂縫,顯示相對低之抗熱度。 Further, Comparative Examples 2 to 5 including a heat-resistant additive (a component different from the heat-resistant additive of the organic-inorganic metal composite) according to an embodiment of the present invention, when compared with Comparative Example 1 excluding a metal atom, Significantly poor penetration is shown, even showing a high hardness change and the remaining weight ratio. Further, when compared with the examples 1 to 8, all the physical properties of the above measurement were remarkably deteriorated, particularly, cracks were generated within 700 hours at 250 ° C, showing relatively low heat resistance.
因此,可以確保的是,根據本發明一實施例之包括抗熱添加物(有機-無機金屬複合物)之可固化有機聚矽氧烷,相較於其他組成物顯示較佳之物理特性。 Therefore, it can be ensured that the curable organopolyoxane including the heat-resistant additive (organic-inorganic metal composite) according to an embodiment of the present invention exhibits better physical properties than the other compositions.
本發明之保護範圍當視後附之申請專利範圍所界定者 為準,而非是藉由上列描述及本文所述之示例性實施例所界定。本發 明之申請專利範圍之等效涵義之內以及申請專利範圍之內的各種潤飾應視為在本發明的範疇之中。 The scope of protection of the present invention is defined by the scope of the appended patent application. The subject matter is defined by the above description and the exemplary embodiments described herein. This hair Various modifications within the meaning of the patent application scope and the scope of the patent application are considered to be within the scope of the invention.
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