CN103342816B - A kind of organic siliconresin and curable organopolysiloxane composition and application - Google Patents
A kind of organic siliconresin and curable organopolysiloxane composition and application Download PDFInfo
- Publication number
- CN103342816B CN103342816B CN201310245790.5A CN201310245790A CN103342816B CN 103342816 B CN103342816 B CN 103342816B CN 201310245790 A CN201310245790 A CN 201310245790A CN 103342816 B CN103342816 B CN 103342816B
- Authority
- CN
- China
- Prior art keywords
- formula
- sio
- organic siliconresin
- minutes
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 27
- 229910020485 SiO4/2 Inorganic materials 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 5
- -1 acetylene alcohol compounds Chemical class 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 16
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 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 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 8
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002683 reaction inhibitor Substances 0.000 claims description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 claims description 2
- 229910003609 H2PtCl4 Inorganic materials 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims description 2
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 2
- PPCBWIPAAXVHIP-UHFFFAOYSA-N [Ti].C(CCCCC(C)C)O Chemical compound [Ti].C(CCCCC(C)C)O PPCBWIPAAXVHIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910020487 SiO3/2 Inorganic materials 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 8
- 230000035939 shock Effects 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 35
- 239000011347 resin Substances 0.000 description 35
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- 239000004954 Polyphthalamide Substances 0.000 description 9
- 229920006375 polyphtalamide Polymers 0.000 description 9
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 description 7
- 229910008051 Si-OH Inorganic materials 0.000 description 7
- 229910020388 SiO1/2 Inorganic materials 0.000 description 7
- 229910006358 Si—OH Inorganic materials 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- JPADPHKEIXYMNG-UHFFFAOYSA-N ethenyl(silyloxy)silane Chemical compound [SiH3]O[SiH2]C=C JPADPHKEIXYMNG-UHFFFAOYSA-N 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 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 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 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 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 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 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 241001249696 Senna alexandrina Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of organic siliconresin and curable organopolysiloxane composition and application.The structural formula of this organic siliconresin forms shown in formula I.The organo-silicon compound in this organic siliconresin and a part with at least 2 hydrogen being combined with silicon atom are mixed, obtains curable organopolysiloxane composition.This curable organopolysiloxane composition is applied on emitting semiconductor encapsulates, and has the advantage that splendid adhesive property, stronger hardness, excellent impact resistance, transparency are high, variable color is little in heat resistant test, luminous efficiency is high, be unlikely to be peel off in thermal shock is tested and show outstanding cementability in PPA and metal adhesive experiment.R1R2 2SiO(R3SiO3/2)a(SiO4/2)b(R4 2SiO)c OSiR2 2R1Formulas I.
Description
Technical field
The present invention relates to a kind of binding agent, particularly to a kind of organic siliconresin and curable organopolysiloxane
Compositions and application.
Background technology
Traditional electronic/electrical device sealing and curing and the curable resin composition of bonding employing are frequently with curable
Composition epoxy resin, to obtain the curing materials of high rigidity, the high grade of transparency and low-thermal-expansion.But, should
Solidfied material excessively rigidity, thermal expansion in the curing process is tended to produce big in electronic/electrical device components interior
Stress makes to occur inside cured product crackle.It addition, in the high power electronic/electric component application of big electric current
Producing substantial amounts of thermal capacitance easily makes the solidfied material of composition epoxy resin turn yellow, and affects luminous efficiency.
In order to reduce stress and improve the deficiencies such as solidfied material xanthochromia, it is thus proposed that utilize organopolysiloxane group
Compound prepares the resin material with the high grade of transparency and low stress, such as Japan by hydrosilylation
Patent application JP2002-327126 and JP2002-338833 proposes to be contained at least 2 and Si-H by a part
Base has the organo-silicon compound of the unsaturated double-bond of reactivity, containing at least 2 Si-H bases in a part
Silicon compound, the emitting semiconductor that hydrosilylation catalyst is formed is coated to protection resin combination.But
The solidfied material hardness of these silicon-types is not enough, lacks the caking property between metal/plastic, uses this material
During encapsulation semiconductor device, during thermal shock experiment at-40～120 DEG C, organic siliconresin easily from metal or
Peel off on person's plastic material.
It is proposed further and utilizes the compositions of epoxy resin and organic siliconresin to prepare curing materials, with
Comprehensively both advantages.Japanese patent application JP2006-041927 utilizes the organic poly-silica containing vinyl
Alkane, organic hydrogen polysiloxanes, addition reaction catalyst and containing epoxy radicals and/or the organic poly-silica of alkoxyl
Alkane, prepares and has high rigidity, the high grade of transparency, thermostability and sunproof cured article, and from wet
Thermal environment will not become white casse shape when returning to room temperature at once.Chinese patent application CN101155792B
Utilize specific chemical structural formula: every a part has the organopolysiloxane of at least two epoxy-functional,
Utilize the diorganosiloxane with ad hoc structure formula, for the firming agent of epoxy resin, prepare tool
There is the cured product of excellent caking property and curing characteristics and excellent flexibility.
But, epoxy resin derived above/organosilicon resin composition curing materials is bonding with PPA/ metal
Power is not enough, still easily peels off from substrate under thermal shock；Especially on the substrate that PPA purity is the highest
Peeling rate is higher.
Summary of the invention
The primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, it is provided that a kind of organic siliconresin
And preparation method thereof.
Another object of the present invention is to provide the curable organopolysiloxane group containing above-mentioned organic siliconresin
Compound and preparation method thereof.
It is still another object of the present invention to provide the application of described curable organopolysiloxane composition.
The purpose of the present invention is achieved through the following technical solutions: a kind of organic siliconresin, and structural formula forms such as Formulas I
Shown in:
R1R2 2SiO(R3SiO3/2)a(SiO4/2)b(R4 2SiO)c OSiR2 2R1
Formulas I；
In Formulas I, each R1Representation hydroxy, amino, carboxyl, alkoxyl, epoxy radicals, alkenyl independently
Or halogen isoreactivity group, particularly preferred hydroxyl, carbon number are alkenyl or the carbon number of 1～10
It it is the epoxy radicals of 1～10；More preferably at least one R1For hydroxyl；Wherein, R1In hydroxyl, alkenyl and
Epoxy radicals is obtained by hydrolyzable silane hydrolyzate, and amino, carboxyl, alkoxyl and halogen are by obtaining after hydrolysis
To polysiloxanes react further and obtain；Reactive group R1The content in component A preferably 0.1～
10%(mol/mol), particularly preferably 0.5～2%(mol/mol)；During less than 0.1%, solidfied material hardness is inclined
Low, and during more than 10%, solidfied material toughness declines a lot；
Each R2Represent the replacement (hydrogen referring on alkyl is to be replaced) that carbon number is 1～10 independently
Or non-substituted monovalent hydrocarbon, or the alkoxyl that carbon number is 1～10, including methyl, ethyl, propyl group,
Isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, neopentyl, hexyl, cyclohexyl, phenyl, toluene
Base (main chain and benzene are joined directly together), xylyl, naphthyl, benzyl (main chain and methyl are joined directly together),
Phenethyl, phenylpropyl, vinyl, pi-allyl, acrylic, isopropenyl, cyclobutenyl, hexenyl, first
Epoxide, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy and tert-butoxy；Preferably carbon
Atomic number is the substituted or non-substituted monovalent hydrocarbon of 1～3, or the alkoxyl that carbon number is 1～2；More
It is preferably methyl；
Each R3Represent the substituted or non-substituted monovalent hydrocarbon that carbon number is 1～10 independently, or carbon is former
Subnumber is the alkoxyl of 1～10, including methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, uncle
Butyl, amyl group, neopentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, benzene first
Base, phenethyl, phenylpropyl, vinyl, pi-allyl, acrylic, isopropenyl, cyclobutenyl, hexenyl,
Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy and tert-butoxy；Preferably
Carbon number is the substituted or non-substituted monovalent hydrocarbon of 1～6, or the alkoxyl that carbon number is 1～2；
More preferably methyl or phenyl；
Each R4Represent substituted or non-substituted monovalent hydrocarbon that carbon number is 1～10 individually, containing epoxy
The substituent group of group or the alkoxyl that carbon number is 1～10, including methyl, ethyl, propyl group, isopropyl,
Butyl, isobutyl group, the tert-butyl group, amyl group, neopentyl, hexyl, cyclohexyl, phenyl, tolyl, diformazan
Phenyl, naphthyl, benzyl, phenethyl, phenylpropyl, vinyl, pi-allyl, acrylic, isopropenyl,
Cyclobutenyl, hexenyl, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy,
Tert-butoxy, 2-epoxy ethyl, 2,3-glycidoxy, γ-(2,3-epoxypropyl) propyl group and β-(3,4
Epoxycyclohexyl)-ethyl or 2-oxetanyl；Preferably carbon number be 1～6 substituted or non-substituted
Monovalent hydrocarbon, or the substituent group containing epoxide group；More preferably phenyl, methyl, vinyl or epoxy ethyl；
R2、R3And R4In at least contain 1 unsaturated monovalent hydrocarbon, in order to silicon hydrogen generation additive reaction,
Improve the mechanical performance of cured product；
The compound represented in Formulas I meets 0.2≤a≤0.9,0≤b≤0.2,0.1≤c≤0.8, and a+b+c=1；
Particularly preferred 0.3≤a≤0.7,0≤b≤0.1,0.2≤c≤0.7；A, b and c represent that it is at main chain (i.e.
(R3SiO3/2)a(SiO4/2)b(R4 2SiO)cMole percent in)；
The viscosity of described organic siliconresin has no particular limits, but recommendation range of viscosities at 25 DEG C is
50～1000000mPa s, preferably at 25 DEG C, range of viscosities is 200～100000mPa s, the most excellent
Being selected in range of viscosities at 25 DEG C is 500～50000, will become to be difficult to operate when viscosity exceedes the upper limit, and viscosity is low
When lower limit, the mechanical performance of cured product will decline；At more preferably 25 DEG C range of viscosities be 6000～
20000。
The preparation method of described organic siliconresin, comprises the steps of:
1. it is the mixed in hydrochloric acid of 37% by tetraethyl orthosilicate, ethanol and mass percent, reaction；
2. phenyltrimethoxysila,e is added, reaction；
3. aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane and 3-glycidyl ether are added
Epoxide hydroxypropyl methyl diethoxy silane, back flow reaction；
4. add tetramethyl divinyl disiloxane, continue back flow reaction；
5. take the organic layer in the product that 4. step obtains, with water, organic layer is washed neutral pH；Add water,
Back flow reaction, concentrating under reduced pressure, obtain organic siliconresin；
Wherein, tetraethyl orthosilicate, ethanol, mass percent be 37% hydrochloric acid, phenyltrimethoxysila,e,
Aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane, 3-glycydoxy methyl
Diethoxy silane and tetramethyl divinyl disiloxane 10.4:30:15:(41.2 in mass ratio～68.3):
(24.7～63.7): 7.9:(7.4～14.8): 1.8 proportionings；
Step 1. described in the condition of reaction be preferably 70 DEG C and react 5 minutes；
Step 2. described in the condition of reaction be preferably 70 DEG C and react 15～120 minutes；
Step 3. described in the condition of back flow reaction be preferably 70 DEG C of back flow reaction 15～120 minutes；
Step 4. described in the condition of back flow reaction be preferably 70 DEG C of back flow reaction 60 minutes；
Step 5. described in the condition of back flow reaction be preferably 70 DEG C of back flow reaction 30～60 minutes；
Step 5. described in the specifically comprising the following steps that step of the organic layer taken in the product that 4. step obtains
4. the product obtained pours separatory funnel into, divides and removes sour water layer, obtains organic layer；
Step 5. described in the consumption of the water added in water be equivalent to the 1/10.4 of tetraethyl orthosilicate quality；
Step 5. described in the condition of concentrating under reduced pressure reduce pressure distillation and concentration preferably with vacuum pump；
A kind of curable organopolysiloxane composition, comprises following component:
(A) above-mentioned organic siliconresin, it at least contains 2 alkenyls being bonded with silicon (i.e. thiazolinyl)；
(B) a part has the organo-silicon compound of at least 2 hydrogen being combined with silicon atom；
Described curable organopolysiloxane composition, also comprises following component:
(C) platinum group metal series catalysts；
(D) metal-complexing catalytic reaction catalyst；
(E) additive reaction inhibitor.
Component (B) is to have the organo-silicon compound of at least 2 hydrogen being combined with silicon atom in a part, logical
The Si-H base crossed in this composition carries out hydrosilylation formation solidification with the unsaturated double-bond in component (A)
Thing；The formula of component (B) is as shown in Formula II:
Hd(R5)eSiO(4-d-e)/2
Formula II；
In Formula II, R5For the identical or different substituted or non-substituted monovalent hydrocarbon without unsaturated aliphatic,
Preferably carbon number be the substituted or non-substituted monovalent hydrocarbon of 1～6, preferably carbon number be 1～3 take
Generation or non-substituted monovalent hydrocarbon, more preferably methyl, ethyl, propyl group, isopropyl, butyl, cyclohexyl,
Phenyl, tolyl, xylyl and benzyl etc.；The hydrogen atom position being combined with silicon does not has special restriction,
Can also be in centre at the end of molecule；
D and e meets 0.1≤d≤2,0.5≤e≤2, and 0.7≤d+e≤3；
Component (B) is organic hydrogen polysiloxanes, and its consumption is the amount that matching component (A) reaches effectively to solidify,
I.e. the Si-H base of component (B) is for the ratio (Si-H/Si-Vi) of the mole of the unsaturated thiazolinyl in component (A)
Being 0.5～4.0, preferably 1.0～3.2, the mol ratio of particularly preferred 1.0～2.8 uses；Solidify during less than 0.5
Not exclusively residual unsaturated alkyl makes heat-resisting xanthochromia degradation, and due to residual Si-H base during more than 4.0
Making cured product be easily deformed, the residual quantity of (B) component too much also results in the mechanicalness of cured product in addition
Can be deteriorated.
The synthesis of component (B) by siloxanes that degree of functionality is 1～3 and with the siloxanes of Si-H base at sulfur
Under the catalysis of acid or hydrochloric acid, hydrolytie polycondensation realizes.
Described degree of functionality be 1～3 siloxanes include dimethyldimethoxysil,ne, dimethyl diethoxy
Silane, MTMS, diethyldiethoxysilane, ethyl trimethoxy silane, diisopropyl
Base dimethoxysilane, aminomethyl phenyl dimethoxysilane, phenyltrimethoxysila,e and diphenyl dimethoxy
Base silane etc.；
The described siloxanes with Si-H base includes methyl dimethoxysilane, 1,1,3,3-tetramethyl two silica
Alkane and phenyidimethoxysilane etc.；
The synthetic method of component (B) can refer to the Chemical Industry Press good fortune pine people, and it is " organic that Wang Yilu writes
Silicon synthesis technique and products application " preparation method of chapter 7 7.2.2.1 containing hydrogen silicone oil: 30 mass parts
Me2HSiOSiHMe2, 50 mass parts PhSi (OMe)3And 30 mass parts Me3SiO(MeHSiO)mSiMe3
Or (MeHSiO)mMixing, the concentrated sulphuric acid adding 7 mass parts mass percents 98% makees catalyst, in room temperature
Lower balance 5h, stratification, remove sour water layer, oil reservoir Na2CO3Neutralize 30min, received after filtration
Rate reaches 95%(mass fraction) purpose product HMe2Si(MeHSiO)3(PhSiO3/2)7SiMe2H。
Component (C) is to coordinate the platinum group metal series catalysts needed for Si-H addition reaction curing reaction, can enumerate
H2PtCl6·mH2O、H2PtCl4·mH2O、K2PtCl6·mH2O、K2PtCl4·mH2O.These catalysis
Agent can be used alone, it is also possible to by above-mentioned 2 kinds or above component with the use of.The consumption of catalyst is
Aforementioned (A) and the 0.1～1000ppm of (B) constituent mass total amount, preferably 1～the scope of 200ppm
Use, more preferably 7ppm.
Component (D) is the metal-complexing catalytic reaction catalyst making epoxy radicals catalyzed ring opening polymerization, specifically may be used
List the titanizings such as titanium tetraisopropylate, isooctanol titanium, four n-butyl titaniums, diisopropoxy bis-acetylacetonate titanium
Compound, the aluminium compound such as triethyl aluminum, aluminium ethoxide, aluminum isopropylate., aluminium acetylacetonate, diethyl zinc
Deng zirconium compoundss such as zinc compound, zirconium-n-butylates；Aforesaid catalyst can be used alone, it is also possible to multiple
Above with the use of.The consumption of component (D) catalyst be (A)～(C) constituent mass total amount 0.05～
10%, preferably 0.1～5%, more preferably 0.4%, during less than 0.05%, curing rate is the slowest, it is possible to the short time
In can not obtain completely crued product, during higher than 10%, curing rate is too fast, and solidification may be caused to produce
Product light transmittance declines.
Component (E) is additive reaction inhibitor, can enumerate: the phosphorus-containing compounds such as triphenylphosphine, tetramethyl
The nitrogen-containing compounds such as ethylenediamine, the sulfur-containing compound such as thiophene, the acetylide such as acetylene alcohols；It is preferably 2-
Phenyl-3-butyne-2-alcohol.According to storage stability and heat cure requirement, different structure inhibitor can be selected also
Can regulate addition, its consumption is preferably the 0.07% of (A)+(B) constituent mass total amount.
In order to increase the cementability of cured product, intensity, operability, resistance to metachrosis etc. further,
In the range of the object of the invention, silane coupler, inorganic reinforcement and filler material, solidification can be added
Catalyst-initiator, antioxidant etc..
The preparation method of described curable organopolysiloxane composition, comprises the steps of: (A)～
(E) component mixing final vacuum sloughs bubble, and solidification obtains curable organopolysiloxane composition.
The condition of described solidification, according to operating condition from lower 168 hours to 200 DEG C of room temperature (25 DEG C)
20 minutes is arbitrary, and can carry out the solidification that multistage temperature is different as required.
Described curable organopolysiloxane composition, it is adaptable to the coating guarantor of coating protection emitting semiconductor
Protective material uses.As emitting semiconductor, light emitting diode (LED), organic electroluminescent can be listed
Original paper (organic EL), laser diode, LED array etc..
The present invention has such advantages as relative to prior art and effect:
(1) curable organopolysiloxane composition that the present invention provides is applied on emitting semiconductor encapsulates,
There is the advantages such as splendid adhesive property, stronger hardness and excellent impact resistance.
(2) using the semiconductor light-emitting apparatus of the organic silicon mixed resin combination protection of the present invention, resin has
Having high transparency and hardness, in heat resistant test, variable color is little, and luminous efficiency is high, tests at thermal shock
In be unlikely to be peel off, and show outstanding cementability in testing with PPA and metal adhesive.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
This.
Embodiment 1
Tetraethyl orthosilicate 10.4g is added flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 41.2g, 70 DEG C
React 30 minutes, add aminomethyl phenyl dimethoxysilane 63.7g, methylvinyldimethoxysilane 7.9g
With 3-glycidyl ether hydroxypropyl methyl diethoxy silane 7.4g, 70 DEG C are refluxed 60 minutes, add tetramethyl two
Vinyl disiloxane 1.8g, continues 70 DEG C and refluxes 60 minutes, pour separatory funnel into, divide and remove sour water layer, have
Machine layer is washed with deionized water neutral pH, pours flask into, adds deionized water 1g, and 70 DEG C are refluxed 30 minutes,
Vacuum pump decompression distillation and concentration, obtain viscosity at 25 DEG C be 6000mPa s(viscometer detection) resin.
Pass through1H NMR、13C NMR、29Si NMR and FT-IR detects, and obtains following data:1H NMR
(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,18H, Si-CH=CH2, 0-0.5,144H, Si-Me),13C NMR(δ, ppm, 0-5, Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR
(δ, ppm, 0-10, SiO1/2, 20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2), FT-IR
(cm-1, 3300-3400, Si-OH, 890-900, Ep), determine the structure of resin (named resin 1)
Formula is as follows:
HOMe2SiO(PhSiO3/2)21(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)35OSi
Me2Vi；Wherein, Me is methyl, Ph be phenyl, Ep be epoxy ethyl, Vi be vinyl.
Therefore, a=21/(21+5+3+6+35)=0.3, b=5/70=0.07, c=44/70=0.63.
Embodiment 2
Tetraethyl orthosilicate 10.4g is added flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 68.3g, 70 DEG C
React 30 minutes, add aminomethyl phenyl dimethoxysilane 44.2g, methylvinyldimethoxysilane 7.9g
With 3-glycidyl ether hydroxypropyl methyl diethoxy silane 7.4g, 70 DEG C are refluxed 60 minutes, add tetramethyl two
Vinyl disiloxane 1.8g, continues 70 DEG C and refluxes 60 minutes, pour separatory funnel into, divide and remove sour water layer, have
Machine layer washes neutral pH, pours flask into, adds deionized water 1g, and 70 DEG C are refluxed 60 minutes, vacuum water
Pump decompression distillation and concentration, obtaining viscosity at 25 DEG C is the resin of 12000mPa s.Pass through1H NMR、13C
NMR、29Si NMR and FT-IR detects, and obtains following data:1H NMR(δ, ppm, 7-8,
280H, Si-Ph, 5.7-6.2,18H, Si-CH=CH2, 0-0.5,102H, Si-Me),13C NMR(δ,
Ppm, 0-5, Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR(δ, ppm, 0-10,
SiO1/2, 20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2), FT-IR(cm-1, 3300-3400,
Si-OH, 890-900, Ep), determine that the structural formula of resin (named resin 2) is as follows:
HOMe2SiO(PhSiO3/2)35(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)21OSi Me2Vi。
Ibid, a=0.5, b=0.07, c=0.43 are calculated.
Embodiment 3
Tetraethyl orthosilicate 10.4g adds flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 61.9g, 70 DEG C
React 30 minutes, add aminomethyl phenyl dimethoxysilane 24.7g, methylvinyldimethoxysilane 7.9g
With 3-glycidyl ether hydroxypropyl methyl diethoxy silane 14.8g, 70 DEG C are refluxed 60 minutes, add tetramethyl
Divinyl disiloxane 1.8g, continues 70 DEG C and refluxes 60 minutes, pour separatory funnel into, divide and remove sour water layer,
Organic layer washes neutral pH, pours flask into, adds deionized water 1g, and 70 DEG C are refluxed 30 minutes, vacuum
Water pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, obtaining viscosity at 25 DEG C is 20000mPa
The resin of s.Pass through1H NMR、13C NMR、29Si NMR and FT-IR detects, and is counted as follows
According to:1H NMR(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,18H, Si-CH=CH2, 0-0.5,
60H, Si-Me),13C NMR(δ, ppm, 0-5, Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR(δ, ppm, 0-10, SiO1/2, 20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2),
FT-IR(cm-1, 3300-3400, Si-OH, 890-900, Ep), determine resin (named resin 3)
Structural formula is as follows:
HOMe2SiO(PhSiO3/2)49(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)7OSi
Me2Vi。
Ibid, a=0.7, b=0.07 and c=0.23 are calculated.
Reactive group R in this embodiment of embodiment 4(1The content in component A be 0.5%)
Tetraethyl orthosilicate 10.4g is added flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 68.3g, 70 DEG C
React 15 minutes, add aminomethyl phenyl dimethoxysilane 44.2g, methylvinyldimethoxysilane 7.9g
With 3-glycidyl ether hydroxypropyl methyl diethoxy silane 7.4g, 70 DEG C are refluxed 15 minutes, add tetramethyl two
Vinyl disiloxane 1.8g, continues 70 DEG C and refluxes 60 minutes, pour separatory funnel into, divide and remove sour water layer, have
Machine layer washes neutral pH, pours flask into, adds deionized water 1g, and 70 DEG C are refluxed 60 minutes, vacuum water
Pump decompression distillation and concentration, obtaining viscosity at 25 DEG C is the resin of 30000mPa s.Pass through1H NMR、13C
NMR、29Si NMR and FT-IR detects, and obtains following data:1H NMR(δ, ppm, 7-8,
155H, Si-Ph, 5.7-6.2,12H, Si-CH=CH2, 0-0.5,63H, Si-Me),13C NMR(δ,
Ppm, 0-5, Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR(δ, ppm, 0-10,
SiO1/2, 20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2), FT-IR(cm-1, 3300-3400,
Si-OH, 890-900, Ep), determine that the structural formula of resin (named resin 4) is as follows:
HOMe2SiO(PhSiO3/2)19(SiO4/2)2(EpMeSiO)2(ViMeSiO)3(MePhSiO)12OSi Me2Vi。
Ibid, a=0.5, b=0.05 and c=0.45 are calculated.
Reactive group R in this embodiment of embodiment 5(1The content in component A be 2%)
Tetraethyl orthosilicate 10.4g is added flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 68.3g, 70 DEG C
React 2 hours, add aminomethyl phenyl dimethoxysilane 44.2g, methylvinyldimethoxysilane 7.9g
With 3-glycidyl ether hydroxypropyl methyl diethoxy silane 7.4g, 70 DEG C are refluxed 2 hours, add tetramethyl two
Vinyl disiloxane 1.8g, continues 70 DEG C and refluxes 60 minutes, pour separatory funnel into, divide and remove sour water layer, have
Machine layer washes neutral pH, pours flask into, adds deionized water 1g, and 70 DEG C are refluxed 60 minutes, vacuum water
Pump decompression distillation and concentration, obtaining viscosity at 25 DEG C is the resin of 4000mPa s.Pass through1H NMR、13C
NMR、29Si NMR and FT-IR detects, and obtains following data:1H NMR(δ, ppm, 7-8,
390H, Si-Ph, 5.7-6.2,30H, Si-CH=CH2, 0-0.5,144H, Si-Me),13C NMR(δ,
Ppm, 0-5, Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR(δ, ppm, 0-10,
SiO1/2, 20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2), FT-IR(cm-1, 3300-3400,
Si-OH, 890-900, Ep), determine that the structural formula of resin (named resin 5) is as follows:
HOMe2SiO(PhSiO3/2)49(SiO4/2)7(EpMeSiO)4(ViMeSiO)9(MePhSiO)29OSi Me2Vi。
Ibid, a=0.5, b=0.07 and c=0.43 are calculated.
Comparative example 1: same as in Example 2, differs only in a few step backflow, causes R1 different
Tetraethyl orthosilicate 10.4g is added flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 68.3g, 70 DEG C
React 30 minutes, add aminomethyl phenyl dimethoxysilane 44.2g, methylvinyldimethoxysilane 7.9g
With 3-glycidyl ether hydroxypropyl methyl diethoxy silane 7.4g, 70 DEG C are refluxed 60 minutes, add tetramethyl two
Vinyl disiloxane 1.8g continues 70 DEG C and refluxes 60 minutes, pours separatory funnel into, divides and remove sour water layer, have
Machine layer washes neutral pH, pours flask, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low boiling into
Point material, obtaining viscosity at 25 DEG C is the resin of 8000mPa s.Pass through1H NMR、13C NMR、29Si
NMR and FT-IR detects, and obtains following data:1H NMR(δ, ppm, 7-8,280H, Si-Ph,
5.7-6.2,24H, Si-CH=CH2, 0-0.5,102H, Si-Me),13C NMR(δ, ppm, 0-5,
Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR(δ, ppm, 0-10, SiO1/2,
20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2), FT-IR(cm-1, 3300-3400, Si-OH,
890-900, Ep), determine that the structural formula of resin (named resin 6) is as follows:
ViMe2SiO(PhSiO3/2)35(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)21OSi Me2Vi。
Comparative example 2: same as in Example 2, differs only in and is not added with 3-glycydoxy methyl two
Ethoxysilane
Tetraethyl orthosilicate 10.4g is added flask, is sequentially added into dehydrated alcohol 30g and concentration is mass percent
The concentrated hydrochloric acid 15g of 37%, 70 DEG C are reacted 5 minutes, rapidly join phenyltrimethoxysila,e 68.3g, 70 DEG C
React 30 minutes, add aminomethyl phenyl dimethoxysilane 44.2g and methylvinyldimethoxysilane
7.9g, 70 DEG C are refluxed 60 minutes, add tetramethyl divinyl disiloxane 1.8g and continue backflow 60 minutes,
Pouring separatory funnel into, divide and remove sour water layer, organic layer washes neutral pH, pours flask into, adds deionized water
1g, 70 DEG C of backflow 60min, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material,
Obtaining viscosity at 25 DEG C is the following structural resin of 10000mPa s.Pass through1H NMR、13C NMR、29Si
NMR and FT-IR detects, and obtains following data:1H NMR(δ, ppm, 7-8,280H, Si-Ph,
5.7-6.2,21H, Si-CH=CH2, 0-0.5,93H, Si-Me),13C NMR(δ, ppm, 0-5,
Si-CH3, 120-140, Si-CH=CH2, Si-Ph),29Si NMR(δ, ppm, 0-10, SiO1/2,
20-50, SiO, 60-80, SiO3/2, 100-110, SiO4/2), FT-IR(cm-1, 3300-3400, Si-OH),
Determine that the structural formula of resin (named resin 7) is as follows:
HOMe2SiO(PhSiO3/2)35(SiO4/2)5(ViMeSiO)6(MePhSiO)21OSi Me2Vi。
Ibid, a=0.52, b=0.08 and c=0.4 are calculated.
By embodiment 1～5 and the resin (title is respectively resin 1～7) of comparative example 1～2 preparation and with
Lower composition carries out mixing (each composition is according to the mass fraction) according to the combination shown in table 1:
(A) represent that structural formula is embodiment 1～5 and the resin of comparative example 1～2 preparation；
(B) branched organic hydrogen polysiloxanes HMe is represented2Si(MeHSiO)3(PhSiO3/2)7SiMe2The synthesis of H
Method: with reference to the Chemical Industry Press good fortune pine people, Wang Yilu write " organosilicon synthesis technique and product should
With " preparation method of chapter 7 7.2.2.1 containing hydrogen silicone oil: 30 mass parts Me2HSiOSiHMe2, 50 mass parts
PhSi(OMe)3, and 30 mass parts Me3SiO(MeHSiO)mSiMe3(DOW CORNING MHX-1107), adds
The concentrated sulphuric acid of 7 mass parts mass percents 98% makees catalyst, at room temperature balances 5h, stratification, removes
Remove sour water layer, oil reservoir Na2CO3Neutralize 30min, obtain yield after filtration and reach 95%(mass fraction)
Purpose product, passes through1H NMR(δ, ppm, 7-8,35H, Si-Ph, 4.9,2H, end group Si-H,
4.8,3H, Si-H in chain, 0-0.5,12H, Si-Me) determine that target product is following structure:
HMe2Si(MeHSiO)3(PhSiO3/2)7SiMe2H。
(C) addition reaction catalyst: the octanol solution (platinum concentration is 5wt%) of chloroplatinic acid；
(D) curing catalysts of ring-opening polymerisation: aluminum isopropylate.；
(E) inhibitor: 2-phenyl-3-butyne-2-alcohol.
(A)～(E) component mixing final vacuum is sloughed bubble, within 4 hours, gathers organic with 150 DEG C of bakings
Silicone composition is heating and curing molding (length × width x thickness=300mm × 300mm × 2mm), outside range estimation
See.It addition, measure hot strength, hard according to Japan's JIS K6301 vulcanite physical parameter testing standard
Degree and elongation at break.Result is listed in table 1.
The characteristic of curable organosilicon resin combination and solidfied material thereof is measured by method as described below.
[refractive index of curable organosilicon resin combination]
At 25 DEG C, curable organosilicon resin composition refractive index, light source profit is measured by Abbe refractometer
With the visible ray of 589nm.
[light transmittance of cured product]
Curable organosilicon resin composition it is clipped between two glass plates and solidifies 4 little at 150 DEG C
Time, then by measuring under any wavelength of the visible ray in 400-700nm wave-length coverage
Automatic spectrophotometer measures the light transmittance through cured product (thickness 0.2mm) at 25 DEG C.Measurement is worn
Crossing combiner and the light transmittance only through glass plate, both differences are the absorbance of cured product.Table 1
Represent under 450nm wavelength, obtain light transmittance.
[hardness of cured product]
Curable organosilicon resin composition is made to form flake by curing molding 4h at 150 DEG C solid
Change product.Gained flake cured product is measured by A type or D type viscometer according to JIS K6253
Hardness.
[bonding strength to polyphthalamide (PPA) resin plate]
Two politef-resin partition (length × width x thickness=50mm × 20mm × 1mm) is clipped in two
Between individual polyphthalamide (PPA) resin plate (length × width x thickness=80mm × 80mm × 1mm),
The remaining space between plate is filled, by fixture fixed assembly also with curable organosilicon resin composition
It is placed in hot-air circulatory stove curing molding 4h at 150 DEG C.Cured product is cooled to room temperature, moves
Except fixture and partition, and on cupping machine, pull aforementioned polyphthalamide resin in the opposite direction
Plate is to measure shearing force.
[bonding strength to sheffield plate]
Two politef-resin partition (length × width x thickness=50mm × 20mm × 1mm) is clipped in two
Between individual sheffield plate (length × width x thickness=80mm × 80mm × 1mm), with curable organosilicon tree
Oil/fat composition fills the remaining space between plate, by fixture fixed assembly and be placed on hot-air and circulate
In stove at 150 DEG C curing molding 4h.Cured product is cooled to room temperature, removes fixture and partition, and
Pull aforementioned sheffield plate to measure shearing force on cupping machine in the opposite direction.
[manufacture method of light-emitting semiconductor device]
By the light-emitting semiconductor device with InGaN luminescence chip is filled silicone resin composition, 80
Solidify 1 hour at DEG C, solidify 4 hours at 150 DEG C, thus the light-emitting semiconductor device made.
[thermal shock test]
The light-emitting semiconductor device of use, carries out being-40 DEG C during 300 low temperature, is 120 DEG C during high temperature
Cold shock testing, measure outward appearance produce cracking number.
[humidity test and Reflow Soldering experiment excessively]
The light-emitting semiconductor device made in the constant temperature and humidity indoor placement 1000 hours of 85 DEG C/85%RH
After, to cross 3 times in reflow soldering apparatus (260 DEG C), be full of cracks generation number and/or the stripping of observing outward appearance produce number.
The evaluation result of above-described embodiment, the coating protection material of comparative example is shown in table 1.
Table 1
Visible, it is right that the curable organopolysiloxane composition of present invention offer is applied in emitting semiconductor encapsulation
PPA and metal have splendid adhesive property, stronger hardness and excellent impact resistance.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned enforcement
The restriction of example, the change made, modifies, replaces under other any spirit without departing from the present invention and principle
In generation, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (8)
1. an organic siliconresin, it is characterised in that structural formula composition is as shown in the one in Formulas I～V:
HOMe2SiO(PhSiO3/2)21(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)35OSi Me2Vi；
Formulas I；
HOMe2SiO(PhSiO3/2)35(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)21OSi Me2Vi；
Formula II；
HOMe2SiO(PhSiO3/2)49(SiO4/2)5(EpMeSiO)3(ViMeSiO)6(MePhSiO)7OSi Me2Vi；
Formula III；
HOMe2SiO(PhSiO3/2)19(SiO4/2)2(EpMeSiO)2(ViMeSiO)3(MePhSiO)12OSi Me2Vi；
Formula IV；
HOMe2SiO(PhSiO3/2)49(SiO4/2)7(EpMeSiO)4(ViMeSiO)9(MePhSiO)29OSi Me2Vi；
Formula V；
Wherein, Me is methyl, Ph be phenyl, Ep be γ-(2,3-epoxy radicals propoxyl group) propyl group, Vi be vinyl.
2. the preparation method of the organic siliconresin described in claim 1, it is characterised in that comprise the steps of:
1. it is the mixed in hydrochloric acid of 37% by tetraethyl orthosilicate, ethanol and mass percent, reaction；
2. phenyltrimethoxysila,e is added, reaction；
3. aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane and 3-glycydoxy methyldiethoxysilane, back flow reaction are added；
4. add tetramethyl divinyl disiloxane, continue back flow reaction；
5. take the organic layer in the product that 4. step obtains, with water, organic layer is washed neutral pH；Add water, back flow reaction, concentrating under reduced pressure, obtain organic siliconresin；
When described organic siliconresin shown in formula I time, tetraethyl orthosilicate, ethanol, mass percent are hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane, 3-glycydoxy methyldiethoxysilane and the tetramethyl divinyl disiloxane proportioning of 10.4:30:15:41.2:63.7:7.9:7.4:1.8 in mass ratio of 37%；
When described organic siliconresin is as shown in Formula II, tetraethyl orthosilicate, ethanol, mass percent are hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane, 3-glycydoxy methyldiethoxysilane and the tetramethyl divinyl disiloxane proportioning of 10.4:30:15:68.3:44.2:7.9:7.4:1.8 in mass ratio of 37%；
When described organic siliconresin is as shown in formula III, tetraethyl orthosilicate, ethanol, mass percent are hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane, 3-glycydoxy methyldiethoxysilane and the tetramethyl divinyl disiloxane proportioning of 10.4:30:15:61.9:24.7:7.9:14.8:1.8 in mass ratio of 37%；
When described organic siliconresin is as shown in formula IV, tetraethyl orthosilicate, ethanol, mass percent are hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane, 3-glycydoxy methyldiethoxysilane and the tetramethyl divinyl disiloxane proportioning of 10.4:30:15:68.3:44.2:7.9:7.4:1.8 in mass ratio of 37%；
When described organic siliconresin shown as a formula V time, tetraethyl orthosilicate, ethanol, mass percent are hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methylvinyldimethoxysilane, 3-glycydoxy methyldiethoxysilane and the tetramethyl divinyl disiloxane proportioning of 10.4:30:15:68.3:44.2:7.9:7.4:1.8 in mass ratio of 37%.
The preparation method of organic siliconresin the most according to claim 2, it is characterised in that:
Step 1. described in the condition of reaction be 70 DEG C and react 5 minutes；
Step 2. described in the condition of reaction as follows: condition during organic siliconresin shown in formula I～III is 70 DEG C and reacts 30 minutes；Condition when preparing the organic siliconresin shown in formula IV is 70 DEG C and reacts 15 minutes；Condition during organic siliconresin shown in formula V is 70 DEG C and reacts 120 minutes；
Step 3. described in the condition of back flow reaction as follows: condition during organic siliconresin shown in formula I～III is 70 DEG C of back flow reaction 60 minutes；Condition when preparing the organic siliconresin shown in formula IV is 70 DEG C of back flow reaction 15 minutes；Condition during organic siliconresin shown in formula V is 70 DEG C of back flow reaction 120 minutes；
Step 4. described in the condition of back flow reaction be 70 DEG C of back flow reaction 60 minutes；
Step 5. described in the condition of back flow reaction as follows: condition during organic siliconresin shown in formula I, III is 70 DEG C of back flow reaction 30 minutes；Condition when preparing the organic siliconresin shown in Formula II, IV and V is 70 DEG C of back flow reaction 60 minutes；
Step 5. described in the organic layer taken in the product that 4. step obtains specifically comprise the following steps that product step 4. obtained pours separatory funnel into, point remove sour water layer, obtain organic layer；
Step 5. described in the consumption of the water added in water be equivalent to the 1/10.4 of tetraethyl orthosilicate quality；
Step 5. described in concentrating under reduced pressure condition for use vacuum pump decompression distillation and concentration.
4. a curable organopolysiloxane composition, it is characterised in that comprise following component:
(A) organic siliconresin described in claim 1；
(B) a part has the organo-silicon compound of at least 2 hydrogen being combined with silicon atom, as shown in formula A:
Hd(R5)eSiO(4-d-e)/2
Formula A；
In formula A, R5For the identical or different substituted or non-substituted monovalent hydrocarbon without unsaturated aliphatic；
D and e meets 0.1≤d≤2,0.5≤e≤2, and 0.7≤d+e≤3；
The consumption of component (B) is the amount that matching component (A) reaches effectively to solidify.
Curable organopolysiloxane composition the most according to claim 4, it is characterised in that:
Described R5For the substituted or non-substituted monovalent hydrocarbon that carbon number is 1～6；
The Si-H base of component (B) is 0.5～4.0 for the ratio of the mole of the unsaturated thiazolinyl in component (A).
Curable organopolysiloxane composition the most according to claim 5, it is characterised in that also comprise following component:
(C) platinum group metal series catalysts；
(D) the metal-complexing catalytic reaction catalyst of epoxy radicals catalyzed ring opening polymerization is made；
(E) additive reaction inhibitor.
Curable organopolysiloxane composition the most according to claim 6, it is characterised in that
The consumption of component (C) is the 0.1～1000ppm of (A) and (B) constituent mass total amount；
The consumption of component (D) is the 0.05～10% of (A)～(C) constituent mass total amount；
The consumption of component (E) is the 0.07% of (A)+(B) constituent mass total amount；
Component (C) is H2PtCl6·mH2O、H2PtCl4·mH2O、K2PtCl6·mH2O、K2PtCl4·mH2O；
Component (D) is at least one in titanium tetraisopropylate, isooctanol titanium, four n-butyl titaniums, diisopropoxy bis-acetylacetonate titanium, triethyl aluminum, aluminium ethoxide, aluminum isopropylate., aluminium acetylacetonate, diethyl zinc and zirconium-n-butylate；
Component (E) is triphenylphosphine, tetramethylethylenediamine, thiophene or acetylene alcohol compounds.
8. the application in the coating protection material of coating protection emitting semiconductor of the curable organopolysiloxane composition described in claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245790.5A CN103342816B (en) | 2013-06-19 | 2013-06-19 | A kind of organic siliconresin and curable organopolysiloxane composition and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245790.5A CN103342816B (en) | 2013-06-19 | 2013-06-19 | A kind of organic siliconresin and curable organopolysiloxane composition and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103342816A CN103342816A (en) | 2013-10-09 |
| CN103342816B true CN103342816B (en) | 2016-08-17 |
Family
ID=49277649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310245790.5A Active CN103342816B (en) | 2013-06-19 | 2013-06-19 | A kind of organic siliconresin and curable organopolysiloxane composition and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103342816B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170016382A (en) * | 2014-06-03 | 2017-02-13 | 다우 코닝 도레이 캄파니 리미티드 | Curable silicone composition and optical semiconductor device |
| CN105199397B (en) | 2014-06-17 | 2018-05-08 | 广州慧谷化学有限公司 | A kind of curable organopolysiloxane composition and semiconductor devices |
| CN104231914B (en) * | 2014-09-16 | 2016-09-14 | 上海应用技术学院 | A kind of optical plastic protective coating and preparation method |
| CN104292465A (en) * | 2014-10-16 | 2015-01-21 | 深圳市宝力科技有限公司 | Epoxy-modified phenyl vinyl silicon resin and preparation method thereof |
| CN105713391B (en) * | 2014-12-03 | 2018-11-09 | 广州慧谷化学有限公司 | Thixotropic organopolysiloxane composition and semiconductor devices |
| CN106317895B (en) * | 2015-06-30 | 2019-09-06 | 广州慧谷化学有限公司 | A kind of curable organopolysiloxane composition and semiconductor devices |
| WO2017146004A1 (en) * | 2016-02-22 | 2017-08-31 | 株式会社ダイセル | Curable resin composition, cured product thereof, and semiconductor device |
| CN105860081B (en) * | 2016-05-30 | 2018-08-10 | 哈尔滨工业大学 | Double cured silicone resins of a kind of photo-thermal and preparation method thereof |
| CN106910403B (en) * | 2017-03-29 | 2019-09-13 | 广州迈普再生医学科技股份有限公司 | Vascular pattern and its preparation method and application |
| JP7249954B2 (en) * | 2017-05-05 | 2023-03-31 | ダウ シリコーンズ コーポレーション | Hydrosilylation-curable silicone resin |
| CN107974087A (en) * | 2017-12-22 | 2018-05-01 | 枞阳县三金颜料有限责任公司 | A kind of high-temperature resistant organic silicon resin |
| CN108192100A (en) * | 2018-01-02 | 2018-06-22 | 广东工业大学 | A kind of photo-curable silicone resin and preparation method thereof, photosensitive resin and application |
| CN108384010A (en) * | 2018-02-28 | 2018-08-10 | 华南理工大学 | A kind of LED packaging plastics epoxidation modification methyl phenyl silicone resin and preparation method thereof |
| CN109749461A (en) * | 2018-12-30 | 2019-05-14 | 苏州桐力光电股份有限公司 | A kind of optical clear silicone resin |
| CN110408031A (en) * | 2019-07-12 | 2019-11-05 | 湖北大学 | Active branching carbon silane with multiterminal functional group and preparation method thereof |
| CN110511669B (en) * | 2019-07-12 | 2021-10-15 | 广州奥松电子股份有限公司 | Organic silicon composition and curing method thereof |
| EP4004117A4 (en) * | 2019-07-26 | 2023-05-03 | Dow Silicones Corporation | Curable organopolysiloxane composition, cured product, and electric/electronic equipment |
| CN111040166A (en) * | 2019-11-28 | 2020-04-21 | 湖北新四海化工股份有限公司 | Environment-friendly moisture-curing silicone resin and preparation method thereof |
| CN110982481A (en) * | 2019-12-19 | 2020-04-10 | 烟台德邦科技有限公司 | High-toughness organic silicon three-proofing adhesive |
| WO2021210421A1 (en) * | 2020-04-16 | 2021-10-21 | 信越化学工業株式会社 | Room-temperature-curable organopolysiloxane composition and article |
| CN111876115A (en) * | 2020-08-18 | 2020-11-03 | 上海澳昌实业有限公司 | Organic silicon modified high-temperature-resistant epoxy structural adhesive and preparation method thereof |
| CN112409979B (en) * | 2020-11-03 | 2023-03-21 | 南京科矽新材料科技有限公司 | Diffusion-preventing watermark-free die bond adhesive for LED |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757650A (en) * | 2011-04-21 | 2012-10-31 | Jsr株式会社 | Solidifying composition, condensate, semiconductor device, and polysiloxane |
-
2013
- 2013-06-19 CN CN201310245790.5A patent/CN103342816B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757650A (en) * | 2011-04-21 | 2012-10-31 | Jsr株式会社 | Solidifying composition, condensate, semiconductor device, and polysiloxane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103342816A (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103342816B (en) | A kind of organic siliconresin and curable organopolysiloxane composition and application | |
| US7851564B2 (en) | Silicone resin composition | |
| CN104245849B (en) | The using method of solidification compound, solidfied material and solidification compound | |
| CN102046700B (en) | Fixing material comprising silane compound polymer and photonic device sealed body | |
| US9346954B2 (en) | Curable resin composition | |
| TWI506095B (en) | Additional hardened siloxane composition, optical element sealing material, and optical element | |
| CN105924974A (en) | Addition-curable silicone resin composition and die attach material for optical semiconductor device | |
| CN103755963A (en) | Polysiloxane thickening agent and preparation method thereof | |
| CN102892812A (en) | Novel organic silicon compound, thermal cure resin composition containing organic silicon compound, cured resin and package material for optical semiconductor | |
| KR20130094715A (en) | Polysiloxane composition, hardened material and optical device | |
| JP5643009B2 (en) | Optical device using organopolysiloxane composition | |
| CN102834465A (en) | Encapsulant for optical semiconductor device and optical semiconductor device using same | |
| CN103665879A (en) | Organic silicon gel composition for high-power LED (light-emitting diode) packaging | |
| CN104755569B (en) | Curable organosilicon composition, its cured product and optical semiconductor device | |
| CN103360603A (en) | Phenyl vinyl silicone resin for packaging LED (light-emitting diode) and preparation method thereof | |
| JP2013543030A (en) | Hybrid silicone composition for light emitting devices | |
| CN103951984A (en) | Solidifiable silicon resin composition and optical semiconductor device using same | |
| CN103571209A (en) | Addition-curable silicone composition and semiconductor device | |
| CN103834178B (en) | Organic silicon resin as well as preparation method and application thereof | |
| CN105368064B (en) | Organopolysiloxane composition and preparation method thereof and semiconductor devices | |
| CN106221237A (en) | A kind of LED encapsulation organic silica gel and preparation method thereof | |
| CN104066770A (en) | Organopolysiloxane | |
| US20170002149A1 (en) | Curable Resin Composition | |
| US20160194457A1 (en) | Curable Resin Composition | |
| CN105623271A (en) | Addition reaction cured resin composition and photosemiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510000, No. 62 Xinye Road, Guangzhou Economic and Technological Development Zone, Luogang District, Guangzhou City, Guangdong Province Patentee after: Guangzhou Huigu New Materials Technology Co.,Ltd. Country or region after: China Address before: No. 62 Yonghe Xinye Road, Luogang District, Guangzhou City, Guangdong Province, 511356 Patentee before: GUANGZHOU HUMAN CHEM Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 62 Xinye Road, Guangzhou Economic and Technological Development Zone, Guangzhou City, Guangdong Province, 510000 Patentee after: Guangzhou Huigu New Materials Technology Co.,Ltd. Country or region after: China Address before: 510000, No. 62 Xinye Road, Guangzhou Economic and Technological Development Zone, Luogang District, Guangzhou City, Guangdong Province Patentee before: Guangzhou Huigu New Materials Technology Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |