CN103342816A - Organic silicone resin, curable organopolysiloxane composition and application - Google Patents
Organic silicone resin, curable organopolysiloxane composition and application Download PDFInfo
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- CN103342816A CN103342816A CN2013102457905A CN201310245790A CN103342816A CN 103342816 A CN103342816 A CN 103342816A CN 2013102457905 A CN2013102457905 A CN 2013102457905A CN 201310245790 A CN201310245790 A CN 201310245790A CN 103342816 A CN103342816 A CN 103342816A
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- -1 hydroxy, amino, carboxyl Chemical group 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 20
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- PXJZCBUXFVZSLL-UHFFFAOYSA-N CO[SiH2]OC.C=CC Chemical compound CO[SiH2]OC.C=CC PXJZCBUXFVZSLL-UHFFFAOYSA-N 0.000 claims description 11
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- 239000010410 layer Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 238000007259 addition reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000003944 tolyl group Chemical group 0.000 claims description 7
- 125000005023 xylyl group Chemical group 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 125000006038 hexenyl group Chemical group 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 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
- 150000002118 epoxides Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 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
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-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 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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 group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 7
- 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 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 2
- 229910020485 SiO4/2 Inorganic materials 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 37
- 239000011347 resin Substances 0.000 description 37
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 12
- 239000004954 Polyphthalamide Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 229920006375 polyphtalamide Polymers 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 8
- 229910008051 Si-OH Inorganic materials 0.000 description 7
- 229910006358 Si—OH Inorganic materials 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
- 238000000034 method Methods 0.000 description 7
- 238000005457 optimization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000005357 flat glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 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
- 238000005476 soldering Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 241001249696 Senna alexandrina Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000000476 acetylides Chemical class 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-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
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-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
- 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
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The invention discloses an organic silicone resin, a curable organopolysiloxane composition and an application. A structural formula of the organic silicone resin is shown as formula I. The curable organopolysiloxane composition is obtained by mixing the organic silicone resin with an organic silicone compound having at least two hydrogen atoms bonded with a silicone atom in one molecule. The curable organopolysiloxane composition can be applied on luminescent semiconductor package. The curable organopolysiloxane composition has the following advantages of excellent adhesive property, relatively strong hardness, excellent impact resistance, high transparency, little color change in a heat resistance test and high luminescent efficiency. Besides, the curable organopolysiloxane composition is not easy to peel off in a thermal shock test and presents excellent adhesive power in adhesive experiments with PPA and metal. The formula I is R1R22SiO(R3SiO3/2)a(SiO4/2)b(R42SiO)cOSiR22R1.
Description
Technical field
The present invention relates to a kind of tackiness agent, particularly a kind of silicone resin and curable organopolysiloxane composition and application.
Background technology
The curable composition epoxy resin of the normal employing of the curable resin composition of traditional electronics/electrical equipment sealing and curing and bonding employing is to obtain the solidify material of high rigidity, high-clarity and low-thermal-expansion.Yet this cured article is rigidity too, and the thermal expansion in solidification process is tended to make cured product inside crackle occur at the big stress of the inner generation of electronics/electrical component.In addition, in the high power electronic/electrical component of big electric current is used, produce the cured article flavescence that a large amount of thermal capacitances easily makes composition epoxy resin, influence luminous efficiency.
In order to reduce stress and to improve deficiencies such as cured article xanthochromia; someone has proposed to utilize organopolysiloxane composition to prepare the resin material with high-clarity and low-stress by addition reaction of silicon with hydrogen; for example Japanese patent application JP2002-327126 and JP2002-338833 propose to have the silicoorganic compound of reactive unsaturated double-bond by containing at least 2 in a part with the Si-H base; the silicon compound that contains at least 2 Si-H bases in a part, the emitting semiconductor lining protection resin combination that silicon hydrogen addition catalyst is formed.Yet the cured article hardness deficiency of these silicon-types, lack and metal/plastic between cohesiveness, when using this material package semiconductor device, during thermal shock experiment under-40～120 ℃, silicone resin is peeled off from metal or plastic material easily.
Further the someone has proposed to utilize the preparation of compositions solidify material of Resins, epoxy and silicone resin, with comprehensive both advantage.Japanese patent application JP2006-041927 utilizes the organopolysiloxane that contains vinyl, organic hydrogen polysiloxanes, addition reaction catalyst and the organopolysiloxane that contains epoxy group(ing) and/or alkoxyl group, prepare have high rigidity, high-clarity, thermotolerance and sunproof solidifying product, and can not become the white casse shape when returning to room temperature from hygrothermal environment at once.Chinese patent application CN101155792B utilizes the specific chemical structure formula: each molecule has the organopolysiloxane of at least two epoxy-functionals, utilization has the diorganosiloxane of ad hoc structure formula, be used for curing agent for epoxy resin, prepare and have good cohesiveness and curing characteristics and good flexible cured product.
Yet the bonding force deficiency of the Resins, epoxy that more than obtains/organosilicon resin composition solidify material and PPA/ metal is still peeled off from substrate under thermal shock easily; Especially it is higher to peel off rate at the not high substrate of PPA purity.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of silicone resin and preparation method thereof with not enough.
Another object of the present invention is to provide curable organopolysiloxane composition that contains above-mentioned silicone resin and preparation method thereof.
A further object of the present invention is to provide the application of described curable organopolysiloxane composition.
Purpose of the present invention is achieved through the following technical solutions: a kind of silicone resin, and structural formula is formed suc as formula shown in the I:
R
1R
2 2SiO(R
3SiO
3/2)
a(SiO
4/2)
b(R
4 2SiO)
c?OSiR
2 2R
1
Formula I;
Among the formula I, each R
1Representation hydroxy, amino, carboxyl, alkoxyl group, epoxy group(ing), alkenyl or halogen isoreactivity group independently, preferred especially hydroxyl, carbonatoms are that 1～10 alkenyl or carbonatoms are 1～10 epoxy group(ing); More preferably at least one R
1Be hydroxyl; Wherein, R
1In hydroxyl, alkenyl and epoxy group(ing) obtain by hydrolyzable silane hydrolyzate, the polysiloxane that amino, carboxyl, alkoxyl group and halogen obtain after by hydrolysis further reaction obtains; Reactive group R
1The content in component A preferably 0.1～10%(mol/mol), particularly preferably in 0.5～2%(mol/mol); Be lower than at 0.1% o'clock, cured article hardness is on the low side, and surpasses at 10% o'clock, and it is a lot of that cured article toughness descends;
Each R
2Represent carbonatoms independently and be 1～10 replacement (referring to that the hydrogen on the alkyl is to be substituted) or the monovalence alkyl of non-replacement, or carbonatoms is 1～10 alkoxyl group, comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, phenyl, tolyl (main chain directly links to each other with benzene), xylyl, naphthyl, phenmethyl (main chain directly links to each other with methyl), styroyl, hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy and tert.-butoxy; Preferred carbonatoms is 1～3 replacement or the monovalence alkyl of non-replacement, or carbonatoms is 1～2 alkoxyl group; Methyl more preferably;
Each R
3Represent carbonatoms independently and be 1～10 replacement or the monovalence alkyl of non-replacement, or carbonatoms is 1～10 alkoxyl group, comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, phenmethyl, styroyl, hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy and tert.-butoxy; Preferred carbonatoms is 1～6 replacement or the monovalence alkyl of non-replacement, or carbonatoms is 1～2 alkoxyl group; Methyl or phenyl more preferably;
Each R
4Represent carbonatoms individually and be 1～10 replacement or the monovalence alkyl of non-replacement, contain the substituting group of epoxide group or carbonatoms and be 1～10 alkoxyl group, comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, phenmethyl, styroyl, hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, the 2-epoxy ethyl, 2, the 3-glycidoxy, γ-(2, the 3-epoxypropyl) propyl group and β-(3,4 epoxycyclohexyl)-ethyl or 2-oxetanyl; Preferred carbonatoms is 1～6 replacement or the monovalence alkyl of non-replacement, or contains the substituting group of epoxide group; More preferably phenyl, methyl, vinyl or epoxy ethyl;
R
2, R
3And R
4In contain 1 unsaturated monovalence alkyl at least so that with silicon hydrogen generation addition reaction, improve the mechanical property of cured product;
The compound of representing among the formula I satisfies 0.2≤a≤0.9,0≤b≤0.2,0.1≤c≤0.8, and a+b+c=1; Preferred especially 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. (R
3SiO
3/2)
a(SiO
4/2)
b(R
4 2SiO)
c) in molecular fraction;
The viscosity of described silicone resin has no particular limits, yet being recommended in 25 ℃ of following range of viscosities is 50～1000000mPas, be 200～100000mPas at 25 ℃ of following range of viscosities preferably, be 500～50000 particularly preferably in 25 ℃ of following range of viscosities, viscosity surpasses last will becoming in limited time and is difficult to operation, and the mechanical property that viscosity is lower than the cured product of prescribing a time limit down will descend; More preferably 25 ℃ of following range of viscosities are 6000～20000.
The preparation method of described silicone resin comprises following steps:
1. be 37% mixed in hydrochloric acid with tetraethoxy, ethanol and mass percent, reaction;
2. add phenyltrimethoxysila,e, reaction;
3. add aminomethyl phenyl dimethoxy silane, methyl ethylene dimethoxy silane and 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, back flow reaction;
4. add tetramethyl divinyl disiloxane, continue back flow reaction;
5. get the organic layer in the product that 4. step obtain, water is washed neutral pH with organic layer; Add water again, back flow reaction, concentrating under reduced pressure obtains silicone resin;
Wherein, tetraethoxy, ethanol, mass percent are that 37% hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxy silane, methyl ethylene dimethoxy silane, 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and tetramethyl divinyl disiloxane are by mass ratio 10.4:30:15:(41.2～68.3): (24.7～63.7): 7.9:(7.4～14.8): 1.8 proportionings;
The condition optimization of the reaction of step described in 1. is 70 ℃ of reactions 5 minutes;
The condition optimization of the reaction of step described in 2. is 70 ℃ of reactions 15～120 minutes;
The condition optimization of the back flow reaction of step described in 3. is 70 ℃ of back flow reaction 15～120 minutes;
The condition optimization of the back flow reaction of step described in 4. is 70 ℃ of back flow reaction 60 minutes;
The condition optimization of the back flow reaction of step described in 5. is 70 ℃ of back flow reaction 30～60 minutes;
The concrete steps of getting organic layer in product that step 4. obtain of step described in 5. are as follows: pour the product that 4. step obtains into separating funnel, divide the disacidify water layer, obtain organic layer;
The consumption of the water that again is added to the water of step described in 5. is equivalent to 1/10.4 of tetraethoxy quality;
The condition optimization of the concentrating under reduced pressure of step described in 5. concentrates for using the vacuum pump underpressure distillation;
A kind of curable organopolysiloxane composition comprises following component:
(A) above-mentioned silicone resin, its contain at least 2 with silicon bonded alkenyl (being thiazolinyl);
(B) have the silicoorganic compound of at least 2 hydrogen of being combined with Siliciumatom in a part;
Described curable organopolysiloxane composition also comprises following component:
(C) platinum metals series catalysts;
(D) metal-complexing catalytic reaction catalyst;
(E) addition reaction inhibitor.
Component (B) is carried out addition reaction of silicon with hydrogen by the unsaturated double-bond in the base of the Si-H in this composition and the component (A) and is formed cured article for having the silicoorganic compound of at least 2 hydrogen of being combined with Siliciumatom in a part; The general formula of component (B) is suc as formula shown in the II:
H
d（R
5）
eSiO
(4-d-e)/2
Formula II;
Among the formula II, R
5Be the identical or different replacement that do not contain unsaturated aliphatic or the monovalence alkyl of non-replacement, preferred carbonatoms is 1～6 replacement or the monovalence alkyl of non-replacement, preferred carbonatoms is 1～3 replacement or the monovalence alkyl of non-replacement, more preferably methyl, ethyl, propyl group, sec.-propyl, butyl, cyclohexyl, phenyl, tolyl, xylyl and phenmethyl etc.; The hydrogen atom position of being combined with silicon does not have special restriction, can be in the centre at the end of molecule yet;
D and e satisfy 0.1≤d≤2,0.5≤e≤2, and 0.7≤d+e≤3;
Component (B) is organic hydrogen polysiloxanes, its consumption is the amount that matching component (A) reaches effective curing, the Si-H base that is component (B) is 0.5～4.0 for the ratio (Si-H/Si-Vi) of the molar weight of the unsaturated thiazolinyl in the component (A), preferred 1.0～3.2, preferred especially 1.0～2.8 mol ratio is used; Be lower than at 0.5 o'clock and solidify incomplete residual unsaturated alkyl and make heat-resisting xanthochromia degradation, and made the cured product easy deformation greater than 4.0 o'clock owing to residual Si-H base, the residual quantity of (B) component too much also can cause the mechanical property variation of cured product in addition.
The synthetic of component (B) is that 1～3 siloxanes and the siloxanes that has Si-H base hydrolytie polycondensation under the catalysis of sulfuric acid or hydrochloric acid are realized by functionality.
Described functionality is that 1～3 siloxanes comprises dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyltrimethoxy silane, diethyl diethoxy silane, ethyl trimethoxy silane, diisopropyl dimethoxy silane, aminomethyl phenyl dimethoxy silane, phenyltrimethoxysila,e and dimethoxydiphenylsilane etc.;
The siloxanes of the described Si-H of having base comprises methyl dimethoxysilane, 1,1,3,3-tetramethyl disiloxane and phenyl dimethoxy silane etc.;
The synthetic method of component (B) can be with reference to the loose people of Chemical Industry Press's good fortune, the method for making of " organosilicon synthesis technique and product application " chapter 7 7.2.2.1 containing hydrogen silicone oil that Wang Yilu writes: 30 mass parts Me
2HSiOSiHMe
2, 50 mass parts PhSi (OMe)
3And 30 mass parts Me
3SiO (MeHSiO)
mSiMe
3Or (MeHSiO)
mMix, the vitriol oil that adds 7 mass parts mass percents 98% is made catalyzer, balance 5h at room temperature, and standing demix is removed the sour water layer, oil reservoir Na
2CO
3In and 30min, obtain yield after the filtration and reach the 95%(massfraction) purpose product HMe
2Si (MeHSiO)
3(PhSiO
3/2)
7SiMe
2H.
Component (C) is in order to cooperate the required platinum metals series catalysts of silicon hydrogen addition curing reaction, can to enumerate H
2PtCl
6MH
2O, H
2PtCl
4MH
2O, K
2PtCl
6MH
2O, K
2PtCl
4MH
2O.These catalyzer can use separately, also can be used by above-mentioned 2 kinds or above component.Catalyst consumption is aforementioned (A) and (B) 0.1～1000ppm of constituent mass total amount, and the scope of preferred 1～200ppm is used, more preferably 7ppm.
Component (D) is for making the metal-complexing catalytic reaction catalyst of epoxy group(ing) catalysis ring-opening polymerization, can list titanium compounds such as titanium tetraisopropylate, isooctyl alcohol titanium, four propyl carbinol titaniums, diisopropoxy bis-acetylacetonate titanium particularly, aluminum compounds such as triethyl aluminum, aluminum ethylate, aluminum isopropylate, aluminium acetylacetonate, zn cpdss such as zinc ethyl, zirconium compoundss such as zirconium-n-butylate; Aforesaid catalyzer can use separately, is used more than also can be multiple.Component (D) catalyst consumption is 0.05～10% of (A)～(C) constituent mass total amount, preferred 0.1～5%, more preferably 0.4%, it is too slow to be lower than 0.05% o'clock curing speed, might can not obtain completely crued product in the short period of time, it is too fast to be higher than 10% o'clock curing speed, and may cause the solidifying product transmittance to descend.
Component (E) is the addition reaction inhibitor, can enumerate: P contained compounds such as triphenylphosphine, nitrogenous compounds such as Tetramethyl Ethylene Diamine, sulfocompounds such as thiophene, acetylides such as acetylene alcohols; Be preferably 2-phenyl-3-butyne-2-alcohol.According to stability in storage and thermofixation requirement, the different structure inhibitor can be selected and add-on can be regulated, its consumption is preferably 0.07% of (A)+(B) constituent mass total amount.
For the cementability that further increases cured product, intensity, operability, anti-metachrosis etc., in the scope that does not break away from the object of the invention, can add silane coupling agent, inorganic reinforcement packing material, curing catalysts inhibitor, antioxidant etc.
The preparation method of described curable organopolysiloxane composition comprises following steps: (A)～(E) component is mixed final vacuum slough bubble, solidify, obtain curable organopolysiloxane composition.
The condition of described curing was arbitrarily in following 168 hours to 200 ℃ following 20 minutes according to operating condition from room temperature (25 ℃), and can carries out the different curing of multistage temperature as required.
Described curable organopolysiloxane composition is applicable to that the lining protecting materials of lining protection emitting semiconductor uses.As emitting semiconductor, can list photodiode (LED), organic electroluminescent original paper (organic EL), laser diode, led array etc.
The present invention has following advantage and effect with respect to prior art:
(1) curable organopolysiloxane composition provided by the invention is applied in the emitting semiconductor encapsulation, has splendid adhesiveproperties, stronger hardness and good advantages such as impact resistance.
(2) semiconductor light-emitting apparatus that uses organic silicon mixed resin combination of the present invention to protect; resin has high transparency and hardness; variable color seldom in oven test; the luminous efficiency height; in thermal shock experiment, be not easy to peel off, and with PPA and metal sticking experiment in show outstanding cementability.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
Tetraethoxy 10.4g is added flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 41.2g fast, 70 ℃ were reacted 30 minutes, add aminomethyl phenyl dimethoxy silane 63.7g, methyl ethylene dimethoxy silane 7.9g and 3-glycidyl ether propyl group methyldiethoxysilane 7.4g, 70 ℃ were refluxed 60 minutes, add tetramethyl divinyl disiloxane 1.8g, continue 70 ℃ and refluxed 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH with deionized water, pour flask into, add deionized water 1g, 70 ℃ were refluxed 30 minutes, the vacuum pump underpressure distillation concentrates, and obtaining 25 ℃ of following viscosity is that the 6000mPas(viscometer detects) resin.By
1H NMR,
13C NMR,
29Si NMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,18H, Si-CH=CH
2, 0-0.5,144H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH, 890-900, Ep), determine that the structural formula of resin (called after resin 1) is as follows:
HOMe
2SiO (PhSiO
3/2)
21(SiO
4/2)
5(EpMeSiO)
3(ViMeSiO)
6(MePhSiO)
35OSiMe
2Vi; Wherein, Me is methyl, and Ph is that phenyl, Ep are that epoxy ethyl, Vi are vinyl.
Therefore, a=21/(21+5+3+6+35)=0.3, b=5/70=0.07, c=44/70=0.63.
Embodiment 2
Tetraethoxy 10.4g is added flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 68.3g fast, 70 ℃ were reacted 30 minutes, add aminomethyl phenyl dimethoxy silane 44.2g, methyl ethylene dimethoxy silane 7.9g and 3-glycidyl ether propyl group methyldiethoxysilane 7.4g, 70 ℃ were refluxed 60 minutes, add tetramethyl divinyl disiloxane 1.8g, continue 70 ℃ and refluxed 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH, pour flask into, add deionized water 1g, 70 ℃ were refluxed 60 minutes, the vacuum pump underpressure distillation concentrates, the resin that to obtain 25 ℃ of following viscosity be 12000mPas.By
1H NMR,
13CNMR,
29Si NMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,18H, Si-CH=CH
2, 0-0.5,102H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH, 890-900, Ep), determine that the structural formula of resin (called after resin 2) is as follows:
HOMe
2SiO(PhSiO
3/2)
35(SiO
4/2)
5(EpMeSiO)
3(ViMeSiO)
6(MePhSiO)
21OSi?Me
2Vi。
The same, calculate a=0.5, b=0.07, c=0.43.
Embodiment 3
Tetraethoxy 10.4g adds flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 61.9g fast, 70 ℃ were reacted 30 minutes, add aminomethyl phenyl dimethoxy silane 24.7g, methyl ethylene dimethoxy silane 7.9g and 3-glycidyl ether propyl group methyldiethoxysilane 14.8g, 70 ℃ were refluxed 60 minutes, add tetramethyl divinyl disiloxane 1.8g, continue 70 ℃ and refluxed 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH, pours flask into, adds deionized water 1g, 70 ℃ were refluxed 30 minutes, the vacuum pump underpressure distillation concentrates, removal of solvent under reduced pressure and low-boiling point material, the resin that to obtain 25 ℃ of following viscosity be 20000mPas.By
1H NMR,
13C NMR,
29Si NMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,18H, Si-CH=CH
2, 0-0.5,60H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH, 890-900, Ep), determine that the structural formula of resin (called after resin 3) is as follows:
HOMe
2SiO(PhSiO
3/2)
49(SiO
4/2)
5(EpMeSiO)
3(ViMeSiO)
6(MePhSiO)
7OSiMe
2Vi。
The same, calculate a=0.7, b=0.07 and c=0.23.
Reactive group R among this embodiment of embodiment 4(
1The content in component A be 0.5%)
Tetraethoxy 10.4g is added flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 68.3g fast, 70 ℃ were reacted 15 minutes, add aminomethyl phenyl dimethoxy silane 44.2g, methyl ethylene dimethoxy silane 7.9g and 3-glycidyl ether propyl group methyldiethoxysilane 7.4g, 70 ℃ were refluxed 15 minutes, add tetramethyl divinyl disiloxane 1.8g, continue 70 ℃ and refluxed 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH, pour flask into, add deionized water 1g, 70 ℃ were refluxed 60 minutes, the vacuum pump underpressure distillation concentrates, the resin that to obtain 25 ℃ of following viscosity be 30000mPas.By
1H NMR,
13CNMR,
29Si NMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,155H, Si-Ph, 5.7-6.2,12H, Si-CH=CH
2, 0-0.5,63H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH, 890-900, Ep), determine that the structural formula of resin (called after resin 4) is as follows:
HOMe
2SiO(PhSiO
3/2)
19(SiO
4/2)
2(EpMeSiO)
2(ViMeSiO)
3(MePhSiO)
12OSi?Me
2Vi。
The same, calculate a=0.5, b=0.05 and c=0.45.
Reactive group R among this embodiment of embodiment 5(
1The content in component A be 2%)
Tetraethoxy 10.4g is added flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 68.3g fast, 70 ℃ were reacted 2 hours, add aminomethyl phenyl dimethoxy silane 44.2g, methyl ethylene dimethoxy silane 7.9g and 3-glycidyl ether propyl group methyldiethoxysilane 7.4g, 70 ℃ were refluxed 2 hours, add tetramethyl divinyl disiloxane 1.8g, continue 70 ℃ and refluxed 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH, pour flask into, add deionized water 1g, 70 ℃ were refluxed 60 minutes, the vacuum pump underpressure distillation concentrates, the resin that to obtain 25 ℃ of following viscosity be 4000mPas.By
1H NMR,
13CNMR,
29Si NMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,390H, Si-Ph, 5.7-6.2,30H, Si-CH=CH
2, 0-0.5,144H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH, 890-900, Ep), determine that the structural formula of resin (called after resin 5) is as follows:
HOMe
2SiO(PhSiO
3/2)
49(SiO
4/2)
7(EpMeSiO)
4(ViMeSiO)
9(MePhSiO)
29OSi?Me
2Vi。
The same, calculate a=0.5, b=0.07 and c=0.43.
Comparative Examples 1: identical with embodiment 2, difference only is few step backflow, causes the R1 difference
Tetraethoxy 10.4g is added flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 68.3g fast, 70 ℃ were reacted 30 minutes, add aminomethyl phenyl dimethoxy silane 44.2g, methyl ethylene dimethoxy silane 7.9g and 3-glycidyl ether propyl group methyldiethoxysilane 7.4g, 70 ℃ were refluxed 60 minutes, add tetramethyl divinyl disiloxane 1.8g and continue 70 ℃ of backflows 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH, pours flask into, and the vacuum pump underpressure distillation concentrates, removal of solvent under reduced pressure and low-boiling point material, the resin that to obtain 25 ℃ of following viscosity be 8000mPas.By
1H NMR,
13C NMR,
29SiNMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,24H, Si-CH=CH
2, 0-0.5,102H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH, 890-900, Ep), determine that the structural formula of resin (called after resin 6) is as follows:
ViMe
2SiO(PhSiO
3/2)
35(SiO
4/2)
5(EpMeSiO)
3(ViMeSiO)
6(MePhSiO)
21OSi?Me
2Vi。
Comparative Examples 2: identical with embodiment 2, difference only is not add 3-glycidyl ether oxygen base propyl group methyldiethoxysilane
Tetraethoxy 10.4g is added flask, adding dehydrated alcohol 30g and concentration successively is the concentrated hydrochloric acid 15g of mass percent 37%, 70 ℃ were reacted 5 minutes, add phenyltrimethoxysila,e 68.3g fast, 70 ℃ were reacted 30 minutes, add aminomethyl phenyl dimethoxy silane 44.2g and methyl ethylene dimethoxy silane 7.9g, 70 ℃ were refluxed 60 minutes, adding tetramethyl divinyl disiloxane 1.8g continues to reflux 60 minutes, pour separating funnel into, divide the disacidify water layer, organic layer is washed neutral pH, pour flask into, add deionized water 1g, 70 ℃ of backflow 60min, the vacuum pump underpressure distillation concentrates, removal of solvent under reduced pressure and low-boiling point material, obtaining 25 ℃ of following viscosity is the following structural resin of 10000mPas.By
1H NMR,
13C NMR,
29SiNMR and FT-IR detect, and obtain following data:
1H NMR(δ, ppm, 7-8,280H, Si-Ph, 5.7-6.2,21H, Si-CH=CH
2, 0-0.5,93H, Si-Me),
13C NMR(δ, ppm, 0-5, Si-CH
3, 120-140, Si-CH=CH
2, Si-Ph),
29Si NMR(δ, ppm, 0-10, SiO
1/2, 20-50, SiO, 60-80, SiO
3/2, 100-110, SiO
4/2), FT-IR(cm
-1, 3300-3400, Si-OH), determine that the structural formula of resin (called after resin 7) is as follows:
HOMe
2SiO(PhSiO
3/2)
35(SiO
4/2)
5(ViMeSiO)
6(MePhSiO)
21OSi?Me
2Vi。
The same, calculate a=0.52, b=0.08 and c=0.4.
Resin (title is respectively resin 1～7) and the following composition of embodiment 1～5 and Comparative Examples 1～2 preparation are mixed (each is formed according to the mass fraction) according to the combination shown in the table 1:
(A) the expression structural formula is the resin of embodiment 1～5 and Comparative Examples 1～2 preparation;
(B) the branched organic hydrogen polysiloxanes HMe of expression
2Si (MeHSiO)
3(PhSiO
3/2)
7SiMe
2The synthetic method of H: with reference to the loose people of Chemical Industry Press's good fortune, the method for making of " organosilicon synthesis technique and product application " chapter 7 7.2.2.1 containing hydrogen silicone oil that Wang Yilu writes: 30 mass parts Me
2HSiOSiHMe
2, 50 mass parts PhSi (OMe)
3, and 30 mass parts Me
3SiO (MeHSiO)
mSiMe
3(DOW CORNING MHX-1107), the vitriol oil that adds 7 mass parts mass percents 98% is made catalyzer, balance 5h at room temperature, standing demix is removed the sour water layer, oil reservoir Na
2CO
3In and 30min, obtain yield after the filtration and reach the 95%(massfraction) the purpose product, by
1H NMR(δ, ppm, 7-8,35H, Si-Ph, 4.9,2H, end group Si-H, 4.8,3H, Si-H in the chain, 0-0.5,12H Si-Me) determines that target product is following structure: HMe
2Si (MeHSiO)
3(PhSiO
3/2)
7SiMe
2H.
(C) addition reaction catalyst: the octanol solution of Platinic chloride (platinum concentration is 5wt%);
(D) curing catalysts of ring-opening polymerization: aluminum isopropylate;
(E) inhibitor: 2-phenyl-3-butyne-2-alcohol.
(A)～(E) component is mixed final vacuum sloughs bubble, with 150 ℃ of bakings 4 hours with the organopolysiloxane composition moulding (length * wide * thick=300mm * 300mm * 2mm), estimate outward appearance that is heating and curing.In addition, measure tensile strength, hardness and elongation at break according to Japanese JIS K6301 vulcanized rubber physical parameter testing standard.The results are shown in table 1.
Measure the characteristic of curable organosilicon resin combination and cured article thereof by method as described below.
[specific refractory power of curable organosilicon resin combination]
Measure curable organic silicon resin composition specific refractory power by the Abbe refractometer down at 25 ℃, light source utilizes the visible light of 589nm.
[transmittance of cured product]
The curable organic silicon resin composition is clipped between two sheet glass and solidified 4 hours down at 150 ℃, the automatic spectrophotometer of measuring under any wavelength of the visible light by can be in the 400-700nm wavelength region is measured the transmittances that pass cured product (thickness 0.2mm) down at 25 ℃ then.Measurement is passed combiner and is only passed the transmittance of sheet glass, and both differences are the transmissivity of cured product.Table 1 is illustrated in and gets transmittance under the 450nm wavelength.
[hardness of cured product]
By making the curable organic silicon resin composition form laminar cured product at 150 ℃ of following curing molding 4h.Measure the hardness of the laminar cured product of gained by A type or D type viscometer according to JIS K6253.
[to the bond strength of polyphthalamide (PPA) resin board]
(length * wide * thick=50mm * 20mm * 1mm) is clipped in two polyphthalamides (PPA) resin board (between length * wide * thick=80mm * 80mm * 1mm) with two tetrafluoroethylene-resin partition, with the remaining space between the curable organic silicon resin composition infill panel, by the anchor clamps fixed assembly and be placed in the hot air circulate stove at 150 ℃ of following curing molding 4h.Cured product is cooled to room temperature, removes anchor clamps and partition, and on tensile testing machine, spur aforementioned polyphthalamide resin plate in the opposite direction to measure shearing force.
[to the bond strength of sheffield plate]
(length * wide * thick=50mm * 20mm * 1mm) is clipped in two sheffield plates (between length * wide * thick=80mm * 80mm * 1mm) with two tetrafluoroethylene-resin partition, with the remaining space between the curable organic silicon resin composition infill panel, by the anchor clamps fixed assembly and be placed in the hot air circulate stove at 150 ℃ of following curing molding 4h.Cured product is cooled to room temperature, removes anchor clamps and partition, and on tensile testing machine, spur aforementioned sheffield plate in the opposite direction to measure shearing force.
[making method of light-emitting semiconductor device]
To have in the light-emitting semiconductor device of InGaN luminescence chip and fill silicone resin composition, and solidify 1 hour down at 80 ℃, 150 ℃ solidified 4 hours down, thus the light-emitting semiconductor device of system.
[thermal shock test]
The light-emitting semiconductor device of use is-40 ℃ when carrying out 300 low temperature, is 120 ℃ cold shock testing during high temperature, measures the number that outward appearance produces cracking.
[humidity test and Reflow Soldering experiment excessively]
The light-emitting semiconductor device of making, is crossed 3 times in reflow soldering apparatus (260 ℃) after 1000 hours in the indoor placement of the fixed temperature and humidity of 85 ℃/85%RH, and the be full of cracks of observing outward appearance produces number and/or peels off the generation number.
The evaluation result of above-described embodiment, comparative example's lining protecting materials is shown in table 1.
Table 1
As seen, curable organopolysiloxane composition provided by the invention is applied in the emitting semiconductor encapsulation upward has splendid adhesiveproperties to PPA and metal, stronger hardness and good impact resistance.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. silicone resin is characterized in that structural formula forms suc as formula shown in the I:
R
1R
2 2SiO(R
3SiO
3/2)
a(SiO
4/2)
b(R
4 2SiO)
c?OSiR
2 2R
1
Formula I;
Among the formula I, each R
1Representation hydroxy, amino, carboxyl, alkoxyl group, epoxy group(ing), alkenyl or halogen independently; Each R
2Represent carbonatoms independently and be 1～10 replacement or the monovalence alkyl of non-replacement, or carbonatoms is 1～10 alkoxyl group; Each R
3Represent carbonatoms independently and be 1～10 replacement or the monovalence alkyl of non-replacement, or carbonatoms is 1～10 alkoxyl group; Each R
4Represent carbonatoms individually and be 1～10 replacement or the monovalence alkyl of non-replacement, the substituting group that contains epoxide group or carbonatoms and be 1～10 alkoxyl group;
R
2, R
3And R
4In contain 1 unsaturated monovalence alkyl at least;
The compound of representing among the formula I satisfies 0.2≤a≤0.9,0≤b≤0.2,0.1≤c≤0.8, and a+b+c=1, and a, b and c represent that it is at main chain (R
3SiO
3/2)
a(SiO
4/2)
b(R
4 2SiO)
cIn molecular fraction.
2. silicone resin according to claim 1 is characterized in that:
Described each R
1Representation hydroxy, carbonatoms are that 1～10 alkenyl or carbonatoms are 1～10 epoxy group(ing) independently;
Described each R
2Represent methylidene, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, phenmethyl, styroyl, hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy or tert.-butoxy independently;
Described each R
3Represent methylidene, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, phenmethyl, styroyl, hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy or tert.-butoxy independently;
Described each R
4Represent methylidene individually, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, phenmethyl, styroyl, hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, the 2-epoxy ethyl, 2, the 3-glycidoxy, γ-(2, the 3-epoxypropyl) propyl group, β-(3,4 epoxycyclohexyl)-ethyl or 2-oxetanyl.
3. silicone resin according to claim 1 is characterized in that:
The viscosity of described silicone resin is 50～1000000mPas at 25 ℃ of following range of viscosities.
4. the preparation method of each described silicone resin of claim 1～3 is characterized in that comprising following steps:
1. be 37% mixed in hydrochloric acid with tetraethoxy, ethanol and mass percent, reaction;
2. add phenyltrimethoxysila,e, reaction;
3. add aminomethyl phenyl dimethoxy silane, methyl ethylene dimethoxy silane and 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, back flow reaction;
4. add tetramethyl divinyl disiloxane, continue back flow reaction;
5. get the organic layer in the product that 4. step obtain, water is washed neutral pH with organic layer; Add water again, back flow reaction, concentrating under reduced pressure obtains silicone resin;
Wherein, tetraethoxy, ethanol, mass percent are that 37% hydrochloric acid, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxy silane, methyl ethylene dimethoxy silane, 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and tetramethyl divinyl disiloxane are by mass ratio 10.4:30:15:(41.2～68.3): (24.7～63.7): 7.9:(7.4～14.8): 1.8 proportionings.
5. the preparation method of silicone resin according to claim 4 is characterized in that:
The condition of the reaction of step described in 1. is 70 ℃ of reactions 5 minutes;
The condition of the reaction of step described in 2. is 70 ℃ of reactions 15～120 minutes;
The condition of the back flow reaction of step described in 3. is 70 ℃ of back flow reaction 15～120 minutes;
The condition of the back flow reaction of step described in 4. is 70 ℃ of back flow reaction 60 minutes;
The condition of the back flow reaction of step described in 5. is 70 ℃ of back flow reaction 30～60 minutes;
The concrete steps of getting organic layer in product that step 4. obtain of step described in 5. are as follows: pour the product that 4. step obtains into separating funnel, divide the disacidify water layer, obtain organic layer;
The consumption of the water that again is added to the water of step described in 5. is equivalent to 1/10.4 of tetraethoxy quality;
The condition of the concentrating under reduced pressure of step described in 5. concentrates for using the vacuum pump underpressure distillation.
6. curable organopolysiloxane composition is characterized in that comprising following component:
(A) each described silicone resin of claim 1～3;
(B) have the silicoorganic compound of at least 2 hydrogen of being combined with Siliciumatom in a part, shown in II:
H
d（R
5）
eSiO
(4-d-e)/2
Formula II;
Among the formula II, R
5Be the identical or different replacement that do not contain unsaturated aliphatic or the monovalence alkyl of non-replacement;
D and e satisfy 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 effective curing.
7. curable organopolysiloxane composition according to claim 6 is characterized in that:
Described R
5For carbonatoms is 1～6 replacement or the monovalence alkyl of non-replacement;
The Si-H base of component (B) is 0.5～4.0 for the ratio of the molar weight of the unsaturated thiazolinyl in the component (A).
8. curable organopolysiloxane composition according to claim 7 is characterized in that also comprising following component:
(C) platinum metals series catalysts;
(D) make the metal-complexing catalytic reaction catalyst of epoxy group(ing) catalysis ring-opening polymerization;
(E) addition reaction inhibitor.
9. curable organopolysiloxane composition according to claim 8 is characterized in that
The consumption of component (C) is (A) and (B) 0.1～1000ppm of constituent mass total amount;
The consumption of component (D) is 0.05～10% of (A)～(C) constituent mass total amount;
The consumption of component (E) is 0.07% of (A)+(B) constituent mass total amount;
Component (C) is H
2PtCl
6MH
2O, H
2PtCl
4MH
2O, K
2PtCl
6MH
2O, K
2PtCl
4MH
2O;
Component (D) is at least a in titanium tetraisopropylate, isooctyl alcohol titanium, four propyl carbinol titaniums, diisopropoxy bis-acetylacetonate titanium, triethyl aluminum, aluminum ethylate, aluminum isopropylate, aluminium acetylacetonate, zinc ethyl and the zirconium-n-butylate;
Component (E) is triphenylphosphine, Tetramethyl Ethylene Diamine, thiophene or acetylene alcohol compounds.
10. the application of the described curable organopolysiloxane composition of claim 6 in the lining protecting materials of lining protection emitting semiconductor.
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