CN103772997B - Curable compositions - Google Patents
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- CN103772997B CN103772997B CN201410025868.7A CN201410025868A CN103772997B CN 103772997 B CN103772997 B CN 103772997B CN 201410025868 A CN201410025868 A CN 201410025868A CN 103772997 B CN103772997 B CN 103772997B
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- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 150000001875 compounds Chemical class 0.000 claims description 99
- -1 organosiloxane compound Chemical class 0.000 claims description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 56
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 229910052710 silicon Inorganic materials 0.000 claims description 36
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 35
- 229910020447 SiO2/2 Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000000565 sealant Substances 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910020485 SiO4/2 Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 150000004678 hydrides Chemical class 0.000 claims description 6
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910020487 SiO3/2 Inorganic materials 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atoms Chemical group 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atoms Chemical group C* 0.000 description 13
- 238000005457 optimization Methods 0.000 description 13
- 238000007792 addition Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 238000006459 hydrosilylation reaction Methods 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 229910002601 GaN Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920000393 Nylon 6/6T Polymers 0.000 description 3
- 239000004954 Polyphthalamide Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003287 optical Effects 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910017083 AlN Inorganic materials 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001815 facial Effects 0.000 description 2
- 125000000524 functional group Chemical group 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
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YZNQITSGDRCUKE-UHFFFAOYSA-N 1-chloropropane Chemical group [CH2]CCCl YZNQITSGDRCUKE-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QDNNHWJJEAUAFQ-UHFFFAOYSA-N C(=CCCCC)[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 Chemical compound C(=CCCCC)[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 QDNNHWJJEAUAFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001884 aluminium oxide Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001447 compensatory Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229950008597 drug INN Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DIIUFWYILXGGIL-UHFFFAOYSA-N ethynylcyclohexane Chemical compound [C]#CC1CCCCC1 DIIUFWYILXGGIL-UHFFFAOYSA-N 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004943 liquid phase epitaxy Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
The invention provides a kind of curable compositions.The invention provides a kind of cured product, this cured product shows light extraction efficiency, crack resistance, hardness, thermal-shock resistance and the bonding strength of excellence after hardening, and this cured product also shows processability and the usability of excellence.Additionally, be possible to prevent surfaces of tacky in cured product and do not cause muddiness etc..
Description
The application is divisional application, the Application No. " 201180006993.8 " of original application, filing date 2011
On January 25, in, invention entitled " curable compositions ".
Technical field
The present invention relates to a kind of curable compositions.
Background technology
Have been obtained for using by GaN compound (such as GaN, GaAlN, InGaN or InAlGaN)
The high-brightness LED product of the compound semiconductor made as Light-Emitting Diode (LED), especially as
There is about 250nm～550nm and launch blueness or the UV LED of wavelength.It addition, use red and green
The technology that color LED is combined with blue led can form high definition full color image.For example, as it is known that by inciting somebody to action
Blue led or UV LED are combined the technology preparing White LED with phosphor.Liquid crystal
Show that the demand of this LED is increased by the back lighting in device (LCD) or conventional illumination the most day by day.
The epoxy resin with high bonding strength and excellent dynamic durability is widely used as LED
Sealant.But, epoxy resin has a problem in that: epoxy resin for blueness to UV wavelength region
Light has low transmission, also demonstrates the light resistance of deterioration.It is therefoie, for example, it is public in Japanese Patent Laid
Open publication No. Hei11-274571,2001-196151 and 2002-226551 have been proposed for solve above-mentioned
The technology of problem.But, the sealant described in those references shows the light resistance of deficiency.
As sunproof material short wavelength range to excellence, it is known that organic siliconresin.
But, the shortcoming of organic siliconresin is: its poor heat resistance, and its surface becomes after hardening
More viscous.It addition, in order to effectively organic siliconresin is used as LED sealant, it is necessary to ensure that the highest folding
The performance of penetrating property, crack resistance, case hardness, bonding strength and thermal-shock resistance.
Summary of the invention
Technical problem
It is an object of the invention to provide a kind of curable compositions.
Technical scheme
The present invention relates to a kind of curable compositions, it comprises the line that (A) is represented by the average composition formula of formula 1
Property organosilicone compounds;(B) the cross-linking organosilicon oxygen alkanisation represented by the average composition formula of formula 2 closes
Thing；(C) the hydrogen siloxane compound represented by formula 3.Described curable compositions coincidence formula 1 and 2:
[formula 1]
(R1R2R3SiO1/2)a(R4R5SiO2/2)b(R6SiO3/2)c(SiO4/2)d
[formula 2]
(R7R8R9SiO1/2)e(R10R11SiO)f(R12SiO3/2)g(SiO4/2)h
[formula 3]
Wherein, at R1To R6In at least one be alkenyl, R1To R6In at least one be virtue
Base, R7To R12In at least one be alkenyl and R7To R12In the situation that at least one is aryl
Under, R1To R12Represent alkoxyl, hydroxyl, epoxy radicals or monovalent hydrocarbon independently；In R at least
In the case of one is aryl, R represents hydrogen, epoxy radicals or monovalent hydrocarbon independently；At a+b+c+d it is
1, e+f+g+h is 1, and (a+b)/(a+b+c+d) is more than 0.9, and (g+4h/3)/(e+2f) is 2 to 5, and g/ (g+h)
In the case of 0.85, a is 0 to 0.5, and b is 0.5 to 0.98, and c is 0 to 0.2, d be 0 to
0.1, e is 0 to 0.5, and f is 0 to 0.3, and g is 0.3 to 0.85, and h is 0 to 0.2, and n is 1 to 10；
[formula 1]
|X(A)-X(B)|<0.4
[formula 2]
|X(B)-X(C)|<0.4
Wherein, X(A)Represent in the aryl on the silicon atom being connected in compound (A) and this compound (A)
The all mol ratio of silicon atom, X(B)Represent the aryl on the silicon atom being connected in compound (B) and this change
The mol ratio of the whole silicon atoms in compound (B), X(C)Represent on the silicon atom being connected in compound (C)
The mol ratio of the whole silicon atoms in aryl and this compound (C).
Will be described in described curable compositions.
Described compositions can be by the alkene being connected on the silicon atom in compound (A) and compound (B)
Base solidifies with the reaction of the hydrogen atom on the silicon atom being connected in compound (C).Described curable composition
The processability (processability) of thing display excellence and usability (workability), and can be provided in solid
There is after change its cured product of crack resistance, hardness, thermal-shock resistance and the bonding strength of excellence.Described
Curable compositions shows excellence reliably and with long-term under harsh conditions (such as high temperature and/or super-humid conditions)
Property.Described curable compositions will not cause muddiness or surfaces of tacky under these harsh conditions.
Described curable compositions comprises the linear organosiloxane chemical combination represented by the average composition formula of formula 1
Thing (A).In this manual, a certain average composition formula the organosilicone compounds represented refers to following
Situation: this compound comprises the one-component represented by described a certain average composition formula, and this compound
Comprise the mixture of at least two component, and averagely the forming by described a certain average group of both components
An accepted way of doing sth represents.
In the average composition formula of formula 1, R1To R6For the substituent group being directly connected on silicon atom, and
And represent alkoxyl, hydroxyl, epoxy radicals or monovalent hydrocarbon independently.Additionally, R1To R6In at least
One represents alkenyl, and R1To R6In at least one represent aryl.In above-mentioned, described monovalence
The example of alkyl can include alkyl, haloalkyl, alkenyl, aryl and aryl alkyl.Described flat
All in composition formula, if it is necessary to described alkoxyl or monovalent hydrocarbon can be taken by suitable substituent group
Generation.
In described average composition formula, described alkoxyl can be containing 1 to 12 carbon atom, preferably 1
To 8 carbon atoms, and the straight chain of more preferably 1 to 4 carbon atom, side chain or cyclic alkoxy, and
Methoxyl group, ethyoxyl or propoxyl group can be preferably included.
In described average composition formula, described alkyl or haloalkyl can be to comprise 1 to 12 carbon atom,
Preferably 1 to 8 carbon atom, and the straight chain of more preferably 1 to 4 carbon atom, side chain or cyclic alkyl or
Haloalkyl, and methyl, ethyl, propyl group, chloromethyl, 3-chloropropyl or 3,3,3-can be preferably included
Trifluoro propyl, but more preferably methyl.
Additionally in described average composition formula, described alkenyl can be containing 2 to 12 carbon atoms, excellent
Select 2 to 8 carbon atoms, and the alkenyl of more preferably 2 to 4 carbon atoms, and can preferably include
Vinyl, pi-allyl, cyclobutenyl, pentenyl or hexenyl, but more preferably vinyl.
Similarly in described average composition formula, described aryl can be containing 6 to 18 carbon atoms, and
The aryl of preferably 6 to 12 carbon atoms, and can preferably include phenyl, tolyl, xylyl and
Naphthyl, but more preferably phenyl.
Similarly in described average composition formula, described aryl alkyl can be containing 6 to 19 carbon atoms,
And the aryl alkyl of preferably 6 to 13 carbon atoms, and benzyl or phenethyl can be preferably included.
In formula 1, R1To R6In at least one be alkenyl.Particularly, the containing of described alkenyl
Amount can be, the alkenyl (Ak) being connected on silicon atom and the whole silicon atoms (Si) in compound (A)
Mol ratio (Ak/Si) is 0.02 to 0.2, preferably 0.02 to 0.15.If this mol ratio (Ak/Si) is more than
0.02, then can suitably keep the reactivity with component (C), and be possible to prevent responseless component
Ooze out from the surface of described cured product.It is it addition, if this mol ratio (Ak/Si) is less than 0.2, the most permissible
Described cured product is made to keep the crack resistance of excellence.
Additionally, in formula 1, R1To R6In at least one can be aryl, preferably phenyl.Cause
This, can effectively control refractive index and the hardness property of described cured product.Particularly, described aryl is (excellent
Select phenyl) content can be, the mol ratio of the whole silicon atoms (Si) in this aryl (Ar) and compound (A)
(Ar/Si) it is 0.3 to 1.3, preferably 0.4 to 1.3, and more preferably 0.6 to 1.3.If this mole
Than (Ar/Si) not less than 0.3, then can make refractive index and the solidification optimization of described cured product, and if
This mol ratio (Ar/Si) is less than 1.3, then can make the optimized viscosity of described compositions.
In above-mentioned, a, b, c and d in average composition formula in formula 1 represent siloxanes list respectively
The mol ratio of unit, and the summation of a, b, c and d is 1；A is 0 to 0.5, and b is 0.5 to 0.98,
C is 0 to 0.2, and d is 0 to 0.1.In order to make the crack resistance optimization of described cured product,
(a+b)/(a+b+c+d) can be more than 0.9, preferably greater than 0.95.Such as, the upper limit of (a+b)/(a+b+c+d)
Can be 1.
In above-mentioned, the linear organosiloxane compound (A) viscosity at 25 DEG C is 1, and 000mPa s is extremely
100,000mPa s, and preferably 1,000mPa s to 50,000mPa s.If described viscosity falls into
State scope, described compositions can be made the most before curing to keep excellent processability and usability, and
The hardness optimization of compositions is made after solidification.
In above-mentioned, linear siloxane compound (A) can also have, and such as 1,000 to 50,000, excellent
Select the weight average molecular weight (M of 1,000 to 30,000w).If the M of organosilicone compounds (A)wThe least
In 1,000, then can provide and show suitable viscosity and there is intensity and the crack resistance of excellence after hardening
Compositions.If additionally, the M of organosilicone compounds (A)wIt is not more than 50,000, then can make
The optimized viscosity of described compositions, thus keeps excellent usability and processability.In this manual,
Term " weight average molecular weight " or " Mw" refer to relative to polystyrene standard conversion and use gel to ooze
The value that chromatography (GPC) records thoroughly.Additionally, unless otherwise noted, otherwise, hereinafter term " molecule
Amount " represent weight average molecular weight.
In one embodiment, the organosilicone compounds being expressed from the next can serve as described organic
Silicone compounds (A), but it is not limited to this.
(ViMe2SiO1/2)2(MePhSiO2/2)30；
(ViMe2SiO1/2)2(Ph2SiO2/2)10(Me2SiO2/2)10；
(ViMe2SiO1/2)2(MePhSiO2/2)20(Ph2SiO2/2)10(Me2SiO2/2)20；
(ViMe2SiO1/2)2(MePhSiO2/2)50(Me2SiO2/2)10；
(ViMe2SiO1/2)2(Me2SiO2/2)50(Ph2SiO2/2)30(PhSiO3/2)5；
(ViMe2SiO1/2)2(ViMeSiO2/2)2(Me2SiO2/2)30(Ph2SiO2/2)30。
In superincumbent formula, " Vi " represents vinyl, and " Me " represents methyl, and " Ph " represents phenyl.
In above-mentioned, linear organosiloxane compound (A) can use method system commonly known in the art
Standby.Such as, linear organosiloxane compound (A) can be by making to comprise hydrolyzable group (such as,
Halogen or alkoxyl) one or more organosiloxanes hydrolysis and condensation prepare.Such as, described hydrolysis
Can carry out in the presence of typical acid catalyst or base catalyst with condensation.It addition, be used for hydrolyzing and contracting
The example of the organosiloxane closed can include by RnSiX(4-n)The compound represented.In formula RnSiX(4-n)
In, X is hydrolyzable group, and can include halogen (such as chlorine) or alkoxyl, and n can be 0
To the integer of 3.Similarly in formula RnSiX(4-n)In, R is the substituent group being connected on silicon atom, and
Can consider that the substituent group of required compound properly selects.Additionally, described linear siloxane compound
The ring-opening reaction of annular siloxane can be utilized in the presence of base catalyst to prepare.It is known in the art many
Plant the method preparing silicone compounds, including method as above, those of ordinary skill in the art
A kind of required organosilicone compounds can be prepared by be suitably used in these methods.
Described curable compositions comprises the cross-linking organosilicon oxygen alkanisation represented by the average composition formula of formula 2
Compound (B).Term " cross-linking organosilicon siloxane compound " refers to must comprise by (RSiO1.5) or (SiO2)
The organosilicone compounds of the siloxane unit represented.In above-mentioned, R is hydroxyl, epoxy radicals or one
Valency alkyl.
Described cross-linking organosilicon siloxane compound (B) is represented by the average composition formula of formula 2.In above-mentioned,
R7To R12Represent the substituent group that is directly connected on silicon atom, and represent independently alkoxyl, hydroxyl,
Epoxy radicals or monovalent hydrocarbon.In above-mentioned, R7To R12In at least one represent alkenyl.It addition,
In above-mentioned, R7To R12In at least one be also represented by aryl.The concrete kind of each substituent group can
With identical with described in Formulas I.
In formula 2, R7To R12In at least one be alkenyl.Particularly, the containing of described alkenyl
Amount is, the whole silicon atoms (Si) in the alkenyl (Ak) being connected on silicon atom and compound (B) mole
It is 0.15 to 0.35 than (Ak/Si), preferably 0.15 to 0.3.If this mol ratio (Ak/Si) is not less than 0.15,
Then can make the reactive optimization with component (C), and be possible to prevent responseless component from described solid
Change and separate out on the surface of product.If it addition, this mol ratio (Ak/Si) is not more than 0.35, then institute can be made
State excellent hardness, crack resistance and the thermal-shock resistance optimization of cured product.
Additionally, in formula 2, R7To R12In at least one can be aryl, preferably phenyl.Cause
This, can make refractive index and the hardness optimization of described cured product.Particularly, described aryl (preferably benzene
Base) content can be, the whole silicon atoms (Si) in this aryl (Ar) and organosilicone compounds (B)
Mol ratio (Ar/Si) is 0.35 to 1.2, preferably 0.35 to 1.1.If this mol ratio (Ar/Si) is not less than
0.35, then can make refractive index and the hardness optimization of described cured product.If it addition, this mol ratio
(Ar/Si) it is not more than 1.2, then can keep suitable viscosity and the thermal-shock resistance of described compositions.
In above-mentioned, e, f, g and h in average composition formula in formula 2 represent siloxanes list respectively
The mol ratio of unit, and the summation of e, f, g and h is 1；E is 0 to 0.5, and f is 0 to 0.3, g
Being 0.3 to 0.85, h is 0 to 0.2.In order to make the intensity of described cured product, crack resistance and heat resistanceheat resistant punching
Hitting property optimization, (g+ (4/3) h)/(e+2f) can drop into the scope of 2 to 5, the scope of preferably 2 to 4,
G/ (g+h) can be more than 0.85, preferably greater than 0.90.Such as, the upper limit of g/ (g+h) can be 1.
The described cross-linking organosilicon siloxane compound (B) viscosity at 25 DEG C can be more than 5,000mPa s,
Preferably greater than 10,000mPa s.Therefore, suitable processability can be kept before curing, and solid
Suitable hardness can be kept after change.
Additionally, the molecular weight of described cross-linking organosilicon siloxane compound (B) can be, such as, 1,000
To 5,000, preferably 1,000 to 4,000.If the molecular weight of organosilicone compounds (B) is not less than
1,000, then can make described compositions strong after the formability of the described compositions before solidification and solidification
Degree optimization, and if the molecular weight of organosiloxane (B) is not more than 5,000, then can make such as viscosity
Performance optimization.
In one embodiment, the organosilicone compounds represented selected from one of following formula can use
Make organosilicone compounds (B), but be not limited to this.
(ViMe2SiO1/2)3(PhSiO3/2)10；
(ViMe2SiO1/2)2(MePhSiO2/2)2(PhSiO3/2)15；
(ViMe2SiO1/2)2(Ph2SiO2/2)(PhSiO3/2)8；
(ViMe2SiO1/2)3(PhSiO3/2)9(SiO4/2)；
(ViMe2SiO1/2)3(MePhSiO2/2)(PhSiO3/2)9(SiO4/2)；
(ViMe2SiO1/2)2(Me2SiO2/2)(MePhSiO2/2)2(Ph2SiO2/2)(PhSiO3/2)19(SiO4/2)。
In superincumbent formula, " Vi " represents vinyl, and " Me " represents methyl, and " Ph " represents phenyl.
In above-mentioned, use and prepare the method for described cross-linking organosilicon siloxane compound (B) and be not subject to especially
Limit, and for example, it is possible to use according to the mode identical with organosilicone compounds (A).
In one embodiment, such as, relative to the linear organosiloxane compound of 100 weight portions
(A), the content of cross-linking organosilicon siloxane compound (B) can be, such as 50 weight portions are to 700 weight
Part, preferably 50 weight portions are to 500 weight portions.In this manual, unit " weight portion " refers to weight
Amount ratio.If the weight ratio of compound (B) is not less than 50 weight portions, then described cured product can be made to protect
Hold excellence intensity, and if the weight ratio of silicone compounds (B) is not more than 700 weight portions, the most permissible
Described cured product is made to keep excellent crack resistance and thermal-shock resistance.
Described curable compositions comprises the hydrogen siloxane compound (C) represented by formula 3.Described siliconization
Compound (C) is containing the hydrogen atom being directly connected on silicon atom.This hydrogen atom can be connected to compound (A)
React with the alkenyl on the silicon atom comprised in compound (B).
In formula 3, R represents hydrogen, epoxy radicals or monovalent hydrocarbon independently.The concrete kind of monovalent hydrocarbon
Can be same as described above.
Described silicone compounds (C) has the hydrogen atom end-blocking that two ends are connected on silicon atom
Strand.In this case, if it is desired, at least one in the R comprised in molecular side chain can
Think hydrogen.Particularly, the hydrogen atom (H) being connected on silicon atom and the whole silicon atoms in compound (C)
(Si) mol ratio (H/Si) can be 0.2 to 0.8, preferably 0.3 to 0.75.If this mol ratio is the least
In 0.2, then described compositions can be made to keep excellent curable, and if this mol ratio is not more than 0.8,
Described compositions then can be made to keep excellent crack resistance and thermal-shock resistance.
Additionally, in formula 3, at least one R can be aryl, preferably phenyl.Therefore, it can make
The refractive index of described cured product and hardness optimization.Particularly, the content of described aryl (preferably phenyl)
Can be, the mol ratio (Ar/Si) of the whole silicon atoms (Si) in this aryl (Ar) and compound (C) be 0.3 to
1, preferably 0.4 to 0.8.If this mol ratio (Ar/Si) is not less than 0.3, then described solidification can be made to produce
The refractive index of thing and hardness optimization.If it addition, this mol ratio (Ar/Si) is not more than 1, then can make
The viscosity of described compositions and crack resistance optimization.
In formula 3, n can be 1 to 10, preferably 1 to 5.Therefore, it can make described solidification produce
Thing keeps excellent intensity and crack resistance.
In above-mentioned, the described silicone compounds (C) viscosity at 25 DEG C can be 500mPa s or little
In 500mPa s, and preferably 300mPa s or less than 300mPa s.If the viscosity of compound (C) falls
Enter above-mentioned scope, then described compositions can be made to keep the processability of excellence, and make described cured product
Keep excellent hardness.
In one embodiment, the molecular weight of described silicone compounds (C) can be, such as, be less than
1,000, preferably smaller than 800.If the molecular weight of compound (C) is more than 1,000, the most described cured product
Intensity may deterioration.The lower limit of the molecular weight of compound (C) is not particularly limited, but can be,
Such as, 250.
In one embodiment, by be selected from down facial in one expression silicone compounds can use
Make compound (C), but be not limited to this.
(HMe2SiO1/2)2(MePhSiO2/2)2；
(HMe2SiO1/2)2(Ph2SiO2/2)1.5；
(HMe2SiO1/2)2(MePhSiO2/2)1.5(Ph2SiO2/2)1.5；
(HMe2SiO1/2)2(Me2SiO2/2)2.5(Ph2SiO2/2)2.5；
(HMe2SiO1/2)2(Me2SiO2/2)2.5(Ph2SiO2/2)2.5；
(HMe2SiO1/2)2(HMeSiO1/2)(Ph2SiO2/2)2；
Upper facial in, " Vi " represents vinyl, and " Me " represents methyl, and " Ph " represents phenyl.
As it has been described above, use is prepared the method for compound (C) and is not particularly limited, and for example, it is possible to
Use according to the mode identical with compound (A) and compound (B).
In one embodiment, the amount of compound (C) can be determined, so that relative to connection
The sum of the alkenyl on silicon atom in compound (A) and compound (B) meets specific molar ratio.Special
Not, the hydrogen atom (H) being connected on the silicon atom in compound (C) be connected to compound (A) and chemical combination
The mol ratio (H/Ak) of the whole alkenyls (Ak) on the silicon atom in thing (B) is 0.8 to 1.2, is preferably
0.85 to 1.15, and more preferably 0.9 to 1.1.By controlling mol ratio as above (H/Ak), can
To provide a kind of compositions, said composition demonstrates processability and the usability of excellence before curing, solid
Demonstrate crack resistance, hardness, thermal-shock resistance and the bonding strength of excellence after change, and said composition is prevented
Produce muddy and tacky the most under severe conditions on surface.
Relative to the compound (A) of 100 weight portions, the content of compound (C) can be that 50 weight portions are to 500
Weight portion, preferably 50 weight portions are to 400 weight portions.
The refractive index of cured product and hardness, all of compound in view of described curable compositions
(A), (B) and (C) can each self-contained aryl being connected on silicon atom therein.The example of this aryl can
To include phenyl.Additionally, the whole virtues being connected in compound (A), (B) and (C) on the silicon atom that comprises
The mol ratio (Ar/Si) of the whole silicon atoms (Si) comprised in base (Ar) and compound (A), (B) and (C) can be excellent
Choosing is more than 0.3 and less than 1.2, and can be more preferably 0.4 to 1.2.If this mol ratio is more than 0.3,
Described cured product then can be made to keep excellent hardness and refractive index.If it addition, this mol ratio sets
For less than 1.2, then can effectively control the viscosity of described compositions.
Additionally, all of compound (A), (B) and (C) can meet formula below 1 and 2:
[formula 1]
|X(A)-X(B)|<0.4
[formula 2]
|X(B)-X(C)|<0.4
Wherein, X(A)Represent the aryl on the silicon atom being connected in compound (A) comprise and this compound (A)
In the mol ratio of whole silicon atoms, X(B)Represent the virtue on the silicon atom being connected in compound (B) comprise
The mol ratio of the whole silicon atoms in base and this compound (B), X(C)Represent and be connected in compound (C) comprise
Silicon atom on aryl and this compound (C) in the mol ratio of whole silicon atoms.
In formula 1 and 2, | X(A)-X(B)| and | X(B)-X(C)| represent X respectively(A)And X(B)Difference exhausted
To value and X(B)And X(C)The absolute value of difference.Herein, each absolute value can be preferably smaller than 0.35.This
Outward, the lower limit of described absolute value is not particularly limited.
If the requirement of the mol ratio coincidence formula of described aryl 1 and 2, then one can be provided to demonstrate
The compositions of the compatibility excellent between component, this component forms described compositions and has before curing
Excellent processability and usability, and can provide a kind of demonstrate excellence after hardening refractive index,
Light transmittance and the compositions of hardness.
Described curable compositions can also comprise hydrosilylation catalysts.This hydrosilylation catalysts
May be used for hydrogen atom and compound (A) or the compound facilitating connection on the silicon atom in compound (C)
(B) reaction of the alkenyl in.The kind that may be used for hydrosilylation catalysts herein is limited the most especially
System, it is possible to use any hydrosilylation catalysts known in the art.The example of such catalyst can
To include platinum, palladium or rhodium catalyst.In one embodiment, it is contemplated that catalytic efficiency etc., can make
Use platinum catalyst.The example of such catalyst can include, but not limited to chloroplatinic acid, platinum tetrachloride,
The olefin complex of platinum, the alkenylsiloxane coordination compound of platinum or the carbonyl-complexes etc. of platinum.
In above-mentioned, the amount of hydrosilylation catalysts is not particularly limited, as long as this hydrosilylation is urged
Agent is deposited with so-called catalytic amount (that is, hydrosilylation catalysts can play the amount of catalyst action)
?.Typically, atomic weight based on platinum, palladium or rhodium, the content of hydrosilylation catalysts can
Think 0.1ppm to 500ppm, preferably 0.2ppm to 100ppm.
Additionally, described curable compositions can also comprise viscosifier, thus improve further various linings
The bonding strength at the end.These viscosifier can improve the autoadhesion intensity to compositions or cured product, and
Especially it is possible to improve the autoadhesion intensity to metal and organic resin.
The example that can be used for viscosifier herein can include, but not limited to containing selected from alkenyl (such as
Vinyl), (methyl) acryloxy, hydrosilane groups (hydrosilyl group) (SiH yl), epoxy radicals,
At least one functional group in alkoxyl, alkoxysilyl, carbonyl and phenyl, preferably at least two kinds
The silane of functional group；Or organo-silicon compound, such as, containing 2 to 30 silicon atoms, preferably 4 to
Ring-type or the linear siloxane of 20 silicon atoms.Above-mentioned viscosifier can be used alone or in combination.
If described compositions comprises viscosifier, then relative to the compound (A) of 100 weight portions, described increasing
The amount of stick can be 0.1 weight portion to 20 weight portions, it is contemplated that the improvement of required bonding strength can
Suitably change to make.
In addition to the aforementioned components, described curable compositions can the most also comprise in following
At least one additive: reaction initiator, such as, 2-methyl-3-butyne-2-alcohol, 2-phenyl-3-1-fourth
Alkynes-2-alcohol (2-phenyl-3-1-butin-2-ol), 3-methyl-3-amyl-1-diene (3-methyl-3-penten-1-in),
3,5-dimethyl-3-hex-1-diene (3,5-dimethyl-3-hexen-1-in), 1,3,5,7-tetramethyl-1,3,5,7-four
Hexenyl cyclotetrasiloxane or Ethynylcyclohexane；Inorganic filler, such as, silicon dioxide, aluminium oxide,
Zirconium oxide or titanium dioxide；The silane (carbon-functional silane) of carbon-sense and partial hydrolysis contracting thereof
Compound, or containing epoxy radicals and/or the silicone compounds of alkoxysilyl；Thixotropic agent, such as,
The atomization silicon dioxide (aerosolized silica) that can use with polyether combined；Electric conductivity provides agent
(conductivity-providing agent), it may for example comprise silver, copper or the metal dust of aluminum, or multiple carbon
Material；With color control agent, such as pigment or dyestuff.
The invention still further relates to a kind of semiconductor device, it includes the semiconductor element sealed with sealant, institute
State the foregoing curable compositions that sealant comprises solid state.
Diode, crystalline substance can be included with the example of the semiconductor element that described curable compositions seals
Body pipe, IGCT, solid-state image collection device (solid image pickup device), integral type IC and
The semiconductor element used in hybrid IC.Additionally, the illustrative examples of described semiconductor device can be wrapped
Include diode, transistor, IGCT, photoelectrical coupler, CCD, integral type IC, hybrid IC,
LSI, VLSI and light emitting diode (LED).
In one embodiment, described semiconductor device can be light emitting diode, this light emitting diode
Including the light-emitting component sealed with sealant, described sealant comprises the foregoing curable combination of solid state
Thing.
The kind that can be used for light-emitting component herein is not particularly limited.It is, for example possible to use by base
Stacking semi-conducting material on plate and the light-emitting component that formed.In this case, described semi-conducting material
Example can include, but not limited to GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN,
InN, AlN, InGaAlN or SiC.Additionally, the example that can be used for substrate herein can include blue precious
Stone, spinelle, SiC, Si, ZnO or GaN single crystal.
In one embodiment, if necessary, it is also possible to shape between substrate and described semi-conducting material
Become cushion.In this case, GaN or AlN can serve as cushion.On substrate, stacking is partly led
The method of body material is not particularly limited, but can include, such as, and MOCVD, HDVPE or liquid
Phase epitaxy method.In above-mentioned, the structure of light-emitting component can include, such as, has MIS knot, PN
Knot or the single-junction structure of PIN junction, heterojunction structure and double-heterostructure.Additionally, described light-emitting component
Can be formed with single or multiple quantum well structure.
In one embodiment, the transmitting wavelength of described light-emitting component can be, such as, 250nm is extremely
550nm, preferably 300nm to 500nm, and more preferably 330nm to 470nm.Transmitted wave
Long expression peak emission wavelength.When the transmitting wavelength of described light-emitting component falls into this wavelength, can obtain
There is longer life and show higher energy efficiency and the white-light luminescent component of color rendering.
Described light emitting diode can be by sealing luminescence with the encapsulant comprising foregoing curable compositions
Element, prepared by the light-emitting component particularly with 250nm to 550nm transmitting wavelength.In this feelings
Under condition, the sealing of described light-emitting component can only use curable compositions as above to carry out, if
If necessary, can carry out with other sealant combination.When being used together at least two sealant,
Light-emitting component can be sealed with curable compositions as above, then seal warp with other sealant
The preliminary light-emitting component sealed；Or can seal with other sealant, then with as above may be used
Solidification compositions seals through the preliminary light-emitting component sealed.May be used for other sealant herein can wrap
Include epoxy resin, organic siliconresin, acryl resin (acryl resin), urea resin (urea resin), acyl
Imide resin (imide resin) or glass.
Such as, seal the method for light-emitting component with curable compositions as above to include: first will be as
Upper described curable compositions is injected in mold die (mold-type cast), will be fixed with illuminating part
The lead frame of part is immersed in curable compositions as above, and makes this curable compositions solidify
Method；Curable compositions as above is injected into and is wherein inserted with in the mould of light-emitting component, and make
The method of this curable compositions solidification；Etc..In this case, described injection curable compositions
The example of method can include using the injection methods such as allotter method, transfer moudling, injection molding.
Additionally, may include that by drop method (dropping), block printing for other encapsulating method herein
Curable compositions as above is applied to send out by method, silk screen print method or mask means (mask process)
On optical element, and make the method that this curable compositions solidifies；Use allotter by described curable composition
Thing is injected in the cup being provided with light-emitting component, and makes the method that this curable compositions solidifies.This
Outward, curable compositions as above may serve as light-emitting component is fixed on lead terminal or outer
Chip adhesive material on shell (package), the passivating film on light-emitting component and base plate for packaging etc..
The method making curable compositions as above solidify is not particularly limited, but permissible, such as,
Within 10 minutes, carried out to 5 hours by heating described compositions at a temperature of 60 DEG C to 200 DEG C, and
Not necessarily, carry out by carrying out at least two-stage cure under conditions of suitable temperature and time.
The shape of hermetic unit is not particularly limited, it may form part of shell mould lens (shell-type lens),
Plane or film shape.
In one embodiment, it is also possible to use the known method of other routine to improve described luminescence
The performance of element.Such as, put forward high performance method described in may include that on the rear surface of light-emitting component
The method that reflection layer or light-collecting layer are set；The side of compensatory chrominance section is formed in the bottom of light-emitting component
Method；It is provided for the method for layer that absorbing wavelength is shorter than the light of main emission peak wavelength on light emitting elements；Close
Seal optical element also uses the method that this light-emitting component moulds by hard material further；Make to send out by through hole
The method that optical diode is fixing；Use flip-chip interconnection method (flip chip interconnection) by light-emitting component even
Receive in lead member, thus the method for the direction extraction light along substrate, etc..
Described light emitting diode is permissible, such as, effectively serves as light source, such as, and liquid crystal indicator
(LCD), multiple sensors, printer or the back light unit of photocopier, for automobile instrument panel, traffic
Lamp, signal lights, the light source of display, for planar illuminant, display, decoration or the light of various lamp
Source.
Beneficial effect
The processability of described curable compositions display excellence and usability.It addition, described curable composition
Crack resistance, thermal-shock resistance and the bonding strength that thing display is excellent, and also the excellent reliability of display and
Long-term reliability under high temperature and/or super-humid conditions.Additionally, described curable compositions additionally provides one
Planting cured product, this cured product is prevented from producing muddiness, and this cured product is prevented from surface
Upper generation viscosity, is therefore possible to prevent surfaces of tacky.
Detailed description of the invention
Hereinafter, with reference to the embodiment designed according to the present invention and the contrast designed not according to the present invention
Example will be further described the present invention；But, the present invention is not limited to embodiment.
In an embodiment, " Vi " represents vinyl, and " Ph " represents phenyl, and " Me " represents methyl, " Ep "
Represent epoxy radicals.
1. the measurement of light transmittance
In embodiment and comparative example, the following light transmittance evaluating cured product.First, by prepared group
Compound is injected between two glass sheets being spaced apart setting with the distance of about 1mm, and 150
DEG C constant temperature under solidify 1 hour to prepare the test sample of 1mm thickness.Then, UV-VIS is used to divide
Photometry, under the wavelength of 450nm, at room temperature measures test sample light transmittance in a thickness direction,
And according to following standard evaluation.
<evaluating the standard of light transmittance>
Zero: 98.5% or more than 98.5% light transmittance
×: 98.5% or less than 98.5% light transmittance
2. the assessment of surface viscosity
Curable compositions is injected in mould, and solidifies 1 hour under the constant temperature of 150 DEG C.So
After, evaluate surface viscosity by the surface of the cured product obtained by touching that catches according to following standard.
<evaluating the standard of surface viscosity>
Zero: surface is the most tacky
△: surface is the most tacky
×: surface is the most tacky
3. the assessment of device performance
The 5630LED encapsulation prepared by polyphthalamide (PPA) is used to carry out evaluating apparatus performance.More
Particularly, curable compositions is assigned in polyphthalamide cup, and solid under the constant temperature of 60 DEG C
Change 30 minutes, then solidify 1 hour under the constant temperature of 150 DEG C, prepare surface mounting LED.Then,
The following thermal-shock resistance evaluating above-mentioned LED and the long-term reliability under high temperature/super-humid conditions.
<evaluating the standard of thermal-shock resistance>
In a cycle, prepared surface mounting LED is placed in lower 30 minutes of the constant temperature of-40 DEG C,
It is subsequently placed in lower 30 minutes of the constant temperature of 100 DEG C, repeats this circulation 10 times.Then, above-mentioned surface is pacified
Dress type LED at room temperature cools down, and evaluates stripping state to determine that thermal-shock resistance is (in each embodiment and right
Ratio is prepared totally 10 surface mounting LEDs, and evaluates stripping state).
<long-term reliability under high temperature/super-humid conditions>
The electric current of 60mA is applied, simultaneously the temperature and 85% of 85 DEG C to prepared surface mounting LED
Relative humidity controlled condition under make this LED run 100 hours.After completing above-mentioned operation, measure
The brightness of LED, to calculate the brightness reduction relative to original intensity, and can according to following standard evaluation
By property.
<evaluation criterion>
Zero: brightness reduces by 10% or less than 10% relative to original intensity
×: brightness reduces by 10% or more than 10% relative to original intensity
Embodiment
Embodiment 1
The method preparation using those of ordinary skill in the art's routine to understand is represented by formula as described below
Compound.By 100g linear organosiloxane compound (formula 1, (a+b)/(a+b+c+d)=1), 300g
Cross-linking organosilicon siloxane compound (formula 2, (g+4h/3)/(e+2f)=2, g/ (g+h)=1) and 98.0g hydrogen silicon
Siloxane compound (formula 3) mixes, and is mixed into wherein by the viscosifier that 10.4g is represented by formula 4.Then,
It is mixed into catalyst (platinum (0)-1,3-diethyl with the Pt (0) content in the obtained mixture amount as 20ppm
Thiazolinyl-1,1,3,3-tetramethyl disiloxane), uniformly mix, and degasification, prepare curable compositions (public
In formula 1 and 2 | X(A)-X(B)| and | X(B)-X(C)| both less than 0.4).
[formula 1]
[ViMe2SiO1/2]2[Me2SiO2/2]9[Ph2SiO2/2]10[PhMeSiO2/2]4
[formula 2]
[ViMeSiO2/2][PhMeSiO2/2][PhSiO3/2]14[ViMe2SiO1/2]3
[formula 3]
[HMe2SiO1/2]2[Ph2SiO2/2]
[formula 4]
[ViMe2SiO1/2]2[EpSiO3/2]2[PhMeSiO2/2]10
Embodiment 2
Except using the linear organosiloxane compound of 100g formula 1,300g as cross-linking organosilicon oxygen
The silicone compounds ((g+4h/3)/(e+2f)=3, g/ (g+h)=1) represented by formula 5 of hydride compounds, 10.0
Outside the viscosifier of g formula 4 and the hydrogen siloxane compound of 115.0g formula 3 are mixed together, according to enforcement
The mode that example 1 is identical prepare curable compositions (in formula 1 and 2 | X(A)-X(B)| and | X(B)-X(C)|
Both less than 0.4).
[formula 5]
[PhSiO3/2]12[ViMe2SiO1/2]4
Embodiment 3
Except using the linear organosiloxane compound of 100g formula 1,300g as cross-linking organosilicon oxygen
The silicone compounds ((g+4h/3)/(e+2f)=4, g/ (g+h)=1) represented by formula 6 of hydride compounds, 10.0
Outside the viscosifier of g formula 4 and the hydrogen siloxane compound of 94.0g formula 3 are mixed together, according to enforcement
The mode that example 1 is identical prepare curable compositions (in formula 1 and 2 | X(A)-X(B)| and | X(B)-X(C)|
Both less than 0.4).
[formula 6]
[PhSiO3/2]16[ViMe2SiO1/2]4
Embodiment 4
Except using the linear organosiloxane compound of 100g formula 1,300g as cross-linking organosilicon oxygen
The silicone compounds ((g+4h/3)/(e+2f)=5, g/ (g+h)=1) represented by formula 7 of hydride compounds, 10.0
Outside the viscosifier of g formula 4 and the hydrogen siloxane compound of 79.0g formula 3 are mixed together, according to enforcement
The mode that example 1 is identical prepare curable compositions (in formula 1 and 2 | X(A)-X(B)| and | X(B)-X(C)|
Both less than 0.4).
[formula 7]
[PhSiO3/2]15[ViMe2SiO1/2]3
Comparative example 1
Except the linear organosiloxane compound making the molecular formula 1 of 100g represent, 300g are as crosslinking
Type silicone compounds represented by formula 8 silicone compounds ((g+4h/3)/(e+2f)=1, g/ (g+h)=
1), outside the hydrogen siloxane compound of the viscosifier of 10.0g formula 4 and 115.0g formula 3 is mixed together, press
According to mode same as in Example 1 prepare curable compositions (in formula 1 and 2 | X(A)-X(B)| and | X(B)
-X(C)| both less than 0.4).
[formula 8]
[ViMeSiO2/2]2[PhMeSiO2/2]2[PhSiO3/2]10[ViMe2SiO1/2]2
Comparative example 2
Except using the linear organosiloxane compound of 100g formula 1,300g as cross-linking organosilicon oxygen
Hydride compounds represented by formula 9 silicone compounds ((g+4h/3)/(e+2f)=about 5.3, g/ (g+h)=
0.8), outside the hydrogen siloxane compound of the viscosifier of 10.0g formula 4 and 88.0g formula 3 is mixed together, press
According to mode same as in Example 1 prepare curable compositions (in formula 1 and 2 | X(A)-X(B)| and | X(B)
-X(C)| both less than 0.4).
[formula 9]
[SiO4/2]2[MeSiO3/2][PhSiO3/2]7[ViMe2SiO1/2]2
Comparative example 3
Except using the linear organosiloxane compound of 100g formula 1,300g as cross-linking organosilicon oxygen
The silicone compounds ((g+4h/3)/(e+2f)=2, g/ (g+h)=1) represented by formula 10 of hydride compounds,
Outside the viscosifier of 10.0g formula 4 and the hydrogen siloxane compound of 118.0g formula 3 are mixed together, according to
The mode that embodiment 1 is identical prepare curable compositions (in formula 1 | X(A)-X(B)| it is 0.4, formula 2
| X(B)-X(C)| less than 0.4).
[formula 10]
[ViMeSiO2/2][PhMeSiO2/2][MeSiO3/2]7[PhSiO3/2]7[ViMe2SiO1/2]3
Comparative example 4
Except by the linear organosiloxane compound of 100g formula 1, the cross-linking organosilicon of 300g formula 2
The hydrogen siloxane compound one that siloxane compound, the viscosifier of 10.0g formula 4 and 80.0g are represented by formula 11
Rise mixing outside, prepare according to the same manner as in Example 1 curable compositions (in formula 1 | X(A)
-X(B)| less than 0.4, formula 2 | X(B)-X(C)| it is 0.4).
[formula 11]
[HMe2SiO1/2]2[PhMeSiO2/2]
The evaluation result of obtained curable compositions is summed up and is listed in table 1 below.
As found out from table 1, it is shown that show after hardening according to the curable compositions of embodiment
Excellent absorbance is without causing surfaces of tacky.Additionally, also show the curable compositions of embodiment
Have in the thermal-shock resistance of excellence, and the long-term reliability test under high temperature/super-humid conditions and show
Fabulous result.
Particularly, in the case of the comparative example 3 not having coincidence formula 1 and 2 simultaneously and comparative example 4,
Described compositions shows the performance of serious deterioration, such as light transmittance, and thermal-shock resistance and reliability.
Claims (10)
1. a curable compositions, this curable compositions comprises:
(A) linear organosiloxane compound, it is represented and weight average molecular weight by the average composition formula of formula 1
Be 1,000 to 50,000；
(B) cross-linking organosilicon siloxane compound, it is represented and Weight-average molecular by the average composition formula of formula 2
Amount is 1,000 to 5,000；With
(C) hydrogen siloxane compound, it is represented by formula 3 and weight average molecular weight is less than 1,000,
And this curable compositions coincidence formula 1 and 2,
Wherein, relative to the described organosilicone compounds (A) of 100 weight portions, described organosiloxane
The content of compound (B) is that 50 weight portions are to 700 weight portions；Wherein, relative to described in 100 weight portions
Organosilicone compounds (A), the content of described hydrogen siloxane compound (C) is that 50 weight portions are to 500 weights
Amount part；
Wherein, in described organosilicone compounds (A), the alkenyl being connected on silicon atom and this silica
The mol ratio of the whole silicon atoms in hydride compounds (A) is 0.02 to 0.2；And wherein, described hydrogen silica
Comprising aryl in hydride compounds (C), the content of described aryl makes described aryl and this hydrogen siloxane chemical combination
The mol ratio (Ar/Si) of the whole silicon atoms in thing (C) is 0.3 to 0.8:
[formula 1]
(R1R2R3SiO1/2)a(R4R5SiO2/2)b(R6SiO3/2)c(SiO4/2)d
[formula 2]
(R7R8R9SiO1/2)e(R10R11SiO)f(R12SiO3/2)g(SiO4/2)h
[formula 3]
Wherein, at R1To R6In at least one be alkenyl, R1To R6In at least one be virtue
Base, R7To R12In at least one be alkenyl and R7To R12In the situation that at least one is aryl
Under, R1To R12Represent alkoxyl, hydroxyl, epoxy radicals or monovalent hydrocarbon independently；In R at least
In the case of one is aryl, R represents hydrogen, epoxy radicals or monovalent hydrocarbon independently；At a+b+c+d
Being 1, e+f+g+h is 1, and (a+b)/(a+b+c+d) is more than 0.9, and (g+4h/3)/(e+2f) is 2 to 5, and g/ (g+h)
In the case of 0.85, a is 0 to 0.5, and b is 0.5 to 0.98, and c is 0 to 0.2, and d is 0 to 0.1, e
Being 0 to 0.5, f is 0 to 0.3, and g is 0.3 to 0.85, and h is 0 to 0.2, and n is 1 to 10；
[formula 1]
|X(A)-X(B)|<0.4
[formula 2]
|X(B)-X(C)|<0.4
Wherein, X(A)Represent the aryl on the silicon atom being connected in described organosilicone compounds (A)
With the mol ratio of the whole silicon atoms in this organosilicone compounds (A), X(B)Represent described in being connected to
In the aryl on silicon atom in organosilicone compounds (B) and this organosilicone compounds (B)
The all mol ratio of silicon atom, X(C)Represent the silicon atom being connected in described hydrogen siloxane compound (C)
On aryl and this hydrogen siloxane compound (C) in the mol ratio of whole silicon atoms.
Curable compositions the most according to claim 1, wherein, is connected to silicon in compound (C)
Whole with on the silicon atom being connected in compound (A) and compound (B) of hydrogen atom (H) on atom
Mol ratio H/Ak of alkenyl Ak is 0.9 to 1.1.
Curable compositions the most according to claim 1, wherein, at described organic siloxane
In compound (B), the alkenyl being connected on silicon atom is former with the whole silicon in this silicone compounds (B)
The mol ratio of son is 0.15 to 0.35.
Curable compositions the most according to claim 1, wherein, described hydrogen siloxane compound
(C) comprising aryl, the content of aryl is this aryl (Ar) and the whole silicon atoms (Si) in compound (C)
Mol ratio (Ar/Si) is 0.4 to 0.8.
Curable compositions the most according to claim 1, wherein, in formula 3, R represents independently
Methyl or phenyl, in formula 3, n is 1 to 5.
Curable compositions the most according to claim 1, wherein, described hydrogen siloxane compound
(C) it is (HMe2SiO1/2)2(MePhSiO2/2)2Or [HMe2SiO1/2]2[Ph2SiO2/2], wherein Me represents
Methyl, Ph represents phenyl.
Curable compositions the most according to claim 1, wherein, at described hydrogen siloxane chemical combination
In thing (C), the hydrogen atom being connected on silicon atom and the whole silicon atoms in this hydrogen siloxane compound (C)
Mol ratio be 0.2 to 0.8.
Curable compositions the most according to claim 1, wherein, is connected to described siliconization
In the aryl on silicon atom in compound (A), (B) and (C) and this silicone compounds (A), (B) and (C)
The mol ratio of whole silicon atoms more than 0.3 and less than 1.2.
9. a light emitting diode, this light emitting diode includes the light-emitting component sealed with sealant,
Described sealant comprises the compositions described in the claim 1 of solid state.
10. a liquid crystal indicator, this liquid crystal indicator includes claim at back light unit
Light emitting diode described in 9.
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-2010-0006700 | 2010-01-25 | ||
| KR20100006700 | 2010-01-25 | ||
| KR1020110007455A KR101152869B1 (en) | 2010-01-25 | 2011-01-25 | Curable resin composition |
| KR10-2011-0007455 | 2011-01-25 |
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| CN1863875A (en) * | 2003-10-01 | 2006-11-15 | 陶氏康宁东丽株式会社 | Curable organopolysiloxane composition and semiconductor device |
| CN101389695A (en) * | 2006-02-24 | 2009-03-18 | 陶氏康宁公司 | Light emitting device encapsulated with silicones and curable silicone compositions for preparing the silicones |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1863875A (en) * | 2003-10-01 | 2006-11-15 | 陶氏康宁东丽株式会社 | Curable organopolysiloxane composition and semiconductor device |
| CN101389695A (en) * | 2006-02-24 | 2009-03-18 | 陶氏康宁公司 | Light emitting device encapsulated with silicones and curable silicone compositions for preparing the silicones |
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