CN105219097B - A kind of curable rubber composition and semiconductor devices - Google Patents
A kind of curable rubber composition and semiconductor devices Download PDFInfo
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- CN105219097B CN105219097B CN201410310156.XA CN201410310156A CN105219097B CN 105219097 B CN105219097 B CN 105219097B CN 201410310156 A CN201410310156 A CN 201410310156A CN 105219097 B CN105219097 B CN 105219097B
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 229920001971 elastomer Polymers 0.000 title claims abstract description 28
- 239000004065 semiconductor Substances 0.000 title claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 31
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 28
- 229910020487 SiO3/2 Inorganic materials 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 229910020447 SiO2/2 Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002118 epoxides Chemical group 0.000 claims description 3
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000006574 non-aromatic ring group Chemical group 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000007711 solidification Methods 0.000 description 11
- 230000008023 solidification Effects 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- -1 Tertiary amine compound Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 125000004344 phenylpropyl group Chemical group 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- 125000005023 xylyl group Chemical group 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 241000218202 Coptis Species 0.000 description 3
- 235000002991 Coptis groenlandica Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 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 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical class C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- NIBADJGLXVMKLY-UHFFFAOYSA-N NC[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)C1=CC=CC=C1 Chemical compound NC[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)C1=CC=CC=C1 NIBADJGLXVMKLY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 201000009310 astigmatism Diseases 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 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 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The defects of in order to overcome the sulfidation-resistance of prior art poor, the invention provides a kind of curable rubber composition and semiconductor devices, it be 4 15Mpa in tensile strength, and elongation at break is 12% 30%, and the composition includes：(A) there is the organopolysiloxane of branched molecular structure, (B) has the poly- Organhydridosiloxaneresins of branched molecular structure, and the described and hydrogen atom content of silicon bonding is 0.2 0.4mol/100g；(C) there is straight-chain molecular structure and in a molecule containing average at least one and the alkenyl of silicon bonding and at least one aromatic group, and the both ends of strand have the nonaromatic epoxy resin for containing or not contain organosilicon containing average at least two epoxide groups in a molecule with the hydroxy-end capped organopolysiloxane with silicon bonding, (D).Compared with prior art, the present invention not only maintains good cold-resistant thermal shock resistance properties, higher index of refraction, stronger hardness, but also has excellent sulfidation-resistance energy and humidity resistance.
Description
Technical field
The present invention relates to a kind of silicon composition, more particularly to a kind of curable rubber composition, and use
The semiconductor devices that the composition solidification is formed.
Background technology
The basic structural unit of organosilicon polymer is made up of silica chain link, and side chain is then various with other by silicon atom
Organic group is connected.Compared with other high polymer materials, organosilicon polymer has following outstanding properties：1. temperature-resistance characteristic, have
Machine silicon product be using silica (Si-O) key as backbone structure, so the heat endurance of organosilicon product is high, (or spoke under high temperature
Penetrate irradiation) chemical bond of molecule is not broken, does not decompose.2. weatherability, the main chain of organosilicon product is-Si-O-, have than
The more preferable heat endurance of other high polymer materials and resistance to irradiation and weather-proof ability, have under natural environment and longer use the longevity
Life.3. electrical insulation properties, organosilicon product all has a good electrical insulation capability, its dielectric loss, proof voltage, Inverter fed motor,
Specific volume resistance and surface resistivity etc. come out at the top in insulating materials, and their electric property by temperature and
The influence very little of frequency.Therefore, it is extensive as one kind of organosilicon product, silicon rubber based on above-mentioned good combination property
Applied in LED light volt industry.
Patent application publication CN103342816A discloses a kind of curable rubber composition, applies in LED
In encapsulation, have the following advantages that：Splendid caking property, stronger hardness, excellent cold-and-heat resistent impact capacity, transparency height etc. are excellent
Point.
Generally, LED packaging part includes light-emitting component and LED support, and the light-emitting component is fixed on the LED support
On, the LED support is generally made up of metallic matrix, and silver coating is provided with the metallic matrix, and the silver coating is used for
To the optically focused or astigmatism of light-emitting component light.Rubber composition is coated on to the silver coating of the light-emitting component and LED support
On, and solidified, that is, it has been basically completed the encapsulation to LED.However, in wet environment, the moisture in air gradually oozes
Thoroughly, light-emitting component can be caused to go wrong, especially for RGB (three coloured light) LED packaging part, it is (single compared to white light
Coloured light) LED packaging part, the requirement to humidity resistance is higher；In addition, in the prior art, LED packaging part is in long-term use
During, the sulphur in surrounding air can corrode silver coating gradually, cause the silver layer sulphide staining, and then cause light decay serious,
It has impact on the service life of LED.
The content of the invention
The technical problems to be solved by the invention are on the premise of the good hardness performance of holding, high refractive index, are overcome
The defects of LED packaging part humidity resistance and sulfidation-resistance for RGB (three coloured light) of prior art can be poor, there is provided a kind of
Resistance to cure time length and the excellent curable rubber composition of humidity resistance.
In order to solve the above technical problems, present invention also offers a kind of semiconductor devices, the semiconductor devices includes hair
The support of optical element and the fixed light-emitting component, wherein, it is coated with the light-emitting component of the present invention curable
The solidfied material of rubber composition.
A kind of curable rubber composition provided by the invention, it is under solid state, in 25 DEG C of temperature, humidity
Tensile strength under the conditions of 60%RH is 4-15Mpa, and elongation at break 12%-30%, refractive index is to equal or exceed 1.45,
The composition includes：
(A) there is branched molecular structure and in a molecule containing average at least three and the alkenyl of silicon bonding and extremely
The organopolysiloxane of a few aromatic group, the content of the aromatic group are more than 10%, and the content of alkenyl is more than
0.1mol/100g；
(B) there is branched molecular structure and in a molecule containing average at least three and the hydrogen atom of silicon bonding and extremely
The poly- Organhydridosiloxaneresins of a few aromatic group, the molar content of the aromatic group are more than 10%, described and silicon bonding
Hydrogen atom content be 0.2-0.4mol/100g；
(C) there is straight-chain molecular structure and containing the average at least one and alkenyl of silicon bonding in a molecule and extremely
A few aromatic group, and strand both ends with the hydroxy-end capped organopolysiloxane with silicon bonding, the aromatics
The molar content of group is more than 10%；
(D) have and contain or not contain the non-aromatic of organosilicon containing average at least two epoxide groups in a molecule
Race's epoxy resin；
(E) dosage is enough the hydrosilylation catalysts for promoting said composition to solidify；
(F) dosage is enough to promote the hydroxyl and epoxy radicals that the curing accelerator of curing reaction occurs.
Wherein, the component (A) is one of main component of the present composition, alkenyl and component in this component
(B) being reacted to each other with the hydrogen atom of silicon bonding in, forms cross-bond, and solidified.The molecular structure of component (A) is branched
It molecular chain structure, can be that part is branched, branched or three-dimensional molecular structure, and should contain in a molecule at least one
SiO3/2Unit.Alkenyl in component (A) can be representative with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl, optimal
Elect vinyl as.Aromatic group in the component (A) can be representative with phenyl, tolyl, xylyl and naphthyl, and benzene
The similar benzene alkyl such as ethyl, phenylpropyl, most preferably phenyl.In order to further improve the firming body of present composition acquisition
Index of refraction, the content of the aromatic group is preferably greater than 20mol%.In order to further improve the component (A) and component (B)
Reactivity, the content of the alkenyl is preferably 0.1-0.4mol/100g；The present invention is to viscous at 25 DEG C in component (A)
Degree is not particularly limited, and can be 10-1000000mPas, preferably 100-100000mPas.
The component (A) preferably comprises the R being aggregated with one another1 3SiO1/2Unit and R3SiO3/2Unit.As the present invention's
One of preferred embodiment, (A) have following average unit formulas,
(R3SiO3/2)a1(R1 3SiO1/2)a3,
Wherein R1Selected from alkenyl that is identical or differing, the substituted or unsubstituted alkyl of unit price, R3It is aromatic group, a1+
A3=1,0.1<a1<0.9,0.1<a3<0.9.R1In alkenyl can use vinyl, acrylic, cyclobutenyl, pentenyl and hexene
Base is representative, most preferably vinyl.The R1In monovalent substituted or unsubstituted alkyl, it may include following radicals：Methyl,
Ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, most preferably methyl.The R3In aromatic group can use
Phenyl, tolyl, xylyl and naphthyl are representative, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably benzene
Base.
For example, the component (A) may include following molecular formula as representative：
(C6H5SiO3/2)a1((CH2=CH) (CH3)2SiO1/2)a3；
(C6H5SiO3/2)a1((CH2=CH)2CH3SiO1/2)a3；
(C6H5SiO3/2)a1(((CH3)3SiO1/2)((CH3)2(CH2=CH) SiO1/2))a3；
The component (A) can further preferably have following average unit formulas,
(R3SiO3/2)a1(R11 3SiO1/2)a31(R11 2R12SiO1/2)a32,
Wherein R11It is identical or differs the substituted or unsubstituted alkyl of unit price, it may include following radicals：Methyl, ethyl,
Propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyls or similar haloalkyl, most preferably
For methyl.R12It is alkenyl, can is representative with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl, most preferably ethene
Base.R3It is phenyl, a1+a31+a32=1,0.1<a1<0.9,0.08<a31<0.4,0.02<a32<0.5.
For example, the component (A) may include following molecular formula as representative：
(C6H5SiO3/2)a1((CH3)3SiO1/2)a31((CH3)2(CH2=CH) SiO1/2)a32；
The component (B) is one of main component of the present composition, the hydrogen atom with silicon bonding in this component
Reacted to each other with the alkenyl in component (A) and component (C), form cross-bond, and solidified.The molecular structure of component (B)
It is branching molecule chain structure, can is that part is branched, branched or three-dimensional molecular structure, and should contains at least in a molecule
One SiO3/2Unit.Aromatic group in component (B) can be representative with phenyl, tolyl, xylyl and naphthyl, and benzene
The similar benzene alkyl such as ethyl, phenylpropyl, most preferably phenyl；The molar content of the aromatic group be more than 10%, it is described with
The hydrogen atom content of silicon bonding is 0.2-0.4mol/100g, the other components of the component (B) in the content range and the present invention
The composition formed, it has resistance to cure time length and excellent humidity resistance, more preferably 0.25-0.35mol/ after solidifying
100g。
The component (B) preferably comprises the R being aggregated with one another2 3SiO1/2Unit and R4SiO3/2Unit.As the present invention's
One of preferred embodiment, (B) have following average unit formulas,
(R4SiO3/2)b1(R2 3SiO1/2)b3,
Wherein R2Selected from monovalent substituted or unsubstituted alkyl and hydrogen atom identical or differ, R4It is aromatic group, b1
+ b3=1,0.5<b1<0.9,0.1<b3<0.5.Monovalent substituted or unsubstituted alkyl in component (B), it may include Xia Shuji
Group：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyls or similar halogen
Substituted alkyl, most preferably methyl.Aromatic group in component (B) can be representative with phenyl, tolyl, xylyl and naphthyl,
And the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.
For example, the component (B) may include following molecular formula as representative：
(C6H5SiO3/2)b1((CH3)2HSiO1/2)b3,
(C6H5SiO3/2)b1(CH3H2SiO1/2)b3,
(C6H5SiO3/2)b1((CH3)3SiO1/2)b31((CH3)2HSiO1/2)b32,
(B) can be more preferably following average unit formulas,
(R4SiO3/2)b1(R22 3SiO1/2)b31(R22 2HSiO1/2)b32,
Wherein R22It is the substituted or unsubstituted alkyl of unit price, it may include following radicals：Methyl, ethyl, propyl group, butyl, penta
Base, hexyl, heptyl or similar alkyl, most preferably chloromethyl, 3- chloropropyls or similar haloalkyl, methyl, R4It is
Phenyl, b1+b31+b32=1,0.5<b1<0.9,0<b31<0.4,0.1<b32<0.5.
For example, the component (B) may include following molecular formula as representative：
(C6H5SiO3/2)b1((CH3)3SiO1/2)b31((CH3)2HSiO1/2)b32,
The component (C) is one of important component of the present composition, is included and silicon bonding simultaneously in this component
Alkenyl and hydroxyl, its alkenyl groups is used to react to each other with the hydrogen atom in component (B) with silicon bonding, forms crosslinking,
And simultaneously hydroxyl be used for the epoxy radicals interreaction in component (D), form cross-bond, and solidified.
The molecular structure of component (C) is straight-chain molecular structure, and should contain at least one SiO in a molecule2/2It is single
Member, and strand both ends with hydroxy-end capped with silicon bonding.It is described as one of the preferred embodiment of the present invention
(C) there are following average unit formulas,
HOSiO(R5 2SiO2/2)cOSiOH,
Wherein R5Selected from alkenyl that is identical or differing, the substituted or unsubstituted alkyl of unit price and aromatic group, 5<c<
5000。
As one of the preferred embodiment of the present invention, (C) has following average unit formulas, HOSiO
(R51R52SiO2/2)c1(R51 2SiO2/2)c2(R51R53SiO2/2)c3OSiOH,
Wherein R51Selected from monovalent substituted or unsubstituted alkyl that is identical or differing, R52Selected from aromatic group, R53It is selected from
Alkenyl, 1<c1<3700,0≤c2<800,1<c3<500.
Component (C) alkenyl groups can be representative with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl, optimal
Elect vinyl as.The substituted or unsubstituted alkyl of unit price in component (C), it may include following radicals：Methyl, ethyl, propyl group, fourth
Base, amyl group, hexyl, heptyl or similar alkyl, most preferably chloromethyl, 3- chloropropyls or similar haloalkyl, methyl.
Aromatic group in the component (C) can be representative with phenyl, tolyl, xylyl and naphthyl, and phenethyl, phenylpropyl
Etc. similar benzene alkyl, most preferably phenyl.In order to further improve the index of refraction of the firming body of present composition acquisition, institute
The molar content for stating aromatic group is preferably greater than 20%.Component (C) the alkenyl groups molar content is preferably 0.01-
0.2mol/100g, hydroxyl molar content are preferably 0.0002-0.2mol/100g.
For example, the component (C) may include following molecular formula as representative：
HOSiO((CH3C6H5SiO2/2)(CH3(CH2=CH) SiO2/2))cOSiOH,
HOSiO(CH3C6H5SiO2/2)c1((CH3)2SiO2/2)c2(CH3(CH2=CH) SiO2/2)c3OSiOH,
The component (D) is one of main component of the present composition, includes epoxy radicals in this component, itself and group
The hydroxyl divided in (C) reacts to each other, and forms cross-bond, and solidified.Component (D) has in a molecule containing averagely extremely
Few two epoxide groups, and aryl is not contained, because the group that the other components of the epoxy resin without aryl and the present invention are formed
Compound, heat endurance is more preferable after solidification.On the basis of the above, the selection to the component (D) is not particularly limited, such as available
Organic-silicon-modified epoxy resin or the epoxy resin without organosilicon, such as 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy
Silane and Cyclopeutadiene type cycloaliphatic epoxy resin are as representative, most preferably cycloaliphatic epoxy resin, such as 3,4- epoxy hexamethylenes
Ylmethyl 3,4- epoxycyclohexyl formic acid esters.In the present invention, the epoxide equivalent of component (D) is not particularly limited, is preferably
100-1000, more preferably 200-800.
In the present invention, component (E) is to promote the alkenyl in component (A) and (C) and the hydrogen original of the silicon bonding in component (B)
The catalyst of hydrosilylation reactions occurs for son.In other words, component (E) is to promote the catalyst of composition solidification.Wherein, this hair
It is bright that catalyst type is not particularly limited, the custom catalystses of this area, such as platinum-type catalyst, rhodium class catalyst or
Palladium class catalyst, the present invention are preferably platinum-type catalyst.Instantiation includes：Platinum black, chloroplatinic acid, the alcoholic solution of chloroplatinic acid, platinum-
Alkenylsiloxane complex, platinum-alkene complex etc., preferably platinum-alkenylsiloxane complex, the present invention, which uses, to be had
Platinum catalyst of the tetramethyl-ethylene base disiloxane as dentate.The dosage of component (E) is not particularly limited, its used in amounts
It is enough to promote said composition curing reaction.
The composition of the present invention also contains curing accelerator (F), and component (F) is to promote the hydroxyl and component in component (C)
(D) reacted between the epoxy radicals in and promote to solidify, the species and dosage of component (F) are not particularly limited, this skill can be used
The conventional selection in art field, for example, this component can with it is following be representative：Tertiary amine compound；Aluminum oxide, zirconium oxide or similar
Organo-metallic compound；And the reaction product of boron complex compound, organic peroxide and above-claimed cpd.Thisization
The instantiation of compound is following：Titanium tetraisopropylate, four octanol titaniums, four n-butyl titaniums, diisopropoxy are double (acetopyruvic acid)
The zinc impregnations such as the aluminium compound such as the titanium compounds such as titanium, triethyl aluminum, aluminium ethoxide, aluminium isopropoxide, aluminium acetylacetonate, diethyl zinc
The zirconium compounds such as compound, four zirconium-n-butylates, most preferably aluminium isopropoxide.
In the curable rubber composition of the present invention, component (G) addition reaction inhibitor is may also include, its effect is
In order to extend the Storage period of the curable rubber composition of the present invention, addition reaction inhibitor is that one kind carries temperature-independent
Property material, heating to a certain extent when lose its inhibition rapidly, and cause composition that curing reaction occurs.Component (G)
The species weight and addition of addition reaction inhibitor are not particularly limited, and this area conventional inhibitor can be used, addition can
Optionally add, for example, component (G) is ethynylcyclohexanol in the present invention, addition is component (A) and (B) gross weight
0.05%.
In the present invention, component (A)-(G) preparation method is not particularly limited, this area usual manner can be used to prepare
Obtain, or it is commercially available.
In the present invention, the content ratio relation of the component (A) and component (B) is not particularly limited, such as component (A)
Weight ratio with component (B) can be 1:99-99:1, more preferably weight ratio is 20:80-80:20.Because of component (A) and component (B)
It is similar branched structure, then arbitrary weight is similar than the composition property of formation, as long as meeting in component (B) and silicon
The reaction enough with the alkenyl generation in component (A) and component (C) of the hydrogen atom of bonding, for example, in component (B) with
The ratio between mole of alkenyl sum in the hydrogen atom and component (A) and component (C) of silicon bonding is preferably 0.9-3.0.
In the present invention, the content ratio relation of the component (A) and component (B) is not particularly limited, such as component (C)
Weight between (D) is than being preferably 90:10-10:90.The weight sum of component (A) and component (B) and component (C) and group
The ratio for dividing the weight sum of (D) is preferably 20:80-80:20.
In the present invention, can by by necessary component (A)-(F) mix, and optionally addO-on therapy (G) and other addition
Agent such as inorganic filler, pigment, fire retardant and heat-resistant agent etc., so as to prepare curable rubber composition.In the present invention, there is provided
A kind of semiconductor devices, including the support of light-emitting component and the fixed light-emitting component, above-mentioned mixed composition is coated with
On the support of the light-emitting component, solidified.Hardening time and temperature can change, for example, first can be at 100 DEG C -150
Kept for 0.5-2 hour carry out one-step solidification at DEG C, then kept for 2-4 hour carry out secondary solidification at 150 DEG C -200 DEG C.
The tensile strength formed under the conditions of 25 DEG C of temperature, humidity 60%RH is 4-15Mpa, preferably 4-10Mpa, and elongation at break is
12%-30%, preferably 12%-20%, index of refraction be equal or exceed 1.45 firming body.By contrast, conventional silicon rubber
Glue composition, which is difficult to form tensile strength and elongation at break and index of refraction, keeps the solidfied material of above-mentioned superperformance, and has
The advantages of resistance to cure time length and excellent humidity resistance.
The measuring method of tensile strength and elongation at break：After obtained composition deaeration, the thin of 2mm thickness is prepared
Piece, 1h is kept at 100 DEG C, after 3h solidifications are then kept at 150 DEG C, piece is processed into dumbbell shaped, at 25 DEG C, 60%RH's
Under the conditions of using universal testing machine test its tensile strength and elongation at break.
Beneficial effects of the present invention：Compared with prior art, curable rubber composition of the invention and its solidification
Semiconductor devices, not only maintain good cold-resistant thermal shock resistance properties, higher index of refraction, stronger hardness, but also have
There are resistance to cure time length and excellent humidity resistance.
Brief description of the drawings
Fig. 1 is the semiconductor packages diagrammatic cross-section that one embodiment of the invention provides；
Reference in Figure of description is as follows：
1st, LED support；2nd, light-emitting component；3rd, electrode；4th, joint line；5th, the firming body of curable rubber composition.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Embodiment, the present invention is described in further detail.It should be appreciated that specific embodiment described herein is only solving
The present invention is released, is not intended to limit the present invention.
Synthetic example 1
Phenyltrimethoxysila,e 70.4g is added into flask, deionized water 15g and concentration are mass percent successively
37% concentrated hydrochloric acid 15g, dimethoxydiphenylsilane 16.6g is rapidly joined, 70 DEG C are flowed back 60 minutes, add tetramethyl diethyl
Alkenyl disiloxane 13.2g continues backflow 60 minutes, pours into separatory funnel, divides and goes sour water layer, and neutral pH is arrived in organic layer washing, falls
Enter flask, add deionized water 1g, 70 DEG C of backflow 60min, vacuum pump, which is evaporated under reduced pressure, to be concentrated, removal of solvent under reduced pressure and low boiling
Material, obtain following structural resin：
(PhSiO3/2)0.61(Ph2SiO)0.18[(CH3)2(CH2=CH) SiO1/2]0.21 (A1)
The component is viscosity is 11000mPas at 25 DEG C organosilicon polysiloxane, and phenyl content is 45%, and second
Alkenyl molar content is in 0.22 mole/100g.
Synthetic example 2
Phenyltrimethoxysila,e 77.3g is added into flask, deionized water 15g and concentration are mass percent successively
37% concentrated hydrochloric acid 15g, 70 DEG C are reacted 5 minutes, add tetramethyl divinyl disiloxane 10g and HMDO
10g continues backflow 120 minutes, pours into separatory funnel, divides and goes sour water layer, and neutral pH is arrived in organic layer washing, pours into flask, addition is gone
Ionized water 1g, 70 DEG C of backflow 60min, vacuum pump, which is evaporated under reduced pressure, to be concentrated, and removal of solvent under reduced pressure and low-boiling point material, is obtained following
Structural resin：(PhSiO3/2)0.74[(CH3)3SiO1/2]0.11[(CH3)2(CH2=CH) SiO1/2]0.15 (A2)
Viscosity is 36000mPas organosilicon polysiloxane at 25 DEG C, and phenyl content is 43%, and vinyl mole
Organic siliconresin of the content in 0.16 mole/100g.
Synthetic example 3
Phenyltrimethoxysila,e 55.3g is added into flask, deionized water 15g and concentration are mass percent successively
37% concentrated hydrochloric acid 15g, 70 DEG C are reacted 5 minutes, add tetramethyl disiloxane 16.2g and HMDO 14.4g after
Continuous backflow 60 minutes, pours into separatory funnel, divides and goes sour water layer, and neutral pH is arrived in organic layer washing, pours into flask, adds deionized water
1g, 70 DEG C of backflow 60min, vacuum pump are evaporated under reduced pressure concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structure tree
Fat：
(PhSiO3/2)0.49[(CH3)3SiO1/2]0.22[(CH3)2HSiO1/2]0.29 (B1)
The component is the organo-silicon compound that viscosity is 300mPas at 25 DEG C, and the molar content of its hydrogen is rubbed 0.35
That/100g, the molar content of phenyl is 30%.
Synthetic example 4
Phenyltrimethoxysila,e 55.3g is added into flask, deionized water 15g and concentration are mass percent successively
37% concentrated hydrochloric acid 15g, 70 DEG C are reacted 5 minutes, add tetramethyl disiloxane 18.3g and HMDO 12.1g after
Continuous backflow 60 minutes, pours into separatory funnel, divides and goes sour water layer, and neutral pH is arrived in organic layer washing, pours into flask, adds deionized water
1g, 70 DEG C of backflow 60min, vacuum pump are evaporated under reduced pressure concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structure tree
Fat：
(PhSiO3/2)0.49[(CH3)3SiO1/2]0.17[(CH3)2HSiO1/2]0.34 (B2)
The component is the organo-silicon compound that viscosity is 210mPas at 25 DEG C, and the molar content of its hydrogen is rubbed 0.40
That/100g, the molar content of phenyl is 30%.
Synthetic example 5
Phenyltrimethoxysila,e 55.3g is added into flask, deionized water 15g and concentration are mass percent successively
37% concentrated hydrochloric acid 15g, 70 DEG C are reacted 5 minutes, are added tetramethyl disiloxane 9.2g and HMDO 26.5g and are continued
Backflow 60 minutes, pours into separatory funnel, divides and goes sour water layer, and neutral pH is arrived in organic layer washing, pours into flask, adds deionized water
1g, 70 DEG C of backflow 60min, vacuum pump are evaporated under reduced pressure concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structure tree
Fat：
(PhSiO3/2)0.49[(CH3)3SiO1/2]0.34[(CH3)2HSiO1/2]0.17 (B3)
The component is the organo-silicon compound that viscosity is 520mPas at 25 DEG C, and the molar content of its hydrogen is rubbed 0.20
That/100g, the molar content of phenyl is 30%.
Synthetic example 6
Phenyltrimethoxysila,e 49.5g is added into flask, deionized water 15g and concentration are mass percent successively
37% concentrated hydrochloric acid 15g, 70 DEG C are reacted 5 minutes, are added tetramethyl disiloxane 21.2g and HMDO 8.8g and are continued
Backflow 60 minutes, pours into separatory funnel, divides and goes sour water layer, and neutral pH is arrived in organic layer washing, pours into flask, adds deionized water
1g, 70 DEG C of backflow 60min, vacuum pump are evaporated under reduced pressure concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structure tree
Fat：
(PhSiO3/2)0.48[(CH3)3SiO1/2]0.09[(CH3)2HSiO1/2]0.43 (B4)
The component is the organo-silicon compound that viscosity is 350mPas at 25 DEG C, and the molar content of its hydrogen is rubbed 0.50
That/100g, the molar content of phenyl is 30%.
Synthetic example 7
By aminomethyl phenyl cyclotetrasiloxane 60.7g, prestox ring tetrasilane 50.3g, the silica of tetramethyl tetravinyl ring four
Alkane 10.2g adds flask, is stirring evenly and then adding into TMAH 2.5g, is warming up to 120 DEG C and reacts 18 hours, Ran Houji
It is continuous to be warming up to 180 DEG C and react 2 hours, then it is warming up to 200 DEG C and vacuumizes and slough low-boiling point material, obtains following structural resin：
HOSiO(Ph CH3SiO2/2)242[(CH3)2SiO2/2]285[CH3(CH2=CH) SiO2/2]44OSiOH (C)
The component is viscosity is 42000mPas at 25 DEG C organo-silicon compound, the molar content of phenyl 40%,
And vinyl molar content is in 0.10 mole/100g.
Put into practice embodiment and comparative example 1-7
By synthetic example 1~7 prepare resin (A) (B) (C) and
(D1) cycloaliphatic epoxy resin：3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters (trade names：
CELLOXIDE 2021P, producer：Daisel chemical industry Co., Ltd)
(D2) 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane (trade name：A-186, producer：The U.S. steps figure)
(E) addition reaction catalyst：The octanol solution (platinum concentration 5wt%) of chloroplatinic acid；
(F) aluminium isopropoxide
(G) inhibitor：2- phenyl -3- butyne-2-alcohols.
(each composition is according to the mass fraction) is mixed according to the combination shown in table 1, obtains the present composition.
Semiconductor devices LED shown in Fig. 1 encapsulates in the following way, there is provided one is fixed with the support 1 of light-emitting component 2
(the auspicious 5050RGB of grace (three coloured light)), wherein the light-emitting component 2 is connected by joint line 4 (being usually gold thread) with electrode 3,
The foregoing curable rubber composition 5 of the present invention is coated on the support 1 for being fixed with light-emitting component 2, solidified.
Obtained each physical and chemical performance of composition is evaluated and tested by following methods.Result is recorded in table 1.
【Hardness】
After obtained composition deaeration, 10g is taken to keep 1h at 100 DEG C, after 3h solidifications are then kept at 150 DEG C,
25 DEG C, three point measurement hardness numbers are taken using shore D type hardness tester meters under conditions of 60%RH, and record average value.
【Refractive index】
Silicon rubber solidfied material is measured at 25 DEG C by Abbe refractometers, light source utilizes 589nm visible ray.
【Tensile strength and elongation at break】
After obtained composition deaeration, the thin slice of 2mm left and right thicknesses is prepared, 1h is kept at 100 DEG C, then 150 DEG C
After lower holding 3h solidifications, piece is processed into dumbbell shaped, at 25 DEG C, it is tested using universal testing machine under conditions of 60%RH
Tensile strength and elongation at break.
【Resistance to vulcanization】
After obtained composition deaeration, dispensing on auspicious 5050 support of grace (chipless gold thread) after 150 DEG C of 2h that dehumidify,
The 1h at 100 DEG C, then at 150 DEG C after 3h solidifications, by cradle hangs in the reagent bottle of the 250ml equipped with 2g sulphur powders, 90
Toasted at DEG C, observe support in silver coating whether blackening, record support blackening time.
【5050RGB (three coloured light) is moistureproof】
After obtained composition deaeration, point on the auspicious 5050RGB supports of grace (having chip gold thread) after 150 DEG C of 2h that dehumidify
Glue, the 1h at 100 DEG C, then lamp bead is placed in 60 DEG C, 52h under the conditions of 60%RH, placed after taking-up after 3h solidifications at 150 DEG C
15-30min, five warm area Reflow Solderings are crossed, 270 DEG C of the highest temperature, are crossed three times.There is dead lamp and split glue being judged to not passing through.
Table 1
Note：Test by being expressed as √, test not by be expressed as ×
As shown in Table 1, it is containing branched structure, simultaneously by (A) component containing branched structure by the present invention
And with (B) component that the hydrogen atom content of silicon bonding is 0.2-0.4mol/100g, with containing alkenyl and hydroxy-end capped straight chain
(C) component of structure and (D) component composition composition containing epoxy radicals, hardness is high after being heating and curing, while resistance to
Cure time is long, humidity resistance is excellent, and can apply to the composition of 5050RGB (three coloured light) support in LED encapsulation.From table
Find out in 1, the hydrogen atom content of (B) component silicon bonding is 0.2-0.4mol/100g, test tensile strength is 4-15MPa and same
When elongation at break 12-30% embodiment, with (B) component silicon hydrogen content be 0.2-0.4mol/100g outside, tensile strength
4-15MPa is not maintained at elongation at break simultaneously to compare with 12-30% comparative example, it is in resistance to cure time and moisture resistance
Energy aspect is respectively provided with prominent excellent effect.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (13)
1. a kind of curable rubber composition, it is characterised in that it is under solid state, in 25 DEG C of temperature, humidity 60%
Tensile strength under the conditions of RH is 4-15Mpa, elongation at break 12%-30%, and refractive index is described to equal or exceed 1.45
Composition includes：
(A) there is branched molecular structure and the alkenyl and at least one containing average at least three with silicon bonding in a molecule
The organopolysiloxane of individual aromatic group, the content of the aromatic group are more than 10%, and the content of alkenyl is more than 0.1mol/
100g；
(B) there is branched molecular structure and the hydrogen atom and at least one containing average at least three with silicon bonding in a molecule
The poly- Organhydridosiloxaneresins of individual aromatic group, the molar content of the aromatic group are more than 10%, the described and hydrogen of silicon bonding
Atom content is 0.2-0.4mol/100g；
(C) there is straight-chain molecular structure and in a molecule containing average at least one and the alkenyl of silicon bonding and at least one
Individual aromatic group, and strand both ends with the hydroxy-end capped organopolysiloxane with silicon bonding, the aromatic group
Molar content be more than 10%；
(D) there is the non-aromatic ring for containing or not contain organosilicon containing average at least two epoxide groups in a molecule
Oxygen tree fat；
(E) dosage is enough the hydrosilylation catalysts for promoting said composition to solidify；
(F) dosage is enough to promote the hydroxyl and epoxy radicals that the curing accelerator of curing reaction occurs.
2. a kind of curable rubber composition according to claim 1, it is characterised in that the tensile strength is 4-
10Mpa, elongation at break 12%-20%.
3. a kind of curable rubber composition according to claim 1, it is characterised in that in the component (B)
It is 0.9-3.0 with the ratio between the hydrogen atom of silicon bonding and the mole of alkenyl sum in component (A) and component (C), component (D)
Epoxide equivalent be 100-1000.
4. a kind of curable rubber composition according to claim 1, it is characterised in that component (A) and component (B)
Between weight ratio be 90:10-10:90；Weight ratio between component (C) and (D) is 90:10-10:90.
5. a kind of curable rubber composition according to claim 1, it is characterised in that component (A) and component (B)
Weight sum and component (C) and the ratio of weight sum of component (D) be 20:80-80:20.
6. a kind of curable rubber composition according to claim 1, it is characterised in that (A) has following
Average unit formula,
(R3SiO3/2)a1(R1 3SiO1/2)a3,
Wherein R1Selected from alkenyl that is identical or differing, the substituted or unsubstituted alkyl of unit price, R3It is aromatic group, a1+a3=
1,0.1<a1<0.9,0.1<a3<0.9.
7. a kind of curable rubber composition according to claim 1, it is characterised in that (A) has following
Average unit formula,
(R3SiO3/2)a1(R11 3SiO1/2)a31(R11 2R12SiO1/2)a32,
Wherein R11It is the substituted or unsubstituted alkyl of unit price, R12It is alkenyl, R3It is phenyl, a1+a31+a32=1,0.1<a1<
0.9,0.08<a31<0.4,0.02<a32<0.5.
8. a kind of curable rubber composition according to claim 1, it is characterised in that (B) has following
Average unit formula,
(R4SiO3/2)b1(R2 3SiO1/2)b3,
Wherein R2Selected from monovalent substituted or unsubstituted alkyl and hydrogen atom identical or differ, R4It is aromatic group, b1+b3
=1,0.5<b1<0.9,0.1<b3<0.5.
9. a kind of curable rubber composition according to claim 1, it is characterised in that (B) has following
Average unit formula,
(R4SiO3/2)b1(R22 3SiO1/2)b31(R22 2HSiO1/2)b32,
Wherein R22It is the substituted or unsubstituted alkyl of unit price, R4It is phenyl, b1+b31+b32=1,0.5<b1<0.9,0<b31<
0.4,0.1<b32<0.5.
10. a kind of curable rubber composition according to claim 1, it is characterised in that (C) has following
Average unit formula,
HOSiO(R5 2SiO2/2)cOSiOH,
Wherein R5Selected from alkenyl that is identical or differing, the substituted or unsubstituted alkyl of unit price and aromatic group, 5<c<5000.
11. a kind of curable rubber composition according to claim 1, it is characterised in that (C) has following
Average unit formula,
HOSiO(R51R52SiO2/2)c1[R51 2SiO2/2]c2[R51R53SiO2/2]c3OSiOH,
Wherein R51Selected from monovalent substituted or unsubstituted alkyl that is identical or differing, R52Selected from aromatic group, R53Selected from alkene
Base, 1<c1<3700,0≤c2<800,1<c3<500.
A kind of 12. curable rubber composition according to claim 1, it is characterised in that chain in the component (C)
Alkenyl molar content is 0.01-0.2mol/100g, and hydroxyl molar content is 0.0002-0.2mol/100g.
13. a kind of semiconductor devices, including the support of light-emitting component and the fixed light-emitting component, it is characterised in that the hair
The solidfied material for the curable rubber composition being coated with optical element described in claim any one of 1-12.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410310156.XA CN105219097B (en) | 2014-06-30 | 2014-06-30 | A kind of curable rubber composition and semiconductor devices |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410310156.XA CN105219097B (en) | 2014-06-30 | 2014-06-30 | A kind of curable rubber composition and semiconductor devices |
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| Publication Number | Publication Date |
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| CN105219097A CN105219097A (en) | 2016-01-06 |
| CN105219097B true CN105219097B (en) | 2017-12-08 |
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| CN101166792A (en) * | 2005-04-27 | 2008-04-23 | 陶氏康宁东丽株式会社 | Curable silicone composition and electronic components |
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| CN101166792A (en) * | 2005-04-27 | 2008-04-23 | 陶氏康宁东丽株式会社 | Curable silicone composition and electronic components |
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