CN105985649B - Curable block type organopolysiloxane composition and semiconductor devices - Google Patents
Curable block type organopolysiloxane composition and semiconductor devices Download PDFInfo
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- CN105985649B CN105985649B CN201510050973.0A CN201510050973A CN105985649B CN 105985649 B CN105985649 B CN 105985649B CN 201510050973 A CN201510050973 A CN 201510050973A CN 105985649 B CN105985649 B CN 105985649B
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 49
- 239000004065 semiconductor Substances 0.000 title claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 50
- 229910020388 SiO1/2 Inorganic materials 0.000 claims abstract description 41
- 229910020447 SiO2/2 Inorganic materials 0.000 claims abstract description 32
- 229910020487 SiO3/2 Inorganic materials 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 56
- 125000003342 alkenyl group Chemical group 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 20
- -1 Siloxanes Chemical class 0.000 claims description 16
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 150000004678 hydrides Chemical class 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 125000003944 tolyl group Chemical group 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 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 9
- 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 9
- 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 9
- 125000005023 xylyl group Chemical group 0.000 description 9
- 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 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 125000004344 phenylpropyl group Chemical group 0.000 description 8
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000011541 reaction mixture 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 5
- 125000006038 hexenyl group Chemical group 0.000 description 5
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- 241000218202 Coptis Species 0.000 description 2
- 235000002991 Coptis groenlandica Nutrition 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- 229910020485 SiO4/2 Inorganic materials 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
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 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 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 201000009310 astigmatism Diseases 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002242 deionisation method Methods 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
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 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
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
Abstract
For the defect for overcoming the cold-resistant thermal shock resistance properties of the prior art poor, the present invention provides a kind of curable block type organopolysiloxane compositions and semiconductor devices, it is in the solid state, at 25 DEG C of temperature, tensile strength under the conditions of humidity 60%RH is 1-8Mpa, elongation at break is 50%-200%, and refractive index is to equal or exceed 1.45, and the composition includes: that (A1) includes R1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nThe block branches structure organopolysiloxane copolymers of unit；(B1) the poly- Organhydridosiloxaneresins of linear chain structure, wherein per molecule has an average of at least one and the hydrogen atom of silicon bonding and at least one aromatic group；(C) dosage is enough to promote the cured hydrosilylation catalysts of the composition.Compared with prior art, the present invention not only maintains good sulfidation-resistance energy, higher refractive index, stronger hardness, but also has excellent cold-resistant thermal shock resistance properties.
Description
Technical field
The present invention relates to a kind of silicon composition, in particular to a kind of curable block type organopolysiloxane composition
Object, and solidify the semiconductor devices constituted using the composition.
Background technique
The basic structural unit of organosilicon polymer is made of silicon oxygen chain link, and it is various with other that side chain then passes through silicon atom
Organic group is connected.Compared with other high molecular materials, organosilicon polymer has following outstanding properties: 1. temperature-resistance characteristics have
Machine silicon product be using silicon oxygen (Si-O) key as backbone structure, so the thermal stability 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 better thermal stability of other high molecular materials and radiation resistance and weather resistance have under natural environment and longer use the longevity
Life.3. electrical insulation properties, organosilicon product all has a good electrical insulation capability, 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 based on above-mentioned good comprehensive performance, as one kind of organosilicon product, organopolysiloxane
It is widely used on LED and photovoltaic industry.
Organopolysiloxane is usually containing the polymer for being independently selected from following siloxy units: (R3SiO1/2)、
(R2SiO2/2)、(RSiO3/2) or (SiO4/2) siloxy units, wherein R is organic group.These siloxy units
Usually referred to separately as M, D, T and Q unit.These siloxy units can combine in many ways with formed cyclic annular, straight chain or
The structure of branch.Depending on the number and type of the siloxy units in organopolysiloxane, resulting polymer architecture
Chemical and physical features be varied." linear chain structure " organopolysiloxane usually mainly (i.e. (R containing D2SiO2/2)) monosilane
Oxygroup unit leads to the polydiorganosiloxanepolyurea as the fluid with different viscosities, this depends on polydiorganosiloxanepolyurea
In D unit number indicated by " degree of polymerization " (or DP).When most of siloxy units are selected from branched structure T (i.e.
(RSiO3/2)) or three-dimensional net structure Q (i.e. (SiO4/2)) siloxy units when, obtain " resin " organopolysiloxane.Have
T or Q siloxy units content in machine polysiloxanes increases, and typically results in polymer with increased hardness and/or glass
Glass shape property.
In general, LED light packaging part includes light-emitting component and LED support, the light-emitting component is fixed on the LED branch
On frame, the LED support is usually made of metallic matrix, and silver coating is equipped on the metallic matrix, and the silver coating is used
In optically focused or astigmatism to light-emitting component light.Organopolysiloxane composition is coated on the light-emitting component and LED support
Silver coating on, and solidified, that is, be basically completed the encapsulation to LED light.However, in the prior art, the cold and hot temperature difference compared with
In big use environment, the solidfied material of the organosiloxane composition is easy cracking, will lead to dead lamp phenomenon when serious, influences
The service life of LED light, in addition, LED light packaging part is in the long-term use, the sulphur in surrounding air can corrode gradually
Silver coating leads to the silver layer sulphide staining, and then causes light decay serious.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the prior art under the premise of keeping good sulfidation-resistance energy
The poor defect of cold-resistant thermal shock, provide that a kind of resistance to vulcanization time is long and the excellent curable block type of cold-resistant thermal impact
Organopolysiloxane composition.
Curable block type organopolysiloxane composition provided by the invention, in the solid state, in temperature 25
DEG C, the tensile strength under the conditions of humidity 60%RH is 1-8Mpa, and elongation at break 50%-200%, refractive index is to be equal to or surpass
1.45 are crossed, the composition includes:
It (A1) include R1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nThe block branches structure of unit is organic
Polysiloxanes, and m is more than or equal to 2, n more than or equal to 2 in each molecule；
(A2) it is independently selected from R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The random branched structure of unit is organic poly-
Siloxanes；
The weight content ratio of the component (A1) and component (A2) is 100:0-25:100；
(B1) the poly- Organhydridosiloxaneresins of linear chain structure, wherein per molecule has an average of at least one and silicon bonding
Hydrogen atom and at least one aromatic group；
(B2) it is independently selected from R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2The random branched structure of unit gathers organic
Hydride siloxane；
The weight content ratio of the component (B1) and component (B2) is 100:0-10:100；
(C) dosage is enough to promote the cured hydrosilylation catalysts of the composition；
Wherein, the R1Selected from identical or different alkenyl, aromatic-free and the list for being free of aliphatic unsaturated bond
The substituted or unsubstituted alkyl of valence, the R2Selected from identical or different alkenyl, aromatic group, aromatic-free and be free of rouge
The substituted or unsubstituted alkyl of unit price of fat race unsaturated bond, the R3It is aromatic group；The R4Selected from identical or different
Aromatic-free and the substituted or unsubstituted alkyl of unit price and hydrogen atom for being free of aliphatic unsaturated bond, the R5Selected from identical or
Different hydrogen atom, aromatic group, aromatic-free and the substituted or unsubstituted hydrocarbon of unit price without aliphatic unsaturated bond
Base, the R6It is aromatic group.
In order to solve the above technical problems, the semiconductor devices includes hair the present invention also provides a kind of semiconductor devices
The bracket of optical element and the fixed light-emitting component, wherein be coated on the light-emitting component of the present invention curable
The solidfied material of block type organopolysiloxane composition.
Beneficial effects of the present invention: compared with prior art, curable block type organopolysiloxane group of the invention
Object and its cured semiconductor devices are closed, good sulfidation-resistance energy, higher refractive index, stronger hardness are not only maintained,
But also there is excellent cold-resistant thermal shock resistance properties.
Detailed description of the invention
Fig. 1 is the semiconductor packages diagrammatic cross-section that one embodiment of the invention provides；
Appended drawing reference in Figure of description is as follows:
1, LED support；2, light-emitting component；3, electrode；4, bonding wire；5, curable organopolysiloxane composition is consolidated
Change body.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below to this
Invention is described in further detail.
In being described below, Vi is referred to as vinyl, and Me is referred to as methyl, and Ph is referred to as phenyl.
In curable block type organopolysiloxane composition provided by the invention:
Component (A1) be include R1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nThe block branches knot of unit
Structure organopolysiloxane.The component (A1) is the main component of the present composition, the alkenyl in component (A1) and (A2)
It reacts to each other jointly with the hydrogen atom in component (B1) and (B2) with silicon bonding, forms cross-bond, and solidified.The present invention
Component (A1) organopolysiloxane be " block " copolymer, it is opposite with " random " copolymer of (A2) and (B2).The block
Copolymer is presented as that in (A1) composition include [R2 2SiO2/2]mBlock unit and [R3SiO3/2]nBlock unit, it is described
[R2 2SiO2/2]mBlock unit is the R for having m repeated arrangement in per molecule2 2SiO2/2The unit, [R3SiO3/2]nBlock unit
To there is the R of n repeated arrangement in per molecule3SiO3/2Unit, wherein n is more than or equal to 2 in each molecule, and m is more than or equal to 2；
More preferably n is more than or equal to 3, and m is more than or equal to 5, and the structure of block within this range makes in molecule while having certain big
Small soft or hard different region guarantees that it keeps preferable ductility while having compared with high crosslink density, to make product
It is provided simultaneously with lower gas permeability and preferable flexibility.
In component (A1), the R1Selected from identical or different alkenyl, aromatic-free and be free of aliphatic unsaturation
The substituted or unsubstituted alkyl of unit price of key, R2Selected from identical or different alkenyl, aromatic group, aromatic-free and be free of
The substituted or unsubstituted alkyl of unit price of aliphatic unsaturated bond, R3It is aromatic group.Alkenyl in the component (A1) can
It is representative with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl, most preferably vinyl.In the component (A1) not
The substituted or unsubstituted alkyl of unit price containing aromatic hydrocarbons and without aliphatic unsaturated bond, it may include following radicals: methyl, ethyl,
Propyl, butyl, amyl, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyl or similar halogenated alkyl, most preferably
For methyl.Aromatic group in the component (A1) can be representative and benzene second with phenyl, tolyl, xylyl and naphthalene
The similar benzene alkyl such as base, phenylpropyl, most preferably phenyl.In order to further increase the anti-of the component (A1) and component (B1)
Ying Xing, the content of the alkenyl are preferably 0.05-0.30mol/100g, and the content of alkenyl within this range makes composition
Crosslink density cause because not too high or too low system be easy cracking or gas permeability it is too high.The present invention is to component (A1)
Viscosity at 25 DEG C is not particularly limited, preferably 500-100000mPas, and viscosity composition within this range has
Application property is preferable simultaneously for preferable ductility.
As one of the preferred embodiment of the present invention, (A1) has following average unit formulas,
([R3SiO3/2]n)a([R2 2SiO2/2]m)b(R1 3SiO1/2)c,
Wherein R1Selected from identical or different alkenyl, the substituted or unsubstituted alkyl of unit price, R2Selected from identical or not phase
Same alkenyl, the substituted or unsubstituted alkyl of unit price and aromatic group, R3It is aromatic group, 0.3 < a < 0.8,0.05 <b <
0.6,0.05 < c < 0.3, and a+b+c=1.Wherein R1And R2In alkenyl can use vinyl, acrylic, cyclobutenyl, pentenyl
It is representative, most preferably vinyl with hexenyl.The R1And R2In the substituted or unsubstituted alkyl of unit price, it may include it is following
Group: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or similar alkyl, most preferably methyl.The R3In virtue
Race's group can be the similar benzene alkyl such as representative and phenethyl, phenylpropyl with phenyl, tolyl, xylyl and naphthalene, most
Preferably phenyl.
For example, the component (A1) may include following molecular formula as representative:
([PhSiO3/2]n)a([ViMeSiO2/2]m)b(Me3SiO1/2)c,
([PhSiO3/2]n)a([Me2SiO2/2]m)b(ViMe2SiO1/2)c,
([PhSiO3/2]n)a([MePhSiO2/2]m)b(ViMe2SiO1/2)c。
Also selectable containing (A2) component in the present composition, (A2) is to be independently selected from R1 3SiO1/2Unit,
R2 2SiO2/2Unit and R3SiO3/2The random branched structure organopolysiloxane of unit.Alkene in the component (A2) and (A1)
Base reacts to each other with the hydrogen atom in component (B1) and (B2) with silicon bonding jointly, forms cross-bond.Component of the invention
It (A2) is " random " copolymer, it is opposite with " block " copolymer of (A1) organopolysiloxane.(A2) can be selected from random
MT and MDT of branched structure and combinations thereof, the MT show as including R1 3SiO1/2Unit and R3SiO3/2The random branch link of unit
Structure；The MDT shows as including R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The random branched structure of unit.
In component (A2), the R1Selected from identical or different alkenyl, aromatic-free and be free of aliphatic unsaturation
The substituted or unsubstituted alkyl of unit price of key, the R2Selected from identical or different alkenyl, aromatic group, aromatic-free and
The substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, the R3It is aromatic group.In the component (A2)
Alkenyl can be representative with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl, most preferably vinyl.The component
(A2) aromatic-free in and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, it may include following radicals:
Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyl or similar halogenated
Alkyl, most preferably methyl.Aromatic group in the component (A2) can be generation with phenyl, tolyl, xylyl and naphthalene
The similar benzene alkyl such as table and phenethyl, phenylpropyl, most preferably phenyl.The present invention is viscous at 25 DEG C to component (A2)
Degree is not particularly limited, preferably greater than 20000mPas, and viscosity composition within this range has preferable intensity and prolongs
Malleability energy.
As one of the preferred embodiment of the present invention, (A2) has following average unit formulas,
(R3SiO3/2)a1(R1 3SiO1/2)c1,
Wherein R1Selected from identical or different alkenyl, the substituted or unsubstituted alkyl of unit price, R3It is aromatic group, 0.7
< a1 < 0.95,0.05 < c1 < 0.3, and a1+c1=1.Wherein R1In alkenyl can use vinyl, acrylic, cyclobutenyl, amylene
Base and hexenyl are representative, most preferably vinyl.The R1In the substituted or unsubstituted alkyl of unit price, it may include Xia Shuji
Group: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or similar alkyl, most preferably methyl.The R3In aromatics
Group can be the similar benzene alkyl such as representative and phenethyl, phenylpropyl with phenyl, tolyl, xylyl and naphthalene, optimal
It is selected as phenyl.
For example, the component (A2) may include following molecular formula as representative:
(PhSiO3/2)a1(Vi2MeSiO1/2)c1,
(PhSiO3/2)a1(Me2ViSiO1/2)c1。
As one of the preferred embodiment of the present invention, (A2) has following average unit formulas,
(R3SiO3/2)a2(R2 2SiO2/2)b2(R1 3SiO1/2)c2,
Wherein R1Selected from identical or different alkenyl, the substituted or unsubstituted alkyl of unit price, R2Selected from identical or not
Identical alkenyl, the substituted or unsubstituted alkyl of unit price and aromatic group, R3It is aromatic group, 0.2 < a2 < 0.8,0.2 <b2 <
0.8,0.05 < c2 < 0.3, and a2+b2+c2=1.Wherein R1And R2In alkenyl can use vinyl, acrylic, cyclobutenyl, penta
Alkenyl and hexenyl are representative, most preferably vinyl.The R1And R2In the substituted or unsubstituted alkyl of unit price, it may include
Following radicals: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or similar alkyl, most preferably methyl.The R3In
Aromatic group can be the similar benzene alkane such as representative and phenethyl, phenylpropyl with phenyl, tolyl, xylyl and naphthalene
Base, most preferably phenyl.
For example, the component (A2) may include following molecular formula as representative:
(PhSiO3/2)a2(ViMeSiO2/2)b2(Me3SiO1/2)c2,
(PhSiO3/2)a2(MePhSiO2/2)b2(ViMe2SiO1/2)c2,
(PhSiO3/2)a2(Me2SiO2/2)b2(ViMe2SiO1/2)c2。
The weight content ratio of the component (A1) and component (A2) is 100:0-25:100, more preferably 100:1-25:
100, the composition within the scope of this content ratio, because containing (A1) component of random branched structure, (A1) component in composition
Make in molecule while having a certain size soft or hard different region herein, guarantees its holding while having compared with high crosslink density
Preferable ductility, so that product be made to be provided simultaneously with lower gas permeability and preferable flexibility, the component (A1) and group
The weight content ratio of (A2) is divided to be more preferably 100:5-30:100.
Component (B1) is the poly- Organhydridosiloxaneresins of linear chain structure, wherein per molecule has an average of at least one and silicon
The hydrogen atom of bonding and at least one aromatic group.The component (B1) is had an effect as crosslinking agent, in the present invention, straight chain
Addition reaction (hydrosilanes occur for the alkenyl in SiH and branched structure component (A1) and (A2) in structural constituent (B1)
Change), the reticular structure of crosslinking is consequently formed.Further, the component (B1) be include R4 3SiO1/2Unit and R5 2SiO2/2
The poly- Organhydridosiloxaneresins of the linear chain structure of unit, R4It is selected from identical or different aromatic-free and unsaturated without aliphatic
The substituted or unsubstituted alkyl of unit price and hydrogen atom of key, R5Not selected from identical or different aromatic-free and without aliphatic
The substituted or unsubstituted alkyl of unit price, hydrogen atom and the aromatic group of saturated bond.Aromatic-free in component (B1) and be free of rouge
The substituted or unsubstituted alkyl of unit price of fat race unsaturated bond, it may include following radicals: methyl, ethyl, propyl, butyl, amyl,
Hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyl or similar halogenated alkyl, most preferably methyl.Component (B1)
In aromatic group can be the similar benzene such as representative and phenethyl, phenylpropyl with phenyl, tolyl, xylyl and naphthalene
Alkyl, most preferably phenyl.Viscosity of the component (B1) at 25 DEG C is not particularly limited in the present invention, preferably 0.1-
1000mPas, viscosity composition within this range has preferable ductility, and application property is preferable simultaneously.
As one of the preferred embodiment of the present invention, (B1) has following average unit formulas,
(R6R5SiO2/2)b5(R4 3SiO1/2)c5,
Wherein R4It is independently selected from the substituted or unsubstituted alkyl of identical or different unit price and hydrogen atom, R5It is independently selected from
The substituted or unsubstituted alkyl of identical or different unit price, aromatic group and hydrogen atom, R6For aromatic group, 0.33 <b5 <
0.8,0.2 < c5 < 0.67, and b5+c5=1.The R4And R5In the substituted or unsubstituted alkyl of unit price, it may include Xia Shuji
Group: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyl or similar halogen
Substituted alkyl, most preferably methyl.The R5And R6In aromatic group can be generation with phenyl, tolyl, xylyl and naphthalene
The similar benzene alkyl such as table and phenethyl, phenylpropyl, most preferably phenyl.
For example, the component (B1) may include following molecular formula as representative:
(PhMeSiO2/2)b5(Me2HSiO1/2)c5,
(PhHSiO2/2)b5(Me3SiO1/2)c5。
Also selectable containing (B2) component in the present composition, (B2) is to be independently selected from R4 3SiO1/2Unit,
R5 2SiO2/2Unit and R6SiO3/2The poly- Organhydridosiloxaneresins of random branched structure of unit.The component (B2) is used as crosslinking agent
And have an effect, the alkenyl in SiH and branched structure component (A1) and (A2) in the present invention, in branched structure component (B2)
Occur addition reaction (hydrosilylation), the reticular structure of crosslinking is consequently formed.Component (B2) of the invention is " random " copolymerization
Object is opposite with " block " copolymer of (A1) organopolysiloxane.(B2) can be selected from the MT and MDT of random branched structure
And combinations thereof, the MT shows as including R4 3SiO1/2Unit and R6SiO3/2The random branched structure of unit；The MDT is shown as
Including R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2The random branched structure of unit.
In component (B2), the R4Selected from identical or different aromatic-free and without the unit price of aliphatic unsaturated bond
Substituted or unsubstituted alkyl and hydrogen atom, the R5Selected from identical or different hydrogen atom, aromatic group, aromatic-free and
The substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, the R6It is aromatic group.Being free of in component (B2)
Aromatic hydrocarbons and the substituted or unsubstituted alkyl of unit price for being free of aliphatic unsaturated bond, it may include following radicals: methyl, ethyl, third
Base, butyl, amyl, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyl or similar halogenated alkyl, most preferably
Methyl.Aromatic group in component (B) can be representative and phenethyl, phenylpropyl alcohol with phenyl, tolyl, xylyl and naphthalene
The similar benzene alkyl such as base, most preferably phenyl.Viscosity of the component (B2) at 25 DEG C is not particularly limited in the present invention, preferably
For 0.1-10000mPas, viscosity composition within this range has preferable ductility, and application property is preferable simultaneously.
As one of the preferred embodiment of the present invention, (B2) has following average unit formulas,
(R6SiO3/2)a4(R5 2SiO2/2)b4(R4 3SiO1/2)c4,
Wherein R4Selected from the substituted or unsubstituted alkyl of identical or different unit price and hydrogen atom, R5Selected from identical or not
The substituted or unsubstituted alkyl of identical unit price, aromatic group and hydrogen atom, R6It is aromatic group, 0.2 < a4 < 0.6,0.2 <b4 <
0.6,0.2 < c4 < 0.6, and a4+b4+c4=1.The R4And R5In the substituted or unsubstituted alkyl of unit price, it may include Xia Shuji
Group: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or similar alkyl, chloromethyl, 3- chloropropyl or similar halogen
Substituted alkyl, most preferably methyl.The R5And R6In aromatic group can be generation with phenyl, tolyl, xylyl and naphthalene
The similar benzene alkyl such as table and phenethyl, phenylpropyl, most preferably phenyl.
For example, the component (B2) may include following molecular formula as representative:
(PhSiO3/2)a4(Me2SiO2/2)b4(Me2HSiO1/2)c4,
(PhSiO3/2)a4(PhMeSiO2/2)b4(Me2HSiO1/2)c4,
(PhSiO3/2)a4(MeHSiO2/2)b4(Me3SiO1/2)c4。
The weight content ratio of the component (B1) and component (B2) is 100:0-10:100, more preferably 100:1-10:
100, the composition within the scope of this content ratio, because containing (B2) component of random branched structure, (B2) component in composition
The crosslink density after composition solidifies is improved herein, keeps composition gas permeability lower, the component (B1) and component (B2)
Weight content ratio is more preferably 100:5-20:100.
In order to further increase present composition acquisition solidified body refractive index, in (A1) and (A2) component
The content of aromatic group is preferably greater than 10mol%, and the sum of the content of aromatic group in component (B1) and (B2) is greater than
10mol%.Further, [the R of described (A1)2 2SiO2/2]mThe content of aromatic group in unit is preferably greater than 10mol%,
And [the R of component (A1)3SiO3/2]nThe content of aromatic group in unit is preferably greater than 10mol%.
In the present invention, the component (A1)+(A2) and component (B1)+(B2) content ratio relationship are not limited especially
System, the composition that arbitrary weight ratio is formed can be with, if meet in component (B1)+(B2) with the hydrogen atom of silicon bonding with
Enough reactions occur for the alkenyl in component (A1)+(A2), such as former with the hydrogen of silicon bonding in component (B1)+(B2)
Son is preferably 0.9-2.0 with the ratio between the mole of alkenyl in component (A1)+(A2).
Relative to the total composition of 100 parts by weight, the dosage of component (A1) and (A2) are preferably 50-95 parts by weight, group
The dosage for dividing (B1) and (B2) is preferably 5-50 parts by weight.
Linear chain structure in the present invention, because of the organopolysiloxane that component (A1) is block branches structure, with component (B1)
Poly- Organhydridosiloxaneresins make composition with certain hard section and with more soft section of long-chain, overall structure flexibility
It is good, in conjunction with the random branched structure crosslink density with higher of (A2) and (B2) and higher intensity, produce similar thermoplastic
Property elastomer have elastomeric effect, the cooling thermal impact of temperature checker make material have preferably elasticity, with substrate
Between better adaptability, will not be ruptured because internal stress is excessive, at the same also have lower gas permeability, prevent gas from entering
Device inside and cause to deteriorate.
In the present invention, component (C) is the Si in the alkenyl and component (B1) and (B2) promoted in component (A1) and (A2)
The catalyst of hydrosilylation reactions occurs for the H atom of bonding.In other words, component (C) is to promote the cured catalyst of composition.
Wherein, catalyst type is not particularly limited in the present invention, the custom catalysts of this field, such as platinum-type catalyst, rhodium
Class catalyst or palladium class catalyst, the present invention are preferably platinum-type catalyst.Specific example includes: platinum black, chloroplatinic acid, chloroplatinic acid
Alcoholic solution, platinum-alkenylsiloxane complex, platinum-alkene complex etc., preferably platinum-alkenylsiloxane complex, this hair
Bright use has platinum catalyst of the tetramethyl-ethylene base disiloxane as dentate.The dosage of component (C) is not limited especially
System, used in amounts are enough to promote the composition curing reaction.
In curable organopolysiloxane composition of the invention, it may also include component (D) addition reaction inhibitor,
Effect is the Storage period in order to extend curable organopolysiloxane composition of the invention, and addition reaction inhibitor is a kind of
Substance with temperature dependency loses rapidly its inhibition when heating to a certain extent, and composition is cured instead
It answers.The type weight and additive amount of the addition reaction inhibitor of component (D) are not particularly limited, and this field can be used routinely to inhibit
Agent, additive amount can be added optionally, for example, component (D) is ethynylcyclohexanol in the present invention, additive amount is component (A) and (B)
The 0.05% of total weight.
In the present invention, the preparation method of component (A1), (A2), (B1), (B2), (C) and (D) is not particularly limited, it can
It is prepared using this field usual manner or commercially available.
In the present invention, can by by component (A1), (B1) and (C) mix, and optionally addO-on therapy (A2), (B2) and
(D) and other additives such as inorganic filler, pigment, fire retardant and heat-resistant agent etc., to prepare curable organic poly- silicon oxygen
Alkane composition.In the present invention, a kind of semiconductor devices is provided, the bracket including light-emitting component and the fixed light-emitting component will
Above-mentioned mixed composition is coated on the bracket of the light-emitting component, is solidified.Curing time and temperature can change,
For example, 0.5-2 hour can be kept to carry out one-step solidification at 100 DEG C -150 DEG C first, then kept at 150 DEG C -200 DEG C
2-4 hour carries out secondary curing.25 DEG C of temperature are formed in, the tensile strength under the conditions of humidity 60%RH is 1-8Mpa, fracture
Elongation is 50%-200%, and refractive index is the solidified body for equaling or exceeding 1.45.In contrast, conventional organopolysiloxane
Composition is difficult to form the solidfied material that tensile strength and elongation at break and refractive index keep above-mentioned superperformance, and has resistance to
The advantages of vulcanization time length and excellent cold-resistant thermal shock resistance properties.
With reference to embodiments, the present invention is further described in detail.It should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
Synthetic example 1
5L four round flask is loaded into phenyl silsesquioxane hydrolysate (DOW CORNING (Dow Corning) 217)
880.0g with toluene 1000.0g.The reaction mixture is heated at reflux 30 minutes.After reaction mixture is cooled to 108 DEG C,
Add the solution for the methyl phenyl silicone oil that end is diacetoxy.The end is the methyl phenyl silicone oil first of diacetoxy
(self-control, methyl phenyl ring siloxane is under alkali effect for benzene 500.0g, the methyl phenyl silicone oil that 3000 end of molecular weight is silanol
Open loop is made) 410g and methyl triacetoxysilane 24g, 2h is stirred at room temperature and is made.At 108 DEG C by end be diacetyl
The methyl phenyl silicone oil of oxygroup is quickly added to phenyl silsesquioxane hydrolyzate solution.The reaction mixture is heated at reflux 2
Hour, tetramethyl divinyl tetramethyl disiloxane 232g, concentrated hydrochloric acid 20g, deionized water 20g are then added, continues to add
Heat reflux 5 hours.Separatory funnel is poured into, divides and goes sour water layer, organic layer washing to neutral pH, vacuum pump vacuum distillation concentration,
Solvent and low-boiling point material is removed under reduced pressure, obtains following structural resin:
([PhSiO3/2]n)0.58([PhMeSiO2/2]12)0.28[(CH3)2(CH2=CH) SiO1/2]0.14 (A1‐1)
Wherein [PhSiO3/2]nFor 217 phenyl silsesquioxane units of DOW CORNING.
The group is divided into the organic block polysiloxanes that the viscosity at 25 DEG C is 5000mPas, and vinyl molar content
In 0.15 mole/100g.
Synthetic example 2
5L four round flask is loaded into phenyl silsesquioxane hydrolysate (DOW CORNING (Dow Corning) 217)
760.0g with toluene 1000.0g.The reaction mixture is heated at reflux 30 minutes.After reaction mixture is cooled to 108 DEG C,
Add the solution for the methyl phenyl silicone oil that end is diacetoxy.The end is the methyl phenyl silicone oil first of diacetoxy
(self-control, methyl phenyl ring siloxane is under alkali effect for benzene 500.0g, the methyl phenyl silicone oil that 650 end of molecular weight is silanol
Open loop is made) 550g and methyl triacetoxysilane 21g, 2h is stirred at room temperature and is made.At 108 DEG C by end be diacetyl
The methyl phenyl silicone oil of oxygroup is quickly added to phenyl silsesquioxane hydrolyzate solution.The reaction mixture is heated at reflux 2
Hour, tetramethyl divinyl tetramethyl disiloxane 172g, concentrated hydrochloric acid 20g, deionized water 20g are then added, continues to add
Heat reflux 5 hours.Separatory funnel is poured into, divides and goes sour water layer, organic layer washing to neutral pH, vacuum pump vacuum distillation concentration,
Solvent and low-boiling point material is removed under reduced pressure, obtains following structural resin:
([PhSiO3/2]n)0.46([PhMeSiO2/2]5)0.37[(CH3)2(CH2=CH) SiO1/2]0.13 (A1‐2)
The group is divided into the organic block polysiloxanes that the viscosity at 25 DEG C is 3000mPas, and vinyl mole contains
Amount is in 0.14 mole/100g.
Synthetic example 3
Flask is added in phenyltrimethoxysila,e 83g, sequentially adds deionized water 15g, toluene 100g and hydroxide
Potassium 0.5g, 25 DEG C are reacted 30 minutes, be then added tetramethyl divinyl disiloxane 10g and hexamethyldisiloxane 10g after
Continuous reflux 6 hours, pours into separatory funnel, divides lixiviating water layer, and flask, vacuum pump decompression are poured into organic layer washing to neutral pH
Solvent and low-boiling point material is removed under reduced pressure in distillation and concentration, obtains following structural resin:
(PhSiO3/2)0.76[(CH3)3SiO1/2]0.10[(CH3)2(CH2=CH) SiO1/2]0.14 (A2‐1)
It is solid that the group, which is divided into the viscosity at 25 DEG C, and vinyl molar content is in 0.15 mole/100g.
Synthetic example 4
Phenyltrimethoxysila,e 62g, aminomethyl phenyl dimethoxysilane 28g are added flask, sequentially add deionization
Water 15g, toluene 100g and potassium hydroxide 0.5g, 25 DEG C are reacted 30 minutes, and tetramethyl divinyl disiloxane is then added
11g continues reflux 6 hours, pours into separatory funnel, divides lixiviating water layer, and organic layer is washed to neutral pH, pours into flask, vacuum water
Pump vacuum distillation concentration, is removed under reduced pressure solvent and low-boiling point material, obtains following structural resin:
(PhSiO3/2)0.61[PhCH3SiO]0.24[(CH3)2(CH2=CH) SiO1/2]0.15 (A2‐2)
It is solid that the group, which is divided into the viscosity at 25 DEG C, and vinyl molar content is in 0.15 mole/100g.
Synthetic example 5
Flask is added in dimethoxydiphenylsilane 65g, successively deionized water 15g and concentration are mass percent
37% concentrated hydrochloric acid 15g, 70 DEG C of reactions, 5 minutes addition tetramethyl disiloxane 26.3g continue reflux 60 minutes, pour into liquid separation leakage
Bucket divides and goes sour water layer, and organic layer washing to neutral pH pours into flask, deionized water 1g, 70 DEG C of reflux 60min, vacuum water is added
Pump vacuum distillation concentration, is removed under reduced pressure solvent and low-boiling point material, obtains following structural resin:
(Ph2SiO2/2)0.53[(CH3)2HSiO1/2]0.47 (B1)
The group is divided into the organo-silicon compound that the viscosity at 25 DEG C is 50mPas, and the molar content of hydrogen is rubbed 0.52
That/100g.
Synthetic example 6
Flask is added in phenyltrimethoxysila,e 49.5g, successively deionized water 15g and concentration are mass percent
37% concentrated hydrochloric acid 15g, 70 DEG C of 5 minutes addition tetramethyl disiloxane 16.4g of reaction and hexamethyldisiloxane 14.1g continues
Reflux 60 minutes, pours into separatory funnel, divides and goes sour water layer, and organic layer washing to neutral pH pours into flask, deionized water is added
1g, 70 DEG C of reflux 60min, vacuum pump vacuum distillation concentration, are removed under reduced pressure solvent and low-boiling point material, obtain following structure tree
Rouge:
(PhSiO3/2)0.48[(CH3)3SiO1/2]0.21[(CH3)2HSiO1/2]0.31 (B2)
The group is divided into the organo-silicon compound that the viscosity at 25 DEG C is 100mPas, and the molar content of hydrogen is rubbed 0.39
That/100g.
Practice embodiment 1
By synthetic example 1~8 prepare resin (A1), (A2), (B1) and (B2) and
(C) addition reaction catalyst: the octanol solution (platinum concentration 5wt%) of chloroplatinic acid；
(D) inhibitor: 2- phenyl -3- butyne-2-alcohol.
(each composition is according to parts by weight) is mixed according to combination shown in table 1, obtains the present composition.
Semiconductor devices LED light shown in FIG. 1 encapsulates in the following way, provides a bracket for being fixed with light-emitting component 2
1, wherein the light-emitting component 2 is connected by bonding wire 4 (usually gold thread) with electrode 3, by foregoing curable of the invention
Organopolysiloxane composition 5 is coated on the bracket 1 for being fixed with light-emitting component 2, is solidified.
Each physical and chemical performance for the composition 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 solidification is then kept at 150 DEG C,
At 25 DEG C, three point measurement hardness numbers are taken using shore D type hardness tester meter under conditions of 60%RH, and record average value.
[refractive index]
Organopolysiloxane solidfied material is measured at 25 DEG C by Abbe refractometer, light source utilizes the visible light of 589nm.
[tensile strength and elongation at break]
After obtained composition deaeration, the thin slice of 2mm thickness is prepared, keeps keeping 3h at 1h and 150 DEG C at 100 DEG C
After solidification, piece is processed into dumbbell shaped, at 25 DEG C, tests its tensile strength using universal testing machine under conditions of 60%RH
And elongation at break.
[resistance to vulcanization]
After obtained composition deaeration, dispensing on auspicious 5730 bracket of grace (chipless gold thread) after the 2h that dehumidifies at 150 DEG C,
1h is kept at 100 DEG C, after 3h solidification is then kept at 150 DEG C, by cradle hangs the 250ml equipped with 2g sulphur powder reagent bottle
In, toasted at 90 DEG C, observe bracket in silver coating whether blackening, record bracket blackening time.
[cooling thermal impact circulation]
The auspicious 5730 white light packaging body of 96 grace is placed in cooling thermal impact case, each circulation is by being kept for 30 points at -40 DEG C
Clock keeps constituting for 30 minutes at 100 DEG C, and cycle alternation, every 100cyc observes dead lamp and splits glue.
Table 1
As shown in Table 1, and do not have in 1-4 of the embodiment of the present invention containing (A1) component with block branches structure
There is the comparative example 3 containing block branches structure to compare, there is more excellent cooling thermal impact performance；
As shown in Table 1, (A1) component in 1-4 of the embodiment of the present invention containing block branches structure and random branch
(A2) the weight content ratio of structure is within range 100:0-25:100, compared with comparative example 1 outside the above range,
With more excellent cooling thermal impact performance；
As shown in Table 1, (B1) component in 1-4 of the embodiment of the present invention containing linear chain structure and branched structure
(B2) weight content ratio is within range 100:0-10:100, compared with comparative example 2 outside the above range, has more
Add excellent cooling thermal impact performance；
As shown in Table 1, (A1) with block branches structure is contained in the embodiment of the present invention 1,2 and 4 and is had
(A2) component of random branched structure, though with structure containing block branches (A1) without the implementation containing random branched structure (A2)
Example 3 is compared, the performance with more excellent resistance to vulcanization.
Beneficial effects of the present invention: compared with prior art, curable block type organopolysiloxane group of the invention
Object and its cured semiconductor devices are closed, good sulfidation-resistance energy, higher refractive index, stronger hardness are not only maintained,
But also there is excellent cold-resistant thermal shock resistance properties.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (16)
1. a kind of curable block type organopolysiloxane composition, which is characterized in that its in the solid state, in temperature 25
DEG C, the tensile strength under the conditions of humidity 60%RH is 1-8Mpa, and elongation at break 50%-200%, refractive index is to be equal to or surpass
1.45 are crossed, the composition includes:
It (A1) include R1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nThe organic poly- silicon oxygen of the block branches structure of unit
Alkane, and m is more than or equal to 2, n more than or equal to 2 in each molecule；
(A2) it is independently selected from R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The organic poly- silicon oxygen of the random branched structure of unit
Alkane；
The weight content ratio of the component (A1) and component (A2) is 100:0-25:100；
(B1) the poly- Organhydridosiloxaneresins of linear chain structure, wherein per molecule has an average of at least one hydrogen original with silicon bonding
Son and at least one aromatic group；
(B2) it is independently selected from R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2The poly- organic hydride of random branched structure of unit
Siloxanes；
The weight content ratio of the component (B1) and component (B2) is 100:0-10:100；
(C) dosage is enough to promote the cured hydrosilylation catalysts of the composition；
Wherein, the R1Selected from identical or different alkenyl, aromatic-free and the unit price substitution for being free of aliphatic unsaturated bond
Or unsubstituted alkyl, the R2Selected from identical or different alkenyl, aromatic group, aromatic-free and be free of aliphatic not
The substituted or unsubstituted alkyl of unit price of saturated bond, the R3It is aromatic group；The R4Selected from identical or different without virtue
Hydrocarbon and the substituted or unsubstituted alkyl of unit price and hydrogen atom for being free of aliphatic unsaturated bond, the R5Selected from identical or not identical
Hydrogen atom, aromatic group, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, the R6
It is aromatic group.
2. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that component
(A1) the sum of content of aromatic group and in (A2) is greater than 10mol%, and component (B1) and the aromatic group in (B2) contain
The sum of amount is greater than 10mol%.
3. the curable block type organopolysiloxane composition of one kind according to claim 2, which is characterized in that component
(A1) [R2 2SiO2/2]mThe content of aromatic group in unit is greater than 10mol%.
4. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that component
(A1) viscosity is 500-100000mPas at 25 DEG C.
5. the curable block type organopolysiloxane composition of one kind according to any one of claims 1-4, special
Sign is that component (A2) viscosity at 25 DEG C is greater than 20000mPas.
6. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that component
(A1) alkenyl content is 0.05-0.30mol/100g.
7. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that each
N is more than or equal to 3, m and is more than or equal to 5 in molecule.
8. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that component
(B1) viscosity is 0.1-1000mPas at 25 DEG C, and component (B2) viscosity at 25 DEG C is 0.1-10000mPas.
9. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that opposite
In the total composition of 100 parts by weight, the dosage of component (A1) and (A2) are 50-95 parts by weight, the use of component (B1) and (B2)
Amount is 5-50 parts by weight.
10. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that institute
Stating (A1) has following average unit formulas,
([R3SiO3/2]n)a([R2 2SiO2/2]m)b(R1 3SiO1/2)c,
Wherein R1Selected from identical or different alkenyl, the substituted or unsubstituted alkyl of unit price, R2Selected from identical or different
Alkenyl, the substituted or unsubstituted alkyl of unit price and aromatic group, R3It is aromatic group, 0.3 < a < 0.8,0.05 <b < 0.6,
0.05 < c < 0.3, and a+b+c=1.
11. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that institute
Stating (A2) has following average unit formulas,
(R3SiO3/2)a1(R1 3SiO1/2)c1,
Wherein R1Selected from identical or different alkenyl, the substituted or unsubstituted alkyl of unit price, R3It is aromatic group, 0.7 < a1 <
0.95,0.05 < c1 < 0.3, and a1+c1=1.
12. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that institute
Stating (A2) has following average unit formulas,
(R3SiO3/2)a2(R2 2SiO2/2)b2(R1 3SiO1/2)c2,
Wherein R1Selected from identical or different alkenyl, the substituted or unsubstituted alkyl of unit price, R2Selected from identical or different
Alkenyl, the substituted or unsubstituted alkyl of unit price and aromatic group, R3It is aromatic group, 0.2 < a2 < 0.8,0.2 <b2 < 0.8,
0.05 < c2 < 0.3, and a2+b2+c2=1.
13. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that institute
Stating component (B1) to be includes R4 3SiO1/2Unit and R5 2SiO2/2The poly- Organhydridosiloxaneresins of the linear chain structure of unit, R4Selected from identical
Or different aromatic-free and the substituted or unsubstituted alkyl of unit price and hydrogen atom without aliphatic unsaturated bond, R5It is selected from
Identical or different aromatic-free and the substituted or unsubstituted alkyl of unit price, hydrogen atom and the virtue for being free of aliphatic unsaturated bond
Race's group.
14. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that institute
Stating (B2) has following average unit formulas,
(R6SiO3/2)a3(R4 3SiO1/2)c3,
Wherein R4Selected from the substituted or unsubstituted alkyl of identical or different unit price and hydrogen atom, R6It is aromatic group, 0.4 < a3
< 0.8,0.2 < c3 < 0.6, and a3+c3=1.
15. the curable block type organopolysiloxane composition of one kind according to claim 1, which is characterized in that institute
Stating (B2) has following average unit formulas,
(R6SiO3/2)a4(R5 2SiO2/2)b4(R4 3SiO1/2)c4,
Wherein R4Selected from the substituted or unsubstituted alkyl of identical or different unit price and hydrogen atom, R5Selected from identical or not identical
The substituted or unsubstituted alkyl of unit price, aromatic group and hydrogen atom, R6It is aromatic group, 0.2 < a4 < 0.6,0.2 <b4 < 0.6,
0.2 < c4 < 0.6, and a4+b4+c4=1.
16. a kind of semiconductor devices, the bracket including light-emitting component and the fixed light-emitting component, which is characterized in that the hair
The solidification of the described in any item curable block type organopolysiloxane compositions of claim 1-15 is coated on optical element
Object.
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