CN105985649A - Curable block organopolysiloxane composition and semiconductor device - Google Patents
Curable block organopolysiloxane composition and semiconductor device Download PDFInfo
- Publication number
- CN105985649A CN105985649A CN201510050973.0A CN201510050973A CN105985649A CN 105985649 A CN105985649 A CN 105985649A CN 201510050973 A CN201510050973 A CN 201510050973A CN 105985649 A CN105985649 A CN 105985649A
- Authority
- CN
- China
- Prior art keywords
- sio
- component
- unit
- aromatic group
- unsubstituted alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 55
- 239000004065 semiconductor Substances 0.000 title claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 53
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 40
- 125000003342 alkenyl group Chemical group 0.000 claims description 33
- 229910020447 SiO2/2 Inorganic materials 0.000 claims description 31
- 229910020487 SiO3/2 Inorganic materials 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000001931 aliphatic group Chemical group 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- -1 polysiloxane Polymers 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 8
- 238000005987 sulfurization reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 125000003944 tolyl group Chemical group 0.000 description 11
- 238000007711 solidification Methods 0.000 description 10
- 230000008023 solidification Effects 0.000 description 10
- 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 9
- 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
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 125000004344 phenylpropyl group Chemical group 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 9
- 125000005023 xylyl group Chemical group 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000001188 haloalkyl group Chemical group 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000010992 reflux Methods 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 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
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect 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
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 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
- 239000002585 base Substances 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
- 239000003292 glue Substances 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
- 229940073561 hexamethyldisiloxane Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000413 hydrolysate Substances 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
- 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 229910018557 Si O Inorganic materials 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
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 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
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas 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
- 238000002156 mixing Methods 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a curable block organopolysiloxane composition and a semiconductor device to overcome the defect of poor cold and heat shock resistance in the prior art. The curable block organopolysiloxane composition has tensile strength of 1 to 8 Mpa, elongation at break of 50 to 200% and a refractive index of no less than 1.45 in a curing state under the conditions of a temperature of 25 DEG C and humidity of 60% RH. The composition comprises (A1) a block branched-chain-structured organopolysiloxane copolymer containing a R13SiO1/2 unit, a [R22SiO2/2]m unit and a [R3SiO3/2]n unit; (B1) straight-chain-structured polyorganohydrosiloxane, each molecule of which has at least one hydrogen atom bonding with silicon and at least one aromatic group on average; and (C) a hydrosilylation catalyst, wherein the amount of the hydrosilylation catalyst is sufficient to promote curing of the composition. Compared with the prior art, the curable block organopolysiloxane composition provided by the invention not only maintains good sulfuration resistance, a high refractive index and high hardness and has excellent cold and heat shock resistance.
Description
Technical field
The present invention relates to a kind of silicon composition, particularly to a kind of curable block type organopolysiloxane composition, and use the semiconductor device of described compositions solidification composition.
Background technology
The basic structural unit of organosilicon polymer is to be made up of silica chain link, and side chain is then connected with other various organic groups by silicon atom.Compared with other macromolecular materials, organosilicon polymer has a following outstanding properties: 1. temperature-resistance characteristic, organosilicon product with silica (Si-O) key as backbone structure, so the heat stability of organosilicon product is high, under high temperature, the chemical bond of (or radiation irradiation) molecule does not ruptures, does not decomposes.2. weatherability, the main chain of organosilicon product is-Si-O-, has heat stability more more preferable than other macromolecular materials and resistance to irradiation and weather-proof ability, has longer service life under natural environment.3. electrical insulation properties, organosilicon product all has good electrical insulation capability, its dielectric loss, proof voltage, Inverter fed motor, specific volume resistance and surface resistivity etc. all come out at the top in insulant, and their electric property is affected the least by temperature and frequency.Therefore, based on above-mentioned good combination property, as the one of organosilicon product, organopolysiloxane is widely used in LED and photovoltaic industry.
Organopolysiloxane is typically containing the polymer 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 are usually referred to separately as M, D, T and Q unit.These siloxy units can combine to form ring-type, the structure of straight or branched in many ways.Depending on number and the type of siloxy units in organopolysiloxane, the chemical and physical features of the polymer architecture of gained is varied from." linear chain structure " organopolysiloxane mainly (i.e. (R Han D2SiO2/2)) siloxy units, it causes the polydiorganosiloxanepolyurea as the fluid with different viscosities, and this depends on " degree of polymerization " (or the DP) indicated by number of the D unit in polydiorganosiloxanepolyurea.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 time, obtain " resin " organopolysiloxane.T or Q siloxy units content in organopolysiloxane increases, and typically results in polymer and has the hardness of increase and/or glassy character.
Generally, LED packaging part includes that light-emitting component and LED support, described light-emitting component are fixed on described LED support, and described LED support is generally made up of metallic matrix, and on described metallic matrix, it being provided with silver coating, described silver coating is used for the optically focused to light-emitting component light or astigmatism.Organopolysiloxane composition is coated on the silver coating of described light-emitting component and LED support, and solidifies, be i.e. basically completed the encapsulation to LED.But, in prior art, in the use environment that the cold and hot temperature difference is bigger, the solidfied material of described organosiloxane composition easily ftractures, and can cause dead lamp phenomenon time serious, have impact on the service life of LED, additionally, LED packaging part is during life-time service, the sulfur in surrounding air can corrode silver coating gradually, cause this silver layer sulphide staining, and then cause light decay serious.
Summary of the invention
The technical problem to be solved is on the premise of keeping good sulfidation-resistance energy, overcome the defect that the cold-hot impact of prior art is poor, it is provided that a kind of resistance to cure time length and the curable block type organopolysiloxane composition of cold-hot impact excellence.
The curable block type organopolysiloxane composition that the present invention provides, it is under solid state, temperature 25 DEG C, hot strength under the conditions of humidity 60%RH is 1-8Mpa, elongation at break is 50%-200%, and refractive index is for equaling or exceeding 1.45, and described compositions includes:
(A1) R is included1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nIn the block branches structure organopolysiloxane of unit, and every a part, m is more than or equal to 2, and n is more than or equal to 2；
(A2) it is independently selected from R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The random branched structure organopolysiloxane of unit；
The weight content ratio of described component (A1) and component (A2) is 100:0-25:100；
(B1) the poly-Organhydridosiloxaneresins of linear chain structure, wherein, per molecule has at least one hydrogen atom being bonded with silicon average and at least one aromatic group；
(B2) it is independently selected from R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2The poly-Organhydridosiloxaneresins of random branched structure of unit；
The weight content ratio of described component (B1) and component (B2) is 100:0-10:100；
(C) consumption be enough to the hydrosilylation catalysts promoting said composition to solidify；
Wherein, described R1Selected from alkenyl that is identical or that differ, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R2Selected from alkenyl that is identical or that differ, aromatic group, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R3It it is aromatic group；Described R4Selected from aromatic-free that is identical or that differ and without the substituted or unsubstituted alkyl of unit price of aliphatic unsaturated bond and hydrogen atom, described R5Selected from hydrogen atom that is identical or that differ, aromatic group, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R6It it is aromatic group.
For solving above-mentioned technical problem, present invention also offers a kind of semiconductor device, described semiconductor device includes light-emitting component and the support of fixing described light-emitting component, wherein, described light-emitting component is coated with the solidfied material of curable block type organopolysiloxane composition of the present invention.
Beneficial effects of the present invention: compared with prior art, the curable block type organopolysiloxane composition of the present invention and the semiconductor device of solidification thereof, not only maintain good sulfidation-resistance energy, higher refractive index, stronger hardness, but also there is the cold-hot impact property of excellence.
Accompanying drawing explanation
Fig. 1 is the semiconductor packages generalized section that one embodiment of the invention provides；
Reference in Figure of description is as follows:
1, LED support；2, light-emitting component；3, electrode；4, joint line；5, the firming body of curable organopolysiloxane composition.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below the present invention is described in further detail.
In below describing, Vi is referred to as vinyl, and Me is referred to as methyl, and Ph is referred to as phenyl.
In the curable block type organopolysiloxane composition that the present invention provides:
Component (A1) is for including R1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nThe block branches structure organopolysiloxane of unit.Described component (A1) is the main component of the present composition, alkenyl in component (A1) and (A2) reacts to each other with the hydrogen atom being bonded with silicon in component (B1) and (B2) jointly, form cross-bond, and solidify.Component (A1) organopolysiloxane of the present invention is " block " copolymer, relative with " randomly " copolymer of (A2) and (B2).Described block copolymer is presented as in (A1) compositions and includes [R2 2SiO2/2]mBlock unit and [R3SiO3/2]nBlock unit, described [R2 2SiO2/2]mBlock unit is to have the R of m repeated arrangement in per molecule2 2SiO2/2Unit, described [R3SiO3/2]nBlock unit is to have the R of n repeated arrangement in per molecule3SiO3/2Unit, wherein, in every a part, n is more than or equal to 2, 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, the structure of block in this range makes to have in molecule the region that a certain size soft or hard is different simultaneously, ensure that it keeps preferable ductility while having relatively high crosslink density, so that product is provided simultaneously with relatively low breathability and preferable pliability.
In component (A1), described R1Selected from alkenyl that is identical or that differ, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, R2Selected from alkenyl that is identical or that differ, aromatic group, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, R3It it is aromatic group.Alkenyl in described component (A1) can be representative, most preferably vinyl with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl.Aromatic-free in described component (A1) and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, following radicals can be included: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, chloromethyl, 3-chloropropyl or similar haloalkyl, most preferably methyl.Aromatic group in described component (A1) can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.In order to improve described component (A1) and the reactivity of component (B1) further, the content of described alkenyl is preferably 0.05-0.30mol/100g, and the content of alkenyl in this range makes the crosslink density of compositions because of will not be too high or too low and cause system easily to ftracture or breathability is the highest.The component (A1) viscosity at 25 DEG C is not particularly limited by the present invention, preferably 500-100000mPa s, and it is preferable that viscosity composition in this range has preferable ductility application property simultaneously.
As one of the preferred embodiment of the present invention, described (A1) has following average unit formula, ([R3SiO3/2]n)a([R2 2SiO2/2]m)b(R1 3SiO1/2)c,
Wherein R1Selected from alkenyl that is identical or that differ, the substituted or unsubstituted alkyl of unit price, R2Selected from alkenyl that is identical or that differ, 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 be representative, most preferably vinyl with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl.Described R1And R2In 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, most preferably methyl.Described R3In aromatic group can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.
Such as, described component (A1) can include that following molecular formula is 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。
In the present composition the most selectable containing (A2) component, (A2) is for being independently selected from R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The random branched structure organopolysiloxane of unit.Alkenyl in described component (A2) and (A1) reacts to each other with the hydrogen atom being bonded with silicon in component (B1) and (B2) jointly, forms cross-bond.The component (A2) of the present invention is " randomly " copolymer, relative with " block " copolymer of (A1) organopolysiloxane.Described (A2) can be selected from MT and MDT of random branched structure and combinations thereof, and described MT shows as including R1 3SiO1/2Unit and R3SiO3/2The random branched structure of unit；Described MDT shows as including R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The random branched structure of unit.
In component (A2), described R1Selected from alkenyl that is identical or that differ, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R2Selected from alkenyl that is identical or that differ, aromatic group, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R3It it is aromatic group.Alkenyl in described component (A2) can be representative, most preferably vinyl with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl.Aromatic-free in described component (A2) and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, following radicals can be included: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, chloromethyl, 3-chloropropyl or similar haloalkyl, most preferably methyl.Aromatic group in described component (A2) can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.The component (A2) viscosity at 25 DEG C is not particularly limited by the present invention, and preferably greater than 20000mPa s, viscosity composition in this range has preferable intensity and ductility.
As one of the preferred embodiment of the present invention, described (A2) has following average unit formula,
(R3SiO3/2)a1(R1 3SiO1/2)c1,
Wherein R1Selected from alkenyl that is identical or that differ, 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 be representative, most preferably vinyl with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl.Described R1In 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, most preferably methyl.Described R3In aromatic group can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.
Such as, described component (A2) can include that following molecular formula is as representative:
(PhSiO3/2)a1(Vi2MeSiO1/2)c1,
(PhSiO3/2)a1(Me2ViSiO1/2)c1。
As one of the preferred embodiment of the present invention, described (A2) has following average unit formula,
(R3SiO3/2)a2(R2 2SiO2/2)b2(R1 3SiO1/2)c2,
Wherein R1Selected from alkenyl that is identical or that differ, the substituted or unsubstituted alkyl of unit price, R2Selected from alkenyl that is identical or that differ, 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 be representative, most preferably vinyl with vinyl, acrylic, cyclobutenyl, pentenyl and hexenyl.Described R1And R2In 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, most preferably methyl.Described R3In aromatic group can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.
Such as, described component (A2) can include that following molecular formula is 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 described component (A1) and component (A2) is 100:0-25:100, more preferably 100:1-25:100, compositions in the range of this content ratio, because compositions contains (A1) component of random branched structure, (A1) component makes to have in molecule the region that a certain size soft or hard is different at this simultaneously, ensure that it keeps preferable ductility while having relatively high crosslink density, so that product is provided simultaneously with relatively low breathability and preferable pliability, the weight content ratio of described component (A1) and component (A2) is more preferably 100:5-30:100.
Component (B1) is the poly-Organhydridosiloxaneresins of linear chain structure, and wherein, per molecule has at least one hydrogen atom being bonded with silicon average and at least one aromatic group.Described component (B1) is had an effect as cross-linking agent, in the present invention, SiH in linear chain structure component (B1) and alkenyl generation additive reaction (hydrosilylation) in branched structure component (A1) and (A2), be consequently formed the network structure of crosslinking.Further, described component (B1) is for including R4 3SiO1/2Unit and R5 2SiO2/2The poly-Organhydridosiloxaneresins of linear chain structure of unit, R4Selected from aromatic-free that is identical or that differ and without the substituted or unsubstituted alkyl of unit price of aliphatic unsaturated bond and hydrogen atom, R5Selected from aromatic-free that is identical or that differ and the substituted or unsubstituted alkyl of unit price, hydrogen atom and aromatic group without aliphatic unsaturated bond.Aromatic-free in component (B1) and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, following radicals can be included: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, chloromethyl, 3-chloropropyl or similar haloalkyl, most preferably methyl.Aromatic group in component (B1) can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.The component (B1) viscosity at 25 DEG C is not particularly limited by the present invention, preferably 0.1-1000mPa s, and it is preferable that viscosity composition in this range has preferable ductility application property simultaneously.
As one of the preferred embodiment of the present invention, described (B1) has following average unit formula,
(R6R5SiO2/2)b5(R4 3SiO1/2)c5,
Wherein R4It is independently selected from the substituted or unsubstituted alkyl of unit price that is identical or that differ and hydrogen atom, R5It is independently selected from the substituted or unsubstituted alkyl of unit price that is identical or that differ, aromatic group and hydrogen atom, R6For aromatic group, 0.33 <b5 < 0.8,0.2 < c5 < 0.67, and b5+c5=1.Described R4And R5In 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-chloropropyl or similar haloalkyl, most preferably methyl.Described R5And R6In aromatic group can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.
Such as, described component (B1) can include that following molecular formula is as representative:
(PhMeSiO2/2)b5(Me2HSiO1/2)c5,
(PhHSiO2/2)b5(Me3SiO1/2)c5。
In the present composition the most selectable containing (B2) component, (B2) is for being independently selected from R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2The poly-Organhydridosiloxaneresins of random branched structure of unit.Described component (B2) is had an effect as cross-linking agent, in the present invention, SiH in branched structure component (B2) and alkenyl generation additive reaction (hydrosilylation) in branched structure component (A1) and (A2), be consequently formed the network structure of crosslinking.The component (B2) of the present invention is " randomly " copolymer, relative with " block " copolymer of (A1) organopolysiloxane.Described (B2) can be selected from MT and MDT of random branched structure and combinations thereof, and described MT shows as including R4 3SiO1/2Unit and R6SiO3/2The random branched structure of unit；Described MDT shows as including R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2The random branched structure of unit.
In component (B2), described R4Selected from aromatic-free that is identical or that differ and without the substituted or unsubstituted alkyl of unit price of aliphatic unsaturated bond and hydrogen atom, described R5Selected from hydrogen atom that is identical or that differ, aromatic group, aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R6It it is aromatic group.Aromatic-free in component (B2) and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, following radicals can be included: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl, chloromethyl, 3-chloropropyl or similar haloalkyl, 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.The component (B2) viscosity at 25 DEG C is not particularly limited by the present invention, preferably 0.1-10000mPa s, and it is preferable that viscosity composition in this range has preferable ductility application property simultaneously.
As one of the preferred embodiment of the present invention, described (B2) has following average unit formula,
(R6SiO3/2)a4(R5 2SiO2/2)b4(R4 3SiO1/2)c4,
Wherein R4Selected from the substituted or unsubstituted alkyl of unit price that is identical or that differ and hydrogen atom, R5Selected from the substituted or unsubstituted alkyl of unit price that is identical or that differ, 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.Described R4And R5In 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-chloropropyl or similar haloalkyl, most preferably methyl.Described R5And R6In aromatic group can be representative with phenyl, tolyl, xylyl and naphthyl, and the benzene alkyl that phenethyl, phenylpropyl etc. are similar, most preferably phenyl.
Such as, described component (B2) can include that following molecular formula is 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 described component (B1) and component (B2) is 100:0-10:100, more preferably 100:1-10:100, compositions in the range of this content ratio, because compositions contains (B2) component of random branched structure, (B2) crosslink density after component improves compositions solidification at this, making compositions breathability lower, the weight content ratio of described component (B1) and component (B2) is more preferably 100:5-20:100.
In order to improve the refractive index of the firming body that the present composition obtains further, the content of the aromatic group in described (A1) and (A2) component is preferably greater than 10mol%, and the content sum of the aromatic group in component (B1) and (B2) is more than 10mol%.Further, described (A1) [R2 2SiO2/2]mThe content of the aromatic group in unit is preferably greater than 10mol%, the and [R of component (A1)3SiO3/2]nThe content of the aromatic group in unit is preferably greater than 10mol%.
In the present invention, the content ratio relation of described component (A1)+(A2) and component (B1)+(B2) is not particularly limited, the compositions that arbitrary weight ratio is formed is the most permissible, as long as the hydrogen atom being bonded with silicon met in component (B1)+(B2) and the alkenyl in component (A1)+(A2) occur enough reactions, the such as hydrogen atom being bonded with silicon in component (B1)+(B2) to be preferably 0.9-2.0 with the ratio of the mole of the alkenyl in component (A1)+(A2).
Relative to the total composition of 100 weight portions, the consumption of component (A1) and (A2) is preferably 50-95 weight portion, and the consumption of component (B1) and (B2) is preferably 5-50 weight portion.
In the present invention, because of the organopolysiloxane that component (A1) is block branches structure, compositions is made to have certain hard section and have soft section of more long-chain with the poly-Organhydridosiloxaneresins of the linear chain structure of component (B1), overall structure pliability is good, random branched structure in conjunction with (A2) and (B2) has higher crosslink density and higher intensity, produce similar thermoplastic elastomers and have elastomeric effect, thermal shock at temperature checker makes material have more preferable elasticity, and the better adaptability between base material, will not rupture because internal stress is excessive, the most also there is relatively low breathability, prevent gas from entering device inside and cause deterioration.
In the present invention, component (C) is the catalyst of the H atom generation hydrosilylation reactions promoting the alkenyl in component (A1) and (A2) to be bonded with the Si in component (B1) and (B2).In other words, component (C) is to promote the catalyst of compositions solidification.Wherein, catalyst type is not particularly limited by the present invention, the custom catalysts of this area, such as platinum-type catalyst, rhodium class catalyst or palladium class catalyst, and the present invention is preferably platinum-type catalyst.Instantiation includes: platinum black, chloroplatinic acid, the alcoholic solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-alkene complex etc., being preferably platinum-alkenylsiloxane complex, the present invention uses has the tetramethyl-ethylene base disiloxane platinum catalyst as dentate.The consumption of component (C) is not particularly limited, and its used in amounts be enough to promote said composition curing reaction.
In the curable organopolysiloxane composition of the present invention, may also include component (D) additive reaction inhibitor, its effect is the storage phase of the curable organopolysiloxane composition in order to extend the present invention, additive reaction inhibitor is a kind of with temperature dependent material, lose rapidly its inhibition when being heated to a certain degree, and make compositions generation curing reaction.Kind weight and the addition of the additive reaction inhibitor of component (D) are not particularly limited, this area conventional inhibitor can be used, addition can optionally add, such as, in the present invention, component (D) is ethynylcyclohexanol, and addition is component (A) and the 0.05% of (B) gross weight.
In the present invention, the preparation method of component (A1), (A2), (B1), (B2), (C) and (D) is not particularly limited, this area usual manner can be used to prepare, or commercially available.
In the present invention, can be by component (A1), (B1) and (C) be mixed, and optionally addO-on therapy (A2), (B2) and (D) and the such as inorganic filler, pigment of other additives, fire retardant and heat-resistant agent etc., thus prepare curable organopolysiloxane composition.In the present invention, it is provided that a kind of semiconductor device, including light-emitting component and the support of fixing described light-emitting component, above-mentioned mixed compositions is coated on the support of described light-emitting component, solidifies.Hardening time and temperature can change, and such as, first can keep 0.5-2 hour carrying out one-step solidification at 100 DEG C-150 DEG C, then keep 2-4 hour carrying out secondary solidification at 150 DEG C-200 DEG C.Being formed at temperature 25 DEG C, the hot strength under the conditions of humidity 60%RH is 1-8Mpa, and elongation at break is 50%-200%, refractive index be equal or exceed 1.45 firming body.By contrast, conventional organopolysiloxane composition is difficult to be formed hot strength and elongation at break and refractive index all keeps the solidfied material of above-mentioned superperformance, and has resistance to cure time length and the advantage of excellent cold-hot impact property.
Below in conjunction with embodiment, the present invention is described in further detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Synthetic example 1
Tetra-mouthfuls of round-bottomed flasks of 5L are loaded onto phenyl silsesquioxane hydrolysate (DOW CORNING (Dow Corning) 217) 880.0g and toluene 1000.0g.This reactant mixture is heated at reflux 30 minutes.After reactant mixture is cooled to 108 DEG C, add the solution of the methyl phenyl silicone oil that end is diacetoxy.Methyl phenyl silicone oil (the self-control that this end is the methyl phenyl silicone oil toluene 500.0g of diacetoxy, molecular weight 3000 end is silanol, methyl phenyl ring siloxane open loop under alkali effect prepares) 410g and methyl triacetoxysilane 24g, 2h is stirred at room temperature and prepares.At 108 DEG C, the methyl phenyl silicone oil that end is diacetoxy is quickly added to phenyl silsesquioxane hydrolyzate solution.This reactant mixture is heated at reflux 2 hours, then adds tetramethyl divinyl tetramethyl disiloxane 232g, concentrated hydrochloric acid 20g, deionized water 20g, continue to be heated to reflux 5 hours.Pouring separatory funnel into, point remove sour water layer, organic layer washes neutral pH, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, 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 unit of DOW CORNING.
This component is that viscosity is the organic block polysiloxanes of 5000mPa s at 25 DEG C, and vinyl molar content is at 0.15 mole/100g.
Synthetic example 2
Tetra-mouthfuls of round-bottomed flasks of 5L are loaded onto phenyl silsesquioxane hydrolysate (DOW CORNING (Dow Corning) 217) 760.0g and toluene 1000.0g.This reactant mixture is heated at reflux 30 minutes.After reactant mixture is cooled to 108 DEG C, add the solution of the methyl phenyl silicone oil that end is diacetoxy.Methyl phenyl silicone oil (the self-control that this end is the methyl phenyl silicone oil toluene 500.0g of diacetoxy, molecular weight 650 end is silanol, methyl phenyl ring siloxane open loop under alkali effect prepares) 550g and methyl triacetoxysilane 21g, 2h is stirred at room temperature and prepares.At 108 DEG C, the methyl phenyl silicone oil that end is diacetoxy is quickly added to phenyl silsesquioxane hydrolyzate solution.This reactant mixture is heated at reflux 2 hours, then adds tetramethyl divinyl tetramethyl disiloxane 172g, concentrated hydrochloric acid 20g, deionized water 20g, continue to be heated to reflux 5 hours.Pouring separatory funnel into, point remove sour water layer, organic layer washes neutral pH, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, obtains following structural resin:
([PhSiO3/2]n)0.46([PhMeSiO2/2]5)0.37[(CH3)2(CH2=CH) SiO1/2]0.13 (A1‐2)
This component is that viscosity is the organic block polysiloxanes of 3000mPa s at 25 DEG C, and vinyl molar content is at 0.14 mole/100g.
Synthetic example 3
Phenyltrimethoxysila,e 83g is added flask, being sequentially added into deionized water 15g, toluene 100g and potassium hydroxide 0.5g, 25 DEG C are reacted 30 minutes, it is subsequently adding tetramethyl divinyl disiloxane 10g and hexamethyl disiloxane 10g and continues backflow 6 hours, pour separatory funnel into, point lixiviating water layer, organic layer washes neutral pH, pour flask into, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structural resin:
(PhSiO3/2)0.76[(CH3)3SiO1/2]0.10[(CH3)2(CH2=CH) SiO1/2]0.14 (A2‐1)
This component is solid for viscosity at 25 DEG C, and vinyl molar content is at 0.15 mole/100g.
Synthetic example 4
By phenyltrimethoxysila,e 62g, aminomethyl phenyl dimethoxysilane 28g adds flask, is sequentially added into deionized water 15g, toluene 100g and potassium hydroxide 0.5g, 25 DEG C are reacted 30 minutes, are subsequently adding tetramethyl divinyl disiloxane 11g, continue backflow 6 hours, pour separatory funnel into, point lixiviating water layer, organic layer washes neutral pH, pour flask into, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structural resin:
(PhSiO3/2)0.61[PhCH3SiO]0.24[(CH3)2(CH2=CH) SiO1/2]0.15 (A2‐2)
This component is solid for viscosity at 25 DEG C, and vinyl molar content is at 0.15 mole/100g.
Synthetic example 5
Dimethoxydiphenylsilane 65g is added flask, deionized water 15g and concentrated hydrochloric acid 15g that concentration is mass percent 37% successively, 70 DEG C of reactions add tetramethyl disiloxane 26.3g for 5 minutes and continue backflow 60 minutes, pour separatory funnel into, divide and remove sour water layer, organic layer washes neutral pH, pours flask into, adds deionized water 1g, 70 DEG C of backflow 60min, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structural resin:
(Ph2SiO2/2)0.53[(CH3)2HSiO1/2]0.47 (B1)
This component is that viscosity is the organo-silicon compound of 50mPa s at 25 DEG C, and the molar content of its hydrogen is at 0.52 mole/100g.
Synthetic example 6
Phenyltrimethoxysila,e 49.5g is added flask, deionized water 15g and concentrated hydrochloric acid 15g that concentration is mass percent 37% successively, 70 DEG C of reactions add tetramethyl disiloxane 16.4g and hexamethyl disiloxane 14.1g for 5 minutes and continue backflow 60 minutes, pour separatory funnel into, divide and remove sour water layer, organic layer washes neutral pH, pour flask into, add deionized water 1g, 70 DEG C of backflow 60min, vacuum pump decompression distillation and concentration, removal of solvent under reduced pressure and low-boiling point material, obtain following structural resin:
(PhSiO3/2)0.48[(CH3)3SiO1/2]0.21[(CH3)2HSiO1/2]0.31 (B2)
This component is that viscosity is the organo-silicon compound of 100mPa s at 25 DEG C, and the molar content of its hydrogen is at 0.39 mole/100g.
Put into 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 is 5wt%) of chloroplatinic acid；
(D) inhibitor: 2-phenyl-3-butyne-2-alcohol.
Carry out mixing (each composition meter by weight) according to the combination shown in table 1, obtain the present composition.
Semiconductor device LED shown in Fig. 1 encapsulates in the following way, one support 1 being fixed with light-emitting component 2 is provided, wherein said light-emitting component 2 is connected with electrode 3 by joint line 4 (usually gold thread), the foregoing curable organopolysiloxane composition 5 of the present invention is coated on the support 1 being fixed with light-emitting component 2, solidifies.
Each physical and chemical performance of the compositions obtained is evaluated and tested by following method.Result is recorded in table 1.
[hardness]
After the compositions deaeration that will obtain, take 10g at 100 DEG C, keep 1h, after then keeping 3h solidification at 150 DEG C, at 25 DEG C, use shore D type hardness tester meter to take three points under conditions of 60%RH and measure hardness number, and record meansigma methods.
[refractive index]
Measuring organopolysiloxane solidfied material at 25 DEG C by Abbe refractometer, light source utilizes the visible ray of 589nm.
[hot strength and elongation at break]
After the compositions deaeration that will obtain, prepare the thin slice of 2mm thickness, after keeping keeping 3h solidification at 1h 150 DEG C at 100 DEG C, sheet is processed into dumbbell shaped, at 25 DEG C, under conditions of 60%RH, utilizes universal testing machine to test its hot strength and elongation at break.
[resistance to sulfuration]
After the compositions deaeration that will obtain, auspicious 5730 supports of grace (chipless gold thread) upper some glue after 150 DEG C of dehumidifying 2h, 1h is kept at 100 DEG C, then after keeping 3h solidification at 150 DEG C, by cradle hangs in the reagent bottle of the 250ml equipped with 2g sulfur powder, toast at 90 DEG C, observe in support silver coating whether blackening, the time of record support blackening.
[thermal shock circulation]
Being placed in thermal shock case by 96 auspicious 5730 white light packaging bodies of grace, each circulation, by-40 DEG C, keeps 30 minutes, at 100 DEG C, keeps 30 minutes constituting, cycle alternation, and every 100cyc observes dead lamp and splits glue.
Table 1
As shown in Table 1, embodiment of the present invention 1-4 contains (A1) component with block branches structure, compared with the comparative example 3 not containing block branches structure, there is more excellent thermal shock performance；
As shown in Table 1, embodiment of the present invention 1-4 contains (A1) component of block branches structure and (A2) weight content ratio of random branched structure within scope 100:0-25:100, with outside the above range comparative example 1 compared with, there is more excellent thermal shock performance；
As shown in Table 1, embodiment of the present invention 1-4 contains (B1) component of linear chain structure and (B2) weight content ratio of branched structure within scope 100:0-10:100, with outside the above range comparative example 2 compared with, there is more excellent thermal shock performance；
As shown in Table 1, containing there is (A1) of block branches structure and there is (A2) component of random branched structure in the embodiment of the present invention 1,2 and 4, though with containing block branches structure (A1) but compared with there is no the embodiment 3 containing random branched structure (A2), there is the performance of the most excellent resistance to sulfuration.
Beneficial effects of the present invention: compared with prior art, the curable block type organopolysiloxane composition of the present invention and the semiconductor device of solidification thereof, not only maintain good sulfidation-resistance energy, higher refractive index, stronger hardness, but also there is the cold-hot impact property of excellence.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (16)
1. a curable block type organopolysiloxane composition, it is characterised in that it is at solid state
Under, temperature 25 DEG C, the hot strength under the conditions of humidity 60%RH is 1-8Mpa, and elongation at break is
50%-200%, refractive index is for equaling or exceeding 1.45, and described compositions includes:
(A1) R is included1 3SiO1/2Unit, [R2 2SiO2/2]mUnit and [R3SiO3/2]nThe block branches knot of unit
In structure organopolysiloxane, and every a part, m is more than or equal to 2, and n is more than or equal to 2；
(A2) it is independently selected from R1 3SiO1/2Unit, R2 2SiO2/2Unit and R3SiO3/2The random side chain of unit
Structure organopolysiloxane；
The weight content ratio of described component (A1) and component (A2) is 100:0-25:100；
(B1) the poly-Organhydridosiloxaneresins of linear chain structure, wherein, per molecule have average at least one with
The hydrogen atom of silicon bonding and at least one aromatic group；
(B2) it is independently selected from R4 3SiO1/2Unit, R5 2SiO2/2Unit and R6SiO3/2Random link of unit
The poly-Organhydridosiloxaneresins of structure；
The weight content ratio of described component (B1) and component (B2) is 100:0-10:100；
(C) consumption be enough to the hydrosilylation catalysts promoting said composition to solidify；
Wherein, described R1Selected from alkenyl that is identical or that differ, aromatic-free and unsaturated without aliphatic
The substituted or unsubstituted alkyl of unit price of key, described R2Selected from alkenyl that is identical or that differ, aromatic group,
Aromatic-free and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R3It it is aromatic group
Group；Described R4Selected from aromatic-free that is identical or that differ and without aliphatic unsaturated bond unit price replace or
Unsubstituted alkyl and hydrogen atom, described R5Selected from hydrogen atom that is identical or that differ, aromatic group, do not contain
Aromatic hydrocarbons and the substituted or unsubstituted alkyl of unit price without aliphatic unsaturated bond, described R6It it is aromatic group.
A kind of curable block type organopolysiloxane composition the most according to claim 1, it is special
Levying and be, the content sum of the aromatic group in component (A1) and (A2) is more than 10mol%, and component
(B1) the content sum of the aromatic group and in (B2) is more than 10mol%.
A kind of curable block type organopolysiloxane composition the most according to claim 3, it is special
Levy and be, [the R of component (A1)2 2SiO2/2]mThe content of the aromatic group in unit is more than 10mol%.
4. according to a kind of curable block type organopolysiloxane composition described in claim 1-3, its
Being characterised by, component (A1) viscosity at 25 DEG C is 500-100000mPa s.
5. according to a kind of curable block type organopolysiloxane composition described in claim 1-4, its
Being characterised by, component (A2) viscosity at 25 DEG C is more than 20000mPa s.
A kind of curable block type organopolysiloxane composition the most according to claim 1, it is special
Levying and be, the alkenyl content of component (A1) is 0.05-0.30mol/100g.
A kind of curable block type organopolysiloxane composition the most according to claim 1, it is special
Levying and be, in every a part, n is more than or equal to 3, and m is more than or equal to 5.
A kind of curable block type organopolysiloxane composition the most according to claim 1, it is special
Levying and be, component (B1) viscosity at 25 DEG C is 0.1-1000mPa s, and component (B2) is viscous at 25 DEG C
Degree is 0.1-10000mPa s.
A kind of curable block type organopolysiloxane composition the most according to claim 1, it is special
Levying and be, relative to the total composition of 100 weight portions, the consumption of component (A1) and (A2) is 50-95
Weight portion, the consumption of component (B1) and (B2) is 5-50 weight portion.
A kind of curable block type organopolysiloxane composition the most according to claim 1, its
Being characterised by, described (A1) has following average unit formula,
([R3SiO3/2]n)a([R2 2SiO2/2]m)b(R1 3SiO1/2)c,
Wherein R1Selected from alkenyl that is identical or that differ, the substituted or unsubstituted alkyl of unit price, R2Selected from phase
Same or that differ 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. a kind of curable block type organopolysiloxane compositions according to claim 1, its
Being characterised by, described (A2) has following average unit formula,
(R3SiO3/2)a1(R1 3SiO1/2)c1,
Wherein R1Selected from alkenyl that is identical or that differ, the substituted or unsubstituted alkyl of unit price, R3It is aromatics
Group, 0.7 < a1 < 0.95,0.05 < c1 < 0.3, and a1+c1=1.
12. a kind of curable block type organopolysiloxane compositions according to claim 1, its
Being characterised by, described (A2) has following average unit formula,
(R3SiO3/2)a2(R2 2SiO2/2)b2(R1 3SiO1/2)c2,
Wherein R1Selected from alkenyl that is identical or that differ, the substituted or unsubstituted alkyl of unit price, R2Selected from phase
Same or that differ 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. a kind of curable block type organopolysiloxane compositions according to claim 1, its
Being characterised by, described component (B1) is for including R4 3SiO1/2Unit and R5 2SiO2/2The linear chain structure of unit is gathered
Organhydridosiloxaneresins, R4Selected from aromatic-free that is identical or that differ and the list without aliphatic unsaturated bond
The substituted or unsubstituted alkyl of valency and hydrogen atom, R5Selected from aromatic-free that is identical or that differ and the most fatty
The substituted or unsubstituted alkyl of unit price, hydrogen atom and the aromatic group of race's unsaturated bond.
14. a kind of curable block type organopolysiloxane compositions according to claim 1, its
Being characterised by, described (B2) has following average unit formula,
(R6SiO3/2)a3(R4 3SiO1/2)c3,
Wherein R4Selected from the substituted or unsubstituted alkyl of unit price that is identical or that differ and hydrogen atom, R6It is aromatics
Group, 0.4 < a3 < 0.8,0.2 < c3 < 0.6, and a3+c3=1.
15. a kind of curable block type organopolysiloxane compositions according to claim 1, its
Being characterised by, described (B2) has following average unit formula,
(R6SiO3/2)a4(R5 2SiO2/2)b4(R4 3SiO1/2)c4,
Wherein R4Selected from the substituted or unsubstituted alkyl of unit price that is identical or that differ and hydrogen atom, R5Selected from phase
Same or that the differ 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. 1 kinds of semiconductor device, including light-emitting component and the support of fixing described light-emitting component, its feature
It is, described light-emitting component is coated with the curable block type described in any one of claim 1-15 organic
The solidfied material of polysiloxane composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510050973.0A CN105985649B (en) | 2015-01-30 | 2015-01-30 | Curable block type organopolysiloxane composition and semiconductor devices |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510050973.0A CN105985649B (en) | 2015-01-30 | 2015-01-30 | Curable block type organopolysiloxane composition and semiconductor devices |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105985649A true CN105985649A (en) | 2016-10-05 |
| CN105985649B CN105985649B (en) | 2019-03-19 |
Family
ID=57034616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510050973.0A Active CN105985649B (en) | 2015-01-30 | 2015-01-30 | Curable block type organopolysiloxane composition and semiconductor devices |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105985649B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541075A (en) * | 2017-09-28 | 2018-01-05 | 广州慧谷化学有限公司 | Heat molten type organopolysiloxane composition, fluorophor sheet material and semiconductor devices |
| CN112280044A (en) * | 2020-11-04 | 2021-01-29 | 山东省科学院新材料研究所 | A kind of low-viscosity high-strength toughened silicone resin composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206649A (en) * | 1997-07-25 | 1999-02-03 | 苗代次郎 | Cloth punching device using rotary punching-head and method thereof and pedestal on cloth punching device |
| CN101111565A (en) * | 2004-12-27 | 2008-01-23 | 陶氏康宁东丽株式会社 | Bonded composite of silicone resin and epoxy resin and a method for manufacturing thereof |
| CN101824222A (en) * | 2009-03-04 | 2010-09-08 | 信越化学工业株式会社 | Composition for encapsulating optical semiconductor and optical semiconductor device using same |
| CN103797073A (en) * | 2011-09-29 | 2014-05-14 | 道康宁东丽株式会社 | Curable silicone composition and cured product thereof |
-
2015
- 2015-01-30 CN CN201510050973.0A patent/CN105985649B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206649A (en) * | 1997-07-25 | 1999-02-03 | 苗代次郎 | Cloth punching device using rotary punching-head and method thereof and pedestal on cloth punching device |
| CN101111565A (en) * | 2004-12-27 | 2008-01-23 | 陶氏康宁东丽株式会社 | Bonded composite of silicone resin and epoxy resin and a method for manufacturing thereof |
| CN101824222A (en) * | 2009-03-04 | 2010-09-08 | 信越化学工业株式会社 | Composition for encapsulating optical semiconductor and optical semiconductor device using same |
| CN103797073A (en) * | 2011-09-29 | 2014-05-14 | 道康宁东丽株式会社 | Curable silicone composition and cured product thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541075A (en) * | 2017-09-28 | 2018-01-05 | 广州慧谷化学有限公司 | Heat molten type organopolysiloxane composition, fluorophor sheet material and semiconductor devices |
| CN107541075B (en) * | 2017-09-28 | 2021-07-23 | 广州慧谷化学有限公司 | Hot-melt organopolysiloxane composition, phosphor sheet, and semiconductor device |
| CN112280044A (en) * | 2020-11-04 | 2021-01-29 | 山东省科学院新材料研究所 | A kind of low-viscosity high-strength toughened silicone resin composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105985649B (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5524017B2 (en) | Addition-curable silicone composition and semiconductor device in which semiconductor element is coated with cured product of the composition | |
| KR102142263B1 (en) | Curable silicone composition and cured product thereof | |
| JP5766883B2 (en) | Adhesiveness imparting agent, adhesive polyorganosiloxane composition, and optical semiconductor device | |
| CN102300931B (en) | Curable silicone composition that provides a highly transparent cured silicone material | |
| KR101868167B1 (en) | Curable organopolysiloxane composition, sealing materials for optical device and optical device | |
| CN108350275A (en) | Addition curable silicone resin component, the manufacturing method of the composition and optical semiconductor device | |
| CN105733269A (en) | Curable silicone resin composition | |
| JP2004186168A (en) | Silicone resin composition for light emitting diode element | |
| CN101300305A (en) | Curable organic silicone composition | |
| JP2008019385A (en) | Curable silicone rubber composition and cured product thereof | |
| JP5971178B2 (en) | Silicone sealing material for solar cell module and solar cell module | |
| TWI754797B (en) | Addition hardening polysiloxane composition, polysiloxane cured product, and optical semiconductor device | |
| TW201248938A (en) | Silicone composition for sealing semiconductor | |
| CN106009687B (en) | Silicone materials, curable silicone compositions and optical devices | |
| JP2010180323A (en) | Curable silicone composition and cured product thereof | |
| JP2014031394A (en) | Addition curable silicone composition, and semiconductor apparatus comprising semiconductor element coated with cured material of said composition | |
| WO2020067015A1 (en) | Organopolysiloxane, silicone resin composition, and optical semiconductor device | |
| JP2006049533A (en) | Resin-sealed light emitting diode device and sealing method | |
| JP7530708B2 (en) | Curable organosilicon resin composition | |
| JP2010109034A (en) | Silicone resin composition for light-emitting diode element, and light-emitting diode element | |
| CN105199397B (en) | A kind of curable organopolysiloxane composition and semiconductor devices | |
| CN105985649B (en) | Curable block type organopolysiloxane composition and semiconductor devices | |
| CN105219097B (en) | A kind of curable rubber composition and semiconductor devices | |
| CN105440694A (en) | An organopolysiloxane composition, a preparing method thereof and a semiconductor device | |
| CN106317895A (en) | Solidifiable organic polysiloxane composition and semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510000, No. 62 Xinye Road, Guangzhou Economic and Technological Development Zone, Luogang District, Guangzhou City, Guangdong Province Patentee after: Guangzhou Huigu New Materials Technology Co.,Ltd. Country or region after: China Address before: No. 62 Xinye Road, Yonghe Economic and Technological Development Zone, Luogang District, Guangzhou City, Guangdong Province, 511356 Patentee before: GUANGZHOU HUMAN CHEM Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 62 Xinye Road, Guangzhou Economic and Technological Development Zone, Guangzhou City, Guangdong Province, 510000 Patentee after: Guangzhou Huigu New Materials Technology Co.,Ltd. Country or region after: China Address before: 510000, No. 62 Xinye Road, Guangzhou Economic and Technological Development Zone, Luogang District, Guangzhou City, Guangdong Province Patentee before: Guangzhou Huigu New Materials Technology Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |