JP2020070402A - Addition-curable silicone resin composition, cured product of the same, and optical semiconductor device - Google Patents
Addition-curable silicone resin composition, cured product of the same, and optical semiconductor device Download PDFInfo
- Publication number
- JP2020070402A JP2020070402A JP2018207307A JP2018207307A JP2020070402A JP 2020070402 A JP2020070402 A JP 2020070402A JP 2018207307 A JP2018207307 A JP 2018207307A JP 2018207307 A JP2018207307 A JP 2018207307A JP 2020070402 A JP2020070402 A JP 2020070402A
- Authority
- JP
- Japan
- Prior art keywords
- sio
- addition
- group
- curable silicone
- silicone resin
- 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
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 26
- 239000011342 resin composition Substances 0.000 title claims abstract description 23
- 230000003287 optical effect Effects 0.000 title claims description 24
- 239000004065 semiconductor Substances 0.000 title claims description 24
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 66
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 56
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 7
- FRBAZRWGNOJHRO-UHFFFAOYSA-N 6-tert-butylperoxycarbonyloxyhexyl (2-methylpropan-2-yl)oxy carbonate Chemical group CC(C)(C)OOC(=O)OCCCCCCOC(=O)OOC(C)(C)C FRBAZRWGNOJHRO-UHFFFAOYSA-N 0.000 claims description 5
- -1 polysiloxane Polymers 0.000 abstract description 50
- 239000000047 product Substances 0.000 description 34
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229940098779 methanesulfonic acid Drugs 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 8
- 239000002683 reaction inhibitor Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- IGJPWUZGPMLVDT-UHFFFAOYSA-N tris(ethenyl)-tris(ethenyl)silyloxysilane Chemical compound C=C[Si](C=C)(C=C)O[Si](C=C)(C=C)C=C IGJPWUZGPMLVDT-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 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
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Die Bonding (AREA)
- Led Device Packages (AREA)
Abstract
Description
本発明は、付加硬化型シリコーン樹脂組成物、その硬化物、及びこれらを用いた光半導体装置に関する。 The present invention relates to an addition-curable silicone resin composition, a cured product thereof, and an optical semiconductor device using the same.
最近、発光ダイオード（以下、「ＬＥＤ」という）素子の封止材及びダイボンド材は、ＬＥＤ素子の明るさ向上により素子の発熱が大きくなってきたため、耐久性が良好なシリコーン樹脂が使用されている（特許文献１、２）。特にダイボンド材においては樹脂が軟らかすぎると、ダイボンド工程の後に行われるワイヤーボンディング工程において、ボンディングができないという不具合が発生するため、高硬度のダイボンド材が求められている。 Recently, as a sealing material and a die-bonding material for a light emitting diode (hereinafter, referred to as “LED”) element, since heat generation of the element has increased due to improvement in brightness of the LED element, a silicone resin having good durability is used. (Patent Documents 1 and 2). Particularly in a die bond material, if the resin is too soft, a defect that bonding cannot be performed occurs in a wire bonding step performed after the die bond step. Therefore, a die bond material having high hardness is required.
また、ＬＥＤデバイスは近年小型化が進んでおり、より接着性の高いダイボンド剤が求められている。ダイボンド剤の接着力が不十分であると、ＬＥＤの製造におけるワイヤーボンディング工程でチップの剥離が発生してしまうなど、製造面で致命的な問題となる。これまのシリコーンダイボンド材は耐久性に優れるものの、接着性が不十分であり、より高いダイシェア強度を有する材料が望まれている。 Further, LED devices have been reduced in size in recent years, and a die bonding agent having higher adhesiveness has been demanded. If the adhesive strength of the die-bonding agent is insufficient, it causes a fatal problem in manufacturing such as chip separation in the wire bonding process in LED manufacturing. Although these silicone die bond materials are excellent in durability, they have insufficient adhesiveness, and a material having higher die shear strength is desired.
本発明は、上記事情に鑑みなされたものであって、硬度及びダイシェア強度に優れた硬化物を与える付加硬化型シリコーン樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an addition-curable silicone resin composition that gives a cured product excellent in hardness and die shear strength.
上記課題を解決するために、本発明では、
（Ａ）下記平均組成式（１）で表され、２５℃における粘度が５００ｍＰａ・ｓ以下であるオルガノポリシロキサン、
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２Ｒ１ＳｉＯ）ｃ（Ｒ１ ２ＳｉＯ）ｄ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ（ＳｉＯ４／２）ｇ （１）
（式中、Ｒ１はそれぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、Ｒ２はそれぞれ同一又は異なっていてもよいアルケニル基である。ａ，ｂ，ｃ，ｄ，ｅ，ｆおよびｇはそれぞれ、ａ≧０、ｂ≧０、ｃ≧０、ｄ≧０、ｅ≧０，ｆ≧０，およびｇ≧０を満たす数であり、ただし、ｂ＋ｃ＋ｅ＞０かつａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ＝１を満たす数である。）
（Ｂ）下記平均組成式（２）で表される分岐状のオルガノポリシロキサン：（Ａ）成分及び（Ｂ）成分の合計１００質量部に対して７０〜９５質量部、
（Ｒ１ ３ＳｉＯ１／２）ｈ（Ｒ２ ３ＳｉＯ１／２）ｉ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｊ（Ｒ２Ｒ１ＳｉＯ）ｋ（Ｒ１ ２ＳｉＯ）ｌ（Ｒ２ＳｉＯ３／２）ｍ（Ｒ１ＳｉＯ３／２）ｎ（ＳｉＯ４／２）ｏ （２）
（式中、Ｒ１及びＲ２は上記と同様である。ｈ，ｉ，ｊ，ｋ，ｌ，ｍ，ｎおよびｏはそれぞれ、ｈ≧０、ｉ＞０，ｊ≧０、ｋ≧０、ｌ≧０，ｍ≧０，ｎ≧０，およびｏ≧０を満たす数であり、ただし、ｍ＋ｎ＋ｏ＞０かつｈ＋ｉ＋ｊ＋ｋ＋ｌ＋ｍ＋ｎ＋ｏ＝１を満たす数である。）
（Ｃ）下記平均組成式（３）で表され、ケイ素原子に結合した水素原子を１分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン、
Ｒ３ ｐＨｑＳｉＯ（４−ｐ−ｑ）／２ （３）
（式中、Ｒ３は、それぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、ｐ及びｑは、０．７≦ｐ≦２．１、０．００１≦ｑ≦１．０、かつ０．８≦ｐ＋ｑ≦３．０を満たす数である。）
（Ｄ）白金族金属系触媒、
を含有するものであることを特徴とする付加硬化型シリコーン樹脂組成物を提供する。
In order to solve the above problems, in the present invention,
(A) An organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 500 mPa · s or less,
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 R 1 SiO) c (R 1 2 SiO) d (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (SiO 4/2 ) g (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R 2 is an alkenyl group which may be the same or different. a, b, c, d, e, f and g are numbers respectively satisfying a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0 and g ≧ 0, However, it is a number that satisfies b + c + e> 0 and a + b + c + d + e + f + g = 1.)
(B) Branched organopolysiloxane represented by the following average composition formula (2): 70 to 95 parts by mass based on 100 parts by mass of the total of the components (A) and (B),
(R 1 3 SiO 1/2 ) h (R 2 3 SiO 1/2 ) i (R 2 R 1 2 SiO 1/2 ) j (R 2 R 1 SiO) k (R 1 2 SiO) 1 (R 2 SiO 3/2 ) m (R 1 SiO 3/2 ) n (SiO 4/2 ) o (2)
(In the formula, R 1 and R 2 are the same as above. H, i, j, k, l, m, n and o are h ≧ 0, i> 0, j ≧ 0, k ≧ 0, It is a number that satisfies l ≧ 0, m ≧ 0, n ≧ 0, and o ≧ 0, provided that m + n + o> 0 and h + i + j + k + l + m + n + o = 1.)
(C) An organohydrogenpolysiloxane represented by the following average composition formula (3), having at least two hydrogen atoms bonded to silicon atoms in one molecule,
R 3 p H q SiO (4 -p-q) / 2 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and p and q are 0.7 ≦ p ≦ 2.1, (A number that satisfies 0.001 ≦ q ≦ 1.0 and 0.8 ≦ p + q ≦ 3.0.)
(D) Platinum group metal-based catalyst,
An addition-curable silicone resin composition comprising:
本発明の付加硬化型シリコーン樹脂組成物であれば、硬度及びダイシェア強度に優れた硬化物を与えることができる。 The addition-curable silicone resin composition of the present invention can give a cured product having excellent hardness and die shear strength.
本発明では、前記（Ａ）成分が下記平均組成式（１ａ）で表される分岐状オルガノポリシロキサンであることが好ましい。
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ （１ａ）
（式中、ａ，ｂ，ｅ，ｆは、ａ＋ｂ＞０、ｂ＋ｅ＞０、ｅ＋ｆ＞０であり、かつ、ａ＋ｂ＋ｅ＋ｆ＝１を満たす数である。）
In the present invention, the component (A) is preferably a branched organopolysiloxane represented by the following average composition formula (1a).
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (1a)
(In the formula, a, b, e, and f are numbers satisfying a + b> 0, b + e> 0, and e + f> 0, and satisfying a + b + e + f = 1.)
このような付加硬化型シリコーン樹脂組成物であれば、硬度及びダイシェア強度により優れた硬化物を与えることができる。 With such an addition-curable silicone resin composition, a cured product excellent in hardness and die shear strength can be provided.
本発明では、前記組成物中のアルケニル基以外のケイ素原子に結合した全一価炭化水素基の８０モル％以上がメチル基であることが好ましい。 In the present invention, it is preferable that 80 mol% or more of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups in the composition are methyl groups.
このような付加硬化型シリコーン樹脂組成物であれば、耐熱性、耐光性（耐紫外線性）、及び、熱ならびに紫外線等のストレスによる変色などの劣化に対する耐性に優れた硬化物を与えることができる。 Such an addition-curable silicone resin composition can give a cured product excellent in heat resistance, light resistance (UV resistance), and resistance to deterioration such as discoloration due to stress such as heat and ultraviolet rays. ..
本発明では、更に、有機過酸化物を含むものであることが好ましい。 In the present invention, it is preferable that it further contains an organic peroxide.
このような付加硬化型シリコーン樹脂組成物であれば、さらに強度の向上した硬化物を与えることができる。 With such an addition-curable silicone resin composition, a cured product having further improved strength can be provided.
この場合、前記有機過酸化物が、１，６−ビス（ｔ−ブチルペルオキシカルボニルオキシ）ヘキサンであることがより好ましい。 In this case, it is more preferable that the organic peroxide is 1,6-bis (t-butylperoxycarbonyloxy) hexane.
このような付加硬化型シリコーン樹脂組成物であれば、さらに一層強度の向上した硬化物を与えることができる。 With such an addition-curable silicone resin composition, a cured product having further improved strength can be provided.
また、本発明は、上記付加硬化型シリコーン樹脂組成物の硬化物であることを特徴とするシリコーン硬化物を提供する。 The present invention also provides a silicone cured product, which is a cured product of the addition-curable silicone resin composition.
このようなシリコーン硬化物であれば、硬度及びダイシェア強度に優れ、基板・ＬＥＤチップ等への接着力が高い組成物、特にＬＥＤ素子等のダイボンディングに用いられるダイボンド材として有用である。 Such a silicone cured product is useful as a composition having excellent hardness and die shear strength and high adhesiveness to substrates, LED chips and the like, particularly as a die bond material used for die bonding of LED elements and the like.
また、本発明は、上記シリコーン硬化物で光半導体素子がダイボンディングされたものである光半導体装置を提供する。 The present invention also provides an optical semiconductor device in which an optical semiconductor element is die-bonded with the above-mentioned silicone cured product.
このような光半導体装置であれば、硬度及びダイシェア強度に優れ、基板・ＬＥＤチップ等への接着力が高いダイボンド材として上記シリコーン硬化物を用いているため、信頼性が高いものとなる。 In such an optical semiconductor device, the silicone cured product is used as a die bond material that is excellent in hardness and die shear strength and has high adhesiveness to substrates, LED chips, and the like, and therefore has high reliability.
以上のように、本発明の付加硬化型シリコーン樹脂組成物であれば、硬度及びダイシェア強度に優れたシリコーン硬化物を与え、ＬＥＤ素子等のダイボンディングに用いられるダイボンド材として特に有用なものである。そして、ダイボンド工程の後に行われるワイヤーボンディング工程において、チップの剥離や、ボンディングができないという不具合が発生し難いため、このシリコーン硬化物で光半導体素子がダイボンディングされた光半導体装置は、信頼性が高く、その生産性も向上する。 As described above, the addition-curable silicone resin composition of the present invention gives a silicone cured product having excellent hardness and die shear strength, and is particularly useful as a die bonding material used for die bonding of LED elements and the like. .. Then, in the wire bonding process performed after the die bonding process, the chip peeling and the defect that the bonding cannot be performed are unlikely to occur. Therefore, the optical semiconductor device in which the optical semiconductor element is die-bonded with the silicone cured product has high reliability. It is expensive and its productivity is improved.
上述のように、硬度及びダイシェア強度に優れた硬化物を与え、ＬＥＤ素子等のダイボンディングに用いられるダイボンド材となるシリコーン硬化物を与えるシリコーン組成物の開発が求められていた。 As described above, there has been a demand for the development of a silicone composition that gives a cured product excellent in hardness and die shear strength and a silicone cured product that serves as a die bonding material used for die bonding of LED elements and the like.
本発明者らは、上記課題について鋭意検討を重ねた結果、後述する（Ａ）、（Ｂ）、（Ｃ）、及び（Ｄ）成分を含む付加硬化型シリコーン組成物であれば、上記課題を達成できることを見出し、本発明を完成させた。 As a result of earnest studies on the above problems, the present inventors have found that the above problems would be solved if the addition-curable silicone composition contains the components (A), (B), (C), and (D) described below. The inventors have found that they can be achieved and completed the present invention.
即ち、本発明は、（Ａ）下記平均組成式（１）で表され、２５℃における粘度が５００ｍＰａ・ｓ以下であるオルガノポリシロキサン、
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２Ｒ１ＳｉＯ）ｃ（Ｒ１ ２ＳｉＯ）ｄ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ（ＳｉＯ４／２）ｇ （１）
（式中、Ｒ１はそれぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、Ｒ２はそれぞれ同一又は異なっていてもよいアルケニル基である。ａ，ｂ，ｃ，ｄ，ｅ，ｆおよびｇはそれぞれ、ａ≧０、ｂ≧０、ｃ≧０、ｄ≧０、ｅ≧０，ｆ≧０，およびｇ≧０を満たす数であり、ただし、ｂ＋ｃ＋ｅ＞０かつａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ＝１を満たす数である。）
（Ｂ）下記平均組成式（２）で表される分岐状のオルガノポリシロキサン：（Ａ）成分及び（Ｂ）成分の合計１００質量部に対して７０〜９５質量部、
（Ｒ１ ３ＳｉＯ１／２）ｈ（Ｒ２ ３ＳｉＯ１／２）ｉ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｊ（Ｒ２Ｒ１ＳｉＯ）ｋ（Ｒ１ ２ＳｉＯ）ｌ（Ｒ２ＳｉＯ３／２）ｍ（Ｒ１ＳｉＯ３／２）ｎ（ＳｉＯ４／２）ｏ （２）
（式中、Ｒ１及びＲ２は上記と同様である。ｈ，ｉ，ｊ，ｋ，ｌ，ｍ，ｎおよびｏはそれぞれ、ｈ≧０、ｉ＞０，ｊ≧０、ｋ≧０、ｌ≧０，ｍ≧０，ｎ≧０，およびｏ≧０を満たす数であり、ただし、ｍ＋ｎ＋ｏ＞０かつｈ＋ｉ＋ｊ＋ｋ＋ｌ＋ｍ＋ｎ＋ｏ＝１を満たす数である。）
（Ｃ）下記平均組成式（３）で表され、ケイ素原子に結合した水素原子を１分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン、
Ｒ３ ｐＨｑＳｉＯ（４−ｐ−ｑ）／２ （３）
（式中、Ｒ３は、それぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、ｐ及びｑは、０．７≦ｐ≦２．１、０．００１≦ｑ≦１．０、かつ０．８≦ｐ＋ｑ≦３．０を満たす数である。）
（Ｄ）白金族金属系触媒、
を含有するものであることを特徴とする付加硬化型シリコーン樹脂組成物である。
That is, the present invention provides (A) an organopolysiloxane represented by the following average composition formula (1), which has a viscosity at 25 ° C. of 500 mPa · s or less,
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 R 1 SiO) c (R 1 2 SiO) d (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (SiO 4/2 ) g (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R 2 is an alkenyl group which may be the same or different. a, b, c, d, e, f and g are numbers respectively satisfying a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0 and g ≧ 0, However, it is a number that satisfies b + c + e> 0 and a + b + c + d + e + f + g = 1.)
(B) Branched organopolysiloxane represented by the following average composition formula (2): 70 to 95 parts by mass based on 100 parts by mass of the total of the components (A) and (B),
(R 1 3 SiO 1/2 ) h (R 2 3 SiO 1/2 ) i (R 2 R 1 2 SiO 1/2 ) j (R 2 R 1 SiO) k (R 1 2 SiO) 1 (R 2 SiO 3/2 ) m (R 1 SiO 3/2 ) n (SiO 4/2 ) o (2)
(In the formula, R 1 and R 2 are the same as above. H, i, j, k, l, m, n and o are h ≧ 0, i> 0, j ≧ 0, k ≧ 0, It is a number that satisfies l ≧ 0, m ≧ 0, n ≧ 0, and o ≧ 0, provided that m + n + o> 0 and h + i + j + k + l + m + n + o = 1.)
(C) An organohydrogenpolysiloxane represented by the following average composition formula (3), having at least two hydrogen atoms bonded to silicon atoms in one molecule,
R 3 p H q SiO (4 -p-q) / 2 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and p and q are 0.7 ≦ p ≦ 2.1, (A number that satisfies 0.001 ≦ q ≦ 1.0 and 0.8 ≦ p + q ≦ 3.0.)
(D) Platinum group metal-based catalyst,
An addition-curable silicone resin composition comprising:
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
［付加硬化型シリコーン組成物］
本発明の付加硬化型シリコーン組成物は、後述する（Ａ）〜（Ｄ）成分を含有するものである。
以下、各成分について詳細に説明する。
[Addition-curable silicone composition]
The addition-curable silicone composition of the present invention contains the components (A) to (D) described below.
Hereinafter, each component will be described in detail.
＜（Ａ）成分＞
（Ａ）成分は、下記平均組成式（１）で表されるオルガノポリシロキサンである。
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２Ｒ１ＳｉＯ）ｃ（Ｒ１ ２ＳｉＯ）ｄ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ（ＳｉＯ４／２）ｇ （１）
（式中、Ｒ１はそれぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、Ｒ２はそれぞれ同一又は異なっていてもよいアルケニル基である。ａ，ｂ，ｃ，ｄ，ｅ，ｆおよびｇはそれぞれ、ａ≧０、ｂ≧０、ｃ≧０、ｄ≧０、ｅ≧０，ｆ≧０，およびｇ≧０を満たす数であり、ただし、ｂ＋ｃ＋ｅ＞０かつａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ＝１を満たす数である。）
<(A) component>
The component (A) is an organopolysiloxane represented by the following average composition formula (1).
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 R 1 SiO) c (R 1 2 SiO) d (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (SiO 4/2 ) g (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R 2 is an alkenyl group which may be the same or different. a, b, c, d, e, f and g are numbers respectively satisfying a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0 and g ≧ 0, However, it is a number that satisfies b + c + e> 0 and a + b + c + d + e + f + g = 1.)
（Ａ）成分の粘度は、２５℃における回転粘度計による測定値が５００ｍＰａ・ｓ以下であり、１００ｍＰａ・ｓ以下であることが好ましい。５００ｍＰａ・ｓを超える場合には、組成物の粘度が高くなるため、ダイボンダーによってＬＥＤ基板に組成物を塗布する工程において取り扱いが困難である。なお、以下において特に断らない限り、粘度は２５℃における回転粘度計による測定値である。 Regarding the viscosity of the component (A), the value measured by a rotational viscometer at 25 ° C. is 500 mPa · s or less, and preferably 100 mPa · s or less. If it exceeds 500 mPa · s, the viscosity of the composition becomes high, so that it is difficult to handle in the step of applying the composition to the LED substrate by the die bonder. Unless otherwise specified below, the viscosity is a value measured by a rotational viscometer at 25 ° C.
Ｒ１で表されるアルケニル基を含まない置換または非置換の一価炭化水素基としては、アルケニル基を有しないものであれば特に限定されるものではないが、炭素数１〜８の置換又は非置換の一価炭化水素が好ましい。この一価炭化水素としては、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基、シクロペンチル基等のシクロアルキル基、フェニル基、トリル基、キシリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、クロロメチル基、クロロプロピル基、クロロシクロヘキシル基等のハロゲン化炭化水素基等が例示される。好ましくはアルキル基であり、特に好ましいのはメチル基である。 The substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group represented by R 1 is not particularly limited as long as it does not have an alkenyl group, but may be a substituted or unsubstituted C 1-8 group. Unsubstituted monovalent hydrocarbons are preferred. Examples of the monovalent hydrocarbon include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, aryl groups such as phenyl group, tolyl group and xylyl group, and benzyl group. Examples thereof include aralkyl groups such as phenylethyl group, halogenated hydrocarbon groups such as chloromethyl group, chloropropyl group and chlorocyclohexyl group. An alkyl group is preferable, and a methyl group is particularly preferable.
Ｒ２で表されるアルケニル基としては、ビニル基、アリル基、エチニル基等の炭素数２〜１０、特に２〜６のアルケニル基が好ましく、特にビニル基が好ましい。 The alkenyl group represented by R 2 is preferably an alkenyl group having 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms, such as vinyl group, allyl group and ethynyl group, and particularly preferably vinyl group.
（Ａ）成分は下記平均組成式（１ａ）で表される分岐状オルガノポリシロキサンであることが好ましい。
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ （１ａ）
（式中、ａ，ｂ，ｅ，ｆは、ａ＋ｂ＞０、ｂ＋ｅ＞０、ｅ＋ｆ＞０であり、かつ、ａ＋ｂ＋ｅ＋ｆ＝１を満たす数である。）
The component (A) is preferably a branched organopolysiloxane represented by the following average composition formula (1a).
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (1a)
(In the formula, a, b, e, and f are numbers satisfying a + b> 0, b + e> 0, and e + f> 0, and satisfying a + b + e + f = 1.)
分岐状オルガノポリシロキサンの具体例としては、下記式で表されるもの等が挙げられる。
（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．５（（ＣＨ３）ＳｉＯ３／２）０．５、
（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．５（（ＣＨ２＝ＣＨ）ＳｉＯ３／２）０．５、
（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．５（（ＣＨ３）ＳｉＯ３／２）０．３（（ＣＨ２＝ＣＨ）ＳｉＯ３／２）０．２、
（（ＣＨ３）３ＳｉＯ１／２）０．４（（ＣＨ２＝ＣＨ）ＳｉＯ３／２）０．６、
（（ＣＨ３）３ＳｉＯ１／２）０．４（（ＣＨ３）ＳｉＯ３／２）０．３（（ＣＨ２＝ＣＨ）ＳｉＯ３／２）０．３
Specific examples of the branched organopolysiloxane include those represented by the following formula.
((CH 2 = CH) ( CH 3) 2 SiO 1/2) 0.5 ((CH 3) SiO 3/2) 0.5,
((CH 2 = CH) ( CH 3) 2 SiO 1/2) 0.5 ((CH 2 = CH) SiO 3/2) 0.5,
((CH 2 = CH) ( CH 3) 2 SiO 1/2) 0.5 ((CH 3) SiO 3/2) 0.3 ((CH 2 = CH) SiO 3/2) 0.2,
((CH 3) 3 SiO 1/2 ) 0.4 ((CH 2 = CH) SiO 3/2) 0.6,
((CH 3) 3 SiO 1/2 ) 0.4 ((CH 3) SiO 3/2) 0.3 ((CH 2 = CH) SiO 3/2) 0.3
（Ａ）成分は、直鎖状の分子構造を有するオルガノポリシロキサンを使用してもよい。
（Ａ）成分の直鎖状オルガノポリシロキサンの具体例としては、両末端メチルフェニルビニル基封鎖ジフェニルシロキサン、片末端メチルフェニルビニル基片末端ジフェニルビニル基封鎖ジフェニルシロキサン、両末端ジフェニルビニル基封鎖ジフェニルシロキサン、両末端ジフェニルビニル基封鎖ジフェニルシロキサン・メチルフェニルシロキサン共重合体、両末端ジメチルビニル基封鎖ジフェニルシロキサン、片末端ジメチルビニル基片末端メチルフェニルビニル基封鎖ジフェニルシロキサン、両末端ジメチルビニル基封鎖メチルフェニルシロキサン、片末端ジメチルビニル基片末端メチルフェニルビニル基封鎖メチルフェニルシロキサン等が挙げられる。上記オルガノポリシロキサンは一種単独でも二種以上を併用してもよい。
As the component (A), an organopolysiloxane having a linear molecular structure may be used.
Specific examples of the straight-chain organopolysiloxane as the component (A) include diphenylsiloxane blocked with methylphenylvinyl groups at both ends, diphenylsiloxane blocked with methylphenylvinyl groups at one end and diphenylvinyl groups blocked at one end with diphenylvinyl groups blocked at both ends. , Diphenylvinyl group-blocked diphenylsiloxane / methylphenylsiloxane copolymer, both terminals dimethylvinyl group-blocked diphenylsiloxane, one terminal dimethylvinyl group, one terminal methylphenylvinyl group-blocked diphenylsiloxane, both terminals dimethylvinyl group-blocked methylphenylsiloxane , One end dimethyl vinyl group, one end methyl phenyl vinyl group blocked methyl phenyl siloxane, and the like. The above organopolysiloxanes may be used alone or in combination of two or more.
上記直鎖状オルガノポリシロキサンの他の具体例としては、下記式で表される化合物が挙げられる。
（Ａ）成分は、一種単独で用いても二種以上を併用してもよい。 As the component (A), one type may be used alone, or two or more types may be used in combination.
＜（Ｂ）成分＞
（Ｂ）成分は下記平均組成式（２）で表される分岐状オルガノポリシロキサンである。
（Ｒ１ ３ＳｉＯ１／２）ｈ（Ｒ２ ３ＳｉＯ１／２）ｉ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｊ（Ｒ２Ｒ１ＳｉＯ）ｋ（Ｒ１ ２ＳｉＯ）ｌ（Ｒ２ＳｉＯ３／２）ｍ（Ｒ１ＳｉＯ３／２）ｎ（ＳｉＯ４／２）ｏ （２）
（式中、Ｒ１及びＲ２は上記と同様である。ｈ，ｉ，ｊ，ｋ，ｌ，ｍ，ｎおよびｏはそれぞれ、ｈ≧０、ｉ＞０，ｊ≧０、ｋ≧０、ｌ≧０，ｍ≧０，ｎ≧０，およびｏ≧０を満たす数であり、ただし、ｍ＋ｎ＋ｏ＞０かつｈ＋ｉ＋ｊ＋ｋ＋ｌ＋ｍ＋ｎ＋ｏ＝１を満たす数である。）
<(B) component>
The component (B) is a branched organopolysiloxane represented by the following average composition formula (2).
(R 1 3 SiO 1/2 ) h (R 2 3 SiO 1/2 ) i (R 2 R 1 2 SiO 1/2 ) j (R 2 R 1 SiO) k (R 1 2 SiO) 1 (R 2 SiO 3/2 ) m (R 1 SiO 3/2 ) n (SiO 4/2 ) o (2)
(In the formula, R 1 and R 2 are the same as above. H, i, j, k, l, m, n and o are h ≧ 0, i> 0, j ≧ 0, k ≧ 0, It is a number that satisfies l ≧ 0, m ≧ 0, n ≧ 0, and o ≧ 0, provided that m + n + o> 0 and h + i + j + k + l + m + n + o = 1.)
Ｒ１は、（Ａ）成分において例示されたものと同様のものが挙げられ、好ましくはアルキル基であり、特に好ましいのはメチル基である。 Examples of R 1 include those similar to those exemplified in the component (A), preferably an alkyl group, and particularly preferably a methyl group.
Ｒ２は、（Ａ）成分において例示されたものと同様のものが挙げられ、好ましくは炭素数２〜１０のアルケニル基、より好ましくは炭素数２〜６のアルケニル基であり、特にビニル基が好ましい。 Examples of R 2 include those similar to those exemplified in the component (A), preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly a vinyl group. preferable.
上記平均組成式（２）中、ｈは０〜０．６５、ｉは０．１〜０．６５、ｊは０〜０．６５、ｋは０〜０．５、ｌは０〜０．５、ｍは０〜０．８、ｎは０〜０．８、ｏは０〜０．６の数であることが好ましい。ｍ＋ｎ＋ｏは好ましくは０．０５以上、より好ましくは０．１〜０．９であり、特に０．２〜０．６の数であることが好ましい。 In the above average composition formula (2), h is 0 to 0.65, i is 0.1 to 0.65, j is 0 to 0.65, k is 0 to 0.5, and 1 is 0 to 0.5. , M is 0 to 0.8, n is 0 to 0.8, and o is preferably 0 to 0.6. m + n + o is preferably 0.05 or more, more preferably 0.1 to 0.9, and particularly preferably 0.2 to 0.6.
（Ｂ）成分中、ケイ素原子に結合したアルケニル基の含有量は、（Ｂ）成分１００ｇああたり０．０１〜１ｍｏｌの範囲であることが好ましく、０．１〜０．６ｍｏｌの範囲であることがより好ましい。上記含有量が０．０１〜１ｍｏｌの範囲であると、架橋反応が十分に進行し、より高い硬度の硬化物が得られる。 In the component (B), the content of the alkenyl group bonded to the silicon atom is preferably in the range of 0.01 to 1 mol per 100 g of the component (B), and in the range of 0.1 to 0.6 mol. Is more preferable. When the content is in the range of 0.01 to 1 mol, the crosslinking reaction proceeds sufficiently and a cured product having higher hardness can be obtained.
（Ｂ）成分のオルガノポリシロキサンは、単離のしやすさの点から重量平均分子量が５００〜１００，０００の範囲であるものが好適である。 The organopolysiloxane as the component (B) preferably has a weight average molecular weight in the range of 500 to 100,000 from the viewpoint of easy isolation.
上記（Ｂ）成分は、Ｒ２ ３ＳｉＯ１／２単位を有すること（即ち、ｉ＞０であること）により、本発明の組成物から得られる硬化物に接着強度を与える事ができる。また、（Ｂ）成分は、ＳｉＯ４／２単位及び／又はＳｉＯ３／２単位からなる分岐構造を必須とするが、さらにメチルビニルシロキシ単位、ジメチルシロキシ単位等のＳｉＯ２／２（ＳｉＯ）単位、ジメチルビニルシロキシ単位、トリメチルシロキシ単位等のＳｉＯ１／２単位を含んでもよい。ＳｉＯ４／２単位及び／又はＳｉＯ３／２単位の含有量は、好ましくは（Ｂ）成分のオルガノポリシロキサン樹脂中の全シロキサン単位の５モル％以上、より好ましくは１０モル〜９０モル％、特に好ましくは２０〜６０モル％である。 Since the component (B) has R 2 3 SiO 1/2 units (that is, i> 0), the cured product obtained from the composition of the present invention can have adhesive strength. Further, the component (B) essentially requires a branched structure composed of SiO 4/2 units and / or SiO 3/2 units, but further contains SiO 2/2 (SiO) units such as methylvinylsiloxy units and dimethylsiloxy units. , SiO 2 units such as dimethylvinylsiloxy units and trimethylsiloxy units. The content of SiO 4/2 units and / or SiO 3/2 units is preferably 5 mol% or more, more preferably 10 mol to 90 mol% of all siloxane units in the organopolysiloxane resin of component (B). Particularly preferably, it is 20 to 60 mol%.
（Ｂ）成分の配合量は、（Ａ）成分及び（Ｂ）成分の合計１００質量部に対して７０〜９５質量部であり、好ましくは７５〜９５質量部であり、より好ましくは８０〜９０質量部である。（Ｂ）成分の配合量が７０質量部未満の場合には、接着性に劣ったり、高硬度の硬化物が得られないことがあり、９５質量部を超える場合には、組成物の粘度が著しく高くなり、転写することが困難となり、組成物をダイボンド材などに用いる際の取り扱いが困難になる。 The blending amount of the component (B) is 70 to 95 parts by mass, preferably 75 to 95 parts by mass, more preferably 80 to 90 parts by mass based on 100 parts by mass of the total of the components (A) and (B). It is a mass part. If the blending amount of the component (B) is less than 70 parts by mass, adhesiveness may be inferior or a cured product with high hardness may not be obtained, and if it exceeds 95 parts by mass, the viscosity of the composition may be low. It becomes remarkably high, transfer becomes difficult, and handling becomes difficult when the composition is used as a die bond material or the like.
（Ｂ）成分の分岐状オルガノポリシロキサンの具体例としては、例えば、以下のものが挙げられる。
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．１（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．２（（ＣＨ３）３ＳｉＯ１／２）０．３５（ＳｉＯ４／２）０．３５、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．２（（ＣＨ３）３ＳｉＯ１／２）０．１（ＳｉＯ４／２）０．７、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．０７（（ＣＨ３）３ＳｉＯ１／２）０．４（ＳｉＯ３／２）０．５３、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．１４（（ＣＨ３）３ＳｉＯ１／２）０．３２（ＳｉＯ３／２）０．５４、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．０７（（ＣＨ３）３ＳｉＯ１／２）０．３３（ＳｉＯ３／２）０．６、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．１（（ＣＨ３）３ＳｉＯ１／２）０．１（（ＣＨ３）２ＳｉＯ）０．２（（ＣＨ３）ＳｉＯ３／２）０．６、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．０７（（ＣＨ３）３ＳｉＯ１／２）０．１３（（ＣＨ３）２ＳｉＯ）０．２（ＳｉＯ４／２）０．６、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．３（ＳｉＯ４／２）０．７、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．２（（ＣＨ３）ＳｉＯ３／２）０．８、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．２（（ＣＨ３）ＳｉＯ３／２）０．６（ＳｉＯ４／２）０．２、
Specific examples of the branched organopolysiloxane of the component (B) include the following.
((CH 2 = CH) 3 SiO 1/2) 0.1 ((CH 2 = CH) (CH 3) 2 SiO 1/2) 0.2 ((CH 3) 3 SiO 1/2) 0.35 (SiO 4/2 ) 0.35 ,
((CH 2 = CH) 3 SiO 1/2) 0.2 ((CH 3) 3 SiO 1/2) 0.1 (SiO 4/2) 0.7,
((CH 2 = CH) 3 SiO 1/2) 0.07 ((CH 3) 3 SiO 1/2) 0.4 (SiO 3/2) 0.53,
((CH 2 = CH) 3 SiO 1/2) 0.14 ((CH 3) 3 SiO 1/2) 0.32 (SiO 3/2) 0.54,
((CH 2 = CH) 3 SiO 1/2) 0.07 ((CH 3) 3 SiO 1/2) 0.33 (SiO 3/2) 0.6,
((CH 2 = CH) 3 SiO 1/2) 0.1 ((CH 3) 3 SiO 1/2) 0.1 ((CH 3) 2 SiO) 0.2 ((CH 3) SiO 3/2 ) 0.6 ,
((CH 2 = CH) 3 SiO 1/2) 0.07 ((CH 3) 3 SiO 1/2) 0.13 ((CH 3) 2 SiO) 0.2 (SiO 4/2) 0.6 ,
((CH 2 = CH) 3 SiO 1/2) 0.3 (SiO 4/2) 0.7,
((CH 2 = CH) 3 SiO 1/2) 0.2 ((CH 3) SiO 3/2) 0.8,
((CH 2 = CH) 3 SiO 1/2) 0.2 ((CH 3) SiO 3/2) 0.6 (SiO 4/2) 0.2,
（Ｂ）成分は、一種単独で用いても二種以上を併用してもよい。 As the component (B), one type may be used alone, or two or more types may be used in combination.
＜（Ｃ）成分＞
（Ｃ）成分は、（Ａ）成分及び（Ｂ）成分中に含まれるアルケニル基とヒドロシリル化反応により架橋する架橋剤として作用する。（Ｃ）成分は、下記平均組成式（３）で表され、ケイ素原子に結合した水素原子（即ち、Ｓｉ−Ｈ基）を１分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサンである。
Ｒ３ ｐＨｑＳｉＯ（４−ｐ−ｑ）／２ （３）
（式中、Ｒ３は、それぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、ｐ及びｑは、０．７≦ｐ≦２．１、０．００１≦ｑ≦１．０、かつ０．８≦ｐ＋ｑ≦３．０、好ましくは１．０≦ｐ≦２．０、０．０１≦ｑ≦１．０、かつ１．５≦ｐ＋ｑ≦２．５を満たす数である。）
<(C) component>
The component (C) acts as a cross-linking agent that cross-links the alkenyl groups contained in the components (A) and (B) by a hydrosilylation reaction. The component (C) is an organohydrogenpolysiloxane represented by the following average composition formula (3) and having at least two hydrogen atoms bonded to silicon atoms (that is, Si—H groups) in one molecule.
R 3 p H q SiO (4 -p-q) / 2 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and p and q are 0.7 ≦ p ≦ 2.1, 0.001 ≦ q ≦ 1.0 and 0.8 ≦ p + q ≦ 3.0, preferably 1.0 ≦ p ≦ 2.0, 0.01 ≦ q ≦ 1.0, and 1.5 ≦ p + q ≦ It is a number that satisfies 2.5.)
（Ｃ）成分の２５℃における粘度は、好ましくは１００ｍＰａ・ｓ以下、より好ましくは５〜１００ｍＰａ・ｓの範囲である。 The viscosity of the component (C) at 25 ° C. is preferably 100 mPa · s or less, more preferably 5 to 100 mPa · s.
Ｒ３は、（Ａ）成分においてＲ１として例示されたものと同様のものが挙げられ、好ましくはアルキル基であり、特に好ましいのはメチル基である。 Examples of R 3 include those similar to those exemplified as R 1 in the component (A), preferably an alkyl group, and particularly preferably a methyl group.
なお、本発明の組成物中のＲ１およびＲ３で表されるアルケニル基以外のケイ素原子に結合した全一価炭化水素基の全数に占めるメチル基の割合は８０モル％以上である（前記全一価炭化水素基の８０モル％以上がメチル基である）ことが好ましく、特に９０モル％以上であることが、耐熱性、耐光性（耐紫外線性）、及び、熱ならびに紫外線等のストレスによる変色などの劣化に対する耐性に優れるため好ましい。 The proportion of methyl groups in the total number of all monovalent hydrocarbon groups bonded to silicon atoms other than the alkenyl groups represented by R 1 and R 3 in the composition of the present invention is 80 mol% or more. 80 mol% or more of all monovalent hydrocarbon groups is preferably a methyl group), and particularly 90 mol% or more is heat resistance, light resistance (UV resistance), and stress such as heat and UV rays. It is preferable because it has excellent resistance to deterioration such as discoloration due to.
（Ｃ）成分は、ケイ素原子に結合した水素原子（Ｓｉ−Ｈ基）を１分子中に少なくとも２個有し、好ましくは２〜２００個、より好ましくは３〜１００個、特に好ましくは４〜５０個である。 The component (C) has at least two hydrogen atoms (Si-H groups) bonded to a silicon atom in one molecule, preferably 2 to 200, more preferably 3 to 100, and particularly preferably 4 to. It is 50 pieces.
（Ｃ）成分のオルガノハイドロジェンポリシロキサンの分子構造は直鎖状、環状、分岐状、三次元網状構造のいずれであってもよいが、一分子中のケイ素原子の数は好ましくは２〜３００個、より好ましくは３〜２００個である。 The molecular structure of the organohydrogenpolysiloxane as the component (C) may be linear, cyclic, branched or three-dimensional network structure, but the number of silicon atoms in one molecule is preferably 2 to 300. The number is more preferably 3 to 200.
（Ｃ）成分のオルガノハイドロジェンポリシロキサンとしては、１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、トリス（ハイドロジェンジメチルシロキシ）メチルシラン、トリス（ハイドロジェンジメチルシロキシ）フェニルシラン、メチルハイドロジェンシクロポリシロキサン、メチルハイドロジェンシロキサン・ジメチルシロキサン環状共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・メチルフェニルシロキサン・ジメチルシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン・ジフェニルシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン・メチルフェニルシロキサン共重合体、（ＣＨ３）２ＨＳｉＯ１／２単位と（ＣＨ３）３ＳｉＯ１／２単位とＳｉＯ４／２単位とからなる共重合体、（ＣＨ３）２ＨＳｉＯ１／２単位とＳｉＯ４／２単位とからなる共重合体、（ＣＨ３）２ＨＳｉＯ１／２単位とＳｉＯ４／２単位と（Ｃ６Ｈ５）３ＳｉＯ１／２単位とからなる共重合体等が挙げられるほか、下記一般式（４）又は（５）で表されるものが挙げられる。
Ｒ３ ３ＳｉＯ［ＳｉＲ３（Ｈ）Ｏ］ｒＳｉＲ３ ３ （４）
環状の［ＳｉＲ３（Ｈ）Ｏ］ｓ （５）
（式中、Ｒ３は前記のとおりであり、ｒは２〜４０、好ましくは８〜３５の整数であり、ｓは６〜８の整数である。）
Examples of the organohydrogenpolysiloxane as the component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, and tris. (Hydrogen dimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methyl hydrogen polysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methyl at both ends Hydrogen siloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both ends, dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane at both ends Dimethyl siloxane / methyl hydrogen siloxane copolymer with both ends dimethyl hydrogen siloxy groups, methyl hydrogen siloxane / diphenyl siloxane copolymer with both ends trimethyl siloxy groups, methyl hydrogen siloxane / diphenyl siloxane with both ends trimethyl siloxy groups Dimethyl siloxane copolymer, trimethylsiloxy group-blocked methyl hydrogen siloxane / methylphenyl siloxane / dimethyl siloxane copolymer at both ends, dimethyl hydrogen siloxy group-blocked methyl hydrogen siloxane / dimethyl siloxane / diphenyl siloxane copolymer at both ends, both Terminal dimethyl hydrogen siloxy group-blocked methyl hydrogen siloxane / dimethyl siloxane / methyl phenyl siloxane Polymer, (CH 3) 2 HSiO 1/2 units and (CH 3) 3 made of SiO 1/2 units and SiO 4/2 units, copolymers, (CH 3) 2 HSiO 1/2 units and SiO 4 And a copolymer composed of (CH 3 ) 2 HSiO 1/2 units, a SiO 4/2 unit, and a (C 6 H 5 ) 3 SiO 1/2 unit, and the like. And those represented by the following general formula (4) or (5).
R 3 3 SiO [SiR 3 (H) O] r SiR 3 3 (4)
Cyclic [SiR 3 (H) O] s (5)
(In the formula, R 3 is as described above, r is an integer of 2 to 40, preferably 8 to 35, and s is an integer of 6 to 8.)
（Ｃ）成分の具体例としては、下記一般式（６）で表されるものや、
Ｍｅ３ＳｉＯ［ＳｉＭｅ（Ｈ）Ｏ］ｒＳｉＭｅ３ （６）
（式中、ｒは前記のとおりである。Ｍｅはメチル基である。）
下記式で表されるもの等が挙げられる。
Me 3 SiO [SiMe (H) O] r SiMe 3 (6)
(In the formula, r is as described above. Me is a methyl group.)
Examples include those represented by the following formula.
（Ｃ）成分のオルガノハイドロジェンポリシロキサンは、一種単独で用いても二種以上を併用してもよい。 The organohydrogenpolysiloxane as the component (C) may be used alone or in combination of two or more.
（Ｃ）成分の配合量は、架橋のバランスの観点から、（Ａ）および（Ｂ）成分中の全ケイ素原子に結合したアルケニル基の合計数に対して（Ｃ）成分中のケイ素原子に結合した水素原子（Ｓｉ−Ｈ基）の数が好ましくは０．５〜５．０倍、より好ましくは０．７〜３．０倍となる量である。このような範囲であれば、架橋が十分に進行し、硬度に優れた硬化物が得られる。 From the viewpoint of cross-linking balance, the blending amount of the component (C) is such that the total number of alkenyl groups bonded to all silicon atoms in the components (A) and (B) is bonded to the silicon atoms in the component (C). The number of hydrogen atoms (Si-H groups) is preferably 0.5 to 5.0 times, more preferably 0.7 to 3.0 times. Within such a range, crosslinking will proceed sufficiently and a cured product with excellent hardness will be obtained.
＜（Ｄ）成分＞
（Ｄ）成分の白金族金属系触媒は、前記（Ａ）〜（Ｃ）成分のヒドロシリル化反応を進行及び促進させるための成分である。
<(D) component>
The platinum group metal-based catalyst of the component (D) is a component for promoting and promoting the hydrosilylation reaction of the components (A) to (C).
白金族金属系触媒は、特に限定されず、例えば、白金、パラジウム、ロジウム等の白金族金属；塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィン類、ビニルシロキサンまたはアセチレン化合物との配位化合物等の白金化合物、テトラキス（トリフェニルホスフィン）パラジウム、クロロトリス（トリフェニルホスフィン）ロジウム等の白金族金属化合物等が挙げられるが、（Ａ）〜（Ｃ）成分との相溶性が良好であり、クロル不純物をほとんど含有しないので、好ましくは塩化白金酸をシリコーン変性したものである。
（Ｄ）成分は、一種単独で用いても二種以上を併用してもよい。
The platinum group metal-based catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium and rhodium; chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinylsiloxanes or acetylene compounds. Examples of the compound include platinum compounds such as position compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium, and chlorotris (triphenylphosphine) rhodium, but they have good compatibility with the components (A) to (C). Since it contains almost no chlorine impurities, chloroplatinic acid is preferably silicone-modified.
As the component (D), one type may be used alone, or two or more types may be used in combination.
（Ｄ）成分の配合量は、触媒としての有効量であればよいが、（Ａ）〜（Ｃ）成分の合計に対して、好ましくは白金族金属元素の質量換算で１〜５００ｐｐｍ、好ましくは３〜１００ｐｐｍ、より好ましくは５〜４０ｐｐｍである。この配合量を適切なものとすると、ヒドロシリル化反応をより効果的に促進させることができる。 The blending amount of the component (D) may be an effective amount as a catalyst, but is preferably 1 to 500 ppm in terms of mass of platinum group metal element based on the total of the components (A) to (C), and preferably It is 3 to 100 ppm, more preferably 5 to 40 ppm. When the compounding amount is appropriate, the hydrosilylation reaction can be promoted more effectively.
＜その他の成分＞
本発明の組成物は、上記（Ａ）〜（Ｄ）成分以外にも、以下に例示するその他の成分を配合してもよい。
<Other ingredients>
In addition to the components (A) to (D) described above, the composition of the present invention may contain other components exemplified below.
有機過酸化物：
本発明においては、有機過酸化物を添加することにより、さらなる樹脂強度の向上を達成することができる。
有機過酸化物としては、例えば、１，６−ビス（ｔ−ブチルペルオキシカルボニルオキシ）ヘキサン、ベンゾイルパーオキサイド、ｔ−ブチルパーベンゾエート、ｏ−メチルベンゾイルパーオキサイド、ｐ−メチルベンゾイルパーオキサイド、ジクミルパーオキサイド、１，１―ビス（ｔ−ブチルパーオキシ）−３，３，３−トリメチルシクロヘキサン、ジ（４−メチルベンゾイルパーオキシ）ヘキサメチレンビスカーボネート等が挙げられるが、１，６−ビス（ｔ−ブチルペルオキシカルボニルオキシ）ヘキサンが好ましい。その添加量は、有効量でよいが、通常、（Ａ）・（Ｂ）成分のオルガノポリシロキサン合計量１００質量部にたいして０．０１〜５質量部、特に０．０５〜３質量部を配合することが好ましい。これらは１種単独で又は２種以上を組み合わせて用いることができる。
Organic peroxide:
In the present invention, the addition of the organic peroxide can further improve the resin strength.
Examples of the organic peroxide include 1,6-bis (t-butylperoxycarbonyloxy) hexane, benzoyl peroxide, t-butyl perbenzoate, o-methyl benzoyl peroxide, p-methyl benzoyl peroxide, dicumyl. Examples thereof include peroxide, 1,1-bis (t-butylperoxy) -3,3,3-trimethylcyclohexane, di (4-methylbenzoylperoxy) hexamethylenebiscarbonate, and 1,6-bis ( t-Butylperoxycarbonyloxy) hexane is preferred. The addition amount thereof may be an effective amount, but usually 0.01 to 5 parts by mass, particularly 0.05 to 3 parts by mass is blended with respect to 100 parts by mass of the total amount of the organopolysiloxane of the components (A) and (B). Preferably. These can be used alone or in combination of two or more.
反応抑制剤：
本発明の組成物には、必要に応じて（Ｄ）成分の付加反応触媒に対して硬化抑制効果を持つ化合物とされている従来公知の反応抑制剤（反応制御剤）を使用することができる。この反応抑制剤としては、トリフェニルホスフィン等のリン含有化合物；トリブチルアミンやテトラメチルエチレンジアミン、ベンゾトリアゾール等の窒素含有化合物；硫黄含有化合物；アセチレン系化合物；ハイドロパーオキシ化合物；マレイン酸誘導体等が例示される。
反応抑制剤による硬化抑制効果の度合いは、反応抑制剤の化学構造によって大きく異なるため、反応抑制剤の配合量は、使用する反応抑制剤ごとに最適な量に調整することが好ましい。通常は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分および（Ｄ）成分の合計１００質量部に対して０．００１〜５質量部が好ましい。
Reaction inhibitor:
In the composition of the present invention, a conventionally known reaction inhibitor (reaction control agent), which is a compound having a curing inhibiting effect on the addition reaction catalyst of the component (D), can be used if necessary. .. Examples of this reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; sulfur-containing compounds; acetylene compounds; hydroperoxy compounds; maleic acid derivatives and the like. To be done.
Since the degree of the curing inhibitory effect of the reaction inhibitor varies greatly depending on the chemical structure of the reaction inhibitor, it is preferable to adjust the amount of the reaction inhibitor to be optimized for each reaction inhibitor used. Usually, 0.001 to 5 parts by mass is preferable for 100 parts by mass of the total of the components (A), (B), (C) and (D).
接着性向上剤：
本組成物には樹脂に対する接着性を高めるために、接着性向上剤を添加してもよい。接着性向上剤としては、付加反応硬化型である本発明の組成物に自己接着性を付与する観点から、接着性を付与する官能基を含有するシラン、シロキサン等の有機ケイ素化合物、非シリコーン系有機化合物等が用いられる。
接着性を付与する官能基の具体例としては、ケイ素原子に結合したビニル基、アリル基等のアルケニル基、水素原子；炭素原子を介してケイ素原子に結合したエポキシ基（例えば、γ−グリシドキシプロピル基、β−（３，４−エポキシシクロヘキシル）エチル基等）や、アクリロキシ基（例えば、γ−アクリロキシプロピル基等）もしくはメタクリロキシ基（例えば、γ−メタクリロキシプロピル基等）；アルコキシシリル基（例えば、エステル構造、ウレタン構造、エーテル構造を１〜２個含有してもよいアルキレン基を介してケイ素原子に結合したトリメトキシシリル基、トリエトキシシリル基、メチルジメトキシシリル基等のアルコキシシリル基等）等が挙げられる。
接着性を付与する官能基を含有する有機ケイ素化合物は、シランカップリング剤、アルコキシシリル基と有機官能性基を有するシロキサン、反応性有機基を有する有機化合物にアルコキシシリル基を導入した化合物等が例示される。
非シリコーン系有機化合物としては、例えば、有機酸アリルエステル、エポキシ基開環触媒、有機チタン化合物、有機ジルコニウム化合物、有機アルミニウム化合物等が挙げられる。
Adhesion improver:
An adhesiveness improver may be added to the composition in order to improve the adhesiveness to the resin. As the adhesion improver, from the viewpoint of imparting self-adhesiveness to the composition of the present invention which is an addition reaction curable type, an organic silicon compound such as silane or siloxane having a functional group imparting adhesiveness, a non-silicone type An organic compound or the like is used.
Specific examples of the functional group imparting adhesiveness include a vinyl group bonded to a silicon atom, an alkenyl group such as an allyl group, a hydrogen atom; an epoxy group bonded to a silicon atom via a carbon atom (eg, γ-glycid Xypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc., acryloxy group (eg, γ-acryloxypropyl group) or methacryloxy group (eg, γ-methacryloxypropyl group); alkoxysilyl Group (for example, alkoxysilyl such as trimethoxysilyl group, triethoxysilyl group, and methyldimethoxysilyl group bonded to a silicon atom through an alkylene group that may contain 1 to 2 ester structures, urethane structures, and ether structures) Groups, etc.) and the like.
Examples of the organosilicon compound containing a functional group that imparts adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and a compound obtained by introducing an alkoxysilyl group into an organic compound having a reactive organic group. It is illustrated.
Examples of non-silicone organic compounds include organic acid allyl esters, epoxy group ring-opening catalysts, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds.
充填剤：
本発明の組成物には、結晶性シリカ、中空フィラー、シルセスキオキサン等の無機質充填剤、及びこれらの充填剤をオルガノアルコキシシラン化合物、オルガノクロロシラン化合物、オルガノシラザン化合物、低分子量シロキサン化合物等の有機ケイ素化合物により表面疎水化処理した充填剤等；シリコーンゴムパウダー、シリコーンレジンパウダー等を充填することが出来る。本成分としては、特にチクソ性を付与できる充填剤を使用することが好ましく、チクソ性を付与することによって作業性、ダイシェア強度に優れる硬化物を得ることができる。
filler:
The composition of the present invention, crystalline silica, hollow filler, inorganic fillers such as silsesquioxane, and these fillers such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds such as It is possible to fill a filler or the like whose surface is hydrophobized with an organosilicon compound; a silicone rubber powder, a silicone resin powder or the like. As this component, it is particularly preferable to use a filler capable of imparting thixotropy, and by imparting thixotropy, a cured product excellent in workability and die shear strength can be obtained.
これらのその他の成分は、一種単独で用いても二種以上を併用してもよい。 These other components may be used alone or in combination of two or more.
なお、ダイボンディング（転写法）における作業性が良好になるため、本発明の付加硬化型シリコーン樹脂組成物の粘度は、２５℃において５〜１００Ｐａ・ｓが好ましく、より好ましくは２０〜５０Ｐａ・ｓである。 Since the workability in die bonding (transfer method) is improved, the viscosity of the addition-curable silicone resin composition of the present invention is preferably 5 to 100 Pa · s at 25 ° C., more preferably 20 to 50 Pa · s. Is.
［硬化物］
さらに、本発明は、付加硬化型シリコーン組成物の硬化物（シリコーン硬化物）を提供する。
[Cured product]
Furthermore, the present invention provides a cured product (silicone cured product) of an addition-curable silicone composition.
本発明の付加硬化型シリコーン組成物の硬化は、公知の条件で行えばよく、一例としては１００〜１８０℃において１０分〜５時間の条件で硬化させることが出来る。 The addition-curable silicone composition of the present invention may be cured under known conditions, and for example, it may be cured at 100 to 180 ° C. for 10 minutes to 5 hours.
本発明の付加硬化型シリコーン組成物の硬化物は、基板・ＬＥＤチップ等への接着力が高い組成物、特にＬＥＤ素子等のダイボンディングに用いられるダイボンド材として有用である。以上のように、本発明のシリコーン硬化物であれば、基板・ＬＥＤチップ等への接着力が高い接着剤とすることができる。 The cured product of the addition-curable silicone composition of the present invention is useful as a composition having high adhesiveness to substrates, LED chips and the like, particularly as a die bond material used for die bonding of LED elements and the like. As described above, the cured silicone product of the present invention can be used as an adhesive having high adhesiveness to substrates, LED chips and the like.
［光半導体装置］
さらに、本発明は、上記硬化物で光半導体素子がダイボンディングされたものである光半導体装置を提供する。
[Optical semiconductor device]
Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded with the above cured product.
本発明の組成物を用いて光半導体素子をダイボンディングする方法の一例としては、本発明の組成物をシリンジに充填し、ディスペンサを用いてパッケージ等の基体上に乾燥状態で５〜１００μｍの厚さとなるように塗布した後、塗布した組成物上に光半導体素子（例えば、発光ダイオード）を配し、該組成物を硬化させることにより、光半導体素子を基体上にダイボンディングする方法が挙げられる。またスキージ皿に組成物を載せ、スキージしながらスタンピングによる方法で基体上に乾燥状態で５〜１００μｍの厚さとなるように塗布した後、塗布した組成物上に光半導体素子を配し、該組成物を硬化させることにより、光半導体素子を基体上にダイボンディングする方法でも良い。組成物の硬化条件は、上述のとおりとすればよい。こうして信頼性の高い、本発明のシリコーン硬化物で光半導体素子がダイボンディングされた光半導体装置とすることができる。 As an example of a method for die-bonding an optical semiconductor device using the composition of the present invention, a syringe is filled with the composition of the present invention, and a dispenser is used to dry a substrate having a thickness of 5 to 100 μm on a substrate such as a package. A method of die-bonding an optical semiconductor element onto a substrate by applying an optical semiconductor element (for example, a light emitting diode) on the applied composition and curing the composition after coating .. Further, the composition is placed on a squeegee dish, and while being squeegeeed, it is applied on a substrate by a method by stamping so as to have a thickness of 5 to 100 μm in a dry state, and then an optical semiconductor element is arranged on the applied composition, A method of die-bonding an optical semiconductor element onto a substrate by curing an object may be used. The curing conditions for the composition may be as described above. In this way, it is possible to obtain a highly reliable optical semiconductor device in which an optical semiconductor element is die-bonded with the silicone cured product of the present invention.
以下、実施例を用いて本発明を具体的に説明するが、これらの実施例は本発明を何ら制限するものではない。なお、分子量はゲル浸透クロマトグラフィー（ＧＰＣ）における標準ポリスチレン換算の重量平均分子量である。２５℃における粘度は回転粘度計による測定値である。
また、各シロキサン単位の略号の意味は下記のとおりである。
Ｍ：（ＣＨ３）３ＳｉＯ１／２
ＭＶｉ：（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２
ＭＶｉ３：（ＣＨ２＝ＣＨ）３ＳｉＯ１／２
Ｄ：（ＣＨ３）２ＳｉＯ２／２
ＤＨ：Ｈ（ＣＨ３）ＳｉＯ２／２
ＤＶｉ：（ＣＨ＝ＣＨ２）（ＣＨ３）ＳｉＯ
Ｔ：（ＣＨ３）ＳｉＯ３／２
Ｑ：ＳｉＯ４／２
Hereinafter, the present invention will be specifically described with reference to examples, but these examples do not limit the present invention at all. The molecular weight is the weight average molecular weight in terms of standard polystyrene in gel permeation chromatography (GPC). The viscosity at 25 ° C is a value measured by a rotational viscometer.
The abbreviations of the siloxane units have the following meanings.
M: (CH 3 ) 3 SiO 1/2
M Vi: (CH 2 = CH ) (CH 3) 2 SiO 1/2
M Vi3 : (CH 2 = CH) 3 SiO 1/2
D: (CH 3 ) 2 SiO 2/2
D H: H (CH 3) SiO 2/2
D Vi : (CH = CH 2 ) (CH 3 ) SiO
T: (CH 3 ) SiO 3/2
Q: SiO 4/2
［合成例１］
撹拌装置、冷却管、滴下ロートおよび温度計を備えた３，０００ｍＬの４つ口フラスコに［（ＣＨ３Ｏ）３ＳｉＯ１／２］２［（ＣＨ３Ｏ）２ＳｉＯ］２で表されるオルガノポリシロキサンを３５２．５ｇ、ヘキサビニルジシロキサンを４５．６ｇ、ヘキサメチルジシロキサンを１８２．３ｇ、イソプロパノール５８ｇを入れ、撹拌しつつメタンスルホン酸６．７ｇを滴下した。その後、水９０ｇを滴下し、６５℃で２時間混合し、反応を行った。そこへキシレン７００ｇを投入したのち、５０％水酸化カリウム水溶液１０．９ｇを加え、昇温して低沸点成分を留去し、１２０℃で５時間反応を行った。添加剤としてメタンスルホン酸３．５ｇを添加し、１２０℃で２時間中和処理を行った。冷却後、濾過を行って、平均構造ＭＶｉ３ ０．０７Ｍ０．４Ｑ０．５３の分岐状オルガノポリシロキサン（Ｂ−１：分子量３，３５０、固形分に対するビニル基量０．２８７ｍｏｌ／１００ｇ）を得た。
[Synthesis example 1]
Represented by [(CH 3 O) 3 SiO 1/2 ] 2 [(CH 3 O) 2 SiO] 2 in a 3,000 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer. 352.5 g of organopolysiloxane, 45.6 g of hexavinyldisiloxane, 182.3 g of hexamethyldisiloxane and 58 g of isopropanol were added, and 6.7 g of methanesulfonic acid was added dropwise with stirring. Then, 90 g of water was added dropwise and mixed at 65 ° C. for 2 hours to carry out a reaction. After 700 g of xylene was added thereto, 10.9 g of a 50% aqueous potassium hydroxide solution was added, the temperature was raised to distill off low-boiling components, and the reaction was carried out at 120 ° C. for 5 hours. 3.5 g of methanesulfonic acid was added as an additive, and the mixture was neutralized at 120 ° C. for 2 hours. After cooling, filtration is carried out to obtain a branched organopolysiloxane having an average structure M Vi3 0.07 M 0.4 Q 0.53 (B-1: molecular weight 3,350, vinyl group amount based on solid content: 0.287 mol / 100 g). ) Got.
［合成例２］
撹拌装置、冷却管、滴下ロートおよび温度計を備えた３，０００ｍＬの４つ口フラスコに［（ＣＨ３Ｏ）３ＳｉＯ１／２］２［（ＣＨ３Ｏ）２ＳｉＯ］２で表されるオルガノポリシロキサンを３５３．５ｇ、ヘキサビニルジシロキサンを９４．８ｇ、ヘキサメチルジシロキサンを１４５．８ｇ、イソプロパノール５９ｇを入れ、撹拌しつつメタンスルホン酸７．５ｇを滴下した。その後、水９０ｇを滴下し、６５℃で２時間混合し、反応を行った。そこへキシレン８００ｇを投入したのち、５０％水酸化カリウム水溶液１２．３ｇを加え、昇温して低沸点成分を留去し、１２０℃で５時間反応を行った。添加剤としてメタンスルホン酸３．９ｇを添加し、１２０℃で２時間中和処理を行った。冷却後、濾過を行って、平均構造ＭＶｉ３ ０．１４Ｍ０．３２Ｑ０．５４の分岐状オルガノポリシロキサン（Ｂ−２：分子量３，６３０、固形分に対するビニル基量０．５６７ｍｏｌ／１００ｇ）を得た。
[Synthesis example 2]
Represented by [(CH 3 O) 3 SiO 1/2 ] 2 [(CH 3 O) 2 SiO] 2 in a 3,000 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer. 353.5 g of organopolysiloxane, 94.8 g of hexavinyldisiloxane, 145.8 g of hexamethyldisiloxane and 59 g of isopropanol were added, and 7.5 g of methanesulfonic acid was added dropwise while stirring. Then, 90 g of water was added dropwise and mixed at 65 ° C. for 2 hours to carry out a reaction. After 800 g of xylene was added thereto, 12.3 g of a 50% aqueous potassium hydroxide solution was added, the temperature was raised to distill off low-boiling components, and the reaction was carried out at 120 ° C. for 5 hours. 3.9 g of methanesulfonic acid was added as an additive, and the mixture was neutralized at 120 ° C. for 2 hours. After cooling, filtration is carried out to obtain a branched organopolysiloxane having an average structure MVi3 0.14 M 0.32 Q 0.54 (B-2: molecular weight 3,630, vinyl group content relative to solid content: 0.567 mol / 100 g). ) Got.
［合成例３］
撹拌装置、冷却管、滴下ロートおよび温度計を備えた３０００ｍＬの４つ口フラスコに［（ＣＨ３Ｏ）３ＳｉＯ１／２］２［（ＣＨ３Ｏ）２ＳｉＯ］２で表されるオルガノポリシロキサンを３５２．５ｇ、ヘキサビニルジシロキサンを３８．６ｇ、ヘキサメチルジシロキサンを１３３．７ｇ、イソプロパノール５２ｇを入れ、撹拌しつつメタンスルホン酸７．１ｇを滴下した。その後、水９０ｇを滴下し、６５℃で２時間混合し、反応を行った。そこへキシレン６００ｇを投入したのち、５０％水酸化カリウム水溶液１３．３ｇを加え、昇温して低沸点成分を留去し、１２０℃で５時間反応を行った。添加剤としてメタンスルホン酸４．３ｇを添加し、１２０℃で２時間中和処理を行った。冷却後、濾過を行って、平均構造ＭＶｉ３ ０．０７Ｍ０．３３Ｑ０．６０の分岐状オルガノポリシロキサン（Ｂ−３：分子量７，８９０、固形分に対するビニル基量０．２６３ｍｏｌ／１００ｇ）を得た。
[Synthesis example 3]
A 3000 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer was placed in an organopolypolysiloxane represented by [(CH 3 O) 3 SiO 1/2 ] 2 [(CH 3 O) 2 SiO] 2. 352.5 g of siloxane, 38.6 g of hexavinyldisiloxane, 133.7 g of hexamethyldisiloxane and 52 g of isopropanol were added, and 7.1 g of methanesulfonic acid was added dropwise while stirring. Then, 90 g of water was added dropwise and mixed at 65 ° C. for 2 hours to carry out a reaction. After 600 g of xylene was added thereto, 13.3 g of 50% aqueous potassium hydroxide solution was added, the temperature was raised to distill off low-boiling components, and the reaction was carried out at 120 ° C. for 5 hours. 4.3 g of methanesulfonic acid was added as an additive, and the mixture was neutralized at 120 ° C. for 2 hours. After cooling, filtration is carried out to obtain a branched organopolysiloxane having an average structure M Vi3 0.07 M 0.33 Q 0.60 (B-3: molecular weight 7,890, vinyl group amount based on solid content: 0.263 mol / 100 g). ) Got.
［合成例４］
撹拌装置、冷却管、滴下ロートおよび温度計を備えた３０００ｍＬの４つ口フラスコにメチルトリメトキシシランを４０８．０ｇ、ヘキサビニルジシロキサンを７０．２ｇ、ジメチルジメトキシシランを６３．０ｇ、イソプロパノール５４ｇを入れ、撹拌しつつメタンスルホン酸６．８ｇを滴下した。その後、水９０ｇを滴下し、６５℃で２時間混合し、反応を行った。そこへキシレン６００ｇを投入したのち、５０％水酸化カリウム水溶液１１．１ｇを加え、昇温して低沸点成分を留去し、１２０℃で５時間反応を行った。添加剤としてメタンスルホン酸３．５ｇを添加し、１２０℃で２時間中和処理を行った。冷却後、濾過を行って、平均構造ＭＶｉ３ ０．１４Ｄ０．１４Ｔ０．７２の分岐状オルガノポリシロキサン（Ｂ−４：分子量２，８９０、固形分に対するビニル基量０．５８６ｍｏｌ／１００ｇ）を得た。
[Synthesis example 4]
To a 3000 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 408.0 g of methyltrimethoxysilane, 70.2 g of hexavinyldisiloxane, 63.0 g of dimethyldimethoxysilane and 54 g of isopropanol were placed. 6.8 g of methanesulfonic acid was added dropwise with stirring. Then, 90 g of water was added dropwise and mixed at 65 ° C. for 2 hours to carry out a reaction. After adding 600 g of xylene thereto, 11.1 g of 50% potassium hydroxide aqueous solution was added, the temperature was raised to distill off low-boiling components, and the reaction was carried out at 120 ° C. for 5 hours. 3.5 g of methanesulfonic acid was added as an additive, and the mixture was neutralized at 120 ° C. for 2 hours. After cooling, filtration is carried out to obtain a branched organopolysiloxane having an average structure MVi3 0.14 D 0.14 T 0.72 (B-4: molecular weight 2,890, vinyl group content relative to solid content: 0.586 mol / 100 g). ) Got.
［比較合成例１］
撹拌装置、冷却管、滴下ロートおよび温度計を備えた３０００ｍＬの４つ口フラスコに［（ＣＨ３Ｏ）３ＳｉＯ１／２］２［（ＣＨ３Ｏ）２ＳｉＯ］２で表されるオルガノポリシロキサンを３５２．５ｇ、１，３−ジビニルテトラメチルジシロキサンを１１１．６ｇ、ヘキサメチルジシロキサンを８９．２ｇ、イソプロパノール５５ｇを入れ、撹拌しつつメタンスルホン酸７．０ｇを滴下した。その後、水９０ｇを滴下し、６５℃で２時間混合し、反応を行った。そこへキシレン５５０ｇを投入したのち、５０％水酸化カリウム水溶液１１．４ｇを加え、昇温して低沸点成分を留去し、１２０℃で５時間反応を行った。添加剤としてメタンスルホン酸３．７ｇを添加し、１２０℃で２時間中和処理を行った。冷却後、濾過を行って、平均構造ＭＶｉ ０．２１Ｍ０．２３Ｑ０．５６の分岐状オルガノポリシロキサン（Ｂ−６：分子量７,８９０）を得た。
[Comparative Synthesis Example 1]
A 3000 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer was placed in an organopolypolysiloxane represented by [(CH 3 O) 3 SiO 1/2 ] 2 [(CH 3 O) 2 SiO] 2. 352.5 g of siloxane, 111.6 g of 1,3-divinyltetramethyldisiloxane, 89.2 g of hexamethyldisiloxane and 55 g of isopropanol were added, and 7.0 g of methanesulfonic acid was added dropwise while stirring. Then, 90 g of water was added dropwise and mixed at 65 ° C. for 2 hours to carry out a reaction. After 550 g of xylene was added thereto, 11.4 g of a 50% aqueous potassium hydroxide solution was added, the temperature was raised to distill off low-boiling components, and the reaction was carried out at 120 ° C. for 5 hours. 3.7 g of methanesulfonic acid was added as an additive, and the mixture was neutralized at 120 ° C. for 2 hours. After cooling, by performing filtration, average structure M Vi 0.21 M 0.23 Q branched organopolysiloxane 0.56 (B-6: molecular weight 7,890) was obtained.
［合成例５］
六塩化白金酸と１，３−ジビニルテトラメチルジシロキサンとの反応生成物を、白金含有量が０．００４質量％となるように、粘度６０ｍＰａ・ｓ、ＭＶｉ ２Ｄ４０で表される直鎖状のジメチルポリシロキサンで稀釈して白金触媒（Ｄ）を調製した。
[Synthesis example 5]
A reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane is directly expressed by a viscosity of 60 mPa · s and M Vi 2 D 40 so that the platinum content is 0.004% by mass. A platinum catalyst (D) was prepared by diluting with chain dimethyl polysiloxane.
［実施例１〜５、比較例１〜３］
表１に示す配合量で下記の各成分を混合し、付加硬化型シリコーン組成物を調製した。
なお、表１における各成分の数値は質量部を表す。［Ｓｉ−Ｈ］／［Ｓｉ−Ｖｉ］値は、（Ａ）成分および（Ｂ）成分中の全ケイ素原子に結合したアルケニル基の合計数に対する（Ｃ）成分中のケイ素原子に結合した水素原子（Ｓｉ−Ｈ基）の数の比（モル比）を表す。
[Examples 1 to 5, Comparative Examples 1 to 3]
The following components were mixed in the amounts shown in Table 1 to prepare an addition-curable silicone composition.
In addition, the numerical value of each component in Table 1 represents a mass part. The [Si-H] / [Si-Vi] value is the hydrogen atom bonded to the silicon atom in the component (C) with respect to the total number of alkenyl groups bonded to all the silicon atoms in the component (A) and the component (B). It represents the ratio (molar ratio) of the number of (Si-H groups).
（Ａ）成分：
（Ａ−１）ＭＶｉ ０．４７Ｔ０．５３で表される、分岐状のオルガノポリシロキサン（２５℃における粘度１７ｍＰａ・ｓ）
（Ａ−２）ＭＶｉ ０．００９７Ｄ０．９９０３（ＭＶｉ ２Ｄ２０４）で表される、両末端がビニル基で封鎖された直鎖状のジメチルポリシロキサン（２５℃における粘度６００ｍＰａ・ｓ）
(A) component:
(A-1) Branched organopolysiloxane represented by M Vi 0.47 T 0.53 (viscosity at 25 ° C. is 17 mPa · s)
(A-2) M Vi 0.0097 D 0.9903 (M Vi 2 D 204 ), a linear dimethylpolysiloxane having both ends blocked with vinyl groups (viscosity 600 mPa · s at 25 ° C.) )
（Ｂ）成分：
（Ｂ−１）合成例１で得られた分岐状オルガノポリシロキサン
（Ｂ−２）合成例２で得られた分岐状オルガノポリシロキサン
（Ｂ−３）合成例３で得られた分岐状オルガノポリシロキサン
（Ｂ−４）合成例４で得られた分岐状オルガノポリシロキサン
(B) component:
(B-1) Branched Organopolysiloxane Obtained in Synthesis Example 1 (B-2) Branched Organopolysiloxane Obtained in Synthesis Example 2 (B-3) Branched Organopolysiloxane Obtained in Synthesis Example 3 Siloxane (B-4) Branched organopolysiloxane obtained in Synthesis Example 4
（比較成分）：
（Ｂ−５）ＭＶｉ ０．０６４Ｍ０．３９８Ｑ０．５３８（ＭＶｉ １．２Ｍ７．４Ｑ１０）で表される分岐状オルガノポリシロキサン（固形分に対するビニル基量０．０８５ｍｏｌ／１００ｇ）
（Ｂ−６）比較合成例１で得られた分岐状オルガノポリシロキサン
(Comparison component):
(B-5) M Vi 0.064 M 0.398 Q 0.538 (M Vi 1.2 M 7.4 Q 10 ) branched organopolysiloxane (vinyl group content 0.085 mol relative to solid content) / 100g)
(B-6) Branched organopolysiloxane obtained in Comparative Synthesis Example 1
（Ｃ）成分：
（Ｃ）Ｍ０．０３７Ｄ０．２６６ＤＨ ０．６９７（Ｍ２Ｄ１４．５ＤＨ ３８）で表されるメチルハイドロジェンシロキサン
Component (C):
(C) M 0.037 D 0.266 DH 0.697 (M 2 D 14.5 DH 38 ) Methyl hydrogen siloxane
（Ｄ）成分：
（Ｄ）合成例５で得られた白金触媒
Component (D):
(D) Platinum catalyst obtained in Synthesis Example 5
その他の成分：
（Ｅ）反応抑制剤：１−エチニルシクロヘキサノール
（Ｆ−１）接着性向上剤：ＤＶｉ ４で表される環状オルガノポリシロキサン
（Ｆ−２）接着性向上剤：トリアリルイソシアヌレート
（Ｆ−３）接着性向上剤：下記式で表される化合物
(E) Reaction inhibitor: 1-ethynylcyclohexanol (F-1) Adhesion improver: Cyclic organopolysiloxane represented by D Vi 4 (F-2) Adhesion improver: Triallyl isocyanurate (F- 3) Adhesion improver: compound represented by the following formula
実施例１〜５、比較例１〜３で得られた付加硬化型シリコーン樹脂組成物について、下記の評価を行い、結果を表２に示した。 The addition-curable silicone resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as follows, and the results are shown in Table 2.
［硬度］
組成物を２ｍｍ厚になるよう型に流し込み、１５０℃×４時間の条件で硬化させた硬化物のＴｙｐｅＤ硬度をＪＩＳ Ｋ６２５３ に準拠して測定した。
[hardness]
The composition was poured into a mold so as to have a thickness of 2 mm, and the Type D hardness of the cured product cured under the conditions of 150 ° C. for 4 hours was measured according to JIS K6253.
［ダイシェア強度］
組成物をダイボンダー（ＡＳＭ社製、ＡＤ−８３０）を用いて、ＳＭＤ５０５０パッケージ（Ｉ−ＣＨＩＵＮ ＰＲＥＣＳＩＯＮ ＩＮＤＵＳＴＲＹ ＣＯ．製、樹脂部：ポリフタルアミド）の銀メッキ電極部に対して、スタンピングにより定量転写し、その上に光半導体素子（ＳｅｍｉＬＥＤｓ社製、ＥＶ−Ｂ３５Ａ、３５ｍｉｌ）を搭載した。作製したパッケージを１５０℃のオーブンで２時間加熱し、組成物を硬化したのち、ボンドテスター（Ｄａｇｅ社製、Ｓｅｒｉｅｓ４０００を用いてダイシェア強度の測定を行った。
組成物の粘度が１００ｍＰａ・ｓを超え、スタンピングによる転写ができなかったものは「転写不可」とした。
[Die shear strength]
Using a die bonder (AD-830 manufactured by ASM), the composition was quantitatively transferred by stamping to a silver-plated electrode portion of an SMD5050 package (I-CHIUN PRECSION INDUSTRY CO., Resin portion: polyphthalamide). Then, an optical semiconductor element (EV-B35A, 35 mil, manufactured by SemiLEDs) was mounted thereon. The prepared package was heated in an oven at 150 ° C. for 2 hours to cure the composition, and then the die shear strength was measured using a bond tester (Series 4000, manufactured by Dage).
A composition having a viscosity of more than 100 mPa · s and which could not be transferred by stamping was designated as “untransferable”.
表２に示したように、実施例１〜５では何れも硬化物の硬度及びダイシェア強度に優れ、ダイボンド剤として優れたものであった。
一方、比較例１及び２では（Ｂ）成分がトリアルケニルシリル基（Ｒ２ ３ＳｉＯ１／２単位）を有しないものであるため、硬化物のダイシェア強度が劣り、ダイボンド剤として不十分なものであった。
また、比較例３は、（Ｂ）成分がトリアルケニルシリル基を含む分岐状オルガノポリシロキサンを含むものの、（Ａ）成分の粘度が高いため転写性に劣り、ダイボンディングが出来なかった。
As shown in Table 2, in Examples 1 to 5, all of the cured products were excellent in hardness and die shear strength, and were excellent as die bonding agents.
On the other hand, in Comparative Examples 1 and 2, since the component (B) does not have a trialkenylsilyl group (R 2 3 SiO 1/2 unit), the die shear strength of the cured product is poor and it is insufficient as a die bonding agent. Met.
Further, in Comparative Example 3, although the component (B) contained a branched organopolysiloxane containing a trialkenylsilyl group, the component (A) had a high viscosity, so the transferability was poor and die bonding could not be performed.
以上のように、本発明の付加硬化型シリコーン樹脂組成物は、硬度及びダイシェア強度に優れたシリコーン硬化物を与え、光半導体素子等のダイボンディングに用いられるダイボンド材として特に有用である。特に、この特長により、ダイボンド工程の後に行われるワイヤーボンディング工程において、チップの剥離や、ボンディングができないという不具合が発生し難いため、このシリコーン硬化物で光半導体素子がダイボンディングされた光半導体装置は、信頼性が高くなるうえ、装置の生産性も向上する。このため、本発明の付加硬化型シリコーン樹脂組成物及びその硬化物は、光半導体装置の技術分野において利用価値が高い。 As described above, the addition-curable silicone resin composition of the present invention provides a silicone cured product having excellent hardness and die shear strength, and is particularly useful as a die bond material used for die bonding of optical semiconductor elements and the like. In particular, due to this feature, in the wire bonding process that is performed after the die bonding process, chip peeling and the problem that the bonding cannot be performed are unlikely to occur. Therefore, an optical semiconductor device in which an optical semiconductor element is die-bonded with this silicone cured product is used. In addition to high reliability, the productivity of the device is also improved. Therefore, the addition-curable silicone resin composition of the present invention and the cured product thereof have high utility value in the technical field of optical semiconductor devices.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is merely an example, and the invention having substantially the same configuration as the technical idea described in the scope of claims of the present invention and exhibiting the same action and effect is the present invention It is included in the technical scope of.
（Ｂ）成分の分岐状オルガノポリシロキサンの具体例としては、例えば、以下のものが挙げられる。
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．１（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．２（（ＣＨ３）３ＳｉＯ１／２）０．３５（ＳｉＯ４／２）０．３５、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．２（（ＣＨ３）３ＳｉＯ１／２）０．１（ＳｉＯ４／２）０．７、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．０７（（ＣＨ３）３ＳｉＯ１／２）０．４（ＳｉＯ ４／２）０．５３、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．１４（（ＣＨ３）３ＳｉＯ１／２）０．３２（ＳｉＯ ４／２）０．５４、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．０７（（ＣＨ３）３ＳｉＯ１／２）０．３３（ＳｉＯ ４／２）０．６、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．１（（ＣＨ３）３ＳｉＯ１／２）０．１（（ＣＨ３）２ＳｉＯ）０．２（（ＣＨ３）ＳｉＯ３／２）０．６、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．０７（（ＣＨ３）３ＳｉＯ１／２）０．１３（（ＣＨ３）２ＳｉＯ）０．２（ＳｉＯ４／２）０．６、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．３（ＳｉＯ４／２）０．７、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．２（（ＣＨ３）ＳｉＯ３／２）０．８、
（（ＣＨ２＝ＣＨ）３ＳｉＯ１／２）０．２（（ＣＨ３）ＳｉＯ３／２）０．６（ＳｉＯ４／２）０．２、
Specific examples of the branched organopolysiloxane of the component (B) include the following.
((CH 2 = CH) 3 SiO 1/2) 0.1 ((CH 2 = CH) (CH 3) 2 SiO 1/2) 0.2 ((CH 3) 3 SiO 1/2) 0.35 (SiO 4/2 ) 0.35 ,
((CH 2 = CH) 3 SiO 1/2) 0.2 ((CH 3) 3 SiO 1/2) 0.1 (SiO 4/2) 0.7,
((CH 2 = CH) 3 SiO 1/2) 0.07 ((CH 3) 3 SiO 1/2) 0.4 (SiO 4/2) 0.53,
((CH 2 = CH) 3 SiO 1/2) 0.14 ((CH 3) 3 SiO 1/2) 0.32 (SiO 4/2) 0.54,
((CH 2 = CH) 3 SiO 1/2) 0.07 ((CH 3) 3 SiO 1/2) 0.33 (SiO 4/2) 0.6,
((CH 2 = CH) 3 SiO 1/2) 0.1 ((CH 3) 3 SiO 1/2) 0.1 ((CH 3) 2 SiO) 0.2 ((CH 3) SiO 3/2 ) 0.6 ,
((CH 2 = CH) 3 SiO 1/2) 0.07 ((CH 3) 3 SiO 1/2) 0.13 ((CH 3) 2 SiO) 0.2 (SiO 4/2) 0.6 ,
((CH 2 = CH) 3 SiO 1/2) 0.3 (SiO 4/2) 0.7,
((CH 2 = CH) 3 SiO 1/2) 0.2 ((CH 3) SiO 3/2) 0.8,
((CH 2 = CH) 3 SiO 1/2) 0.2 ((CH 3) SiO 3/2) 0.6 (SiO 4/2) 0.2,
Claims (7)
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２Ｒ１ＳｉＯ）ｃ（Ｒ１ ２ＳｉＯ）ｄ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ（ＳｉＯ４／２）ｇ （１）
（式中、Ｒ１はそれぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、Ｒ２はそれぞれ同一又は異なっていてもよいアルケニル基である。ａ，ｂ，ｃ，ｄ，ｅ，ｆおよびｇはそれぞれ、ａ≧０、ｂ≧０、ｃ≧０、ｄ≧０、ｅ≧０，ｆ≧０，およびｇ≧０を満たす数であり、ただし、ｂ＋ｃ＋ｅ＞０かつａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ＝１を満たす数である。）
（Ｂ）下記平均組成式（２）で表される分岐状のオルガノポリシロキサン：（Ａ）成分及び（Ｂ）成分の合計１００質量部に対して７０〜９５質量部、
（Ｒ１ ３ＳｉＯ１／２）ｈ（Ｒ２ ３ＳｉＯ１／２）ｉ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｊ（Ｒ２Ｒ１ＳｉＯ）ｋ（Ｒ１ ２ＳｉＯ）ｌ（Ｒ２ＳｉＯ３／２）ｍ（Ｒ１ＳｉＯ３／２）ｎ（ＳｉＯ４／２）ｏ （２）
（式中、Ｒ１及びＲ２は上記と同様である。ｈ，ｉ，ｊ，ｋ，ｌ，ｍ，ｎおよびｏはそれぞれ、ｈ≧０、ｉ＞０，ｊ≧０、ｋ≧０、ｌ≧０，ｍ≧０，ｎ≧０，およびｏ≧０を満たす数であり、ただし、ｍ＋ｎ＋ｏ＞０かつｈ＋ｉ＋ｊ＋ｋ＋ｌ＋ｍ＋ｎ＋ｏ＝１を満たす数である。）
（Ｃ）下記平均組成式（３）で表され、ケイ素原子に結合した水素原子を１分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン、
Ｒ３ ｐＨｑＳｉＯ（４−ｐ−ｑ）／２ （３）
（式中、Ｒ３は、それぞれ同一又は異なっていてもよい、アルケニル基を含まない置換または非置換の一価炭化水素基であり、ｐ及びｑは、０．７≦ｐ≦２．１、０．００１≦ｑ≦１．０、かつ０．８≦ｐ＋ｑ≦３．０を満たす数である。）
（Ｄ）白金族金属系触媒、
を含有するものであることを特徴とする付加硬化型シリコーン樹脂組成物。 (A) An organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 500 mPa · s or less,
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 R 1 SiO) c (R 1 2 SiO) d (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (SiO 4/2 ) g (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R 2 is an alkenyl group which may be the same or different. a, b, c, d, e, f and g are numbers respectively satisfying a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0 and g ≧ 0, However, it is a number that satisfies b + c + e> 0 and a + b + c + d + e + f + g = 1.)
(B) Branched organopolysiloxane represented by the following average composition formula (2): 70 to 95 parts by mass based on 100 parts by mass of the total of the components (A) and (B),
(R 1 3 SiO 1/2 ) h (R 2 3 SiO 1/2 ) i (R 2 R 1 2 SiO 1/2 ) j (R 2 R 1 SiO) k (R 1 2 SiO) 1 (R 2 SiO 3/2 ) m (R 1 SiO 3/2 ) n (SiO 4/2 ) o (2)
(In the formula, R 1 and R 2 are the same as above. H, i, j, k, l, m, n and o are h ≧ 0, i> 0, j ≧ 0, k ≧ 0, It is a number that satisfies l ≧ 0, m ≧ 0, n ≧ 0, and o ≧ 0, provided that m + n + o> 0 and h + i + j + k + l + m + n + o = 1.)
(C) An organohydrogenpolysiloxane represented by the following average composition formula (3), having at least two hydrogen atoms bonded to silicon atoms in one molecule,
R 3 p H q SiO (4 -p-q) / 2 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and p and q are 0.7 ≦ p ≦ 2.1, (A number that satisfies 0.001 ≦ q ≦ 1.0 and 0.8 ≦ p + q ≦ 3.0.)
(D) Platinum group metal-based catalyst,
An addition-curable silicone resin composition comprising:
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ２Ｒ１ ２ＳｉＯ１／２）ｂ（Ｒ２ＳｉＯ３／２）ｅ（Ｒ１ＳｉＯ３／２）ｆ （１ａ）
（式中、ａ，ｂ，ｅ，ｆは、ａ＋ｂ＞０、ｂ＋ｅ＞０、ｅ＋ｆ＞０であり、かつ、ａ＋ｂ＋ｅ＋ｆ＝１を満たす数である。） The addition-curable silicone resin composition according to claim 1, wherein the component (A) is a branched organopolysiloxane represented by the following average composition formula (1a).
(R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (R 2 SiO 3/2 ) e (R 1 SiO 3/2 ) f (1a)
(In the formula, a, b, e, and f are numbers satisfying a + b> 0, b + e> 0, and e + f> 0, and satisfying a + b + e + f = 1.)
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