CN112442333B - 热固性有机硅树脂组合物及光学半导体装置用芯片贴装材料 - Google Patents
热固性有机硅树脂组合物及光学半导体装置用芯片贴装材料 Download PDFInfo
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- CN112442333B CN112442333B CN202010909736.6A CN202010909736A CN112442333B CN 112442333 B CN112442333 B CN 112442333B CN 202010909736 A CN202010909736 A CN 202010909736A CN 112442333 B CN112442333 B CN 112442333B
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- silicone resin
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- thermosetting silicone
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- 239000011342 resin composition Substances 0.000 title claims abstract description 114
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 108
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims description 35
- 230000003287 optical effect Effects 0.000 title claims description 23
- 239000004065 semiconductor Substances 0.000 title claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 76
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 63
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 31
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 30
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 238000009835 boiling Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000007259 addition reaction Methods 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000000413 hydrolysate Substances 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical group [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 3
- FBSNEJXXSJHKHX-UHFFFAOYSA-N CC1=C(C(C=C1)([Pt]C)C)C Chemical group CC1=C(C(C=C1)([Pt]C)C)C FBSNEJXXSJHKHX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 20
- 239000004332 silver Substances 0.000 abstract description 20
- 229910052737 gold Inorganic materials 0.000 abstract description 18
- 239000010931 gold Substances 0.000 abstract description 18
- 239000002318 adhesion promoter Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 47
- -1 siloxanes Chemical class 0.000 description 38
- 239000000758 substrate Substances 0.000 description 35
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 239000000356 contaminant Substances 0.000 description 14
- 238000011109 contamination Methods 0.000 description 14
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 14
- 229910000679 solder Inorganic materials 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
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- 238000000465 moulding Methods 0.000 description 5
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- JBBQCTPRTVBNQD-UHFFFAOYSA-N CC1=C(C(C=C1)([Pt+2]C)C)C Chemical compound CC1=C(C(C=C1)([Pt+2]C)C)C JBBQCTPRTVBNQD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 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 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 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
- 238000001704 evaporation Methods 0.000 description 2
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- 125000006038 hexenyl group Chemical group 0.000 description 2
- 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 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 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
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- GGVUYAXGAOIFIC-UHFFFAOYSA-K cerium(3+);2-ethylhexanoate Chemical compound [Ce+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O GGVUYAXGAOIFIC-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
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- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
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Abstract
本发明提供一种热固性有机硅树脂组合物,其对于金焊垫部的污染性低,且与银引线框架的粘合性优异。本发明的热固性有机硅树脂组合物含有下述(A‑1)~(D)成分:(A‑1)含烯基的直链状有机聚硅氧烷;(A‑2)式(1)的支链状有机聚硅氧烷,(R1 3SiO1/2)a(R2 3SiO1/2)b(SiO4/2)c (1);(B‑1)式(2)的支链状有机氢聚硅氧烷,(HR2 2SiO1/2)d(R2 3SiO1/2)e(SiO4/2)f (2);(B‑2)式(3)的直链状有机氢聚硅氧烷,(R2 3SiO1/2)2(HR2SiO2/2)x(R2 2SiO2/2)y (3);(C)粘合助剂,其由含环氧基的支链状有机聚硅氧烷组成;(D)催化剂,其由0价铂络合物与+2价铂络合物和/或+4价铂络合物的组合组成。
Description
技术领域
本发明涉及一种热固性有机硅树脂组合物以及由该树脂组合物构成的光学半导体装置用芯片贴装(die attach)材料。
背景技术
与灯泡或荧光灯等以往的发光装置相比,光学半导体(LED)因其耗电少且寿命长的优点,近年来得到急速普及。当制作光学半导体装置时,首先在光学半导体基板上的规定位置涂布被称为芯片贴装材料的固化性树脂组合物,该组合物的目的在于使光学半导体芯片固定于基板上。芯片贴装材料的涂布方法一般为以下两种方法:施加压力使已填充于针筒中的树脂从安装于针筒前端的针头中吐出并转印到基板上的点胶(dispensing)法;及将转印针压抵在以薄膜状态铺展在树脂盘上的树脂上后,将附着有树脂的针压抵在基板上而进行转印的戳印(stamping)法。然后,进行将底部多由蓝宝石形成的LED芯片压接在所涂布的树脂组合物的顶部的固晶(die bonding)工序,然后,经过使上述树脂组合物固化的工序,进行利用金线将多由金形成的光学半导体芯片的电极焊垫部与基板上的多由银形成的导电性引线框架部位接合的引线键合(wire bonding)工序。引线键合工序中,一边施加超声波一边将形成于毛细管前端部的金焊球压抵在电极焊垫部上,此时,当LED芯片未被充分固定在基板上时,会发生下述问题:压抵时超声波向周围扩散,从而无法以充分的强度接合金线。此外,经过后续工序制作LED装置后,若在点灯操作中LED芯片从基板上浮起,则可能会不能充分进行由为发热体的LED芯片向基板的散热,会引起操作不良。因此,为了将LED芯片充分固定在基板上,在芯片贴装材料中,使用一种能够得到高强度且高粘合性的固化物的固化性树脂组合物。
此外,从赋予耐热性和耐光性的角度出发,在多用于照明用途的高输出蓝色LED装置中,多使用甲基硅酮类等加成固化性有机硅树脂组合物作为芯片贴装材料,但是有报道称因所使用的加成固化性有机硅树脂组合物或光学半导体芯片的种类、或树脂组合物的固化条件等各种原因,而导致树脂组合物固化时在光学半导体芯片的金电极焊垫部上形成污染物。当电极焊垫部存在污染物时,会在后续的引线键合工序中造成不良影响,因此成为问题。这样的污染物被认为起因于加成固化性有机硅树脂组合物中所含有的低分子硅氧烷,特别是下述情形已成为问题:具有与硅原子键合的氢原子(氢甲硅烷基(hydrosilylgroup))的低分子硅氧烷在固化时被加热,从而挥发,并通过水解反应等在电极焊垫部形成覆膜、或凝胶化而作为污染物附着在电极焊垫部上。已知通过减少树脂组合物中的具有氢甲硅烷基的低分子硅氧烷的含量,能够减少加热固化时附着于LED芯片电极焊垫部的污染物的量,且引线键合性得以提高。
此外,为了强化LED芯片在基板上的固定性,芯片贴装材料通常以能够在芯片周围形成焊角(fillet)部的量转印于基板上并进行芯片的压接。此时,当树脂的滞留性较低时,焊角部会比刚压抵芯片后更薄地向周围展开。在这样的情况下,由于树脂的表面积变大,因此固化时树脂组合物中的具有SiH基(氢甲硅烷基)的低分子硅氧烷变得更容易挥发,对LED芯片电极焊垫部的污染物附着性变高。
进一步,与以往的环氧树脂相比,甲基硅酮类等加成固化性有机硅树脂组合物基于树脂的极性等原因而与基板的粘合性较差。特别是在作为芯片贴装材料的被粘物的LED芯片底部的蓝宝石和银引线框架部位中,与后者的粘合性较差的倾向较大。通常在LED封装中,在引线框架上模制成型有被称为反射器的白色树脂,与使用聚邻苯二甲酰胺等热塑性树脂的情况相比,当将与成型金属模具的粘合性更高的环氧树脂模塑料(以下称为“EMC”)用于反射器构件时,为了提升脱模性,通常会添加规定量的蜡。由EMC成型的LED封装会经过基于酸或碱的化学蚀刻工序、或基于喷砂清理(blast cleaning)的物理蚀刻工序等,但是当模制工序中渗出至引线框架的蜡成分未通过蚀刻工序充分去除时,引线框架部位与芯片贴装材料的粘合性变差。
日本特开2013-254893号公报(专利文献1)中报告了:通过使用在金电极部上设置有包含镍(Ni)或钽(Ta)的金属保护层的LED芯片,即使在使用了由高电极污染性的加成固化性有机硅树脂构成的芯片贴装材料的情况下,也能够表现出良好的引线键合性。然而,由于与没有保护层的普通LED芯片相比,具有这样的保护层的LED芯片的制造成本高,因此要求芯片贴装材料本身电极污染性低。
此外,日本特开2016-122828号公报(专利文献2)中报告了:通过在由EMC成型的LED封装的银引线框架上使用硫类光泽剂,从而提升LED装置的发光效率,但当以这样的方式在银表面上使用光泽剂时,芯片贴装材料的粘合性有可能会下降,对芯片贴装材料而言,要求具有更高的与基材的粘合性。
例如,日本特开2008-255227号公报(专利文献3)中报告了:在加成固化性有机硅树脂组合物中,树脂组合物中所含有的低分子硅氧烷成分中除了以D3、D4为代表的无官能的低分子硅氧烷以外,还包含大量的含有作为反应性基团的SiH基的低分子硅氧烷。特别是记载了:通过使聚合度为10以下且一分子中具有1个以上SiH基的低分子硅氧烷为有机硅树脂组合物整体的一定质量%以下,能够抑制在加热固化时污染物附着于周围,然而,由于实施例中的加成固化性有机硅树脂组合物的JIS K6249所规定的以A型硬度计所测得的固化物的硬度为32~66而较软,因此当用作LED装置用芯片贴装材料时,对于粘合强度会有所担忧。
此外,日本特开2012-12434号公报(专利文献4)中报告了一种加成固化性有机硅树脂组合物,其JIS K 6253所规定的D型硬度计硬度为30~70,且有机氢硅氧烷成分同时使用了在侧链具有氢甲硅烷基的直链状有机聚硅氧烷与在末端具有氢甲硅烷基的支链状有机聚有机硅烷,该组合物的透光性与粘合性的耐久性优异,但是该专利文献并未提及以下方面:当用作LED装置用芯片贴装材料时,固化时对LED芯片上的金焊垫部的污染性。
由此,对于以往的加成固化性有机硅树脂组合物,特别是其在被用作LED装置用芯片贴装材料时,存在固化时对LED芯片电极焊垫部的污染发生附着、引线键合性下降的问题;或与由反射器构件成型的光学半导体基板上的银引线框架部位的粘合性不充分的问题。
现有技术文献
专利文献
专利文献1:日本特开2013-254893号公报
专利文献2:日本特开2016-122828号公报
专利文献3:日本特开2008-255227号公报
专利文献4:日本特开2012-012434号公报
发明内容
本发明要解决的技术问题
本发明鉴于上述情况而完成,其目的在于提供一种固化时对LED芯片上的金焊垫部的污染性低,且与由反射器构件成型的基板上的银引线框架的粘合性优异的热固性有机硅树脂组合物、及由该组合物构成的光学半导体装置用芯片贴装材料。
解决技术问题的技术手段
为了解决上述问题,本发明提供一种热固性有机硅树脂组合物,其特征在于,含有作为必要成分的下述(A-1)、(A-2)、(B-1)、(B-2)、(C)、及(D)成分:
(A-1)直链状有机聚硅氧烷,其在一分子中具有2个以上碳原子数为2~8的烯基;
(A-2)支链状有机聚硅氧烷,其由下述式(1)表示,且在一分子中具有2个以上碳原子数为2~8的烯基,其重均分子量Mw为4000~9000,分散度Mw/Mn为2.0以上,
(R1 3SiO1/2)a(R2 3SiO1/2)b(SiO4/2)c (1)
式(1)中,R1为碳原子数为2~8的烯基,R2为碳原子数为1~12的烷基,a、b、c为满足0<a<0.15、0<b<0.6、0<c<0.7且a+b+c=1的数;
(B-1)支链状有机氢聚硅氧烷,其由下述式(2)表示,其在一分子中具有2个以上直接键合于硅原子的氢原子,且25℃时呈液状,其重均分子量Mw为1500~6000,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,
(HR2 2SiO1/2)d(R2 3SiO1/2)e(SiO4/2)f (2)
式(2)中,R2各自与所述R2相同,d、e、f为满足0<d<0.6、0≤e<0.4、0<f<0.6且d+e+f=1的数;
(B-2)直链状有机氢聚硅氧烷,其由下述式(3)表示,其中,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,
(R2 3SiO1/2)2(HR2SiO2/2)x(R2 2SiO2/2)y (3)
式(3)中,R2各自与所述R2相同,x和y为0.60≤(x/(x+y))≤0.95的正数,且30≤x+y≤120;
(C)粘合助剂成分,其由以下述式(4)表示的支链状有机聚硅氧烷组成,其中,该有机聚硅氧烷的重均分子量为1500~6000,环氧当量为250~500g/eq,
(MeSiO3/2)m(EpSiO3/2)n(EpMeSiO2/2)p(Me2SiO2/2)q(ViMeSiO2/2)r(R3O1/2)s (4)
式(4)中,Me为甲基,Ep为具有环氧基的一价有机基团,Vi为乙烯基,R3为碳原子数为1~12的烷基,m、n、p、q、r、s为0≤m<0.35、0≤n<0.35、0≤p<0.35、0.15≤(n+p)/(m+n+p+q+r+s)≤0.35、0.4≤q<0.7、0<r<0.1、0≤s<0.05且m+n+p+q+r+s=1的数;
(D)加成反应催化剂,其由0价铂络合物与+2价铂络合物和/或+4价铂络合物的组合组成,相对于所述(A-1)成分~所述(C)成分的合计100质量份,作为该(D)成分的添加量的0价铂络合物中的铂元素量t(ppm)、+2价铂络合物中的铂元素量u(ppm)、+4价铂络合物中的铂元素量v(ppm),满足0<t<3、5<u+v<30。
若为这样的热固性有机硅树脂组合物,则固化时对LED芯片上的金焊垫部的污染性低,且与由反射器构件成型的基板上的银引线框架的粘合性优异。
本发明的热固性有机硅树脂组合物中,在所述(D)成分中,+2价铂络合物可以为二(乙酰丙酮)铂(II),+4价铂络合物可以为(三甲基)甲基环戊二烯铂(IV)。
若为上述(D)成分,则热固性有机硅树脂组合物的固化反应变佳。
本发明的热固性有机硅树脂组合物能够进一步含有作为(E)稀释剂的烃化合物,该烃化合物在大气压1013hPa下的沸点在200℃以上且低于350℃的范围内,并且25℃时呈液体。
这种(E)成分能够调节本发明的热固性有机硅树脂组合物的黏度,能够提升操作性。
本发明的热固性有机硅树脂组合物的所述(A-1)成分的直链状有机聚硅氧烷可以为由下述式(5)表示的含烯基的直链状有机聚硅氧烷。
式(5)中,R4独立地为碳原子数为2~8的烯基或碳原子数为1~12的烷基,R2为碳原子数为1~12的烷基,k为k>0的整数且为使直链状有机聚硅氧烷的以JIS Z 8803:2011中记载的方法所测得的25℃时的运动黏度为10~1000000mm2/s的数。
本发明的热固性有机硅树脂组合物中,以这种(A-1)成分为佳。
此外,本发明中,针对所述(B-1)成分,优选以JIS K 7117-1:1999中记载的方法所测得的25℃时的所述(B-1)成分的黏度为10Pa·s以上。
若(B-1)成分满足上述黏度,则由于有机氢聚硅氧烷本身的挥发性较低,因此本发明的热固性有机硅树脂组合物能够进一步抑制在固化时污染物附着于周围。
此外,本发明的热固性有机硅树脂组合物中,优选所述(B-1)成分为HR2 2SiO1/2单元来源、R2 3SiO1/2单元来源及SiO4/2单元来源的共水解缩合物,且所述SiO4/2单元来源为四烷氧基硅烷的部分水解物。
若将四烷氧基硅烷的部分水解缩合物用于上述SiO4/2单元来源,则能够获得一种重均分子量变大且挥发性的含氢甲硅烷基的低分子硅氧烷的含量较少的有机氢聚硅氧烷,因此能够使本发明的热固性有机硅树脂组合物变得更佳。
本发明的热固性有机硅树脂组合物中,优选所述(A-2)、(B-1)及(B-2)成分的R2中的全部R2的90摩尔%以上为甲基。
这样的热固性有机硅树脂组合物在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的耐变色性优异。
此外,本发明还提供一种光学半导体装置用芯片贴装材料,其由上述热固性有机硅树脂组合物构成。
本发明的热固性有机硅树脂组合物在固化时对LED芯片上的金焊垫部的污染性低,且能够赋予与由反射器构件成型的基板上的银引线框架良好的粘合性,因此能够适合用于电器电子零件用途,因而能够适合用作光学半导体装置用芯片贴装材料。
发明效果
根据本发明的热固性有机硅树脂组合物,当用作LED用芯片贴装材料时,固化时对光学半导体芯片上的金焊垫部的污染性变低,且能够赋予良好的引线键合性,与由反射器构件成型的基板上的银引线框架的粘合性优异,因此可靠性变高,因而本发明的热固性有机硅树脂组合物作为LED用芯片贴装材料是极为有用的。
具体实施方式
本发明的发明人为了达成上述目的而进行了深入研究,结果发现当将一种含有下述(A-1)~(D)成分的热固性有机硅树脂组合物用作光学半导体装置用芯片贴装材料时,其在固化时对LED芯片上的金焊垫部的污染性低,且与由反射器构件成型的基板上的银引线框架的粘合性优异,从而完成了本发明。
即,本发明为一种热固性有机硅树脂组合物,其特征在于,含有作为必要成分的下述(A-1)、(A-2)、(B-1)、(B-2)、(C)、及(D)成分:
(A-1)直链状有机聚硅氧烷,其在一分子中具有2个以上碳原子数为2~8的烯基;
(A-2)支链状有机聚硅氧烷,其由下述式(1)表示,且在一分子中具有2个以上碳原子数为2~8的烯基,其重均分子量Mw为4000~9000,分散度Mw/Mn为2.0以上,
(R1 3SiO1/2)a(R2 3SiO1/2)b(SiO4/2)c (1)
式(1)中,R1为碳原子数为2~8的烯基,R2为碳原子数为1~12的烷基,a、b、c为满足0<a<0.15、0<b<0.6、0<c<0.7且a+b+c=1的数;
(B-1)支链状有机氢聚硅氧烷,其由下述式(2)表示,其在一分子中具有2个以上直接键合于硅原子的氢原子,且25℃时呈液状,其重均分子量Mw为1500~6000,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,
(HR2 2SiO1/2)d(R2 3SiO1/2)e(SiO4/2)f (2)
式(2)中,R2各自与所述R2相同,d、e、f为满足0<d<0.6、0≤e<0.4、0<f<0.6且d+e+f=1的数;
(B-2)直链状有机氢聚硅氧烷,其由下述式(3)表示,其中,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,
(R2 3SiO1/2)2(HR2SiO2/2)x(R2 2SiO2/2)y (3)
式(3)中,R2各自与所述R2相同,x和y为0.60≤(x/(x+y))≤0.95的正数,且30≤x+y≤120;
(C)粘合助剂成分,其由以下述式(4)表示的支链状有机聚硅氧烷组成,其中,该有机聚硅氧烷的重均分子量为1500~6000,环氧当量为250~500g/eq,
(MeSiO3/2)m(EpSiO3/2)n(EpMeSiO2/2)p(Me2SiO2/2)q(ViMeSiO2/2)r(R3O1/2)s (4)
式(4)中,Me为甲基,Ep为具有环氧基的一价有机基团,Vi为乙烯基,R3为碳原子数为1~12的烷基,m、n、p、q、r、s为满足0≤m<0.35、0≤n<0.35、0≤p<0.35、0.15≤(n+p)/(m+n+p+q+r+s)≤0.35、0.4≤q<0.7、0<r<0.1、0≤s<0.05且m+n+p+q+r+s=1的数;
(D)加成反应催化剂,其由0价铂络合物与+2价铂络合物和/或+4价铂络合物的组合组成,相对于所述(A-1)成分~所述(C)成分的合计100质量份,作为该(D)成分的添加量的0价铂络合物中的铂元素量t(ppm)、+2价铂络合物中的铂元素量u(ppm)、+4价铂络合物中的铂元素量v(ppm),满足0<t<3、5<u+v<30。
以下,对本发明进行详细说明,但是本发明不限定于这些说明。
本发明的热固性有机硅树脂组合物含有作为必要成分的上述(A-1)、(A-2)、(B-1)、(B-2)、(C)、及(D)成分。
根据本发明的热固性有机硅树脂组合物,在用作LED用芯片贴装材料时,固化时对光学半导体芯片上的金焊垫部的污染性变低,且能够赋予良好的引线键合性,与由反射器构件成型的基板上的银引线框架的粘合性优异,因此可靠性变高。
作为表现出该效果的原因,认为可能是:与使用通常用于热固性有机硅树脂组合物中的有机氢聚硅氧烷的情况相比,通过以特定的组合来使用上述特定的有机氢聚硅氧烷,所获得的热固性有机硅树脂组合物中具有氢甲硅烷基的挥发性的低分子硅氧烷的含量较少;以能够在规定的固化时间内充分固定LED芯片的强度进行固化;及保持了固化性良好且同时树脂中有助于粘合的成分能够与基材充分亲和(馴染)的平衡等。
本发明的热固性有机硅树脂组合物含有作为必要成分的上述(A-1)、(A-2)、(B-1)、(B-2)、(C)、及(D)成分,除了这些成分以外,还可根据需要包含其他成分。以下,对构成本发明的热固性有机硅树脂组合物的成分进行说明。
<(A-1)直链状有机聚硅氧烷>
(A-1)成分为一种直链状有机聚硅氧烷,其在一分子中具有2个以上碳原子数为2~8的烯基。关于除烯基以外的基团,并无特别限定,可列举出烷基。作为(A-1)成分,优选仅分子链两末端具有键合于硅原子的烯基的直链状有机聚硅氧烷,特别优选由下述通式(5)表示的直链状有机聚硅氧烷。
式(5)中,R4独立地为碳原子数为2~8的烯基或碳原子数为1~12的烷基,R2为碳原子数为1~12的烷基,k为k>0的整数且为使直链状有机聚硅氧烷的以JIS Z 8803:2011中记载的方法所测得的25℃时的运动黏度为10~1000000mm2/s的数。
上述式(5)中,作为R4的碳原子数为2~8的烯基、特别是碳原子数为2~6的烯基,具体而言,可例示出乙烯基、烯丙基、异丙烯基、丁烯基、戊烯基、己烯基、环己烯基等。此外,作为碳原子数为1~12的烷基、特别是碳原子数为1~10的烷基,具体而言,可例示出甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、新戊基、己基、环己基、辛基、壬基、癸基等烷基等。作为上述R4的烯基,特别优选乙烯基,此外,若考虑到由所获得的加成固化性有机硅树脂组合物(热固性有机硅树脂组合物)制作的有机硅固化物在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的耐变色性,则作为烷基,优选甲基、乙基、丙基、异丙基等烷基,特别优选甲基。
此外,作为R2的碳原子数为1~12的烷基、特别是碳原子数为1~10的烷基,可例示出与上述作为R4的烷基所例示的相同的烷基,其中,基于与上述相同的理由,特别优选甲基。
与侧链具有烯基的有机聚硅氧烷相比,由上述式(5)表示的仅两末端含有烯基的直链状有机聚硅氧烷的反应性优异,并且树脂固化物的延展优异,因此有不易发生龟裂等的优点。
(A-1)成分的直链状有机聚硅氧烷的运动黏度在25℃时优选在10~1000000mm2/s的范围内,更优选在10~100000mm2/s的范围内。若在25℃时的运动黏度低于上述范围,则所获得的固化物的强度有时会变低;若在25℃时的运动黏度高于上述范围,则组合物的黏度变高,因此涂布性有时会下降。此外,当(A-1)成分为2种以上的混合物时,优选该混合物的运动黏度在25℃时在10~1000000mm2/s的范围内。另外,在本发明中,运动黏度为以JISZ 8803:2011中记载的方法于25℃下通过奥氏黏度计(Ostwald viscometer)所测得的值。
作为(A-1)成分,具体而言,可例示出以下化合物。
上述式中,k与上述k相同。
<(A-2)支链状有机聚硅氧烷>
(A-2)成分为一种支链状有机聚硅氧烷,其由下述式(1)表示,且在一分子中具有2个以上碳原子数为2~8的烯基,其重均分子量Mw为4000~9000,分散度Mw/Mn为2.0以上。
(R1 3SiO1/2)a(R2 3SiO1/2)b(SiO4/2)c (1)
式(1)中,R1为碳原子数为2~8的烯基,R2为碳原子数为1~12的烷基,a、b、c为满足0<a<0.15、0<b<0.6、0<c<0.7且a+b+c=1的数。
上述式(1)中,作为R1的碳原子数为2~8的烯基、特别是碳原子数为2~6的烯基,具体而言,可例示出乙烯基、烯丙基、异丙烯基、丁烯基、戊烯基、己烯基、环己烯基;特别优选乙烯基。
上述式(1)中,作为R2的碳原子数为1~12的烷基、特别是碳原子数为1~10的烷基,具体而言,可例示出甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、新戊基、己基、环己基、辛基、壬基、癸基等烷基等。若考虑到由所获得的加成固化性有机硅树脂组合物制作的有机硅固化物在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的耐变色性,则作为上述R2的烷基,优选甲基、乙基、丙基、异丙基等烷基,特别优选甲基。
与在R2SiO2/2单元(D单元)或RSiO3/2单元(T单元)具有烯基的有机聚硅氧烷相比,以这样的方式仅在R3SiO1/2单元(M单元)具有烯基的支链状有机聚硅氧烷与具有氢甲硅烷基的有机氢聚硅氧烷的反应性优异,因此固化时能够抑制含氢甲硅烷基的低分子硅氧烷飞散至周围而成为污染物。
上述(A-2)成分的重均分子量Mw在4000~9000的范围内,特别优选在5000~8000的范围内。若上述支链状有机聚硅氧烷的重均分子量在上述范围内,则容易与(C)成分的极性产生差异,因此树脂组合物固化时能够赋予充分的与基材的粘合性。当上述支链状有机聚硅氧烷的重均分子量低于上述范围时,可能会无法获得充分的粘合性;当上述支链状有机聚硅氧烷的重均分子量高于上述范围时,操作性可能会下降。另外,本发明中提及的重均分子量Mw是指以下述条件所测得的通过凝胶渗透色谱(GPC)而得到的以聚苯乙烯作为标准物质的重均分子量。
上述(A-2)成分的分散度Mw/Mn为2.0以上,优选为2.5以上。当分散度Mw/Mn小于2.0时,操作性可能会下降。另外,所述Mn是指以下述条件所测得的通过凝胶渗透色谱(GPC)而得到的以聚苯乙烯作为标准物质的数均分子量。
[测定条件]
·洗脱液:四氢呋喃(THF)
·流量:0.6mL/min
·检测器:示差折射率检测器(RI)
·色谱柱:TSK Guardcolumn SuperH-L
·TSKgel SuperH4000(6.0mm内径(I.D.)×15cm×1)
·TSKgel SuperH3000(6.0mmI.D.×15cm×1)
·TSKgel SuperH2000(6.0mmI.D.×15cm×2)
(均为TOSOH CORPORATION制造)
·色谱柱温度:40℃
·试样注入量:20μL(浓度为0.5质量%的THF溶液)
此外,相对于硅氧烷单元的合计a+b+c=1,上述式(1)中的R1 3SiO1/2单元的上述含率a在0<a<0.15的范围内,优选在0.05≤a≤0.1的范围内。此外,相对于硅氧烷单元的合计a+b+c=1,R2 3SiO1/2单元的上述含率b为0<b<0.6,优选在0.3≤b<0.5的范围内。进一步,相对于硅氧烷单元的合计a+b+c=1,SiO4/2单元的上述含率c为0<c<0.7,优选在0.4≤c≤0.6的范围内。
上述(A-2)成分可通过下述方式而容易地合成:将作为各单元来源的化合物以上述范围内的含率进行混合,并在例如酸的存在下进行共水解缩合。
此处,作为上述R1 3SiO1/2单元来源,可例示出由下述结构式表示的三有机氯硅烷、三有机烷氧基硅烷及六有机二硅氧烷等有机硅化合物,但是能够使用的R1 3SiO1/2单元来源不限定于这些有机硅化合物。
此处,作为上述R2 3SiO1/2单元来源,可例示出由下述结构式表示的三有机氯硅烷、三有机烷氧基硅烷及六有机二硅氧烷等有机硅化合物,但是能够使用的R2 3SiO1/2单元来源不限定于这些有机硅化合物。
此处,作为上述SiO4/2单元来源,可例示出由下述结构式表示的四氯硅烷和四烷氧基硅烷等有机硅化合物,但是能够使用的SiO4/2单元来源不限定于这些有机硅化合物。
作为上述(A-1)成分和(A-2)成分在热固性有机硅树脂组合物中的掺合量,优选以质量比计在(A-1):(A-2)=55:45~85:15的范围内,特别优选在60:40~80:20的范围内。若(A-1)成分的掺合量在上述范围内,则所获得的有机硅固化物的强度或硬度成为充分的所必要的强度或硬度,因此优选。
<(B-1)支链状有机氢聚硅氧烷>
本发明的(B-1)成分为一种支链状有机氢聚硅氧烷,其由下述式(2)表示,其在一分子中具有2个以上直接键合于硅原子的氢原子,且25℃时呈液状,该聚硅氧烷的重均分子量为1500~6000,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下。
(HR2 2SiO1/2)d(R2 3SiO1/2)e(SiO4/2)f (2)
式(2)中,R2各自与上述R2相同,d、e、f为满足0<d<0.6、0≤e<0.4、0<f<0.6且d+e+f=1的数。
此处,25℃时呈液状是指具有能够在25℃下以旋转黏度计测定黏度的流动性。
上述(B-1)成分作为交联剂发挥作用,通过上述(A-1)成分和(A-2)成分中的键合于硅原子的烯基(特别优选乙烯基)与(B-1)成分中的键合于硅原子的氢原子(氢甲硅烷基)进行加成反应,由本发明的热固性有机硅树脂组合物形成有机硅固化物。
上述式(2)中,R2各自与上述R2相同。若考虑到由所获得的加成固化性有机硅树脂组合物制作的有机硅固化物在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的耐变色性,则作为上述R2的烷基,优选甲基、乙基、丙基、异丙基等烷基,特别优选甲基。
这种支链状有机氢聚硅氧烷由于仅在M单元上具有氢甲硅烷基,因此反应性高,且固化时能够无关低分子地抑制含氢甲硅烷基的硅氧烷飞散至周围而成为污染物。此外,由于含有SiO4/2单元(Q单元),因此能够提升所获得的固化物的强度。
此外,相对于硅氧烷单元的合计d+e+f=1,上述式(2)中的HR2 2SiO1/2单元的上述含率d在0<d<0.6的范围内,优选在0.2≤d≤0.5的范围内。此外,相对于硅氧烷单元的合计d+e+f=1,R2 3SiO1/2单元的上述含率e为0≤e<0.4,优选在0≤e≤0.3的范围内。进一步,相对于硅氧烷单元的合计d+e+f=1,SiO4/2单元的上述含率f为0<f<0.6,优选在0.45≤f≤0.55的范围内。
此外,(B-1)成分的有机氢聚硅氧烷的重均分子量在1500以上6000以下的范围内,优选在2500以上5000以下的范围内。当上述有机氢聚硅氧烷的重均分子量小于1500时,污染物附着在周围的程度可能会变高;当上述有机氢聚硅氧烷的重均分子量超过6000时,操作性可能会下降,因此不优选。
上述(B-1)成分中,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,优选为2.5质量%以下,进一步优选为1质量%以下。若上述含氢甲硅烷基的低分子有机硅化合物含量超过上述值,则无法抑制固化时含氢甲硅烷基的低分子有机硅化合物挥发并在周围形成附着物。另外,含氢甲硅烷基的低分子有机硅化合物的含量可以为0质量%。
另外,本发明中提及的硅原子数为1~10的含氢甲硅烷基的有机硅化合物的含量是指以下述条件所测得的通过气相色谱而定量的该有机硅化合物的含量。
[测定条件]
·装置:GC-2014(Shimadzu Corporation制造)
·色谱柱:商品名称:HP-5MS(Agilent Technologies公司制造,内径:0.25mm,长度:30m,填充材料:[(5%-苯基)-甲基聚硅氧烷]
·检测器:火焰离子化检测仪(FID,检测仪温度:300℃)
·试样:将1.0g试样溶解于10mL的正十四烷/丙酮标准溶液(浓度:20μg/mL)而成的物质设为样品。
·注入量:1μL
·烘箱温度:50℃-280℃/23分钟-280℃/17分钟
·载流气体:种类:氦气,线速:34.0cm/s
此外,上述(B-1)成分的液状的支链状有机氢聚硅氧烷优选以JIS K7117-1:1999中记载的方法所测得的25℃时的黏度为10Pa·s以上,更优选为200Pa·s以上。当(B-1)成分满足上述黏度时,由于有机氢聚硅氧烷本身的挥发性较低,因此能够抑制固化时污染物附着于周围。另外,在本发明中,液状物质是指具有能够在25℃下以旋转黏度计测定黏度的流动性的物质,特别是指25℃时的黏度为10000Pa·s以下的物质。
进一步,(B-1)成分的支链状有机氢聚硅氧烷的氢甲硅烷基量优选为0.1~2mol/100g,特别优选为0.2~0.9mol/100g。
上述(B-1)成分能够与上述(A-2)成分同样地通过下述方式而容易地合成:将作为各单元来源的化合物以上述范围内的含率进行混合,并在例如酸的存在下进行共水解缩合。
此处,作为HR2 2SiO1/2单元来源,可例示出由下述结构式表示的四甲基二硅氧烷等有机硅化合物,但是能够使用的HR2 2SiO1/2单元来源不限定于此有机硅化合物。
此处,作为R2 3SiO1/2单元来源,可例示出与上述(A-2)成分中的R2 3SiO1/2单元来源相同的有机硅化合物。
作为上述SiO4/2单元来源,并无特别限定,可例示出与上述(A-2)成分中的SiO4/2单元来源相同的有机硅化合物。其中,优选将四烷氧基硅烷的部分水解物用作原料,特别优选由下述结构式表示的四甲氧基硅烷和/或四乙氧基硅烷的部分水解缩合物。
作为四烷氧基硅烷的部分水解物,可使用市售品,可列举出例如作为聚硅酸甲酯的M-Silicate 51(产品名称,Tama Chemicals Co.,Ltd.制造)。
如此,优选(B-1)成分为HR2 2SiO1/2单元来源、R2 3SiO1/2单元来源及SiO4/2单元来源的共水解缩合物,且所述SiO4/2单元来源为四烷氧基硅烷的部分水解物。
若将四烷氧基硅烷的部分水解缩合物用于上述SiO4/2单元来源,则能够获得一种重均分子量变大且挥发性的含氢甲硅烷基的低分子硅氧烷的含量少的有机氢聚硅氧烷。
另外,当将四烷氧基硅烷的部分水解缩合物用于上述SiO4/2单元来源时,优选该部分水解缩合物中所包含的四烷氧基硅烷等单体组分的含量少。单体组分的含量优选为10质量%以下,特别优选为5质量%以下。若在该部分水解缩合物中单体组分较多,则上述(B-1)成分中包含较多的挥发性的含氢甲硅烷基的低分子硅氧烷,因此固化时对周围的污染性可能会变高。
<(B-2)直链状有机氢聚硅氧烷>
本发明的(B-2)成分为一种直链状有机氢聚硅氧烷,其由下述式(3)表示,且含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下。
(R2 3SiO1/2)2(HR2SiO2/2)x(R2 2SiO2/2)y (3)
式(3)中,R2各自与上述R2相同,x和y为0.60≤(x/(x+y))≤0.95的正数,且30≤x+y≤120。
上述(B-2)成分与上述(B-1)成分同样作为交联剂发挥作用,通过上述(A-1)成分和(A-2)成分中的键合于硅原子的烯基(特别优选乙烯基)与(B-2)成分中的键合于硅原子的氢原子(氢甲硅烷基)进行加成反应,由本发明的热固性有机硅组合物形成有机硅固化物。
关于上述式(3)中的HR2SiO2/2单元的含量x和R2 2SiO2/2单元的含量y的关系,在0.60≤(x/(x+y))≤0.95的范围内,优选在0.70≤(x/(x+y))≤0.90的范围内。此外,该关系在30≤x+y≤120的范围内,优选在40≤x+y≤110的范围内。
上述式(3)中,R2各自与上述R2相同。若考虑到由所获得的加成固化性有机硅树脂组合物制作的有机硅固化物在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的耐变色性,作为上述R2的烷基,优选甲基、乙基、丙基、异丙基等烷基,特别优选甲基。
这种直链状有机氢聚硅氧烷由于在D单元上包含丰富的具有键合于硅原子的氢原子的硅氧烷单元,因此在进行加成固化反应时能够通过位阻(steric hindrance)来调节固化性。此外,与基材的湿润性高,且因位阻无法加入与烯基的加成固化反应而残留的氢甲硅烷基通过加成反应催化剂转化成羟基甲硅烷基(hydroxysilyl),能够有助于提升与基材的粘合性。
与上述(B-1)成分相同,上述(B-2)成分中,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,优选为2.5质量%以下,更优选为1质量%以下。若上述含氢甲硅烷基的低分子有机硅化合物的含量超过5质量%,则容易在固化时含氢甲硅烷基的低分子有机硅化合物挥发并在周围形成附着物,因此不优选。另外,含氢甲硅烷基的低分子有机硅化合物的含量可以为0质量%。
进一步,(B-2)成分的直链状有机氢聚硅氧烷的氢甲硅烷基量优选为0.7~1.5mol/100g,特别优选为1.0~1.4mol/100g。
作为(B-2)成分的直链状有机氢聚硅氧烷,具体而言,可例示出以下的直链状有机氢聚硅氧烷。
上述式中,x、y与上述x、y相同。
对于上述(B-1)成分和(B-2)成分在热固性有机硅树脂组合物中的掺合量,优选以质量比计在(B-1):(B-2)=95:5~70:30的范围内,特别优选在90:10~75:25的范围内。若(B-1)成分的掺合量为所述上限值以下,则固化反应的进展不会变得过快,能够充分表现出与基材的粘合性,因此优选;若(B-1)成分的掺合量为所述下限值以上,则能够以规定的固化时间获得充分硬度的有机硅固化物,因此优选。
此外,对于(B-1)成分与(B-2)成分合计的掺合量,相对于热固性有机硅树脂组合物整体中的键合于硅原子的烯基的合计1摩尔,优选上述(B-1)成分与(B-2)成分中的键合于硅原子的氢原子的合计在1.0~2.0摩尔的范围内,特别优选在1.1~1.5摩尔的范围内。若(B-1)成分和(B-2)成分中的键合于硅原子的氢原子的合计量在上述范围内,则固化反应能够顺利进行,从而能够在与基材的粘合性高的状态下获得有机硅固化物。
另外,本发明的热固性有机硅树脂组合物中,上述(A-2)、(B-1)及(B-2)成分的R2中,优选全部的R2的90摩尔%以上为甲基,更优选95摩尔%以上为甲基。若在此范围内,则在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的耐变色性优异。
<(C)粘合助剂>
(C)成分的粘合助剂是为了在本发明的热固性有机硅树脂组合物固化时表现出与基材的粘合性而掺合的成分,其为一种支链状有机聚硅氧烷,其由下述式(4)表示,且重均分子量为1500~6000,环氧当量为250~500g/eq。
(MeSiO3/2)m(EpSiO3/2)n(EpMeSiO2/2)p(Me2SiO2/2)q(ViMeSiO2/2)r(R3O1/2)s (4)
式(4)中,Me为甲基,Ep为具有环氧基的一价有机基团,Vi为乙烯基,R3为碳原子数为1~12的烷基,m、n、p、q、r、s为满足0≤m<0.35、0≤n<0.35、0≤p<0.35、0.15≤(n+p)/(m+n+p+q+r+s)≤0.35、0.4≤q<0.7、0<r<0.1、0≤s<0.05且m+n+p+q+r+s=1的数。
上述式(4)中,作为由Ep表示的具有环氧基的一价有机基团,具体而言,可例示出3-环氧丙氧丙基、2-(3,4-环氧环己基)乙基、5,6-环氧己基、7,8-环氧辛基等有机基团;特别是从在掺合于有机硅树脂组合物的状态下的保存稳定性的角度出发,作为Ep,优选3-环氧丙氧丙基。
如此,重均分子量大且环氧当量小的支链状有机聚硅氧烷由于与(A-2)成分的极性差较大,因此固化时容易转移至与基材之间的界面上,因此能够表现出良好的粘合性。此外,由于在D单元上具有乙烯基,因此会通过加成固化反应被导入有机硅树脂组合物中,固化后能够抑制渗出,进一步与在M单元上具有乙烯基的情况相比,由于较温和地导入组合物中,因此能够给予与基材充分亲和的余地。进一步,由于包含较多的二甲基硅氧烷单元,因此对由上述(A-1)~(B-2)成分组成的基础树脂(base resin)的相容性变好,并且能够将在高温条件下或在波长为450nm的蓝色光下进行了长时间放置时的变色性抑制得较低。
此外,相对于硅氧烷单元的合计m+n+p+q+r+s=1,上述式(4)中的MeSiO3/2单元的上述含率m在0≤m<0.35的范围内,特别优选在0≤m≤0.3的范围内。此外,相对于硅氧烷单元的合计m+n+p+q+r+s=1,EpSiO3/2单元的上述含率n在0≤n<0.35的范围内,特别优选在0≤n≤0.3的范围内。进一步,相对于硅氧烷单元的合计m+n+p+q+r+s=1,EpMeSiO2/2单元的上述含率p在0≤p<0.35的范围内,特别优选在0≤p≤0.3的范围内。再进一步,相对于硅氧烷单元的合计m+n+p+q+r+s=1,Me2SiO2/2单元的上述含率q为0.4≤q<0.7,特别优选在0.45≤q≤0.65的范围内。再进一步,相对于硅氧烷单元的合计m+n+p+q+r+s=1,ViMeSiO2/2单元的上述含率r为0<r<0.1,特别优选在0<r≤0.08的范围内。进一步,相对于硅氧烷单元的合计m+n+p+q+r+s=1,R3O1/2单元的上述含率s为0≤s<0.05,优选在0≤s≤0.03的范围内。
此外,上述式(4)的重均分子量在1500~6000的范围内,优选在2000~5000的范围内。当重均分子量超过上述范围时,有机硅树脂固化物的外观可能会变混浊;当重均分子量小于上述范围时,可能无法获得充分的与基材的粘合性。
进一步,上述式(4)的环氧当量在250~500g/eq的范围内,优选在300~450的范围内。当环氧当量超过上述范围时,可能无法获得充分的与基材的粘合性;当环氧当量小于上述范围时,有机硅树脂固化物的外观可能会变混浊。
上述(C)成分能够通过下述方式而容易地合成:将作为各单元来源的化合物以上述范围内的含率进行混合,并在例如碱的存在下进行共水解缩合。
此处,作为上述EpSiO3/2单元来源和EpMeSiO2/2单元来源,可例示出由下述结构式表示的有机硅化合物,但是能够使用的EpSiO3/2单元来源和EpMeSiO2/2单元来源不限定于这些有机硅化合物。
相对于热固性有机硅树脂组合物整体100质量份,(C)成分的掺合量优选在0.5~10质量份的范围内,特别优选在1~8质量份的范围内。若(C)成分的掺合量为0.5质量份以上,则与基材的粘合性优异,因此优选;若为10质量份以下,则使有机硅树脂固化物的外观不会变混浊而呈透明,因此优选。
<(D)加成反应催化剂>
(D)成分的加成反应催化剂是为了进行本发明的热固性有机硅树脂组合物的加成固化反应而掺合的成分。
(D)成分由0价铂络合物与+2价铂络合物和/或+4价铂络合物的组合组成,相对于(A-1)成分~(C)成分的合计100质量份,作为该(D)成分的添加量的0价铂络合物中的铂元素量t(ppm)、+2价铂络合物中的铂元素量u(ppm)、+4价铂络合物中的铂元素量v(ppm),满足0<t<3、5<u+v<30的范围。0价铂络合物有助于热固性反应的启动,可例示出铂(0)的四甲基四乙烯基环四硅氧烷络合物、铂(0)的1,3-二乙烯基四甲基二硅氧烷络合物等。与0价铂络合物相比,+2价铂络合物和+4价铂络合物通过加热使配位子脱离从而表现出活性的情形较慢,通过与上述0价铂络合物组合,与单独使用0价铂络合物的情况相比,能够进一步控制固化性。作为+2价铂络合物,可例示出二(乙酰丙酮)铂(II);此外,作为+4价铂络合物,可例示(三甲基)甲基环戊二烯铂(IV)。若0价铂络合物中的铂元素量t(ppm)、+2价铂络合物中的铂元素量u(ppm)、及+4价铂络合物中的铂元素量v(ppm)在上述范围外,则固化的启动不佳,且不能温和地进行固化反应,因此当用作光学半导体装置用芯片贴装材料时,固化时对金电极焊垫部的污染较多,变得无法充分表现出与基材的粘合性。
本发明的热固性有机硅树脂组合物含有作为必要成分的上述(A-1)、(A-2)、(B-1)、(B-2)及(C)、(D)成分,但可根据需要而含有(E)稀释剂等。
<(E)稀释剂>
(E)成分的稀释剂为一种25℃时呈液体的烃化合物,其在大气压(1013hPa)下的沸点在200℃以上且低于350℃的范围内。作为(E)成分的稀释剂,优选脂肪族烃化合物。
(E)成分的稀释剂是为了调节本发明的热固性有机硅组合物的黏度而掺合的成分,相对于热固性有机硅树脂组合物整体100质量份,该(E)成分的掺合量优选在0.5~10质量份的范围内,特别优选在1~8质量份的范围内。若(E)成分的掺合量低于上述上限,则加热固化时不会发生部分溶剂残留,不会使所获得的树脂固化物的强度下降。若高于上述下限,则操作性良好。
此外,(E)成分在大气压(1013hPa)下的沸点为200℃以上且低于350℃,优选在220℃以上330℃以下的范围内。若(E)成分的沸点为上述下限以上,则在对涂布于基板上的树脂进行LED芯片接合的工序中,操作性不会下降,也不会发生因溶剂挥发导致增黏而使树脂无法以充分的范围在芯片的底部展开。此外,若(E)成分的沸点为上述上限以下,则加热固化时不会发生部分溶剂残留,不会使所获得的树脂固化物的强度下降。
进一步,由于有可能成为本发明的热固性有机硅树脂组合物的加成阻碍,因此(E)成分优选经脱硫处理,特别优选硫组分低于1ppm。此外,从与本发明的热固性有机硅树脂组合物的相容性的角度出发,(E)成分的苯胺点特别优选为100℃以下。
作为(E)成分的稀释剂,可以为单一的烃化合物,也可以为多种化合物的混合物。当使用混合物时,只要沸点的上下限值(初沸点~终点(或干点))在上述优选的沸点范围内即可。作为所述稀释剂,能够使用市售品。具体而言,可例示TOTAL公司的“HydrosealG232H”(沸点为238~261℃)、“Hydroseal G240H”(沸点为255~282℃)、“HydrosealG250H”(沸点为258~326℃)、“Hydroseal G270H”(沸点为258~287℃)、“Hydroseal G3H”(沸点为277~321℃)、“Hydroseal G400H”(沸点为305~347℃);Exxon Mobil公司的“ExxsolTM D95”(沸点为222~242℃)、“ExxsolTM D110”(沸点为248~265℃)、“ExxsolTMD130”(沸点为279~313℃)、“IsoperTM M”(沸点为224~254℃);Idemitsu Kosan Co.,Ltd.的“IP2028”(沸点为213~262℃);这些稀释剂可以单独使用1种,也可混合使用2种以上。
这种由烃化合物组成的稀释剂,与有机硅树脂的相容性高,并且与有机硅树脂相比,表面张力较高,因此芯片压接后能够提升树脂滞留性。当树脂滞留性高时,能够将树脂部的表面积保持得较小,因此固化时能够降低树脂组合物中的具有氢甲硅烷基的低分子硅氧烷发生飞散的风险。此外,芯片周围的焊角能够保持刚压接后的形状,因此能够抑制芯片的强化效果下降。
<其他成分>
此外,除了上述(A)~(E)成分以外,本发明的热固性有机硅树脂组合物中还可根据需要适当掺合各种公知的添加剂。
[无机填充材料]
出于提升所获得的固化物的强度的目的或赋予触变性并提升芯片贴装材料的涂布操作性的目的,本发明的热固性有机硅树脂组合物中可适当掺合无机填充材料。作为无机填充材料,可例示出例如气相二氧化硅、气相二氧化钛等。特别是,从所获得的固化物的透明性的角度出发,优选使用气相二氧化硅作为无机填充材料。
当添加无机填充材料时,相对于热固性有机硅树脂组合物整体100质量份,无机填充材料的掺合量能够优选设为20质量份以下,更优选在1~10质量份的范围内。特别是,当使用气相二氧化硅作为无机填充材料时,从与加成固化性有机硅树脂的亲和性的角度出发,优选使二氧化硅表面经疏水性基团处理。作为疏水性基团,具体而言,可列举出三甲基甲硅烷基或二甲基甲硅烷基等硅氧烷类。
此外,通过进行表面处理,还具有下述效果:抑制所述(C)成分中所包含的环氧基与气相二氧化硅表面的羟基甲硅烷基的相互作用,改善保存稳定性。因此,作为气相二氧化硅,优选经充分的表面处理,具体而言,优选使用比表面积为150m2/g以上250m2/g以下的气相二氧化硅,特别优选使用比表面积为170m2/g以上230m2/g以下的气相二氧化硅。作为经以上述硅氧烷类官能团进行表面处理后的气相二氧化硅,可列举出下述作为市售品的气相二氧化硅:日本AEROSIL公司的经三甲基甲硅烷基进行表面处理后的R812(比表面积为230~290m2/g)及RX300(比表面积为180~220m2/g);经二甲基甲硅烷基进行表面处理后的R976(比表面积为225~275m2/g)、R976S(比表面积为215~265m2/g)等。
[固化抑制剂]
出于调节固化速度等的目的,本发明的热固性有机硅树脂组合物中可掺合固化抑制剂。作为固化抑制剂,可列举出例如选自由四甲基四乙烯基环四硅氧烷或六乙烯基二硅氧烷、1,3-二乙烯基四甲基二硅氧烷等含乙烯基的有机聚硅氧烷;乙炔基环己醇或3-甲基-1-丁炔-3-醇等炔醇类及其硅烷改性物或硅氧烷改性物;氢过氧化物、四甲基乙二胺、苯并三唑、异氰脲酸三烯丙酯、马来酸烷酯、及它们的混合物组成的组中的化合物。掺合固化抑制剂时,相对于有机硅树脂组合物整体100质量份,优选添加0.001~1.0质量份,特别优选添加0.005~0.5质量份。
[耐热性提升剂]
出于提升在高温环境下的抗裂性的目的,本发明的热固性有机硅树脂组合物中可掺合耐热性提升剂。耐热性提升剂针对在180℃以上等高温环境下进行的有机硅树脂的氧化劣化,具有例如通过切断二甲基硅氧烷链长等抑制树脂硬度增高的效果。作为耐热性提升剂,可列举出例如三(2-乙基己酸)铈(III)、三烷氧基铈(III)、及铈(III)的硅氧烷改性体等。
相对于热固性有机硅树脂组合物整体100质量份,耐热性提升剂的掺合量优选以金属元素的质量单位计在0.1~100ppm的范围内,更优选在1~50ppm的范围内。若耐热性提升剂的掺合量在上述范围内,则高温环境下的抗裂性不会下降,也不会发生因有机硅树脂固化物的着色而导致的透光率的大幅下降。此外,当芯片贴装材料的涂布方法为戳印法时,由于以薄膜状态放置在树脂盘上,因此优选使用水解性低的耐热性提升剂。
<固化方法>
本发明的热固性有机硅树脂组合物在涂布于基板上后,可根据用途而加以固化,可优选在温度为100~200℃的范围内进行加热固化,更优选在温度为150~170℃的范围内进行加热固化。若加热温度在上述范围内,则基材与树脂固化物的粘合强度不会下降,也不会发生因溶剂的急速挥发而导致产生气泡或树脂发生劣化。另外,上述加热固化时间可以为1~4小时,并且也可采用阶段固化的方式。
通过以特定的组合使用上述特定的有机氢聚硅氧烷,本发明的热固性有机硅树脂组合物在固化时对LED芯片上的金焊垫部的污染性低,且能够赋予良好的与由反射器构件成型的基板上的银引线框架的粘合性,因此能够适合用于电器电子零件用途,具体而言,能够适合用作光学半导体装置用芯片贴装材料。
实施例
以下,示出合成例、实施例及比较例来具体地说明本发明,但是本发明不受限于下述实施例。另外,份是指“质量份”,Me表示“甲基”,Vi表示“乙烯基”,Ep’表示“γ-环氧丙氧丙基”。此外,SiVi基量是指键合于硅原子的乙烯基的量。
[合成例1]
·有机氢聚硅氧烷(b1-1)
将盐酸水溶液滴入6mol以(HMe2Si)2O表示的有机二硅氧烷、3mol的聚硅酸甲酯(产品名称:M-Silicate 51,Tama Chemicals Co.,Ltd.制造,单体组分为4.3质量%以下)的异丙醇溶液中,并在室温(25℃)下搅拌5小时。加入甲苯进行稀释,并分离废酸,进行水洗直至有机层成为中性。将有机层脱水后,于150℃减压下利用提馏(stripping)操作来馏除溶剂,获得作为25℃时的黏度为1200Pa·s的无色透明液状物质的有机氢聚硅氧烷(b1-1)。所获得的(b1-1)的构成硅氧烷单元由50摩尔%的HMe2SiO1/2单元、50摩尔%的SiO4/2单元表示,通过GPC测定而得到的重均分子量Mw为3500,氢甲硅烷基量为0.72mol/100g。此外,经测定,(b1-1)中的硅原子数为1~10的含氢甲硅烷基的有机硅化合物的含量为0.34质量%。
[合成例2]
·有机氢聚硅氧烷(b1-2)
将盐酸水溶液滴入6mol以(HMe2Si)2O表示的有机二硅氧烷、12mol以(MeO)4Si表示的四烷氧基硅烷的异丙醇溶液中,并在室温(25℃)下搅拌5小时。加入甲苯进行稀释,并分离废酸,进行水洗直至有机层成为中性。将有机层脱水后,于150℃减压下利用提馏操作来馏除溶剂,获得作为25℃时的黏度为280Pa·s的无色透明液状物质的有机氢聚硅氧烷(b1-2)。所获得的(b1-2)的构成硅氧烷单元由52摩尔%的HMe2SiO1/2单元、48摩尔%的SiO4/2单元表示,通过GPC测定而得到的重均分子量Mw为3100,氢甲硅烷基量为0.74mol/100g。此外,经测定,(b1-2)中的硅原子数为1~10的含氢甲硅烷基的有机硅化合物的含量为28.4质量%。
<(A-1)成分>
(a1-1):由下述式表示的有机聚硅氧烷,其SiVi基量为0.045mol/100g,25℃时的运动黏度为55mm2/s,且25℃时呈液体,
(ViMe2SiO1/2)2(Me2SiO2/2)50。
<(A-2)成分>
(a2-1):有机聚硅氧烷,其硅氧烷单元由6.2摩尔%Vi3SiO1/2单元、45.8摩尔%Me3SiO1/2单元、48.0摩尔%SiO4/2单元表示,SiVi基量为0.198mol/100g,通过GPC测定而得到的重均分子量Mw为7500,分散度Mw/Mn为3.0,且25℃时呈固体。
(a2-2):有机聚硅氧烷,其硅氧烷单元由6.2摩尔%Vi3SiO1/2单元、45.8摩尔%Me3SiO1/2单元、48.0摩尔%SiO4/2单元表示,SiVi基量为0.195mol/100g,通过GPC测定而得到的重均分子量Mw为3800,分散度Mw/Mn为1.8,且25℃时呈固体。
<(B-1)成分>
(b1-1):上述合成例1中获得的有机氢聚硅氧烷;
(b1-2):上述合成例2中获得的有机氢聚硅氧烷。
<(B-2)成分>
(b2-1):由下述式表示的有机氢聚硅氧烷,其氢甲硅烷基量为1.13mol/100g,硅原子数为1~10的含氢甲硅烷基的有机硅化合物的含量为0.01质量%,25℃时的运动黏度为45mm2/s,且25℃时呈液体,
(Me3SiO1/2)2(HMeSiO2/2)36(Me2SiO2/2)12。
(b2-2):由下述式表示的有机氢聚硅氧烷,其氢甲硅烷基量为1.35mol/100g,硅原子数为1~10的含氢甲硅烷基的有机硅化合物的含量为0.01质量%,25℃时的运动黏度为140mm2/s,且25℃时呈液体,
(Me3SiO1/2)2(HMeSiO2/2)86(Me2SiO2/2)1。
(b2-3):由下述式表示的有机氢聚硅氧烷,其氢甲硅烷基量为1.55mol/100g,硅原子数为1~10的含氢甲硅烷基的有机硅化合物的含量为0.02质量%,25℃时的运动黏度为23mm2/s,且25℃时呈液体,
(Me3SiO1/2)2(HMeSiO2/2)38。
<(C)成分>
(c-1):有机聚硅氧烷,其硅氧烷单元由29摩尔%Ep’SiO3/2单元、64摩尔%Me2SiO2/2单元、6摩尔%ViMeSiO2/2单元、1摩尔%MeO1/2单元表示,通过GPC测定而得到的重均分子量Mw为2400,SiVi基量为0.05mol/100g,环氧当量为330g/eq,25℃时的运动黏度为350mm2/s,且25℃时的性状为液体。
(c-2):有机聚硅氧烷,其硅氧烷单元由25摩尔%MeSiO3/2单元、22摩尔%Ep’MeSiO2/2单元、47摩尔%Me2SiO2/2单元、5摩尔%ViMeSiO2/2单元、1摩尔%MeO1/2单元表示,通过GPC测定而得到的重均分子量Mw为3100,SiVi基量为0.05mol/100g,环氧当量为435g/eq,25℃时的运动黏度为360mm2/s,且25℃时的性状为液体。
(c-3):有机聚硅氧烷,其硅氧烷单元由20摩尔%MeSiO3/2单元、9摩尔%Ep’MeSiO2/2单元、65摩尔%Me2SiO2/2单元、5摩尔%ViMeSiO2/2单元、1摩尔%MeO1/2单元表示,通过GPC测定而得到的重均分子量Mw为1900,SiVi基量为0.05mol/100g,环氧当量为850g/eq,25℃时的运动黏度为105mm2/s,且25℃时的性状为液体。
<(D)成分>
(d-1):铂(0)的四甲基四乙烯基环四硅氧烷络合物的四甲基四乙烯基环四硅氧烷溶液,其铂含量为2质量%,SiVi基量为1.15mol/100g。
(d-2):二(乙酰丙酮)铂(II)的甲苯溶液,其铂含量为1质量%。
(d-3):(三甲基)甲基环戊二烯铂(IV)的甲苯溶液,其铂含量为1质量%。
<(E)成分>
(e-1):TOTAL公司制造的烃溶剂“Hydroseal G240H”
[大气压(1013hPa)下的沸点:255~282℃]
<无机填充材料>
(f-1):日本AEROSIL公司制造的气相二氧化硅“RX300”
[实施例1~4、比较例1~8]
根据表1所示的掺合比(数值是质量份)来制备实施例1~4及比较例1~8的加成固化性有机硅树脂组合物(热固性有机硅树脂组合物),并根据下述所示的试验方法来评价该组合物的硬度、固化时非污染性、引线键合性、粘合性。各测定结果如表1所示。
(a)硬度
使用热风循环式干燥机,以150℃对加成固化性有机硅树脂组合物加热3小时,由此制作有机硅固化物。依据JIS K 6253-3:2012,使用D型硬度计对该有机硅固化物进行测定。
(b)固化时非污染性
通过使用了镀金板的以下方法,评价加成固化性有机硅树脂组合物固化时的污染性。
将加成固化性有机硅树脂组合物1.0g与根据电镀法实施了镀金的面积为2cm2的镀金板,以有机硅树脂与镀金板不接触的方式一起配置在容积为30cm3的铝制密封容器中,并使用热风循环式干燥机,以150℃加热3小时。加热后,在容器被密封的状态下将该容器冷却至25℃,并从容器中取出镀金板后,通过肉眼来观察镀金板表面的污染物附着情况。
另外,对于固化时的非污染性,将附着于镀金板表面的污染物的比例小于镀金板表面的总面积的5%的评价为“良(○)”,将为5%以上但小于25%的评价为“可接受(△)”,将为25%以上的评价为“不合格(×)”。
(c)引线键合性
根据以下方法来评价加成固化性有机硅树脂组合物的引线键合性。
将树脂以规定量涂布在引线框架部为镀银、反射器构件为EMC且成型后通过化学蚀刻进行了清洗的SMD型3030封装的各空腔(cavity)中央部上,并将LED芯片(GeneLiteInc.制造:B2424(610μm□))进行固晶后,以密封状态装入铝制袋中,并使用热风循环式干燥机,以150℃加热3小时进行固化。然后,在该袋被密封的状态下,使该容器冷却至常温(25℃),并从袋中取出引线框架。然后,使用直径30μm的金线,并通过引线键合机(SHINKAWALTD.制造:UTC-1000super)将LED芯片上的电极与引线框架表面接合,然后以JESD22-B116中记载的方法,通过焊接强度测试仪(bond tester,Nordson AdvancedTechnology(Japan)K.K.制造:Dage4000)对位于LED芯片电极上的第一焊球部(p侧/n侧电极合计100个)的焊球剪切强度进行测定。
另外,引线键合性是通过在尝试引线键合操作的合计100个电极中,根据无法形成第一焊球部且未能引线键合的电极的个数(无法引线键合数)、及能够形成第一焊球部且进行了焊球剪切强度测定的所有第一焊球部的焊球剪切强度的平均值来进行评价的。此时,对于焊球剪切强度的评价,将在使用了热固性环氧树脂银糊料(产品名称:X-43-5603-7AQ,Shin-Etsu Chemical Co.,Ltd.制造)的情况下的焊球剪切强度的平均值设为100%时,计算在使用了实施例1~4及比较例1~8中所示的加成固化性有机硅树脂组合物的情况下的焊球剪切强度的平均值相当于多少%,从而进行评价。
(d)粘合性
将树脂以规定量涂布在引线框架部为镀银、反射器构件为EMC且成型后通过化学蚀刻进行了清洗的SMD型3030封装的各空腔中央部上,并将LED芯片(GeneLite Inc.制造:B2424(610μm□))进行固晶后,使用热风循环式干燥机,以150℃加热3小时进行固化。加热后,将所取出的封装冷却至25℃,然后通过焊接强度测试仪(Nordson AdvancedTechnology(Japan)K.K.制造:Dage4000),以试验数量为50的方式对各树脂测定LED芯片与银镀覆的粘合强度,并计算平均粘合强度。测定后,利用显微镜观察银镀覆表面,将银镀覆侧的平均残余树脂以面积比计为70%以上的评价为“树脂残余良(○)”,将为40%以上但小于70%的评价为“可接受(△)”,将小于40%的评价为“不合格(×)”,从而评价破坏形态。
由上述评价试验的结果可知,本发明(实施例1~4)的热固性有机硅树脂组合物在固化时对光学半导体芯片上的金焊垫部的污染性较低,且与由反射器构件成型的基板上的银引线框架的粘合性优异。
另一方面,具有烯基的支链状有机聚硅氧烷的重均分子量、分散度小于本发明所规定的重均分子量、分散度的比较例1的热固性有机硅树脂组合物的粘合性较差;支链状有机氢聚硅氧烷含有超过5质量%的含氢甲硅烷基的硅原子数为1~10的有机硅化合物的比较例2、及直链状有机氢聚硅氧烷未满足式(3)的x、y的比较例3的热固性有机硅树脂组合物的固化时非污染性、引线键合性较差。此外,(D)成分仅为0价铂络合物的比较例5、8的热固性有机硅树脂组合物的粘合性较差;(D)成分仅为+2价铂络合物或+4价铂络合物的比较例6、7的热固性有机硅树脂组合物的固化时非污染性、引线键合性较差。包含环氧当量超过本发明的上限值的粘合助剂的比较例4、8未能获得充分的与基材的粘合性。
由此可知,在本发明的范围外的比较例1~8的热固性有机硅树脂组合物无法同时满足固化时非污染性和粘合性这两者。因此,确定本发明的热固性有机硅树脂组合物作为光学半导体装置用芯片贴装材料是极为有用的。
另外,本发明并不限定于上述实施方式。上述实施方式仅为例示,任何具有实质上与本发明的申请专利范围所记载的技术构思相同的构成且发挥相同技术效果的方案,皆包含在本发明的保护范围内。
Claims (14)
1.一种热固性有机硅树脂组合物,其特征在于,含有作为必要成分的下述(A-1)、(A-2)、(B-1)、(B-2)、(C)、及(D)成分:
(A-1)直链状有机聚硅氧烷,其在一分子中具有2个以上碳原子数为2~8的烯基;
(A-2)支链状有机聚硅氧烷,其由下述式(1)表示,且在一分子中具有2个以上碳原子数为2~8的烯基,其重均分子量Mw为4000~9000,分散度Mw/Mn为2.0以上,
(R1 3SiO1/2)a(R2 3SiO1/2)b(SiO4/2)c(1)
式(1)中,R1为碳原子数为2~8的烯基,R2为碳原子数为1~12的烷基,a、b、c为满足0<a<0.15、0<b<0.6、0<c<0.7且a+b+c=1的数;
(B-1)支链状有机氢聚硅氧烷,其由下述式(2)表示,其在一分子中具有2个以上直接键合于硅原子的氢原子,且25℃时呈液状,其重均分子量Mw为1500~6000,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,
(HR2 2SiO1/2)d(R2 3SiO1/2)e(SiO4/2)f(2)
式(2)中,R2各自与所述R2相同,d、e、f为满足0<d<0.6、0≤e<0.4、0<f<0.6且d+e+f=1的数;
(B-2)直链状有机氢聚硅氧烷,其由下述式(3)表示,其中,含有氢甲硅烷基的硅原子数为1~10的有机硅化合物的含量为5质量%以下,
(R2 3SiO1/2)2(HR2SiO2/2)x(R2 2SiO2/2)y(3)
式(3)中,R2各自与所述R2相同,x和y为0.60≤(x/(x+y))≤0.95的正数,且30≤x+y≤120;
(C)粘合助剂成分,其由以下述式(4)表示的支链状有机聚硅氧烷组成,其中,该有机聚硅氧烷的重均分子量为1500~6000,环氧当量为250~500g/eq,
(MeSiO3/2)m(EpSiO3/2)n(EpMeSiO2/2)p(Me2SiO2/2)q(ViMeSiO2/2)r(R3O1/2)s(4)
式(4)中,Me为甲基,Ep为具有环氧基的一价有机基团,Vi为乙烯基,R3为碳原子数为1~12的烷基,m、n、p、q、r、s为满足0≤m<0.35、0≤n<0.35、0≤p<0.35、0.15≤(n+p)/(m+n+p+q+r+s)≤0.35、0.4≤q<0.7、0<r<0.1、0≤s<0.05且m+n+p+q+r+s=1的数;
(D)加成反应催化剂,其由0价铂络合物与+2价铂络合物和/或+4价铂络合物的组合组成,相对于所述(A-1)成分~所述(C)成分的合计100质量份,作为所述(D)成分的添加量的0价铂络合物中的铂元素量t(ppm)、+2价铂络合物中的铂元素量u(ppm)、+4价铂络合物中的铂元素量v(ppm),满足0<t<3、5<u+v<30,
在所述热固性有机硅树脂组合物中,所述(A-1)成分和所述(A-2)成分的掺合量,以质量比计在(A-1):(A-2)=55:45~85:15的范围内;所述(B-1)成分和所述(B-2)成分的掺合量,以质量比计在(B-1):(B-2)=95:5~70:30的范围内;相对于所述热固性有机硅树脂组合物整体100质量份,所述(C)成分的掺合量在0.5~10质量份的范围内。
2.根据权利要求1所述的热固性有机硅树脂组合物,其特征在于,在所述(D)成分中,+2价铂络合物为二(乙酰丙酮)铂(II)。
3.根据权利要求1所述的热固性有机硅树脂组合物,其特征在于,在所诉(D)成分中,+4价铂络合物为(三甲基)甲基环戊二烯铂(IV)。
4.根据权利要求2所述的热固性有机硅树脂组合物,其特征在于,在所述(D)成分中,+4价铂络合物为(三甲基)甲基环戊二烯铂(IV)。
5.根据权利要求1所述的热固性有机硅树脂组合物,其特征在于,进一步含有作为(E)稀释剂的烃化合物,所述烃化合物在大气压1013hPa下的沸点在200℃以上且低于350℃的范围内,并且25℃时呈液体。
6.根据权利要求2所述的热固性有机硅树脂组合物,其特征在于,进一步含有作为(E)稀释剂的烃化合物,所述烃化合物在大气压1013hPa下的沸点在200℃以上且低于350℃的范围内,并且25℃时呈液体。
7.根据权利要求3所述的热固性有机硅树脂组合物,其特征在于,进一步含有作为(E)稀释剂的烃化合物,所述烃化合物在大气压1013hPa下的沸点在200℃以上且低于350℃的范围内,并且25℃时呈液体。
8.根据权利要求4所述的热固性有机硅树脂组合物,其特征在于,进一步含有作为(E)稀释剂的烃化合物,所述烃化合物在大气压1013hPa下的沸点在200℃以上且低于350℃的范围内,并且25℃时呈液体。
9.根据权利要求1所述的热固性有机硅树脂组合物,其特征在于,所述(A-1)成分的直链状有机聚硅氧烷为由下述式(5)表示的含烯基的直链状有机聚硅氧烷,
式(5)中,R4独立地为碳原子数为2~8的烯基或碳原子数为1~12的烷基,R2为碳原子数为1~12的烷基,k为k>0的整数且为使直链状有机聚硅氧烷的以JIS Z 8803:2011中记载的方法所测得的25℃时的运动黏度为10~1000000mm2/s的数。
10.根据权利要求1所述的热固性有机硅树脂组合物,其特征在于,针对所述(B-1)成分,以JIS K 7117-1:1999中记载的方法所测得的25℃时的所述(B-1)成分的黏度为10Pa·s以上。
11.根据权利要求1所述的热固性有机硅树脂组合物,其特征在于,所述(B-1)成分为HR2 2SiO1/2单元来源、R2 3SiO1/2单元来源及SiO4/2单元来源的共水解缩合物,所述SiO4/2单元来源为四烷氧基硅烷的部分水解物。
12.根据权利要求1~11中任一项所述的热固性有机硅树脂组合物,其特征在于,所述(A-2)、(B-1)及(B-2)成分的R2中,全部R2的90摩尔%以上为甲基。
13.一种光学半导体装置用芯片贴装材料,其由权利要求1~11中任一项所述的热固性有机硅树脂组合物构成。
14.一种光学半导体装置用芯片贴装材料,其由权利要求12所述的热固性有机硅树脂组合物构成。
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