WO2012164636A1 - 半導体封止用シリコーン組成物 - Google Patents
半導体封止用シリコーン組成物 Download PDFInfo
- Publication number
- WO2012164636A1 WO2012164636A1 PCT/JP2011/006287 JP2011006287W WO2012164636A1 WO 2012164636 A1 WO2012164636 A1 WO 2012164636A1 JP 2011006287 W JP2011006287 W JP 2011006287W WO 2012164636 A1 WO2012164636 A1 WO 2012164636A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sio
- group
- formula
- represented
- polyorganosiloxane
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 238000007789 sealing Methods 0.000 title claims abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 49
- -1 siloxane unit Chemical group 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 238000003860 storage Methods 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000007423 decrease Effects 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 64
- 238000005538 encapsulation Methods 0.000 claims description 18
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 238000011067 equilibration Methods 0.000 claims description 10
- 238000010559 graft polymerization reaction Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229910020487 SiO3/2 Inorganic materials 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 57
- 229920002050 silicone resin Polymers 0.000 description 57
- 239000008096 xylene Substances 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 12
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000001723 curing Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000005372 silanol group Chemical group 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- 238000010533 azeotropic distillation Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000005051 trimethylchlorosilane Substances 0.000 description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 239000005054 phenyltrichlorosilane Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004954 Polyphthalamide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- PEQHCACQYBJVIC-UHFFFAOYSA-L cesium;potassium;dihydroxide Chemical compound [OH-].[OH-].[K+].[Cs+] PEQHCACQYBJVIC-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 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
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 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
- 230000003301 hydrolyzing effect Effects 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 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
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006375 polyphtalamide Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 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
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical group CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000003637 basic solution 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical group CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- 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
-
- 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
- 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
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- 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
- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Definitions
- the present invention relates to a silicone composition for semiconductor encapsulation, and relates to a silicone composition suitable as a sealing material for sealing an optical semiconductor element such as an LED (light emitting diode).
- An LED lamp known as an optical semiconductor device has a structure in which an LED die-bonded to a supporting substrate is sealed with a sealing material made of a transparent resin.
- a composition mainly composed of an epoxy resin has been used as a sealing material for sealing the LED.
- the composition which has silicone (polyorganosiloxane) as a main component is being used as a sealing material.
- the addition reaction curable silicone composition is cured in a short time by heating, so that it has good productivity and is suitable as an LED sealing material.
- the hardened silicone cured product has no surface tackiness, it has an advantage that it can prevent adhesion of dust and adhesion between LEDs.
- the hardened silicone cured product is more fragile than the epoxy resin, and has problems such as cracking and peeling from the base material in the reliability test such as curing or moisture absorption reflow.
- the solvent-soluble organopolysiloxane (A) component is prepared by a hydrosilylation reaction using the same type of catalyst as the hydrosilylation reaction catalyst (C) component, so the component (A) is prepared.
- the catalyst used in the process may remain, and the stability when mixed with the component (B) deteriorates.
- the present invention has been made to solve such problems, and forms a cured product having an appropriate elastic modulus, and can greatly reduce the elastic modulus of the cured product by heating.
- the purpose is to provide goods.
- the inventors of the present invention have a bifunctional siloxane unit containing a siloxane unit that does not participate in a hydrosilylation reaction including a trifunctional unit at a predetermined ratio and that contains an alkenyl group. It has been found that by using a polyorganosiloxane containing a monofunctional siloxane unit as a base polymer, the storage modulus of the cured product can be significantly reduced by heating, and the present invention has been made.
- the silicone composition for semiconductor encapsulation of the present invention is represented by (A) (a1) at least represented by the formula: R 1 SiO 3/2 (wherein R 1 represents an alkyl group or an aryl group). 60 to 99 parts by weight of an organosiloxane containing a functional siloxane unit and not participating in hydrosilylation reaction, and (a2) formula: R 2 2 SiO 2/2 (wherein R 2 represents an alkenyl group, an alkyl group or an aryl group) And at least one in the molecule is an alkenyl group.) And / or the formula: R 2 3 SiO 1/2 (wherein R 2 is as described above).
- polyorganosiloxane having an average of one or more alkenyl groups in one molecule obtained by reacting 40 to 1 part by weight of an organosiloxane containing a monofunctional siloxane unit represented And (B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule and having a viscosity of 1 to 1000 mPa ⁇ s at 25 ° C.
- the amount of hydrogen atoms bonded to silicon atoms is 0.5 to 3.0 moles per mole of alkenyl groups bonded to the atoms, and (C) the catalyst amount of the platinum-based catalyst,
- the storage elastic modulus is characterized by a drop of 40% or more at 25 to 50 ° C.
- a cured product having an appropriate storage elastic modulus and whose storage elastic modulus is greatly reduced by heating can be formed.
- the stress caused by thermal expansion of the cured product due to heat generated from the semiconductor element can be relieved. Therefore, generation
- the component (A) is a main component for imparting a significant decrease (a decrease of 40% or more from 25 ° C. to 50 ° C.) due to heating of the storage elastic modulus of the cured product, which is a feature of the present invention.
- Component (A) is a polyorganosiloxane having an average of one or more alkenyl groups in one molecule, (a1) 60 to 99 parts by weight of organosiloxane not involved in the hydrosilylation reaction, and (a2) the hydrosilylation reaction. It is obtained by reacting 40 to 1 part by weight of an organosiloxane containing a bifunctional siloxane unit having an alkenyl group involved and / or a monofunctional siloxane unit having an alkenyl group.
- the component (a2) may contain either one of a bifunctional siloxane unit having an alkenyl group or a monofunctional siloxane unit having an alkenyl group, or may contain both. Further, it may contain a bifunctional and / or monofunctional siloxane unit not containing an alkenyl group.
- the organosiloxane not involved in the hydrosilylation reaction contains at least a trifunctional siloxane unit represented by the formula: R 1 SiO 3/2 .
- a bifunctional siloxane unit having an alkenyl group is represented by the formula: R 2 2 SiO 2/2
- a monofunctional siloxane unit having an alkenyl group is represented by the formula: R 2 3 SiO 1/2.
- R 1 represents an alkyl group or an aryl group
- R 2 represents an alkenyl group, an alkyl group or an aryl group
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and an octyl group, and a methyl group is more preferable.
- the aryl group include a phenyl group and a tolyl group, and a phenyl group is more preferable.
- the alkenyl group include a vinyl group, an allyl group, a butenyl group, a petenyl group, and a hexenyl group, and a vinyl group is more preferable.
- (a2) at least one of the molecules is an alkenyl group, and among R 2 possessed by the monofunctional siloxane unit, (a2) molecule At least one of them is an alkenyl group.
- the component (A) has an average of 1 or more alkenyl groups in one molecule. Further, from the viewpoint of increasing the refractive index of the cured product, 20 to 70 mol% of all organic groups bonded to the silicon atom of the component (a1) are preferably phenyl groups, and 40 to 60 mol% are phenyl groups. More preferably, it is a group.
- the polyorganosiloxane of component (A) is, for example, an average unit formula: (R 1 SiO 3/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO (3-n) / 2 Y n ) c (R 1 2 SiO (2-m) / 2 Y m )
- R 1 represents an alkyl group or an aryl group
- R 2 represents an alkenyl group, an alkyl group, or an aryl group
- Y represents an alkoxy group or a hydroxyl group.
- the alkyl group, aryl group, and alkenyl group are the same as those described above, and are preferably a methyl group, a phenyl group, and a vinyl group, respectively.
- the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group and an ethoxy group are more preferable.
- n 1 or 2
- m 1 or 2
- the siloxane unit represented by the formula: R 1 SiO (3-n) / 2 Y n is a bifunctional siloxane unit or a monofunctional siloxane unit.
- the siloxane unit represented by R 1 2 SiO (2-m) / 2 Y m is a monofunctional siloxane unit.
- a and b are positive numbers
- c and d are 0 or positive numbers
- a + b + c + d 1.0, 0.2 ⁇ (a + c) / (a + b + c + d) ⁇ 0.8, 0.2 ⁇ (b + d ) / (A + b + c + d) ⁇ 0.8, 0 ⁇ c / (a + b + c + d) ⁇ 0.15, 0 ⁇ d / (a + b + c + d) ⁇ 0.15.
- e is 0 or a positive number
- f is a positive number, and is a number satisfying 0 ⁇ e ⁇ 100 and 3 ⁇ f ⁇ 20.
- the bonding position of the alkenyl group is not limited. Even if bonded to the silicon atom of R 2 3 SiO 1/2 unit or bonded to the silicon atom of R 2 2 SiO 2/2 unit in (R 2 2 SiO 2/2 ) e , (R 2 2 SiO 2/2 ) may be bonded to silicon atoms of R 2 2 SiO 2/2 units in f, and the polyorganosiloxane of the component (A) represented by the unit formula is 1 on average in one molecule. It suffices to have at least one alkenyl group.
- the weight loss rate (heating weight loss rate) of such component (A) after heating at 150 ° C. for 1 hour is 3% by weight or less. That is, the nonvolatile content after heating at 150 ° C. for 1 hour is preferably 97% by weight or more.
- the heating loss rate of the component (A) exceeds 3% by weight, it may cause cracking during and after curing, which is not preferable.
- the polyorganosiloxane of component (A) blocks the alkenyl group-containing organosiloxane (II) and / or (III) in step (2) from the polyorganosiloxane (I) obtained in the following step (1). It is preferable to produce by polymerization or graft polymerization / equilibration reaction.
- step (1) a polyorganosiloxane obtained by hydrolyzing or partially hydrolyzing a silane compound represented by the formulas: R 1 SiX 3 and R 1 2 SiX 2 under the presence of a basic catalyst This is a step of polymerization (condensation) below.
- R 1 represents an alkyl group or an aryl group.
- the alkyl group and aryl group are the same as those described above, and are preferably a methyl group and a phenyl group, respectively.
- X represents a halogen group, an alkoxy group, or a hydroxyl group.
- the halogen group include a chloro group, a bromo group, and a fluoro group, and a chloro group is more preferable.
- the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group and an ethoxy group are more preferable.
- the heating temperature / time for the polymerization (condensation) reaction is preferably 80 ° C. to 150 ° C. for 3 hours or longer.
- step (2) the polyorganosiloxane (I) represented by the average unit formula obtained in the step (1), a linear polyorganosiloxane (II) containing an alkenyl group and / or an alkenyl group are added.
- the cyclic polyorganosiloxane (III) contained is subjected to block polymerization or graft polymerization / equilibration reaction in the presence of a basic catalyst.
- the linear polyorganosiloxane (II) is represented by the formula: (R 2 3 SiO 1/2 ) 2 (R 2 2 SiO 2/2 ) e .
- the cyclic polyorganosiloxane (III) is represented by the formula: (R 2 2 SiO 2/2 ) f .
- R 2 represents an alkenyl group, an alkyl group or an aryl group. Examples of the alkyl group, aryl group, and alkenyl group are the same as those described above, and are preferably a methyl group, a phenyl group, and a vinyl group, respectively.
- the bonding position of the alkenyl group is not limited as long as at least one of the linear polyorganosiloxane (II) and the cyclic polyorganosiloxane (III) has an alkenyl group.
- the heating temperature and time for block polymerization or graft polymerization / equilibration reaction are preferably 130 ° C. to 150 ° C. for 3 hours or longer.
- Component (B) is a cross-linking agent, and is a polyorganohydrogensiloxane containing 2 or more, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule.
- the number of silicon atoms in one molecule is preferably 2-50, and more preferably 4-20.
- R 3 is a substituted or unsubstituted monovalent hydrocarbon group excluding an alkenyl group.
- R 3 examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and an octyl group; Aryl groups; aralkyl groups such as benzyl and phenylethyl groups; and those in which some or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, bromine or cyano groups, such as chloro Examples thereof include hydrocarbon groups having 1 to 12 carbon atoms such as a methyl group, a bromoethyl group, a trifluoropropyl group, and a cyanoethyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable and a methyl group is more preferable from the viewpoint
- X and y are positive numbers. It is a positive number satisfying 0.8 ⁇ x ⁇ 2.2, 0.002 ⁇ y ⁇ 1, 0.8 ⁇ x + y ⁇ 3, preferably 1 ⁇ x ⁇ 2.2, 0.01 ⁇ y ⁇ 1, a positive number satisfying 1.8 ⁇ x + y ⁇ 2.5.
- the hydrogen atom may be bonded to the silicon atom at the end of the molecular chain, may be bonded to the silicon atom in the middle of the molecular chain, or may be bonded to both.
- the molecular structure of the component (B) may be any of linear, branched, cyclic or three-dimensional network, but R 3 2 HSiO 1/2 unit (R 3 is as described above) and SiO 4 / A three-dimensional network containing 2 units is preferred.
- the viscosity of component (B) at 25 ° C. is preferably 1000 mPa ⁇ s or less, and more preferably in the range of 1 to 500 mPa ⁇ s.
- the blending amount of the component (B) is such that the hydrogen atom bonded to the silicon atom is 0.1 mol per mol of the alkenyl group bonded to the silicon atom of the component (A) (alkenyl group bonded to the silicon atom of (a2)).
- the amount is 5 to 3.0 mol, preferably 0.7 to 2.0 mol. If the amount is less than 0.5 mol, sufficient crosslinking cannot be obtained. On the other hand, when the amount exceeds 3.0 mol, unreacted Si—H groups remain, and the physical properties after curing tend to change with time.
- the platinum-based catalyst of the component (C) is a catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the hydrogen atom bonded to the silicon atom in the component (B), and promoting the curing of the composition. It is.
- a known platinum-based catalyst can be used as a catalyst used in the hydrosilylation reaction. Examples thereof include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins or vinyl siloxane, platinum bisacetoacetate, and the like.
- the compounding amount of the component may be an amount necessary for curing, and can be appropriately adjusted according to a desired curing rate. Usually, it is 0.5 to 300 ppm in terms of platinum element based on the total weight of the composition, preferably 1 to 20 ppm from the viewpoint of transparency of the cured product and cost.
- Adhesion imparting agent can be mix
- adhesion-imparting agent organosilane or an organosiloxane oligomer having 2 to 50, preferably 4 to 20, silicon atoms can be used.
- alkoxy functional group-containing alkoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) )
- Alkenyl group-containing alkoxysilane such as silane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- Amino group-containing alkoxysilanes such as ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, acrylic groups such as ⁇ -me
- organosiloxane oligomer 1: 1 of a SiH group-containing siloxane oligomer represented by the formula: ⁇ -methacryloxypropyltrimethoxysilane represented by the formula: CH 2 ⁇ C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 Mention may be made of addition reaction products.
- the amount of these adhesion-imparting agents is preferably 10 parts by weight or less per 100 parts by weight of component (A). If the blending amount exceeds 10 parts by weight, it is uneconomical in terms of cost.
- a reaction inhibitor a reinforcing or non-reinforcing fine powder filler, a dye, a pigment, a flame retardant imparting agent, and a heat resistance improving agent are optionally added.
- an oxidation-resistant deterioration agent, a wavelength adjusting agent, a solvent, and the like may be added in a range that does not affect the transparency after curing and in a range that does not impair the object of the present invention.
- each component is not particularly limited, and the basic components (A) to (C) and the optional components described above are well-known kneaders. And kneading method.
- the two liquids may be stored separately, and the two liquids may be mixed and used at the time of use. In that case, the mixture of component (A) and component (C) is used as the first liquid, and the mixture of component (B) and other optional components (such as a reaction inhibitor) is used as the second liquid. Sometimes both solutions can be mixed.
- Examples of the kneader include a planetary mixer, a three-roller, a kneader, and a Shinagawa mixer that are provided with a heating unit and a cooling unit, if necessary, and these can be used alone or in combination.
- the semiconductor sealing silicone composition of the present invention is liquid and preferably has a viscosity at 25 ° C. of 0.5 to 50 Pa ⁇ s.
- a viscosity at 25 ° C. 0.5 to 50 Pa ⁇ s.
- the viscosity exceeds 50 Pa ⁇ s, for example, workability when potting an LED is deteriorated.
- it is less than 0.5 Pa ⁇ s dripping tends to occur when potting.
- the curing method of the silicone composition for semiconductor encapsulation is not particularly limited. Curing proceeds by heating at room temperature or 50 to 200 ° C., but heating is preferred for rapid curing. In the case of heating, the heating time can be appropriately adjusted according to the heating temperature.
- the cured product is in the form of a hard rubber or a flexible resin.
- the storage elastic modulus of the cured product of the silicone composition for semiconductor encapsulation of the present invention is reduced by 40% or more by heating from 25 ° C to 50 ° C. It is preferable to decrease by 70% or more. That is, the storage elastic modulus at 50 ° C. of the cured product is lower than the storage elastic modulus at 25 ° C. by 40% or more, more preferably 70% or more. Accordingly, when used as a sealing material for a semiconductor element, it is possible to relieve stress caused by thermal expansion due to heat generated from the semiconductor element, and to prevent generation of cracks and peeling from the substrate. Even when the storage elastic modulus of the cured product is reduced by heating, the decrease in storage elastic modulus is less than 40%, or the storage elastic modulus is increased by heating. The stress caused by the expansion cannot be sufficiently relaxed, and the generation of cracks and peeling from the substrate cannot be prevented.
- the storage elastic modulus of the cured product is appropriately adjusted by changing the proportion (wt%) of the siloxane unit not involved in the hydrosilylation reaction in component (A) and the composition of each component (A) to (C). can do.
- the storage elastic modulus at 25 ° C. can be adjusted to 1 ⁇ 10 6 to 2 ⁇ 10 7 Pa, and can be adjusted to decrease by 40 to 98%, more preferably 70 to 80% at 50 ° C.
- the storage elastic modulus can be obtained by a viscoelasticity measuring device. When the rate of decrease in the storage elastic modulus at 50 ° C. is less than 40%, the stress caused by thermal expansion cannot be sufficiently relaxed, so that the generation of cracks and peeling from the substrate cannot be sufficiently prevented. .
- Me represents a methyl group
- Ph represents a phenyl group
- Vi represents a vinyl group.
- the viscosity is a value at 25 ° C.
- the weight average molecular weight is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC) using THF (tetrahydrofuran) as a solvent.
- GPC gel permeation chromatography
- THF tetrahydrofuran
- the silicone composition was set on an ARES viscoelasticity measuring device (Reometric Scientific) (diameter 8 mm, thickness 1 mm), heated at 50 ° C. per minute, cured at 150 ° C. for 1 hour, After cooling at a rate of 5 ° C. per minute in the temperature range up to ⁇ 50 ° C., the storage elastic modulus was measured under the conditions of torsional strain 0.5% and frequency 1 Hz.
- reaction mixture was cooled, 254 g of methanol was added and stirred for 15 minutes, and then allowed to stand for 30 minutes for liquid separation. A mixed solution of hydrochloric acid and methanol was separated into the upper layer, and a reaction product was separated into the lower layer.
- the (aa1) unit: (Me 2 SiO 2/2 ) 0.30 (Me 2 SiO 1/2 OMe) 0.03 is formed from the starting material (Aa1).
- (Aa2) unit: (Ph 2 SiO 2/2 ) 0.30 (Ph 2 SiO 1/2 OMe) 0.04 is produced from the starting material (Aa2)
- (aa3) unit: (PhSiO 3/2 ) 0.27 ⁇ PhSiO 1/2 (OMe) 2 ⁇ 0.03 (PhSiO 2/2 OMe) 0.03 is produced from the starting material (Aa3).
- the lower layer hydrochloric acid solution is removed, and the upper layer silanol group-containing resin xylene solution is returned to the flask, and 1200 g of ion-exchanged water is added thereto and heated.
- the mixture is heated at the reflux temperature (70 to 80 ° C.) of the mixture.
- the water washing operation was performed for a minute.
- the mixture was again transferred to a separatory funnel and allowed to stand for 45 minutes, and a xylene solution of silanol group-containing resin was separated in the upper layer, and a hydrochloric acid solution was separated in the lower layer.
- the same operation was repeated, and it was confirmed that the hydrochloric acid content in the xylene solution of the silanol group-containing resin was 0.1 ppm or less.
- the xylene solution of the silanol group-containing resin thus obtained was heated under reduced pressure to distill off the solvent, and the nonvolatile content (measured for nonvolatile content by heating at 105 ° C. for 3 hours) was concentrated to 65% by weight. Thereafter, xylene was added to adjust the nonvolatile content to 60% by weight.
- Synthesis Example 1 [Synthesis of Silicone Resin A1] (First step) Diluted by adding 700 g of xylene to 255 g of intermediate product AA (silicone resin having a methoxy group), 0.6 g of a 50 wt% concentration (hereinafter simply referred to as 50%) and 0.6 g of aqueous cesium hydroxide and 200 g of water were added. Then, hydrolysis was carried out by heating. In infrared absorption spectrum measurement, the reaction was continued until characteristic absorption derived from a methoxy group having a wave number of 2800 cm ⁇ 1 disappeared.
- intermediate product AA siliconcone resin having a methoxy group
- 50% 0.6 g of a 50 wt% concentration
- aqueous cesium hydroxide and 200 g of water were added. Then, hydrolysis was carried out by heating. In infrared absorption spectrum measurement, the reaction was continued until characteristic absorption derived from a methoxy group having a wave number of
- This silicone resin A1 has an average unit formula: (Me 2 SiO 2/2 ) 0.33 (Ph 2 SiO 2/2 ) 0.34 (PhSiO 3/2 ) 0.33 in terms of charge amount.
- both ends vinylpolyphenylsiloxane and cyclic methylvinylsiloxane are split, and graft polymerization is performed on the reaction product obtained in the first step, whereby silicone resin A1 is obtained.
- the viscosity of the obtained silicone resin A1 was 120 Pa ⁇ s, and the non-volatile content measured by heating at 150 ° C. for 1 hour was 99.0% by weight (hereinafter simply referred to as “%”, meaning a heating loss rate of 1.0%).
- the weight average molecular weight was 1056, and the degree of dispersion was 1.35.
- the dispersity is a numerical value representing the molecular weight distribution, and is obtained by weight average molecular weight (Mw) / number average molecular weight (Mn). The closer the degree of dispersion is to 1, the narrower the molecular weight distribution.
- the number of vinyl groups in one molecule of the silicone resin A1 is 1.2 on average.
- Synthesis Example 2 [Synthesis of Silicone Resin A2] (First step) 300 g of xylene was added to 595 g of the intermediate product AA (silicone resin having a methoxy group) for dilution, and 0.7 g of a 50% aqueous cesium hydroxide solution and 200 g of water were added thereto, followed by heating for hydrolysis. In the infrared absorption spectrum measurement, the reaction was continued until the characteristic absorption derived from the methoxy group at 2800 cm ⁇ 1 disappeared.
- the intermediate product AA silicone resin having a methoxy group
- This silicone resin A2 has an average unit formula: (Me 2 SiO 2/2 ) 0.33 (Ph 2 SiO 2/2 ) 0.34 (PhSiO 3/2 ) 0.33 in terms of charge amount.
- both ends vinylpolyphenylsiloxane and cyclic methylvinylsiloxane are split, and graft polymerization is performed on the reaction product obtained in the first step, whereby silicone resin A2 is obtained.
- the viscosity of the obtained silicone resin A2 was 7500 Pa ⁇ s, the nonvolatile content measured by heating at 150 ° C. for 1 hour was 99.0%, the weight average molecular weight was 2950, and the dispersity was 2.05.
- the number of vinyl groups in one molecule of the silicone resin A2 is 1.8 on average.
- the resulting silicone resin A3 had a viscosity of 0.6 Pa ⁇ s, a nonvolatile content measured by heating at 150 ° C. for 1 hour, 99.0%, a weight average molecular weight of 870, and a dispersity of 1.24. .
- the number of vinyl groups in one molecule of this silicone resin A3 is 1.0 on average.
- Synthesis Example 4 [Synthesis of Silicone Resin A4] After adding 30 g of cyclic polymethylvinylsiloxane (Vi amount 11.6 mmol / g) to 450 g (effective resin content 270 g) of the intermediate product BB (silicone resin having a silanol group), 230 g of xylene was added for dilution. To this, 0.3 g of 50% aqueous potassium cesium hydroxide solution was added and heated, and reacted at xylene reflux temperature for 5 hours to effect block polymerization and equilibration.
- the non-volatile content of the obtained silicone resin A4 measured by heating at 150 ° C. for 1 hour was 99.0%, the weight average molecular weight was 1550, and the dispersity was 1.49.
- the number of vinyl groups in one molecule of this silicone resin A4 is 1.8 on average.
- Synthesis Example 5 [Synthesis of Silicone Resin A5] (First step) To 490 g of the intermediate product AA (silicone resin having a methoxy group), 300 g of xylene was added for dilution, 1.4 g of 50% aqueous potassium cesium hydroxide solution and 200 g of water were added, and the mixture was heated for hydrolysis. In the infrared absorption spectrum measurement, the hydrolysis reaction was continued until the characteristic absorption derived from the methoxy group at 2800 cm ⁇ 1 disappeared.
- This silicone resin A5 is converted into a charged amount base, and an average unit formula: (Me 2 SiO 2/2 ) 0.33 (Ph 2 SiO 2/2 ) 0.34 (PhSiO 3/2 ) 0.33
- the viscosity of the obtained silicone resin A5 was 100 Pa ⁇ s, the nonvolatile content measured by heating at 150 ° C. for 1 hour was 98.0%, the weight average molecular weight was 3370, and the dispersity was 2.40.
- the number of vinyl groups in one molecule of the silicone resin A5 is 4.2 on average.
- Synthesis Example 6 [Synthesis of Silicone Resin A6] A flask was charged with 800 g of xylene and 2000 g of ion-exchanged water and heated to 80 ° C. with stirring. To this, 356.1 g of phenyltrichlorosilane, 688.5 g of diphenyldichlorosilane, 86.4 g of vinylmethyldichlorosilane, dimethyl A mixed solution of 6.6 g of dichlorosilane was dropped over 3 hours, and hydrolysis was performed at 80 ° C. Then, it moved to the separatory funnel and left still for 45 minutes and liquid-separated. A silicone resin xylene solution separated into the upper layer, and a hydrochloric acid solution separated into the lower layer.
- the viscosity of the obtained silicone resin A6 was 200 Pa ⁇ s, the nonvolatile content measured by heating at 150 ° C. for 1 hour was 99.4%, the weight average molecular weight was 1905, and the dispersity was 1.52.
- the number of vinyl groups in one molecule of the silicone resin A6 is 1.4 on average.
- Example 1 100 parts by weight of the silicone resin A1 obtained in Synthesis Example 1, (B) the viscosity is 20 mPa ⁇ s, and the average unit formula: (SiO 2 ) [H (CH 3 ) 2 SiO 1/2 ] 2 9 parts by weight of the polyorganohydrogensiloxane and 3 ppm of (C) vinyl dimer platinum complex as platinum amount were added and kneaded to obtain a silicone composition for semiconductor encapsulation. The properties of this composition were measured and the results are shown in Table 1. In Table 1, the H / Vi ratio indicates the molar ratio between hydrogen atoms bonded to silicon atoms and vinyl groups bonded to silicon atoms in the components (A) and (B).
- MH 2 Q represents a polyorganohydrogensiloxane represented by an average unit formula: (SiO 2 ) [H (CH 3 ) 2 SiO 1/2 ] 2.
- MH 2 D Ph2 indicates a polyorganohydrogensiloxane represented by the formula: [H (CH 3 ) 2 SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ].
- M Vi D Ph 15 D 20 M Vi is a formula used in Comparative Examples 1 to 4 described later: (Me 2 ViSiO 1/2 ) 2 (Ph 2 SiO 2/2 ) 15 (Me 2 SiO 2/2 ) The linear polyorganosiloxane represented by 20 is shown.
- Examples 6 to 10 Silicone resins A1 to A5 obtained in Synthesis Examples 1 to 5, and (B) polyorganohydrogensiloxane represented by an average unit formula: (SiO 2 ) [H (CH 3 ) 2 SiO 1/2 ] 2 , (C) The vinyl dimer platinum complex and the adhesion promoters (D1) and (D2) were blended and kneaded with the compositions shown in Table 2, respectively, to obtain a silicone composition for semiconductor encapsulation. The properties of these compositions were measured and the results are shown in Table 2.
- the adhesion-imparting agent (D1) has the formula: A 1: 1 addition reaction product of a SiH group-containing siloxane oligomer represented by ⁇ -methacryloxypropyltrimethoxysilane is used, and ⁇ -glycidoxypropyltrimethoxy is used as the adhesion-imparting agent (D2).
- Silane trade name TSL8350, manufactured by Momentive was used.
- the H / Vi ratio in Table 2 is the molar ratio between the hydrogen atom bonded to the silicon atom and the vinyl group bonded to the silicon atom in the component (A) and the component (B) excluding the adhesion-imparting agent (D1). Indicates the ratio.
- Example 11 Silicone resin A1 obtained in Synthesis Example 1 and a polyorganohydrogensiloxane represented by (B) average unit formula: (SiO 2 ) [H (CH 3 ) 2 SiO 1/2 ] 2 (viscosity 20 mPa ⁇ s) ), And a polyorganohydrogensiloxane (viscosity 10 mPa ⁇ s) represented by the formula: [H (CH 3 ) 2 SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ], (C ) Vinyl dimer platinum complexes were blended and kneaded in the compositions shown in Table 1 to obtain a silicone composition for semiconductor encapsulation. The properties of this composition were measured and the results are shown in Table 1.
- Example 12 Silicone resin A1 obtained in Synthesis Example 1 and a polyorganohydrogensiloxane represented by (B) average unit formula: (SiO 2 ) [H (CH 3 ) 2 SiO 1/2 ] 2 (viscosity 20 mPa ⁇ s) ), And a polyorganohydrogensiloxane (viscosity 10 mPa ⁇ s) represented by the formula: [H (CH 3 ) 2 SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ], (C )
- the vinyl dimer platinum complex and the adhesion-imparting agents (D1) and (D2) were blended in the compositions shown in Table 2 and kneaded to obtain a silicone composition for semiconductor encapsulation. The properties of this composition were measured and the results are shown in Table 2.
- Comparative Example 1 The linear resin represented by the silicone resin A6 obtained in Synthesis Example 6 and the formula: (Me 2 ViSiO 1/2 ) 2 (Ph 2 SiO 2/2 ) 15 (Me 2 SiO 2/2 ) 20 Organosiloxane, (B) polyorganohydrogensiloxane represented by average unit formula: (SiO 2 ) [H (CH 3 ) 2 SiO 1/2 ] 2 and (C) vinyl dimer platinum complex are respectively shown in Table 3. Were mixed and kneaded to obtain a silicone composition for semiconductor encapsulation. The properties of this composition were measured and the results are shown in Table 3.
- the H / Vi ratio in Table 3 is the molar ratio between the hydrogen atom bonded to the silicon atom and the vinyl group bonded to the silicon atom in the component (A) and the component (B) excluding the adhesion-imparting agent (D1). Indicates the ratio.
- the compositions of Examples 1 to 12 can give a hardened product having a high hardness, and the storage elastic modulus of the cured product is easily and significantly lowered by heating. Therefore, by using this composition, the stress generated during heat curing and moisture reflow can be relieved, crack generation and peeling from the substrate can be improved, and the reliability of semiconductor devices such as LEDs is greatly improved. You can see that
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Abstract
Description
(A)成分は、本発明の特徴である硬化物の貯蔵弾性率の加熱による大幅な低下(25℃から50℃で40%以上低下)を付与するうえで、主要な成分である。
R1 2SiO(2-m)/2Ymで表されるシロキサン単位は1官能型シロキサン単位である。
(R1SiO3/2)a(R1 2SiO2/2)b(R1SiO(3-n)/2Yn)c(R1 2SiO(2-m)/2Ym)dで表されるポリオルガノシロキサン(I)を得ることができる。なお、a、b、n、mは、いずれも前述の範囲にある正数であり、c、dは、いずれも前述の範囲にある0または正数である。
(B)成分は架橋剤であり、1分子中にケイ素原子に結合した水素原子(Si-H基)を2個以上、好ましくは3個以上含有するポリオルガノハイドロジェンシロキサンである。1分子中のケイ素原子数は、2~50であることが好ましく、4~20であることがさらに好ましい。
(C)成分の白金系触媒は、(A)成分中のアルケニル基と(B)成分中のケイ素原子に結合した水素原子とのヒドロシリル化反応を促進し、組成物の硬化を進めるための触媒である。(C)成分としては、ヒドロシリル化反応に用いられる触媒として周知の白金系触媒を使用することができる。例えば白金黒、塩化第二白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類やビニルシロキサンとの錯体、白金ビスアセトアセテート等が挙げられる。
本発明の半導体封止用シリコーン組成物には、(D)接着性付与剤を配合することができる。(D)接着性付与剤としては、オルガノシラン、またはケイ素原子数2~50個、好ましくは4~20個のオルガノシロキサンオリゴマーを用いることができる。例えば、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ官能性基含有アルコキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ(メトキシエトキシ)シラン等のアルケニル基含有アルコキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、N-β(アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-β(アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン等のアミノ基含有アルコキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-アクリロキシプロピルトリメトキシシラン等のアクリル基又はメタクリル基含有アルコキシシラン、メルカプトプロピルトリメトキシシラン等のメルカプト基含有アルコキシシランなどのアルコキシシランが挙げられる。
23℃において、Type A型硬度計により測定した。
シリコーン組成物をARES粘弾性測定装置(Reometric Scientific社製)にセットし(直径8mm、厚さ1mm)、毎分50℃で昇温後、150℃×1時間で硬化させた後、150℃~-50℃までの温度範囲で毎分5℃の割合で冷却して、貯蔵弾性率をねじれ歪0.5%、振動数1Hzの条件で測定した。
シリコーン組成物をシリンジに充填し、PPA(ポリフタルアミド)樹脂製パッケージ(5×5×1mm)に充填した。100℃×3時間の加熱後、150℃×1時間加熱し、組成物を硬化させた。冷却後、マイクロスコープを用いてクラック、剥離の発生数を調べた。その後、85℃/85%RHで3時間吸湿させて、リフローオーブン(Max260℃)で加熱した。冷却後、マイクロスコープを用いてクラック、剥離の発生数を調べた。
(Aa1)ジメチルジクロロシラン129g(1モル)、(Aa2)ジフェニルジクロロシラン255g(1モル)、(Aa3)フェニルトリクロロシラン212g(1モル)の混合物に、水38gとメタノール237gからなるメタノール水溶液を滴下し、共加水分解を行った。滴下終了後、60~70℃の還流温度で30分間加熱し、共加水分解反応を完了させた。その後、反応混合物を冷却し、メタノール254gを加えて15分間撹拌した後、30分間静置して分液を行った。塩酸とメタノールの混合溶液が上層に、反応生成物が下層に分離した。
フラスコに、キシレン400g、メチルトリクロロシラン214.2g(1.4モル)、ジメチルジクロロシラン34.1g(0.26モル)、ジフェニルジクロロシラン282.4g(1.1モル)、フェニルトリクロロシラン454.0g(2.1モル)を仕込み、混合してオルガノシランのキシレン溶液を調製した。また、別のフラスコに、イオン交換水1950g、アセトン850g、メタノール245gを仕込み、混合溶液を調製した。この混合溶液を撹拌しながら、先に調製したオルガノシランのキシレン溶液を30分間かけて滴下し、滴下終了後10分間撹拌を継続して加水分解を行った。その後、分液漏斗に移し、45分間静置して分液を行った。上層にシラノール基を有するシリコーンレジンのキシレン溶液が、下層に塩酸溶液が分離した。
(第1の工程)
中間生成物AA(メトキシ基を有するシリコーンレジン)255gにキシレン700gを加えて希釈し、これに濃度50重量%(以下、単に50%と示す。)水酸化セシウム水溶液0.6gと水200gを加え、加熱して加水分解を行った。赤外吸収スペクトル測定において、波数2800cm-1のメトキシ基に由来する特性吸収が消失するまで反応を継続した。こうして、平均分子式(単位式):(Me2SiO2/2)0.33(Ph2SiO2/2)0.34(PhSiO3/2)0.33で示されるメトキシ基を有しないシリコーンレジン重合物のキシレン溶液を得た。
第1の工程で得られた反応生成物に、両末端にビニル基を有するポリフェニルシロキサン(Vi量0.43mmol/g)15gと環状ポリメチルビニルシロキサン(Vi量11.6mmol/g)30gを加え、キシレン還流温度で5時間反応させてグラフト重合と平衡化を行った。冷却後、トリメチルクロロシラン0.3gを加えて中和した後、キシレン溶液を水で洗浄し分液操作により水層を除く操作(水洗操作)を行った。水洗操作を繰り返し、水層が中性になった後、キシレン層に残存する水をキシレンと共沸することにより除いた。こうして脱水の完了したキシレン層をろ過した後、キシレンを減圧留去することにより、シリコーンレジンA1を得た。
(第1の工程)
中間生成物AA(メトキシ基を有するシリコーンレジン)595gにキシレン300gを加えて希釈し、これに50%水酸化セシウム水溶液0.7gと水200gを加え、加熱して加水分解を行った。赤外吸収スペクトル測定において、2800cm-1のメトキシ基に由来する特性吸収が消失するまで反応を継続した。
第1の工程で得られた反応生成物に、両末端にビニル基を有するポリフェニルシロキサン(Vi量0.43mmol/g)70gと環状ポリメチルビニルシロキサン(Vi量11.6mmol/g)35gを加え、キシレン還流温度で5時間反応させてグラフト重合と平衡化を行った。冷却後、トリメチルクロロシラン0.5gを加えて中和した後、キシレン溶液を水で洗浄し分液操作により水層を除く操作(水洗操作)を行った。水洗操作を繰り返し、水層が中性になった後、キシレン層に残存する水をキシレンと共沸することにより除いた。こうして脱水の完了したキシレン層をろ過した後、キシレンを減圧留去することにより、シリコーンレジンA2を得た。
中間生成物AA(メトキシ基を有するシリコーンレジン)270gに環状ポリメチルビニルシロキサン(Vi量11.6mmol/g)30gを加えた後、キシレン700gを加えて希釈した。これに50%水酸化セシウム水溶液0.3gを加えて加熱し、キシレン還流温度で5時間反応させてブロック重合と平衡化を行った。冷却後、トリメチルクロロシラン0.3gを加えて中和した後、キシレン溶液を水で洗浄し分液操作により水層を除く操作(水洗操作)を行った。水洗操作を繰り返し、水層が中性になった後、キシレン層に残存する水をキシレンと共沸することにより除いた。こうして脱水の完了したキシレン層をろ過した後、キシレンを減圧留去することにより、シリコーンレジンA3を得た。
中間生成物BB(シラノール基を有するシリコーンレジン)450g(有効樹脂分270g)に環状ポリメチルビニルシロキサン(Vi量11.6mmol/g)30gを加えた後、キシレン230gを加えて希釈した。これに50%水酸化セシウムカリウム水溶液0.3gを加えて加熱し、キシレン還流温度で5時間反応させてブロック重合と平衡化を行った。冷却後、トリメチルクロロシラン0.7gを加えて中和した後、キシレン溶液を水で洗浄し分液操作により水層を除く操作(水洗操作)を行った。水洗操作を繰り返し、水層が中性になった後、キシレン層に残存する水をキシレンと共沸することにより除いた。こうして脱水の完了したキシレン層をろ過した後、キシレンを減圧留去することにより、シリコーンレジンA4を得た。
(第1の工程)
中間生成物AA(メトキシ基を有するシリコーンレジン)490gにキシレン300gを加えて希釈し、これに50%水酸化セシウムカリウム水溶液1.4gと水200gを加え、加熱して加水分解を行った。赤外吸収スペクトル測定において、2800cm-1のメトキシ基に由来する特性吸収が消失するまで加水分解反応を継続した。
第1の工程で得られた反応生成物に、両末端にビニル基を有するポリフェニルシロキサン(Vi量0.43mmol/g)140gと環状ポリメチルビニルシロキサン(Vi量11.6mmol/g)70gを加え、キシレン還流温度で5時間反応させてグラフト重合と平衡化を行った。冷却後、トリメチルクロロシラン1.3gを加えて中和した後、キシレン溶液を水で洗浄し分液操作により水層を除く操作(水洗操作)を行った。水洗操作を繰り返し、水層が中性になった後、キシレン層に残存する水をキシレンと共沸することにより除いた。こうして脱水の完了したキシレン層をろ過した後、キシレンを減圧留去することにより、シリコーンレジンA5を得た。
フラスコにキシレン800gとイオン交換水2000gを仕込み、撹拌しながら80℃になるまで加熱した後、これに、フェニルトリクロロシラン356.1g、ジフェニルジクロロシラン688.5g、ビニルメチルジクロロシラン86.4g、ジメチルジクロロシラン6.6gの混合液を3時間かけて滴下し、80℃で加水分解を行った。その後、分液漏斗に移し、45分間静置して分液を行った。上層にシリコーンレジンのキシレン溶液が、下層に塩酸溶液が分離した。
(Me2SiO2/2)0.01(MeViSiO2/2)0.11(Ph2SiO2/2)0.48(PhSiO3/2)0.27(Me3SiO1/2)0.13
で表されるシリコーンレジンA6を得た。
合成例1で得られたシリコーンレジンA1を100重量部に、(B)粘度が20mPa・sであり、平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサン9重量部と、(C)ビニルダイマー白金錯体を白金量として3ppm添加、混練して、半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表1に示した。なお、表1において、H/Vi比は、(A)成分と(B)成分における、ケイ素原子に結合した水素原子とケイ素原子に結合したビニル基とのモル比を示す。
また、表1ならびに後述する表2および表3において、MH 2Qは、平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表わされるポリオルガノハイドロジェンシロキサンを示し、MH 2DPh2は、式:[H(CH3)2SiO1/2]2[(C6H5)2SiO2/2]で表わされるポリオルガノハイドロジェンシロキサンを示している。また、MViDPh 15D20MViは、後述する比較例1~4で使用する式:(Me2ViSiO1/2)2(Ph2SiO2/2)15(Me2SiO2/2)20で表される直鎖状のポリオルガノシロキサンを示している。
合成例2~5で得られたシリコーンレジンA2~A5と、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサンおよび(C)ビニルダイマー白金錯体を、それぞれ表1に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。これらの組成物の特性を測定し、結果を表1に示した。
合成例1~5で得られたシリコーンレジンA1~A5と、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサン、(C)ビニルダイマー白金錯体、および接着性付与剤(D1)、(D2)を、それぞれ表2に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。これらの組成物の特性を測定し、結果を表2に示した。
合成例1で得られたシリコーンレジンA1と、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサン(粘度20mPa・s)、および式:[H(CH3)2SiO1/2]2[(C6H5)2SiO2/2]で表されるポリオルガノハイドロジェンシロキサン(粘度10mPa・s)と、(C)ビニルダイマー白金錯体を、それぞれ表1に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表1に示した。
合成例1で得られたシリコーンレジンA1と、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサン(粘度20mPa・s)、および式:[H(CH3)2SiO1/2]2[(C6H5)2SiO2/2]で表されるポリオルガノハイドロジェンシロキサン(粘度10mPa・s)と、(C)ビニルダイマー白金錯体と、接着性付与剤(D1)、(D2)を、それぞれ表2に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表2に示した。
合成例6で得られたシリコーンレジンA6と、式:(Me2ViSiO1/2)2(Ph2SiO2/2)15(Me2SiO2/2)20で表される直鎖状のポリオルガノシロキサンと、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサンおよび(C)ビニルダイマー白金錯体を、それぞれ表3に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表3に示した。
式:(Me2ViSiO1/2)2(Ph2SiO2/2)15(Me2SiO2/2)20で表される直鎖状のポリオルガノシロキサンと、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサンおよび(C)ビニルダイマー白金錯体を、それぞれ表3に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表3に示した。
合成例6で得られたシリコーンレジンA6と、式:(Me2ViSiO1/2)2(Ph2SiO2/2)15(Me2SiO2/2)20で表される直鎖状のポリオルガノシロキサンと、(B)平均単位式:(SiO2)[H(CH3)2SiO1/2]2で表されるポリオルガノハイドロジェンシロキサンと、(C)ビニルダイマー白金錯体、および接着性付与剤(D1)、(D2)を、それぞれ表3に示す組成で配合して混練し、半導体封止用シリコーン組成物を得た。これらの組成物の特性を測定し、結果を表3に示した。なお、表3におけるH/Vi比は、接着性付与剤(D1)を除いた(A)成分と(B)成分における、ケイ素原子に結合した水素原子とケイ素原子に結合したビニル基とのモル比を示す。
Claims (6)
- (A)(a1)少なくとも式:R1SiO3/2(式中、R1はアルキル基またはアリール基を示す。)で表される3官能型シロキサン単位を含む、ヒドロシリル化反応に関与しないオルガノシロキサン60~99重量部と、(a2)式:R2 2SiO2/2(式中、R2はアルケニル基、アルキル基またはアリール基を示し、分子中少なくとも1つはアルケニル基である。)で表される2官能型シロキサン単位および/または式:R2 3SiO1/2(式中、R2は上記のとおりである。)で表される1官能型シロキサン単位を含むオルガノシロキサン40~1重量部、を反応させて得られる、1分子中に平均1個以上のアルケニル基を有するポリオルガノシロキサン100重量部と、
(B)1分子中にケイ素原子に結合した水素原子を2個以上有し、25℃における粘度が1~1000mPa・sであるポリオルガノハイドロジェンシロキサンを、前記(A)成分のケイ素原子に結合したアルケニル基1モルに対して、ケイ素原子に結合した水素原子が0.5~3.0モルとなる量と、
(C)白金系触媒の触媒量をそれぞれ含有し、
硬化物の貯蔵弾性率が25℃から50℃で40%以上低下することを特徴とする半導体封止用シリコーン組成物。 - 当該半導体封止用シリコーン組成物の硬化物の貯蔵弾性率が、25℃から50℃で70%以上低下することを特徴とする請求項1記載の半導体封止用シリコーン組成物。
- 前記(A)成分の150℃で1時間加熱後の不揮発分が97重量%以上であることを特徴とする請求項1または2記載の半導体封止用シリコーン組成物。
- 前記(a1)成分のケイ素原子に結合した全有機基の20~70モル%がフェニル基であることを特徴とする請求項1乃至3のいずれか1項記載の半導体封止用シリコーン組成物。
- 前記(A)成分のポリオルガノシロキサンが、平均単位式:(R1SiO3/2)a(R1 2SiO2/2)b(R1SiO(3-n)/2Yn)c(R1 2SiO(2-m)/2Ym)dで表される第1のオルガノシロキサンと、式:(R2 3SiO1/2)2(R2 2SiO2/2)eで表される第2のオルガノシロキサンと、式:(R2 2SiO2/2)fで表される第3のオルガノシロキサンを、g:h:iの重量比(%)で反応させて得られるポリマーであることを特徴とする請求項1乃至4のいずれか1項記載の半導体封止用シリコーン組成物。
(式中、R1はアルキル基またはアリール基を示し、R2はアルケニル基、アルキル基またはアリール基を示し、Yはアルコキシ基または水酸基を示す。nは1または2であり、mは1である。aは正数、bは正数、cは0または正数、dは0または正数であり、a+b+c+d=1.0、0.2<(a+c)/(a+b+c+d)<0.8、0.2<(b+d)/(a+b+c+d)<0.8、0≦c/(a+b+c+d)<0.15、0≦d/(a+b+c+d)<0.15となる数である。また、eは0または正数、fは正数であり、0≦e≦100、3≦f≦20となる数である。さらに、g、h、iはそれぞれ、60≦g≦99、0≦h≦20、0≦i≦20、g+h+i=100となる数である。) - 前記(A)成分のポリオルガノシロキサンが、以下の工程(1)で得られたポリオルガノシロキサン(I)に、工程(2)で、アルケニル基を含有する直鎖状オルガノシロキサン(II)および/またはアルケニル基を含有する環状オルガノシロキサン(III)を、ブロック重合またはグラフト重合・平衡化反応させることにより得られたものであることを特徴とする請求項5記載の半導体封止用シリコーン組成物。
工程(1)
式:R1SiX3およびR1 2SiX2(式中、R1はアルキル基またはアリール基を示し、Xはハロゲン基、アルコキシ基、または水酸基を示す。)で表されるシラン化合物を酸性条件下加水分解または部分加水分解して得られるポリオルガノシロキサンを、塩基性触媒の存在下で重合させて、平均単位式:
(R1SiO3/2)a(R1 2SiO2/2)b(R1SiO(3-n)/2Yn)c(R1 2SiO(2-m)/2Ym)d(式中、Yはアルコキシ基または水酸基を示す。nは1または2であり、mは1である。aは正数、bは正数、cは0または正数、dは0または正数であり、a+b+c+d=1.0、0.2<(a+c)/(a+b+c+d)<0.8、0.2<(b+d)/(a+b+c+d)<0.8、0≦c/(a+b+c+d)<0.15、0≦d/(a+b+c+d)<0.15となる数である。)で表されるポリオルガノシロキサン(I)を得る工程
工程(2)
前記ポリオルガノシロキサン(I)に、式:(R2 3SiO1/2)2(R2 2SiO2/2)e(式中、R2はアルケニル基、アルキル基またはアリール基を示す。eは0または正数であり、0≦e≦100となる数である。)で表されるアルケニル基含有の直鎖状ポリオルガノシロキサン(II)、および/または式:(R2 2SiO)f(式中、R2は上記のとおりである。fは正数であり、3≦f≦20となる数である。)で表されるアルケニル基含有の環状ポリオルガノシロキサンを、塩基性触媒の存在化でブロック重合またはグラフト重合・平衡化反応させる工程
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KR101695529B1 (ko) * | 2014-01-28 | 2017-01-11 | 주식회사 엘지화학 | 경화체 |
CN105199397B (zh) * | 2014-06-17 | 2018-05-08 | 广州慧谷化学有限公司 | 一种可固化的有机聚硅氧烷组合物及半导体器件 |
WO2015194158A1 (ja) * | 2014-06-20 | 2015-12-23 | 東レ・ダウコーニング株式会社 | ホットメルト性シリコーンおよび硬化性ホットメルト組成物 |
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PL3274395T3 (pl) | 2015-03-24 | 2020-07-27 | Elkem Silicones France Sas | Sposób otrzymywania żywicy silikonowej stabilnej podczas przechowywania |
KR101579710B1 (ko) * | 2015-11-12 | 2015-12-22 | 동우 화인켐 주식회사 | 광학적층체 및 이를 포함하는 화상표시장치 |
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