JP3609971B2 - Adhesive silicone elastomer film - Google Patents
Adhesive silicone elastomer film Download PDFInfo
- Publication number
- JP3609971B2 JP3609971B2 JP35931199A JP35931199A JP3609971B2 JP 3609971 B2 JP3609971 B2 JP 3609971B2 JP 35931199 A JP35931199 A JP 35931199A JP 35931199 A JP35931199 A JP 35931199A JP 3609971 B2 JP3609971 B2 JP 3609971B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silicone elastomer
- elastomer film
- film
- adhesive silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002379 silicone rubber Polymers 0.000 title claims description 50
- 239000000853 adhesive Substances 0.000 title claims description 33
- 230000001070 adhesive effect Effects 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 8
- 239000004651 Radiation Curable Silicone Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002534 radiation-sensitizing agent Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 44
- -1 2-ethylhexyl group Chemical group 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003112 inhibitor 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004945 silicone rubber 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
- BWZAUXRKSMJLMH-UHFFFAOYSA-N 1,1-diethoxyethylbenzene Chemical compound CCOC(C)(OCC)C1=CC=CC=C1 BWZAUXRKSMJLMH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone 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
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 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 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
- 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 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 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
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
Landscapes
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Die Bonding (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、電子部品の接着性フィルムとして有用な接着性シリコーンエラストマーフィルム、それを用いたシリコーンエラストマーフィルム被覆体及び構造体に関する。
【０００２】
【従来の技術】
従来、半導体デバイスのダイボンディング用やＴＡＢテープの接着用途にエポキシ系の接着性フィルムが使用されている。しかし、これらの接着性フィルムは、耐熱性が不十分であり、また低弾性化が不可能であるという問題を有する（高弾性体では、例えば２つの異種の基板間に接着層として貼り合わせて使用した場合、熱的及び機械的応力を緩和し難く、製品の信頼性を低下させる）。一方、シリコーン系の接着性フィルムは一般に高耐熱性で低弾性であるが、十分な接着性と作業性を有し、容易に製造できるものは知られていない。
【０００３】
【発明が解決しようとする課題】
本発明の課題は、取扱いが簡単で、均一な形状のクリーンなフィルムとして短時間に製造でき、使用時の工程を合理化でき、しかも低弾性で十分な耐熱性、接着性及び加工性を有する接着性シリコーンエラストマーフィルム、それを用いたシリコーンエラストマーフィルム被覆体及び構造体を提供することである。
【０００４】
【課題を解決するための手段】
本発明は、
（Ａ）一般式（Ｉ）：
【０００５】
【化２】
（Ｂ）放射線増感剤、及び
（Ｃ）一般式（ＩＩＩ）：
Ｓｉ（ＯＲ６）４ （ＩＩＩ）
（式中、Ｒ６ は非置換又は置換の低級アルキル基である。）
で示されるアルコキシシラン及びその部分加水分解縮合物よりなる群から選ばれる少なくとも１種の化合物、
を含有する放射線硬化性シリコーンゴム組成物をフィルム状に成形し、得られたフィルムを放射線硬化させることにより得られる接着性シリコーンエラストマーフィルムを提供する。
【０００６】
また本発明は、上記シリコーンエラストマーフィルムで基体の一部又は全部を覆い、次いで加熱して該フィルムを硬化させることにより得られるシリコーンエラストマーフィルム被覆体を提供する。
更に本発明は、上記シリコーンエラストマーフィルムを二つの基体間に挟み、次いで加熱して該フィルムを硬化させて両基体を相互に結合させることにより得られる構造体を提供する。
更に本発明は、上記接着性シリコーンエラストマーフィルムをダイと該ダイを装着すべき基体の所定箇所との間に挟んで配置し、該フィルムを該ダイと基体との間で加熱して硬化させる、ことを特徴とするダイボンディング方法を提供する。
【０００７】
【発明の実施の形態】
＜接着性シリコーンエラストマーフィルム＞
本発明の接着性シリコーンエラストマーフィルムに使用される放射線硬化性シリコーンゴム組成物は、下記（Ａ）〜（Ｃ）成分を含有してなる。なお、本発明で云う接着性シリコーンエラストマーフィルムは、シートを含むものである。
（Ａ）オルガノポリシロキサン：
（Ａ）成分のオルガノポリシロキサンはベースポリマーとして使用される成分であって、上記一般式（Ｉ）で表される。
【０００８】
一般式（Ｉ）において、Ｒ１は同一でも異なってもよく、炭素原子数１〜９、好ましくは炭素原子数１〜６の非置換又は置換の１価炭化水素基である。この１価炭化水素基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、２−エチルヘキシル基、オクチル基、ノニル基等のアルキル基；シクロヘキシル基、シクロヘプチル基等のシクロアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等のアルケニル基；フェニル基、トリル基等のアリール基；ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基；又はこれらの基の炭素原子に結合した水素原子の少なくとも一部をハロゲン原子、シアノ基等の置換基で置換した、クロロメチル基、シアノエチル基、トリフルオロプロピル基などの基等が挙げられるが、Ｒ１の５０モル％以上がメチル基で、且つ２５モル％以下がフェニル基であるものが好ましい。
【０００９】
一般式（Ｉ）において、Ｘは上記一般式（ＩＩ）で表される基である。一般式（ＩＩ）におけるＲ２は炭素原子数２〜４の２価炭化水素基又は酸素原子であるが、耐水性の点から好ましくは２価炭化水素基である。この２価炭化水素基の具体例としては、エチレン基、プロピレン基、メチルエチレン基、テトラメチレン基等の炭素原子数２〜４のアルキレン基が挙げられるが、好ましくはエチレン基である。
【００１０】
一般式（ＩＩ）におけるＲ３は１〜３個、好ましくは２〜３個、更に好ましくは３個の（メタ）アクリロイル基〔特に（メタ）アクリロイロキシ基〕を有する炭素原子数４〜２５の１価有機基である。Ｒ３における（メタ）アクリロイル基の具体例としてはＣＨ２＝ＣＨＣＯＯ−、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ−、ＣＨ２＝ＣＨＣＯ−、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ−等のアクリル官能性基、メタクリル官能性基などが挙げられる。このような（メタ）アクリロイル基を含むＲ３の１価有機基の具体例としては、ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２−、［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２］３Ｃ−ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）３Ｃ−ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）２Ｃ（Ｃ２Ｈ５）ＣＨ２−等の、１〜３個のアクリロイロキシ基又はメタクリロイロキシ基で置換された炭素原子数１〜１０、好ましくは炭素原子数２〜６のアルキル基などが挙げられるが、好ましくはＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２−、［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２］３Ｃ−ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）３Ｃ−ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）２Ｃ（Ｃ２Ｈ５）ＣＨ２−、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２−、［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２］２Ｃ（Ｃ２Ｈ５）−ＣＨ２−）及び（ＣＨ２＝ＣＨＣＯＯＣＨ２）［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２］ＣＨ−、更に好ましくは［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２］３Ｃ−ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）３Ｃ−ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）２Ｃ（Ｃ２Ｈ５）ＣＨ２−、（ＣＨ２＝ＣＨＣＯＯＣＨ２）［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２］ＣＨ−である。一般式（ＩＩ）におけるＲ４は同一でも異なってもよく、炭素原子数１〜９、好ましくは炭素原子数１〜６の非置換又は置換の１価炭化水素基である。Ｒ４の１価炭化水素基の具体例としては、一般式（Ｉ）におけるＲ１として例示したものと同じものが挙げられるが、 Ｒ１の場合と同様に、Ｒ４の５０モル％以上がメチル基で、且つ２５モル％以下がフェニル基であるものが好ましい。一般式（ＩＩ）におけるＲ５は炭素原子数１〜１８、好ましくは炭素原子数１〜８の１価炭化水素基である。Ｒ５の１価炭化水素基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ネオペンチル基等のアルキル基；シクロヘキシル基等のシクロアルキル基；フェニル基等のアリール基；アリル基、プロペニル基、ブテニル基等のアルケニル基等が挙げられるが、好ましくはアルケニル基等の脂肪族不飽和基を除くものが使用される。また一般式（ＩＩ）において、ｎは１〜３の整数、ｍは０〜２の整数で、且つｎ及びｍは１≦ｎ＋ｍ≦３を満足するが、ｎ＝１の時Ｒ３は複数個（即ち、２個又は３個）の（メタ）アクリロイル基を有する。
【００１１】
一般式（Ｉ）において、Ｌは８〜１０，０００、好ましくは４８〜１，０００の整数である。
一般式（Ｉ）で示されるオルガノポリシロキサンとしては、具体的に下記のものを例示することができる。
【００１２】
【化３】
【化４】
【化５】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
【化１４】
【化１５】
【化１６】
【化１７】
【化１８】
【化１９】
【化２０】
【化２１】
【化２２】
【化２３】
【化２４】
【００３４】
【化２５】
【００３５】
（Ａ）成分のオルガノポリシロキサンは感放射線性基として−ＯＲ３基を有している〔即ち、分子鎖両末端の各々に複数個（即ち、２〜９個）の（メタ）アクリロイル基を有している〕ので、紫外線等の放射線照射により容易に硬化するという特徴を持っている。このオルガノポリシロキサンは単独で、又は２種以上組み合わせて使用することができる。
【００３６】
上記一般式（Ｉ）のオルガノポリシロキサンは、例えば、対応するクロロシロキサンと活性水酸基を有する（メタ）アクリロイル官能性化合物との脱塩化水素反応等により製造することができる。ここでクロロシロキサンとしては下記式で表されるものが例示される。
【００３７】
【化２６】
活性水酸基を有する（メタ）アクリロイル官能性化合物としては、２−ヒドロキシエチル（メタ）アクリレート、メチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、２−ヒドロキシ−１−アクリロキシ−３−メタクリロキシプロパン等が例示されるが、目的とするオルガノポリシロキサンが１つのケイ素原子に複数個（２〜９個）の（メタ）アクリロイル基を有することが好ましいことから、メチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート及び２−ヒドロキシ−１−アクリロキシ−３−メタクリロキシプロパンが好ましく、ペンタエリスリトールトリ（メタ）アクリレートが更に好ましい。
【００３９】
（Ｂ）放射線増感剤：
（Ｂ）成分の放射線増感剤としては、特に限定されないが、好ましくはベンゾフェノン、１−ヒドロキシシクロヘキシル−フェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オンなどのベンゾイル化合物（又はフェニルケトン化合物）、好ましくはカルボニル基のα−位の炭素原子上にヒドロキシ基を有するベンゾイル化合物（又はフェニルケトン化合物）；２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビスアシルモノオルガノフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキサイド等のオルガノホスフィンオキサイド化合物；更にイソブチルベンゾインエーテル等のベンゾインエーテル化合物；アセトフェノンジエチルケタール等のケタール化合物；チオキサントン系化合物；アセトフェノン系化合物等が例示される。これらは単独で又は２種以上組み合わせて使用することができる。（Ｂ）成分の配合量は、（Ａ）成分１００重量部に対して、通常０．５〜１０重量部、好ましくは１．０〜５．０重量部である。
【００４０】
（Ｃ）アルコキシシラン及び／又はその部分加水分解縮合物：
（Ｃ）成分のアルコキシシランは前記一般式（ＩＩＩ）で表され、接着助剤として各種基体に対し良好な接着性を付与する成分である。
一般式（ＩＩＩ）において、Ｒ６は炭素原子数１〜６程度の、好ましくは１〜４の低級アルキル基、又は炭素原子数１〜３個のアルコキシ基で置換された炭素原子数１〜３個の低級アルキル基である。該低級アルキル基の具体例としてはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等が挙げられ、また上記アルコキシ置換低級アルキル基としては、メトキシメチル基、メトキシエチル基、エトキシメチル基、エトキシエチル基等が挙げられる。
【００４１】
なお、アルコキシシランの部分加水分解縮合物とは、該アルコキシ基の加水分解縮合反応によって生成する、分子中に少なくとも１個、好ましくは２個以上のアルコキシ基が残存するシロキサン化合物（特に、ケイ素原子数が２〜１００個、好ましくは２〜３０個程度のシロキサンオリゴマー）を意味する。
一般式（ＩＩＩ）のアルコキシシランもその部分加水分解縮合物も各々単独で又は２種以上組み合わせて使用することができ、また一般式（ＩＩＩ）のアルコキシシランとその部分加水分解縮合物とを混合して使用することもできる。
（Ｃ）成分の配合量は、（Ｂ）成分の場合と同様、（Ａ）成分１００重量部に対して、通常０．５〜１０重量部、好ましくは１．０〜５．０重量部である。
【００４２】
その他の任意成分：
本発明で使用される放射線硬化性シリコーンゴム組成物には、硬化時の収縮率、得られる硬化物の熱膨張係数、機械的強度、耐熱性、耐薬品性、難燃性、熱膨張係数、ガス透過率等を適宜調整するために、必要に応じて各種添加剤を配合することができる。添加剤としては、例えば、煙霧質シリカ、沈降性シリカ、溶融シリカ、粉砕シリカ、結晶シリカ、シリカエアロゲル、石英粉末、ガラス繊維、酸化鉄、酸化チタン、炭酸カルシウム、炭酸マグネシウム等の無機質充填剤；ヒドロキノン、メトキシヒドロキノン等の重合禁止剤（ポットライフ延長剤）等が挙げられる。
また、各種基材に対する接着性をより速やかに発現させるために、チタン酸エステル、チタンキレート化合物等の有機チタン化合物を配合することもできる。
【００４３】
組成物の調製：
本発明で使用される放射線硬化性シリコーンゴム組成物は上記（Ａ）〜（Ｃ）成分及び必要に応じてその他の添加剤を混合することにより調製される。こうして得られる放射線硬化性シリコーンゴム組成物は、用途に応じ低粘度（液状）からペースト状又はコンパンド状が可能で、フィルム等の成形物への加工が容易であり、また紫外線等の放射線により短時間で硬化し、接着性のあるシリコーンエラストマー成型品（硬化物）を与えるという特徴を持っている。
【００４４】
接着性シリコーンエラストマーフィルムの製造：
接着性シリコーンエラストマーフィルムは、上記で得られたシリコーンゴム組成物が低粘度ならば、例えばフィルム又はシート状の金型へ流し込む等の方法でフィルム又はシートに成形し、またシリコーンゴム組成物が高粘度やコンパウンド状であれば、カレンダーロールやインジェクション成形機等でフィルム又はシート状に成形し、得られたフィルム状成型品に紫外線等の放射線を短時間照射することにより製造される。なお、本発明では上記組成物はフィルム状又はシート状に成形するが、組成物自体は他のいかなる形状に成形することも可能である。
こうして得られる本発明の接着性シリコーンエラストマーフィルムは、通常、必要に応じて、０．０１〜２．００ｍｍの範囲の厚さにされる。
【００４５】
放射線としては、紫外線、遠赤外線、電子線、Ｘ線、γ線などが挙げられるが、装置の手軽さ、扱いの容易性などから、紫外線を使用することが好ましい。紫外線を発する光源としては、例えば高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアークランプ及びキセノンランプ等が挙げられる。放射線の照射量は、組成物の厚さによって異なり、例えば厚み２ｍｍに対して紫外線（ピーク：３２０〜３９０ｎｍ）を２００〜２，４００ｍＪ／ｃｍ２、好ましくは４００〜１，６００ ｍＪ／ｃｍ２である。
【００４６】
用途：
本発明の接着性シリコーンエラストマーフィルムは、各種電子部品の被覆剤、接着剤等、特に接着剤、例えば半導体素子のダイボンディング剤として有用である。
【００４７】
＜シリコーンエラストマー被覆体及び構造体＞
本発明のシリコーンエラストマー被覆体は、以上のようにして得られるシリコーンエラストマーフィルムで基体の一部又は全部を覆い、次いで加熱して該フィルムを硬化させることにより製造される。また本発明の構造体は、シリコーンエラストマーフィルムを二つの基体（例えば、物品の二つの部分）間に挟み、次いで通常圧着下で、加熱して該フィルムを硬化させて両部分を相互に結合させることにより製造される。シリコーンエラストマーフィルムは接着性を有するので、上記被覆体又は構造体の接着層として有効に働く。ダイボンディングの場合を例に説明すると、本発明の接着性シリコーンエラストマーフィルムをダイと該ダイを装着すべき基体（リードフレームやパッケージ）の所定箇所との間に挟んで配置し、該フィルムを該ダイと基体との間で加熱して硬化させる。こうしてダイボンディングが完了する。
【００４８】
これらの被覆体及び構造体の製造に使用される基体としては、特に限定されないが、シリコン、ガラス、アルミニウム、ポリカーボネート、ポリイミド、ガラスエポキシ等が例示できる。加熱温度は、通常６０〜２００℃、好ましくは１００〜１８０℃である。加熱時間は通常１分〜２時間である。
【００４９】
【実施例】
以下に本発明を実施例によって説明する。なお、例中、部は重量部、式中のＭｅはメチル基、Ｐｈはフェニル基、Ｅｔはエチル基を表す。
【００５０】
〔実施例１〕
攪拌装置、還流冷却器、滴下ロート、乾燥空気導入器を取り付けた１，０００ｍｌの反応装置に、下記平均式：
【００５１】
【化２７】
【００５２】
【化２８】
次にこのオルガノポリシロキサン１００部に２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン２部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド１部、テトラメトキシシラン３部を混合し、放射線硬化性オルガノポリシロキサン組成物を得た。
【００５４】
この組成物をＮｉメッキ金型（縦１００ｍｍ×横１００ｍｍ、深さ１ｍｍ）に流し込み、８０Ｗ／ｃｍ２のメタルハライド水銀灯２灯を備えたコンベア炉内で２秒間、紫外線を照射し（照射量８００ｍＪ／ｃｍ２）、放射線硬化させた。得られた接着性シリコーンエラストマーフィルムの硬さをＪＩＳ Ｋ６３０１に従って測定した。なお、硬さはスプリング式Ａ型試験機で測定した。その結果を表１に示す。
【００５５】
次に、上記シリコーンエラストマーフィルムを縦２５ｍｍ×横１０ｍｍに切り、基体（基板）としてアルミニウム、シリコンウエハ、ポリイミドフィルム、ガラス又はポリカーボネートの各２枚のテストピース間に挟み、これを１００ｇｆ／ｃｍ２で圧着し、１５０℃で６０分間加熱硬化させて構造体を製造し、せん断接着力を測定した。その結果を表２に示す。
【００５６】
〔実施例２〕
テトラメトキシシランの代わりに下記式：
【００５７】
【化２９】
【００５８】
〔実施例３〕
テトラメトキシシランの代わりに下記式：
【００５９】
【化３０】
【００６０】
〔比較例１〕
テトラメトキシシランを添加しなかった他は実施例１と同様にして組成物を調製し、この組成物を用いて接着性シリコーンエラストマーフィルム及び構造体を製造し、実施例１と同様の試験を行った。その結果を表１及び表２に示す。
〔比較例２〕
テトラメトキシシランの代わりにアクリロキシプロピルトリメトキシシランを用いた他は実施例１と同様にして組成物を調製し、この組成物を用いて接着性シリコーンエラストマーフィルム及び構造体を製造し、実施例１と同様の試験を行った。その結果を表１及び表２に示す。
〔比較例３〕
テトラメトキシシランの代わりに下記式：
【００６１】
【化３１】
【００６２】
【表１】
【００６３】
【表２】
【００６４】
【発明の効果】
本発明の接着性シリコーンエラストマーフィルムは、下記のような利点を有する。
（１）短時間で放射線硬化して得られるので、製造時間が短縮できる上、均一な形状で得られるので、接着した製品の品質を安定化でき、しかもクリーンなフィルムとして得られる。
（２）加工性が良いので、カットにより定型の接着層を形成することができる。
（３）低弾性であるため、２つの異なる基板の貼り合わせにおける熱的及び機械的応力を緩和し、接着した製品の信頼性を向上できる。
（４）硬化物であるため、取扱いが簡単である。
（５）フィルム状成形品として供給されるため、使用時の工程（接着した製品を製造する工程）が合理化できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive silicone elastomer film useful as an adhesive film for electronic components, and a silicone elastomer film covering and structure using the same.
[0002]
[Prior art]
Conventionally, epoxy-based adhesive films have been used for die bonding of semiconductor devices and TAB tape bonding. However, these adhesive films have problems that heat resistance is insufficient and low elasticity cannot be achieved (in the case of a high elastic body, for example, an adhesive layer is bonded between two different substrates). When used, it is difficult to relieve thermal and mechanical stresses and reduce product reliability). On the other hand, silicone-based adhesive films generally have high heat resistance and low elasticity, but there are no known films that have sufficient adhesion and workability and can be easily manufactured.
[0003]
[Problems to be solved by the invention]
The problem of the present invention is that it is easy to handle, can be produced in a short time as a clean film of uniform shape, can streamline the process at the time of use, and has low elasticity and sufficient heat resistance, adhesiveness and workability A silicone elastomer film, and a silicone elastomer film covering and structure using the same.
[0004]
[Means for Solving the Problems]
The present invention
(A) General formula (I):
[0005]
[Chemical formula 2]
(B) radiosensitizer, and (C) general formula (III):
Si (OR 6 ) 4 (III)
(In the formula, R 6 represents an unsubstituted or substituted lower alkyl group.)
At least one compound selected from the group consisting of alkoxysilanes represented by the above and partial hydrolysis condensates thereof,
The adhesive silicone elastomer film obtained by shape | molding the radiation-curable silicone rubber composition containing this in the shape of a film, and carrying out radiation curing of the obtained film is provided.
[0006]
The present invention also provides a silicone elastomer film covering obtained by covering a part or all of a substrate with the silicone elastomer film and then heating to cure the film.
The present invention further provides a structure obtained by sandwiching the silicone elastomer film between two substrates and then heating to cure the film to bond the substrates together.
Further, the present invention is arranged by sandwiching the adhesive silicone elastomer film between a die and a predetermined portion of a substrate on which the die is to be mounted, and heating the film between the die and the substrate to be cured. A die bonding method is provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
<Adhesive silicone elastomer film>
The radiation curable silicone rubber composition used for the adhesive silicone elastomer film of the present invention comprises the following components (A) to (C). The adhesive silicone elastomer film referred to in the present invention includes a sheet.
(A) Organopolysiloxane:
The (A) component organopolysiloxane is a component used as a base polymer and is represented by the above general formula (I).
[0008]
In the general formula (I), R 1 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group. Group, alkyl group such as nonyl group; cycloalkyl group such as cyclohexyl group, cycloheptyl group; alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group; phenyl group, tolyl group, etc. An aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group; or a chloro group in which at least some of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a substituent such as a halogen atom or a cyano group methyl group, cyanoethyl group, and a group such as trifluoropropyl group, 5 of R 1 It is preferable that 0 mol% or more is a methyl group and 25 mol% or less is a phenyl group.
[0009]
In the general formula (I), X is a group represented by the above general formula (II). R 2 in the general formula (II) is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and is preferably a divalent hydrocarbon group from the viewpoint of water resistance. Specific examples of the divalent hydrocarbon group include alkylene groups having 2 to 4 carbon atoms such as ethylene group, propylene group, methylethylene group and tetramethylene group, with ethylene group being preferred.
[0010]
R 3 in the general formula (II) is 1 to 4 carbon atoms having 1 to 3, preferably 2 to 3, more preferably 3 (meth) acryloyl groups [particularly (meth) acryloyloxy groups]. Valent organic group. Specific examples of the (meth) acryloyl group in R 3 is CH 2 = CHCOO-, CH 2 = C (CH 3) COO-, CH 2 = CHCO-, CH 2 = C (CH 3) CO- of acrylic functional And a methacryl functional group. Specific examples of the R 3 monovalent organic group containing such a (meth) acryloyl group include CH 2 ═CHCOOCH 2 CH 2 —, [CH 2 ═C (CH 3 ) COOCH 2 ] 3 C—CH 2 —. , (CH 2 ═CHCOOCH 2 ) 3 C—CH 2 —, (CH 2 ═CHCOOCH 2 ) 2 C (C 2 H 5 ) CH 2 —, etc., substituted with 1 to 3 acryloyloxy groups or methacryloyloxy groups An alkyl group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and the like, preferably CH 2 ═CHCOOCH 2 CH 2 —, [CH 2 ═C (CH 3 ) COOCH 2 ] 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 2 C (C 2 H 5) CH 2 -, CH 2 = C (CH 3 COOCH 2 CH 2 -, [CH 2 = C (CH 3) COOCH 2] 2 C (C 2 H 5) -CH 2 -) and (CH 2 = CHCOOCH 2) [ CH 2 = C (CH 3) COOCH 2 ] CH-, more preferably [CH 2 = C (CH 3 ) COOCH 2] 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 2 C ( C 2 H 5) CH 2 - , (CH 2 = CHCOOCH 2) [CH 2 = C (CH 3) COOCH 2] is CH-. R 4 in the general formula (II) may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group for R 4 include the same groups as those exemplified as R 1 in the general formula (I). However, as in the case of R 1 , 50 mol% or more of R 4 Those having a methyl group and 25 mol% or less of a phenyl group are preferred. R 5 in the general formula (II) is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples of the monovalent hydrocarbon group for R 5 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and neopentyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group An alkenyl group such as an allyl group, a propenyl group, or a butenyl group, and the like, but preferably an alkenyl group other than an aliphatic unsaturated group such as an alkenyl group is used. In the general formula (II), n is an integer of 1 to 3, m is an integer of 0 to 2, and n and m satisfy 1 ≦ n + m ≦ 3, but when n = 1, there are a plurality of R 3. (That is, 2 or 3) (meth) acryloyl groups.
[0011]
In the general formula (I), L is an integer of 8 to 10,000, preferably 48 to 1,000.
Specific examples of the organopolysiloxane represented by the general formula (I) include the following.
[0012]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
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[0035]
The organopolysiloxane of component (A) has —OR 3 group as a radiation sensitive group [that is, a plurality of (that is, 2 to 9) (meth) acryloyl groups at each of both ends of the molecular chain. Therefore, it is easily cured by irradiation with radiation such as ultraviolet rays. These organopolysiloxanes can be used alone or in combination of two or more.
[0036]
The organopolysiloxane of the general formula (I) can be produced, for example, by a dehydrochlorination reaction between a corresponding chlorosiloxane and a (meth) acryloyl functional compound having an active hydroxyl group. Here, examples of the chlorosiloxane include those represented by the following formula.
[0037]
Embedded image
Examples of the (meth) acryloyl functional compound having an active hydroxyl group include 2-hydroxyethyl (meth) acrylate, methylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacrylate. Roxypropane and the like are exemplified, but since the target organopolysiloxane preferably has a plurality (2 to 9) (meth) acryloyl groups on one silicon atom, methylolpropane di (meth) acrylate is preferred. Pentaerythritol tri (meth) acrylate and 2-hydroxy-1-acryloxy-3-methacryloxypropane are preferred, and pentaerythritol tri (meth) acrylate is more preferred.
[0039]
(B) Radiosensitizer:
Although it does not specifically limit as a radiosensitizer of (B) component, Preferably it is benzophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and other benzoyl compounds (or phenyl ketone compounds), preferably benzoyl compounds having a hydroxy group on the α-position carbon atom of the carbonyl group (or phenyl Ketone compounds); organophosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyl monoorganophosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Oxide compound Further benzoin ether compounds such as isobutyl benzoin ether; ketal compounds such as acetophenone diethyl ketal; thioxanthone compounds; acetophenone compounds and the like. These can be used alone or in combination of two or more. (B) The compounding quantity of component is 0.5-10 weight part normally with respect to 100 weight part of (A) component, Preferably it is 1.0-5.0 weight part.
[0040]
(C) Alkoxysilane and / or its partial hydrolysis condensate:
Component (C), alkoxysilane, is represented by the general formula (III), and is a component that imparts good adhesion to various substrates as an adhesion aid.
In the general formula (III), R 6 is a lower alkyl group having about 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, or 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms. Lower alkyl groups. Specific examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. The alkoxy-substituted lower alkyl group includes a methoxymethyl group, A methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, etc. are mentioned.
[0041]
The partially hydrolyzed condensate of alkoxysilane is a siloxane compound (particularly a silicon atom) produced by a hydrolytic condensation reaction of the alkoxy group and having at least one, preferably two or more alkoxy groups remaining in the molecule. A siloxane oligomer having a number of 2 to 100, preferably about 2 to 30.
The alkoxysilane of the general formula (III) and the partial hydrolysis condensate thereof can be used alone or in combination of two or more, and the alkoxysilane of the general formula (III) and the partial hydrolysis condensate thereof are mixed. Can also be used.
(C) The compounding quantity of component is 0.5-10 weight part normally with respect to 100 weight part of (A) component like the case of (B) component, Preferably it is 1.0-5.0 weight part. is there.
[0042]
Other optional ingredients:
The radiation curable silicone rubber composition used in the present invention has a shrinkage rate upon curing, a thermal expansion coefficient of the resulting cured product, mechanical strength, heat resistance, chemical resistance, flame resistance, thermal expansion coefficient, In order to adjust gas permeability etc. suitably, various additives can be mix | blended as needed. Examples of the additive include inorganic fillers such as fumed silica, precipitated silica, fused silica, ground silica, crystalline silica, silica airgel, quartz powder, glass fiber, iron oxide, titanium oxide, calcium carbonate, and magnesium carbonate; Examples thereof include polymerization inhibitors (pot life extenders) such as hydroquinone and methoxyhydroquinone.
Moreover, in order to express the adhesiveness with respect to various base materials more rapidly, organic titanium compounds, such as a titanic acid ester and a titanium chelate compound, can also be mix | blended.
[0043]
Preparation of the composition:
The radiation-curable silicone rubber composition used in the present invention is prepared by mixing the components (A) to (C) and other additives as necessary. The radiation curable silicone rubber composition thus obtained can be made into a paste or a compound from a low viscosity (liquid) depending on the application, can be easily processed into a molded product such as a film, and can be shortened by radiation such as ultraviolet rays. It has the characteristics of being cured in time and giving an adhesive silicone elastomer molded product (cured product).
[0044]
Production of adhesive silicone elastomer film:
If the silicone rubber composition obtained above has a low viscosity, the adhesive silicone elastomer film is formed into a film or sheet by, for example, pouring into a film or sheet mold, and the silicone rubber composition has a high viscosity. If it is a viscosity or a compound shape, it is manufactured by forming it into a film or a sheet with a calendar roll or an injection molding machine, and irradiating the obtained film-shaped molded product with radiation such as ultraviolet rays for a short time. In the present invention, the composition is formed into a film or a sheet, but the composition itself can be formed into any other shape.
The adhesive silicone elastomer film of the present invention thus obtained is usually adjusted to a thickness in the range of 0.01 to 2.00 mm as required.
[0045]
Examples of the radiation include ultraviolet rays, far-infrared rays, electron beams, X-rays, and γ rays. However, it is preferable to use ultraviolet rays because of the ease of handling and easy handling of the apparatus. Examples of the light source that emits ultraviolet light include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a xenon lamp. The dose of radiation depends on the thickness of the composition, for example, ultraviolet rays thickness 2 mm (peak: 320~390nm) the 200~2,400mJ / cm 2, preferably 400 to 1,600 mJ / cm 2 is there.
[0046]
Use:
The adhesive silicone elastomer film of the present invention is useful as a coating agent and adhesive for various electronic components, particularly as an adhesive, for example, a die bonding agent for semiconductor elements.
[0047]
<Silicone elastomer coating and structure>
The silicone elastomer coating of the present invention is produced by covering part or all of a substrate with the silicone elastomer film obtained as described above, and then curing the film by heating. The structure of the present invention also includes a silicone elastomer film sandwiched between two substrates (eg, two parts of an article) and then heated under normal pressure to cure the film and bond the parts together. It is manufactured by. Since the silicone elastomer film has adhesiveness, it effectively works as an adhesive layer of the covering or structure. The case of die bonding will be described as an example. The adhesive silicone elastomer film of the present invention is disposed between a die and a predetermined portion of a substrate (lead frame or package) to which the die is to be attached, Heat and cure between the die and the substrate. Thus, die bonding is completed.
[0048]
Although it does not specifically limit as a base | substrate used for manufacture of these coating bodies and structures, A silicon | silicone, glass, aluminum, a polycarbonate, a polyimide, glass epoxy, etc. can be illustrated. The heating temperature is usually 60 to 200 ° C, preferably 100 to 180 ° C. The heating time is usually 1 minute to 2 hours.
[0049]
【Example】
Hereinafter, the present invention will be described by way of examples. In the examples, parts represent parts by weight, Me in the formula represents a methyl group, Ph represents a phenyl group, and Et represents an ethyl group.
[0050]
[Example 1]
In a 1,000 ml reactor equipped with a stirrer, reflux condenser, dropping funnel and dry air introducer, the following average formula:
[0051]
Embedded image
[0052]
Embedded image
Next, 100 parts of this organopolysiloxane was mixed with 2 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 3 parts of tetramethoxysilane. As a result, a radiation-curable organopolysiloxane composition was obtained.
[0054]
This composition was poured into a Ni plating mold (length 100 mm × width 100 mm, depth 1 mm) and irradiated with ultraviolet rays for 2 seconds in a conveyor furnace equipped with two 80 W / cm 2 metal halide mercury lamps (irradiation amount 800 mJ / cm 2 ) and radiation cured. The hardness of the obtained adhesive silicone elastomer film was measured according to JIS K6301. The hardness was measured with a spring type A type testing machine. The results are shown in Table 1.
[0055]
Next, the silicone elastomer film is cut into 25 mm length × 10 mm width and sandwiched between two test pieces of aluminum, silicon wafer, polyimide film, glass or polycarbonate as a substrate (substrate), and this is 100 gf / cm 2 . The structure was manufactured by heat-curing at 150 ° C. for 60 minutes, and the shear adhesive strength was measured. The results are shown in Table 2.
[0056]
[Example 2]
Instead of tetramethoxysilane the following formula:
[0057]
Embedded image
[0058]
Example 3
Instead of tetramethoxysilane the following formula:
[0059]
Embedded image
[0060]
[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that tetramethoxysilane was not added, and an adhesive silicone elastomer film and a structure were produced using this composition. The same test as in Example 1 was performed. It was. The results are shown in Tables 1 and 2.
[Comparative Example 2]
A composition was prepared in the same manner as in Example 1 except that acryloxypropyltrimethoxysilane was used instead of tetramethoxysilane, and an adhesive silicone elastomer film and a structure were produced using this composition. The same test as 1 was conducted. The results are shown in Tables 1 and 2.
[Comparative Example 3]
Instead of tetramethoxysilane the following formula:
[0061]
Embedded image
[0062]
[Table 1]
[Table 2]
[0064]
【The invention's effect】
The adhesive silicone elastomer film of the present invention has the following advantages.
(1) Since it can be obtained by radiation curing in a short time, the production time can be shortened and the product can be obtained in a uniform shape, so that the quality of the bonded product can be stabilized and the film can be obtained as a clean film.
(2) Since the processability is good, a regular adhesive layer can be formed by cutting.
(3) Since it has low elasticity, it can relieve thermal and mechanical stress in bonding of two different substrates and improve the reliability of the bonded product.
(4) Since it is a cured product, it is easy to handle.
(5) Since it is supplied as a film-like molded product, the process at the time of use (process for producing a bonded product) can be rationalized.
Claims (8)
（Ｂ）放射線増感剤、及び
（Ｃ）一般式(III)：
Si(OR6)4 (III)
（式中、R6 は非置換又は置換の、炭素原子数１〜６のアルキル基である。）
で示されるアルコキシシラン及びその部分加水分解縮合物よりなる群から選ばれる少なくとも１種の化合物、
を含有する放射線硬化性シリコーンゴム組成物をフィルム状に成形し、得られたフィルムを放射線硬化させることにより得られる接着性シリコーンエラストマーフィルム。(A) General formula (I):
(B) radiosensitizer, and (C) general formula (III):
Si (OR 6 ) 4 (III)
(Wherein R 6 is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms .)
At least one compound selected from the group consisting of alkoxysilanes represented by the above and partial hydrolysis condensates thereof,
An adhesive silicone elastomer film obtained by forming a radiation-curable silicone rubber composition containing a resin into a film and curing the resulting film by radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35931199A JP3609971B2 (en) | 1998-12-18 | 1999-12-17 | Adhesive silicone elastomer film |
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| Application Number | Priority Date | Filing Date | Title |
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| JP36093898 | 1998-12-18 | ||
| JP10-360938 | 1998-12-18 | ||
| JP35931199A JP3609971B2 (en) | 1998-12-18 | 1999-12-17 | Adhesive silicone elastomer film |
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| Publication Number | Publication Date |
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| JP2000234060A JP2000234060A (en) | 2000-08-29 |
| JP3609971B2 true JP3609971B2 (en) | 2005-01-12 |
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| JP4185292B2 (en) * | 2002-02-15 | 2008-11-26 | 信越化学工業株式会社 | Radiation curable silicone rubber composition and adhesive silicone elastomer film |
| JP4726383B2 (en) * | 2002-02-15 | 2011-07-20 | 信越化学工業株式会社 | Radiation curable silicone rubber composition and adhesive silicone elastomer film |
| JP4185450B2 (en) * | 2002-12-11 | 2008-11-26 | 信越化学工業株式会社 | Radiation curable silicone rubber composition, adhesive silicone elastomer film comprising the composition, structure using the composition, and method for producing the same |
| JP4805229B2 (en) * | 2007-08-27 | 2011-11-02 | 信越化学工業株式会社 | Electronic components sealed or coated with radiation curable silicone rubber composition |
| JP7452135B2 (en) * | 2020-03-17 | 2024-03-19 | 東洋紡株式会社 | Method for manufacturing polyimide film laminate |
| JP7282712B2 (en) | 2020-04-08 | 2023-05-29 | 信越化学工業株式会社 | Silicone composition for die bonding, cured product thereof, and optical semiconductor device |
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