JP4727139B2 - Silicone adhesive composition and adhesive tape - Google Patents
Silicone adhesive composition and adhesive tape Download PDFInfo
- Publication number
- JP4727139B2 JP4727139B2 JP2003389464A JP2003389464A JP4727139B2 JP 4727139 B2 JP4727139 B2 JP 4727139B2 JP 2003389464 A JP2003389464 A JP 2003389464A JP 2003389464 A JP2003389464 A JP 2003389464A JP 4727139 B2 JP4727139 B2 JP 4727139B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- sio
- sensitive adhesive
- adhesive composition
- 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
- 239000000203 mixture Substances 0.000 title claims description 49
- 239000013464 silicone adhesive Substances 0.000 title description 24
- 239000002390 adhesive tape Substances 0.000 title description 19
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 60
- -1 amine compound Chemical class 0.000 claims description 47
- 229920001296 polysiloxane Polymers 0.000 claims description 40
- 229910004298 SiO 2 Chemical group 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000007259 addition reaction Methods 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 239000002985 plastic film Substances 0.000 claims description 5
- 229920006255 plastic film Polymers 0.000 claims description 5
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 4
- KJDMMCYMVUTZSN-UHFFFAOYSA-N (1-ethynylcyclohexyl)oxy-trimethylsilane Chemical compound C[Si](C)(C)OC1(C#C)CCCCC1 KJDMMCYMVUTZSN-UHFFFAOYSA-N 0.000 claims description 2
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 2
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 claims description 2
- ZCTILCZSUSTVHT-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-yloxy(trimethyl)silane Chemical compound CC(C)CC(C)(C#C)O[Si](C)(C)C ZCTILCZSUSTVHT-UHFFFAOYSA-N 0.000 claims description 2
- NFCHUEIPYPEHNE-UHFFFAOYSA-N bis(2,2-dimethylbut-3-ynoxy)-dimethylsilane Chemical compound C#CC(C)(C)CO[Si](C)(C)OCC(C)(C)C#C NFCHUEIPYPEHNE-UHFFFAOYSA-N 0.000 claims description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 2
- JNRUXZIXAXHXTN-UHFFFAOYSA-N trimethyl(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(C)C JNRUXZIXAXHXTN-UHFFFAOYSA-N 0.000 claims description 2
- NWMVPLQDJXJDEW-UHFFFAOYSA-N trimethyl(3-methylpent-1-yn-3-yloxy)silane Chemical compound CCC(C)(C#C)O[Si](C)(C)C NWMVPLQDJXJDEW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 239000000853 adhesive Substances 0.000 description 44
- 230000001070 adhesive effect Effects 0.000 description 44
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 13
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、特にステンレス鋼などに粘着剤を貼りつけ、２８０℃の加熱エージングをおこなったのち、粘着剤を剥がしても糊残りしないシリコーン粘着剤組成物及び粘着テープに関する。 The present invention relates to a silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that do not leave any adhesive even after the pressure-sensitive adhesive is peeled off, particularly after attaching a pressure-sensitive adhesive to stainless steel or the like and performing heat aging at 280 ° C.
シリコーン粘着剤を使用した粘着テープや粘着ラベルは、シリコーン粘着剤層が耐熱性、耐寒性、耐候性、電気絶縁性及び耐薬品性に優れることから、アクリル系粘着剤、ゴム系粘着剤、ウレタン系粘着剤、エポキシ系粘着剤では変質・劣化してしまうような厳しい環境下で使用されている。 Adhesive tapes and labels that use silicone adhesives are acrylic adhesives, rubber adhesives, urethanes, because the silicone adhesive layer has excellent heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. -Based adhesives and epoxy-based adhesives are used in harsh environments that may be altered or deteriorated.
たとえば部品製造時や加工の際に加熱処理を行う場合、全面もしくは部分的に保護したりマスキングや仮固定が必要になることがある。このような用途に用いられる粘着テープには２５０℃の加熱後でも剥離が可能となるシリコーン粘着剤を用いたものが好適である。しかし、近年従来よりも高温での加熱処理が行われるようになり、シリコーン粘着剤の耐熱性も向上させる必要が生じている。 For example, when heat treatment is performed at the time of manufacturing parts or during processing, it may be necessary to protect the entire surface or a part, masking or temporary fixing. As the pressure-sensitive adhesive tape used for such applications, those using a silicone pressure-sensitive adhesive that can be peeled even after heating at 250 ° C. are suitable. However, in recent years, heat treatment at a higher temperature than before has been performed, and it has become necessary to improve the heat resistance of the silicone adhesive.
一例をあげると，電子部品実装における鉛フリーハンダの実用化に伴い、電子部品を基板にハンダ付けするリフロー温度などが従来よりも高温となり、ピーク温度が２８０℃に達することもある。したがって、このような高温下においても粘着剤が剥がれてはならず、さらに処理が終了すれば被着対に移行したり残留することなく剥がせることが必要である。 As an example, with the practical application of lead-free solder in electronic component mounting, the reflow temperature for soldering electronic components to a substrate becomes higher than before, and the peak temperature may reach 280 ° C. Therefore, the pressure-sensitive adhesive must not be peeled off even at such a high temperature, and it is necessary that the adhesive can be peeled off without being transferred or remaining after the treatment is completed.
従来のシリコーン粘着剤を用いた粘着テープを金属部分に貼りつけたりマスキングし、１５０〜２５０℃の高温の履歴を受けた場合粘着テープを剥がして除去するとき金属部分に粘着剤が残留したり、粘着テープの基材から粘着剤層が金属部分に移行してしまうことがあった。これを糊残りという。これはシリコーン粘着剤が加熱によって酸化され劣化し、これに伴い粘着剤層の凝集力が低下し、粘着剤層が破壊されたことによる。 Attaching or masking a conventional adhesive tape using a silicone adhesive to a metal part. When receiving a high temperature history of 150 to 250 ° C. When removing the adhesive tape by removing the adhesive tape, the adhesive remains on the metal part. The pressure-sensitive adhesive layer sometimes moved from the tape base material to the metal portion. This is called glue residue. This is because the silicone pressure-sensitive adhesive is oxidized and deteriorated by heating, and the cohesive force of the pressure-sensitive adhesive layer is reduced accordingly, and the pressure-sensitive adhesive layer is destroyed.
一方、半導体部品や銅製のリードフレーム積層部品の製造時に、シリコーン粘着剤に酸化防止剤を含有させた粘着テープを用いることで、２００℃程度，数時間の工程でも粘着剤の劣化が起こらなくなることが公知である。（特許文献１参照） On the other hand, when manufacturing semiconductor parts and copper lead frame laminated parts, the adhesive does not deteriorate even in a process of about 200 ° C for several hours by using an adhesive tape containing an antioxidant in a silicone adhesive. Is known. (See Patent Document 1)
また、付加反応硬化型のシリコーン粘着剤組成物にフェノール系酸化防止剤を含有させることにより、銅などの金属に対して糊残りしないシリコーン粘着剤を得ることができ、金属、特に銅や銅合金、鉄などの被着体に貼りつけたりマスキングし、１５０〜２５０℃の高温の履歴を受けた場合でも、糊残りを起こさず、きれいに剥離することが可能なシリコーン粘着剤組成物及び粘着テープを提供する。（特許文献２参照） In addition, by adding a phenolic antioxidant to the addition reaction curable silicone pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive that does not remain on a metal such as copper can be obtained. A silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape that can be peeled off without causing adhesive residue even when applied to an adherend such as iron or masked and subjected to a high temperature history of 150 to 250 ° C. To do. (See Patent Document 2)
しかしながら上記のように酸化防止剤を添加したシリコーン粘着剤に２８０℃を超える高温の履歴を与えると，特にその金属が銅や銅合金、鉄などの金属であれば、粘着テープを剥がして除去するときに糊残りが発生することがある。 However, when the silicone adhesive added with an antioxidant as described above is given a high temperature history exceeding 280 ° C., particularly if the metal is a metal such as copper, copper alloy, or iron, the adhesive tape is peeled off and removed. Sometimes glue residue occurs.
本発明は、上記事情を改善したもので、金属，特にステンレス鋼などの被着体に貼りつけたりマスキングし，２８０℃の高温の履歴を受けた場合でも、糊残りを起こさず、きれいに剥離することが可能なシリコーン粘着剤組成物および粘着テープを提供することを目的とする。 The present invention is an improvement of the above situation, and it can be applied to an adherend such as metal, especially stainless steel, or masked, and even when subjected to a high temperature history of 280 ° C., it does not cause adhesive residue and peels cleanly. An object of the present invention is to provide a silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that can be used.
本発明者は、上記目的を達成するため鋭意検討を行った結果、シリコーン粘着剤組成物に対してヒンダードアミン化合物を添加することにより、金属，特にステンレス鋼などに粘着剤を貼りつけ、２８０℃の加熱エージングをおこなったのち、粘着剤を剥がしてもステンレス鋼に対して糊残りせず，きれいに剥離することが可能であるという効果を達成するものであることを知見し、本発明をなすに至った。
本発明に用いられるシリコーン粘着剤組成物としては、有機過酸化物硬化型、付加反応硬化型等のいずれでもよい。
As a result of intensive studies to achieve the above-mentioned object, the present inventor attaches a pressure-sensitive adhesive to a metal, particularly stainless steel, by adding a hindered amine compound to the silicone pressure-sensitive adhesive composition. After carrying out heat aging, it was found that even if the adhesive was peeled off, no adhesive residue was left on the stainless steel and it was possible to achieve an effect that it can be peeled cleanly, leading to the present invention. It was.
The silicone pressure-sensitive adhesive composition used in the present invention may be either an organic peroxide curable type or an addition reaction curable type.
従って、本発明の過酸化物硬化型シリコーン粘着剤組成物としては次のものが用いられる。
（Ａ）ポリジオルガノシロキサン ２０〜８０重量部
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン（Ｒ１は炭素数１から１０の１価炭化水素基．） ８０〜２０重量部
（Ｃ）次式で示される構造を含有するヒンダードアミン化合物 （Ａ）、（Ｂ）の合計１００重量部に対して ０．０１〜１．０重量部
Therefore, the following are used as the peroxide curable silicone pressure-sensitive adhesive composition of the present invention.
(A) 20 to 80 parts by weight of polydiorganosiloxane (B) 0.5 unit of R 1 3 SiO and SiO 2 unit, and a molar ratio of R 1 3 SiO 0.5 unit / SiO 2 unit of 0.6 to 1.7 polyorganosiloxane (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) A hindered amine compound containing a structure represented by the following formula (A), (B ) 0.01 to 1.0 part by weight with respect to a total of 100 parts by weight
（Ｒは炭素数１から６の１価炭化水素基。）
（Ｄ）有機過酸化物硬化剤
（Ａ）、（Ｂ）の合計１００重量部に対して ０．１〜５．０重量部
を含有する過酸化物硬化型シリコーン粘着剤組成物を提供する。また、本発明は、プラスチックフィルムの少なくとも１面に上記のシリコーン粘着剤組成物の硬化物層が積層されていることを特徴とする粘着テープを提供する。
(R is a monovalent hydrocarbon group having 1 to 6 carbon atoms.)
(D) Provided is a peroxide-curable silicone pressure-sensitive adhesive composition containing 0.1 to 5.0 parts by weight with respect to 100 parts by weight as a total of the organic peroxide curing agents (A) and (B). Moreover, this invention provides the adhesive tape characterized by laminating | curing the hardened | cured material layer of said silicone adhesive composition on at least 1 surface of a plastic film.
付加反応硬化型シリコーン粘着剤組成物としては次のものが用いられる。
（Ａ'）１分子中に２個以上のアルケニル基を有するポリジオルガノシロキサン ２０〜８０重量部
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン（Ｒ１は炭素数１から１０の１価炭化水素基。） ８０〜２０重量部
（Ｃ）次式で示される構造を含有するヒンダードアミン化合物 （Ａ'）、（Ｂ）の合計１００重量部に対して ０．０１〜１．０重量部
The following are used as the addition reaction curable silicone pressure-sensitive adhesive composition.
(A ′) 20 to 80 parts by weight of a polydiorganosiloxane having two or more alkenyl groups in one molecule (B) containing R 1 3 SiO 0.5 units and SiO 2 units, and R 1 3 SiO 0.5 Polyorganosiloxane having a unit / SiO 2 unit molar ratio of 0.6 to 1.7 (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) 0.01 to 1.0 part by weight based on 100 parts by weight of the total amount of the hindered amine compound (A ′) and (B)
（Ｒは上記で示したと同じ基。）
（Ｅ）ＳｉＨ基を含有するポリオルガノシロキサン （Ａ'）成分中のアルケニル基に対する（Ｅ）成分中のＳｉＨ基のモル比が０．５〜２ ０となる量
（Ｆ）制御剤 （Ａ'）、（Ｂ）の合計１００重量部に対して ０〜８．０重量部
（Ｇ）白金触媒 （Ａ'）、（Ｂ）成分の合計に対し白金分として１〜５０００ｐｐｍ
を含有する付加反応型シリコーン粘着剤組成物を提供する。また、本発明は、プラスチックフィルムの少なくとも１面に上記のシリコーン粘着剤組成物の硬化物層が積層されていることを特徴とする粘着テープを提供する。
(R is the same group as shown above.)
(E) Polyorganosiloxane containing SiH groups (A ') Amount (F) controlling agent (A') The molar ratio of SiH groups in component (E) to alkenyl groups in component (A) is 0.5 to 20 ), 0 to 8.0 parts by weight with respect to a total of 100 parts by weight of (B) (G) Platinum catalyst (A '), 1 to 5000 ppm as a platinum content with respect to the total of components (B)
An addition reaction type silicone pressure-sensitive adhesive composition is provided. Moreover, this invention provides the adhesive tape characterized by laminating | curing the hardened | cured material layer of said silicone adhesive composition on at least 1 surface of a plastic film.
本発明により、金属、特にステンレスなどの被着体に貼りつけたりマスキングし、２８０℃の高温の履歴を受けた場合でも、糊残りを起こさず、きれいに剥離することが可能なシリコーン粘着剤組成物および粘着テープを得ることができる。 According to the present invention, a silicone pressure-sensitive adhesive composition that can be adhered and masked to an adherend such as metal, particularly stainless steel, and can be peeled cleanly without causing adhesive residue even when subjected to a high temperature history of 280 ° C. An adhesive tape can be obtained.
本発明の過酸化物硬化型シリコーン粘着剤組成物としては次のものが用いられる。
（Ａ）ポリジオルガノシロキサン ２０〜８０重量部
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン（Ｒ１は炭素数１から１０の１価炭化水素基．） ８０〜２０重量部
（Ｃ）次式で示される構造を含有するヒンダードアミン化合物 （Ａ）、（Ｂ）の合計１００重量部に対して ０．０１〜１．０重量部
The following are used as the peroxide-curable silicone pressure-sensitive adhesive composition of the present invention.
(A) 20 to 80 parts by weight of polydiorganosiloxane (B) 0.5 unit of R 1 3 SiO and SiO 2 unit, and a molar ratio of R 1 3 SiO 0.5 unit / SiO 2 unit of 0.6 to 1.7 polyorganosiloxane (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) A hindered amine compound containing a structure represented by the following formula (A), (B ) 0.01 to 1.0 part by weight with respect to a total of 100 parts by weight
（Ｒは炭素数１から６の１価炭化水素基。）
（Ｄ）有機過酸化物硬化剤
（Ａ）、（Ｂ）の合計１００重量部に対して ０．１〜５．０重量部
を含有する過酸化物硬化型シリコーン粘着剤組成物を提供する。また、本発明は、プラスチックフィルムの少なくとも１面に上記のシリコーン粘着剤組成物の硬化物層が積層されていることを特徴とする粘着テープを提供する。
(R is a monovalent hydrocarbon group having 1 to 6 carbon atoms.)
(D) Provided is a peroxide-curable silicone pressure-sensitive adhesive composition containing 0.1 to 5.0 parts by weight with respect to 100 parts by weight as a total of the organic peroxide curing agents (A) and (B). Moreover, this invention provides the adhesive tape characterized by laminating | curing the hardened | cured material layer of said silicone adhesive composition on at least 1 surface of a plastic film.
この場合、これらシリコーン粘着剤組成物及び粘着テープは、金属特にステンレス鋼のマスキングテープ用として有効に用いられる。 In this case, the silicone pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape are effectively used for metal, particularly stainless steel masking tape.
以下、更に詳述すると、（Ａ）成分はポリジオルガノシロキサンであり、下記式で示されるものであることが好ましい。
Ｒ２ ３ＳｉＯ−（Ｒ２ ２ＳｉＯ）ｐ −ＳｉＲ２ ３
Ｒ２ ２（ＨＯ）ＳｉＯ−（Ｒ２ ２ＳｉＯ ）ｐ −ＳｉＲ２ ２（ＯＨ）
式中、Ｒ２は同一または異種の炭素数１から１０の炭化水素基で、耐熱性を向上させるためにはケイ素原子に結合する全有機基のうち０から３５モル％、特に２から２０モル％がフェニル基であるように選定される。さらに、全シロキサン単位のうち１から３５モル％特に２から２０モル％がジフェニルシロキサン単位であることが好ましい。ｐはこのポリジオルガノシロキサンの２５℃における粘度を５００ ｍＰａ・ｓ以上とする数。
More specifically, the component (A) is polydiorganosiloxane, and is preferably represented by the following formula.
R 2 3 SiO— (R 2 2 SiO) p —SiR 2 3
R 2 2 (HO) SiO— (R 2 2 SiO) p —SiR 2 2 (OH)
In the formula, R 2 is the same or different hydrocarbon group having 1 to 10 carbon atoms, and in order to improve heat resistance, 0 to 35 mol%, particularly 2 to 20 mol, of all organic groups bonded to the silicon atom. % Is selected to be a phenyl group. Furthermore, it is preferable that 1 to 35 mol%, particularly 2 to 20 mol% of all siloxane units are diphenylsiloxane units. p is a number that makes the viscosity of this polydiorganosiloxane at 25 ° C. 500 mPa · s or more.
ここで、Ｒ２としては、炭素数１〜１０の一価炭化水素基が好ましく、例示すると、メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、トリル基などのアリール基などであり、特にメチル基、フェニル基が好ましい。 Here, as R 2 , a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a cycloalkyl group such as a cyclohexyl group, phenyl Group, an aryl group such as a tolyl group, and a methyl group and a phenyl group are particularly preferable.
このポリジオルガノシロキサンの性状はオイル状、生ゴム状であればよい。（Ａ）成分の粘度は２５℃において、オイル状のものであれば５００ｍＰａ・ｓ以上。特に１０、０００ ｍＰａ・ｓ以上が好ましい。５００ｍＰａ・ｓ以下では硬化性が低下したり、凝集力（保持力）が低下するため不適である。また、生ゴム状のものであれば、３０％の濃度となるようにトルエンで溶解したときの粘度が１００、０００ ｍＰａ・ｓ以下が好ましい。１００、０００ ｍＰａ・ｓを越えると、組成物が高粘度となりすぎて製造時の撹拌が困難になる。さらに、（Ａ）成分は２種以上を併用してもよい。 The polydiorganosiloxane may be in the form of oil or raw rubber. The viscosity of the component (A) is at least 500 mPa · s if it is oily at 25 ° C. In particular, 10,000 mPa · s or more is preferable. If it is 500 mPa · s or less, the curability is lowered or the cohesive force (holding force) is lowered, which is not suitable. Moreover, if it is a raw rubber-like thing, the viscosity when it melt | dissolves with toluene so that it may become a 30% density | concentration is preferable 100,000 mPa * s or less. If it exceeds 100,000 mPa · s, the composition becomes too viscous and stirring during production becomes difficult. Furthermore, (A) component may use 2 or more types together.
（Ｂ）成分はＲ１ ３ＳｉＯ０．５単位（Ｒ１は炭素数１から１０の１価炭化水素基。）およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサンである。Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６未満では粘着力やタックが低下することがあり、１．７を越えると粘着力や保持力が低下することがある。Ｒ１は、メチル基、エチル基 、プロピル基、ブチル基などのアルキル基、シクロアルキル基、フェニル基、ビニル基、アリル基、ヘキセニル基があげられる。メチル基が好ましい。 The component (B) contains R 1 3 SiO 0.5 unit (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) and SiO 2 unit, and R 1 3 SiO 0.5 unit / SiO 2 unit Is a polyorganosiloxane having a molar ratio of 0.6 to 1.7. If the molar ratio of R 1 3 SiO 0.5 unit / SiO 2 unit is less than 0.6, the adhesive force and tack may be lowered, and if it exceeds 1.7, the adhesive force and holding force may be lowered. Examples of R 1 include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and a hexenyl group. A methyl group is preferred.
（Ｂ）成分はＯＨ基を含有していてもよく、ＯＨ基含有量は４．０重量％以下のものが好ましい。ＯＨ基が４．０重量％を超えるものは粘着剤の硬化性が低下する理由により好ましくない。また、本発明の特性を損なわない範囲でＲ１ＳｉＯ1.5単位，Ｒ１ 2ＳｉＯ単位を（Ｂ）成分中に含有させることも可能である。なお、（Ｂ）成分は２種以上を併用してもよい。 Component (B) may contain OH groups, and the OH group content is preferably 4.0% by weight or less. The case where the OH group exceeds 4.0% by weight is not preferable because the curability of the pressure-sensitive adhesive is lowered. Further, R 1 SiO 1.5 units and R 1 2 SiO units may be contained in the component (B) as long as the characteristics of the present invention are not impaired. In addition, (B) component may use 2 or more types together.
（Ａ）、（Ｂ）成分は単純に混合したものを使用してもよいし、（Ａ）成分に次式のものを含有する場合、
Ｒ２ 2（ＨＯ）ＳｉＯ−（Ｒ２ ２ＳｉＯ）p−ＳｉＲ２ 2（ＯＨ）
（ｐは上記したと同じである。）
Components (A) and (B) may be simply mixed, or when component (A) contains the following formula:
R 2 2 (HO) SiO— (R 2 2 SiO) p —SiR 2 2 (OH)
(P is the same as described above.)
（Ａ）、（Ｂ）成分を縮合反応物として使用してもよい。縮合反応を行うには、トルエンなどの溶剤に溶解した（Ａ）、（Ｂ）成分の混合物をアルカリ性触媒を用い、室温乃至還流下で反応させればよい。 The components (A) and (B) may be used as a condensation reaction product. In order to perform the condensation reaction, a mixture of components (A) and (B) dissolved in a solvent such as toluene may be reacted at room temperature or under reflux using an alkaline catalyst.
（Ａ）、（Ｂ）成分の配合比は重量比として２０／８０〜８０／２０、特に３０／７０〜７０／３０とすることが好ましい。（Ａ）成分のポリジオルガノシロキサンの配合比が２０／８０より低いと粘着力や保持力が低下し、８０／２０を越えると粘着力やタックが低下する。 The blending ratio of the components (A) and (B) is preferably 20/80 to 80/20, particularly 30/70 to 70/30 as a weight ratio. When the blending ratio of the polydiorganosiloxane as the component (A) is lower than 20/80, the adhesive strength and holding power decrease, and when it exceeds 80/20, the adhesive strength and tack decrease.
（Ｃ）成分はヒンダードアミン化合物。特に分子中に下式の構造を有するものが好ましい。 Component (C) is a hindered amine compound. Particularly preferred are those having the following structure in the molecule.
ここで、Ｒは炭素数１から６の１価炭化水素基であり、例示すると、メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基などのアリール基などであり、特にメチル基が好ましい。
Here, R is a monovalent hydrocarbon group having 1 to 6 carbon atoms. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group or the like An aryl group, and a methyl group is particularly preferable.
具体的には、 In particular,
（Ｃ）成分の配合量は成分（Ａ）、（Ｂ）の合計１００重量部に対して０．０１〜１重量部の範囲であればよい。とくに０．０５〜０．５重量部が好ましい。０．０１重量部未満では耐熱性向上の効果がなく、１重量部を越えると保持力が低下することがある。（Ｃ）成分は２種以上を併用してもよい。 (C) The compounding quantity of a component should just be the range of 0.01-1 weight part with respect to a total of 100 weight part of a component (A) and (B). Particularly preferred is 0.05 to 0.5 parts by weight. If it is less than 0.01 part by weight, there is no effect of improving heat resistance, and if it exceeds 1 part by weight, the holding power may be lowered. (C) 2 or more types may be used together.
（Ｄ）成分は有機過酸化物硬化剤で、具体的にはジベンゾイルパーオキサイド、４、４'−ジメチルジベンゾイルパーオキサイド、３、３'−ジメチルジベンゾイルパーオキサイド、２、２'−ジメチルジベンゾイルパーオキサイド、２、２'、４、４'−テトラクロロジベンゾイルパーオキサイド、クミルパーオキサイド、などを例示できる。 Component (D) is an organic peroxide curing agent, specifically dibenzoyl peroxide, 4,4′-dimethyldibenzoyl peroxide, 3,3′-dimethyldibenzoyl peroxide, 2,2′-dimethyl. Examples include dibenzoyl peroxide, 2, 2 ′, 4, 4′-tetrachlorodibenzoyl peroxide, cumyl peroxide, and the like.
（Ｄ）成分の配合量は成分（Ａ）、（Ｂ）の合計１００重量部に対して０．１〜５重量部の範囲であればよい。とくに１〜４重量部が好ましい。０．１重量部未満では硬化性や保持力が低下することがある。５重量部を越えると粘着剤層に着色が生じたり、保持力が低下することがある。（Ｄ）成分の形態は特に限定されない。（Ｄ）成分の単独、（Ｄ）成分を有機溶剤に希釈したもの、水に分散させたもの、シリコーンオイルに分散させペースト状にしたもの、などがあげられる。（Ｄ）成分は２種以上を併用してもよい。 (D) The compounding quantity of a component should just be the range of 0.1-5 weight part with respect to a total of 100 weight part of component (A) and (B). 1 to 4 parts by weight is particularly preferable. If it is less than 0.1 part by weight, curability and holding power may be lowered. If it exceeds 5 parts by weight, the pressure-sensitive adhesive layer may be colored or the holding power may be reduced. The form of (D) component is not specifically limited. (D) component alone, (D) component diluted in organic solvent, water dispersed, silicone oil dispersed in paste, and the like. (D) A component may use 2 or more types together.
付加反応硬化型シリコーン粘着剤組成物としては次のものが用いられる。
（Ａ'）１分子中に２個以上のアルケニル基を有するポリジオルガノシロキサン ２０〜８０重量部
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン（Ｒ１は炭素数１から１０の１価炭化水素基。） ８０〜２０重量部
（Ｃ）次式で示される構造を含有するヒンダードアミン化合物 （Ａ'）、（Ｂ）の合計１００重量部に対して ０．０１〜１．０重量部
The following are used as the addition reaction curable silicone pressure-sensitive adhesive composition.
(A ′) 20 to 80 parts by weight of a polydiorganosiloxane having two or more alkenyl groups in one molecule (B) containing R 1 3 SiO 0.5 units and SiO 2 units, and R 1 3 SiO 0.5 Polyorganosiloxane having a unit / SiO 2 unit molar ratio of 0.6 to 1.7 (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) 0.01 to 1.0 part by weight based on 100 parts by weight of the total amount of the hindered amine compound (A ′) and (B)
（Ｒは上記で示したと同じ基。）
（Ｅ）ＳｉＨ基を含有するポリオルガノシロキサン （Ａ'）成分中のアルケニル基に対する（Ｅ）成分中のＳｉＨ基のモル比が０．５〜２ ０となる量
（Ｆ）制御剤 （Ａ'）、（Ｂ）の合計１００重量部に対して ０〜８．０重量部
（Ｇ）白金触媒 （Ａ'）、（Ｂ）成分の合計に対し白金分として１〜５０００ｐｐｍ
を含有する付加反応型シリコーン粘着剤組成物を提供する。また、本発明は、プラスチックフィルムの少なくとも１面に上記のシリコーン粘着剤組成物の硬化物層が積層されていることを特徴とする粘着テープを提供する。
(R is the same group as shown above.)
(E) Polyorganosiloxane containing SiH groups (A ') Amount (F) controlling agent (A') The molar ratio of SiH groups in component (E) to alkenyl groups in component (A) is 0.5 to 20 ), 0 to 8.0 parts by weight with respect to a total of 100 parts by weight of (B) (G) Platinum catalyst (A '), 1 to 5000 ppm as a platinum content with respect to the total of components (B)
An addition reaction type silicone pressure-sensitive adhesive composition is provided. Moreover, this invention provides the adhesive tape characterized by laminating | curing the hardened | cured material layer of said silicone adhesive composition on at least 1 surface of a plastic film.
この場合、これらシリコーン粘着剤組成物及び粘着テープは、金属特にステンレス鋼のマスキングテープ用として有効に用いられる。 In this case, the silicone pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape are effectively used for metal, particularly stainless steel masking tape.
以下、更に詳述すると、（Ａ'）成分はアルケニル基含有ポリジオルガノシロキサンであり、下記式で示されるものであることが好ましい。
Ｒ４ (3-a)ＸaＳｉＯ−（Ｒ４ＸＳｉＯ）ｍ−（Ｒ４ 2ＳｉＯ）ｎ−ＳｉＲ４ (3-a)Ｘa
Ｒ４ 2（ＨＯ）ＳｉＯ−（Ｒ４ＸＳｉＯ）ｍ＋２−（Ｒ４ 2ＳｉＯ）ｎ−ＳｉＲ４ 2（ＯＨ）
（式中、Ｒ４は脂肪属不飽和結合を有さない１価炭化水素基、Ｘはアルケニル基含有有機基であり、ａは０〜３の整数、好ましくは１、ｍは０以上、ｎは１００以上の数であり、ａとｍは同時に０にならない。また、ｍ＋ｎはこのポリジオルガノシロキサンの２５℃における粘度を５００ ｍＰａ・ｓ以上とする数である。）
More specifically, the component (A ′) is an alkenyl group-containing polydiorganosiloxane, and is preferably represented by the following formula.
R 4 (3-a) X a SiO— (R 4 XSiO) m — (R 4 2 SiO) n —SiR 4 (3-a) X a
R 4 2 (HO) SiO— (R 4 XSiO) m + 2 − (R 4 2 SiO) n —SiR 4 2 (OH)
(In the formula, R 4 is a monovalent hydrocarbon group having no aliphatic unsaturated bond, X is an alkenyl group-containing organic group, a is an integer of 0 to 3, preferably 1, m is 0 or more, n Is a number of 100 or more, and a and m are not 0 at the same time, and m + n is a number that makes this polydiorganosiloxane have a viscosity at 25 ° C. of 500 mPa · s or more.)
ここで、Ｒ４としては、炭素数１〜１０のものが好ましく、例示すると、メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、トリル基などのアリール基などであり、特にメチル基、フェニル基が好ましい。 Here, as R 4 , those having 1 to 10 carbon atoms are preferable. For example, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, phenyl group and tolyl group An aryl group such as a methyl group and a phenyl group are particularly preferable.
Ｘのアルケニル基含有有機基としては、炭素数２〜１０のものが好ましく、ビニル基、アリル基、ヘキセニル基、オクテニル基、アクリロイルプロピル基、アクリロイルメチル基、メタクリロイルプロピル基、シクロヘキセニルエチル基、ビニルオキシプロピル基などであり、特に、工業的にはビニル基が好ましい。 The alkenyl group-containing organic group represented by X is preferably one having 2 to 10 carbon atoms, such as vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclohexenylethyl group, vinyl. An oxypropyl group is preferred, and a vinyl group is particularly preferred industrially.
このポリジオルガノシロキサンの性状はオイル状、生ゴム状であればよい。
（Ａ'）成分の粘度は２５℃において、オイル状のものであれば１０００ｍＰａ・ｓ以上。特に１０、０００ ｍＰａ・ｓ以上が好ましい。１０００ｍＰａ・ｓ以下では硬化性が低下したり、凝集力（保持力）が低下するため不適である。また、生ゴム状のものであれば、３０％の濃度となるようにトルエンで溶解したときの粘度が１００、０００ ｍＰａ・ｓ以下が好ましい。１００、０００ ｍＰａ・ｓを越えると、組成物が高粘度となりすぎて製造時の撹拌が困難になる。さらに、（Ａ'）成分は２種以上を併用してもよい。
The polydiorganosiloxane may be in the form of oil or raw rubber.
If the viscosity of the component (A ′) is oily at 25 ° C., it is 1000 mPa · s or more. In particular, 10,000 mPa · s or more is preferable. If it is 1000 mPa · s or less, the curability is lowered and the cohesive force (holding force) is lowered, which is not suitable. Moreover, if it is a raw rubber-like thing, the viscosity when it melt | dissolves with toluene so that it may become a 30% density | concentration is preferable 100,000 mPa * s or less. If it exceeds 100,000 mPa · s, the composition becomes too viscous and stirring during production becomes difficult. Furthermore, (A ') component may use 2 or more types together.
（Ｂ）成分はＲ１ ３ＳｉＯ０．５単位（Ｒ３は前記）およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサンである。Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６未満では粘着力やタックが低下することがあり、１．７を越えると粘着力や保持力が低下することがある。ＯＨ基を含有していてもよく、ＯＨ基含有量は４．０重量％以下のものが好ましい。ＯＨ基が４．０重量％を超えるものは粘着剤の硬化性が低下する理由により好ましくない。 The component (B) contains R 1 3 SiO 0.5 units (R 3 is as described above) and SiO 2 units, and the molar ratio of R 1 3 SiO 0.5 units / SiO 2 units is 0.6 to 1.7. Is a polyorganosiloxane. If the molar ratio of R 1 3 SiO 0.5 unit / SiO 2 unit is less than 0.6, the adhesive force and tack may be lowered, and if it exceeds 1.7, the adhesive force and holding force may be lowered. An OH group may be contained, and the OH group content is preferably 4.0% by weight or less. The case where the OH group exceeds 4.0% by weight is not preferable because the curability of the pressure-sensitive adhesive is lowered.
（Ｂ）成分は２種以上を併用してもよい。また、本発明の特性を損なわない範囲でＲ１ＳｉＯ１．５単位、Ｒ１ ２ＳｉＯ単位を（Ｂ）成分中に含有させることも可能である。 (B) 2 or more types of components may be used together. It is also possible to within a range that does not impair the characteristics of the present invention contains R 1 SiO 1.5 units, a R 1 2 SiO units (B) component.
（Ａ'）成分、（Ｂ）成分は単純に混合したものを用いてもよいし、（Ａ'）成分に次式のものを含有する場合、
Ｒ４ 2（ＨＯ）ＳｉＯ−（Ｒ４ＸＳｉＯ）ｍ＋２−（Ｒ４ 2ＳｉＯ）ｎ−ＳｉＲ４ 2（ＯＨ）
（ｍ、ｎは上記と同じ数を表す。Ｒ４は上記したと同じ基。）
（Ａ'）成分、（Ｂ）成分を縮合反応物として使用してもよい。縮合反応を行うには、トルエンなどの溶剤に溶解した（Ａ'）、（Ｂ）成分の混合物をアルカリ性触媒を用い、室温乃至還流下で反応させればよい。
(A ') component, (B) component may use what was mixed simply, and when (A') component contains the following formula,
R 4 2 (HO) SiO— (R 4 XSiO) m + 2 − (R 4 2 SiO) n —SiR 4 2 (OH)
(M and n represent the same numbers as above. R 4 is the same group as described above.)
Component (A ′) and component (B) may be used as the condensation reaction product. In order to perform the condensation reaction, a mixture of the components (A ′) and (B) dissolved in a solvent such as toluene may be reacted at room temperature to reflux using an alkaline catalyst.
（Ａ'）、（Ｂ）成分の配合比は２０／８０〜８０／２０とすればよい。特に３０／７０〜７０／３０とすることが好ましい。（Ａ'）成分のポリジオルガノシロキサンの配合比が２０／８０より低いと粘着力や保持力が低下し、８０／２０を越えると粘着力やタックが低下する。 The blending ratio of the components (A ′) and (B) may be 20/80 to 80/20. In particular, the ratio is preferably 30/70 to 70/30. When the blending ratio of the polydiorganosiloxane as the component (A ′) is lower than 20/80, the adhesive strength and holding power decrease, and when it exceeds 80/20, the adhesive strength and tack decrease.
（Ｃ）成分はヒンダードアミン化合物であり、前記と同じものである。 (C) A component is a hindered amine compound and is the same as the above.
（Ｅ）成分は架橋剤で、１分子中にケイ素原子に結合した水素原子を少なくとも２個、好ましくは３個以上有するオルガノヒドロポリシロキサンであり、直鎖状、分岐状、環状のものを使用できる。 Component (E) is a crosslinking agent, which is an organohydropolysiloxane having at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule, and uses linear, branched, or cyclic ones. it can.
（Ｅ）成分として、下記式のものを例示することができるが、これらのものには限定されない。 (E) As a component, the thing of a following formula can be illustrated, However, It is not limited to these.
（Ｒ1は前記の炭化水素であり、ｂは０または１、ｘ，ｙは０以上の整数．ｂが０のときは，ｘは２以上であり、このオルガノヒドロポリシロキサンの２５℃における粘度が１〜５，０００ｍＰａ・ｓとなる数を示す。また、ｓは２以上の整数、ｔは０以上の整数で、かつｓ＋ｔ≧３、好ましくは８≧ｓ＋ｔ≧３の整数を示す。）
(R 1 is the above-mentioned hydrocarbon, b is 0 or 1, x, y is an integer of 0 or more. When b is 0, x is 2 or more, and the viscosity of this organohydropolysiloxane at 25 ° C. Is a number from 1 to 5,000 mPa · s, and s is an integer of 2 or more, t is an integer of 0 or more, and s + t ≧ 3, preferably 8 ≧ s + t ≧ 3.
このオルガノヒドロポリシロキサンの２５℃における粘度は、１〜５，０００ｍＰａ・ｓであることが好ましく、５〜５００ｍＰａ・ｓがさらに好ましい。２種以上の混合物でもよい。 The viscosity of this organohydropolysiloxane at 25 ° C. is preferably 1 to 5,000 mPa · s, more preferably 5 to 500 mPa · s. A mixture of two or more kinds may be used.
（Ｅ）成分の使用量は（Ａ'）成分中のアルケニル基に対する（Ｅ）成分中のＳｉＨ基のモル比が０．５〜２０、特に０．８〜１５の範囲となるように配合することが好ましい。０．５未満では架橋密度が低くなり、これにともない保持力が低くなることがあり、２０を超えると架橋密度が高くなり十分な粘着力及びタックが得られないことがある。また、２０を越えると処理液の使用可能時間が短くなる場合がある。 The amount of component (E) used is such that the molar ratio of SiH groups in component (E) to alkenyl groups in component (A ′) is in the range of 0.5 to 20, particularly 0.8 to 15. It is preferable. If it is less than 0.5, the crosslinking density is lowered, and the holding force may be lowered accordingly. If it exceeds 20, the crosslinking density is increased, and sufficient adhesive force and tack may not be obtained. On the other hand, if it exceeds 20, the usable time of the treatment liquid may be shortened.
（Ｆ）成分は制御剤であり、シリコーン粘着剤組成物を調合ないし基材に塗工する際に加熱硬化の以前に処理液が増粘やゲル化をおこさないようにするために添加するものである。具体例としては、３−メチル−１−ブチン−３−オール、３−メチル−１−ペンチン−３−オール、３，５−ジメチル−１−ヘキシン−３−オール、１−エチニルシクロヘキサノール、３−メチル−３−トリメチルシロキシ−１−ブチン、３−メチル−３−トリメチルシロキシ−１−ペンチン、３，５−ジメチル−３−トリメチルシロキシ−１−ヘキシン、１−エチニル−１−トリメチルシロキシシクロヘキサン、ビス（２，２−ジメチル−３−ブチノキシ）ジメチルシラン、１，３，５，７−テトラメチル−１，３，５，７−テトラビニルシクロテトラシロキサン、１，１，３，３−テトラメチル−１，３−ジビニルジシロキサンなどが挙げられる。 Component (F) is a control agent, and is added to prevent the treatment liquid from thickening or gelling before heat-curing when the silicone adhesive composition is prepared or applied to the substrate. It is. Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl -1,3-divinyldisiloxane and the like.
（Ｆ）成分の配合量は成分（Ａ'）、（Ｂ）成分の合計１００重量部に対して０〜８．０重量部の範囲であればよく、特に０．０５〜２．０重量部が好ましい。８．０重量部を超えると硬化性が低下することがある。 The blending amount of the component (F) may be in the range of 0 to 8.0 parts by weight, particularly 0.05 to 2.0 parts by weight, based on 100 parts by weight of the total of the components (A ′) and (B). Is preferred. If it exceeds 8.0 parts by weight, the curability may be lowered.
（Ｇ）成分は白金系触媒であり、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコールとの反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサンとの反応物などが挙げられる。 Component (G) is a platinum-based catalyst, containing chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and containing chloroplatinic acid and a vinyl group A reaction product with siloxane can be used.
添加量は（Ａ'）、（Ｂ）成分の合計に対し、白金分として１〜５，０００ｐｐｍ、特に５〜２，０００ｐｐｍとすることが好ましい。１ｐｐｍ未満では硬化性が低下し、架橋密度が低くなり、保持力が低下することがあり、５，０００ｐｐｍを超えると処理浴の使用可能時間が短くなる場合がある。 The amount added is preferably 1 to 5,000 ppm, particularly preferably 5 to 2,000 ppm in terms of platinum with respect to the total of components (A ′) and (B). If it is less than 1 ppm, the curability is lowered, the crosslinking density is lowered, and the holding power may be lowered. If it exceeds 5,000 ppm, the usable time of the treatment bath may be shortened.
上記の付加反応硬化型シリコーン粘着剤に、更に耐熱性を改善する目的で（Ｈ）成分のフェノール系酸化防止剤を添加してもよい。
（Ｈ）成分としては、特に分子中に下式の構造を有するものが好ましい。
In order to further improve the heat resistance, a phenolic antioxidant as component (H) may be added to the above addition reaction curable silicone pressure-sensitive adhesive.
As the component (H), those having a structure of the following formula in the molecule are particularly preferable.
具体的には下記が挙げられる。 Specific examples include the following.
（mは０以上、ｎは１以上の整数）
(M is 0 or more, n is an integer of 1 or more)
（Ｈ）成分の添加量は（Ａ’）、（Ｂ）成分の合計１００重量部に対して０．１〜１０重量部、０．１重量部以下では高温履歴を受けた場合の糊残り防止効果が十分発揮されず、１０重量部以上では保持力が低下することがある。 Component (H) is added in an amount of 0.1 to 10 parts by weight based on the total of 100 parts by weight of component (A ′) and (B). The effect is not sufficiently exhibited, and the holding power may be reduced at 10 parts by weight or more.
本発明のシリコーン粘着剤組成物には、上記各成分以外に任意成分を添加することができる。例えば、ポリジメチルシロキサン、ポリジメチルジフェニルシロキサンなどの非反応性のポリオルガノシロキサン、さらに、フェノール系、キノン系、アミン系、リン系、ホスファイト系、イオウ系、チオエーテル系などの酸化防止剤、トリアゾール系、ベンゾフェノン系などの光安定剤、リン酸エステル系、ハロゲン系、リン系、アンチモン系などの難燃剤、カチオン活性剤、アニオン活性剤、非イオン系活性剤などの帯電防止剤、塗工の際の粘度を下げるための溶剤として、トルエン、キシレン等の芳香族系溶剤、ヘキサン、オクタン、イソパラフィンなどの脂肪族系溶剤、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、酢酸エチル、酢酸イソブチルなどのエステル系溶剤、ジイソプロピルエーテル、１，４−ジオキサンなどのエーテル系溶剤、又はこれらの混合溶剤、染料、顔料などが使用される。 In addition to the above components, optional components can be added to the silicone pressure-sensitive adhesive composition of the present invention. For example, non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane, antioxidants such as phenolic, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based and thioether-based compounds, triazole -Based, benzophenone-based light stabilizers, phosphate ester-based, halogen-based, phosphorus-based, antimony-based flame retardants, cationic surfactants, anionic surfactants, nonionic surfactants and other antistatic agents, coating As solvents for reducing the viscosity, aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, octane and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, isobutyl acetate and the like Ester solvent, diisopropyl ether, 1,4-dio Ether solvents such as Sun, or a mixed solvent, a dye, a pigment is used.
上記のように配合されたシリコーン粘着剤組成物は、種々の基材に塗工し、所定の条件にて硬化させることにより粘着剤層を得ることができる。
基材としては、ポリエステル、ポリテトラフルオロエチレン、ポリイミド、ポリフェニレンスルフィド、ポリアミド、ポリカーボネート、ポリスチレン、ポリプロピレン、ポリエチレン、ポリ塩化ビニルなどのプラスチックフィルム、アルミニウム箔、銅箔などの金属箔、和紙、合成紙、ポリエチレンラミネート紙などの紙、布、ガラス繊維、これらのうちの複数を積層してなる複合基材が挙げられる。
The silicone pressure-sensitive adhesive composition formulated as described above can be applied to various substrates and cured under predetermined conditions to obtain a pressure-sensitive adhesive layer.
As the base material, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, polyvinyl chloride and other metal films, aluminum foil, copper foil and other metal foil, Japanese paper, synthetic paper, Examples thereof include paper such as polyethylene laminated paper, cloth, glass fiber, and a composite base material formed by laminating a plurality of these.
これらの基材と粘着層の密着性を向上させるためにプライマー処理、コロナ処理、エッチング処理、プラズマ処理したものを用いてもよい。 In order to improve the adhesion between these substrates and the adhesive layer, a primer-treated, corona-treated, etched or plasma-treated material may be used.
塗工方法は、公知の塗工方式を用いて塗工すればよく、コンマコーター、リップコーター、ロールコーター、ダイコーター、ナイフコーター、ブレードコーター、ロッドコーター、キスコーター、グラビアコーター、スクリーン塗工、浸漬塗工、キャスト塗工などが挙げられる。
塗工量としては、硬化したあとの粘着剤層の厚みとして２〜２００μｍ、特に３〜１００μｍとすることができる。
The coating method may be applied using a known coating method, comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, dipping. Examples thereof include coating and cast coating.
The coating amount can be 2 to 200 μm, particularly 3 to 100 μm, as the thickness of the adhesive layer after curing.
硬化条件としては、過酸化物硬化型のものは１００〜２００℃で３０秒から１０分、付加反応型のものとしては８０から１３０℃で３０秒〜３分とすればよいがこの限りではない。 As curing conditions, the peroxide curing type may be 100 to 200 ° C. for 30 seconds to 10 minutes, and the addition reaction type may be 80 to 130 ° C. for 30 seconds to 3 minutes, but is not limited thereto. .
上記のように基材に直接塗工して粘着テープを製造してもよいし、剥離コーティングを行った剥離フィルムや剥離紙に塗工し、硬化を行った後、上記の基材に貼り合わせる転写法により粘着テープを製造してもよい。 As described above, it may be applied directly to a substrate to produce an adhesive tape, or it is applied to a release film or release paper that has been release coated, cured, and then bonded to the above substrate. An adhesive tape may be produced by a transfer method.
本発明のシリコーン粘着剤組成物を用いて製造した粘着テープによりマスキングが可能な被着体としては特に限定されないが，次のものを例示できる。ステンレス，銅，鉄，などの金属，これらの表面がメッキ処理や防錆処理された金属，ガラス，陶磁器，セラミックス，ポリテトラフロロエチレン，ポリイミド，エポキシ樹脂，ノボラック樹脂などの樹脂，さらにこれらのうちの複数が複合されて構成されたものである。 Although it does not specifically limit as an adherend which can be masked with the adhesive tape manufactured using the silicone adhesive composition of this invention, The following can be illustrated. Metal such as stainless steel, copper, iron, etc., metal whose surface is plated or rust-proofed, glass, ceramics, ceramics, polytetrafluoroethylene, polyimide, epoxy resin, novolac resin, etc. A plurality of these are combined.
以下、実施例と比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、例中の部は重量部を示したものであり、特性値は下記の試験方法による測定値を示す。また、Ｍｅはメチル基、Ｐｈはフェニル基、Ｂｕはブチル基、Ｖｉはビニル基を表す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the part in an example shows a weight part and a characteristic value shows the measured value by the following test method. Me represents a methyl group, Ph represents a phenyl group, Bu represents a butyl group, and Vi represents a vinyl group.
糊残り性
シリコーン粘着剤組成物溶液を、厚み２５μｍ、幅２５ｍｍのポリイミドフィルムに硬化後の厚みが４０μｍとなるようにアプリケータを用いて塗工した後、１３０℃、１分の条件で加熱し硬化させ、粘着テープを作成した。この粘着テープを金属板（研磨したステンレス板）に貼りつけ、重さ２ｋｇのゴム層で被覆されたローラーを１往復させることにより圧着した後、２８０℃の乾燥機中で放置した。所定時間後に金属板を取り出し、室温まで冷やした後、粘着テープを剥がして、粘着剤層が凝集破壊し金属板の表面に粘着剤が残留するかどうかを観察した。糊残りなく剥離できるものを○、一部糊残りするものを△、ほぼ全面が糊残りするものを×とした。
The adhesive adhesive silicone adhesive composition solution was applied to a polyimide film having a thickness of 25 μm and a width of 25 mm using an applicator so that the thickness after curing was 40 μm, and then heated at 130 ° C. for 1 minute. Cured to create an adhesive tape. This adhesive tape was affixed to a metal plate (polished stainless steel plate), pressed by reciprocating a roller covered with a rubber layer weighing 2 kg, and then left in a dryer at 280 ° C. After a predetermined time, the metal plate was taken out and cooled to room temperature, and then the pressure-sensitive adhesive tape was peeled off, and it was observed whether the pressure-sensitive adhesive layer cohesively failed and the pressure-sensitive adhesive remained on the surface of the metal plate. The ones that can be peeled without any adhesive residue are marked with ◯, the ones with a part of the glue remaining are marked with Δ, and the ones with almost the whole glue remaining are marked with ×.
粘着力
糊残り性評価と同様の方法で粘着テープを作成し、この粘着テープをステンレス板に貼りつけ、重さ２ｋｇのゴム層で被覆されたローラーを１往復させることにより圧着した。室温で約２０時間放置した後、引っ張り試験機を用いて３００ｍｍ／分の速度で１８０゜の角度でテープをステンレス板から引き剥がすのに要する力（Ｎ／２５ｍｍ）を測定した。
A pressure-sensitive adhesive tape was prepared in the same manner as in the evaluation of adhesive strength and adhesiveness. This pressure-sensitive adhesive tape was attached to a stainless steel plate and pressed by reciprocating a roller covered with a rubber layer having a weight of 2 kg. After standing at room temperature for about 20 hours, the force (N / 25 mm) required to peel the tape from the stainless steel plate at an angle of 180 ° at a speed of 300 mm / min was measured using a tensile tester.
保持力
糊残り性評価と同様の方法で粘着テープを作成した。この粘着テープをステンレス板の下端に粘着面積が２５×２５ｍｍとなるように貼りつけ、粘着テープの下端に重さ１ｋｇの荷重をかけ、２５０℃で１時間、垂直に放置した後のずれ距離を読みとり顕微鏡で測定した。
A pressure-sensitive adhesive tape was prepared in the same manner as in the evaluation of the holding power adhesive residue. The adhesive tape is affixed to the lower end of the stainless steel plate so that the adhesive area is 25 × 25 mm, a weight of 1 kg is applied to the lower end of the adhesive tape, and the deviation distance after being left vertically at 250 ° C. for 1 hour Reading was measured with a microscope.
［実施例１］
３０％の濃度となるようにトルエンで溶解したときの粘度が ４２、０００ ｍＰａ・ｓであり、６モル％のジフェニルシロキサン単位を有し、分子鎖末端がＯＨ基で封鎖されたフェニル基含有ポリジメチルシロキサン（４５部）、
Ｍｅ３ＳｉＯ０．５単位、ＳｉＯ２単位からなるポリシロキサン（Ｍｅ３ＳｉＯ０．５単位／ＳｉＯ２単位＝０。８０）の６０％トルエン溶液（９２部）、トルエン（３０部）からなる溶液を還流させながら４時間加熱した。放冷したのち次式のヒンダードアミン化合物Ｉ（旭電化社製 アデカスタブＬＡ５７）（０．２部）を添加し混合した。
[Example 1]
The viscosity when dissolved in toluene to a concentration of 30% is 42,000 mPa · s, has 6 mol% of diphenylsiloxane units, and the molecular chain ends are blocked with OH groups. Dimethylsiloxane (45 parts),
60% toluene solution (92 parts) and toluene (30 parts) solution of polysiloxane (Me 3 SiO 0.5 unit / SiO 2 unit = 0.80) composed of 0.5 units of Me 3 SiO and SiO 2 units Was heated at reflux for 4 hours. After allowing to cool, hindered amine compound I (Adeka Stub LA57 manufactured by Asahi Denka Co., Ltd.) (0.2 parts) of the following formula was added and mixed.
上記の混合物（シロキサン分６０％）（１００部）に、ベンゾイルパーオキサイドの５０％シリコーンペースト（２．４部）、トルエン（５０部）を混合し、シロキサン分約４０％のシリコーン粘着剤組成物溶液を調製した。このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。 50% silicone paste (2.4 parts) of benzoyl peroxide and toluene (50 parts) are mixed with the above mixture (siloxane content 60%) (100 parts), and a silicone pressure-sensitive adhesive composition having a siloxane content of about 40%. A solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
実施例２
実施例１でヒンダードアミン化合物Ｉのかわりに、下式のヒンダードアミン化合物II（旭電化社製 アデカスタブＬＡ５２）（０．２部）を添加したシリコーン粘着剤組成物溶液を調製した。
Example 2
Instead of hindered amine compound I in Example 1, a silicone pressure-sensitive adhesive composition solution was prepared by adding hindered amine compound II of the following formula (Adeka Stub LA52 manufactured by Asahi Denka Co., Ltd.) (0.2 parts).
このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。
This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
実施例３
実施例１でフェニル基含有ジメチルポリシロキサンのかわりに、３０％の濃度となるようにトルエンで溶解したときの粘度が ６７、０００ ｍＰａ・ｓであり、分子鎖末端がＯＨ基で封鎖されたポリジメチルシロキサン（４５部）を用いたシリコーン粘着剤組成物溶液を調製した。
このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。
Example 3
In Example 1, instead of the phenyl group-containing dimethylpolysiloxane, a viscosity of 67,000 mPa · s when dissolved in toluene so as to have a concentration of 30% and a molecular chain terminal blocked with an OH group A silicone pressure-sensitive adhesive composition solution using dimethylsiloxane (45 parts) was prepared.
This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
比較例１
実施例１でヒンダードアミン化合物Ｉを添加しないシリコーン粘着剤組成物溶液を調製した。
このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。
Comparative Example 1
In Example 1, a silicone pressure-sensitive adhesive composition solution to which no hindered amine compound I was added was prepared.
This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
比較例２
実施例１でヒンダードアミン化合物Ｉのかわりに、次式のフェノール系酸化防止剤III（チバ・スペシャルティー・ケミカルズ社製、ＩＲＧＡＮＯＸ １３３０）（０．５部）を添加したシリコーン粘着剤組成物溶液を調製した。このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。
Comparative Example 2
In Example 1, instead of the hindered amine compound I, a silicone pressure-sensitive adhesive composition solution prepared by adding a phenolic antioxidant III of the following formula (IRGANOX 1330) (0.5 parts) manufactured by Ciba Specialty Chemicals Co., Ltd. was prepared. did. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
実施例４
３０％の濃度となるようにトルエンで溶解したときの粘度が２７０００ｍＰａ・ｓであり、０．１５モル％のメチルビニルシロキサン単位および１０モル％のジフェニルシロキサン単位を有し、分子鎖末端がＳｉＭｅ２Ｖｉ基で封鎖されたビニル基およびフェニル基含有ポリジメチルシロキサン（４５部）、
Ｍｅ３ＳｉＯ０．５単位、ＳｉＯ２単位からなるポリシロキサン（Ｍｅ３ＳｉＯ０．５単位／ＳｉＯ２単位＝０．８０）の６０％トルエン溶液 （９２部）、トルエン（３０部）からなる溶液に、ヒンダードアミン化合物Ｉ（０．２部）、次式の架橋剤（０．１６部）、エチニルシクロヘキサノール（０．１部）を添加し混合した。
Ｍｅ３ＳｉＯ−［ＭｅＨＳｉＯ］４０−ＳｉＭｅ３
Example 4
When dissolved in toluene so as to have a concentration of 30%, the viscosity is 27000 mPa · s, 0.15 mol% of methylvinylsiloxane units and 10 mol% of diphenylsiloxane units, and the molecular chain terminal is SiMe 2. A vinyl and phenyl group-containing polydimethylsiloxane blocked with Vi groups (45 parts),
Me 3 SiO 0.5 units, a 60% solution of a polysiloxane consisting of SiO 2 units (Me 3 SiO 0.5 units / SiO 2 units = 0.80) (92 parts), a toluene (30 parts) solution The hindered amine compound I (0.2 part), the crosslinking agent of the following formula (0.16 part), and ethynylcyclohexanol (0.1 part) were added and mixed.
Me 3 SiO— [MeHSiO] 40 —SiMe 3
上記の混合物（シロキサン分６０％）（１００部）にトルエン（５０部）、白金触媒ＣＡＴ−ＰＬ−５０Ｔ（信越化学工業社製）（０．５部）を添加しさらに混合し、シロキサン分約４０％のシリコーン粘着剤組成物溶液を調製した。このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。 To the above mixture (siloxane content 60%) (100 parts), toluene (50 parts) and platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.5 parts) were added and further mixed to obtain a siloxane content of about A 40% silicone adhesive composition solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
比較例３
実施例４でヒンダードアミン化合物Ｉのかわりに、前記のフェノール系酸化防止剤III（０．５部）を添加したシリコーン粘着剤組成物溶液を調製した。このシリコーン粘着剤の糊残り性、粘着力、保持力を測定した。結果を表１に示す。
Comparative Example 3
In Example 4, instead of the hindered amine compound I, a silicone pressure-sensitive adhesive composition solution in which the above-mentioned phenolic antioxidant III (0.5 part) was added was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.
実施例５
３０％の濃度となるようにトルエンで溶解したときの粘度が２７，０００ ｍＰａ・ｓであり、０．１５モル％のメチルビニルシロキサン単位および１０モル％のジフェニルシロキサン単位を有し、分子鎖末端がＳｉＭｅ２Ｖｉ基で封鎖されたビニル基およびフェニル基含有ポリジメチルシロキサン（４５部）、
Ｍｅ３ＳｉＯ０．５単位及びＳｉＯ２単位からなるポリシロキサン（Ｍｅ３ＳｉＯ０．５単位／ＳｉＯ２単位＝０．８０）の６０％トルエン溶液 （９２部）、トルエン（３０部）、からなる溶液に、ヒンダードアミン化合物Ｉ（０．２部）、フェノール系酸化防止剤III（０．５部）、次式の架橋剤（０．１６部）とエチニルシクロヘキサノール（０．１部）を添加し混合した。
Ｍｅ３ＳｉＯ−［ＭｅＨＳｉＯ］４０−ＳｉＭｅ３
Example 5
Viscosity when dissolved in toluene to a concentration of 30% is 27,000 mPa · s, has 0.15 mol% methylvinylsiloxane units and 10 mol% diphenylsiloxane units, and has molecular chain terminals Vinyl group- and phenyl group-containing polydimethylsiloxane blocked with SiMe 2 Vi groups (45 parts),
It consists of 60% toluene solution (92 parts) and toluene (30 parts) of polysiloxane (Me 3 SiO 0.5 unit / SiO 2 unit = 0.80) composed of 0.5 units of Me 3 SiO and 2 units of SiO 2. To the solution is added hindered amine compound I (0.2 parts), phenolic antioxidant III (0.5 parts), a crosslinking agent of the following formula (0.16 parts) and ethynylcyclohexanol (0.1 parts). Mixed.
Me 3 SiO— [MeHSiO] 40 —SiMe 3
上記の混合物（シロキサン分６０％）（１００部）にトルエン（５０部）、白金触媒ＣＡＴ−ＰＬ−５０Ｔ（信越化学工業社製）（０．５部）を添加してさらに混合し，シロキサン分約４０％のシリコーン粘着剤組成物溶液を調製した。このシリコーン粘着剤の糊残り性，粘着力，保持力を測定した結果を表１に示す。 To the above mixture (siloxane content 60%) (100 parts), toluene (50 parts) and platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.5 parts) were added and further mixed to obtain a siloxane content. About 40% silicone adhesive composition solution was prepared. Table 1 shows the results of measurement of adhesive residue, adhesive strength, and retention strength of this silicone adhesive.
Claims (7)
（Ｂ）Ｒ １ ３ ＳｉＯ ０．５ 単位およびＳｉＯ ２ 単位を含有し、Ｒ １ ３ ＳｉＯ ０．５ 単位／ＳｉＯ ２ 単位のモル比が０．６〜１．７であるポリオルガノシロキサン（Ｒ １ は炭素数１から１０の１価炭化水素基。） ８０〜２０重量部
（Ｃ）次式で示される構造を含有するヒンダードアミン化合物
（Ａ）、（Ｂ）の合計１００重量部に対して ０．０１〜１．０重量部
（Ｄ）有機過酸化物硬化剤
（Ａ）、（Ｂ）の合計１００重量部に対して ０．１〜５．０重量部
を含有する過酸化物硬化型シリコーン粘着剤組成物。 (A) 20 to 80 parts by weight of polydiorganosiloxane (B) 0.5 unit of R 1 3 SiO and SiO 2 unit, and a molar ratio of R 1 3 SiO 0.5 unit / SiO 2 unit of 0.6 to Polyorganosiloxane which is 1.7 (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) A hindered amine compound containing a structure represented by the following formula
0.01 to 1.0 part by weight based on 100 parts by weight of (A) and (B)
(D) Organic peroxide curing agent A peroxide-curing silicone pressure-sensitive adhesive composition containing 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the total of (A) and (B).
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位およびＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン（Ｒ１は炭素数１から１０の１価炭化水素基。） ８０〜２０重量部
（Ｃ）次式で示される構造を含有するヒンダードアミン化合物
（Ａ’）、（Ｂ）の合計１００重量部に対して ０．０１〜１．０重量部
（Ｅ）ＳｉＨ基を含有するポリオルガノシロキサン
（Ａ’）成分中のアルケニル基に対する（Ｅ）成分中のＳｉＨ基のモル比が０．５〜２０となる量、および
（Ｇ）白金触媒 （Ａ’）、（Ｂ）成分の合計に対し白金分として１〜５０００ｐｐｍ
を含有する付加反応型シリコーン粘着剤。 (A ′) 20 to 80 parts by weight of a polydiorganosiloxane having two or more alkenyl groups in one molecule (B) containing R 1 3 SiO 0.5 units and SiO 2 units, and R 1 3 SiO 0.5 Polyorganosiloxane having a unit / SiO 2 unit molar ratio of 0.6 to 1.7 (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) Hindered amine compound containing a structure
0.01 to 1.0 part by weight based on 100 parts by weight of (A ′) and (B)
(E) polyorganosiloxane containing SiH groups (A ′) an amount in which the molar ratio of SiH groups in component ( E ) to alkenyl groups in component is 0.5 to 20, and (G) platinum catalyst (A '), 1 to 5000 ppm as platinum content with respect to the total of component (B)
An addition reaction type silicone pressure sensitive adhesive.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003389464A JP4727139B2 (en) | 2002-11-28 | 2003-11-19 | Silicone adhesive composition and adhesive tape |
| TW92133415A TWI272298B (en) | 2002-11-28 | 2003-11-27 | Silicone adhesive composition and adhesive tape thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002344919 | 2002-11-28 | ||
| JP2002344919 | 2002-11-28 | ||
| JP2003389464A JP4727139B2 (en) | 2002-11-28 | 2003-11-19 | Silicone adhesive composition and adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004190013A JP2004190013A (en) | 2004-07-08 |
| JP4727139B2 true JP4727139B2 (en) | 2011-07-20 |
Family
ID=32774840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003389464A Expired - Fee Related JP4727139B2 (en) | 2002-11-28 | 2003-11-19 | Silicone adhesive composition and adhesive tape |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4727139B2 (en) |
| TW (1) | TWI272298B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005272697A (en) * | 2004-03-25 | 2005-10-06 | Shin Etsu Chem Co Ltd | Curable silicone resin composition, sealing material for optical semiconductor and optical semiconductor device |
| JP2006028311A (en) * | 2004-07-14 | 2006-02-02 | Shin Etsu Chem Co Ltd | Silicone adhesive composition having excellent heat resistance and production method |
| FR2879612B1 (en) * | 2004-12-21 | 2007-05-04 | Rhodia Chimie Sa | SILICONE ELASTOMER COMPOSITION, ADHESIVE, MONOCOMPONENT AND CROSS-LINKABLE BY POLYADDITION |
| JP2006199498A (en) * | 2004-12-22 | 2006-08-03 | Konica Minolta Holdings Inc | Inkjet printer and recorded product produced thereby |
| JP4516008B2 (en) * | 2005-12-12 | 2010-08-04 | 信越ポリマー株式会社 | Manufacturing method of holding jig |
| US7560166B2 (en) | 2005-12-28 | 2009-07-14 | 3M Innovative Properties Company | Adhesive article, composite article, and methods of making the same |
| JP4505645B2 (en) * | 2006-02-17 | 2010-07-21 | フジコピアン株式会社 | Affixing the fixed sheet |
| JP4505644B2 (en) * | 2006-02-17 | 2010-07-21 | フジコピアン株式会社 | Fixed sheet |
| JP4505646B2 (en) * | 2006-02-20 | 2010-07-21 | フジコピアン株式会社 | Fixed sheet |
| JP4505649B2 (en) * | 2006-03-23 | 2010-07-21 | フジコピアン株式会社 | Fixed sheet |
| JP5019893B2 (en) * | 2007-01-26 | 2012-09-05 | リンテック株式会社 | Re-peelable pressure-sensitive adhesive sheet and coating film protection method |
| JP5309714B2 (en) * | 2007-07-04 | 2013-10-09 | 信越化学工業株式会社 | Silicone pressure-sensitive adhesive composition having antistatic properties and silicone pressure-sensitive adhesive tape |
| FR2919615A1 (en) * | 2007-08-02 | 2009-02-06 | Bluestar Silicones France Soc | ADHESIVE SILICONE ELASTOMERIC COMPOSITION |
| WO2009028455A1 (en) | 2007-08-27 | 2009-03-05 | Lintec Corporation | Releasable adhesive sheet and method for protecting incompletely cured coating film |
| JP5338626B2 (en) * | 2009-11-10 | 2013-11-13 | 信越化学工業株式会社 | Silicone adhesive composition and adhesive film |
| JP5963395B2 (en) * | 2011-03-04 | 2016-08-03 | タツタ電線株式会社 | Protective tape |
| JP5592330B2 (en) * | 2011-10-07 | 2014-09-17 | 信越化学工業株式会社 | Temporary adhesive composition and thin wafer manufacturing method using the same |
| JP6024839B2 (en) | 2014-01-31 | 2016-11-16 | 信越化学工業株式会社 | Organopolysiloxane compound, method for producing the same, and addition-curable silicone composition |
| WO2017002702A1 (en) * | 2015-07-01 | 2017-01-05 | Dic株式会社 | Stabilizer compound, liquid crystal composition and display element |
| KR101985637B1 (en) | 2016-03-08 | 2019-06-03 | 디아이씨 가부시끼가이샤 | Liquid crystal composition and liquid crystal display element using same |
| JP6733241B2 (en) | 2016-03-18 | 2020-07-29 | 信越化学工業株式会社 | Addition curable silicone rubber composition, method for producing the same and cured product |
| JP6691802B2 (en) * | 2016-03-29 | 2020-05-13 | アイカ工業株式会社 | Silicone adhesive composition and adhesive tape |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0286678A (en) * | 1988-09-21 | 1990-03-27 | Shin Etsu Chem Co Ltd | Pressure-sensitive silicone adhesive composition |
| JPH07188471A (en) * | 1993-12-28 | 1995-07-25 | Sekisui Chem Co Ltd | Polyolefin resin film and surface-protected film |
| JP2000265646A (en) * | 1999-03-19 | 2000-09-26 | Sekisui Chem Co Ltd | Floor component |
| JP2001345415A (en) * | 2000-06-01 | 2001-12-14 | Nitto Denko Corp | Lead frame laminate and manufacturing method of semiconductor component |
| JP2001354939A (en) * | 2000-06-14 | 2001-12-25 | Shin Etsu Chem Co Ltd | Silicone pressure-sensitive adhesive composition |
| JP2002030264A (en) * | 2000-07-18 | 2002-01-31 | Lintec Corp | Tacky agent composition and tacky optical member using the same |
| JP2002302606A (en) * | 2001-01-30 | 2002-10-18 | Dow Corning Toray Silicone Co Ltd | Room temperature-curable silicone rubber composition |
-
2003
- 2003-11-19 JP JP2003389464A patent/JP4727139B2/en not_active Expired - Fee Related
- 2003-11-27 TW TW92133415A patent/TWI272298B/en not_active IP Right Cessation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0286678A (en) * | 1988-09-21 | 1990-03-27 | Shin Etsu Chem Co Ltd | Pressure-sensitive silicone adhesive composition |
| JPH07188471A (en) * | 1993-12-28 | 1995-07-25 | Sekisui Chem Co Ltd | Polyolefin resin film and surface-protected film |
| JP2000265646A (en) * | 1999-03-19 | 2000-09-26 | Sekisui Chem Co Ltd | Floor component |
| JP2001345415A (en) * | 2000-06-01 | 2001-12-14 | Nitto Denko Corp | Lead frame laminate and manufacturing method of semiconductor component |
| JP2001354939A (en) * | 2000-06-14 | 2001-12-25 | Shin Etsu Chem Co Ltd | Silicone pressure-sensitive adhesive composition |
| JP2002030264A (en) * | 2000-07-18 | 2002-01-31 | Lintec Corp | Tacky agent composition and tacky optical member using the same |
| JP2002302606A (en) * | 2001-01-30 | 2002-10-18 | Dow Corning Toray Silicone Co Ltd | Room temperature-curable silicone rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200417591A (en) | 2004-09-16 |
| JP2004190013A (en) | 2004-07-08 |
| TWI272298B (en) | 2007-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4727139B2 (en) | Silicone adhesive composition and adhesive tape | |
| JP4784720B2 (en) | Adhesive tape | |
| JP5309714B2 (en) | Silicone pressure-sensitive adhesive composition having antistatic properties and silicone pressure-sensitive adhesive tape | |
| KR101149235B1 (en) | Silicone Pressure-sensitive Adhesive Composition and Pressure-sensitive Adhesive Tape | |
| KR101529060B1 (en) | Silicone-based pressure-sensitive adhesive composition and pressure-sensitive tape or sheet | |
| JP5130995B2 (en) | Solvent-free silicone adhesive composition | |
| US8247502B2 (en) | Addition reaction-curable silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape | |
| JP5553395B2 (en) | Laminated body including silicone adhesive layer | |
| JP5115300B2 (en) | Silicone adhesive composition and silicone adhesive tape with good substrate adhesion | |
| JP4648011B2 (en) | Silicone adhesive composition containing no aromatic solvent and adhesive tape, sheet or label coated with the same | |
| US7476446B2 (en) | Silicone adhesive composition and an adhesive tape thereof | |
| JP2004091703A (en) | Conductive silicone self-adhesive composition and self-adhesive tape | |
| JP4761020B2 (en) | Solvent-free silicone adhesive composition | |
| JP4180353B2 (en) | Silicone adhesive composition and adhesive tape | |
| JP2006028311A (en) | Silicone adhesive composition having excellent heat resistance and production method | |
| CN112513218B (en) | Silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or film using the same | |
| JP2013173944A (en) | Laminate including silicone adhesive layer | |
| US20040157064A1 (en) | Silicone adhesive composition and an adhesive tape thereof | |
| JP2008024777A (en) | Addition curable silicone adhesive composition for silicone rubber and adhesive tape obtained from the composition | |
| JP4919098B2 (en) | Organic peroxide-curing silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape | |
| JP4678817B2 (en) | Silicone composition for pressure-sensitive adhesive and pressure-sensitive adhesive tape obtained from the composition | |
| JP4123349B2 (en) | Laminated article of silicone release layer and silicone adhesive layer and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051117 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091211 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100119 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100317 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20100317 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101201 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101220 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110412 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110413 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4727139 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140422 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |