JP4678817B2 - Silicone composition for pressure-sensitive adhesive and pressure-sensitive adhesive tape obtained from the composition - Google Patents
Silicone composition for pressure-sensitive adhesive and pressure-sensitive adhesive tape obtained from the composition Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims description 85
- 229920001296 polysiloxane Polymers 0.000 title claims description 66
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 54
- 230000001070 adhesive effect Effects 0.000 claims description 81
- 239000000853 adhesive Substances 0.000 claims description 80
- -1 siloxane unit Chemical group 0.000 claims description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 125000003342 alkenyl group Chemical group 0.000 claims description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 29
- 239000002390 adhesive tape Substances 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 114
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000013464 silicone adhesive Substances 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 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
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- KJDMMCYMVUTZSN-UHFFFAOYSA-N (1-ethynylcyclohexyl)oxy-trimethylsilane Chemical compound C[Si](C)(C)OC1(C#C)CCCCC1 KJDMMCYMVUTZSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 239000004215 Carbon black (E152) Substances 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 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 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ZMKOJNOAFRBHTG-UHFFFAOYSA-N ethenyl(ethenylsilyloxy)silane Chemical compound C=C[SiH2]O[SiH2]C=C ZMKOJNOAFRBHTG-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- WQVRVGMFOZQPMR-UHFFFAOYSA-N ethynoxy-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)OC#C WQVRVGMFOZQPMR-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 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
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 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
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester 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
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 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 description 1
- 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 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、粘着剤用シリコーン組成物及び該組成物からなる粘着層を有する粘着テープであって、該組成物から得られる粘着層を有する粘着テープを銅等の被着体上に貼って２５０〜３００℃に加熱した後に該テープを剥離しても、該被着体上に該組成物由来の物質を残さないことを特徴とする粘着剤用シリコーン組成物及び該組成物から得られる粘着テープに関する。 The present invention relates to a pressure-sensitive adhesive silicone composition and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the composition, the pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer obtained from the composition being pasted on an adherend such as copper. A silicone composition for pressure-sensitive adhesives and a pressure-sensitive adhesive tape obtained from the composition do not leave a substance derived from the composition on the adherend even if the tape is peeled after heating to ˜300 ° C. About.
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、他の粘着剤、たとえば、アクリル系、ゴム系、ウレタン系、及びエポキシ系粘着剤では変質又は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 adhesive labels that use silicone adhesives have other adhesives such as acrylic and rubber because the silicone adhesive layer has excellent heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. It is used in a severe environment where the adhesive, the urethane, and the epoxy adhesive are deteriorated or deteriorated.
そのような環境の1つとして、２５０℃以上の加熱に曝される環境がある。例えば、半導体部品のリフロー工程や樹脂封止工程におけるマスキング、部品の仮固定用途である。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。 One such environment is an environment that is exposed to heating above 250 ° C. For example, it is used for masking in the reflow process and resin sealing process of semiconductor parts, and for temporary fixing of parts. In recent years, heat treatment at a higher temperature than before has been performed, and it has been necessary to improve the heat resistance of the silicone adhesive.
例えば、電子部品実装における鉛フリーハンダの実用化に伴い、リフロー温度が従来よりも高温となり、リフロー炉内でのピーク温度が２８０℃に達することもある。斯かる高温下においても粘着剤が剥がれてはならず、さらに、処理終了後には、被着体上に汚染物質を何ら残すことなく、剥がせることが必要である。 For example, with the practical application of lead-free solder in electronic component mounting, the reflow temperature becomes higher than before, and the peak temperature in the reflow furnace may reach 280 ° C. Even under such high temperatures, the pressure-sensitive adhesive must not be peeled off. Further, after the treatment is completed, it is necessary to remove the adhesive without leaving any contaminants on the adherend.
しかし、従来のシリコーン粘着剤を用いた粘着テープでは、１５０〜２００℃の高温の履歴を受けた後に剥離された場合、被着体に粘着剤が残留したり、粘着テープの基材テープから粘着剤層が金属部分に移行したりすることがあった。本発明において、このような現象を糊残りという。 However, with a pressure-sensitive adhesive tape using a conventional silicone pressure-sensitive adhesive, if it is peeled off after receiving a high temperature history of 150 to 200 ° C., the pressure-sensitive adhesive remains on the adherend or sticks from the base tape of the pressure-sensitive adhesive tape. The agent layer sometimes moved to the metal part. In the present invention, such a phenomenon is called adhesive residue.
斯かる糊残りをなくすために、粘着テープのシリコーン系バインダーに酸化防止剤を配合することが知られている（特許文献１）。 In order to eliminate such adhesive residue, it is known to add an antioxidant to the silicone binder of the adhesive tape (Patent Document 1).
また、付加反応硬化型の粘着剤用シリコーン組成物にフェノール系酸化防止剤を配合することによって、銅などの金属上に粘着テープの形態で施与して１５０〜２５０℃に加熱した後であっても、糊残り無く剥離可能である粘着剤用シリコーン組成物が知られている（特許文献２）。 In addition, by adding a phenolic antioxidant to the addition reaction curable adhesive silicone composition, it was applied in the form of an adhesive tape on a metal such as copper and heated to 150-250 ° C. However, a silicone composition for pressure-sensitive adhesives that can be peeled without any adhesive residue is known (Patent Document 2).
しかしながら上記の各シリコーン粘着剤を２５０℃以上の高温に曝すと、酸化防止剤が劣化して糊残り防止効果が得られなくなる。また、被着体が銅や銅合金、鉄などの金属である場合、金属表面が酸化されて、シリコーン粘着剤とより強固に結合して、糊残りが発生することがある。 However, if each of the above silicone pressure-sensitive adhesives is exposed to a high temperature of 250 ° C. or higher, the antioxidant is deteriorated and the effect of preventing adhesive residue cannot be obtained. In addition, when the adherend is a metal such as copper, copper alloy, or iron, the metal surface may be oxidized and more strongly bonded to the silicone pressure-sensitive adhesive, resulting in adhesive residue.
本発明は、上記事情に鑑みなされたもので、例えば金属等の被着体上に貼りつけて２５０℃以上の高温に曝された場合でも、糊残りを起こさず、きれいに剥離することが可能な粘着テープ及び該テープを与える粘着剤用シリコーン組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances. For example, even when it is attached onto an adherend such as metal and exposed to a high temperature of 250 ° C. or higher, it can be peeled cleanly without causing adhesive residue. An object of the present invention is to provide an adhesive tape and a silicone composition for an adhesive that gives the tape.
即ち、本発明は、（Ａ）１分子中に少なくとも２個のアルケニル基を有し、アルケニル基含有量が0.0015〜0.06モル／100ｇである、ポリオルガノシロキサンを２０〜９５質量部、
（Ｂ）Ｒ1 3ＳｉＯ0.5単位およびＳｉＯ2単位を含有し、ＳｉＯ2単位モル数に対するＲ1 3ＳｉＯ0.5単位モル数の比が０．６〜１．７であるポリオルガノシロキサン（Ｒ1は互いに異なっていてよい、脂肪族の不飽和結合を含まない、炭素数１〜１０の１価炭化水素基）を８０〜５質量部（但し、（Ａ）成分と（Ｂ）成分の合計は１００質量部である）、
（Ｃ）ＳｉＨ基を含むシロキサン単位とＳｉＨ基を含まないシロキサン単位のモル比が５／５〜９／１であり、１分子中にＳｉＨ基を３個以上含有するポリオルガノシロキサンを、（Ａ）成分中のアルケニル基モル数に対する（Ｃ）成分中のＳｉＨ基モル数の比が３〜１５となる量
を含む粘着剤用シリコーン組成物であって、
(1)該組成物を、硬化後の厚みが２８〜３２μmになるように２５ｍｍ巾のポリイミドテープ上に塗布した後110℃〜140℃で１〜３分加熱して粘着テープを調製し、
(2)該粘着テープの粘着面側をステンレス鋼表面に圧着した後、室温で１８〜２２時間放置後に、２５℃において引張り試験機を用いて、３００ｍｍ／分の引張り速度で測定した
該テープの１８０度剥離が０．０５〜４Ｎ／２５ｍｍであることを特徴とする粘着剤用シリコーン組成物である。
上記本発明の好ましい態様は以下のとおりである。
さらに（Ｄ）制御剤を（Ａ）と（Ｂ）の合計１００質量部に対して０〜８．０質量部、及び、（Ｅ）白金触媒を（Ａ）と（Ｂ）の合計１００質量部に対して、白金分として１〜５０００ｐｐｍを含むことを特徴とする上記粘着剤用シリコーン組成物。
ポリオルガノシロキサン（Ａ）のアルケニル基含有量が0.002〜0.04モル／100ｇである、上記粘着剤用シリコーン組成物。
ポリオルガノシロキサン（Ｃ）が、（Ａ）成分中のアルケニル基モル数に対する（Ｃ）成分中のＳｉＨ基モル数の比が３〜１５となる量で含まれる、上記粘着剤用シリコーン組成物。
ポリオルガノシロキサン（Ｃ）が、下記式で表されるポリオルガノシロキサンからなる群より選ばれる少なくとも１種を含むことを特徴とする上記粘着剤用シリコーン組成物。
（Ｆ）ヒンダードアミン化合物を（Ａ）と（Ｂ）の合計１００質量部に対して０．０１〜１質量部、および／または、（Ｇ）フェノール系酸化防止剤を（Ａ）と（Ｂ）の合計１００質量部に対して０．１〜１０質量部をさらに含むことを特徴とする上記粘着剤用シリコーン組成物。
また、本発明は、基材テープと、該基材テープ上に施与された粘着層からなる粘着テープにおいて、該粘着層が、上記粘着剤用シリコーン組成物のいずれかを含むことを特徴とする粘着テープである。
That is, the present invention provides (A) 20 to 95 parts by mass of a polyorganosiloxane having at least two alkenyl groups in one molecule and having an alkenyl group content of 0.0015 to 0.06 mol / 100 g.
(B) a polyorganosiloxane containing R 1 3 SiO 0.5 units and SiO 2 units, wherein the ratio of the number of moles of R 1 3 SiO 0.5 units to the number of moles of SiO 2 units is 0.6 to 1.7 (R 1 is 80 to 5 parts by mass of a monovalent hydrocarbon group having 1 to 10 carbon atoms which does not contain an aliphatic unsaturated bond and may be different from each other (provided that the total of component (A) and component (B) is 100 Parts by mass)
(C) A polyorganosiloxane having a molar ratio of a siloxane unit containing a SiH group to a siloxane unit containing no SiH group of 5/5 to 9/1 and containing 3 or more SiH groups in one molecule is (A A silicone composition for pressure-sensitive adhesives containing an amount such that the ratio of the number of moles of SiH groups in component (C) to the number of moles of alkenyl groups in component) is 3-15 ,
(1) The composition was coated on a 25 mm wide polyimide tape so that the thickness after curing was 28 to 32 μm, and then heated at 110 ° C. to 140 ° C. for 1 to 3 minutes to prepare an adhesive tape,
(2) After pressure-bonding the pressure-sensitive adhesive side of the pressure-sensitive adhesive tape to the stainless steel surface, the tape was measured for 18 to 22 hours at room temperature and then measured at a tensile rate of 300 mm / min using a tensile tester at 25 ° C. 180 degree peeling is 0.05-4N / 25mm, It is a silicone composition for adhesives characterized by the above-mentioned.
The preferred embodiments of the present invention are as follows.
Furthermore, (D) the control agent is 0 to 8.0 parts by mass with respect to 100 parts by mass in total of (A) and (B), and (E) the platinum catalyst is 100 parts by mass in total of (A) and (B). The above-mentioned silicone composition for pressure-sensitive adhesives, which contains 1 to 5000 ppm as platinum content.
The said silicone composition for adhesives whose alkenyl group content of a polyorganosiloxane (A) is 0.002-0.04 mol / 100g.
The silicone composition for pressure-sensitive adhesives, wherein the polyorganosiloxane (C) is contained in an amount such that the ratio of the number of moles of SiH groups in the component (C) to the number of moles of alkenyl groups in the component (A) is 3 to 15.
The above-mentioned silicone composition for pressure-sensitive adhesives, wherein the polyorganosiloxane (C) contains at least one selected from the group consisting of polyorganosiloxanes represented by the following formula.
(F) 0.01-1 part by mass of the hindered amine compound with respect to a total of 100 parts by mass of (A) and (B), and / or (G) the phenolic antioxidant of (A) and (B) The said silicone composition for adhesives characterized by further containing 0.1-10 mass parts with respect to a total of 100 mass parts.
Further, the present invention is a pressure-sensitive adhesive tape comprising a base tape and a pressure-sensitive adhesive layer applied on the base tape, wherein the pressure-sensitive adhesive layer contains any one of the above silicone compositions for pressure-sensitive adhesives. It is an adhesive tape.
上記本発明の粘着剤用シリコーン組成物を使用すれば、２５０℃以上に加熱された後であっても、糊残り無く剥離可能である粘着テープが得られる。該粘着テープは、金属特にプリント基板の回線保護のマスキングテープ用として有用である。また、本発明の粘着剤用シリコーン組成物は、従来のものより粘着力が小さいため、幅広の粘着テープやシートを広い面積の被着体に貼りつけた場合でも剥離が容易なテープを得ることができる。さらに、常温に於いても粘着力が小さいため、窓ガラス、表示装置などに貼る貼り替えが可能な遮光フィルム、反射防止フィルム、保護フィルム、傷つき防止フィルム用などにも適する。 If the silicone composition for pressure-sensitive adhesives of the present invention is used, a pressure-sensitive adhesive tape that can be peeled without adhesive residue even after being heated to 250 ° C. or higher can be obtained. The adhesive tape is useful as a masking tape for line protection of metal, particularly printed circuit boards. Moreover, since the silicone composition for pressure-sensitive adhesives of the present invention has a lower adhesive strength than conventional ones, a tape that can be easily peeled even when a wide pressure-sensitive adhesive tape or sheet is attached to an adherend having a large area is obtained. Can do. Furthermore, since the adhesive strength is small even at room temperature, it is suitable for a light-shielding film, an antireflection film, a protective film, an anti-scratch film, etc. that can be pasted on a window glass or a display device.
本発明のシリコーン組成物は、アルケニル基を有するポリオルガノシロキサンと、Ｒ1 3ＳｉＯ0.5単位およびＳｉＯ2単位を有するポリオルガノシロキサンと、ＳｉＨ基を含有するポリオルガノシロキサンとを含み、下記評価方法（以降、「糊残り性評価方法」と言う場合がある）：
(1)シリコーン組成物を、硬化後の厚みが２８〜３２μmになるように基材テープ上に塗布した後110℃〜140℃で１〜３分加熱して粘着テープを調製し、
(2)該粘着テープの粘着面側をステンレス鋼表面に圧着した後、最高温度２５０℃〜３００℃で、少なくとも10分間加熱し、次いで、
(3)室温まで冷却した後、該テープを手動によりステンレス鋼から剥がして、ステンレス鋼表面を目視観察する、
において、ステンレス鋼表面上にシリコーン組成物由来の残存物が何も観察されないことを特徴とする。該評価法は、実際の半導体部品製造工程、特にリフロー工程、を反映する。ステップ(1)において、市販の基材テープ、例えばポリイミド、ポリテトラフルオロエチレン、ポリフェニレンスルフィド、ポリアミド、ポリカーボネート等ポリマーテープ、アルミニウム箔、銅箔などの金属箔テープ、和紙、合成紙、ポリエチレンラミネート紙などの紙テープ、布、ガラス繊維製のテープを使用することができ、糊残りの有無は外基材テープの種類には依存しない。ステップ(2)において、工程における特性要求に応じて、最高温度及び最高温度の維持時間を適宜調整すれば、顧客ニーズに応える組成物を製造するための評価基準となる。また、ステンレス鋼以外の金属、例えば、銅、アルミニウム、金メッキ付き銅、及び銅合金等、のいずれかを使用することができる。ステップ(3)の観察は、機器分析法によることも可能であるが、発明者らが検討したところ、目視観察で残渣が認められなければ、部品の後処理において何ら問題を生じなかった。
The silicone composition of the present invention includes a polyorganosiloxane having an alkenyl group, a polyorganosiloxane having an R 1 3 SiO 0.5 unit and an SiO 2 unit, and a polyorganosiloxane containing an SiH group, and the following evaluation method ( Hereinafter, it may be referred to as “adhesive residue evaluation method”):
(1) The silicone composition was applied on a base tape so that the thickness after curing was 28 to 32 μm, and then heated at 110 ° C. to 140 ° C. for 1 to 3 minutes to prepare an adhesive tape,
(2) After pressure-bonding the adhesive side of the adhesive tape to the stainless steel surface, heating at a maximum temperature of 250 ° C. to 300 ° C. for at least 10 minutes,
(3) After cooling to room temperature, the tape is manually peeled from the stainless steel, and the stainless steel surface is visually observed.
In the above, no residue derived from the silicone composition is observed on the stainless steel surface. The evaluation method reflects an actual semiconductor component manufacturing process, particularly a reflow process. In step (1), commercially available base tape, for example, polymer tape such as polyimide, polytetrafluoroethylene, polyphenylene sulfide, polyamide, polycarbonate, metal foil tape such as aluminum foil, copper foil, Japanese paper, synthetic paper, polyethylene laminated paper, etc. Paper tape, cloth, and glass fiber tape can be used, and the presence or absence of adhesive residue does not depend on the type of outer base tape. In step (2), if the maximum temperature and the maintenance time of the maximum temperature are appropriately adjusted according to the characteristic requirements in the process, it becomes an evaluation standard for producing a composition that meets customer needs. Moreover, any metal other than stainless steel, for example, copper, aluminum, copper with gold plating, copper alloy, or the like can be used. The observation in step (3) can be performed by an instrumental analysis method. However, as a result of examination by the inventors, if no residue was observed by visual observation, no problem was caused in the post-processing of the part.
好ましくは、本発明のシリコーン組成物は、上記ステップ(1)において基材テープとして２５ｍｍ巾のポリイミドテープを使用して調製された粘着テープを、室温で１８〜２２時間放置後に、２５℃において、引張り試験機を用いて、３００ｍｍ／分の引張り速度で測定した該テープの１８０度剥離が、０．０５〜４Ｎ／２５ｍｍ、より好ましくは０．０５〜３Ｎ／２５ｍｍである。本剥離強度は、室温での粘着性の指標となり、後述の実施例で示すように、剥離強度が前記下限値未満であると、被着体に粘着せず、前記上限値を超えると、糊残りを生じる。但し、１８０度剥離は、基材の弾性に依存するので、テープの用途に応じて、適宜選定することが好ましい。 Preferably, in the silicone composition of the present invention, the pressure-sensitive adhesive tape prepared using a 25 mm-wide polyimide tape as the base tape in the above step (1) is left at room temperature for 18 to 22 hours, and then at 25 ° C. The 180 degree peeling of the tape measured with a tensile tester at a pulling speed of 300 mm / min is 0.05 to 4 N / 25 mm, more preferably 0.05 to 3 N / 25 mm. The peel strength is an index of adhesiveness at room temperature, and as shown in the examples described later, when the peel strength is less than the lower limit value, the adherence to the adherend is not achieved. Produce the rest. However, since 180 degree peeling depends on the elasticity of the substrate, it is preferable to select appropriately according to the application of the tape.
上記糊残り性及び粘着性を満たすシリコーン組成物は、下記成分（Ａ）〜（Ｃ）：
（Ａ）１分子中に少なくとも２個のアルケニル基を有し、アルケニル基含有量が0.0015〜0.06モル／100ｇである、ポリオルガノシロキサンを２０〜９５質量部、
（Ｂ）Ｒ1 3ＳｉＯ0.5単位およびＳｉＯ2単位を含有し、ＳｉＯ2単位モル数に対するＲ1 3ＳｉＯ0.5単位モル数の比、即ち、Ｒ1 3ＳｉＯ0.5単位モル数／ＳｉＯ2単位モル数、が０．６〜１．７であるポリオルガノシロキサン（但しＲ1は互いに異なっていてよい、脂肪族の不飽和結合を含まない、炭素数１〜１０の１価炭化水素基）を８０〜５質量部（但し、（Ａ）成分と（Ｂ）成分の合計は１００質量部である）、
（Ｃ）ＳｉＨ基を含むシロキサン単位とＳｉＨ基を含まないシロキサン単位のモル比が５／５〜９／１であり、１分子中にＳｉＨ基を３個以上含有するポリオルガノシロキサンを、（Ａ）成分中のアルケニル基モル数に対する（Ｃ）成分中のＳｉＨ基モル数の比、即ち、（Ｃ）成分中のＳｉＨ基モル数／（Ａ）成分中のアルケニル基モル数、が３〜１５となる量を含む粘着剤用シリコーン組成物である。
さらには、
（Ｄ）制御剤を（Ａ）と（Ｂ）の合計１００質量部に対して０〜８．０質量部、及び、
（Ｅ）白金触媒を（Ａ）と（Ｂ）の合計１００質量部に対して、白金分として１〜５０００ｐｐｍを含む粘着剤用シリコーン組成物である。
以下、各成分について説明する。
The silicone composition satisfying the above adhesive residue and adhesiveness includes the following components (A) to (C):
(A) 20 to 95 parts by mass of a polyorganosiloxane having at least two alkenyl groups in one molecule and having an alkenyl group content of 0.0015 to 0.06 mol / 100 g,
(B) containing R 1 3 SiO 0.5 units and SiO 2 units, R 1 3 SiO 0.5 units moles relative to the number of SiO 2 units moles, i.e., R 1 3 SiO 0.5 units moles / SiO 2 units moles , Is 0.6 to 1.7 (provided that R 1 may be different from each other and does not contain an aliphatic unsaturated bond, and is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 5 parts by mass (however, the sum of component (A) and component (B) is 100 parts by mass)
(C) A polyorganosiloxane having a molar ratio of a siloxane unit containing a SiH group to a siloxane unit containing no SiH group of 5/5 to 9/1 and containing 3 or more SiH groups in one molecule is (A ) The ratio of the number of moles of SiH groups in component (C) to the number of moles of alkenyl groups in component, that is, the number of moles of SiH groups in component (C) / the number of moles of alkenyl groups in component (A) is 3-15. It is the silicone composition for adhesives containing the quantity used as.
Moreover,
(D) 0 to 8.0 parts by mass of the control agent with respect to 100 parts by mass in total of (A) and (B), and
(E) It is a silicone composition for pressure-sensitive adhesives containing 1 to 5000 ppm as a platinum content with respect to a total of 100 parts by mass of (A) and (B).
Hereinafter, each component will be described.
アルケニル基含有ポリオルガノシロキサン（Ａ）は、（Ｃ）成分中のＳｉＨ基と付加反応をして、ポリマー網目構造を形成する。ポリオルガノシロキサン（Ａ）中のアルケニル基の量は、１分子中に少なくとも２個であり、且つ、ポリオルガノシロキサン（Ａ）１００ｇ中のモル数が、0.0015〜0.06モル、好ましくは、0.002〜0.05、より好ましくは0.002〜0.04である。アルケニル基が１分子中に２つ未満であると、ポリシロキサンの網目構造が形成されない。また、ポリオルガノシロキサン（Ａ）中でのアルケニル基の量が前記下限値未満では、糊残りを生じ易くなり、前記上限値を超えると粘着性が不充分となる。 The alkenyl group-containing polyorganosiloxane (A) undergoes an addition reaction with the SiH group in the component (C) to form a polymer network structure. The amount of alkenyl groups in the polyorganosiloxane (A) is at least 2 per molecule, and the number of moles in 100 g of the polyorganosiloxane (A) is 0.0015 to 0.06 mol, preferably 0.002 to 0.05. More preferably, it is 0.002 to 0.04. When the number of alkenyl groups is less than 2 in one molecule, a polysiloxane network structure is not formed. Further, when the amount of alkenyl groups in the polyorganosiloxane (A) is less than the lower limit, adhesive residue tends to occur, and when the amount exceeds the upper limit, the tackiness becomes insufficient.
ポリオルガノシロキサン（Ａ）は、下記式で示されるもののいずれか又はこれらの混合物であることが好ましい。
R1 (3-a)XaSiO-(R1XSiO)m-(R1 2SiO)n-SiR1 (3-a)Xa
R1 2(HO)SiO-(R1XSiO)m+2-(R1 2SiO)n-SiR1 2(OH)
（式中、Ｒ1は互いに異なっていてよい、脂肪族の不飽和結合を含まない１価炭化水素基であり、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。）
The polyorganosiloxane (A) is preferably any one represented by the following formula or a mixture thereof.
R 1 (3-a) X a SiO- (R 1 XSiO) m- (R 1 2 SiO) n -SiR 1 (3-a) X a
R 1 2 (HO) SiO- (R 1 XSiO) m + 2- (R 1 2 SiO) n -SiR 1 2 (OH)
Wherein R 1 is a monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond and may be different from each other, 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. )
上式において、Ｒ1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、なかでもメチル基及びフェニル基が好ましい。 In the above formula, R 1 is preferably one having 1 to 10 carbon atoms. 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 An aryl group such as a group, among which a methyl group and a phenyl group are 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、及びビニルオキシプロピル基などが例示され、なかでも、工業的にはビニル基が好ましい。 As the alkenyl group-containing organic group of X, those having 2 to 10 carbon atoms are preferable, vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclohexenylethyl group, and A vinyloxypropyl group is exemplified, and among them, a vinyl group is preferred industrially.
ポリオルガノシロキサン（Ａ）の性状はオイル状もしくは生ゴム状であってよい。ポリオルガノシロキサン（Ａ）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。粘度が前記下限値未満では、均一な塗工が困難となり、又、硬化性が高くなり過ぎて、架橋密度が上がるため粘着力が発現しない場合がある。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。粘度が該値を越えると、組成物の撹拌が困難になる。なお、（Ａ）成分は、２種以上のポリオルガノシロキサンの混合物であってもよい。 The property of the polyorganosiloxane (A) may be oily or raw rubbery. The viscosity of the polyorganosiloxane (A) is preferably 1000 mPa · s or more, particularly 10,000 mPa · s or more if it is oily at 25 ° C. If the viscosity is less than the lower limit, uniform coating becomes difficult, and the curability becomes too high, and the crosslink density increases, so that the adhesive force may not be exhibited. Moreover, if it is a raw rubber-like thing, the viscosity when it melt | dissolves with toluene so that it may become a density | concentration of 30% is preferable below 100,000 mPa * s. When the viscosity exceeds this value, stirring of the composition becomes difficult. The component (A) may be a mixture of two or more polyorganosiloxanes.
（Ｂ）成分は、Ｒ1 3ＳｉＯ0.5単位（Ｒ １ 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、好ましくは０．７〜１．０であるポリオルガノシロキサンである。Ｒ1 3ＳｉＯ0.5単位／ＳｉＯ2単位のモル比が前記範囲外であると、粘着力、タック、又は保持力が低下することがある。 The component (B) contains R 1 3 SiO 0.5 units ( R 1 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, preferably It is a polyorganosiloxane that is 0.7 to 1.0. When the molar ratio of R 1 3 SiO 0.5 unit / SiO 2 unit is out of the above range, the adhesive force, tack or holding force may be lowered.
ポリオルガノシロキサン（Ｂ）は、ＯＨ基を含有していてもよく、ＯＨ基含有量は４．０質量％以下のものが好ましい。ＯＨ基が４．０質量％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単位及び／又はＲ1 2ＳｉＯ単位を含有してもよい。（Ｂ）成分は、２種以上のオルガノシロキサンの混合物であってもよい。また、（Ｂ）成分同士で縮合した形態で配合されてもよい。 The polyorganosiloxane (B) may contain an OH group, and the OH group content is preferably 4.0% by mass or less. The case where the OH group exceeds 4.0% by mass is not preferable because the curability of the pressure-sensitive adhesive is lowered. Further, within a range not to impair the characteristics of the present invention may contain R 1 SiO 1.5 units and / or R 1 2 SiO units. Component (B) may be a mixture of two or more organosiloxanes. Moreover, you may mix | blend with the form condensed with (B) components.
（Ａ）成分と（Ｂ）成分は、夫々、独立に組成物に配合してもよいし、（Ａ）成分と（Ｂ）成分の縮合物として配合してもよい。例えば、（Ａ）成分が次式のポリオルガノポリシロキサンを含有する場合、
R1 2(HO)SiO-(R1XSiO)m+2-(R1 2SiO)n-SiR1 2(OH)
（Ｒ1、ｍ、ｎは上記ポリオルガノシロキサン（Ａ）について上記したのと同様である。）
（Ｂ）成分と縮合反応する。縮合反応を行うには、トルエンなどの溶剤に溶解した（Ａ）成分と（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 component (A) and the component (B) may be blended independently in the composition, or may be blended as a condensate of the component (A) and the component (B). For example, when the component (A) contains a polyorganopolysiloxane of the following formula:
R 1 2 (HO) SiO- (R 1 XSiO) m + 2- (R 1 2 SiO) n -SiR 1 2 (OH)
(R 1 , m, and n are the same as described above for the polyorganosiloxane (A).)
(B) Condensation reaction with component. In order to perform the condensation reaction, a mixture of the component (A) and the component (B) dissolved in a solvent such as toluene may be reacted at room temperature to reflux using an alkaline catalyst.
上記縮合反応する場合の、（Ａ）成分／（Ｂ）成分の混合重量比は、２０／８０〜９５／５、好ましくは３０／７０〜７０／３０である。（Ａ）成分のポリジオルガノシロキサンの配合比が前記範囲外であると、組成物の粘着力が不充分となる。 In the case of the condensation reaction, (A) component / (B) weight ratio of the components is 20 / 80-95 / 5, preferably 30 / 70-70 / 30. When the blending ratio of the polydiorganosiloxane as the component (A) is out of the above range, the adhesive strength of the composition becomes insufficient.
（Ｃ）成分は、上述したように、ポリオルガノシロキサン（Ａ）と反応して架橋構造を形成する。（Ｃ）成分は、１分子中にＳｉＨ基を少なくとも３個以上有するポリオルガノシロキサンであり、直鎖状、分岐状、環状のいずれであってもよい。 As described above, the component (C) reacts with the polyorganosiloxane (A) to form a crosslinked structure. Component (C) is a polyorganosiloxane having at least 3 SiH groups in one molecule, and may be any of linear, branched, and cyclic.
好ましくは、ポリオルガノシロキサン（Ｃ）は、ＳｉＨ基を含むシロキサン単位と、ＳｉＨ基を含まないシロキサン単位とを含む。好ましくは、（ＳｉＨ基を含むシロキサン単位／ＳｉＨ基を含まないシロキサン単位）のモル比が、５／５〜９／１、より好ましくは６／４〜８／２である。 Preferably, the polyorganosiloxane (C) includes a siloxane unit containing a SiH group and a siloxane unit not containing a SiH group. The molar ratio of (siloxane unit containing SiH group / siloxane unit not containing SiH group) is preferably 5/5 to 9/1, more preferably 6/4 to 8/2.
ＳｉＨ基を含むシロキサン単位と、ＳｉＨ基を含まないシロキサン単位とを含むポリオルガノシロキサン（Ｃ）の好ましいものとして、下記式で表されるポリオルガノシロキサン（Ｃ）のいずれか、又は、混合物を例示することができる。
上記ポリオルガノシロキサンは、ｙ又はｔが１以上の整数であり、ＳｉＨ基を含むシロキサン単位に加えて、ＳｉＨ基を含まないシロキサン単位を含む。これらの単位は、ブロックとして含まれていても、ランダムに含まれていてもよい。ポリオルガノシロキサン（Ｃ）が、ＳｉＨ基を含有するシロキサン単位のみで構成されていると、２５０℃を超える高温の熱履歴を与えた場合、糊残り評価において、非常に軽度な「糊残り」とも言い得る「粘着剤の痕跡」が認められる場合がある。
As a preferable example of the polyorganosiloxane (C) containing a siloxane unit containing an SiH group and a siloxane unit containing no SiH group, any one or a mixture of the polyorganosiloxane (C) represented by the following formula is exemplified. can do.
In the polyorganosiloxane, y or t is an integer of 1 or more, and includes a siloxane unit not containing a SiH group in addition to a siloxane unit containing a SiH group. These units may be included as blocks or randomly. When the polyorganosiloxane (C) is composed of only siloxane units containing SiH groups, when a high temperature thermal history exceeding 250 ° C. is given, in the adhesive residue evaluation, even a very mild “adhesive residue” There may be a “trace of adhesive” that can be said.
このオルガノポリシロキサン（Ｃ）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。 The organopolysiloxane (C) has a viscosity at 25 ° C. of preferably 1 to 5,000 mPa · s, more preferably 5 to 500 mPa · s.
（Ｃ）成分の使用量は（Ａ）成分中のアルケニル基モル数に対する（Ｃ）成分中のＳｉＨ基のモル数比、即ち、（Ｃ）成分中のＳｉＨ基のモル数／（Ａ）成分中のアルケニル基モル数、が０．１〜２０、好ましくは１〜１５、より好ましくは３〜１５の範囲である。（Ｃ）成分が前記下限値未満の量では架橋が不十分となり、これに伴い、粘着力の上昇、保持力の低下、又は糊残りの増加を来す場合がある。一方、前記上限値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、前記上限値を超えると、組成物の使用可能時間が短くなる場合がある。 The amount of component (C) used is the ratio of the number of moles of SiH groups in component (C) to the number of moles of alkenyl groups in component (A), that is, the number of moles of SiH groups in component (C) / component (A). The number of moles of the alkenyl group in the range is from 0.1 to 20, preferably from 1 to 15, and more preferably from 3 to 15. If the amount of the component (C) is less than the lower limit, crosslinking is insufficient, and this may lead to an increase in adhesive strength, a decrease in holding power, or an increase in adhesive residue. On the other hand, when the upper limit is exceeded, the crosslink density increases and sufficient adhesive strength and tack may not be obtained. Moreover, when the said upper limit is exceeded, the usable time of a composition may become short.
（Ｄ）成分は制御剤であり、粘着剤用シリコーン組成物が、加熱硬化の前に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。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。好ましくは、１−エチニルシクロヘキサノール、１，１，ジメチル−１―トリメチルシロキシ−エチンなどが使用される。 The component (D) is a control agent, and is added so that the silicone composition for pressure-sensitive adhesives does not thicken or gelate before heat curing. 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- Examples include 1,3-divinyldisiloxane. Preferably, 1-ethynylcyclohexanol, 1,1, dimethyl-1-trimethylsiloxy-ethyne and the like are used.
（Ｄ）成分の配合量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して０〜８．０質量部の範囲であればよく、特に０．０５〜２．０質量部が好ましい。前記上限値を超えて添加すると、硬化性が低下することがある。 (D) The compounding quantity of a component should just be the range of 0-8.0 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and 0.05-2.0 mass parts especially. Is preferred. If the content exceeds the upper limit, curability may be lowered.
（Ｅ）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、なかでも、塩化白金酸とビニル基含有シロキサンとの反応物が好ましく、商品名ＣＡＴ−ＰＬ−50Ｔ（信越化学工業製）で市販されている。 Component (E) 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 of siloxane and the like can be mentioned. Among them, a reaction product of chloroplatinic acid and a vinyl group-containing siloxane is preferable, and is commercially available under the trade name CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.).
（Ｅ）成分の添加量は（Ａ）成分と（Ｂ）成分の合計１００質量部に対し、白金分として１〜５，０００ｐｐｍ、特に５〜２，０００ｐｐｍとすることが好ましい。添加量が前記下限値未満では硬化性が低下して架橋密度が不十分となり、粘着力の上昇、保持力の低下、糊残りの増加を来すことがある。一方、前記上限値を超えると、組成物の使用可能時間が短くなる場合があり、また触媒は高価であるので、経済的にも不利である。 The amount of component (E) added is preferably 1 to 5,000 ppm, particularly preferably 5 to 2,000 ppm as platinum content, with respect to a total of 100 parts by mass of component (A) and component (B). When the addition amount is less than the lower limit, the curability is lowered and the crosslinking density becomes insufficient, which may cause an increase in adhesive strength, a decrease in holding power, and an increase in adhesive residue. On the other hand, if the upper limit is exceeded, the usable time of the composition may be shortened, and the catalyst is expensive, which is economically disadvantageous.
本発明の粘着剤用シリコーン組成物に、更に耐熱性を改善する目的で（Ｆ）ヒンダードアミン化合物を添加しても良い。（Ｆ）ヒンダードアミン化合物は分子中に下式の構造を有するものが好ましい。 A hindered amine compound (F) may be added to the silicone composition for pressure-sensitive adhesives of the present invention for the purpose of further improving heat resistance. (F) The hindered amine compound preferably has a structure of the following formula in the molecule.
上記構造を含むヒンダードアミン化合物の例を以下に示す。
（Ｆ）成分の配合量は、成分（Ａ）と（Ｂ）の合計１００質量部に対して０．０１〜１質量部、好ましくは０．０５〜０．５質量部である。配合量が前記下限値未満では糊残り性改良の効果が小さく、前記上限値を越えると粘着性が損なわれることがある。（Ｆ）成分として、２種以上のアミン化合物を併用してもよい。 (F) The compounding quantity of a component is 0.01-1 mass part with respect to a total of 100 mass parts of a component (A) and (B), Preferably it is 0.05-0.5 mass part. If the blending amount is less than the lower limit, the effect of improving the adhesive residue is small, and if it exceeds the upper limit, the tackiness may be impaired. As the component (F), two or more amine compounds may be used in combination.
上記ヒンダードアミン化合物（Ｆ）に代えて、又は、加えて、更に耐熱性を改善する目的で（Ｇ）成分のフェノール系酸化防止剤を添加してもよい。フェノール系酸化防止剤（Ｇ）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。 Instead of or in addition to the hindered amine compound (F), a phenol-based antioxidant as the component (G) may be added for the purpose of further improving the heat resistance. As the phenolic antioxidant (G), those having a structure of the following formula in the molecule are particularly preferable.
上記構造を有するフェノール系酸化防止剤の例を以下に示す。
（Ｇ）成分の添加量は成分（Ａ）と（Ｂ）の合計１００質量部に対して０．１〜１０質量部、好ましくは０．５〜５質量部である。配合量が、前記下限値未満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、前記上限値超では、粘着特性を阻害することがある。 (G) The addition amount of a component is 0.1-10 mass parts with respect to a total of 100 mass parts of a component (A) and (B), Preferably it is 0.5-5 mass parts. If the blending amount is less than the lower limit value, the adhesive residue preventing effect when receiving a high temperature history is not sufficiently exhibited, and if it exceeds the upper limit value, the adhesive properties may be impaired.
本発明の粘着剤用シリコーン組成物には、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、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、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-mentioned components, optional components can be added to the silicone composition for pressure-sensitive adhesives of the present invention. For example, non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane, antioxidants such as phenols, quinones, and thioethers, light stabilizers such as triazoles and benzophenones, and phosphate esters -Based, halogen-based, antimony-based flame retardants, cationic surfactants, anionic surfactants, non-ionic surfactants and other antistatic agents, and solvents such as toluene and xylene as solvents for reducing viscosity during coating Aliphatic solvents, aliphatic solvents such as hexane, octane, isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and isobutyl acetate, ether solvents such as diisopropyl ether and 1,4-dioxane Solvent or mixed solvent or dye , Such as a pigment is used.
上記のように配合された粘着剤用シリコーン組成物は、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とすることができる。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 composition for pressure-sensitive adhesives blended as described above can be formed into a pressure-sensitive adhesive layer by coating on various substrates and curing them under predetermined conditions. As a base material, plastic films such as polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, polyvinyl chloride, metal foil such as aluminum foil, copper 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.
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、プラズマ処理された基材を用いてもよい。 In order to improve the adhesion between the base material and the adhesive layer, a primer-treated, corona-treated, etching-treated, or plasma-treated substrate 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。また、塗工量は用途に応じて設定されるが、典型的には、硬化したあとの粘着剤層の厚みとして２〜２００μｍ、マスキングテープ用途には、５〜５０μｍである。 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. Moreover, although the coating amount is set according to the use, it is typically 2 to 200 μm as the thickness of the pressure-sensitive adhesive layer after being cured, and 5 to 50 μm for the masking tape use.
塗布された組成物の硬化条件は塗工量等に応じて適宜調整されるが、典型的には８０〜１３０℃で３０秒〜３分である。 The curing conditions of the applied composition are adjusted as appropriate according to the coating amount and the like, but typically 80 to 130 ° C. for 30 seconds to 3 minutes.
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、剥離コーティングが施された剥離性フィルムや剥離紙に塗工して硬化を行った後、基材を貼り合わせて粘着層を転写することによって粘着テープを製造してもよい。 As described above, it may be applied directly to the base material to produce an adhesive tape, or it is applied to a release film or release paper with a release coating and cured, and then the base material is bonded. Then, the adhesive tape may be manufactured by transferring the adhesive layer.
本発明の粘着剤用シリコーン組成物を用いて製造した粘着テープの被着体は特に限定されない。例えば、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、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た複合材上に粘着させることができる。
［実施例］
The adherend of the adhesive tape manufactured using the silicone composition for adhesives of this invention is not specifically limited. For example, metals such as stainless steel, copper, iron, etc., metals whose surfaces are plated or rust-proofed, glass, ceramics, ceramics, polytetrafluoroethylene, polyimide, epoxy, novolac resins, etc. A plurality of them can be adhered onto a composite material.
[Example]
以下、実施例と比較例を示して本発明をより詳細に説明するが、本発明は下記の実施例に制限されるものではない。以下において、部数は質量部数であり、Ｍｅはメチル基、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 in detail, this invention is not restrict | limited to the following Example. Below, a part is a mass part, Me represents a methyl group, Vi represents a vinyl group.
各例で調製した組成物を、下記の糊残り性評価法及び粘着力評価法に従い評価した。
糊残り性
粘着剤用シリコーン組成物溶液を、厚み２５μｍ、幅２５ｍｍのポリイミドフィルムに硬化後の厚みが３０μｍとなるようにアプリケータを用いて塗工した後、１３０℃、１分の条件で加熱して硬化させ、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、該テープ基材上で１往復させることにより該テープを圧着した後、金属板を２８０℃の恒温槽中で放置した。表１に示す所定時間後に金属板を取り出し、室温まで冷やした後、粘着テープを手で剥がして、金属板の表面に粘着剤由来の物質が残留するかどうかを目視観察した。糊残りなく剥離できたものをＡ、一部糊残りするものをＢ、ほぼ全面が糊残りするものをＣとした。
The composition prepared in each example was evaluated according to the following adhesive residue evaluation method and adhesive strength evaluation method.
The silicone composition solution for adhesive residue adhesive is 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 is 30 μm, and then heated at 130 ° C. for 1 minute. And cured to produce an adhesive tape. This adhesive tape is attached to a metal plate (polished stainless steel plate), and after pressing the tape by reciprocating a roller covered with a rubber layer weighing 2 kg on the tape base material, It was left in a constant temperature bath at 280 ° C. After a predetermined time shown in Table 1, the metal plate was taken out and cooled to room temperature, and then the adhesive tape was peeled off by hand to visually observe whether the substance derived from the adhesive remained on the surface of the metal plate. A piece was peeled off without any adhesive residue, A was left partially glued, and C was left almost entirely.
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、同様の方法によりステンレス板に圧着した。室温で約２０時間放置した後、２５℃において、引っ張り試験機を用いて３００ｍｍ／分の引張り速度で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 by the same method as the adhesive strength evaluation, and was pressed onto a stainless steel plate by the same method. 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 pulling speed of 300 mm / min was measured at 25 ° C. at 25 ° C. .
３０％トルエン溶液での粘度が２７０００ｍＰａ・ｓであり、アルケニル基含有量が0.007モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン４０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１００部及びトルエン３０部からなる溶液に、下式で表されるＳｉＨ基を１分子中に３つ以上有するポリオルガノシロキサン（Ｃ）１．２５部と、エチニルシクロヘキサノール０．１部を添加して混合した。
Ｍｅ3ＳｉＯ−［ＭｅＨＳｉＯ］45−［Ｍｅ2ＳｉＯ］17−ＳｉＭｅ3
上記の混合物（シロキサン分６０％）１００部にトルエン５０部と、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％の粘着剤用シリコーン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、粘着力測定した結果を表１に示す。
The viscosity in a 30% toluene solution is 27000 mPa · s, the alkenyl group content is 0.007 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 40 parts of vinyl group-containing polydimethylsiloxane, Me 3 SiO to a solution of 60% toluene solution of 100 parts and 30 parts of toluene polysiloxane consisting of 0.5 units and SiO 2 units (Me 3 SiO 0.5 units / SiO 2 unit = 0.80), an SiH group represented by the following formula 1.25 parts of polyorganosiloxane (C) having 3 or more per molecule and 0.1 part of ethynylcyclohexanol were added and mixed.
Me 3 SiO— [MeHSiO] 45 — [Me 2 SiO] 17 —SiMe 3
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 part of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. An agent silicone composition solution was prepared. Table 1 shows the results of measurement of adhesive residue and adhesive strength of this silicone adhesive.
３０％トルエン溶液での粘度が２１５００ｍＰａ・ｓであり、アルケニル基含有量が0.02モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン４０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１００部、及びトルエン（３０部）からなる溶液に、実施例１で使用したポリオルガノシロキサン（Ｃ）３．６７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。
上記の混合物（シロキサン分６０％）１００部にトルエン５０部と、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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
The viscosity in a 30% toluene solution is 21500 mPa · s, the alkenyl group content is 0.02 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 40 parts of vinyl group-containing polydimethylsiloxane, Me 3 SiO In Example 1, a polysiloxane composed of 0.5 units and SiO 2 units (Me 3 SiO 0.5 units / SiO 2 units = 0.80) in a 60% toluene solution and 100 parts toluene (30 parts) was used. 3.67 parts of polyorganosiloxane (C) and ethynylcyclohexanol (0.1 part) were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 part of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. An agent silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
３０％トルエン溶液での粘度が２４０００ｍＰａ・ｓであり、アルケニル基含有量が0.04モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン４０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１００部、及びトルエン３０部からなる溶液に、実施例１で使用したポリオルガノシロキサン（Ｃ）７．３４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。
上記の混合物（シロキサン分６０％）１００部にトルエン５０部と、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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
The viscosity in a 30% toluene solution is 24000 mPa · s, the alkenyl group content is 0.04 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 40 parts of vinyl group-containing polydimethylsiloxane, Me 3 SiO The polyorgano used in Example 1 was added to 100 parts of a 60% toluene solution of polysiloxane consisting of 0.5 units and SiO 2 units (Me 3 SiO 0.5 units / SiO 2 units = 0.80) and 30 parts of toluene. 7.34 parts of siloxane (C) and 0.1 part of ethynylcyclohexanol were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 part of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. An agent silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
３０％トルエン溶液での粘度が２７０００ｍＰａ・ｓであり、アルケニル基含有量が0.007モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン６０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６７部、及びトルエン３０部からなる溶液に、実施例１で使用したポリオルガノシロキサン（Ｃ）１．８７部と、エチニルシクロヘキサノール０．１部を添加して混合した。
上記の混合物（シロキサン分６０％）１００部にトルエン５０部と、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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
The viscosity in a 30% toluene solution is 27000 mPa · s, the alkenyl group content is 0.007 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 60 parts vinyl group-containing polydimethylsiloxane, Me 3 SiO The polyorgano used in Example 1 in a solution consisting of 67 parts of a 60% toluene solution of polysiloxane consisting of 0.5 units and SiO 2 units (Me 3 SiO 0.5 units / SiO 2 units = 0.80) and 30 parts toluene. 1.87 parts of siloxane (C) and 0.1 part of ethynylcyclohexanol were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 part of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. An agent silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
３０％トルエン溶液での粘度が粘度が２７０００ｍＰａ・ｓであり、アルケニル基含有量が0.002モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン９０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＝０．９０）の６０％トルエン溶液 １６．７部、トルエン３０部からなる溶液に、実施例１で使用したポリオルガノシロキサン（Ｃ）０．８３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。
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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
The viscosity in a 30% toluene solution is 27000 mPa · s, the alkenyl group content is 0.002 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 90 parts of vinyl group-containing polydimethylsiloxane, Me Used in Example 1 for a solution consisting of 16.7 parts of a 60% toluene solution of polysiloxane composed of 3 SiO 0.5 units and SiO 2 units (Me 3 SiO 0.5 units / SiO 2 units = 0.90) and 30 parts of toluene. 0.83 part of the polyorganosiloxane (C) and 0.1 part of ethynylcyclohexanol were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 parts of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. A silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
実施例１の粘着剤用シリコーン組成物溶液に、さらに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部を添加して混合した。
実施例１の粘着剤用シリコーン組成物溶液に、さら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）を添加した粘着剤用シリコーン組成物溶液を調製した。
比較例１
３０％トルエン溶液での粘度が粘度が２００００ｍＰａ・ｓであり、アルケニル基含有量が0.0014モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン４０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１００部、トルエン３０部からなる溶液に、実施例１で使用したポリオルガノシロキサン（Ｃ）０．２８部、エチニルシクロヘキサノール（０．１部）を添加して混合した。
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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
Comparative Example 1
The viscosity in a 30% toluene solution is 20000 mPa · s, the alkenyl group content is 0.0014 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 40 parts of a vinyl group-containing polydimethylsiloxane, Me 3 SiO 0.5 units, a 60% solution 100 parts of a polysiloxane consisting of SiO 2 units (Me 3 SiO 0.5 units / SiO 2 unit = 0.80), a solution consisting of 30 parts of toluene, poly used in example 1 Organosiloxane (C) 0.28 part and ethynylcyclohexanol (0.1 part) were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 parts of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. A silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
参考例１
３０％トルエン溶液での粘度が２３０００ｍＰａ・ｓであり、アルケニル基含有量が0.07モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン４０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１００部、トルエン３０部からなる溶液に、実施例１で使用したポリオルガノシロキサン（Ｃ）１２．５部、エチニルシクロヘキサノール（０．１部）を添加して混合した。
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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
Reference example 1
The viscosity in a 30% toluene solution is 23000 mPa · s, the alkenyl group content is 0.07 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 40 parts of vinyl group-containing polydimethylsiloxane, Me 3 SiO The polyorganosiloxane used in Example 1 in a solution of 100 parts of a 60% toluene solution of polysiloxane (Me 3 SiO 0.5 unit / SiO 2 unit = 0.80) composed of 0.5 units and SiO 2 units and 30 parts of toluene. (C) 12.5 parts and ethynylcyclohexanol (0.1 part) were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 parts of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. A silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
比較例２
３０％トルエン溶液での粘度が２４０００ｍＰａ・ｓであり、アルケニル基含有量が0.007モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン４０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 １００部、トルエン３０部からなる溶液に、次式の架橋剤０．８７部、エチニルシクロヘキサノール０．１部を添加して混合した。
Ｍｅ3ＳｉＯ−［ＭｅＨＳｉＯ］40−ＳｉＭｅ3
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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
Comparative Example 2
The viscosity in a 30% toluene solution is 24000 mPa · s, the alkenyl group content is 0.007 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 40 parts of vinyl group-containing polydimethylsiloxane, Me 3 SiO 0.5 units, a 60% solution 100 parts of a polysiloxane consisting of SiO 2 units (Me 3 SiO 0.5 units / SiO 2 unit = 0.80), a solution consisting of 30 parts of toluene, the following equation of the crosslinking agent 0.87 parts Then, 0.1 part of ethynylcyclohexanol was added and mixed.
Me 3 SiO— [MeHSiO] 40 —SiMe 3
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 parts of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. A silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
比較例３
３０％トルエン溶液での粘度が２７０００ｍＰａ・ｓであり、アルケニル基含有量が0.007モル／100ｇであり、分子鎖末端がＳｉＭｅ2Ｖｉ基で封鎖されたビニル基含有ポリジメチルシロキサン６０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 ６７部、トルエン３０部からなる溶液に、比較例２で使用した架橋剤１．３１部、エチニルシクロヘキサノール０．１部を添加して混合した。
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％の粘着剤用シリコーン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、粘着力を測定した結果を表１に示す。
Comparative Example 3
The viscosity in a 30% toluene solution is 27000 mPa · s, the alkenyl group content is 0.007 mol / 100 g, the molecular chain terminal is blocked with SiMe 2 Vi groups, 60 parts vinyl group-containing polydimethylsiloxane, Me 3 SiO 60% solution 67 parts of 0.5 units, polysiloxane comprising a SiO 2 units (Me 3 SiO 0.5 units / SiO 2 unit = 0.80), a solution consisting of 30 parts of toluene, were used in Comparative example 2 the crosslinking agent 1 .31 parts and 0.1 part of ethynylcyclohexanol were added and mixed.
To 100 parts of the above mixture (siloxane content 60%), 50 parts of toluene and 0.5 parts of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed further, and an adhesive having a siloxane content of about 40%. A silicone composition solution was prepared. Table 1 shows the results of measuring the adhesive residue and adhesive strength of this silicone adhesive.
表１から分かるように、本発明の粘着剤用シリコーン組成物から得られた粘着層は、２８０℃もの高温に１０分以上曝された後であっても、被着体に糊を残すことこなく、きれいに剥離される。従って、本発明の組成物から得られる粘着テープは、２５０℃以上のリフロー工程等において、マスクテープ又は仮止めテープとして非常に有用である。 As can be seen from Table 1, the pressure-sensitive adhesive layer obtained from the silicone composition for pressure-sensitive adhesives of the present invention can leave glue on the adherend even after being exposed to a high temperature of 280 ° C. for 10 minutes or more. There is no peeling. Therefore, the pressure-sensitive adhesive tape obtained from the composition of the present invention is very useful as a mask tape or a temporary fixing tape in a reflow process at 250 ° C. or higher.
Claims (6)
（Ｂ）Ｒ1 3ＳｉＯ0.5単位およびＳｉＯ2単位を含有し、ＳｉＯ2単位モル数に対するＲ1 3ＳｉＯ0.5単位モル数の比が０．６〜１．７であるポリオルガノシロキサン（Ｒ1は互いに異なっていてよい、脂肪族の不飽和結合を含まない、炭素数１〜１０の１価炭化水素基）を８０〜５質量部（但し、（Ａ）成分と（Ｂ）成分の合計は１００質量部である）、
（Ｃ）ＳｉＨ基を含むシロキサン単位とＳｉＨ基を含まないシロキサン単位のモル比が５／５〜９／１であり、１分子中にＳｉＨ基を３個以上含有するポリオルガノシロキサンを、（Ａ）成分中のアルケニル基モル数に対する（Ｃ）成分中のＳｉＨ基モル数の比が３〜１５となる量
を含む粘着剤用シリコーン組成物であって、
(1)該組成物を、硬化後の厚みが２８〜３２μmになるように２５ｍｍ巾のポリイミドテープ上に塗布した後110℃〜140℃で１〜３分加熱して粘着テープを調製し、
(2)該粘着テープの粘着面側をステンレス鋼表面に圧着した後、室温で１８〜２２時間放置後に、２５℃において引張り試験機を用いて、３００ｍｍ／分の引張り速度で測定した
該テープの１８０度剥離が０．０５〜４Ｎ／２５ｍｍであることを特徴とする粘着剤用シリコーン組成物。 (A) 20 to 95 parts by mass of a polyorganosiloxane having at least two alkenyl groups in one molecule and having an alkenyl group content of 0.0015 to 0.06 mol / 100 g,
(B) a polyorganosiloxane containing R 1 3 SiO 0.5 units and SiO 2 units, wherein the ratio of the number of moles of R 1 3 SiO 0.5 units to the number of moles of SiO 2 units is 0.6 to 1.7 (R 1 is 80 to 5 parts by mass of a monovalent hydrocarbon group having 1 to 10 carbon atoms which does not contain an aliphatic unsaturated bond and may be different from each other (provided that the total of component (A) and component (B) is 100 Parts by mass)
(C) A polyorganosiloxane having a molar ratio of a siloxane unit containing a SiH group to a siloxane unit containing no SiH group of 5/5 to 9/1 and containing 3 or more SiH groups in one molecule is (A A silicone composition for pressure-sensitive adhesives containing an amount such that the ratio of the number of moles of SiH groups in component (C) to the number of moles of alkenyl groups in component) is 3-15 ,
(1) The composition was coated on a 25 mm wide polyimide tape so that the thickness after curing was 28 to 32 μm, and then heated at 110 ° C. to 140 ° C. for 1 to 3 minutes to prepare an adhesive tape,
(2) After pressure-bonding the pressure-sensitive adhesive side of the pressure-sensitive adhesive tape to the stainless steel surface, the tape was measured for 18 to 22 hours at room temperature and then measured at a tensile rate of 300 mm / min using a tensile tester at 25 ° C. 180 degree peeling is 0.05-4N / 25mm, The silicone composition for adhesives characterized by the above-mentioned.
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