WO2023195268A1 - Silicone pressure-sensitive adhesive composition, silicone pressure-sensitive adhesive, pressure-sensitive adhesive film, image display device, and method for evaluating silicone pressure-sensitive adhesive - Google Patents
Silicone pressure-sensitive adhesive composition, silicone pressure-sensitive adhesive, pressure-sensitive adhesive film, image display device, and method for evaluating silicone pressure-sensitive adhesive Download PDFInfo
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- WO2023195268A1 WO2023195268A1 PCT/JP2023/007158 JP2023007158W WO2023195268A1 WO 2023195268 A1 WO2023195268 A1 WO 2023195268A1 JP 2023007158 W JP2023007158 W JP 2023007158W WO 2023195268 A1 WO2023195268 A1 WO 2023195268A1
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- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- pressure
- silicone pressure
- silicone
- film
- Prior art date
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 181
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 64
- 239000000853 adhesive Substances 0.000 claims abstract description 63
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 10
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- -1 polyethylene terephthalate Polymers 0.000 claims description 71
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 229910001220 stainless steel Inorganic materials 0.000 claims description 26
- 239000010935 stainless steel Substances 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 20
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 20
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 239000002530 phenolic antioxidant Substances 0.000 claims description 7
- 150000003568 thioethers Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract 2
- 229910020485 SiO4/2 Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
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- 238000001723 curing Methods 0.000 description 13
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 238000004040 coloring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 3
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- 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
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 3
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 125000001624 naphthyl group Chemical group 0.000 description 3
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
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- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
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- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- UYQYTUYNNYZATF-UHFFFAOYSA-N 6-methyl-4,6-bis(octylsulfanylmethyl)cyclohexa-1,3-dien-1-ol Chemical compound CCCCCCCCSCC1=CC=C(O)C(C)(CSCCCCCCCC)C1 UYQYTUYNNYZATF-UHFFFAOYSA-N 0.000 description 1
- NBPOOCGXISZKSX-UHFFFAOYSA-N 6-methylheptyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)CCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NBPOOCGXISZKSX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-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
- 238000013006 addition curing Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 125000000129 anionic group Chemical group 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
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- VYCDFODYRFOXDA-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-undecoxypiperidin-4-yl) carbonate Chemical compound C1C(C)(C)N(OCCCCCCCCCCC)C(C)(C)CC1OC(=O)OC1CC(C)(C)N(OCCCCCCCCCCC)C(C)(C)C1 VYCDFODYRFOXDA-UHFFFAOYSA-N 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIJXJNIXOVENFT-UHFFFAOYSA-J dicalcium 2,6-ditert-butyl-4-(3-phosphonatopropyl)phenol Chemical compound [Ca+2].[Ca+2].CC(C)(C)C1=CC(CCCP([O-])([O-])=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CCCP([O-])([O-])=O)=CC(C(C)(C)C)=C1O QIJXJNIXOVENFT-UHFFFAOYSA-J 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- JEWSTVAZLFGEOX-UHFFFAOYSA-N ethenyl-ethenylsilyloxy-methylsilane Chemical compound C(=C)[SiH](O[SiH2]C=C)C JEWSTVAZLFGEOX-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 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
- 125000006038 hexenyl group Chemical group 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 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
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
Definitions
- the present invention relates to a silicone pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive, a pressure-sensitive adhesive film, an image display device, and a method for evaluating silicone pressure-sensitive adhesives.
- silicone-based pressure-sensitive adhesives Compared to acrylic adhesives, silicone-based pressure-sensitive adhesives have superior tack, adhesion, and holding power required for pressure-sensitive adhesives.
- silicone has the characteristics of excellent heat resistance, cold resistance, and electrical properties, so it is widely used in various adhesive products such as electrical insulation tape, heat-resistant tape, and masking tape.
- Silicone pressure-sensitive adhesives can be classified into addition reaction curing types, condensation reaction curing types, and peroxide curing types based on their curing mechanism. Among these, addition reaction curing types are widely used because they have good reactivity and do not generate by-products.
- silicone-based pressure-sensitive adhesives are being studied for use in the field of display elements such as smart devices (Patent Document 1).
- Patent Document 2 discloses a silicone-based pressure-sensitive adhesive that leaves little adhesive residue on the adherend surface, but the adhesive strength in a 180° peel test is as low as 0.05 to 4 N/25 mm, which is not sufficient. do not have.
- Patent Documents 3 and 4 are characterized by less adhesive residue on the adherend surface, but the adhesive strength is still not sufficient. Furthermore, there is no mention of the coloring of the pressure-sensitive adhesive, and the appearance and transparency are unknown.
- the evaluation method for adhesive residue on the adhesive layer is ambiguous, based on senses such as visual observation and finger touch, and the essential evaluation of whether or not the adhesive layer remains is difficult. A method is needed.
- the present invention was made in view of the above circumstances, and provides a pressure-sensitive adhesive that has both high adhesive strength and excellent peelability (less adhesive residue), has little coloring and is highly transparent, and a pressure-sensitive adhesive.
- the purpose is to provide an evaluation method.
- a silicone pressure sensitive adhesive composition comprising: (A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g, (In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000.
- R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200.
- R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5.
- :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
- D hydrosilylation reaction catalyst, as well as,
- E A silicone pressure sensitive adhesive composition is provided that includes an antioxidant.
- the silicone pressure-sensitive adhesive composition specified in this way can be used as a silicone pressure-sensitive adhesive composition that has both excellent adhesive strength and removability, and provides a silicone pressure-sensitive adhesive with little coloring. .
- the number of hydrogen atoms bonded to silicon atoms in the component (B) is preferably 0.2 to 50 per alkenyl group in the component (A).
- the resulting silicone pressure-sensitive adhesive will have better adhesive strength and releasability.
- the antioxidant contains two or more kinds of antioxidants.
- the antioxidant contains a phenolic antioxidant and a thioether antioxidant.
- the present invention also provides a silicone pressure-sensitive adhesive obtained by curing the silicone pressure-sensitive adhesive composition described above.
- Such a silicone pressure-sensitive adhesive has both excellent adhesive strength and releasability, and has little coloring.
- the silicone pressure-sensitive adhesive of the present invention has an adhesive force of 5.0 N/25 mm or more at a room temperature of 23° C. and a pulling speed of 300 mm/min in a 180° peel test specified in JIS Z 0237. It is preferable.
- Such a silicone pressure-sensitive adhesive has sufficient adhesive strength.
- the silicone pressure-sensitive adhesive of the present invention was tested in a 180° peel test specified in JIS Z 0237 of a polyethylene terephthalate film on the adhered surface after the peel test, at a room temperature of 23°C and a pulling speed of 300 mm/min. It is preferable that the adhesive force is 0.1 N/25 mm or less.
- Such a silicone pressure-sensitive adhesive has excellent releasability.
- the silicone pressure-sensitive adhesive of the present invention preferably has a b * value of 0.15 or less at a thickness of 300 ⁇ m in the L * a * b * color system defined in JIS Z 8781-4.
- Such a silicone pressure-sensitive adhesive has little yellow coloring and has excellent transparency.
- the present invention provides a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer made of the silicone pressure-sensitive adhesive described above.
- Such a pressure-sensitive adhesive film has both excellent adhesive strength and removability, and has little discoloration.
- the present invention provides an image display device including a pressure-sensitive adhesive layer made of the above-mentioned silicone pressure-sensitive adhesive.
- Such an image display device has excellent reliability and visibility.
- the present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising: (1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material; (2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min.
- a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min.
- a method for evaluating a silicone pressure-sensitive adhesive is provided, which includes a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
- the fourth step is a step of determining the quality of the silicone pressure-sensitive adhesive based on whether the adhesive force satisfies 0.1 N/25 mm or less.
- the silicone pressure-sensitive adhesive composition of the present invention provides a silicone pressure-sensitive adhesive that has both high adhesive strength and excellent releasability (less adhesive residue), and has little coloring, so it has excellent reworkability and transparency.
- the silicone pressure-sensitive adhesive composition of the present invention having such excellent properties is useful for laminating pressure-sensitive adhesive films and image display devices.
- the inventors of the present invention have discovered that by using a specific addition-curing silicone composition, a silicone pressure-sensitive adhesive with excellent adhesive strength and removability, and with little coloring can be created.
- the present invention was completed by discovering that the present invention can be obtained, and also by discovering a method for quantitatively evaluating pressure-sensitive adhesives.
- a silicone pressure sensitive adhesive composition comprising: (A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g, (In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000.
- R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200.
- R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5.
- :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
- D hydrosilylation reaction catalyst, as well as,
- E A silicone pressure sensitive adhesive composition containing an antioxidant.
- the present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising: (1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material; (2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min.
- a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min.
- the silicone pressure-sensitive adhesive composition of the present invention contains the following components (A) to (E).
- Component (A) in the silicone pressure-sensitive adhesive composition of the present invention is a straight line represented by the following average formula (1) and having an alkenyl group content bonded to a silicon atom of 0.0010 to 0.010 mol/100g. It is a linear organopolysiloxane.
- R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000. .
- R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different, and examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, Alkyl groups having 1 to 12 carbon atoms such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl group; phenyl, naphthyl group Aryl groups with 6 to 12 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl groups; alkylaryl groups with 7 to 12 carbon atoms such as benzyl,
- Examples thereof include aralkyl groups having 7 to 12 carbon atoms, and alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, hexenyl, octenyl, decenyl, and dodecenyl groups.
- alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, hexenyl, octenyl, decenyl, and dodecenyl groups.
- methyl group, phenyl group, and vinyl group are preferred.
- 0.0010 to 0.010 mol/100g of component (A) as a whole is an alkenyl group, and the amount of alkenyl groups is preferably 0.0015 to 0.005 mol/100g. If the amount of alkenyl group is less than 0.0010 mol/100 g, crosslinking with component (B) described below will be insufficient, resulting in insufficient releasability of the resulting pressure-sensitive adhesive, and Adhesive residue is likely to occur when peeled off, and on the other hand, if it exceeds 0.010 mol/100g, the adhesive force of the resulting pressure-sensitive adhesive may decrease.
- n is a number from 3,000 to 15,000, preferably from 5,000 to 10,000.
- the pressure-sensitive adhesive may have insufficient adhesive strength and releasability.
- the property of component (A) may be oil-like or raw rubber-like. If it is oily, its viscosity at 25° C. is preferably 1,000 mPa ⁇ s or more, more preferably 10,000 mPa ⁇ s or more. In addition, if it is raw rubber-like, it is preferable that the viscosity of the solution when dissolved in toluene to a concentration of 30% is 5,000 to 100,000 mPa ⁇ s, and 10,000 to 50,000 mPa. - s is more preferable.
- the viscosity is a value measured at 25°C using a B-type rotational viscometer.
- linear organopolysiloxane of component (A) include dimethylsiloxane with dimethylvinylsiloxy groups at both ends, methylvinylsiloxane with trimethylsiloxy at both ends, dimethylsiloxane with methylphenylvinylsiloxy at both ends, Examples include diphenylsiloxane with methylphenylvinylsiloxy groups endblocked at both ends, and methylphenylsiloxane endblocked with methylphenylvinylsiloxy groups at both ends.
- Component (A) may be used alone or in combination of two or more.
- Component (B) in the silicone pressure-sensitive adhesive composition of the present invention is represented by the following average formula (2), and has a content of hydrogen atoms (SiH groups) bonded to silicon atoms of 0.0010 to 0.020 mol. /g, and is a component that crosslinks with the alkenyl group contained in component (A) through a hydrosilylation reaction.
- R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200.
- R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other; the monovalent hydrocarbon group having 1 to 12 carbon atoms is hydrosilylated; Those containing no reactive carbon-carbon unsaturated bonds are preferred, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl.
- n-decyl cyclopentyl, cyclohexyl, and other alkyl groups having 1 to 12 carbon atoms
- phenyl, naphthyl, and other aryl groups having 6 to 12 carbon atoms
- tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl Examples include alkylaryl groups having 7 to 12 carbon atoms such as pentylphenyl and hexylphenyl; aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl; methyl and phenyl groups are particularly preferred.
- the amount of hydrogen atoms (SiH groups) in R 2 is 0.0010 to 0.020 mol/g, preferably 0.0020 to 0.010 mol/g, based on the entire component (B). If the amount of SiH groups is less than 0.0010 mol/g, crosslinking with the component (A) will be insufficient, resulting in insufficient releasability of the resulting pressure-sensitive adhesive, making it difficult to peel off from the adherend. On the other hand, if it exceeds 0.020 mol/g, it is difficult to synthesize due to its structure, and the adhesive force of the resulting pressure-sensitive adhesive may decrease. .
- m is a number from 0 to 200, preferably from 50 to 100. When m exceeds 200, the pressure-sensitive adhesive may have insufficient adhesive strength and releasability.
- linear organohydrogenpolysiloxane of component (B) include dimethylsiloxane with dimethylhydrogensiloxy groups blocked at both ends, methylhydrogensiloxane/dimethylsiloxane copolymer blocked with trimethylsiloxy groups at both ends , phenylhydrogensiloxane/dimethylsiloxane copolymer blocked with dimethylphenylsiloxy groups on both ends, methylhydrogensiloxane/diphenylsiloxane copolymer blocked with dimethylphenylsiloxy groups on both ends, diphenylpolysiloxane blocked with methylphenylhydrogensiloxy groups on both ends, Examples include a dimethylsiloxane/diphenylsiloxane/methylhydrogensiloxane copolymer blocked with methylphenylhydrogensiloxy groups at both ends, and a dimethylsiloxane/diphenylsiloxane/dipheny
- Component (B) may be used alone or in combination of two or more.
- the molar ratio of the hydrosilyl group in component (B) to the alkenyl group in component (A) is preferably 0.2 to 50, more preferably 1.0 to 10.
- the blending amount of component (B) is such that the number of SiH groups in component (B) is preferably 0.2 to 50, more preferably 0.5 to 50 per alkenyl group in component (A).
- the amount is 10.0, more preferably in the range of 1.0 to 5.0. Within this range, the resulting pressure-sensitive adhesive will have superior adhesive strength and releasability.
- Component ( C ) in the silicone pressure-sensitive adhesive composition of the present invention has (R 3 3 SiO 1/2 ) units and (SiO 4/2 ) units; :(SiO 4/2 ) unit ratio is in the range of 0.5:1 to 1.8:1.
- R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, which may be the same or different from each other; Specific examples of groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl.
- Alkyl groups having 1 to 12 carbon atoms such as groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; Tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl groups, etc.
- a part of R 3 may be a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and the content of the hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom is determined based on the total number of R 3 . It is preferably 4% or less.
- alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy groups, and methoxy groups and ethoxy groups preferable.
- halogen atom examples include chlorine and bromine.
- the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5 to 1.8:1, preferably 0.7 to 1.2:1. If the constituent unit ratio of component (C) does not satisfy the above conditions, the pressure-sensitive adhesive may have insufficient adhesive strength or releasability.
- Component (C) may contain R 3 SiO 3/2 units and/or R 3 2 SiO 2/2 units depending on the purpose.
- Component (C) may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of component (C) is not particularly limited, but is preferably in the range of 1,000 to 20,000, more preferably 2,000 to 10,000. Note that the weight average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC) using toluene as a developing solvent.
- the blending amount of component (C) is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of component (A). Within this range, the resulting pressure-sensitive adhesive will have superior adhesive strength and releasability.
- Component (D) in the silicone pressure-sensitive adhesive composition of the present invention is a hydrosilylation reaction catalyst, and examples thereof include platinum-based, rhodium-based, palladium-based, iron-based, ruthenium-based, iron/cobalt-based catalysts, and the like.
- platinum-based catalysts are preferred because of their high ability to promote hydrosilylation.
- platinum-based catalysts include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, reaction products of chloroplatinic acid and olefin compounds, and chloroplatinic acid and vinyl group-containing siloxanes.
- reaction product of chloroplatinic acid and a vinyl group-containing siloxane is preferred, and for example, a commercially available product such as the product name CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used. I can do it.
- the blending amount of component (D) may be a catalytic amount, and is not particularly limited, but is from 0.01 to 0.01 in terms of the metal in component (D) based on the total mass of the silicone pressure-sensitive adhesive composition of the present invention.
- a range of 500 mass ppm is preferred, and a range of 0.05 to 100 mass ppm is more preferred.
- Component (E) in the silicone pressure-sensitive adhesive composition of the present invention is an antioxidant used for the purpose of preventing transparency from being impaired due to coloring of the composition, and includes phenolic antioxidants, thioether Antioxidants such as antioxidants, amine antioxidants, phosphite antioxidants, and the like can be appropriately selected and used.
- phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-t-butylphenol), 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butylidenebis-(6-t-butyl-3-methylphenol), 4,4' -thiobis(6-t-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio-diethylenebis[ 3-(3,5-di-t-butyl-4
- phenolic antioxidants in addition to the phenol hydroxyl group, compounds containing at least one of a phosphorus atom, a sulfur atom, and an amine in the same molecule are also listed, although this overlaps with the examples below.
- thioether antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaerythyl.
- Lythyltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis(6-t-butyl-3-methylphenol), 2 , 2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,6-bis(dodecylthiomethyl)-o-cresol, 2,4-1bis [(octylthio)methyl]-o-cresol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, etc. Can be mentioned.
- amine antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, and 2,4-bis-( Examples include n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine.
- phosphite-based antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, bis(3,5-di-t-butyl-4-hydroxybenzyl ethylphosphonate) calcium, tris(2,4 -di-t-butylphenyl) phosphite, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, and the like.
- antioxidants can be used as the antioxidant, and examples of such commercially available products include ADEKA STAB AO-60, ADEKA STAB AO-50, ADEKA STAB AO-80, and ADEKA STAB AO manufactured by ADEKA Corporation.
- ADK STAB AO-412S ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA -82, ADK STAB LA-87, ADK STAB LA-402AF, ADK STAB LA-502XP, ADK STAB 2112, ADK STAB PEP-36; Irganox 1010, Irganox 1010FF, Irganox 1035, Irga manufactured by BASF Japan Co., Ltd.
- Nox 1035FF Irganox 1076, Irganox 1076FF, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259, Irganox 3114 , Irganox 5057, Irganox 565, Irgafoss 168; manufactured by Sumitomo Chemical Co., Ltd.
- Sumilizer GA-80 Sumilizer MDP-S, Sumilizer WX-R, Sumilizer WX-RC, Sumilizer TP-D; manufactured by Sumika Chemtex Co., Ltd. Examples include Sumilizer BBM-S.
- Each of the antioxidants shown above may be used alone or in combination of two or more types, and it is preferable to use two or more types in combination because it can improve the coloring prevention effect. Among these, it is more preferable to use a phenolic antioxidant and a thioether antioxidant in combination. Although the upper limit of the number of types of antioxidants is not particularly limited, for example, three or less types of antioxidants can be used in combination.
- the blending amount of component (E) is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, per 100 parts by mass of component (A). Within this range, a better coloring prevention effect can be obtained.
- reaction control agent In the silicone pressure-sensitive adhesive composition of the present invention, a known reaction control agent having a reaction control effect on the hydrosilylation reaction catalyst of component (D) may be used.
- a reaction control agent 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-tetra Examples include methyl-1,
- the silicone pressure-sensitive adhesive composition of the present invention may be used for the purpose of mixing components (A) to (E) and other components added as necessary, and/or for controlling the viscosity of the silicone pressure-sensitive adhesive composition.
- An organic solvent may be added for the purpose of adjustment.
- organic solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as heptane, octane, and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and isobutyl acetate.
- Examples include solvents, ether solvents such as diisopropyl ether and 1,4-dioxane, and mixed solvents thereof.
- Components other than (A) to (E) may be added to the silicone pressure-sensitive adhesive composition of the present invention, if necessary.
- non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane
- heat-resistant aids such as hindered amine compounds
- light stabilizers such as triazoles and benzophenones
- phosphoric acid esters and halogens.
- antimony-based flame retardants and antistatic agents such as cationic activators, anionic activators, and nonionic activators.
- the silicone pressure-sensitive adhesive composition of the present invention can be made into a silicone pressure-sensitive adhesive by curing.
- the curing conditions for the silicone pressure-sensitive adhesive composition are appropriately adjusted depending on the coating amount, etc., but are typically 80 to 130° C. and 30 seconds to 3 minutes.
- the adherend of the silicone pressure-sensitive adhesive of the present invention is not particularly limited.
- metals such as stainless steel, copper, and iron, metals whose surfaces have been plated or rust-proofed, glass, ceramics, ceramics, resins such as polytetrafluoroethylene, polyimide, epoxy, and novolac resins, and these materials.
- resins such as polytetrafluoroethylene, polyimide, epoxy, and novolac resins
- the silicone pressure-sensitive adhesive of the present invention preferably has an adhesive force of 5.0 N/25 mm or more at a room temperature of 23° C. and a pulling speed of 300 mm/min in a 180° peel test specified in JIS Z 0237. .
- Such a silicone pressure sensitive adhesive has sufficient adhesive strength.
- the silicone pressure-sensitive adhesive of the present invention preferably has an adhesive force of 5.0 N/25 mm or more and 15 N/25 mm or less at a room temperature of 23° C. and a tensile speed of 300 mm/min in the above tensile test.
- the silicone pressure-sensitive adhesive of the present invention was tested in a 180° peel test specified in JIS Z 0237 of a polyethylene terephthalate film on the adhered surface after the above-mentioned peel test at a room temperature of 23°C and a tensile speed of 300 mm/min. It is preferable that the adhesive force is 0.1 N/25 mm or less. Such a silicone pressure-sensitive adhesive has excellent releasability.
- the silicone pressure-sensitive adhesive of the present invention has an adhesion strength of 0 N/25 mm or more at a room temperature of 23°C and a pulling speed of 300 mm/min in the above 180° peel test of a polyethylene terephthalate film on the adhered surface after the above peel test. More preferably, it is 0.1 N/25 mm or less.
- the silicone pressure-sensitive adhesive of the present invention preferably has a b * value of 0.15 or less at a thickness of 300 ⁇ m in the L * a * b * color system defined in JIS Z 8781-4.
- a b * value of 0.15 or less indicates that the cured layer is not colored yellow, and meets the required characteristics when used as a pressure-sensitive adhesive for display applications, etc. Note that the b * value of 0.15 or less also indicates that the cured layer is substantially transparent.
- the silicone pressure-sensitive adhesive of the present invention more preferably has a b * value of -0.15 or more and 0.15 or less.
- the silicone pressure-sensitive adhesive composition of the present invention can be applied to various film substrates and cured to produce a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer.
- Base materials include plastic films such as polyethylene terephthalate, polyimide, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, and polyvinyl chloride; metal foils such as aluminum foil and copper foil; Examples include paper such as Japanese paper, synthetic paper, and polyethylene laminate paper, cloth, glass fiber, and composite substrates formed by laminating multiple of these materials.
- a base material that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used, but from the viewpoint of simplifying the work process, these It is preferable not to use this method.
- Coating may be performed using any known coating method, including comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, and dipping. Examples include coating, cast coating, etc.
- the coating amount is set depending on the application, but typically the thickness of the silicone pressure-sensitive adhesive layer after curing is 1 to 500 ⁇ m, for display device members 100 to 300 ⁇ m, and for masking tape applications. The thickness is preferably 5 to 50 ⁇ m.
- a pressure-sensitive adhesive film may be produced by applying the silicone pressure-sensitive adhesive composition directly to a substrate as described above, or a silicone pressure-sensitive adhesive composition may be applied to a release film or release paper with a release coating and cured. After this, a pressure sensitive adhesive film may be produced by laminating the substrates together and transferring the silicone pressure sensitive adhesive layer.
- the silicone pressure-sensitive adhesive composition of the present invention can be cured to form a pressure-sensitive adhesive layer, and an image display device including the same can be manufactured.
- Such an image display device has excellent reliability and visibility.
- the silicone composition of the present invention has excellent releasability (less adhesive residue).
- the releasability can be evaluated by an evaluation method comprising the following steps (1) to (4). With this method of evaluating silicone pressure-sensitive adhesives, it is possible to quantitatively evaluate the releasability without relying on visual observation, finger touch, or other sensations.
- a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min.
- Step (1) is a step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material, and the method for producing the pressure-sensitive adhesive film is particularly limited.
- pressure-sensitive adhesive films can be prepared, for example, by the production methods listed above.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably about 30 ⁇ m.
- Step (2) is a step in which the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is pressure-bonded to the surface of the stainless steel plate, and then peeled off at 180° to the stainless steel plate at a tensile speed of 300 mm/min.
- the crimping and peeling conditions in this step are in accordance with the 180° peeling test specified in JIS Z 0237, but a curing step may be provided after crimping if necessary.
- Step (3) is to pressure-bond a polyethylene terephthalate film within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after step (2), and then apply the polyethylene terephthalate film at a tensile speed of 300 mm/min. This is a process of measuring the adhesive force when peeled off at 180° to a stainless steel plate.
- step (3) adhesive force will be generated when the polyethylene terephthalate film is peeled off in step (3).
- the crimping and peeling conditions in this step are based on the 180° peeling test specified in JIS Z 0237, but if necessary, a curing step may be provided after the polyethylene terephthalate film is crimped.
- Step (4) is a step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive force in step (3), and depending on whether the adhesive force satisfies 0.1 N/25 mm or less, the silicone pressure-sensitive adhesive Preferably, this is a step of determining the quality of the pressure-sensitive adhesive. With such an evaluation method, it is possible to perform a more practical evaluation of the releasability of silicone pressure-sensitive adhesives.
- the viscosity is a value measured at 25°C using a B-type rotational viscometer
- Mw weight average molecular weight
- GPC gel permeation chromatography
- Examples 1 to 13 Comparative Examples 1 to 5
- the following components were mixed in the formulations (parts by mass) shown in Tables 1 and 2 to prepare a silicone pressure-sensitive adhesive composition.
- Linear organopolysiloxane (A-2)
- R 2 is a methyl group and a hydrogen atom (B-3)
- (C) Component (C-1) A three-dimensional network organopolysiloxane having a constituent unit ratio expressed as ((CH 3 ) 3 SiO 1/2 ) 0.67 (SiO 4/2 ) 1.00 and an Mw of 3,400. 60% by mass toluene solution (C-2) ((CH 3 ) 3 SiO 1/2 ) 1.75 (SiO 4/2 ) A three-dimensional network having a constituent unit ratio expressed as 1.00 and having an Mw of 7,400. 60% by mass toluene solution of organopolysiloxane
- E Component: (E-1) Phenolic antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.) (E-2) Thioether antioxidant: ADEKA STAB AO-412S (manufactured by ADEKA Co., Ltd.) (E-3) Phosphite antioxidant: ADEKA STAB PEP-36 (manufactured by ADEKA Co., Ltd.)
- the resulting silicone pressure-sensitive adhesive composition was evaluated for adhesive strength, peelability, and b * value by the following methods, and the results are shown in Tables 3 and 4.
- the silicone pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate film having a width of 25 mm so that the thickness after curing would be 30 ⁇ m, and then heated at 130° C. for 1 minute to produce a pressure-sensitive adhesive film.
- This pressure-sensitive adhesive film was pressure-bonded to a stainless steel plate using a roller weighing 2 kg according to JIS Z 0237, and then cured at 25° C. for 24 hours.
- the force (N/25 mm) required to peel the cured pressure-sensitive adhesive film from the stainless steel plate was measured by a 180° peel test at a room temperature of 23° C. and a pulling speed of 300 mm/min.
- Examples 1 to 13 using the silicone pressure-sensitive adhesive compositions of the present invention exhibited excellent adhesive strength and peelability (little adhesive residue), and had a low b * It had a value. Furthermore, compared to Examples 1 and 2 in which one antioxidant was used alone, Examples 3 to 13 in which two antioxidants were used in combination had lower b * values.
- Examples 3 and 5 to 13 in which phenol-based and thioether-based antioxidants were used in combination, had particularly low b * values, indicating that there was very little coloration.
- Comparative Example 1 Comparative Example 2, and Comparative Example 3 containing a hydrosilyl group in which the amount of hydrosilyl group is less than 0.0010 mol/g in place of component (B), the amount required for peeling off in the peelability test was It can be seen that the strength was high and adhesive residue was generated.
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Abstract
The present invention is a silicone pressure-sensitive adhesive composition that contains: (A) an organopolysiloxane which is represented by average formula (1) and in which the content of silicon atom-bonded alkenyl groups is 0.0010-0.010 mol/100 g; (B) an organohydrogenpolysiloxane which is represented by average formula (2) and in which the content of silicon atom-bonded hydrogen atoms is 0.0010-0.020 mol/g; (C) an organopolysiloxane having (R3 3SiO1/2) units and (SiO4/2) units; (D) a hydrosilylation reaction catalyst; and (E) an antioxidant. Due to this configuration, it is possible to provide a pressure-sensitive adhesive which exhibits both high adhesive strength and excellent release properties, undergoes little coloration, and exhibits high transparency. (In the formula, R1 is a monovalent hydrocarbon group, and n is a number between 3000 and 15,000) (In the formula, R2 is a monovalent hydrocarbon group or a hydrogen atom, and m is a number between 0 and 200)
Description
本発明は、シリコーン感圧接着剤組成物、シリコーン感圧接着剤、感圧接着フィルム、画像表示装置及びシリコーン感圧接着剤の評価方法に関する。
The present invention relates to a silicone pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive, a pressure-sensitive adhesive film, an image display device, and a method for evaluating silicone pressure-sensitive adhesives.
シリコーン系感圧接着剤は、アクリル系のものと比較して、感圧接着剤に必要とされるタック、粘着力、保持力に優れている。加えて、シリコーンの特徴である優れた耐熱性、耐寒性、電気特性などを具備しているため、電気絶縁テープ、耐熱テープ、マスキングテープ等の各種粘着製品に幅広く利用されている。
Compared to acrylic adhesives, silicone-based pressure-sensitive adhesives have superior tack, adhesion, and holding power required for pressure-sensitive adhesives. In addition, silicone has the characteristics of excellent heat resistance, cold resistance, and electrical properties, so it is widely used in various adhesive products such as electrical insulation tape, heat-resistant tape, and masking tape.
シリコーン系感圧接着剤は、その硬化機構から付加反応硬化型、縮合反応硬化型、過酸化物硬化型に分類することができる。中でも、付加反応硬化型が、反応性が良好な点や、副生物を発生しない点から広く利用されている。
Silicone pressure-sensitive adhesives can be classified into addition reaction curing types, condensation reaction curing types, and peroxide curing types based on their curing mechanism. Among these, addition reaction curing types are widely used because they have good reactivity and do not generate by-products.
また、シリコーン系感圧接着剤はその透明性を活かして、スマートデバイス等の表示素子分野への利用の検討が進められている（特許文献１）。
Further, by taking advantage of its transparency, silicone-based pressure-sensitive adhesives are being studied for use in the field of display elements such as smart devices (Patent Document 1).
近年、接着剤を貼り合わせた後に再度引き剥がして再利用するリワーク性の観点や、工程上の歩留まり向上といった観点から、樹脂、又は金属等の被着体に貼り合わせ、引き剥がした際に被着体面への糊残りが少ない感圧接着剤組成物が注目されている。そのため、感圧接着剤には、上述した透明性に加えて、被着体に対する優れた接着力と、糊残り無く引き剥がす剥離性の両立が求められている。
In recent years, from the viewpoint of reworkability in which adhesives are pasted together and then peeled off again for reuse, and from the viewpoint of improving yield in the process, adhesives have been pasted onto adherends such as resin or metal, and when peeled off, there is no damage. Pressure-sensitive adhesive compositions that leave little adhesive residue on the adherent surface are attracting attention. Therefore, in addition to the above-mentioned transparency, pressure-sensitive adhesives are required to have both excellent adhesion to adherends and removability that allows them to be peeled off without leaving any adhesive residue.
特許文献２では、被着体面への糊残りが少ないシリコーン系感圧接着剤が開示されているが、１８０°引き剥がし試験による粘着力が０．０５～４Ｎ／２５ｍｍと低く、十分とは言えない。
Patent Document 2 discloses a silicone-based pressure-sensitive adhesive that leaves little adhesive residue on the adherend surface, but the adhesive strength in a 180° peel test is as low as 0.05 to 4 N/25 mm, which is not sufficient. do not have.
同様に、特許文献３、４においても、被着体面への糊残りが少ないことを特徴としているが、粘着力は依然として十分とは言えない。また、感圧接着剤の着色等についての言及は無く、外観や透明性については不明である。
Similarly, Patent Documents 3 and 4 are characterized by less adhesive residue on the adherend surface, but the adhesive strength is still not sufficient. Furthermore, there is no mention of the coloring of the pressure-sensitive adhesive, and the appearance and transparency are unknown.
また、上述した文献全てに共通して、接着層の糊残りの評価方法は、目視や指触等、感覚による曖昧なものであり、接着層が残存しているか否かについての本質的な評価方法が求められている。
In addition, in common with all of the above-mentioned documents, the evaluation method for adhesive residue on the adhesive layer is ambiguous, based on senses such as visual observation and finger touch, and the essential evaluation of whether or not the adhesive layer remains is difficult. A method is needed.
本発明は、上記事情に鑑みなされたもので、高い粘着力と優れた剥離性（糊残りの少なさ）を両立し、着色が少なく透明性の高い感圧接着剤、及び、感圧接着剤の評価方法を提供することを目的とする。
The present invention was made in view of the above circumstances, and provides a pressure-sensitive adhesive that has both high adhesive strength and excellent peelability (less adhesive residue), has little coloring and is highly transparent, and a pressure-sensitive adhesive. The purpose is to provide an evaluation method.
上記目的を達成するために、本発明では、
シリコーン感圧接着剤組成物であって、
（Ａ）下記平均式（１）で表され、ケイ素原子に結合したアルケニル基の含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサン、
（式中、Ｒ１は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基であり、ｎは、３，０００～１５，０００の数である。）
（Ｂ）下記平均式（２）で表され、ケイ素原子に結合した水素原子の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサン、
（式中、Ｒ２は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基または水素原子であり、ｍは、０～２００の数である。）
（Ｃ）（Ｒ３ ３ＳｉＯ１／２）単位（式中、Ｒ３は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子である）、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサン、
（Ｄ）ヒドロシリル化反応触媒、
及び、
（Ｅ）酸化防止剤
を含むシリコーン感圧接着剤組成物を提供する。 In order to achieve the above object, the present invention:
A silicone pressure sensitive adhesive composition comprising:
(A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g,
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000. .)
(B) a linear organohydrogenpolysiloxane represented by the following average formula (2) and having a content of hydrogen atoms bonded to silicon atoms of 0.0010 to 0.020 mol/g;
(In the formula, R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200. )
(C) (R 3 3 SiO 1/2 ) unit (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5. :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
(D) hydrosilylation reaction catalyst,
as well as,
(E) A silicone pressure sensitive adhesive composition is provided that includes an antioxidant.
シリコーン感圧接着剤組成物であって、
（Ａ）下記平均式（１）で表され、ケイ素原子に結合したアルケニル基の含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサン、
（Ｂ）下記平均式（２）で表され、ケイ素原子に結合した水素原子の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサン、
（Ｃ）（Ｒ３ ３ＳｉＯ１／２）単位（式中、Ｒ３は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子である）、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサン、
（Ｄ）ヒドロシリル化反応触媒、
及び、
（Ｅ）酸化防止剤
を含むシリコーン感圧接着剤組成物を提供する。 In order to achieve the above object, the present invention:
A silicone pressure sensitive adhesive composition comprising:
(A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g,
(B) a linear organohydrogenpolysiloxane represented by the following average formula (2) and having a content of hydrogen atoms bonded to silicon atoms of 0.0010 to 0.020 mol/g;
(C) (R 3 3 SiO 1/2 ) unit (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5. :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
(D) hydrosilylation reaction catalyst,
as well as,
(E) A silicone pressure sensitive adhesive composition is provided that includes an antioxidant.
このように特定されたシリコーン感圧接着剤組成物であれば、優れた粘着力と剥離性を両立し、着色が少ないシリコーン感圧接着剤を与えるシリコーン感圧接着剤組成物とすることができる。
The silicone pressure-sensitive adhesive composition specified in this way can be used as a silicone pressure-sensitive adhesive composition that has both excellent adhesive strength and removability, and provides a silicone pressure-sensitive adhesive with little coloring. .
このとき、前記（Ｂ）成分中のケイ素原子に結合した水素原子の数が、前記（Ａ）成分中のアルケニル基１個に対し０．２～５０個であることが好ましい。
At this time, the number of hydrogen atoms bonded to silicon atoms in the component (B) is preferably 0.2 to 50 per alkenyl group in the component (A).
このようなシリコーン感圧接着剤組成物であれば、得られるシリコーン感圧接着剤が、接着力および剥離性により優れるものとなる。
With such a silicone pressure-sensitive adhesive composition, the resulting silicone pressure-sensitive adhesive will have better adhesive strength and releasability.
また、前記酸化防止剤が、２種以上の酸化防止剤を含むことが好ましい。
Furthermore, it is preferable that the antioxidant contains two or more kinds of antioxidants.
また、前記酸化防止剤が、フェノール系酸化防止剤及びチオエーテル系酸化防止剤を含むものであることがより好ましい。
Moreover, it is more preferable that the antioxidant contains a phenolic antioxidant and a thioether antioxidant.
このようなシリコーン感圧接着剤組成物であれば、より着色が少なく透明性に優れたシリコーン感圧接着剤が得られる。
With such a silicone pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive with less coloring and excellent transparency can be obtained.
また、本発明では、上記のシリコーン感圧接着剤組成物を硬化してなるものであるシリコーン感圧接着剤を提供する。
The present invention also provides a silicone pressure-sensitive adhesive obtained by curing the silicone pressure-sensitive adhesive composition described above.
このようなシリコーン感圧接着剤は、優れた粘着力と剥離性を両立し、着色が少ないものとなる。
Such a silicone pressure-sensitive adhesive has both excellent adhesive strength and releasability, and has little coloring.
このとき、本発明のシリコーン感圧接着剤は、ＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ｍｉｎでの粘着力が、５．０Ｎ／２５ｍｍ以上であることが好ましい。
At this time, the silicone pressure-sensitive adhesive of the present invention has an adhesive force of 5.0 N/25 mm or more at a room temperature of 23° C. and a pulling speed of 300 mm/min in a 180° peel test specified in JIS Z 0237. It is preferable.
このようなシリコーン感圧接着剤は、粘着力が十分なものとなる。
Such a silicone pressure-sensitive adhesive has sufficient adhesive strength.
また、本発明のシリコーン感圧接着剤は、前記引き剥がし試験後の被着面に対するポリエチレンテレフタレートフィルムのＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ｍｉｎでの粘着力が０．１Ｎ／２５ｍｍ以下であることが好ましい。
Furthermore, the silicone pressure-sensitive adhesive of the present invention was tested in a 180° peel test specified in JIS Z 0237 of a polyethylene terephthalate film on the adhered surface after the peel test, at a room temperature of 23°C and a pulling speed of 300 mm/min. It is preferable that the adhesive force is 0.1 N/25 mm or less.
このようなシリコーン感圧接着剤は、剥離性に優れるものとなる。
Such a silicone pressure-sensitive adhesive has excellent releasability.
また、本発明のシリコーン感圧接着剤は、ＪＩＳ Ｚ ８７８１－４に規定されるＬ＊ａ＊ｂ＊表色系における厚み３００μｍでのｂ＊値が０．１５以下であることが好ましい。
Further, the silicone pressure-sensitive adhesive of the present invention preferably has a b * value of 0.15 or less at a thickness of 300 μm in the L * a * b * color system defined in JIS Z 8781-4.
このようなシリコーン感圧接着剤は、黄色の着色が少なく透明性に優れるものとなる。
Such a silicone pressure-sensitive adhesive has little yellow coloring and has excellent transparency.
また、本発明では、上記のシリコーン感圧接着剤からなる感圧接着剤層を備えた感圧接着フィルムを提供する。
Furthermore, the present invention provides a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer made of the silicone pressure-sensitive adhesive described above.
このような感圧接着フィルムは、優れた粘着力と剥離性を両立し、着色が少ないものとなる。
Such a pressure-sensitive adhesive film has both excellent adhesive strength and removability, and has little discoloration.
また、本発明では、上記のシリコーン感圧接着剤からなる感圧接着剤層を備えた画像表示装置を提供する。
Furthermore, the present invention provides an image display device including a pressure-sensitive adhesive layer made of the above-mentioned silicone pressure-sensitive adhesive.
このような画像表示装置は、信頼性および視認性に優れるものとなる。
Such an image display device has excellent reliability and visibility.
また、本発明では、シリコーン感圧接着剤の評価方法であって、
（１）シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する第１の工程と、
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程と
を備えるシリコーン感圧接着剤の評価方法を提供する。 The present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising:
(1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A method for evaluating a silicone pressure-sensitive adhesive is provided, which includes a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
（１）シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する第１の工程と、
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程と
を備えるシリコーン感圧接着剤の評価方法を提供する。 The present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising:
(1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A method for evaluating a silicone pressure-sensitive adhesive is provided, which includes a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
このようなシリコーン感圧接着剤の評価方法であれば、目視や指触等の感覚によらず、剥離性を定量的に評価する事ができる。
With this method of evaluating silicone pressure-sensitive adhesives, it is possible to quantitatively evaluate the releasability without relying on visual observation or touch with the fingers.
前記第４の工程を、前記粘着力が０．１Ｎ／２５ｍｍ以下を満たすか否かによってシリコーン感圧接着剤の良否を判定する工程とすることが好ましい。
It is preferable that the fourth step is a step of determining the quality of the silicone pressure-sensitive adhesive based on whether the adhesive force satisfies 0.1 N/25 mm or less.
このような評価方法であれば、シリコーン感圧接着剤の剥離性についてより実用的な評価を行うことができる。
With such an evaluation method, it is possible to perform a more practical evaluation of the releasability of silicone pressure-sensitive adhesives.
本発明のシリコーン感圧接着剤組成物は、高い粘着力と優れた剥離性（糊残りの少なさ）を両立し、着色が少ないシリコーン感圧接着剤を与えることから、リワーク性及び透明性に優れ、このような特性を有する本発明のシリコーン感圧接着剤組成物は、感圧接着フィルムや画像表示装置の貼合せ等に有用である。
The silicone pressure-sensitive adhesive composition of the present invention provides a silicone pressure-sensitive adhesive that has both high adhesive strength and excellent releasability (less adhesive residue), and has little coloring, so it has excellent reworkability and transparency. The silicone pressure-sensitive adhesive composition of the present invention having such excellent properties is useful for laminating pressure-sensitive adhesive films and image display devices.
上述のように、粘着力と剥離性を両立し、着色が少なく透明性の高い感圧接着剤、及び、感圧接着剤の定量的な評価方法の開発が求められていた。
As mentioned above, there has been a need to develop a pressure-sensitive adhesive that has both adhesion and releasability, less coloring, and high transparency, as well as a quantitative evaluation method for pressure-sensitive adhesives.
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、特定の付加硬化型シリコーン組成物を使用することで、粘着力および剥離性に優れ、着色の少ないシリコーン感圧接着剤が得られることを見出し、また、更に定量的に感圧接着剤を評価する方法を見出し、本発明を完成させた。
As a result of extensive studies to achieve the above object, the inventors of the present invention have discovered that by using a specific addition-curing silicone composition, a silicone pressure-sensitive adhesive with excellent adhesive strength and removability, and with little coloring can be created. The present invention was completed by discovering that the present invention can be obtained, and also by discovering a method for quantitatively evaluating pressure-sensitive adhesives.
即ち、本発明は、
シリコーン感圧接着剤組成物であって、
（Ａ）下記平均式（１）で表され、ケイ素原子に結合したアルケニル基の含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサン、
（式中、Ｒ１は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基であり、ｎは、３，０００～１５，０００の数である。）
（Ｂ）下記平均式（２）で表され、ケイ素原子に結合した水素原子の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサン、
（式中、Ｒ２は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基または水素原子であり、ｍは、０～２００の数である。）
（Ｃ）（Ｒ３ ３ＳｉＯ１／２）単位（式中、Ｒ３は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子である）、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサン、
（Ｄ）ヒドロシリル化反応触媒、
及び、
（Ｅ）酸化防止剤
を含むシリコーン感圧接着剤組成物である。 That is, the present invention
A silicone pressure sensitive adhesive composition comprising:
(A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g,
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000. .)
(B) a linear organohydrogenpolysiloxane represented by the following average formula (2) and having a content of hydrogen atoms bonded to silicon atoms of 0.0010 to 0.020 mol/g;
(In the formula, R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200. )
(C) (R 3 3 SiO 1/2 ) unit (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5. :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
(D) hydrosilylation reaction catalyst,
as well as,
(E) A silicone pressure sensitive adhesive composition containing an antioxidant.
シリコーン感圧接着剤組成物であって、
（Ａ）下記平均式（１）で表され、ケイ素原子に結合したアルケニル基の含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサン、
（Ｂ）下記平均式（２）で表され、ケイ素原子に結合した水素原子の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサン、
（Ｃ）（Ｒ３ ３ＳｉＯ１／２）単位（式中、Ｒ３は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子である）、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサン、
（Ｄ）ヒドロシリル化反応触媒、
及び、
（Ｅ）酸化防止剤
を含むシリコーン感圧接着剤組成物である。 That is, the present invention
A silicone pressure sensitive adhesive composition comprising:
(A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g,
(B) a linear organohydrogenpolysiloxane represented by the following average formula (2) and having a content of hydrogen atoms bonded to silicon atoms of 0.0010 to 0.020 mol/g;
(C) (R 3 3 SiO 1/2 ) unit (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5. :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
(D) hydrosilylation reaction catalyst,
as well as,
(E) A silicone pressure sensitive adhesive composition containing an antioxidant.
また、本発明は、シリコーン感圧接着剤の評価方法であって、
（１）シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する第１の工程と、
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程と
を備えるシリコーン感圧接着剤の評価方法である。 The present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising:
(1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A method for evaluating a silicone pressure-sensitive adhesive, including a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
（１）シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する第１の工程と、
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程と
を備えるシリコーン感圧接着剤の評価方法である。 The present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising:
(1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A method for evaluating a silicone pressure-sensitive adhesive, including a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
以下、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be explained in detail, but the present invention is not limited thereto.
本発明のシリコーン感圧接着剤組成物は、下記（Ａ）～（Ｅ）成分を含むものである。
The silicone pressure-sensitive adhesive composition of the present invention contains the following components (A) to (E).
［（Ａ）成分］
本発明のシリコーン感圧接着剤組成物における（Ａ）成分は、下記平均式（１）で表され、ケイ素原子に結合したアルケニル基含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサンである。
（式中、Ｒ１は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基であり、ｎは、３，０００～１５，０００の数である。）
[(A) Component]
Component (A) in the silicone pressure-sensitive adhesive composition of the present invention is a straight line represented by the following average formula (1) and having an alkenyl group content bonded to a silicon atom of 0.0010 to 0.010 mol/100g. It is a linear organopolysiloxane.
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000. .)
本発明のシリコーン感圧接着剤組成物における（Ａ）成分は、下記平均式（１）で表され、ケイ素原子に結合したアルケニル基含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサンである。
Component (A) in the silicone pressure-sensitive adhesive composition of the present invention is a straight line represented by the following average formula (1) and having an alkenyl group content bonded to a silicon atom of 0.0010 to 0.010 mol/100g. It is a linear organopolysiloxane.
Ｒ１は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基であり、一価炭化水素基としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－オクチル、ｎ－デシル、シクロペンチル、シクロヘキシル基等の炭素原子数１～１２のアルキル基；フェニル、ナフチル基等の炭素原子数６～１２のアリール基；トリル、キシリル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル基等の炭素原子数７～１２のアルキルアリール基；ベンジル、フェネチル基等の炭素原子数７～１２のアラルキル基、ビニル、アリル、ブテニル、ヘキセニル、オクテニル、デセニル、ドデセニル基等の炭素原子数２～１２のアルケニル基等が挙げられる。中でも、メチル基、フェニル基、ビニル基が好ましい。
R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different, and examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, Alkyl groups having 1 to 12 carbon atoms such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl group; phenyl, naphthyl group Aryl groups with 6 to 12 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl groups; alkylaryl groups with 7 to 12 carbon atoms such as benzyl, phenethyl groups, etc. Examples thereof include aralkyl groups having 7 to 12 carbon atoms, and alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, hexenyl, octenyl, decenyl, and dodecenyl groups. Among these, methyl group, phenyl group, and vinyl group are preferred.
Ｒ１のうち、（Ａ）成分全体にして０．００１０～０．０１０モル／１００ｇがアルケニル基であり、アルケニル基量が０．００１５～０．００５モル／１００ｇであることが好ましい。アルケニル基量が０．００１０モル／１００ｇ未満であると、後述する（Ｂ）成分との架橋が不足することにより、得られる感圧接着剤の剥離性が不十分なものとなり、被着体から剥がした際の糊残りが発生しやすくなり、一方、０．０１０モル／１００ｇを超えると、得られる感圧接着剤の粘着力が低下する場合がある。
Of R 1 , 0.0010 to 0.010 mol/100g of component (A) as a whole is an alkenyl group, and the amount of alkenyl groups is preferably 0.0015 to 0.005 mol/100g. If the amount of alkenyl group is less than 0.0010 mol/100 g, crosslinking with component (B) described below will be insufficient, resulting in insufficient releasability of the resulting pressure-sensitive adhesive, and Adhesive residue is likely to occur when peeled off, and on the other hand, if it exceeds 0.010 mol/100g, the adhesive force of the resulting pressure-sensitive adhesive may decrease.
ｎは、３，０００～１５，０００の数であり、５，０００～１０，０００であることが好ましい。ｎが上記範囲を満たさない場合、感圧接着剤の粘着力や剥離性が不十分なものとなる場合がある。なお、ｎ＝１５，０００を超えるオルガノポリシロキサンは、粘度が非常に高いために合成が困難である。また、取り扱い性も悪く実使用には堪えない。
n is a number from 3,000 to 15,000, preferably from 5,000 to 10,000. When n does not satisfy the above range, the pressure-sensitive adhesive may have insufficient adhesive strength and releasability. It should be noted that organopolysiloxanes with n=15,000 or more are difficult to synthesize because of their extremely high viscosity. In addition, the handleability is poor and it cannot be used in actual use.
（Ａ）成分の性状はオイル状または生ゴム状であってよい。その粘度は、オイル状のものであれば２５℃において１，０００ｍＰａ・ｓ以上が好ましく、１０，０００ｍＰａ・ｓ以上がより好ましい。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溶液の粘度が、５，０００～１００，０００ｍＰａ・ｓのものが好ましく、１０，０００～５０，０００ｍＰａ・ｓのものがより好ましい。
The property of component (A) may be oil-like or raw rubber-like. If it is oily, its viscosity at 25° C. is preferably 1,000 mPa·s or more, more preferably 10,000 mPa·s or more. In addition, if it is raw rubber-like, it is preferable that the viscosity of the solution when dissolved in toluene to a concentration of 30% is 5,000 to 100,000 mPa・s, and 10,000 to 50,000 mPa. - s is more preferable.
なお、粘度はＢ型回転粘度計で測定した２５℃における値である。
Note that the viscosity is a value measured at 25°C using a B-type rotational viscometer.
（Ａ）成分の直鎖状オルガノポリシロキサンの具体的な例としては、両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン、両末端トリメチルシロキシ基封鎖メチルビニルシロキサン、両末端メチルフェニルビニルシロキシ基封鎖ジメチルシロキサン、両末端メチルフェニルビニルシロキシ基封鎖ジフェニルシロキサン、両末端メチルフェニルビニルシロキシ基封鎖メチルフェニルシロキサンなどが挙げられる。
Specific examples of the linear organopolysiloxane of component (A) include dimethylsiloxane with dimethylvinylsiloxy groups at both ends, methylvinylsiloxane with trimethylsiloxy at both ends, dimethylsiloxane with methylphenylvinylsiloxy at both ends, Examples include diphenylsiloxane with methylphenylvinylsiloxy groups endblocked at both ends, and methylphenylsiloxane endblocked with methylphenylvinylsiloxy groups at both ends.
（Ａ）成分は一種単独でも二種以上を併用してもよい。
Component (A) may be used alone or in combination of two or more.
［（Ｂ）成分］
本発明のシリコーン感圧接着剤組成物における（Ｂ）成分は、下記平均式（２）で表され、ケイ素原子に結合した水素原子（ＳｉＨ基）の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサンであり、（Ａ）成分中に含まれるアルケニル基とヒドロシリル化反応により架橋する成分である。
（式中、Ｒ２は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基または水素原子であり、ｍは、０～２００の数である。）
[(B) Component]
Component (B) in the silicone pressure-sensitive adhesive composition of the present invention is represented by the following average formula (2), and has a content of hydrogen atoms (SiH groups) bonded to silicon atoms of 0.0010 to 0.020 mol. /g, and is a component that crosslinks with the alkenyl group contained in component (A) through a hydrosilylation reaction.
(In the formula, R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200. )
本発明のシリコーン感圧接着剤組成物における（Ｂ）成分は、下記平均式（２）で表され、ケイ素原子に結合した水素原子（ＳｉＨ基）の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサンであり、（Ａ）成分中に含まれるアルケニル基とヒドロシリル化反応により架橋する成分である。
Component (B) in the silicone pressure-sensitive adhesive composition of the present invention is represented by the following average formula (2), and has a content of hydrogen atoms (SiH groups) bonded to silicon atoms of 0.0010 to 0.020 mol. /g, and is a component that crosslinks with the alkenyl group contained in component (A) through a hydrosilylation reaction.
Ｒ２は互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基または水素原子であり、炭素数１～１２の一価炭化水素基としては、ヒドロシリル化反応性炭素－炭素不飽和結合を含まないものが好ましく、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－オクチル、ｎ－デシル、シクロペンチル、シクロヘキシル基等の炭素原子数１～１２のアルキル基；フェニル、ナフチル基等の炭素原子数６～１２のアリール基；トリル、キシリル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル基等の炭素原子数７～１２のアルキルアリール基；ベンジル、フェネチル基等の炭素原子数７～１２のアラルキル基等が挙げられ、メチル基、フェニル基が特に好ましい。
R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other; the monovalent hydrocarbon group having 1 to 12 carbon atoms is hydrosilylated; Those containing no reactive carbon-carbon unsaturated bonds are preferred, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl. , n-decyl, cyclopentyl, cyclohexyl, and other alkyl groups having 1 to 12 carbon atoms; phenyl, naphthyl, and other aryl groups having 6 to 12 carbon atoms; tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, Examples include alkylaryl groups having 7 to 12 carbon atoms such as pentylphenyl and hexylphenyl; aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl; methyl and phenyl groups are particularly preferred.
Ｒ２のうち、水素原子（ＳｉＨ基）の量は、（Ｂ）成分全体に対して０．００１０～０．０２０モル／ｇであり、０．００２０～０．０１０モル／ｇが好ましい。ＳｉＨ基量が０．００１０モル／ｇ未満であると、上記（Ａ）成分との架橋が不足することにより、得られる感圧接着剤の剥離性が不十分なものとなり、被着体から剥がした際の糊残りが発生しやすくなり、一方、０．０２０モル／ｇを超えるものは、構造上合成が困難であることに加え、得られる感圧接着剤の粘着力が低下する場合がある。
The amount of hydrogen atoms (SiH groups) in R 2 is 0.0010 to 0.020 mol/g, preferably 0.0020 to 0.010 mol/g, based on the entire component (B). If the amount of SiH groups is less than 0.0010 mol/g, crosslinking with the component (A) will be insufficient, resulting in insufficient releasability of the resulting pressure-sensitive adhesive, making it difficult to peel off from the adherend. On the other hand, if it exceeds 0.020 mol/g, it is difficult to synthesize due to its structure, and the adhesive force of the resulting pressure-sensitive adhesive may decrease. .
ｍは、０～２００の数であり、５０～１００であることが好ましい。ｍが２００を超えると、感圧接着剤の粘着力や剥離性が不十分なものとなる場合がある。
m is a number from 0 to 200, preferably from 50 to 100. When m exceeds 200, the pressure-sensitive adhesive may have insufficient adhesive strength and releasability.
（Ｂ）成分の直鎖状オルガノハイドロジェンポリシロキサンの具体的な例としては、例えば、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン共重合体、両末端ジメチルフェニルシロキシ基封鎖フェニルハイドロジェンシロキサン・ジメチルシロキサン共重合体、両末端ジメチルフェニルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、両末端メチルフェニルハイドロジェンシロキシ基封鎖ジフェニルポリシロキサン、両末端メチルフェニルハイドロジェンシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジフェニルハイドロジェンシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン・メチルハイドロジェンシロキサン共重合体等が挙げられる。
Specific examples of the linear organohydrogenpolysiloxane of component (B) include dimethylsiloxane with dimethylhydrogensiloxy groups blocked at both ends, methylhydrogensiloxane/dimethylsiloxane copolymer blocked with trimethylsiloxy groups at both ends , phenylhydrogensiloxane/dimethylsiloxane copolymer blocked with dimethylphenylsiloxy groups on both ends, methylhydrogensiloxane/diphenylsiloxane copolymer blocked with dimethylphenylsiloxy groups on both ends, diphenylpolysiloxane blocked with methylphenylhydrogensiloxy groups on both ends, Examples include a dimethylsiloxane/diphenylsiloxane/methylhydrogensiloxane copolymer blocked with methylphenylhydrogensiloxy groups at both ends, and a dimethylsiloxane/diphenylsiloxane/methylhydrogensiloxane copolymer blocked with diphenylhydrogensiloxy groups at both ends.
（Ｂ）成分は、単独で用いても二種以上併用してもよい。
Component (B) may be used alone or in combination of two or more.
（Ａ）成分中のアルケニル基に対して（Ｂ）成分中のヒドロシリル基のモル比が０．２～５０となるものが好ましく、モル比が１．０～１０となるものがより好ましい。
The molar ratio of the hydrosilyl group in component (B) to the alkenyl group in component (A) is preferably 0.2 to 50, more preferably 1.0 to 10.
（Ｂ）成分の配合量は、（Ａ）成分中のアルケニル基１個に対して（Ｂ）成分中のＳｉＨ基の数が、好ましくは０．２～５０個、より好ましくは０．５～１０．０個、更に好ましくは１．０～５．０の範囲となる量である。このような範囲であれば、得られる感圧接着剤が、接着力および剥離性により優れるものとなる。
The blending amount of component (B) is such that the number of SiH groups in component (B) is preferably 0.2 to 50, more preferably 0.5 to 50 per alkenyl group in component (A). The amount is 10.0, more preferably in the range of 1.0 to 5.0. Within this range, the resulting pressure-sensitive adhesive will have superior adhesive strength and releasability.
［（Ｃ）成分］
本発明のシリコーン感圧接着剤組成物における（Ｃ）成分は、（Ｒ３ ３ＳｉＯ１／２）単位、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサンである。 [(C) Component]
Component ( C ) in the silicone pressure-sensitive adhesive composition of the present invention has (R 3 3 SiO 1/2 ) units and (SiO 4/2 ) units; :(SiO 4/2 ) unit ratio is in the range of 0.5:1 to 1.8:1.
本発明のシリコーン感圧接着剤組成物における（Ｃ）成分は、（Ｒ３ ３ＳｉＯ１／２）単位、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサンである。 [(C) Component]
Component ( C ) in the silicone pressure-sensitive adhesive composition of the present invention has (R 3 3 SiO 1/2 ) units and (SiO 4/2 ) units; :(SiO 4/2 ) unit ratio is in the range of 0.5:1 to 1.8:1.
Ｒ３は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子であり、一価炭化水素基の具体例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－オクチル、ｎ－デシル、シクロペンチル、シクロヘキシル基等の炭素原子数１～１２のアルキル基；フェニル、ナフチル基等の炭素原子数６～１２のアリール基；トリル、キシリル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル基等の炭素原子数７～１２のアルキルアリール基；ベンジル、フェネチル基等の炭素原子数７～１２のアラルキル基などが挙げられる。中でも、メチル基及びフェニル基が好ましい。
R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, which may be the same or different from each other; Specific examples of groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl. Alkyl groups having 1 to 12 carbon atoms such as groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; Tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl groups, etc. Alkylaryl groups having 7 to 12 carbon atoms; aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl groups; and the like. Among them, methyl group and phenyl group are preferred.
Ｒ３の一部が、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子であってもよく、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子の含有量は、Ｒ３の全数のうち４％以下であることが好ましい。
A part of R 3 may be a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and the content of the hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom is determined based on the total number of R 3 . It is preferably 4% or less.
炭素数１～４のアルコキシ基の具体例としては、メトキシ、エトキシ、ｎ－プロポキシ、イソプロポキシ、ｎ－ブトキシ、イソブトキシ、ｓｅｃ－ブトキシ、ｔｅｒｔ－ブトキシ基等が挙げられ、メトキシ基、エトキシ基が好ましい。
Specific examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy groups, and methoxy groups and ethoxy groups preferable.
ハロゲン原子としては、塩素、臭素等が挙げられる。
Examples of the halogen atom include chlorine and bromine.
（Ｒ３
３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比は、０．５～１．８：１であり、０．７～１．２：１が好ましい。（Ｃ）成分の構成単位比が上記を満たさない場合、感圧接着剤の粘着力や剥離性が不十分なものとなる場合がある。
The ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5 to 1.8:1, preferably 0.7 to 1.2:1. If the constituent unit ratio of component (C) does not satisfy the above conditions, the pressure-sensitive adhesive may have insufficient adhesive strength or releasability.
（Ｃ）成分は、目的に応じてＲ３ＳｉＯ３／２単位及び／又はＲ３
２ＳｉＯ２／２単位を含有していてもよい。
Component (C) may contain R 3 SiO 3/2 units and/or R 3 2 SiO 2/2 units depending on the purpose.
（Ｃ）成分は、単独で用いても二種以上併用してもよい。
Component (C) may be used alone or in combination of two or more.
（Ｃ）成分の重量平均分子量（Ｍｗ）は、特に限定されないが、好ましくは１，０００～２０，０００、より好ましくは２，０００～１０，０００の範囲である。なお、重量平均分子量は、トルエンを展開溶媒として用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算値である。
The weight average molecular weight (Mw) of component (C) is not particularly limited, but is preferably in the range of 1,000 to 20,000, more preferably 2,000 to 10,000. Note that the weight average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC) using toluene as a developing solvent.
（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対して、５０～３００質量部が好ましく、１００～２００質量部がより好ましい。このような範囲であれば、得られる感圧接着剤が、接着力および剥離性により優れるものとなる。
The blending amount of component (C) is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of component (A). Within this range, the resulting pressure-sensitive adhesive will have superior adhesive strength and releasability.
［（Ｄ）成分］
本発明のシリコーン感圧接着剤組成物における（Ｄ）成分は、ヒドロシリル化反応触媒であり、白金系、ロジウム系、パラジウム系、鉄系、ルテニウム系、鉄／コバルト系触媒等が挙げられる。中でも、ヒドロシリル化を促進する能力の高さから、白金系触媒が好ましい。白金系触媒は、具体的には塩化白金酸、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が、中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、例えば、商品名ＣＡＴ－ＰＬ－５０Ｔ（信越化学工業（株）製）等の市販品を用いることができる。 [(D) Component]
Component (D) in the silicone pressure-sensitive adhesive composition of the present invention is a hydrosilylation reaction catalyst, and examples thereof include platinum-based, rhodium-based, palladium-based, iron-based, ruthenium-based, iron/cobalt-based catalysts, and the like. Among these, platinum-based catalysts are preferred because of their high ability to promote hydrosilylation. Specifically, platinum-based catalysts include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, reaction products of chloroplatinic acid and olefin compounds, and chloroplatinic acid and vinyl group-containing siloxanes. Among them, a reaction product of chloroplatinic acid and a vinyl group-containing siloxane is preferred, and for example, a commercially available product such as the product name CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used. I can do it.
本発明のシリコーン感圧接着剤組成物における（Ｄ）成分は、ヒドロシリル化反応触媒であり、白金系、ロジウム系、パラジウム系、鉄系、ルテニウム系、鉄／コバルト系触媒等が挙げられる。中でも、ヒドロシリル化を促進する能力の高さから、白金系触媒が好ましい。白金系触媒は、具体的には塩化白金酸、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が、中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、例えば、商品名ＣＡＴ－ＰＬ－５０Ｔ（信越化学工業（株）製）等の市販品を用いることができる。 [(D) Component]
Component (D) in the silicone pressure-sensitive adhesive composition of the present invention is a hydrosilylation reaction catalyst, and examples thereof include platinum-based, rhodium-based, palladium-based, iron-based, ruthenium-based, iron/cobalt-based catalysts, and the like. Among these, platinum-based catalysts are preferred because of their high ability to promote hydrosilylation. Specifically, platinum-based catalysts include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, reaction products of chloroplatinic acid and olefin compounds, and chloroplatinic acid and vinyl group-containing siloxanes. Among them, a reaction product of chloroplatinic acid and a vinyl group-containing siloxane is preferred, and for example, a commercially available product such as the product name CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used. I can do it.
（Ｄ）成分の配合量は、触媒量でよく、特に限定されないが、本発明のシリコーン感圧接着剤組成物の質量の合計に対して、（Ｄ）成分中の金属換算で０．０１～５００質量ｐｐｍの範囲が好ましく、０．０５～１００質量ｐｐｍの範囲がより好ましい。
The blending amount of component (D) may be a catalytic amount, and is not particularly limited, but is from 0.01 to 0.01 in terms of the metal in component (D) based on the total mass of the silicone pressure-sensitive adhesive composition of the present invention. A range of 500 mass ppm is preferred, and a range of 0.05 to 100 mass ppm is more preferred.
［（Ｅ）成分］
本発明のシリコーン感圧接着剤組成物における（Ｅ）成分は、組成物が着色することによって透明性が損なわれることを防止する目的で用いられる酸化防止剤であり、フェノール系酸化防止剤、チオエーテル系酸化防止剤、アミン系酸化防止剤、ホスファイト系酸化防止剤等の酸化防止剤から適宜選択して用いることができる。 [(E) component]
Component (E) in the silicone pressure-sensitive adhesive composition of the present invention is an antioxidant used for the purpose of preventing transparency from being impaired due to coloring of the composition, and includes phenolic antioxidants, thioether Antioxidants such as antioxidants, amine antioxidants, phosphite antioxidants, and the like can be appropriately selected and used.
本発明のシリコーン感圧接着剤組成物における（Ｅ）成分は、組成物が着色することによって透明性が損なわれることを防止する目的で用いられる酸化防止剤であり、フェノール系酸化防止剤、チオエーテル系酸化防止剤、アミン系酸化防止剤、ホスファイト系酸化防止剤等の酸化防止剤から適宜選択して用いることができる。 [(E) component]
Component (E) in the silicone pressure-sensitive adhesive composition of the present invention is an antioxidant used for the purpose of preventing transparency from being impaired due to coloring of the composition, and includes phenolic antioxidants, thioether Antioxidants such as antioxidants, amine antioxidants, phosphite antioxidants, and the like can be appropriately selected and used.
フェノール系酸化防止剤の具体例としては、２，６－ジ－ｔ－ブチル－４－メチルフェノール、ｎ－オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、２，２’－メチレンビス－（４－メチル－６－ｔ－ブチルフェノール）、３，９－ビス［２－〔３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、４，４’－ブチリデンビス－（６－ｔ－ブチル－３－メチルフェノール）、４，４’－チオビス（６－ｔ－ブチル－３－メチルフェノール）、テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、２，２－チオ－ジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ’－ヘキサメチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオンアミド］、イソオクチル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、４，６－ビス（ドデシルチオメチル）－ｏ－クレゾール、ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）カルシウム、２，４－ビス［（オクチルチオ）メチル］－ｏ－クレゾール、１，６－ヘキサンジオール－ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－ｔ－ブチル－６－（３－ｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート、２－［１－（２－ヒドロキシ－３，５－ジ－ｔ－ペンチルフェニル）エチル］－４，６－ジ－ｔ－ペンチルフェニルアクリレート、２，２’－メチレンビス－（４－エチル－６－ｔ－ブチルフェノール）、２，６－ジ－ｔ－ブチル－４－エチルフェノール、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、トリエチレングリコール－ビス［３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート］、トリス（３，５－ジ－ｔ－ブチル－４ヒドロキシベンジル）イソシアヌレート、ジエチル［〔３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル〕メチル］ホスホネート、２，５，７，８－テトラメチル－２（４’，８’，１２’－トリメチルトリデシル）クロマン－６－オール、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン等が挙げられる。
Specific examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-t-butylphenol), 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butylidenebis-(6-t-butyl-3-methylphenol), 4,4' -thiobis(6-t-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio-diethylenebis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide ], isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl- 4-Hydroxybenzyl)benzene, 4,6-bis(dodecylthiomethyl)-o-cresol, bis(3,5-di-t-butyl-4-hydroxybenzylethylphosphonate)calcium, 2,4-bis[ (octylthio)methyl]-o-cresol, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-t-butyl-6-(3 -t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di -t-pentylphenyl acrylate, 2,2'-methylenebis-(4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-4-ethylphenol, 1,1,3-tris(2 -Methyl-4-hydroxy-5-t-butylphenyl)butane, triethylene glycol-bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], tris(3,5-di -t-butyl-4hydroxybenzyl)isocyanurate, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 2,5,7,8-tetramethyl-2 (4',8',12'-trimethyltridecyl)chroman-6-ol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)- Examples include 1,3,5-triazine.
なお、フェノール系酸化防止剤では、フェノール水酸基に加え、以下の例示と重複するが、リン原子、硫黄原子、アミンのいずれかを少なくとも一つ以上同一分子中に含む化合物も列挙した。
As for the phenolic antioxidants, in addition to the phenol hydroxyl group, compounds containing at least one of a phosphorus atom, a sulfur atom, and an amine in the same molecule are also listed, although this overlaps with the examples below.
チオエーテル系酸化防止剤の具体例としては、ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート、ペンタエリスリチルテトラキス（３－ラウリルチオプロピオネート）、ジトリデシル－３，３’－チオジプロピオネート、２－メルカプトベンズイミダゾール、４，４’－チオビス（６－ｔ－ブチル－３－メチルフェノール）、２，２－チオ－ジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、４，６－ビス（ドデシルチオメチル）－ｏ－クレゾール、２，４－１ビス［（オクチルチオ）メチル］－ｏ－クレゾール、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン等が挙げられる。
Specific examples of thioether antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaerythyl. Lythyltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis(6-t-butyl-3-methylphenol), 2 , 2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,6-bis(dodecylthiomethyl)-o-cresol, 2,4-1bis [(octylthio)methyl]-o-cresol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, etc. Can be mentioned.
アミン系酸化防止剤の具体例としては、Ｎ，Ｎ’－ジアリル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジ－ｓｅｃ－ブチル－ｐ－フェニレンジアミン、オクチル化ジフェニルアミン、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン等が挙げられる。
Specific examples of amine antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, and 2,4-bis-( Examples include n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine.
ホスファイト系酸化防止剤の具体例としては、トリスノニルフェニルホスファイト、トリフェニルホスファイト、ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）カルシウム、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、ジエチル［〔３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル〕メチル］ホスホネート等が挙げられる。
Specific examples of phosphite-based antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, bis(3,5-di-t-butyl-4-hydroxybenzyl ethylphosphonate) calcium, tris(2,4 -di-t-butylphenyl) phosphite, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, and the like.
また、酸化防止剤としては、各種市販品を用いることもでき、そのような市販品としては、例えば、（株）ＡＤＥＫＡ製のアデカスタブＡＯ－６０、アデカスタブＡＯ－５０、アデカスタブＡＯ－８０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－４１２Ｓ、アデカスタブＬＡ－５２、アデカスタブＬＡ－５７、アデカスタブＬＡ－６３Ｐ、アデカスタブＬＡ－６８、アデカスタブＬＡ－７２、アデカスタブＬＡ－７７Ｙ、アデカスタブＬＡ－７７Ｇ、アデカスタブＬＡ－８１、アデカスタブＬＡ－８２、アデカスタブＬＡ－８７、アデカスタブＬＡ－４０２ＡＦ、アデカスタブＬＡ－５０２ＸＰ、アデカスタブ２１１２、アデカスタブＰＥＰ－３６；ビーエーエスエフ（ＢＡＳＦ）ジャパン（株）製のイルガノックス１０１０、イルガノックス１０１０ＦＦ、イルガノックス１０３５、イルガノックス１０３５ＦＦ、イルガノックス１０７６、イルガノックス１０７６ＦＦ、イルガノックス１０９８、イルガノックス１１３５、イルガノックス１３３０、イルガノックス１７２６、イルガノックス１４２５ＷＬ、イルガノックス１５２０Ｌ、イルガノックス２４５、イルガノックス２４５ＦＦ、イルガノックス２５９、イルガノックス３１１４、イルガノックス５０５７、イルガノックス５６５、イルガフォス１６８；住友化学（株）製スミライザー ＧＡ－８０、スミライザー ＭＤＰ－Ｓ、スミライザー ＷＸ－Ｒ、スミライザー ＷＸ－ＲＣ、スミライザー ＴＰ－Ｄ；住化ケムテックス（株）製Ｓｕｍｉｌｉｚｅｒ ＢＢＭ－Ｓ等が挙げられる。
Furthermore, various commercially available products can be used as the antioxidant, and examples of such commercially available products include ADEKA STAB AO-60, ADEKA STAB AO-50, ADEKA STAB AO-80, and ADEKA STAB AO manufactured by ADEKA Corporation. -330, ADK STAB AO-412S, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA -82, ADK STAB LA-87, ADK STAB LA-402AF, ADK STAB LA-502XP, ADK STAB 2112, ADK STAB PEP-36; Irganox 1010, Irganox 1010FF, Irganox 1035, Irga manufactured by BASF Japan Co., Ltd. Nox 1035FF, Irganox 1076, Irganox 1076FF, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259, Irganox 3114 , Irganox 5057, Irganox 565, Irgafoss 168; manufactured by Sumitomo Chemical Co., Ltd. Sumilizer GA-80, Sumilizer MDP-S, Sumilizer WX-R, Sumilizer WX-RC, Sumilizer TP-D; manufactured by Sumika Chemtex Co., Ltd. Examples include Sumilizer BBM-S.
以上で示した各酸化防止剤は、１種単独で用いても、２種以上を組み合わせて用いてもよく、２種以上を併用することが着色防止効果を向上できる点から好ましい。中でも、フェノール系酸化防止剤とチオエーテル系酸化防止剤とを併用することがより好ましい。酸化防止剤の種類の数の上限は特に限定されないが、例えば３種以下の酸化防止剤を併用できる。
Each of the antioxidants shown above may be used alone or in combination of two or more types, and it is preferable to use two or more types in combination because it can improve the coloring prevention effect. Among these, it is more preferable to use a phenolic antioxidant and a thioether antioxidant in combination. Although the upper limit of the number of types of antioxidants is not particularly limited, for example, three or less types of antioxidants can be used in combination.
（Ｅ）成分の配合量は、（Ａ）成分１００質量部に対して、０．０１～１質量部が好ましく、０．１～０．５質量部がより好ましい。このような範囲であればより良好な着色防止効果が得られる。
The blending amount of component (E) is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, per 100 parts by mass of component (A). Within this range, a better coloring prevention effect can be obtained.
［反応制御剤］
本発明のシリコーン感圧接着剤組成物には、（Ｄ）成分のヒドロシリル化反応触媒に対して反応制御効果を持つ公知の反応制御剤を使用してもよい。反応制御剤としては、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、１，１，ジメチル－１－トリメチルシロキシ－エチンなどが挙げられ、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－エチンである。 [Reaction control agent]
In the silicone pressure-sensitive adhesive composition of the present invention, a known reaction control agent having a reaction control effect on the hydrosilylation reaction catalyst of component (D) may be used. As a reaction control agent, 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-tetra Examples include methyl-1,3-divinyldisiloxane, 1,1,dimethyl-1-trimethylsiloxy-ethyne, and preferred are 1-ethynylcyclohexanol and 1,1,dimethyl-1-trimethylsiloxy-ethyne. .
本発明のシリコーン感圧接着剤組成物には、（Ｄ）成分のヒドロシリル化反応触媒に対して反応制御効果を持つ公知の反応制御剤を使用してもよい。反応制御剤としては、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、１，１，ジメチル－１－トリメチルシロキシ－エチンなどが挙げられ、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－エチンである。 [Reaction control agent]
In the silicone pressure-sensitive adhesive composition of the present invention, a known reaction control agent having a reaction control effect on the hydrosilylation reaction catalyst of component (D) may be used. As a reaction control agent, 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-tetra Examples include methyl-1,3-divinyldisiloxane, 1,1,dimethyl-1-trimethylsiloxy-ethyne, and preferred are 1-ethynylcyclohexanol and 1,1,dimethyl-1-trimethylsiloxy-ethyne. .
［有機溶剤］
本発明のシリコーン感圧接着剤組成物には、上記（Ａ）～（Ｅ）成分および必要に応じて添加されるその他の成分を混合する目的及び／又はシリコーン感圧接着剤組成物の粘度を調整する目的で、有機溶剤を添加してもよい。有機溶剤の具体例としては、トルエン、キシレン等の芳香族系溶剤、ヘプタン、オクタン、イソパラフィン等の脂肪族系溶剤、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等が挙げられる。 [Organic solvent]
The silicone pressure-sensitive adhesive composition of the present invention may be used for the purpose of mixing components (A) to (E) and other components added as necessary, and/or for controlling the viscosity of the silicone pressure-sensitive adhesive composition. An organic solvent may be added for the purpose of adjustment. Specific examples of organic solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as heptane, octane, and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and isobutyl acetate. Examples include solvents, ether solvents such as diisopropyl ether and 1,4-dioxane, and mixed solvents thereof.
本発明のシリコーン感圧接着剤組成物には、上記（Ａ）～（Ｅ）成分および必要に応じて添加されるその他の成分を混合する目的及び／又はシリコーン感圧接着剤組成物の粘度を調整する目的で、有機溶剤を添加してもよい。有機溶剤の具体例としては、トルエン、キシレン等の芳香族系溶剤、ヘプタン、オクタン、イソパラフィン等の脂肪族系溶剤、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等が挙げられる。 [Organic solvent]
The silicone pressure-sensitive adhesive composition of the present invention may be used for the purpose of mixing components (A) to (E) and other components added as necessary, and/or for controlling the viscosity of the silicone pressure-sensitive adhesive composition. An organic solvent may be added for the purpose of adjustment. Specific examples of organic solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as heptane, octane, and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and isobutyl acetate. Examples include solvents, ether solvents such as diisopropyl ether and 1,4-dioxane, and mixed solvents thereof.
［その他の成分］
本発明のシリコーン感圧接着剤組成物には、必要に応じて（Ａ）～（Ｅ）以外の成分を添加してもよい。具体的には、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、ヒンダードアミン化合物などの耐熱助剤、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などが挙げられる。 [Other ingredients]
Components other than (A) to (E) may be added to the silicone pressure-sensitive adhesive composition of the present invention, if necessary. Specifically, non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane, heat-resistant aids such as hindered amine compounds, light stabilizers such as triazoles and benzophenones, phosphoric acid esters, and halogens. and antimony-based flame retardants, and antistatic agents such as cationic activators, anionic activators, and nonionic activators.
本発明のシリコーン感圧接着剤組成物には、必要に応じて（Ａ）～（Ｅ）以外の成分を添加してもよい。具体的には、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、ヒンダードアミン化合物などの耐熱助剤、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などが挙げられる。 [Other ingredients]
Components other than (A) to (E) may be added to the silicone pressure-sensitive adhesive composition of the present invention, if necessary. Specifically, non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane, heat-resistant aids such as hindered amine compounds, light stabilizers such as triazoles and benzophenones, phosphoric acid esters, and halogens. and antimony-based flame retardants, and antistatic agents such as cationic activators, anionic activators, and nonionic activators.
［シリコーン感圧接着剤］
本発明のシリコーン感圧接着剤組成物は、硬化させることによりシリコーン感圧接着剤とすることができる。シリコーン感圧接着剤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。 [Silicone pressure sensitive adhesive]
The silicone pressure-sensitive adhesive composition of the present invention can be made into a silicone pressure-sensitive adhesive by curing. The curing conditions for the silicone pressure-sensitive adhesive composition are appropriately adjusted depending on the coating amount, etc., but are typically 80 to 130° C. and 30 seconds to 3 minutes.
本発明のシリコーン感圧接着剤組成物は、硬化させることによりシリコーン感圧接着剤とすることができる。シリコーン感圧接着剤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。 [Silicone pressure sensitive adhesive]
The silicone pressure-sensitive adhesive composition of the present invention can be made into a silicone pressure-sensitive adhesive by curing. The curing conditions for the silicone pressure-sensitive adhesive composition are appropriately adjusted depending on the coating amount, etc., but are typically 80 to 130° C. and 30 seconds to 3 minutes.
本発明のシリコーン感圧接着剤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。
The adherend of the silicone pressure-sensitive adhesive of the present invention is not particularly limited. For example, metals such as stainless steel, copper, and iron, metals whose surfaces have been plated or rust-proofed, glass, ceramics, ceramics, resins such as polytetrafluoroethylene, polyimide, epoxy, and novolac resins, and these materials. Several of them can be adhered onto a composite material.
本発明のシリコーン感圧接着剤は、ＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ｍｉｎでの粘着力が、５．０Ｎ／２５ｍｍ以上であることが好ましい。このようなシリコーン感圧接着剤は、粘着力が十分なものとなる。本発明のシリコーン感圧接着剤は、上記引張試験において、室温２３℃、引張り速度３００ｍｍ／ｍｉｎでの粘着力が、５．０Ｎ／２５ｍｍ以上１５Ｎ／２５ｍｍ以下であることがより好ましい。
The silicone pressure-sensitive adhesive of the present invention preferably has an adhesive force of 5.0 N/25 mm or more at a room temperature of 23° C. and a pulling speed of 300 mm/min in a 180° peel test specified in JIS Z 0237. . Such a silicone pressure sensitive adhesive has sufficient adhesive strength. The silicone pressure-sensitive adhesive of the present invention preferably has an adhesive force of 5.0 N/25 mm or more and 15 N/25 mm or less at a room temperature of 23° C. and a tensile speed of 300 mm/min in the above tensile test.
また、本発明のシリコーン感圧接着剤は、上記引き剥がし試験後の被着面に対するポリエチレンテレフタレートフィルムのＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ ｍｉｎでの粘着力が０．１Ｎ／２５ｍｍ以下であることが好ましい。このようなシリコーン感圧接着剤は、剥離性に優れるものとなる。本発明のシリコーン感圧接着剤は、上記引き剥がし試験後の被着面に対するポリエチレンテレフタレートフィルムの上記１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ ｍｉｎでの粘着力が０Ｎ／２５ｍｍ以上０．１Ｎ／２５ｍｍ以下であることがより好ましい。
In addition, the silicone pressure-sensitive adhesive of the present invention was tested in a 180° peel test specified in JIS Z 0237 of a polyethylene terephthalate film on the adhered surface after the above-mentioned peel test at a room temperature of 23°C and a tensile speed of 300 mm/min. It is preferable that the adhesive force is 0.1 N/25 mm or less. Such a silicone pressure-sensitive adhesive has excellent releasability. The silicone pressure-sensitive adhesive of the present invention has an adhesion strength of 0 N/25 mm or more at a room temperature of 23°C and a pulling speed of 300 mm/min in the above 180° peel test of a polyethylene terephthalate film on the adhered surface after the above peel test. More preferably, it is 0.1 N/25 mm or less.
また、本発明のシリコーン感圧接着剤は、ＪＩＳ Ｚ ８７８１－４に規定されるＬ＊ａ＊ｂ＊表色系における厚み３００μｍでのｂ＊値が０．１５以下であることが好ましい。ｂ＊値が０．１５以下であることは、硬化層が黄色に着色していないことを表しており、ディスプレイ用途等に感圧接着剤として使用する場合の要求特性に合致している。なお、ｂ＊値が０．１５以下であることは硬化層が実質的に透明であることも示している。本発明のシリコーン感圧接着剤は、ｂ＊値が－０．１５以上０．１５以下であることがより好ましい。
Further, the silicone pressure-sensitive adhesive of the present invention preferably has a b * value of 0.15 or less at a thickness of 300 μm in the L * a * b * color system defined in JIS Z 8781-4. A b * value of 0.15 or less indicates that the cured layer is not colored yellow, and meets the required characteristics when used as a pressure-sensitive adhesive for display applications, etc. Note that the b * value of 0.15 or less also indicates that the cured layer is substantially transparent. The silicone pressure-sensitive adhesive of the present invention more preferably has a b * value of -0.15 or more and 0.15 or less.
［感圧接着フィルム］
本発明のシリコーン感圧接着剤組成物は、各種フィルム基材に塗工し硬化させることにより、感圧接着剤層を備えた感圧接着フィルムを製造することができる。 [Pressure sensitive adhesive film]
The silicone pressure-sensitive adhesive composition of the present invention can be applied to various film substrates and cured to produce a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer.
本発明のシリコーン感圧接着剤組成物は、各種フィルム基材に塗工し硬化させることにより、感圧接着剤層を備えた感圧接着フィルムを製造することができる。 [Pressure sensitive adhesive film]
The silicone pressure-sensitive adhesive composition of the present invention can be applied to various film substrates and cured to produce a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer.
基材としては、ポリエチレンテレフタレート、ポリイミド、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。
Base materials include plastic films such as polyethylene terephthalate, polyimide, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, and polyvinyl chloride; metal foils such as aluminum foil and copper foil; Examples include paper such as Japanese paper, synthetic paper, and polyethylene laminate paper, cloth, glass fiber, and composite substrates formed by laminating multiple of these materials.
基材とシリコーン感圧接着剤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が、作業工程の簡略化の観点から、これらの方法を用いないことが好ましい。
In order to improve the adhesion between the base material and the silicone pressure-sensitive adhesive layer, a base material that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used, but from the viewpoint of simplifying the work process, these It is preferable not to use this method.
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、硬化した後のシリコーン感圧接着剤層の厚みとして１～５００μｍ、表示装置用部材としては１００～３００μｍ、マスキングテープ用途としては５～５０μｍであることが好ましい。
Coating may be performed using any known coating method, including comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, and dipping. Examples include coating, cast coating, etc. The coating amount is set depending on the application, but typically the thickness of the silicone pressure-sensitive adhesive layer after curing is 1 to 500 μm, for display device members 100 to 300 μm, and for masking tape applications. The thickness is preferably 5 to 50 μm.
上記のように基材に直接塗工して感圧接着フィルム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シリコーン感圧接着剤組成物を塗工して硬化を行った後、基材を貼り合わせてシリコーン感圧接着剤層を転写することによって感圧接着フィルムを製造してもよい。
A pressure-sensitive adhesive film may be produced by applying the silicone pressure-sensitive adhesive composition directly to a substrate as described above, or a silicone pressure-sensitive adhesive composition may be applied to a release film or release paper with a release coating and cured. After this, a pressure sensitive adhesive film may be produced by laminating the substrates together and transferring the silicone pressure sensitive adhesive layer.
［画像表示装置］
また、本発明のシリコーン感圧接着剤組成物は、硬化させることにより感圧接着剤層を形成し、それを備えた画像表示装置を製造することができる。このような画像表示装置は、信頼性および視認性に優れるものとなる。 [Image display device]
Further, the silicone pressure-sensitive adhesive composition of the present invention can be cured to form a pressure-sensitive adhesive layer, and an image display device including the same can be manufactured. Such an image display device has excellent reliability and visibility.
また、本発明のシリコーン感圧接着剤組成物は、硬化させることにより感圧接着剤層を形成し、それを備えた画像表示装置を製造することができる。このような画像表示装置は、信頼性および視認性に優れるものとなる。 [Image display device]
Further, the silicone pressure-sensitive adhesive composition of the present invention can be cured to form a pressure-sensitive adhesive layer, and an image display device including the same can be manufactured. Such an image display device has excellent reliability and visibility.
［シリコーン感圧接着剤の評価方法］
本発明のシリコーン組成物は、剥離性（糊残りの少なさ）に優れる。剥離性は、下記の（１）～（４）の工程を備える評価方法により評価することができる。このようなシリコーン感圧接着剤の評価方法であれば、目視や指触等の感覚によらず、剥離性を定量的に評価する事ができる。 [Evaluation method of silicone pressure sensitive adhesive]
The silicone composition of the present invention has excellent releasability (less adhesive residue). The releasability can be evaluated by an evaluation method comprising the following steps (1) to (4). With this method of evaluating silicone pressure-sensitive adhesives, it is possible to quantitatively evaluate the releasability without relying on visual observation, finger touch, or other sensations.
本発明のシリコーン組成物は、剥離性（糊残りの少なさ）に優れる。剥離性は、下記の（１）～（４）の工程を備える評価方法により評価することができる。このようなシリコーン感圧接着剤の評価方法であれば、目視や指触等の感覚によらず、剥離性を定量的に評価する事ができる。 [Evaluation method of silicone pressure sensitive adhesive]
The silicone composition of the present invention has excellent releasability (less adhesive residue). The releasability can be evaluated by an evaluation method comprising the following steps (1) to (4). With this method of evaluating silicone pressure-sensitive adhesives, it is possible to quantitatively evaluate the releasability without relying on visual observation, finger touch, or other sensations.
（１）シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する第１の工程と、
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程 (1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程 (1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
工程（１）は、シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する工程であり、感圧接着フィルムの製造方法としては特に限定されないが、例えば上記で挙げられた製造方法により感圧接着フィルムを準備することができる。また、感圧接着剤層の厚みは、特に限定されるものではないが、３０μｍ程度とすることが好ましい。
Step (1) is a step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material, and the method for producing the pressure-sensitive adhesive film is particularly limited. However, pressure-sensitive adhesive films can be prepared, for example, by the production methods listed above. Further, the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably about 30 μm.
工程（２）は、上記感圧接着フィルムの感圧接着剤層を、ステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎでステンレス鋼板に対して１８０°に引き剥がす工程である。
Step (2) is a step in which the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is pressure-bonded to the surface of the stainless steel plate, and then peeled off at 180° to the stainless steel plate at a tensile speed of 300 mm/min.
本工程における圧着および引き剥がし条件は、ＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験に準じるが、必要に応じて圧着後に養生工程を設けてもよい。
The crimping and peeling conditions in this step are in accordance with the 180° peeling test specified in JIS Z 0237, but a curing step may be provided after crimping if necessary.
工程（３）は、上記工程（２）の後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内にポリエチレンテレフタレートフィルムを圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する工程である。
Step (3) is to pressure-bond a polyethylene terephthalate film within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after step (2), and then apply the polyethylene terephthalate film at a tensile speed of 300 mm/min. This is a process of measuring the adhesive force when peeled off at 180° to a stainless steel plate.
前記工程（２）の後のステンレス鋼板に感圧接着剤層の残存（糊残り）が発生していた場合、工程（３）においてポリエチレンテレフタレートフィルムを引き剥がす際に粘着力が発生する。なお、本工程における圧着および引き剥がし条件は、ＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験に準じるが、必要に応じてポリエチレンテレフタレートフィルムを圧着した後に養生工程を設けてもよい。
If there is any residual pressure sensitive adhesive layer (adhesive residue) on the stainless steel plate after step (2), adhesive force will be generated when the polyethylene terephthalate film is peeled off in step (3). Note that the crimping and peeling conditions in this step are based on the 180° peeling test specified in JIS Z 0237, but if necessary, a curing step may be provided after the polyethylene terephthalate film is crimped.
工程（４）は、上記工程（３）における粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する工程であり、前記粘着力が０．１Ｎ／２５ｍｍ以下を満たすか否かによってシリコーン感圧接着剤の良否を判定する工程であることが好ましい。このような評価方法であれば、シリコーン感圧接着剤の剥離性についてより実用的な評価を行うことができる。
Step (4) is a step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive force in step (3), and depending on whether the adhesive force satisfies 0.1 N/25 mm or less, the silicone pressure-sensitive adhesive Preferably, this is a step of determining the quality of the pressure-sensitive adhesive. With such an evaluation method, it is possible to perform a more practical evaluation of the releasability of silicone pressure-sensitive adhesives.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明はこれによって限定されるものではない。なお、粘度は、Ｂ型回転粘度計を用いて測定した２５℃における値であり、重量平均分子量（Ｍｗ）は、トルエンを展開溶媒として用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算値である。
Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The viscosity is a value measured at 25°C using a B-type rotational viscometer, and the weight average molecular weight (Mw) is a polystyrene equivalent value measured by gel permeation chromatography (GPC) using toluene as a developing solvent. be.
［実施例１～１３、比較例１～５］
表１及び表２に示した配合（質量部）で下記の各成分を混合し、シリコーン感圧接着剤組成物を調製した。 [Examples 1 to 13, Comparative Examples 1 to 5]
The following components were mixed in the formulations (parts by mass) shown in Tables 1 and 2 to prepare a silicone pressure-sensitive adhesive composition.
表１及び表２に示した配合（質量部）で下記の各成分を混合し、シリコーン感圧接着剤組成物を調製した。 [Examples 1 to 13, Comparative Examples 1 to 5]
The following components were mixed in the formulations (parts by mass) shown in Tables 1 and 2 to prepare a silicone pressure-sensitive adhesive composition.
（Ａ）成分：
（Ａ－１）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００２０モル／１００ｇ）であり、ｎ＝６，３００であり、３０質量％トルエン溶液の粘度が２５，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－２）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００６８モル／１００ｇ）であり、ｎ＝６，６００であり、３０質量％トルエン溶液の粘度が１９，５００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－５）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００１２モル／１００ｇ）であり、ｎ＝７，２００であり、３０質量％トルエン溶液の粘度が２４，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－６）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００９４モル／１００ｇ）であり、ｎ＝６，３００であり、３０質量％トルエン溶液の粘度が１８，１００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－７）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００３０モル／１００ｇ）であり、ｎ＝３，２００であり、３０質量％トルエン溶液の粘度が１，４５８ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－８）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００２１モル／１００ｇ）であり、ｎ＝１４，５００であり、３０質量％トルエン溶液の粘度が３５，１００ｍＰａ・ｓである直鎖状オルガノポリシロキサン (A) Component:
(A-1) In the average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0020 mol/100 g), n = 6,300, and the viscosity of the 30% by mass toluene solution is 25,000 mPa・s Linear organopolysiloxane (A-2) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0068 mol/100 g), and n = 6 , 600, and the viscosity of a 30% by mass toluene solution is 19,500 mPa・s. In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0012 mol/100 g), n = 7,200, and the viscosity of a 30% by mass toluene solution is 24,000 mPa s (A-6) above average formula (1) , R 1 is a methyl group and a vinyl group (vinyl value 0.0094 mol/100 g), n = 6,300, and the viscosity of a 30% by mass toluene solution is 18,100 mPa·s. Polysiloxane (A-7) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0030 mol/100 g), n = 3,200, and a 30% by mass toluene solution. Linear organopolysiloxane (A-8) having a viscosity of 1,458 mPa·s In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0021 mol/100 g), and n = 14,500, and the viscosity of a 30% by mass toluene solution is 35,100 mPa・s.
（Ａ－１）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００２０モル／１００ｇ）であり、ｎ＝６，３００であり、３０質量％トルエン溶液の粘度が２５，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－２）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００６８モル／１００ｇ）であり、ｎ＝６，６００であり、３０質量％トルエン溶液の粘度が１９，５００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－５）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００１２モル／１００ｇ）であり、ｎ＝７，２００であり、３０質量％トルエン溶液の粘度が２４，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－６）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００９４モル／１００ｇ）であり、ｎ＝６，３００であり、３０質量％トルエン溶液の粘度が１８，１００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－７）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００３０モル／１００ｇ）であり、ｎ＝３，２００であり、３０質量％トルエン溶液の粘度が１，４５８ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ－８）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００２１モル／１００ｇ）であり、ｎ＝１４，５００であり、３０質量％トルエン溶液の粘度が３５，１００ｍＰａ・ｓである直鎖状オルガノポリシロキサン (A) Component:
(A-1) In the average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0020 mol/100 g), n = 6,300, and the viscosity of the 30% by mass toluene solution is 25,000 mPa・s Linear organopolysiloxane (A-2) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0068 mol/100 g), and n = 6 , 600, and the viscosity of a 30% by mass toluene solution is 19,500 mPa・s. In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0012 mol/100 g), n = 7,200, and the viscosity of a 30% by mass toluene solution is 24,000 mPa s (A-6) above average formula (1) , R 1 is a methyl group and a vinyl group (vinyl value 0.0094 mol/100 g), n = 6,300, and the viscosity of a 30% by mass toluene solution is 18,100 mPa·s. Polysiloxane (A-7) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0030 mol/100 g), n = 3,200, and a 30% by mass toluene solution. Linear organopolysiloxane (A-8) having a viscosity of 1,458 mPa·s In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0021 mol/100 g), and n = 14,500, and the viscosity of a 30% by mass toluene solution is 35,100 mPa・s.
比較成分：
（Ａ’－３）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．０００４モル／１００ｇ）であり、ｎ＝８，０００であり、３０質量％トルエン溶液の粘度が２３，５００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ’－４）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００２５モル／１００ｇ）であり、ｎ＝１，２００であり、粘度が１１３，０００Ｐａ・ｓである直鎖状オルガノポリシロキサン
（Ａ’－９）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．０１２３モル／１００ｇ）であり、ｎ＝６，０００であり、３０質量％トルエン溶液の粘度が１２，１１０ｍＰａ・ｓである直鎖状オルガノポリシロキサン Comparative ingredients:
(A'-3) In the average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0004 mol/100 g), n = 8,000, and the viscosity of a 30% by mass toluene solution is linear organopolysiloxane (A'-4) whose average is 23,500 mPa·s (A'-4) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0025 mol/100 g), and n = 1,200 and a viscosity of 113,000 Pa·s (A'-9) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0123 mol/100g), n=6,000, and the viscosity of a 30% by mass toluene solution is 12,110 mPa·s.
（Ａ’－３）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．０００４モル／１００ｇ）であり、ｎ＝８，０００であり、３０質量％トルエン溶液の粘度が２３，５００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
（Ａ’－４）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．００２５モル／１００ｇ）であり、ｎ＝１，２００であり、粘度が１１３，０００Ｐａ・ｓである直鎖状オルガノポリシロキサン
（Ａ’－９）前記平均式（１）において、Ｒ１がメチル基及びビニル基（ビニル価０．０１２３モル／１００ｇ）であり、ｎ＝６，０００であり、３０質量％トルエン溶液の粘度が１２，１１０ｍＰａ・ｓである直鎖状オルガノポリシロキサン Comparative ingredients:
(A'-3) In the average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0004 mol/100 g), n = 8,000, and the viscosity of a 30% by mass toluene solution is linear organopolysiloxane (A'-4) whose average is 23,500 mPa·s (A'-4) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0025 mol/100 g), and n = 1,200 and a viscosity of 113,000 Pa·s (A'-9) In the above average formula (1), R 1 is a methyl group and a vinyl group (vinyl value 0.0123 mol/100g), n=6,000, and the viscosity of a 30% by mass toluene solution is 12,110 mPa·s.
（Ｂ）成分：
（Ｂ－１）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．００５５モル／ｇ）であり、ｍ＝９０であり、粘度が１００ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン
（Ｂ－３）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．００１９モル／ｇ）であり、ｍ＝２８であり、粘度が２５ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン
（Ｂ－４）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．００３５モル／ｇ）であり、ｍ＝３２であり、粘度が２７ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン
（Ｂ－５）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．０１７モル／ｇ）であり、ｍ＝３８であり、粘度が２０ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン (B) Component:
(B-1) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0055 mol/g), m = 90, and a linear chain having a viscosity of 100 mPa・s Organohydrogenpolysiloxane (B-3) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0019 mol/g), m = 28, and a viscosity of 25 mPa・S linear organohydrogenpolysiloxane (B-4) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0035 mol/g), and m = 32 Linear organohydrogenpolysiloxane (B-5) with a viscosity of 27 mPa·s In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.017 mol/g) , m = 38, and a linear organohydrogenpolysiloxane with a viscosity of 20 mPa・s
（Ｂ－１）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．００５５モル／ｇ）であり、ｍ＝９０であり、粘度が１００ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン
（Ｂ－３）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．００１９モル／ｇ）であり、ｍ＝２８であり、粘度が２５ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン
（Ｂ－４）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．００３５モル／ｇ）であり、ｍ＝３２であり、粘度が２７ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン
（Ｂ－５）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．０１７モル／ｇ）であり、ｍ＝３８であり、粘度が２０ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン (B) Component:
(B-1) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0055 mol/g), m = 90, and a linear chain having a viscosity of 100 mPa・s Organohydrogenpolysiloxane (B-3) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0019 mol/g), m = 28, and a viscosity of 25 mPa・S linear organohydrogenpolysiloxane (B-4) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0035 mol/g), and m = 32 Linear organohydrogenpolysiloxane (B-5) with a viscosity of 27 mPa·s In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.017 mol/g) , m = 38, and a linear organohydrogenpolysiloxane with a viscosity of 20 mPa・s
比較成分：
（Ｂ’－２）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．０００４モル／ｇ）であり、ｍ＝４５であり、粘度が５０ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン Comparative ingredients:
(B'-2) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0004 mol/g), m = 45, and the viscosity is 50 mPa・s. Chain organohydrogen polysiloxane
（Ｂ’－２）前記平均式（２）において、Ｒ２がメチル基及び水素原子（ヒドロシリル基量０．０００４モル／ｇ）であり、ｍ＝４５であり、粘度が５０ｍＰａ・ｓである直鎖状オルガノハイドロジェンポリシロキサン Comparative ingredients:
(B'-2) In the above average formula (2), R 2 is a methyl group and a hydrogen atom (hydrosilyl group amount 0.0004 mol/g), m = 45, and the viscosity is 50 mPa・s. Chain organohydrogen polysiloxane
（Ｃ）成分：
（Ｃ－１）（（ＣＨ３）３ＳｉＯ１／２）0.67（ＳｉＯ４／２）1.00で表される構成単位比を有し、Ｍｗが３，４００である三次元網目状オルガノポリシロキサンの６０質量％トルエン溶液
（Ｃ－２）（（ＣＨ３）３ＳｉＯ１／２）1.75（ＳｉＯ４／２）1.00で表される構成単位比を有し、Ｍｗが７，４００である三次元網目状オルガノポリシロキサンの６０質量％トルエン溶液 (C) Component:
(C-1) A three-dimensional network organopolysiloxane having a constituent unit ratio expressed as ((CH 3 ) 3 SiO 1/2 ) 0.67 (SiO 4/2 ) 1.00 and an Mw of 3,400. 60% by mass toluene solution (C-2) ((CH 3 ) 3 SiO 1/2 ) 1.75 (SiO 4/2 ) A three-dimensional network having a constituent unit ratio expressed as 1.00 and having an Mw of 7,400. 60% by mass toluene solution of organopolysiloxane
（Ｃ－１）（（ＣＨ３）３ＳｉＯ１／２）0.67（ＳｉＯ４／２）1.00で表される構成単位比を有し、Ｍｗが３，４００である三次元網目状オルガノポリシロキサンの６０質量％トルエン溶液
（Ｃ－２）（（ＣＨ３）３ＳｉＯ１／２）1.75（ＳｉＯ４／２）1.00で表される構成単位比を有し、Ｍｗが７，４００である三次元網目状オルガノポリシロキサンの６０質量％トルエン溶液 (C) Component:
(C-1) A three-dimensional network organopolysiloxane having a constituent unit ratio expressed as ((CH 3 ) 3 SiO 1/2 ) 0.67 (SiO 4/2 ) 1.00 and an Mw of 3,400. 60% by mass toluene solution (C-2) ((CH 3 ) 3 SiO 1/2 ) 1.75 (SiO 4/2 ) A three-dimensional network having a constituent unit ratio expressed as 1.00 and having an Mw of 7,400. 60% by mass toluene solution of organopolysiloxane
（Ｄ）成分：
（Ｄ－１）白金触媒：ＣＡＴ－ＰＬ－５０Ｔ（信越化学工業（株）製） (D) Component:
(D-1) Platinum catalyst: CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.)
（Ｄ－１）白金触媒：ＣＡＴ－ＰＬ－５０Ｔ（信越化学工業（株）製） (D) Component:
(D-1) Platinum catalyst: CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.)
（Ｅ）成分：
（Ｅ－１）フェノール系酸化防止剤：イルガノックス１０１０（ＢＡＳＦジャパン（株）製）
（Ｅ－２）チオエーテル系酸化防止剤：アデカスタブＡＯ－４１２Ｓ（（株）ＡＤＥＫＡ製）
（Ｅ－３）ホスファイト系酸化防止剤：アデカスタブＰＥＰ－３６（（株）ＡＤＥＫＡ製） (E) Component:
(E-1) Phenolic antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.)
(E-2) Thioether antioxidant: ADEKA STAB AO-412S (manufactured by ADEKA Co., Ltd.)
(E-3) Phosphite antioxidant: ADEKA STAB PEP-36 (manufactured by ADEKA Co., Ltd.)
（Ｅ－１）フェノール系酸化防止剤：イルガノックス１０１０（ＢＡＳＦジャパン（株）製）
（Ｅ－２）チオエーテル系酸化防止剤：アデカスタブＡＯ－４１２Ｓ（（株）ＡＤＥＫＡ製）
（Ｅ－３）ホスファイト系酸化防止剤：アデカスタブＰＥＰ－３６（（株）ＡＤＥＫＡ製） (E) Component:
(E-1) Phenolic antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.)
(E-2) Thioether antioxidant: ADEKA STAB AO-412S (manufactured by ADEKA Co., Ltd.)
(E-3) Phosphite antioxidant: ADEKA STAB PEP-36 (manufactured by ADEKA Co., Ltd.)
その他成分：
（Ｆ－１）反応制御剤：エチニルシクロヘキサノール Other ingredients:
(F-1) Reaction control agent: ethynylcyclohexanol
（Ｆ－１）反応制御剤：エチニルシクロヘキサノール Other ingredients:
(F-1) Reaction control agent: ethynylcyclohexanol
得られたシリコーン感圧接着剤組成物について、下記の方法により粘着力、剥離性及びｂ＊値の評価を行った結果を表３及び表４に示した。
The resulting silicone pressure-sensitive adhesive composition was evaluated for adhesive strength, peelability, and b * value by the following methods, and the results are shown in Tables 3 and 4.
［粘着力］
シリコーン感圧接着剤組成物を、硬化後の厚みが３０μｍになるように幅２５ｍｍのポリエチレンテレフタレートフィルム上に塗布した後、１３０℃で１分加熱して感圧接着フィルムを作製した。この感圧接着フィルムを、ＪＩＳ Ｚ ０２３７に準じ質量２ｋｇのローラーを用いてステンレス鋼板に圧着した後、２５℃で２４時間養生した。養生した感圧接着フィルムを、室温２３℃、引張速度３００ｍｍ／ｍｉｎの１８０°引き剥がし試験によって、ステンレス鋼板から引き剥がすのに要する力（Ｎ／２５ｍｍ）を測定した。 [Adhesive force]
The silicone pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate film having a width of 25 mm so that the thickness after curing would be 30 μm, and then heated at 130° C. for 1 minute to produce a pressure-sensitive adhesive film. This pressure-sensitive adhesive film was pressure-bonded to a stainless steel plate using a roller weighing 2 kg according to JIS Z 0237, and then cured at 25° C. for 24 hours. The force (N/25 mm) required to peel the cured pressure-sensitive adhesive film from the stainless steel plate was measured by a 180° peel test at a room temperature of 23° C. and a pulling speed of 300 mm/min.
シリコーン感圧接着剤組成物を、硬化後の厚みが３０μｍになるように幅２５ｍｍのポリエチレンテレフタレートフィルム上に塗布した後、１３０℃で１分加熱して感圧接着フィルムを作製した。この感圧接着フィルムを、ＪＩＳ Ｚ ０２３７に準じ質量２ｋｇのローラーを用いてステンレス鋼板に圧着した後、２５℃で２４時間養生した。養生した感圧接着フィルムを、室温２３℃、引張速度３００ｍｍ／ｍｉｎの１８０°引き剥がし試験によって、ステンレス鋼板から引き剥がすのに要する力（Ｎ／２５ｍｍ）を測定した。 [Adhesive force]
The silicone pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate film having a width of 25 mm so that the thickness after curing would be 30 μm, and then heated at 130° C. for 1 minute to produce a pressure-sensitive adhesive film. This pressure-sensitive adhesive film was pressure-bonded to a stainless steel plate using a roller weighing 2 kg according to JIS Z 0237, and then cured at 25° C. for 24 hours. The force (N/25 mm) required to peel the cured pressure-sensitive adhesive film from the stainless steel plate was measured by a 180° peel test at a room temperature of 23° C. and a pulling speed of 300 mm/min.
［剥離性］
幅２５ｍｍのポリエチレンテレフタレートフィルムを、上記粘着力試験後のステンレス鋼板上の上記粘着テープを剥がした部分と重ね、ＪＩＳ Ｚ ０２３７に準じ質量２ｋｇのローラーを用いて圧着した後、２５℃で２４時間養生した。養生したポリエチレンテレフタレートフィルムを、室温２３℃、引張速度３００ｍｍ／ｍｉｎの１８０°引き剥がし試験によって、ステンレス鋼板から引き剥がすのに要する力（Ｎ／２５ｍｍ）を測定した。 [Releasability]
A polyethylene terephthalate film with a width of 25 mm was overlapped with the part of the stainless steel plate from which the adhesive tape had been peeled off after the adhesive force test, and the film was pressed using a roller weighing 2 kg according to JIS Z 0237, and then cured at 25°C for 24 hours. did. The force (N/25 mm) required to peel the cured polyethylene terephthalate film from the stainless steel plate was measured by a 180° peel test at a room temperature of 23° C. and a tensile speed of 300 mm/min.
幅２５ｍｍのポリエチレンテレフタレートフィルムを、上記粘着力試験後のステンレス鋼板上の上記粘着テープを剥がした部分と重ね、ＪＩＳ Ｚ ０２３７に準じ質量２ｋｇのローラーを用いて圧着した後、２５℃で２４時間養生した。養生したポリエチレンテレフタレートフィルムを、室温２３℃、引張速度３００ｍｍ／ｍｉｎの１８０°引き剥がし試験によって、ステンレス鋼板から引き剥がすのに要する力（Ｎ／２５ｍｍ）を測定した。 [Releasability]
A polyethylene terephthalate film with a width of 25 mm was overlapped with the part of the stainless steel plate from which the adhesive tape had been peeled off after the adhesive force test, and the film was pressed using a roller weighing 2 kg according to JIS Z 0237, and then cured at 25°C for 24 hours. did. The force (N/25 mm) required to peel the cured polyethylene terephthalate film from the stainless steel plate was measured by a 180° peel test at a room temperature of 23° C. and a tensile speed of 300 mm/min.
［ｂ＊値］
シリコーン組成物を硬化後の厚みが３００μｍになるようにガラス板上に塗布した後、６０℃で１時間放置した後、１３０℃で３分間硬化させ、サンプルを作成した。当該サンプルをＪＩＳ Ｚ ８７８１－４に規定されるＬ＊ａ＊ｂ＊表色系でｂ＊値を測定した。 [b * value]
The silicone composition was coated on a glass plate so as to have a thickness of 300 μm after curing, left at 60° C. for 1 hour, and then cured at 130° C. for 3 minutes to prepare a sample. The b * value of the sample was measured using the L * a * b * color system specified in JIS Z 8781-4.
シリコーン組成物を硬化後の厚みが３００μｍになるようにガラス板上に塗布した後、６０℃で１時間放置した後、１３０℃で３分間硬化させ、サンプルを作成した。当該サンプルをＪＩＳ Ｚ ８７８１－４に規定されるＬ＊ａ＊ｂ＊表色系でｂ＊値を測定した。 [b * value]
The silicone composition was coated on a glass plate so as to have a thickness of 300 μm after curing, left at 60° C. for 1 hour, and then cured at 130° C. for 3 minutes to prepare a sample. The b * value of the sample was measured using the L * a * b * color system specified in JIS Z 8781-4.
表３及び表４に示されるように、本発明のシリコーン感圧接着剤組成物を用いた実施例１～１３では、優れた粘着力及び剥離性（糊残りの少なさ）を示し、低いｂ＊値を有していた。また、酸化防止剤をそれぞれ１種単独で使用した実施例１，２と比較して、酸化防止剤を２種併用した実施例３～１３では、より低いｂ＊値を有している。
As shown in Tables 3 and 4, Examples 1 to 13 using the silicone pressure-sensitive adhesive compositions of the present invention exhibited excellent adhesive strength and peelability (little adhesive residue), and had a low b * It had a value. Furthermore, compared to Examples 1 and 2 in which one antioxidant was used alone, Examples 3 to 13 in which two antioxidants were used in combination had lower b * values.
中でも、フェノール系、チオエーテル系酸化防止剤を併用した実施例３、５～１３では、特に低いｂ＊値を有しており、着色が極めて少ないことが分かる。
Among them, Examples 3 and 5 to 13, in which phenol-based and thioether-based antioxidants were used in combination, had particularly low b * values, indicating that there was very little coloration.
一方、（Ａ）成分に代えてビニル価が０．００１０モル／１００ｇ未満であるオルガノポリシロキサンを用いた比較例１、ビニル価が０．０１０モル／１００ｇを超えるオルガノポリシロキサンを用いた比較例５、及び、前記（１）式においてｎの範囲を満たさないオルガノポリシロキサンを用いた比較例２では、粘着力が低くなっている。また、比較例１、比較例２、並びに、（Ｂ）成分に代えてヒドロシリル基量が０．００１０モル／ｇ未満であるヒドロシリル基を含む比較例３では、剥離性試験において引き剥がすのに要する力が高く、糊残りが発生したことが分かる。
On the other hand, Comparative Example 1 using an organopolysiloxane with a vinyl value of less than 0.0010 mol/100g in place of component (A), and Comparative Example using an organopolysiloxane with a vinyl value of more than 0.010 mol/100g. 5 and Comparative Example 2 using an organopolysiloxane that does not satisfy the range of n in formula (1) above, the adhesive strength is low. Moreover, in Comparative Example 1, Comparative Example 2, and Comparative Example 3 containing a hydrosilyl group in which the amount of hydrosilyl group is less than 0.0010 mol/g in place of component (B), the amount required for peeling off in the peelability test was It can be seen that the strength was high and adhesive residue was generated.
また、酸化防止剤を添加していない比較例４では、ｂ＊値が０．１５を超え、実質的に着色しており透明性が損なわれる結果となった。
Furthermore, in Comparative Example 4 in which no antioxidant was added, the b * value exceeded 0.15, resulting in substantial coloration and impaired transparency.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
Note that the present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present invention and has similar effects is the present invention. covered within the technical scope of.
Claims (12)
- シリコーン感圧接着剤組成物であって、
（Ａ）下記平均式（１）で表され、ケイ素原子に結合したアルケニル基の含有量が０．００１０～０．０１０モル／１００ｇである直鎖状オルガノポリシロキサン、
（Ｂ）下記平均式（２）で表され、ケイ素原子に結合した水素原子の含有量が０．００１０～０．０２０モル／ｇである直鎖状オルガノハイドロジェンポリシロキサン、
（Ｃ）（Ｒ３ ３ＳｉＯ１／２）単位（式中、Ｒ３は、互いに同一又は異なっていてもよい、置換又は非置換の炭素数１～１２の一価炭化水素基、水酸基、炭素数１～４のアルコキシ基又はハロゲン原子である）、及び（ＳｉＯ４／２）単位を有し、（Ｒ３ ３ＳｉＯ１／２）単位：（ＳｉＯ４／２）単位の比が０．５：１～１．８：１の範囲である三次元網目状オルガノポリシロキサン、
（Ｄ）ヒドロシリル化反応触媒、
及び、
（Ｅ）酸化防止剤
を含むものであることを特徴とするシリコーン感圧接着剤組成物。 A silicone pressure sensitive adhesive composition comprising:
(A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g,
(B) a linear organohydrogenpolysiloxane represented by the following average formula (2) and having a content of hydrogen atoms bonded to silicon atoms of 0.0010 to 0.020 mol/g;
(C) (R 3 3 SiO 1/2 ) unit (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5. :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
(D) hydrosilylation reaction catalyst,
as well as,
(E) A silicone pressure-sensitive adhesive composition containing an antioxidant. - 前記（Ｂ）成分中のケイ素原子に結合した水素原子の数が、前記（Ａ）成分中のアルケニル基１個に対し０．２～５０個であることを特徴とする請求項１に記載のシリコーン感圧接着剤組成物。 2. The method according to claim 1, wherein the number of hydrogen atoms bonded to silicon atoms in the component (B) is 0.2 to 50 per alkenyl group in the component (A). Silicone pressure sensitive adhesive composition.
- 前記酸化防止剤が、２種以上の酸化防止剤を含むものであることを特徴とする請求項１又は請求項２記載のシリコーン感圧接着剤組成物。 The silicone pressure-sensitive adhesive composition according to claim 1 or 2, wherein the antioxidant contains two or more types of antioxidants.
- 前記酸化防止剤が、フェノール系酸化防止剤及びチオエーテル系酸化防止剤を含むものであることを特徴とする請求項１から請求項３のいずれか一項に記載のシリコーン感圧接着剤組成物。 The silicone pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the antioxidant contains a phenolic antioxidant and a thioether antioxidant.
- 請求項１から請求項４のいずれか一項に記載のシリコーン感圧接着剤組成物を硬化してなるものであることを特徴とするシリコーン感圧接着剤。 A silicone pressure-sensitive adhesive characterized by being formed by curing the silicone pressure-sensitive adhesive composition according to any one of claims 1 to 4.
- ＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ｍｉｎでの粘着力が、５．０Ｎ／２５ｍｍ以上であることを特徴とする請求項５に記載のシリコーン感圧接着剤。 The silicone texture according to claim 5, characterized in that the adhesive strength at a room temperature of 23° C. and a pulling speed of 300 mm/min is 5.0 N/25 mm or more in a 180° peel test specified in JIS Z 0237. Pressure adhesive.
- 前記引き剥がし試験後の被着面に対するポリエチレンテレフタレートフィルムのＪＩＳ Ｚ ０２３７に規定される１８０°引き剥がし試験において、室温２３℃、引張り速度３００ｍｍ／ｍｉｎでの粘着力が０．１Ｎ／２５ｍｍ以下であることを特徴とする請求項６に記載のシリコーン感圧接着剤。 In the 180° peel test specified in JIS Z 0237 of the polyethylene terephthalate film on the adhered surface after the peel test, the adhesive strength at room temperature 23 ° C. and pulling speed 300 mm/min is 0.1 N/25 mm or less. 7. The silicone pressure sensitive adhesive according to claim 6.
- ＪＩＳ Ｚ ８７８１－４に規定されるＬ＊ａ＊ｂ＊表色系における厚み３００μｍでのｂ＊値が０．１５以下である請求項５から請求項７のいずれか一項に記載のシリコーン感圧接着剤。 The silicone texture according to any one of claims 5 to 7, wherein the L * a*b * b * value at a thickness of 300 μm in the color system defined in JIS Z 8781-4 is 0.15 or less. Pressure adhesive.
- 請求項５から請求項８のいずれか一項に記載のシリコーン感圧接着剤からなる感圧接着剤層を備えたものであることを特徴とする感圧接着フィルム。 A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer made of the silicone pressure-sensitive adhesive according to any one of claims 5 to 8.
- 請求項５から請求項８のいずれか一項に記載のシリコーン感圧接着剤からなる感圧接着剤層を備えたものであることを特徴とする画像表示装置。 An image display device comprising a pressure-sensitive adhesive layer made of the silicone pressure-sensitive adhesive according to any one of claims 5 to 8.
- シリコーン感圧接着剤の評価方法であって、
（１）シリコーン感圧接着剤からなる感圧接着剤層を基材の一方の面に備えた感圧接着フィルムを準備する第１の工程と、
（２）前記感圧接着フィルムの感圧接着剤層を、ＪＩＳ Ｚ ０２３７に準じステンレス鋼板表面に圧着した後、引張速度３００ｍｍ／ｍｉｎで感圧接着フィルムをステンレス鋼板に対して１８０°に引き剥がす第２の工程と、
（３）ポリエチレンテレフタレートフィルムを、ＪＩＳ Ｚ ０２３７に準じ、前記第２の工程後のステンレス鋼板における前記感圧接着フィルムを引き剥がした後の範囲内に圧着した後、引張速度３００ｍｍ／ｍｉｎで前記ポリエチレンテレフタレートフィルムをステンレス鋼板に対して１８０°に引き剥がした際の粘着力を測定する第３の工程と、
（４）前記粘着力に基づいて、前記シリコーン感圧接着剤の良否を判定する第４の工程と
を備えるものとすることを特徴とするシリコーン感圧接着剤の評価方法。 A method for evaluating a silicone pressure sensitive adhesive, the method comprising:
(1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material;
(2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min. a second step;
(3) In accordance with JIS Z 0237, a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min. A third step of measuring the adhesive force when the terephthalate film is peeled off at 180° from the stainless steel plate;
(4) A method for evaluating a silicone pressure-sensitive adhesive, comprising a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength. - 前記第４の工程を、前記粘着力が０．１Ｎ／２５ｍｍ以下を満たすか否かによってシリコーン感圧接着剤の良否を判定する工程とすることを特徴とする請求項１１に記載のシリコーン感圧接着剤の評価方法。 The silicone pressure-sensitive adhesive according to claim 11, wherein the fourth step is a step of determining the quality of the silicone pressure-sensitive adhesive depending on whether the adhesive force satisfies 0.1 N/25 mm or less. How to evaluate adhesives.
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| JP2006016555A (en) * | 2004-07-02 | 2006-01-19 | Dow Corning Toray Co Ltd | Silicone-based pressure-sensitive adhesive and adhesive tape |
| JP2008024777A (en) * | 2006-07-19 | 2008-02-07 | Shin Etsu Chem Co Ltd | Addition curable silicone adhesive composition for silicone rubber and adhesive tape obtained from the composition |
| JP2011102336A (en) * | 2009-11-10 | 2011-05-26 | Shin-Etsu Chemical Co Ltd | Silicone adhesive composition, and adhesive film |
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| JP2019089913A (en) * | 2017-11-14 | 2019-06-13 | 信越化学工業株式会社 | Addition-curable silicone adhesive composition |
| JP2021123628A (en) * | 2020-02-04 | 2021-08-30 | アイカ工業株式会社 | Adhesive silicone resin composition and adhesive film coated with the same |
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- 2023-02-27 WO PCT/JP2023/007158 patent/WO2023195268A1/en unknown
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| JP2006016555A (en) * | 2004-07-02 | 2006-01-19 | Dow Corning Toray Co Ltd | Silicone-based pressure-sensitive adhesive and adhesive tape |
| JP2008024777A (en) * | 2006-07-19 | 2008-02-07 | Shin Etsu Chem Co Ltd | Addition curable silicone adhesive composition for silicone rubber and adhesive tape obtained from the composition |
| JP2011102336A (en) * | 2009-11-10 | 2011-05-26 | Shin-Etsu Chemical Co Ltd | Silicone adhesive composition, and adhesive film |
| JP2019089913A (en) * | 2017-11-14 | 2019-06-13 | 信越化学工業株式会社 | Addition-curable silicone adhesive composition |
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| JP2021123628A (en) * | 2020-02-04 | 2021-08-30 | アイカ工業株式会社 | Adhesive silicone resin composition and adhesive film coated with the same |
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