JP4506146B2 - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JP4506146B2 JP4506146B2 JP2003357460A JP2003357460A JP4506146B2 JP 4506146 B2 JP4506146 B2 JP 4506146B2 JP 2003357460 A JP2003357460 A JP 2003357460A JP 2003357460 A JP2003357460 A JP 2003357460A JP 4506146 B2 JP4506146 B2 JP 4506146B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive composition
- group
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 67
- 239000000853 adhesive Substances 0.000 title description 38
- 230000001070 adhesive effect Effects 0.000 title description 38
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 103
- -1 benzotriazole compound Chemical class 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 150000004292 cyclic ethers Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 235000013824 polyphenols Nutrition 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 125000003566 oxetanyl group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000000758 substrate Substances 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- YYTNQIHMFFPVME-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxetane Chemical compound C1COC1.CC(=C)C(O)=O YYTNQIHMFFPVME-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RPRHUUXXSFWGTM-UHFFFAOYSA-N 2-(2-tert-butyl-6,6-dimethylheptyl)benzene-1,4-diol Chemical compound CC(C)(C)CCCC(C(C)(C)C)CC1=CC(O)=CC=C1O RPRHUUXXSFWGTM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- ULEVTQHCVWIDPC-UHFFFAOYSA-N 2-(methylamino)ethyl prop-2-enoate Chemical compound CNCCOC(=O)C=C ULEVTQHCVWIDPC-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- CQNQNWUSTVCIDH-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(6-methylheptoxy)phenol Chemical compound OC1=CC(OCCCCCC(C)C)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 CQNQNWUSTVCIDH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- KZPMXWBRKHQGQJ-UHFFFAOYSA-N 2-methyl-4-(oxiran-2-yl)but-2-enoic acid oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound O1C(CC=C(C(=O)O)C)C1.C(C(=C)C)(=O)OCC1CO1 KZPMXWBRKHQGQJ-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OYGYNUPKLMDVHM-UHFFFAOYSA-N 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(N2N=C3C=CC=CC3=N2)=C1O OYGYNUPKLMDVHM-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 241000907681 Morpho Species 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UUZCWFUAZDSTKU-UHFFFAOYSA-N N-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide N-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound N(=NC(C(=O)NCCO)(C)C)C(C(=O)NCCO)(C)C.N(=NC(C(=O)NC(CO)(CO)CO)(C)C)C(C(=O)NC(CO)(CO)CO)(C)C UUZCWFUAZDSTKU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZFGUAQSDWQIVMM-UHFFFAOYSA-N n'-hydroxy-2-methylbutanimidamide Chemical compound CCC(C)C(N)=NO ZFGUAQSDWQIVMM-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- XQAABEDPVQWFPN-UHFFFAOYSA-N octyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=CC=CC3=N2)=C1O XQAABEDPVQWFPN-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- WVSZBAHKLHXQFN-UHFFFAOYSA-N tetrahydrate;dihydrochloride Chemical compound O.O.O.O.Cl.Cl WVSZBAHKLHXQFN-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、粘着剤溶液中に架橋システムをもち塗工乾燥時に架橋する粘着剤であって、なおかつ保存安定性と凝集力のバランスが改善された粘着剤組成物および粘着シートならびにその製造方法に関するものである。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having a crosslinking system in a pressure-sensitive adhesive solution and crosslinking at the time of coating and drying, and having an improved balance between storage stability and cohesive force, and a method for producing the same. Is.
溶剤型粘着剤は、その分子量が比較的小さいため、そのまま塗工、有機溶媒を乾燥して使用したのでは、分子間の凝集力が不足し、所望の物性、(保持力、耐熱性、糊はみ出し試験の結果等)は得られない。そのため架橋剤として、多官能のイソシアネート、エポキシ化合物等が使われてきた。これらの硬化剤は粘着剤が塗工される直前に、投入されるものであり、その粘着剤は2液型と言われる。しかしながら、硬化剤を混合する場合、分量を間違う可能性があることと、間違った場合直接検証することが難しく、投入後の使用可能時間(ポットライフ)が数時間であるため作業性に難がある。また、反応性に富んだイソシアネートを作業者が秤量するため、安全性の観点からも1液型のほうがより好ましい。 Solvent-type pressure-sensitive adhesives have a relatively low molecular weight, so if they are used as they are, and the organic solvent is dried and used, the cohesive strength between the molecules is insufficient, and the desired physical properties (holding power, heat resistance, glue) The result of the overhang test etc. is not obtained. For this reason, polyfunctional isocyanates, epoxy compounds and the like have been used as crosslinking agents. These curing agents are added immediately before the adhesive is applied, and the adhesive is said to be a two-component type. However, when mixing the curing agent, it is difficult to verify the amount in the wrong amount, and if it is wrong, it is difficult to verify directly, and workability is difficult because the usable time (pot life) after charging is several hours. is there. Moreover, since the operator weighs isocyanate having a high reactivity, the one-component type is more preferable from the viewpoint of safety.
一方、1液型の粘着剤においては、上記架橋系あるいは塗料等で用いられている架橋系をそのまま応用すればよいと考えられるが、粘着剤分野において用いられるポリマーの分子量が大きいため、そのまま架橋剤を投入したのでは保存安定性(シェルフライフ)に問題があり、長期保存においてゲル化してしまう。つまりポリマー鎖の長さから、一部が架橋しても分子量の増大効果が大きく、粘度の増大が激しい。 On the other hand, in the one-pack type pressure-sensitive adhesive, it is considered that the crosslinking system or the crosslinking system used in paints may be applied as it is. However, since the molecular weight of the polymer used in the pressure-sensitive adhesive field is large, When the agent is added, there is a problem in storage stability (shelf life), and gelation occurs during long-term storage. That is, due to the length of the polymer chain, the effect of increasing the molecular weight is great even if a part of the polymer is crosslinked, and the viscosity is greatly increased.
保存安定性のある一液型の粘着剤としては、アルコール系溶剤等でブロックされた錯化合物であるアルミ、チタンキレート架橋剤を内包したものが知られているが、溶剤選択の限定や、凝集力不足等の問題があった。 As one-pack type adhesives with storage stability, aluminum and titanium chelate cross-linking agents that are complex compounds blocked with alcoholic solvents are known. There were problems such as lack of power.
架橋剤としてメチルエチルケトンオキシム等でブロックされたブロックイソシアネートも知られているが、シェルフライフと反応性を両立させるには、極端な高温での塗工、乾燥が必要となる。つまり、解ブロック温度が低いものは反応性が高いかわりに常温でも反応してしまい、シェルフライフが短い。解ブロック温度が高いものはシェルフライフが長いが、塗工乾燥時の温度を極端に高温にする必要があった。 A blocked isocyanate blocked with methyl ethyl ketone oxime or the like is also known as a crosslinking agent. However, in order to achieve both shelf life and reactivity, coating and drying at an extremely high temperature are required. In other words, those having a low deblocking temperature react at room temperature instead of high reactivity, and the shelf life is short. A high deblocking temperature has a long shelf life, but the temperature during coating and drying must be extremely high.
特許文献1には、ベンゾトリアゾール系およびヒンダードアミン系UV吸収剤を含有し、またグリシジルメタクリレートを含有するアクリル重合体を含む粘着剤が記載されている。 Patent Document 1 describes a pressure-sensitive adhesive containing an acrylic polymer containing a benzotriazole-based and hindered amine-based UV absorber and also containing glycidyl methacrylate.
特許文献2には、プライマー組成物にベンゾトリアゾール系化合物、グリシジルメタクリレートを含有するアクリル重合体を含む粘着剤が記載されている。 Patent Document 2 describes a pressure-sensitive adhesive containing an acrylic polymer containing a benzotriazole-based compound and glycidyl methacrylate in a primer composition.
しかしながら特許文献1は、環状エーテル基とカルボキシル基を必須成分とするものではない。また発明の目的自体が耐光性の向上であり、粘着剤を成り立たせるに重要な塗液のシェルフライフについては記載されていない。 However, Patent Document 1 does not contain a cyclic ether group and a carboxyl group as essential components. Further, the object of the invention itself is to improve light resistance, and the shelf life of the coating liquid important for realizing the pressure-sensitive adhesive is not described.
また、特許文献2は低分子量のプライマー組成物であって粘着剤としての機能ははたせず、分子量が高いゆえにゲル化しやすい粘着剤の保存安定性の問題を解決する技術の提示には至っていない。
以上のように、比較的分子量の大きいアクリル重合体を用いる粘着剤は、保存安定性を実用的なレベルで向上させる技術は知られていなかった。
As described above, a technology for improving the storage stability at a practical level has not been known for an adhesive using an acrylic polymer having a relatively large molecular weight.
そこで、本発明は粘着シートとなったときの凝集力向上成分である架橋成分を含みながら、溶剤一液型粘着剤の保存安定性を改善することを目的とする。 Therefore, an object of the present invention is to improve the storage stability of a solvent one-component pressure-sensitive adhesive while containing a crosslinking component which is a cohesive force improving component when it becomes a pressure-sensitive adhesive sheet.
本発明は、アルキル基の炭素数が1から14である(メタ)アクリル酸アルキルエステル、環状エーテル基をもつエチレン性単量体0.2から1.8phr、重合性不飽和カルボン酸4から8phr、および必要に応じて上記以外の共重合可能なエチレン性不飽和単量体を共重合させてなる重量平均分子量30万以上のアクリル重合体からなることを特徴とする粘着剤組成物である。 The present invention relates to (meth) acrylic acid alkyl ester having 1 to 14 carbon atoms in the alkyl group, ethylenic monomer having cyclic ether group of 0.2 to 1.8 phr, polymerizable unsaturated carboxylic acid of 4 to 8 phr, and necessary The pressure-sensitive adhesive composition comprises an acrylic polymer having a weight average molecular weight of 300,000 or more obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than those described above.
更に本発明は、環状エーテル基が、グリシジル基、オキセタン基、または脂環式エポキシ基である上記粘着剤組成物である。
更に本発明は、重合性不飽和カルボン酸がアクリル酸である上記粘着剤組成物である。
Furthermore, this invention is the said adhesive composition whose cyclic ether group is a glycidyl group, an oxetane group, or an alicyclic epoxy group.
Furthermore, this invention is the said adhesive composition whose polymerizable unsaturated carboxylic acid is acrylic acid.
更に本発明は、ベンゾトリアゾール系化合物、アミノエーテル系ヒンダードアミン化合物、ヒドロキシフェニルトリアジン化合物、ポリフェノール系化合物、またはアルキルフェノール系化合物から選ばれる保存安定剤を含む上記粘着剤組成物である。 Furthermore, this invention is the said adhesive composition containing the storage stabilizer chosen from a benzotriazole type compound, an amino ether type hindered amine compound, a hydroxyphenyl triazine compound, a polyphenol type compound, or an alkylphenol type compound.
更に本発明は、上記粘着剤組成物と溶剤とからなる粘着剤組成物である。 Furthermore, this invention is an adhesive composition which consists of the said adhesive composition and a solvent.
更に本発明は、上記粘着剤組成物を塗工、乾燥してなる粘着シートである。 Furthermore, this invention is an adhesive sheet formed by applying and drying the above-mentioned adhesive composition.
更に本発明は、乾燥温度が100℃〜150℃で製造された上記粘着シートの製造方法である。 Furthermore, this invention is a manufacturing method of the said adhesive sheet manufactured with the drying temperature of 100 to 150 degreeC.
本発明は環状エーテル基とカルボキシル基を持つ一液型粘着剤において、環状エーテル基とカルボキシル基の量、添加剤としてベンゾトリアゾール系化合物、アミノエーテル系ヒンダードアミン化合物、ヒドロキシフェニルトリアジン化合物、ポリフェノール系化合物、アルキルフェノール系化合物を用いることとその量、粘着剤の固形分、分子量を調整することによって、粘着剤の保存安定性と得られた粘着シートの凝集力といった相反する特性を両立させた。 The present invention is a one-pack type pressure-sensitive adhesive having a cyclic ether group and a carboxyl group, the amount of the cyclic ether group and the carboxyl group, as additives, benzotriazole compounds, amino ether hindered amine compounds, hydroxyphenyl triazine compounds, polyphenol compounds, By using an alkylphenol compound and adjusting the amount thereof, the solid content of the pressure sensitive adhesive, and the molecular weight, the storage stability of the pressure sensitive adhesive and the conflicting properties such as the cohesive strength of the obtained pressure sensitive adhesive sheet were made compatible.
本発明に使用するアルキル基の炭素数が1から14であるラジカル重合可能な(メタ)アクリル酸エステルとしては、直鎖または分岐脂肪族アルコ−ルのアクリル酸エステル及び対応するメタクリル酸エステル、具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル等が挙げられ、その含有量は60から95.8phrが望ましい。なお、phrとは(part hundred resin)の略で、アクリル重合体に対する重量百分率をあらわす。 Examples of the radically polymerizable (meth) acrylic acid ester having 1 to 14 carbon atoms in the alkyl group used in the present invention include linear or branched aliphatic alcohol acrylic acid esters and the corresponding methacrylic acid esters. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Decyl acrylate, dodecyl (meth) acrylate, etc., and the content is preferably 60 to 95.8 phr. In addition, phr is an abbreviation for (part hundred resin) and represents a weight percentage with respect to the acrylic polymer.
本発明に使用する環状エーテル基をもつエチレン性単量体としては、グリシジルアクリレ−ト、グリシジルメタクリレ−ト(メタクリル酸グリシジル)、アリルグリシジルエーテル、オキセタンメタクリレート 、アリルオキセタン、1.2-エポキシ-4-ビニルシクロヘキサン、3、4-エポキシシクロヘキシルメチルアクリレート、3、4-エポキシシクロヘキシルメチルメタアクリレートテトラヒドロフルフリルアクリレート、テトラヒドロフルフリルメタクリレート等が挙げられる。 Examples of the ethylenic monomer having a cyclic ether group used in the present invention include glycidyl acrylate, glycidyl methacrylate (glycidyl methacrylate), allyl glycidyl ether, oxetane methacrylate, allyl oxetane, and 1.2-epoxy-4. -Vinylcyclohexane, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate and the like.
環状エーテル基をもつエチレン性単量体含有量は0.2から1.8phrであり、好ましくは0.6から1.2phrである。0.2phr以下であると粘着シートとなったときの凝集力、接着力が不足し、1.8phr以上となると合成時にカルボキシル基と反応しゲル化する場合がある。また粘着剤溶液の保存安定性も悪化し架橋系の制御が難しくなる。 The content of ethylenic monomer having a cyclic ether group is 0.2 to 1.8 phr, preferably 0.6 to 1.2 phr. When it is 0.2 phr or less, the cohesive force and adhesive force when it becomes a pressure-sensitive adhesive sheet are insufficient, and when it is 1.8 phr or more, it may react with a carboxyl group during synthesis and gel. In addition, the storage stability of the pressure-sensitive adhesive solution is deteriorated, and it is difficult to control the crosslinking system.
本発明における重合性不飽和カルボン酸としては、アクリル酸、メタクリル酸、無水マレイン酸、マレイン酸、イタコン酸、クロトン酸が挙げられる。その含有量は4から8phrであり、5から7phrであることが好ましい。含有量が4phr以下であると粘着シートとなったときの凝集力、接着力が不足し、8phr以上となると合成時に環状エーテル基と反応しゲル化する場合がある。また粘着剤溶液の保存安定性も悪化し架橋系の制御が難しくなる。 Examples of the polymerizable unsaturated carboxylic acid in the present invention include acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, and crotonic acid. Its content is 4 to 8 phr, preferably 5 to 7 phr. When the content is 4 phr or less, the cohesive force and adhesive force when the pressure-sensitive adhesive sheet is obtained are insufficient. In addition, the storage stability of the pressure-sensitive adhesive solution is deteriorated, and it is difficult to control the crosslinking system.
本発明における共重合可能なエチレン性不飽和単量体としては、ヒドロキシル基、メチロ−ル基、アミノ基、アミド基、エチレンイミン基及びイソシアネ−ト基等の官能基含有単量体があり、具体例として(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸2−ヒドロキシエチル、ポリエチレングリコ−ルアクリレ−ト、ビニルイソシアネ−ト等、N−メチロ−ルアクリルアミド、N−メチロ−ルメタクリルアミド、N−メチルアミノエチルアクリレ−ト、N−トリブチルアミノエチルアクリレ−ト、N,N−ジメチルアミノエチルアクリレ−ト、N,N−ジメチルアミノエチルメタクリレ−ト、N,N−ジエチルアミノエチルメタクリレ−ト、アクリルアミド、メタクリルアミド、ビニルピロリドン、アクリロイルモルフォリン、N−ビニルホルムアミド、等が挙げられ、その含有量は0から5phrが望ましい。 As the copolymerizable ethylenically unsaturated monomer in the present invention, there are functional group-containing monomers such as hydroxyl group, methylol group, amino group, amide group, ethyleneimine group and isocyanate group, Specific examples include 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol acrylate, vinyl isocyanate, N-methylol acrylamide, N-methylol methacryl. Amides, N-methylaminoethyl acrylate, N-tributylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N- Diethylaminoethyl methacrylate, acrylamide, methacrylamide, vinyl pyrrolidone, acryloyl morpho Emissions, N- vinylformamide, etc., and the content thereof is 5phr desirably from 0.
上記以外の共重合可能なエチレン性不飽和単量体としては、ビニルエステル、ビニルピリジン、酢酸ビニル、プロピオン酸ビニル、スチレン、α-メチルスチレン、アクリロニトリル、メタクリロニトリル、イソボロニル(メタ)アクリレート、ブタジエン、クロロプレン等も共重合に供することができ、その含有量は0から40phrが望ましい。 Other copolymerizable ethylenically unsaturated monomers include vinyl esters, vinyl pyridine, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, isobornyl (meth) acrylate, butadiene Also, chloroprene can be used for copolymerization, and its content is preferably 0 to 40 phr.
本発明における粘着剤組成物の溶剤としては、酢酸エチル、酢酸ブチル、トルエン、キシレン、メタノール、エタノール、イソプロピルアルコール、イソブチルアルコール、メチルエチルケトン、メチルアミルケトン、メチルイソブチルケトン、アセトン、ヘキサン、シクロヘキサノン等を用いることができる。 As the solvent of the pressure-sensitive adhesive composition in the present invention, ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, acetone, hexane, cyclohexanone, etc. are used. be able to.
本発明のアクリル重合体の重量平均分子量は30万以上200万未満が望ましく、より好ましくは50万以上70万以下が適当である。分子量が低すぎれば粘着シートとなったときの凝集力、接着力が不足する。分子量が大きすぎると合成時にゲル化する場合がある。また必要以上に粘度が上昇するためハンドリング性も悪くなり、粘着剤溶液の保存安定性も悪化する。 The weight average molecular weight of the acrylic polymer of the present invention is preferably from 300,000 to less than 2,000,000, more preferably from 500,000 to 700,000. If the molecular weight is too low, the cohesive force and adhesive force when it becomes a pressure-sensitive adhesive sheet are insufficient. If the molecular weight is too large, gelation may occur during synthesis. In addition, since the viscosity increases more than necessary, the handling properties also deteriorate, and the storage stability of the pressure-sensitive adhesive solution also deteriorates.
また、本発明における粘着剤組成物の固形分は15%以上70%未満が好ましく、25%以上40%未満がより好ましい。 Further, the solid content of the pressure-sensitive adhesive composition in the present invention is preferably 15% or more and less than 70%, and more preferably 25% or more and less than 40%.
合成反応に用いる重合開始剤としては特に限定されないが、具体的には、アルキルパーオキサイド、t−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、p−メタンヒドロパーオキサイド、イソブチルパーオキサイド、ラウロリルパーオキサイド、3,5,5−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、t−ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジクロルベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、3,3,5−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、ジ−イソブチルパーオキシジカーボネート、ジ−2−エチルヘキシルパーオキシジカーボネート、t−ブチルパーオキシイソブチレート等の有機過酸化物、アゾビスイソブチロニトリル、ジメチルアゾジイソブチレート、2,2−アゾビス(2,4−ジメチルバレロニトリル)、2,2−アゾビス(2−メチルブチロニトリル)、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、4,4’−アゾビス−4−シアノバレリックアシッドのアンモニウム(アミン)塩、2,2’−アゾビス(2−メチルアミドオキシム)ジヒドロクロライド、2,2’−アゾビス(2−メチルブタンアミドオキシム)ジヒドロクロライドテトラヒドレート、2,2’−アゾビス{2−メチル−N−〔1,1−ビス(ヒドロキシメチル)−2−ヒドロキシエチル〕−プロピオンアミド}、2,2’−アゾビス〔2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド〕、等が挙げられる。 Although it does not specifically limit as a polymerization initiator used for a synthesis reaction, Specifically, alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, isobutyl peroxide, laurolyl peroxide 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutylperoxydicarbonate, Organic peroxides such as 2-ethylhexyl peroxydicarbonate and t-butylperoxyisobutyrate, azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis (2,4-dimethylvaleronitrile) ), 2,2-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, 4,4′-azobis-4-cyanovaleric acid ammonium (amine) salt 2,2′-azobis (2-methylamidooxime) dihydrochloride, 2,2′-azobis (2-methylbutanamidoxime) dihydrochloride tetrahydrate, 2,2′-azobis {2-methyl-N— [1,1-bis (hydroxymethyl) -2-hydroxyethyl] -propionamide} 2,2'-azobis [2-methyl-N-(2-hydroxyethyl) - propionamide], and the like.
初期接着力の向上または特定基材への接着力の向上を目的として、本発明の粘着剤組成物には粘着性付与剤を含有する事も出来る。例えば、ロジン樹脂、フェノール樹脂、ポリテルペン、アセチレン樹脂、石油系炭化水素樹脂、エチレン酢酸ビニル共重合体、合成ゴム、天然ゴム等を粘着性付与剤として粘着剤組成中に含有しても良い。具体的には、スーパーエステルA−75(荒川化学社製)、スーパーエステルA−100(荒川化学社製)、スーパーエステルA−125(荒川化学社製)等のロジンエステル、ペンセルD125(荒川化学社製)、ペンセルD160(荒川化学社製)、リカタックPCJ(理化ファインテック社製)等の重合ロジンエステル、ニカノールHP−100(三菱ガス化学社製)、ニカノールHP−150(三菱ガス化学社製)、ニカノールH−80等のキシレン樹脂、YSポリスターT−115(ヤスハラケミカル社製)、マイテックG125(ヤスハラケミカル社製)等のテルペンフェノール樹脂、FTR−6120(三井石油化学社製)、FTR−6100(三井石油化学社製)等の石油樹脂、その他、クマロンインデン樹脂、テルペン樹脂、スチレン樹脂、エチレン/酢酸ビニル樹脂等が挙げられる。
ベンゾトリアゾール系化合物の例としては2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-3’-5’-ジ・tertブチルフェニル)ベンゾトリアゾール、3-(2H-ベンゾトリアゾール-2-イル)-5-(1,1-ジメチルエチル)-4-ヒドロキシベンゼンプロパン酸のC7-9の枝分かれまたは直鎖のアルキルエステル(チバスペシャリティケミカルズ社製、商品名TINUVIN384-2)、2-(2H-ベンゾトリアゾール-2-イル)-4、6-ビス(1-メチル-1-フェニルエチル)フェノールが挙げられる。
For the purpose of improving the initial adhesive strength or the adhesive strength to a specific substrate, the pressure-sensitive adhesive composition of the present invention may contain a tackifier. For example, a rosin resin, a phenol resin, a polyterpene, an acetylene resin, a petroleum hydrocarbon resin, an ethylene vinyl acetate copolymer, a synthetic rubber, a natural rubber or the like may be included in the pressure-sensitive adhesive composition as a tackifier. Specifically, super ester A-75 (manufactured by Arakawa Chemical Co., Ltd.), super ester A-100 (manufactured by Arakawa Chemical Co., Ltd.), rosin ester such as super ester A-125 (manufactured by Arakawa Chemical Co., Ltd.), Pencel D125 (Arakawa Chemical Co., Ltd.) ), Pencel D160 (Arakawa Chemical Co., Ltd.), Ricacac PCJ (Rika Finetech Co., Ltd.) and other polymerized rosin esters, Nikanol HP-100 (Mitsubishi Gas Chemical Co., Ltd.), Nikanol HP-150 (Mitsubishi Gas Chemical Co., Ltd.) ), Xylene resins such as Nikanol H-80, terpene phenol resins such as YS Polystar T-115 (manufactured by Yashara Chemical Co., Ltd.), Mytec G125 (manufactured by Yashara Chemical Co., Ltd.), FTR-6120 (manufactured by Mitsui Petrochemical Co., Ltd.), FTR-6100 Petroleum resins such as Mitsui Petrochemical Co., Ltd., Coumarone Indene Resin, Terpene Tree , Styrene resin, an ethylene / vinyl acetate resins.
Examples of benzotriazole compounds include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-5'-di-tertbutylphenyl) benzotriazole, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid C7-9 branched or straight chain alkyl ester (trade name TINUVIN384, manufactured by Ciba Specialty Chemicals) -2), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol.
ヒドロキシフェニルトリアジン化合物としては、2-[4-[(2-ヒドロキシ-3-ドデシルオキシプロピル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1、3、5-トリアジンと2-[4-[(2-ヒドロキシ-3-トリデシルオキシプロピル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1、3、5-トリアジンの混合物、2、4-ビス(2、4-ジメチルフェニル)-6-(2-ヒドロキシ-4-イソ-オクチルオキシフェニル)-s-トリアジンが挙げられる。 Examples of the hydroxyphenyl triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3 5-triazine and 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3, And a mixture of 5-triazines, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine.
アミノエーテル系ヒンダードアミン化合物としてはチバ・スペシャリティ・ケミカルズ社製、TINUVIN123が挙げられる。 Examples of the amino ether hindered amine compound include TINUVIN123 manufactured by Ciba Specialty Chemicals.
ポリフェノール系化合物としては、2、5-ジ-tert-ブチルハイドロキノン、2、5-ジ-tert-ブチルアミルハイドロキノン等が挙げられる。
アルキルフェノール系化合物としては、4、4‘-ブチリデンビス(6-tert-ブチル-3-メチルフェノール、1、1-ビス(4-ヒドロキシフェニル)シクロヘキサン、2、6-ジ-tert-ブチル-4-メチルフェノール、2,2-メチレンビス(4-メチル-6-tert-ブチルフェノール)等が挙げられる。
Examples of the polyphenol compound include 2,5-di-tert-butylhydroquinone and 2,5-di-tert-butylamylhydroquinone.
Examples of alkylphenol compounds include 4,4′-butylidenebis (6-tert-butyl-3-methylphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,6-di-tert-butyl-4-methyl. Examples include phenol and 2,2-methylenebis (4-methyl-6-tert-butylphenol).
また上記保存安定剤は一種類のみならず、定められた重量部内で混合して用いてもよい。また、アミノエーテル系ヒンダードアミン化合物とベンゾトリアゾール系化合物またはヒドロキシフェニルトリアジン化合物を混合してもちいると、相乗的効果を示す場合がある。 Further, the storage stabilizer is not limited to one type, and may be used by mixing within a predetermined part by weight. Further, when an amino ether-based hindered amine compound and a benzotriazole-based compound or a hydroxyphenyltriazine compound are mixed, a synergistic effect may be exhibited.
保存安定剤の量としては溶解度以内であればとくに限定されないが、粘着剤組成物全体に対して0.001から0.02倍量であり、より好ましくは0.0015から0.005倍量である。0.001倍量未満であれば添加の効果が小さく、0.02倍量以上添加すると、種類によっては粘着剤の着色が大きくなり、商品性を損なったり、かえって環状エーテル基とカルボキシル基の架橋反応を促進しゲル化してしまう場合がある。 The amount of the storage stabilizer is not particularly limited as long as it is within the solubility, but it is 0.001 to 0.02 times, more preferably 0.0015 to 0.005 times the whole pressure-sensitive adhesive composition. If the amount is less than 0.001 times, the effect of addition is small, and if added more than 0.02 times, depending on the type, the coloring of the pressure-sensitive adhesive increases, and the merchantability is impaired, or the crosslinking reaction between the cyclic ether group and the carboxyl group is promoted. It may be gelled.
粘着層自体に遮光性、濃度感を持たせたり、特定の色をつけるため、粘着剤に染料や顔料、充填剤を添加することもできる。 In order to give the pressure-sensitive adhesive layer itself a light-shielding property and density, or to give a specific color, dyes, pigments and fillers can be added to the pressure-sensitive adhesive.
本発明における重合条件としては、特に限定されないが、例えば、攪拌器、温度計、滴下ロート、還流器を備えた重合槽において、60から85℃程度で有機溶媒の沸点においての還流反応が挙げられる。まず反応単量体および溶剤、反応開始剤の一部を重合槽に仕込み、60から85℃程度に昇温する。還流状態となったら概温度を維持したまま攪拌をおこないながら、約1〜3時間かけて残った単量体、および溶剤、反応開始剤を滴下又は分割添加して、その後同温度で1〜4時間程度熟成する。最後に冷却分として残しておいた溶剤を加えてもよい。上記工程中、または工程後に粘着付与剤や保存安定剤等の各種添加剤を加えることができる。 The polymerization conditions in the present invention are not particularly limited, and examples thereof include a reflux reaction at a boiling point of an organic solvent at about 60 to 85 ° C. in a polymerization tank equipped with a stirrer, a thermometer, a dropping funnel, and a reflux device. . First, a reaction monomer, a solvent, and a part of a reaction initiator are charged into a polymerization tank, and the temperature is raised to about 60 to 85 ° C. Stirring while maintaining the approximate temperature when refluxed, the remaining monomer, solvent, and reaction initiator were dropped or dividedly added over about 1 to 3 hours, and then 1 to 4 at the same temperature. Ripen for about an hour. Finally, a solvent left as a cooling component may be added. Various additives such as a tackifier and a storage stabilizer can be added during or after the above process.
本発明の粘着剤シートは、剥離材上に粘着剤をコンマコーター、リバースコーター、スロットダイコーター等で塗工し、乾燥した後に粘着剤層の上に基材を積層しプレスする、転写塗工により得ることができる。かかる粘着剤シートにおける粘着剤の塗工量は乾燥重量で2〜50g/m2 であることが好ましく、5〜25g/m2 であることがより好ましい。 The pressure-sensitive adhesive sheet of the present invention is a transfer coating in which a pressure-sensitive adhesive is coated on a release material with a comma coater, reverse coater, slot die coater, etc., dried, and then laminated and pressed on a pressure-sensitive adhesive layer. Can be obtained. The coating amount of the pressure-sensitive adhesive in the pressure-sensitive adhesive sheet is preferably 2 to 50 g / m 2 by dry weight, and more preferably 5 to 25 g / m 2 .
逆に、基材上に粘着剤をコンマコーター、リバースコーター、スロットダイコーター等で塗工し、乾燥した後に粘着剤層の上に剥離材を積層しプレスする、ダイレクト塗工によっても得ることができる。かかる粘着剤シートにおける粘着剤の塗工量は乾燥重量で2〜50g/m2 であることが好ましく、5〜25g/m2 であることがより好ましい。ダイレクト塗工の場合、粘着剤の基材への投錨性がよくなることから、反応の早い一液硬化型粘着剤には適していると言える。 Conversely, the adhesive can be applied on the substrate with a comma coater, reverse coater, slot die coater, etc., dried and then laminated with a release material on the adhesive layer and pressed to obtain it by direct coating. it can. The coating amount of the pressure-sensitive adhesive in the pressure-sensitive adhesive sheet is preferably 2 to 50 g / m 2 by dry weight, and more preferably 5 to 25 g / m 2 . In the case of direct coating, the anchoring property of the pressure-sensitive adhesive to the base material is improved.
本発明の粘着剤の塗工方式は限定されないが、例えば、コンマコーター、ダイコーター、スロットダイコーター、カーテンコーター、ロールコーター、リバースロールコーター、グラビアコーター等が挙げられる。 Although the coating method of the adhesive of this invention is not limited, For example, a comma coater, a die coater, a slot die coater, a curtain coater, a roll coater, a reverse roll coater, a gravure coater etc. are mentioned.
塗工速度は特に限定されないが、3m/分から1000m/分が好適、より好ましくは10m/分から 60 m/分が好適である。 The coating speed is not particularly limited, but is preferably 3 m / min to 1000 m / min, more preferably 10 m / min to 60 m / min.
次に実施例により本発明を説明するが、本発明はこれらに限定されない。
分子量の測定はGPC(ゲルパーミエーションクロマトグラフィー)を用いる。GPCは溶媒に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーである。分子量の決定はポリスチレン換算で行った。
粘度の測定はBL型粘度計において、ローター4番、60回転毎分の条件で行った。
本発明において、保持力の測定は以下の手順で行った。粘着シートを100×25mmに断裁し、その一方の端の25×25mmの面積の部分を23℃65%RH雰囲気下でステンレス板に貼り付け、2kgのロールで一往復して圧着する。その試験片を40℃の雰囲気において20分放置後、1kgの重りを吊り下げて、落下するまでの時間、あるいは一定時間後の貼り付け面のズレ(クリープ状態)を測定した。
EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited to these.
The molecular weight is measured using GPC (gel permeation chromatography). GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. The molecular weight was determined in terms of polystyrene.
Viscosity was measured on a BL type viscometer under conditions of rotor No. 4 and 60 revolutions per minute.
In the present invention, the holding force was measured by the following procedure. The pressure-sensitive adhesive sheet is cut to 100 × 25 mm, and a 25 × 25 mm area portion at one end thereof is attached to a stainless steel plate in an atmosphere of 23 ° C. and 65% RH. The test piece was left in an atmosphere of 40 ° C. for 20 minutes, then a 1 kg weight was suspended, and the time until dropping or the displacement (creep state) of the attached surface after a certain time was measured.
[実施例1]
攪拌器、温度計、滴下ロート、還流器を備えた重合槽において、アクリル酸2−エチルヘキシル180g、アクリル酸ブチル57g、アクリル酸メチル40g、アクリル酸18g、メタクリル酸グリシジル2.75g、アゾビスイソブチルニトリル0.45g、酢酸エチル274gからなる原料を、1/2に分け滴下ロートおよび反応釜に仕込んだ。系内を窒素ガスで飽和させて攪拌し、反応系を昇温し、リフラックスした後に滴下を開始した。滴下終了後、さらに攪拌しながら3時間熟成した後、酢酸エチルを加え冷却し、固形分が30重量%のアクリル重合体を含む溶液を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。
この粘着剤の粘度を測定したところ、2100mPa・sであり、GPC(ゲルパーミエーションクロマトグラフィー)により重量平均分子量を測定したところ59万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 1]
In a polymerization tank equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 180 g of 2-ethylhexyl acrylate, 57 g of butyl acrylate, 40 g of methyl acrylate, 18 g of acrylic acid, 2.75 g of glycidyl methacrylate, 0.45 azobisisobutylnitrile g and a raw material consisting of 274 g of ethyl acetate were divided in half and charged into a dropping funnel and a reaction kettle. The system was saturated with nitrogen gas and stirred, and the temperature of the reaction system was raised and refluxing was started. After completion of the dropwise addition, the mixture was further aged for 3 hours with stirring, and then cooled by adding ethyl acetate to obtain a solution containing an acrylic polymer having a solid content of 30% by weight. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage.
The viscosity of the pressure-sensitive adhesive was measured and found to be 2100 mPa · s. The weight average molecular weight measured by GPC (gel permeation chromatography) was 590,000.
This pressure-sensitive adhesive composition was coated on a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例2]
実施例1においてアクリル酸の量が22gである以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。
この粘着剤の粘度を測定したところ、2200mPa・sであり、GPCにより重量平均分子量を測定したところ60万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 2]
A pressure-sensitive adhesive composition was obtained in the same manner except that the amount of acrylic acid in Example 1 was 22 g. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage.
The viscosity of the pressure-sensitive adhesive was measured and found to be 2200 mPa · s. The weight average molecular weight measured by GPC was 600,000.
This pressure-sensitive adhesive composition was coated on a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例3]
実施例1においてメタクリル酸グリシジルの量が4.8gである以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。
この粘着剤の粘度を測定したところ、2300mPa・sであり、GPCにより重量平均分子量を測定したところ61万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 3]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the amount of glycidyl methacrylate was 4.8 g. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage.
The viscosity of the pressure-sensitive adhesive was measured and found to be 2300 mPa · s. The weight average molecular weight measured by GPC was 610,000.
This pressure-sensitive adhesive composition was coated on a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例4]
仕込み、反応は実施例1と同様にし、冷却に用いる酢酸エチルの量を変えて、固形分が35重量%のアクリル重合体を含む溶液を得た。ここに(メタ)アクリル酸共重合物溶液に対して0.002倍量の2-ヒドロキシフェニルトリアジン化合物(商品名TINUVIN400、チバ・スペシャリティ・ケミカルズ株式会社製)をくわえ、常温で30分間攪拌し、本発明の粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。
本粘着剤の粘度を測定したところ、3000mPa・sであり、GPCにより重量平均分子量を測定したところ59万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 4]
The charging and reaction were the same as in Example 1, and the amount of ethyl acetate used for cooling was changed to obtain a solution containing an acrylic polymer having a solid content of 35% by weight. Add 0.002 times the amount of 2-hydroxyphenyltriazine compound (trade name TINUVIN400, manufactured by Ciba Specialty Chemicals Co., Ltd.) to the (meth) acrylic acid copolymer solution, and stir at room temperature for 30 minutes. An adhesive composition was obtained. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage.
The viscosity of the pressure-sensitive adhesive was measured and found to be 3000 mPa · s. The weight average molecular weight measured by GPC was 590,000.
This pressure-sensitive adhesive composition was coated on a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例5]
実施例4において、2-ヒドロキシフェニルトリアジン化合物が2-ヒドロキシフェニルベンゾトリアゾール化合物(商品名Tinuvin384-2、チバ・スペシャリティ・ケミカルズ株式会社製)に変わった以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。この組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 5]
In Example 4, a pressure-sensitive adhesive composition was obtained in the same manner except that the 2-hydroxyphenyltriazine compound was changed to a 2-hydroxyphenylbenzotriazole compound (trade name Tinuvin384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.). . The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage. This composition was applied to a polyester substrate, dried at 110 ° C., and the adhesive surface was laminated with release paper to obtain an adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例6]
実施例4において、2-ヒドロキシフェニルトリアジン化合物がアミノエーテル系ヒンダードアミン化合物(商品名Tinuvin123、チバ・スペシャリティ・ケミカルズ株式会社製)に変わった以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。この組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 6]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 4, except that the 2-hydroxyphenyltriazine compound was changed to an amino ether-based hindered amine compound (trade name Tinuvin123, manufactured by Ciba Specialty Chemicals Co., Ltd.). The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage. This composition was applied to a polyester substrate, dried at 110 ° C., and the adhesive surface was laminated with release paper to obtain an adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例7]
実施例4において、2-ヒドロキシフェニルトリアジン化合物がポリフェノール系化合物(2,5-ジ-tert-ブチルハイドロキノン)に変わった以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。この組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 7]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 4 except that the 2-hydroxyphenyltriazine compound was changed to a polyphenol compound (2,5-di-tert-butylhydroquinone). The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage. This composition was applied to a polyester substrate, dried at 110 ° C., and the adhesive surface was laminated with release paper to obtain an adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例8]
実施例1において、メタクリル酸グリシジルの代わりに、オキセタンメタクリレートを用いた以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。この組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 8]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that oxetane methacrylate was used instead of glycidyl methacrylate. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage. This composition was applied to a polyester substrate, dried at 110 ° C., and the adhesive surface was laminated with release paper to obtain an adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例9]
実施例1において、メタクリル酸グリシジルの代わりに、3、4-エポキシシクロヘキシルメチルアクリレートを用いた以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。この組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 9]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that 3,4-epoxycyclohexylmethyl acrylate was used instead of glycidyl methacrylate. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage. This composition was applied to a polyester substrate, dried at 110 ° C., and the adhesive surface was laminated with release paper to obtain an adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[実施例10]
実施例1において、原料組成をアクリル酸2−エチルヘキシル180g、アクリル酸メチル97g、アクリル酸18g、メタクリル酸グリシジル2.75g、アゾビスイソブチルニトリル0.45g、酢酸エチル274gとした以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。
この粘着剤組成物の粘度を測定したところ、2200mPa・sであり、GPCにより重量平均分子量を測定したところ61万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Example 10]
In the same manner as in Example 1, except that the raw material composition was 180 g of 2-ethylhexyl acrylate, 97 g of methyl acrylate, 18 g of acrylic acid, 2.75 g of glycidyl methacrylate, 0.45 g of azobisisobutylnitrile, and 274 g of ethyl acetate. I got a thing. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage.
The viscosity of the pressure-sensitive adhesive composition was measured and found to be 2200 mPa · s. The weight average molecular weight measured by GPC was 610,000.
This pressure-sensitive adhesive composition was coated on a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[比較例1]
実施例1においてメタクリル酸グリシジルの量が6gである以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存したところ増粘した。本粘着剤の粘度を測定したところ、2400mPa・sであり、GPCにより重量平均分子量を測定したところ63万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Comparative Example 1]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the amount of glycidyl methacrylate was 6 g. The pressure-sensitive adhesive composition was thickened when stored at 50 ° C. for 2 weeks. The viscosity of the adhesive was measured and found to be 2400 mPa · s. The weight average molecular weight measured by GPC was 630,000.
This pressure-sensitive adhesive composition was coated on a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[比較例2]
実施例1においてアクリル酸の量が28gである以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存したところ増粘した。本粘着剤の粘度を測定したところ、2400mPa・sであり、GPCにより重量平均分子量を測定したところ63万であった。
この粘着剤組成物をポリエステル基材に塗工し、110℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、70000秒後にて重りは落下しなかった。
[Comparative Example 2]
A pressure-sensitive adhesive composition was obtained in the same manner except that the amount of acrylic acid in Example 1 was 28 g. The pressure-sensitive adhesive composition was thickened when stored at 50 ° C. for 2 weeks. The viscosity of the adhesive was measured and found to be 2400 mPa · s. The weight average molecular weight measured by GPC was 630,000.
This pressure-sensitive adhesive composition was applied to a polyester substrate, dried at 110 ° C., and the pressure-sensitive adhesive surface was laminated with release paper to obtain a pressure-sensitive adhesive sheet. When this sheet was used for a holding force test, the weight did not fall after 70000 seconds.
[比較例3]
実施例4において、2-ヒドロキシフェニルトリアジン化合物がヒンダードアミン化合物(商品名Tinuvin292、チバ・スペシャリティ・ケミカルズ株式会社製)に変わった以外は同様にして粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存したところゲル化した。
[Comparative Example 3]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 4 except that the 2-hydroxyphenyltriazine compound was changed to a hindered amine compound (trade name Tinuvin292, manufactured by Ciba Specialty Chemicals Co., Ltd.). When this pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, it gelled.
[比較例4]
実施例1に同様にして粘着剤組成物を得た。この組成物をポリエステル基材に塗工し、80℃で乾燥させ、剥離紙で粘着面をラミネートし粘着シートを得た。このシートを用いて保持力の試験を行ったところ、50000秒後にて重りは落下した。
[Comparative Example 4]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1. This composition was applied to a polyester substrate, dried at 80 ° C., and the adhesive surface was laminated with release paper to obtain an adhesive sheet. When this sheet was used for a holding force test, the weight dropped after 50000 seconds.
[比較例5]
実施例1において、重合時に使用した酢酸エチル274gを、酢酸エチル443gとトルエン111gにした以外は同様にして、粘着剤組成物を得た。この粘着剤組成物を50℃で2週間保存し、粘度を測定したところ、保存前と比べ、粘度の変化は見られなかった。
この粘着剤の粘度を測定したところ、700mPa・sであり、GPCにより重量平均分子量を測定したところ20万であった。
実施例1と同様にして粘着シートを得、これを用いて保持力の試験を行ったところ、200秒後にて重りは落下した。
実施例、比較例の結果は表1にまとめて記載した。
[Comparative Example 5]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that 274 g of ethyl acetate used in the polymerization was changed to 443 g of ethyl acetate and 111 g of toluene. The pressure-sensitive adhesive composition was stored at 50 ° C. for 2 weeks, and the viscosity was measured. As a result, no change in viscosity was observed compared to before storage.
When the viscosity of this pressure-sensitive adhesive was measured, it was 700 mPa · s, and when the weight average molecular weight was measured by GPC, it was 200,000.
When a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 and a holding power test was performed using the pressure-sensitive adhesive sheet, the weight dropped after 200 seconds.
The results of Examples and Comparative Examples are summarized in Table 1.
経時粘度評価
○:50℃2週間保存試験における増粘が10%未満
×:50℃2週間保存試験における増粘が10%以上
保持力評価
○:保持力試験において70000秒落下せず。
×:保持力試験において70000秒以内に落下。
Viscosity evaluation over time ○: Thickness is less than 10% at 50 ° C for 2 weeks storage test ×: Thickness is 10% or more at 50 ° C for 2 weeks storage test ○: Does not fall for 70000 seconds in the retention strength test
×: Dropped within 70000 seconds in holding force test.
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JPH05105799A (en) * | 1991-07-03 | 1993-04-27 | Mitsui Toatsu Chem Inc | Emulsion composition |
JPH06100849A (en) * | 1992-09-21 | 1994-04-12 | Dainippon Ink & Chem Inc | Pressure-sensitive adhesive |
JPH08217946A (en) * | 1995-02-17 | 1996-08-27 | Toyo Ink Mfg Co Ltd | Liquid resin composition and its production |
-
2003
- 2003-10-17 JP JP2003357460A patent/JP4506146B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05105799A (en) * | 1991-07-03 | 1993-04-27 | Mitsui Toatsu Chem Inc | Emulsion composition |
JPH06100849A (en) * | 1992-09-21 | 1994-04-12 | Dainippon Ink & Chem Inc | Pressure-sensitive adhesive |
JPH08217946A (en) * | 1995-02-17 | 1996-08-27 | Toyo Ink Mfg Co Ltd | Liquid resin composition and its production |
Also Published As
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JP2004300405A (en) | 2004-10-28 |
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