JP6515395B2 - Adhesive and adhesive sheet - Google Patents
Adhesive and adhesive sheet Download PDFInfo
- Publication number
- JP6515395B2 JP6515395B2 JP2018091960A JP2018091960A JP6515395B2 JP 6515395 B2 JP6515395 B2 JP 6515395B2 JP 2018091960 A JP2018091960 A JP 2018091960A JP 2018091960 A JP2018091960 A JP 2018091960A JP 6515395 B2 JP6515395 B2 JP 6515395B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- monomer
- weight
- acrylate
- 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.)
- Active
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- 230000001070 adhesive effect Effects 0.000 title claims description 37
- 239000000853 adhesive Substances 0.000 title claims description 36
- 239000000178 monomer Substances 0.000 claims description 102
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 78
- -1 aziridine compound Chemical class 0.000 claims description 58
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 43
- 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 claims description 43
- 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 claims description 43
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 229920006243 acrylic copolymer Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 11
- 239000004033 plastic Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920000098 polyolefin Polymers 0.000 description 9
- 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 8
- 238000011156 evaluation Methods 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229920005672 polyolefin resin Polymers 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000002928 artificial marble Substances 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-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
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- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、プラスチック等への貼り付けに好適に使用できる粘着剤および粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet which can be suitably used for sticking to a plastic or the like.
粘着剤から形成した粘着剤層を有する粘着シートは、取り扱いが容易であることからラベルや接着用途として幅広い分野で使用されている。例えば、粘着シートをプラスチック等の容器のラベルとして使用することは一般的であるが、当該プラスチック容器がポリプロピレンやポリエチレン等のポリオレフィン樹脂である場合、ポリオレフィン樹脂は、極性が低いため粘着シートを貼り付けたときの粘着力が低くラベルが剥がれやすいという問題があった。また、化粧品容器など意匠性が高いプラスチック容器は、ラベルとして使用する粘着シートにも透明性が求められる場合が多い。さらには、シャンプー容器など浴室などで使用される日用品のプラスチック容器に用いられる粘着シートには、高温高湿環境下に曝された場合でも粘着シートの透明性が維持できる耐白化性が求められていた。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive is widely used as a label or adhesive application because it is easy to handle. For example, although it is common to use an adhesive sheet as a label of a container such as plastic, when the plastic container is a polyolefin resin such as polypropylene or polyethylene, the polyolefin resin has a low polarity and the adhesive sheet is attached. There is a problem that the adhesive strength is low and the label is easy to peel off. In addition, a plastic container having high designability such as a cosmetic container often requires transparency for an adhesive sheet used as a label. Furthermore, the pressure-sensitive adhesive sheet used in plastic containers for daily necessities such as shampoo containers used in the bathroom is required to have whitening resistance that can maintain the transparency of the pressure-sensitive adhesive sheet even when exposed to high temperature and high humidity The
そこで、特許文献１には、炭素数８個以上のアルキル基を有する（メタ）アクリル酸アルキルエステルの占める割合が３０重量％以上のアクリル系共重合体、及び粘着付与樹脂としてロジンまたはその誘導体と水添石油樹脂とを含む粘着剤が開示されている。 Therefore, in Patent Document 1, an acrylic copolymer in which the proportion of (meth) acrylic acid alkyl ester having an alkyl group having 8 or more carbon atoms is 30% by weight or more, and rosin as a tackifying resin or a derivative thereof An adhesive comprising a hydrogenated petroleum resin is disclosed.
また、特許文献２には、アクリル系共重合体１００質量部と、重量平均分子量が１０００以上３００００未満のアクリル系共重合体１〜７０質量部と、水素添加型粘着付与樹脂１〜５０質量部とを含む粘着剤が開示されている。 Further, in Patent Document 2, 100 parts by mass of an acrylic copolymer, 1 to 70 parts by mass of an acrylic copolymer having a weight average molecular weight of 1,000 to less than 30,000, and 1 to 50 parts by mass of a hydrogenated tackifying resin And a pressure-sensitive adhesive containing the
また、特許文献３には、６５〜９４．５重量％のアクリル酸エステルと、０．５〜５重量％の極性架橋性モノマーと、５〜３０重量％の非極性モノマーの反応生成物とを含むコポリマー１００部に対して、３０〜７０部の水素添加炭化水素粘着付与剤と、０．０１〜３部の架橋剤とを含む粘着剤が開示されている。 Further, Patent Document 3 discloses a reaction product of 65 to 94.5% by weight of acrylic ester, 0.5 to 5% by weight of polar crosslinkable monomer, and 5 to 30% by weight of nonpolar monomer. An adhesive comprising 30 to 70 parts of a hydrogenated hydrocarbon tackifier and 0.01 to 3 parts of a crosslinking agent is disclosed per 100 parts of the copolymer contained.
また、特許文献４には、炭素数が２〜１４のアルキル基を有するアクリル系単量体２０〜８０重量％および芳香族基を有する単量体８０〜２０重量％を単量体単位として含有するアクリル系共重合体１００重量部に対し、芳香族環またはその水添物を有してなり、かつ屈折率１．５３〜１．７５のタッキファイヤーを２０〜１５０重量部を含む粘着剤が開示されている。 Further, Patent Document 4 contains, as a monomer unit, 20 to 80% by weight of an acrylic monomer having an alkyl group having 2 to 14 carbon atoms and 80 to 20% by weight of a monomer having an aromatic group. An adhesive comprising 20 to 150 parts by weight of tackifier having an aromatic ring or a hydrogenated product thereof and having a refractive index of 1.53 to 1.75 per 100 parts by weight of the acrylic copolymer to be It is disclosed.
また、特許文献５には、アクリル酸ブチル３０〜７０重量％と、アクリル酸２−エチルヘキシル１０〜５０重量％と、分子内にビシクロ環構造を有するラジカル重合性モノマー成分５〜３０重量％とを含有するアクリル系共重合体１００重量部と、粘着付与剤３〜６０重量部とを含む粘着剤が開示されている。 Further, in Patent Document 5, 30 to 70% by weight of butyl acrylate, 10 to 50% by weight of 2-ethylhexyl acrylate, and 5 to 30% by weight of a radically polymerizable monomer component having a bicyclo ring structure in the molecule An adhesive comprising 100 parts by weight of the contained acrylic copolymer and 3 to 60 parts by weight of a tackifier is disclosed.
しかし、特許文献１の粘着剤は、アクリル系重合体との相溶性が悪い水添石油樹脂を含むので粘着剤の透明性が低い問題があった。
また、特許文献２の紫外線硬化型粘着剤は、粘着剤層と基材の密着性が低く、また、プラスチック容器を廃棄する際に、容器側に粘着剤層が残留しやすいため分別処理が難しく環境適性が低かった、また、硬化剤を使用していないため、粘着力等の物性調整が難しいという問題があった。
特許文献３の粘着剤は、水素添加炭化水素粘着付与剤を多量に配合しているため、アクリル系重合体との相溶性が悪く、透明性が低いという問題があった。
特許文献４の粘着剤は、透明性は良好であったものの、ポリオレフィンに対する粘着力が低いという問題があった。
特許文献５の粘着剤は、ＳＵＳ等の極性が高い部材に対する粘着力は高いものの、極性が低いポリオレフィンに対する粘着力、および耐白化性が低い問題があった。
However, the pressure-sensitive adhesive of Patent Document 1 has a problem that the transparency of the pressure-sensitive adhesive is low because the pressure-sensitive adhesive contains a hydrogenated petroleum resin having poor compatibility with the acrylic polymer.
In addition, the ultraviolet-curable pressure-sensitive adhesive of Patent Document 2 has low adhesion between the pressure-sensitive adhesive layer and the substrate, and when the plastic container is discarded, separation treatment is difficult because the pressure-sensitive adhesive layer tends to remain on the container side. There was a problem that adjustment of physical properties such as adhesion was difficult because the environmental suitability was low and no curing agent was used.
Since the pressure-sensitive adhesive of Patent Document 3 contains a large amount of a hydrogenated hydrocarbon tackifier, there is a problem that the compatibility with the acrylic polymer is poor and the transparency is low.
Although the pressure-sensitive adhesive of Patent Document 4 has good transparency, it has a problem of low adhesion to polyolefin.
The pressure-sensitive adhesive of Patent Document 5 has high adhesion to members with high polarity such as SUS, but has a problem of low adhesion to polyolefins with low polarity and low whitening resistance.
本発明は、透明性、およびポリオレフィン樹脂に対する粘着力が良好であり、耐白化性が優れた粘着シートを形成できる粘着剤の提供を目的とする。 An object of the present invention is to provide a pressure-sensitive adhesive which can form a pressure-sensitive adhesive sheet which is excellent in transparency, adhesion to a polyolefin resin, and excellent in whitening resistance.
本発明の粘着剤は、アクリル系共重合体と、ロジン系樹脂と、硬化剤とを含み、前記アクリル系共重合体が、アクリル酸ブチル６０〜９８．５重量％と、カルボキシル基含有モノマー１〜９．９重量％と、モノマー（Ｘ）０．５〜２０重量％とを含むモノマー混合物を溶液重合してなり、前記モノマー（Ｘ）が、ホモポリマーのガラス転移温度が１５℃以上、かつ２５℃の水１００ｍｌに対する溶解度が１ｇ未満である。 The pressure-sensitive adhesive of the present invention comprises an acrylic copolymer, a rosin resin, and a curing agent, and the acrylic copolymer comprises 60 to 98.5% by weight of butyl acrylate and a carboxyl group-containing monomer 1 The solution mixture is obtained by solution polymerization of a monomer mixture containing 9.9% by weight and 0.5 to 20% by weight of monomer (X), and said monomer (X) has a glass transition temperature of homopolymer of 15 ° C. or more, and The solubility in 100 ml of water at 25 ° C. is less than 1 g.
上記の本発明によれば、主モノマーのアクリル酸ブチルと、ガラス転移温度が高く水に溶解し難いモノマー（Ｘ）とを溶液重合したアクリル系共重合体、およびロジン系樹脂を含む粘着剤を塗工して形成した粘着剤層を備えた粘着シートは、透明性が高く、ポリオレフィンに対する粘着力が良好であることに加え、耐白化性が優れる効果が得られた。 According to the above-mentioned present invention, an adhesive comprising an acrylic copolymer obtained by solution polymerization of butyl acrylate as a main monomer and a monomer (X) having a high glass transition temperature and being difficult to dissolve in water, and a pressure-sensitive adhesive containing a rosin resin The pressure-sensitive adhesive sheet provided with the pressure-sensitive adhesive layer formed by coating has high transparency, good adhesion to polyolefin, and excellent whitening resistance.
本発明により、本発明は、透明性、およびポリオレフィン樹脂に対する粘着力が良好であり、耐白化性が優れた粘着シートを形成できる粘着剤を提供できる。 According to the present invention, the present invention can provide a pressure-sensitive adhesive which can form a pressure-sensitive adhesive sheet which is excellent in transparency, adhesion to a polyolefin resin, and excellent in whitening resistance.
本発明について詳細に説明する前に用語を定義する。まず、シート、フィルムおよびテープは同義語である。（メタ）アクリル酸は、アクリル酸およびメタクリル酸を含む。（メタ）アクリレートは、アクリレートおよびメタクリレートを含む。モノマーはエチレン性不飽和二重結合含有単量体である。被着体は、粘着シートを貼り付ける相手方をいう。 Before describing the invention in detail, the terms are defined. First, sheet, film and tape are synonymous. (Meth) acrylic acid includes acrylic acid and methacrylic acid. (Meth) acrylates include acrylates and methacrylates. The monomer is an ethylenically unsaturated double bond-containing monomer. An adherend means the other party who sticks an adhesive sheet.
本発明の粘着剤は、アクリル系共重合体と、ロジン系樹脂と、硬化剤とを含む。前記アクリル系共重合体は、アクリル酸ブチル６０〜９８．５重量％と、カルボキシル基含有モノマー１〜９．９重量％と、モノマー（Ｘ）０．５〜２０重量％とを含むモノマー混合物を溶液重合して得る。そして前記モノマー（Ｘ）は、ホモポリマーのガラス転移温度が１５℃以上、かつ２５℃の水１００ｍｌに対する溶解度が１ｇ未満である性質を有する。
本発明の粘着剤は、粘着シートに加工して使用することが好ましい。
The pressure-sensitive adhesive of the present invention comprises an acrylic copolymer, a rosin resin, and a curing agent. The acrylic copolymer is a monomer mixture containing 60 to 98.5% by weight of butyl acrylate, 1 to 9.9% by weight of a carboxyl group-containing monomer, and 0.5 to 20% by weight of a monomer (X). Obtained by solution polymerization. The monomer (X) has a property that the glass transition temperature of the homopolymer is 15 ° C. or higher and the solubility in 100 ml of water at 25 ° C. is less than 1 g.
The pressure-sensitive adhesive of the present invention is preferably processed into a pressure-sensitive adhesive sheet and used.
一般に粘着剤の対ポリオレフィン粘着力を向上させるには、ロジン系樹脂を多量に配合することが知られている。しかし、ロジン系樹脂を多量に配合すると粘着剤が白濁してしまうので、透明フィルム基材の粘着シートには使用し難い問題があった。本発明では、モ
ノマー（Ｘ）を使用しモノマー混合物を溶液重合する。前記モノマー（Ｘ）は共重合性が低いので、モノマー（Ｘ）ユニットを多く含んだ共重合体が存在するため、ロジン系樹脂とアクリル系共重合体の相溶性を向上させていると推測している。そのため、本発明では、対ポリオレフィン粘着力と透明性を両立できた。
Generally, it is known to blend a rosin-based resin in a large amount in order to improve the adhesion of the adhesive to the polyolefin. However, when the rosin-based resin is blended in a large amount, the pressure-sensitive adhesive becomes cloudy, and there is a problem that it is difficult to use the pressure-sensitive adhesive sheet of the transparent film substrate. In the present invention, monomer (X) is used to solution polymerize the monomer mixture. Since the monomer (X) has low copolymerizability, it is presumed that the compatibility between the rosin resin and the acrylic copolymer is improved because there is a copolymer containing a large amount of monomer (X) units. ing. Therefore, in the present invention, both the adhesion to polyolefin and the transparency can be achieved.
本発明でアクリル系重合体は、アクリル酸ブチル６０〜９８．５重量％と、カルボキシル基含有モノマー１〜９．９重量％と、ホモポリマーのガラス転移温度が１５℃以上、かつ２５℃の水１００ｍｌに対する溶解度が１ｇ未満であるモノマー（Ｘ）０．５〜２０重量％とを必須モノマーとし、その他のモノマーを任意モノマーとしたモノマー混合物を溶液重合した共重合体である。 In the present invention, the acrylic polymer comprises 60 to 98.5% by weight of butyl acrylate, 1 to 9.9% by weight of carboxyl group-containing monomer, and water having a glass transition temperature of homopolymer of 15 ° C. or more and 25 ° C. It is a copolymer obtained by solution polymerization of a monomer mixture containing, as an essential monomer, 0.5 to 20% by weight of a monomer (X) having a solubility of less than 1 g in 100 ml and other monomers as optional monomers.
アクリル酸ブチルは、モノマー混合物の主モノマーでありモノマー混合物１００重量％中に６０〜９８．５重量％を使用することが必要であり、６５〜９０重量％がより好ましい。アクリル酸ブチルを主モノマーとしたことで粘着力と凝集力の両立が容易になる。 Butyl acrylate is the main monomer of the monomer mixture and it is necessary to use 60 to 98.5 wt% in 100 wt% of the monomer mixture, with 65 to 90 wt% being more preferred. By using butyl acrylate as the main monomer, it is easy to achieve both the cohesion and the cohesion.
カルボキシル基含有モノマーは、硬化剤との架橋反応の架橋点として機能し、モノマー混合物１００重量％中に１〜９．９重量％を使用することが必要であり、１〜９重量％がより好ましく、２〜８重量％がさらに好ましい。カルボキシル基含有モノマーを１〜９．９重量％使用することで、所望の架橋密度が得やすく、さらにアクリル系共重合体とロジン系樹脂との相溶性が確保できる。 The carboxyl group-containing monomer functions as a crosslinking point of the crosslinking reaction with the curing agent, and it is necessary to use 1 to 9.9% by weight in 100% by weight of the monomer mixture, and 1 to 9% by weight is more preferable. And 2 to 8% by weight are more preferable. By using 1 to 9.9% by weight of the carboxyl group-containing monomer, a desired crosslinking density can be easily obtained, and furthermore, the compatibility between the acrylic copolymer and the rosin resin can be secured.
カルボキシル基含有モノマーは、例えば（メタ）アクリル酸、フタル酸モノヒドロキシエチルアクリル酸エステル、ｐ−カルボキシベンジルアクリル酸エステル、エチレンオキサイド変性（エチレンオキサイド付加モル数：（２〜１８）フタル酸アクリル酸エステル、コハク酸モノヒドロキシエチルアクリル酸エステル、アクリル酸β−カルボキシエチル、イタコン酸等が挙げられる。これらの中でも、（メタ）アクリル酸が好ましい。 The carboxyl group-containing monomer is, for example, (meth) acrylic acid, phthalic acid monohydroxyethyl acrylate, p-carboxybenzyl acrylate, ethylene oxide modified (ethylene oxide addition mole number: (2 to 18) phthalic acrylate And succinic acid monohydroxyethyl acrylate, acrylic acid β-carboxyethyl, itaconic acid etc. Among these, (meth) acrylic acid is preferable.
モノマー（Ｘ）は、ホモポリマーのガラス転移温度（以下、Ｔｇともいう）が１５℃以上、かつ２５℃の水１００ｍｌに対する溶解度が１ｇ未満の性質を有する。本発明で２５℃の水１００ｍｌに対して１ｇ未満が溶解する性質とは、２５℃の環境下で水１００ｍＬにモノマーを混合し１時間攪拌した後に、水とモノマーが分離せずに均一な状態を保持できる最大量が１ｇ未満であり、モノマーが水に溶解し難い指標を意味する。モノマーが極性の高い水に溶解しないことは、モノマーの極性が低いことを意味する。一般的にモノマーの極性を示す指標として、溶解度パラメーター（以下、ＳＰ値ともいう）を用いる場合が多いが、モノマーの分子骨格から算出されるＳＰ値よりも、モノマーの水に対する溶解度を指標とした場合の方が、本発明の課題解決に寄与するモノマーを選択することができる。
また、モノマー（Ｘ）は、アクリル系共重合体のＴｇを高めて被着体との密着性を向上させながら、アクリル系共重合体とロジン系樹脂との相溶性を確保する機能を有する。また、モノマー（Ｘ）の性質を換言すると、主としてメタクリロイル基または嵩高い構造を有するともいえる。モノマー（Ｘ）は、モノマー混合物中０．５〜２０重量％が必要であり、２〜１８重量％がより好ましい。０．５〜２０重量％の範囲で使用することで密着性がより向上する。
また、モノマー（Ｘ）のホモポリマーのＴｇは１５℃以上がひつようである。Ｔｇが１５℃以上になることで密着性がより向上する。
なお、モノマー（Ｘ）のＴｇの上限値は、本発明の課題を解決できれば良いので特に限定しないが、２００℃程度である。
The monomer (X) has a property that the glass transition temperature (hereinafter also referred to as Tg) of the homopolymer is 15 ° C. or higher, and the solubility in 100 ml of water at 25 ° C. is less than 1 g. In the present invention, the property that less than 1 g dissolves in 100 ml of water at 25 ° C. means that 100 mL of water is mixed with the monomer under the environment of 25 ° C. and stirred for 1 hour. The maximum amount that can be retained is less than 1 g, which means that the monomer is difficult to dissolve in water. The insolubility of the monomer in highly polar water means that the polarity of the monomer is low. In general, solubility parameter (hereinafter also referred to as SP value) is often used as an index indicating the polarity of the monomer, but the solubility of the monomer in water is used as an index rather than the SP value calculated from the molecular skeleton of the monomer. In the case, it is possible to select a monomer that contributes to the solution of the problem of the present invention.
In addition, the monomer (X) has a function of securing the compatibility between the acrylic copolymer and the rosin resin while raising the Tg of the acrylic copolymer to improve the adhesion to the adherend. In addition, in other words, the properties of the monomer (X) can be said to mainly have a methacryloyl group or a bulky structure. The monomer (X) is required to be 0.5 to 20% by weight in the monomer mixture, and 2 to 18% by weight is more preferable. Adhesion is further improved by using in the range of 0.5 to 20% by weight.
Also, the Tg of the homopolymer of monomer (X) should be 15 ° C. or more. Adhesiveness improves more because Tg becomes 15 ° C or more.
The upper limit of the Tg of the monomer (X) is not particularly limited as long as it can solve the problems of the present invention, but is about 200 ° C.
モノマー（Ｘ）は、例えば、メタクリル酸エチル（Ｔｇ：６５℃）、メタクリル酸プロピル（Ｔｇ：３５℃）、メタクリル酸イソプロピル（Ｔｇ：８１℃）、メタクリル酸ブチ
ル（Ｔｇ：２０℃）、メタクリル酸イソブチル（Ｔｇ：５３℃）、アクリル酸ｔ−ブチル（Ｔｇ：７３℃）、およびメタクリル酸ｔ−ブチル（Ｔｇ：１１８℃）等の（メタ）アクリル酸アルキルエステル；
メタクリル酸フェノキシエチル（Ｔｇ：５４℃）、メタクリル酸ベンジル（Ｔｇ：５４℃）、アクリル酸シクロヘキシル（Ｔｇ：１９℃）、メタクリル酸シクロヘキシル（Ｔｇ：８３℃）、アクリル酸イソボルニル（Ｔｇ：９７℃）、およびメタクリル酸イソボルニル（Ｔｇ：１８０℃）等の芳香環または脂環構造を有する（メタ）アクリル酸エステル；
スチレン（Ｔｇ：１００℃）、およびα−メチルスチレン（Ｔｇ：１６８℃）などのビニルモノマー等が挙げられる。なお、これらモノマーのＴｇは、ホモポリマーのＴｇである。
Monomer (X) is, for example, ethyl methacrylate (Tg: 65 ° C.), propyl methacrylate (Tg: 35 ° C.), isopropyl methacrylate (Tg: 81 ° C.), butyl methacrylate (Tg: 20 ° C.), methacrylic acid (Meth) acrylic acid alkyl esters such as isobutyl (Tg: 53 ° C.), t-butyl acrylate (Tg: 73 ° C.), and t-butyl methacrylate (Tg: 118 ° C.);
Phenoxyethyl methacrylate (Tg: 54 ° C), benzyl methacrylate (Tg: 54 ° C), cyclohexyl acrylate (Tg: 19 ° C), cyclohexyl methacrylate (Tg: 83 ° C), isobornyl acrylate (Tg: 97 ° C) And (meth) acrylic acid esters having an aromatic ring or alicyclic structure such as isobornyl methacrylate (Tg: 180 ° C.);
Examples thereof include vinyl monomers such as styrene (Tg: 100 ° C.) and α-methylstyrene (Tg: 168 ° C.). In addition, Tg of these monomers is Tg of a homopolymer.
本発明でその他のモノマーは、アクリル酸ブチル、カルボキシル基含有モノマー、およびモノマー（Ｘ）以外のモノマーである。
その他のモノマーは、粘着剤の透明性や粘着力を損なわないモノマーであれば良い。具体的には、例えば水酸基含有モノマー、アミド結合含有モノマー、エポキシ基含有モノマー、およびアミノ基含有モノマー等の反応性官能基を有するモノマー、（メタ）アクリル酸アルキルエステルモノマー、芳香環含有モノマー、アルコキシ（ポリ）アルキレンオキサイド含有モノマーおよびその他ビニルモノマー等が挙げられる。
Other monomers in the present invention are butyl acrylate, a carboxyl group-containing monomer, and a monomer other than the monomer (X).
Other monomers may be used as long as they do not impair the transparency and adhesion of the pressure-sensitive adhesive. Specifically, for example, monomers having reactive functional groups such as hydroxyl group-containing monomers, amide bond-containing monomers, epoxy group-containing monomers, and amino group-containing monomers, (meth) acrylic acid alkyl ester monomers, aromatic ring-containing monomers, alkoxy Examples include (poly) alkylene oxide-containing monomers and other vinyl monomers.
水酸基含有モノマーは、例えば、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸３−ヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸８−ヒドロキシオクチルなどの（メタ）アクリル酸ヒドロキシアルキルエステルや、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレングリコールモノ（メタ）アクリル酸エステル、１，４−シクロヘキサンジメタノールモノ（メタ）アクリル酸エステルなどのグリコールモノ（メタ）アクリル酸エステル、カプロラクトン変性（メタ）アクリル酸エステル、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミドなどのＮ−ヒドロキシアルキル（メタ）アクリルアミドが挙げられる。
これらの中でも、ホモポリマーのガラス転移温度が１５℃以上であるメタクリル酸２−ヒドロキシエチル（Ｔｇ：７１℃）、メタクリル酸２−ヒドロキシプロピル（Ｔｇ：２６℃）、１，４−シクロヘキサンジメタノールモノアクリル酸エステル（Ｔｇ：１８℃）、Ｎ−ヒドロキシエチル（メタ）アクリルアミド（Ｔｇ：９８℃）等は、ポリオレフィンに対する粘着力がより向上する場合があるため好ましい。
The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) (Meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and polyethylene glycol Glycol mono (meth) acrylic acid ester such as mono (meth) acrylic acid ester, polypropylene glycol mono (meth) acrylic acid ester, 1,4-cyclohexanedimethanol mono (meth) acrylic acid ester, caprolactone modified (meth) acrylic acid Ester, N- hydroxymethyl (meth) acrylamide, N- hydroxyethyl (meth) acrylamide such as N- hydroxyalkyl (meth) acrylamide.
Among these, 2-hydroxyethyl methacrylate (Tg: 71 ° C.), 2-hydroxypropyl methacrylate (Tg: 26 ° C.), 1,4-cyclohexanedimethanol mono, having a homopolymer having a glass transition temperature of 15 ° C. or higher. Acrylic acid ester (Tg: 18 ° C.), N-hydroxyethyl (meth) acrylamide (Tg: 98 ° C.), etc. are preferable because the adhesion to polyolefin may be further improved.
水酸基含有モノマーは、モノマー混合物１００重量％中、１〜２０重量％を含むことが好ましく、水酸基含有モノマーとモノマー（Ｘ）との合計量が２０重量％以下になるように含むことがより好ましい。水酸基含有モノマーを適量使用することで粘着力と透明性をより高度に両立できる。 The hydroxyl group-containing monomer preferably contains 1 to 20% by weight in 100% by weight of the monomer mixture, and more preferably the total content of the hydroxyl group-containing monomer and the monomer (X) is 20% by weight or less. By using an appropriate amount of a hydroxyl group-containing monomer, it is possible to achieve a high degree of compatibility between adhesion and transparency.
アミド結合含有モノマーは、例えば（メタ）アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ、Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、ジアセトンアクリルアミド、Ｎ−(ブトキシメチル)アクリルアミド等の（メタ）アクリルアミド系化合物；Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、およびアクリロイルモルホリン等の複素環含有化合物等が挙げられる。 The amide bond-containing monomer is, for example, (meth) acrylamide, N-methyl acrylamide, N-isopropyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (Meth) acrylamide compounds such as acrylamide and N- (butoxymethyl) acrylamide; and heterocycle-containing compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloyl morpholine.
エポキシ基含有モノマーは、例えば（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジル、および（メタ）アクリル酸３，４−エポキシシクロヘキシルメチル
等が挙げられる。
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.
アミノ基含有モノマーは、例えば（メタ）アクリル酸モノメチルアミノエチル、（メタ）アクリル酸モノエチルアミノエチル、（メタ）アクリル酸モノメチルアミノプロピル、および（メタ）アクリル酸モノエチルアミノプロピル等の（メタ）アクリル酸モノアルキルアミノエステル等が挙げられる。 The amino group-containing monomer is, for example, (meth) such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. Acrylic acid monoalkyl amino ester etc. are mentioned.
アミド結合含有モノマー、エポキシ基含有モノマーおよびアミノ基含有モノマーは、モノマー混合物１００重量％中、それぞれ０．１〜１重量部を含むことが好ましい。 The amide bond-containing monomer, the epoxy group-containing monomer and the amino group-containing monomer preferably each comprise 0.1 to 1 part by weight in 100% by weight of the monomer mixture.
（メタ）アクリル酸アルキルエステルモノマーは、例えば（メタ）アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル、および（メタ）アクリル酸イソオクタデシル等が挙げられる。 Examples of (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate (meth ) 2-ethylhexyl acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, and isooctadecyl (meth) acrylate Etc.
（メタ）アクリル酸アルキルエステルモノマーは、モノマー混合物１００重量％中、０．１〜２０重量部を含むことが好ましい。 The (meth) acrylic acid alkyl ester monomer preferably contains 0.1 to 20 parts by weight in 100% by weight of the monomer mixture.
芳香環含有モノマーは、例えばアクリル酸フェノキシエチル、アクリル酸ベンジル、（メタ）アクリル酸フェノキシジエチレングリコール、および（メタ）アクリル酸エチレンオキサイド変性ノニルフェノール等が挙げられる。 Examples of the aromatic ring-containing monomer include phenoxyethyl acrylate, benzyl acrylate, phenoxydiethylene glycol (meth) acrylate, and ethylene oxide-modified nonylphenol (meth) acrylate.
芳香環含有モノマーは、モノマー混合物１００重量％中、０．１〜１０重量部を含むことが好ましい。 The aromatic ring-containing monomer preferably comprises 0.1 to 10 parts by weight in 100% by weight of the monomer mixture.
アルコキシ（ポリ）アルキレンオキサイド含有モノマーは、例えばアクリル酸２−メトキシエチル、アクリル酸２−エトキシエチル、アクリル酸２−フェノキシエチル、メトキシポリエチレングリコール（メタ）アクリル酸エステル、エトキシポリエチレングリコール（メタ）アクリル酸エステル、メトキシポリプロピレングリコール（メタ）アクリル酸エステル、エトキシポリプロピレングリコール（メタ）アクリル酸エステル、フェノキシポリエチレングリコール（メタ）アクリル酸エステル、およびフェノキシポリプロピレングリコール（メタ）アクリル酸エステル等が挙げられる。 The alkoxy (poly) alkylene oxide-containing monomer is, for example, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylic acid Ester, methoxy polypropylene glycol (meth) acrylic acid ester, ethoxy polypropylene glycol (meth) acrylic acid ester, phenoxy polyethylene glycol (meth) acrylic acid ester, phenoxy polypropylene glycol (meth) acrylic acid ester, etc. may be mentioned.
アルコキシ（ポリ）アルキレンオキサイド含有モノマーは、モノマー混合物１００重量％中、０．１〜１０重量部を含むことが好ましい。 The alkoxy (poly) alkylene oxide-containing monomer preferably comprises 0.1 to 10 parts by weight in 100% by weight of the monomer mixture.
その他ビニルモノマーは、酢酸ビニル、およびアクリロニトリルなどが挙げられるがこれらに限定されない。 Other vinyl monomers include, but are not limited to, vinyl acetate, acrylonitrile and the like.
その他ビニルモノマーは、モノマー混合物１００重量％中、０．１〜１０重量部を含むことが好ましい。 The other vinyl monomer is preferably contained in an amount of 0.1 to 10 parts by weight in 100% by weight of the monomer mixture.
アクリル系共重合体は、モノマー混合物に重合開始剤を加え、溶液重合することで得る。前記溶液重合に使用する溶剤は、例えば、酢酸メチル、酢酸エチル、酢酸ｎ−ブチル、酢酸イソブチル、トルエン、キシレン、ヘキサン、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、ｎ−プロパノール、およびイソプロパノール等が好ましく、酢酸エチルがより好ましい。
溶剤は単独また２種類以上を併用できる。
An acrylic copolymer is obtained by adding a polymerization initiator to a monomer mixture and performing solution polymerization. The solvent used for the solution polymerization is, for example, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol and the like Is preferred, and ethyl acetate is more preferred.
The solvents may be used alone or in combination of two or more.
前記溶液重合は、モノマー混合物１００重量部に対して重合開始剤を０．００１〜１重量部程度加えて重合を行うことが好ましい。通常、重合は、窒素気流下で、５０℃〜９０℃程度の温度で６時間〜２０時間行うことができる。また、重合の際、連鎖移動剤を使用して共重合体の重量平均分子量を適宜調整することができる。 The solution polymerization is preferably performed by adding about 0.001 to 1 part by weight of a polymerization initiator to 100 parts by weight of the monomer mixture. In general, the polymerization can be carried out at a temperature of about 50 ° C. to 90 ° C. for 6 hours to 20 hours under a nitrogen stream. In addition, at the time of polymerization, a chain transfer agent can be used to appropriately adjust the weight average molecular weight of the copolymer.
本発明においてアクリル系共重合体の重量平均分子量（以下、Ｍｗという）は、３０万〜１８０万が好ましく、４０万〜１５０万がより好ましく、５０万〜１３０万がさらに好ましい。Ｍｗを３０万〜１８０万の範囲にすることで、粘着物性と塗工性の両立が容易になる。なお、本発明でＭｗは、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定したポリスチレン換算の値である。 In the present invention, the weight average molecular weight (hereinafter referred to as Mw) of the acrylic copolymer is preferably 300,000 to 1,800,000, more preferably 400,000 to 1,500,000, and still more preferably 500,000 to 1,300,000. By making Mw into the range of 300,000-1,800,000, coexistence of adhesion physical property and coating property becomes easy. In the present invention, Mw is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
前記連鎖移動剤は、例えばｎ−ドデシルメルカプタン、メルカプトイソブチルアルコール、メルカプト酢酸、２−メルカプトエタノール、チオグリコール酸、チオグルコール酸２−エチルヘキシル、２，３−ジメルカプト−１−プロパノール、グリシジルメルカプタン、α−メチルスチレンダイマー、四塩化炭素、クロロホルム、およびハイドロキノン等が挙げられる。
連鎖移動剤は、モノマー混合物１００重量部に対して０．０１〜１重量部程度を使用できる。
The chain transfer agent includes, for example, n-dodecyl mercaptan, mercapto isobutyl alcohol, mercapto acetic acid, 2-mercapto ethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol, glycidyl mercaptan, α-methyl Styrene dimer, carbon tetrachloride, chloroform, hydroquinone and the like can be mentioned.
The chain transfer agent can be used in an amount of about 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer mixture.
前記重合開始剤は、アゾ系化合物および有機過酸化物が一般的である。 The polymerization initiator is generally an azo compound and an organic peroxide.
アゾ系化合物は、例えば２，２'−アゾビスイソブチロニトリル、２，２'−アゾビス（２−メチルブチロニトリル）、１，１'−アゾビス（シクロヘキサン１−カルボニトリル
）、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（２，４−ジメチル−４−メトキシバレロニトリル）、ジメチル２，２'−アゾビス（２−メチ
ルプロピオネート）、４，４'−アゾビス（４−シアノバレリック酸）、２，２'−アゾビス（２−ヒドロキシメチルプロピオニトリル）、および２，２'−アゾビス（２−（２−
イミダゾリン−２−イル）プロパン）等が挙げられる。
The azo compounds are, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-carbonitrile), 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4 , 4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis (2- (2- (2- (2-hydroxymethylpropionitrile))
Imidazolin-2-yl) propane) and the like.
有機過酸化物は、例えば過酸化ベンゾイル、ｔ−ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ（２−エトキシエチル）パーオキシジカーボネート、ｔ−ブチルパーオキシネオデカノエート、ｔ−ブチルパーオキシビバレート、（３，５，５−トリメチルヘキサノイル）パーオキシド、ジプロピオニルパーオキシド、ジアセチルパーオキシド等が挙げられる。
重合開始剤は、単独または２種以上を併用できる。
The organic peroxide is, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di (2-ethoxyethyl) peroxy dicarbonate , T-butyl peroxy neodecanoate, t-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
The polymerization initiator can be used alone or in combination of two or more.
本発明において硬化剤は、イソシアネート化合物、エポキシ化合物、アジリジン化合物、金属キレート、およびアミン化合物からなる群より選択される１種以上が好ましく、エポキシ化合物、金属キレート、およびアジリジン化合物がより好ましい。 In the present invention, the curing agent is preferably one or more selected from the group consisting of an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate, and an amine compound, and more preferably an epoxy compound, a metal chelate, and an aziridine compound.
エポキシ化合物は、例えばビスフェノールＡ−エピクロロヒドリン型のエポキシ系樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン、１、３−ビス（Ｎ、Ｎ’−ジグリシジルアミノメチル）シクロヘキサン、およびＮ，Ｎ，Ｎ'，Ｎ'−テトラグリシジルアミノフェニルメタン等が挙げられる。 The epoxy compound is, for example, an epoxy resin of bisphenol A-epichlorohydrin type, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, Trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane, and N , N, N ′, N′-tetraglycidylaminophenylmethane and the like.
アジリジン化合物は、例えばＮ，Ｎ’−ジフェニルメタン−４，４'−ビス（１−アジ
リジンカルボキサイト）、Ｎ，Ｎ’−トルエン−２，４−ビス（１−アジリジンカルボキサイト）、ビスイソフタロイル−１−（２−メチルアジリジン）、トリ−１−アジリジニルホスフィンオキサイド、Ｎ，Ｎ’−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキサイト）、２，２’−ビスヒドロキシメチルブタノール−トリス［３−（１−アジリジニル）プロピオネート］、トリメチロールプロパントリ−β−アジリジニルプロピオネート、テトラメチロールメタントリ−β−アジリジニルプロピオネート、およびトリス−２，４，６−（１−アジリジニル）−１、３、５−トリアジン等が挙げられる。
The aziridine compound is, for example, N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxite), N, N'-toluene-2,4-bis (1-aziridinecarboxite), bisisophthaloyl -1- (2-methylaziridine), tri-1-aziridinyl phosphine oxide, N, N'-hexamethylene-1,6-bis (1-aziridine carboxylate), 2,2'-bishydroxymethyl butanol Tris [3- (1-aziridinyl) propionate], trimethylolpropane tri-β-aziridinyl propionate, tetramethylolmethane tri-β-aziridinyl propionate, and tris-2,4,6- (1-aziridinyl) -1, 3, 5- triazine etc. are mentioned.
金属キレートは、例えばアルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロムおよびジルコニウムなどの多価金属と、アセチルアセトンまたはアセト酢酸エチルとの配位化合物等が挙げられる。 Examples of the metal chelate include coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium and acetylacetone or ethyl acetoacetate.
イソシアネート化合物は、例えばトリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、およびポリメチレンポリフェニルイソシアネート等のジイソシアネートとトリメチロールプロパン等のポリオール化合物とのアダクト体、ならびにそのビュレット体、ならびにそのイソシアヌレート体、ならびに前記ジイソシアネートと、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、およびポリイソプレンポリオール等のうちのいずれかのポリオールとのアダクト体などの分子内に３個以上のイソシアネート基を有する化合物；
トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、およびポリメチレンポリフェニルイソシアネート等のジイソシアネート、ならびにヘキサメチレンジイソシアネートのアロファネート体等の分子内に２個のイソシアネート基を有する化合物；等が挙げられる。これらの中でも、トリレンジイソシアネートのトリメチロールプロパンアダクト体が、粘着物性を容易に調整できるため好ましい。なお、イソシアネート基の個数は平均個数である。
Examples of the isocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, An adduct of a diisocyanate such as polymethylene polyphenyl isocyanate and a polyol compound such as trimethylolpropane, and its burette, and its isocyanurate, as well as the diisocyanate, polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, And Compounds having 3 or more isocyanate groups in the molecule, such as an adduct with any of the polyols of the polyisoprene polyol;
Tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenyl isocyanate Etc., and compounds having two isocyanate groups in the molecule such as allophanate of hexamethylene diisocyanate; and the like. Among these, a trimethylolpropane adduct of tolylene diisocyanate is preferable because adhesion properties can be easily adjusted. The number of isocyanate groups is an average number.
アミン化合物は、例えばヘキサメチレンジアミン、トリエチルジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチルテトラミン、イソホロンジアミン、アミノ樹脂、およびメチレン樹脂等が挙げられる。
硬化剤は単独または２種以上を併用できる。
Examples of the amine compound include hexamethylene diamine, triethyl diamine, polyethylene imine, hexamethylene tetramine, diethylene triamine, triethyl tetramine, isophorone diamine, amino resin, and methylene resin.
The curing agents may be used alone or in combination of two or more.
硬化剤は、アクリル系共重合体１００重量部に対して、０．０１〜６重量部を含むことが好ましい。０．０１〜６重量部を含むと粘着剤層の凝集力と粘着力のバランスを取ることが容易になる。 The curing agent preferably contains 0.01 to 6 parts by weight with respect to 100 parts by weight of the acrylic copolymer. When it contains 0.01 to 6 parts by weight, it becomes easy to balance the cohesion and adhesion of the pressure-sensitive adhesive layer.
本発明の粘着剤は、さらにロジン系樹脂を含むことが必要である。粘着剤がロジン系樹脂を含むとポリオレフィンに対する粘着力がより向上する。 The pressure-sensitive adhesive of the present invention needs to further contain a rosin resin. When the pressure-sensitive adhesive contains a rosin resin, the adhesion to polyolefin is further improved.
ロジン系樹脂は、ガムロジン、トール油ロジン、ウッドロジンの未変性ロジンをアルコールなどでエステル化したロジンエステルや、未変性ロジンを変性した不均化ロジン、重合ロジン、水添ロジンなどの変性ロジン、これら変性ロジンをさらにアルコールなどでエステル化した不均化ロジンエステル、重合ロジンエステル、水添ロジンエステルなどの変性ロジンエステル、未変性ロジンにフェノールを付加したロジンフェノール等が好ましい
。これらの中でも粘着力および透明性がより向上するためロジンエステル、および変性ロジンエステルが好ましい。なお、ロジンエステルおよび変性ロジンエステルには、エステル化に用いたアルコールなどの水酸基の一部が未反応で残存している場合もある。エステル化に用いるアルコールは、メタノールなどの単官能アルコール、エチレングリコールなどの２官能アルコール、グリセリンなどの３官能アルコール、およびペンタエリスリトールなどの４官能アルコールが挙げられるが、アクリル系共重合体との相溶性を考慮すると３官能以下のアルコールが好ましい。
ロジン系樹脂は、単独または２種以上を併用できる。
Rosin-based resins include gum rosin, tall oil rosin, rosin ester obtained by esterifying unmodified rosin of wood rosin with alcohol and the like, disproportionated rosin modified by unmodified rosin, modified rosin such as polymerized rosin and hydrogenated rosin, and the like Preferred are disproportionated rosin esters obtained by further esterifying modified rosin with an alcohol, modified rosin esters such as polymerized rosin esters and hydrogenated rosin esters, and rosin phenols in which phenol is added to unmodified rosin. Among these, rosin esters and modified rosin esters are preferable because adhesion and transparency are further improved. In the rosin ester and the modified rosin ester, part of hydroxyl groups such as alcohol used for esterification may remain unreacted. Examples of alcohols used for esterification include monofunctional alcohols such as methanol, bifunctional alcohols such as ethylene glycol, trifunctional alcohols such as glycerin, and tetrafunctional alcohols such as pentaerythritol, but the phase with an acrylic copolymer In consideration of solubility, trifunctional or less alcohol is preferable.
The rosin resins can be used alone or in combination of two or more.
ロジン系樹脂の軟化点は、４０〜１１０℃が好ましい。軟化点を４０〜１１０℃にすると粘着力および透明性を両立することが容易となる。 The softening point of the rosin resin is preferably 40 to 110 ° C. When the softening point is 40 to 110 ° C., it is easy to achieve both the adhesive strength and the transparency.
ロジン系樹脂は、アクリル系共重合体１００重量部に対して、１０〜６０重量部配合することが好ましく、２０〜５０重量部がより好ましい。 The rosin resin is preferably blended in an amount of 10 to 60 parts by weight, and more preferably 20 to 50 parts by weight, with respect to 100 parts by weight of the acrylic copolymer.
本発明の粘着剤は、課題が解決できる範囲であれば他の粘着付与樹脂を含んでも良い。例えば、テルペン樹脂、脂環族炭化水素樹脂、脂肪族石油樹脂、芳香族石油樹脂、アルキルフェノールホルムアルデヒド樹脂（油性フェノール樹脂）等が好ましい。他の粘着付与樹脂は、単独または２種以上を併用できる。 The pressure-sensitive adhesive of the present invention may contain another tackifying resin as long as the problem can be solved. For example, terpene resin, alicyclic hydrocarbon resin, aliphatic petroleum resin, aromatic petroleum resin, alkylphenol formaldehyde resin (oil-based phenol resin) and the like are preferable. Other tackifying resins may be used alone or in combination of two or more.
前記他の粘着付与樹脂は、アクリル系共重合体１００重量部に対して、１５重量部以下を配合することが好ましく、特に脂環族炭化水素樹脂、および脂肪族石油樹脂は、それぞれ５重量部以下配合することが好ましい。 The other tackifying resin is preferably blended in an amount of 15 parts by weight or less based on 100 parts by weight of the acrylic copolymer, and particularly 5 parts by weight each of the alicyclic hydrocarbon resin and the aliphatic petroleum resin It is preferable to mix | blend below.
本発明の粘着剤は、本発明の課題解決ができる範囲で、任意成分として各種樹脂、硬化触媒、シランカップリング剤、オイル、軟化剤、染料、顔料、酸化防止剤、紫外線吸収剤、耐候安定剤、可塑剤、充填剤、老化防止剤および帯電防止剤等を配合しても良い。 The pressure-sensitive adhesive of the present invention has various resins, curing catalysts, silane coupling agents, oils, softeners, dyes, pigments, antioxidants, ultraviolet light absorbers, weathering stability, as optional components within the scope of the present invention. Agents, plasticizers, fillers, anti-aging agents, antistatic agents, etc. may be blended.
本発明の粘着剤は、化粧品、日用品、食品などのポリオレフィン樹脂等のプラスチック容器へのの貼り付け用粘着剤として好適であるほか、一般ラベル・シール、粘着性光学フィルム、塗料、弾性壁材、塗膜防水材、床材、粘着性付与剤、粘着剤、積層構造体用粘着剤、シーリング剤、成形材料、表面改質用コーティング剤、バインダー（磁気記録媒体、インキバインダー、鋳物バインダー、焼成レンガバインダー、グラフト材、マイクロカプセル、グラスファイバーサイジング等）、ウレタンフォーム（硬質、半硬質、軟質）、ウレタンＲＩＭ、ＵＶ・ＥＢ硬化樹脂、ハイソリッド塗料、熱硬化型エラストマー、マイクロセルラー、繊維加工剤、可塑剤、吸音材料、制振材料、界面活性剤、ゲルコート剤、人工大理石用樹脂、人工大理石用耐衝撃性付与剤、インキ用樹脂、フィルム（ラミネート粘着剤、保護フィルム等）、合わせガラス用樹脂、反応性希釈剤、各種成形材料、弾性繊維、人工皮革、合成皮革等の原料として、又、各種樹脂添加剤およびその原料等としても非常に有用に使用できる。 The pressure-sensitive adhesive of the present invention is suitable as a pressure-sensitive adhesive for sticking to plastic containers such as polyolefin resins of cosmetics, daily necessities, food etc., and also general labels and seals, adhesive optical films, paints, elastic wall materials, Coating film waterproofing material, flooring, tackifier, adhesive, adhesive for laminated structure, sealing agent, molding material, surface modifying coating agent, binder (magnetic recording medium, ink binder, casting binder, fired brick Binder, graft material, microcapsule, glass fiber sizing, etc., urethane foam (hard, semi-rigid, soft), urethane RIM, UV / EB cured resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, Plasticizer, sound absorbing material, damping material, surfactant, gel coating agent, resin for artificial marble, for artificial marble Impact resistance agent, resin for ink, film (laminate adhesive, protective film, etc.), resin for laminated glass, reactive diluent, various molding materials, elastic fiber, artificial leather, synthetic leather, etc. It can be used very usefully as a resin additive and its raw material etc.
本発明の粘着シートは、基材、および本発明の粘着剤から形成した粘着剤層を備えていることが好ましい。また別の態様として、芯材の両面に粘着剤層を有する両面粘着シート、または基材および芯材を有さず粘着剤層のみで構成されたキャスト粘着シートも好ましい。前記粘着剤層は、粘着剤を基材上に塗工し、乾燥することで形成できる。または、粘着剤を剥離性シート上に塗工し、乾燥して粘着剤層を形成した後、基材を貼り合わせることで形成できる。なお粘着剤層の基材と接しない面に剥離性シートを貼り合わせることはいうまでもない。 The pressure-sensitive adhesive sheet of the present invention preferably comprises a substrate and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention. As another aspect, a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of a core material, or a cast pressure-sensitive adhesive sheet having only a pressure-sensitive adhesive layer without a substrate and a core material is also preferable. The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive on a substrate and drying. Alternatively, the pressure-sensitive adhesive may be coated on a peelable sheet and dried to form a pressure-sensitive adhesive layer, and then the substrate may be attached. Needless to say, the peelable sheet is attached to the surface of the pressure-sensitive adhesive layer which is not in contact with the substrate.
前記粘着剤を塗工する際に、溶液重合で説明した溶剤を添加して粘度を調整することが
できる。
At the time of applying the pressure-sensitive adhesive, the viscosity can be adjusted by adding the solvent described in the solution polymerization.
前記基材は、例えばセロハン、プラスチック、ゴム、発泡体、布帛、ゴムびき布、樹脂含浸布、ガラス、および木材等が好ましい。基材の形状は、板状およびフィルム状を選択できるが、取り扱いが容易であるフィルム状が好ましい。基材は、単独または２種以上の積層体を使用できる。 The substrate is preferably, for example, cellophane, plastic, rubber, foam, fabric, rubber cloth, resin-impregnated cloth, glass, wood and the like. Although the shape of a base material can select plate shape and a film shape, the film shape which is easy to handle is preferable. The substrate may be used alone or in combination of two or more.
前記プラスチックは、例えばポリビニルアルコール、トリアセチルセルロース、ポリプロピレン、ポリエチレン、ポリシクロオレフィン、エチレン−酢酸ビニル共重合体等のポリオレフィン；ポリエチレンテレフタレート、ポリブチレンテレフタレート、およびポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリノルボルネン、ポリアリレート、ポリアクリル、ポリフェニレンサルファイドム、ポリスチレン、ポリアミド、およびポリイミド；等が挙げられる。 The plastic is, for example, polyvinyl alcohol, triacetyl cellulose, polypropylene, polyethylene, polycycloolefin, polyolefin such as ethylene-vinyl acetate copolymer; polyester such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonate, polynorbornene , Polyarylates, polyacrylics, polyphenylene sulfides, polystyrenes, polyamides, and polyimides, and the like.
粘着剤の塗工方法は、特に制限は無く、例えばマイヤーバー、アプリケーター、刷毛、スプレー、ローラー、グラビアコーター、ダイコーター、リップコーター、コンマコーター、ナイフコーター、リバースコ−ター、およびスピンコーター等が挙げられる。塗工に際して乾燥工程を行うことが好ましい。乾燥装置は、特に制限は無く、例えば熱風乾燥機、赤外線ヒーターおよび減圧法等が挙げられる。乾燥温度は、通常６０〜１６０℃程度である。 The method for applying the pressure-sensitive adhesive is not particularly limited, and examples thereof include a Mayer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a die coater, a lip coater, a comma coater, a knife coater, a reverse coater, and a spin coater. Be It is preferable to perform a drying process at the time of coating. The drying apparatus is not particularly limited, and examples thereof include a hot air dryer, an infrared heater, and a pressure reduction method. The drying temperature is usually about 60 to 160 ° C.
粘着剤層の厚さは、０．１〜３００μｍが好ましく、１〜１００μｍがより好ましい。０．１〜３００μｍの範囲にあることで粘着物性を適切な範囲に調整できる。 0.1-300 micrometers is preferable and, as for the thickness of an adhesive layer, 1-100 micrometers is more preferable. By being in the range of 0.1 to 300 μm, the adhesive property can be adjusted to an appropriate range.
本発明の粘着シートの粘着剤層は、そのゲル分率が２５〜７０重量％であることが好ましく、３０〜６５重量％がより好ましい。ゲル分率が２５〜７０重量％であることで、密着性、凝集力をより高いレベルで両立できる。なお、本発明でゲル分率は、所定の大きさの粘着シートをＳＵＳメッシュ（目開き：０．０７７ｍｍ、線径：０．０５ｍｍ）に貼り付けた後、酢酸エチルに浸漬し、５０℃で２４時間抽出した後、１００℃で３０分乾燥後、下記数式（１）で算出した数値である。
数式（１） ゲル分率（重量％）＝（Ｇ２／Ｇ１）×１００
Ｇ１：酢酸エチルで抽出する前の粘着剤層の重量
Ｇ２：酢酸エチルで抽出・乾燥した後の粘着剤層の重量
The gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably 25 to 70% by weight, and more preferably 30 to 65% by weight. When the gel fraction is 25 to 70% by weight, adhesion and cohesion can be simultaneously achieved at a higher level. In the present invention, the gel fraction is obtained by sticking a pressure-sensitive adhesive sheet of a predetermined size on a SUS mesh (mesh size: 0.077 mm, wire diameter: 0.05 mm) and then immersing in ethyl acetate at 50 ° C. After extracting for 24 hours, after drying for 30 minutes at 100 degreeC, it is the numerical value computed by following Numerical formula (1).
Formula (1) Gel fraction (% by weight) = (G2 / G1) × 100
G1: Weight of adhesive layer before extraction with ethyl acetate
G2: Weight of adhesive layer after extraction and drying with ethyl acetate
本発明の粘着シートは、ポリオレフィンを始めとするプラスチック、ガラス、ダンボール、および金属等といった高極性から低極性まで被着体を選ばずに様々な用途で使用できる。具体的には、化粧品容器、シャンプー等のトイレタリー容器、医薬品容器、食品容器、飲料容器等のプラスチック容器、各種容器用ガラス瓶、窓ガラス、ディスプレイ用ガラス、梱包用ダンボール、および各種容器用途の金属缶等が挙げられる。 The pressure-sensitive adhesive sheet of the present invention can be used in various applications from high polarity to low polarity such as plastics such as polyolefins, glass, cardboard, metals and the like without selecting adherends. Specifically, cosmetic containers, toiletry containers such as shampoos, pharmaceutical containers, food containers, plastic containers such as beverage containers, glass bottles for various containers, window glass, glass for displays, packing cardboard, and metal cans for various container applications Etc.
次に本発明の実施例を示して更に詳細を説明するが、本発明はこれらによって限定されるものではない。例中、「部」とは「重量部」、「％」とは「重量％」をそれぞれ意味するものとする。 EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In the examples, "parts" means "parts by weight", and "%" means "% by weight", respectively.
［アクリル系重合体の合成］
（合成例１）
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器（以下、単に「反応容器」と記述する。）に窒素雰囲気下、アクリル酸ブチル８４部、アクリル酸４部、メタクリル酸ブチル１２部、酢酸エチル７０部、２，２'−アゾビスイソブチロニトリル（以下「ＡＩＢＮ」と記述する。）０．０１５部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＡＩＢＮ ０．０３部を反応溶液に添加し６時間反応を継続した。その後、反応容器を冷却し酢酸エチル１３０部を加え、重量平均分子量１０４万のアクリル系共重合体溶液を得た。
[Synthesis of acrylic polymer]
Synthesis Example 1
Under a nitrogen atmosphere, 84 parts of butyl acrylate and 4 parts of acrylic acid in a reaction vessel (hereinafter simply referred to as “reaction vessel”) equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe. 12 parts of butyl methacrylate, 70 parts of ethyl acetate, and 0.015 parts of 2,2'-azobisisobutyro nitrile (hereinafter referred to as "AIBN") were charged. The mixture was heated with stirring to confirm the start of the polymerization reaction, and reacted at reflux temperature for 2 hours. Then, 0.03 parts of AIBN was added to the reaction solution, and the reaction was continued for 6 hours. Thereafter, the reaction vessel was cooled and 130 parts of ethyl acetate was added to obtain an acrylic copolymer solution having a weight average molecular weight of 1,040,000.
（合成例２）
反応容器に窒素雰囲気下、アクリル酸ブチル８８部、アクリル酸４部、メタクリル酸ブチル８部、酢酸エチル１５０部、ＡＩＢＮ ０．０３部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＡＩＢＮ ０．０３部を反応溶液に添加し６時間反応を継続した。その後、反応容器を冷却し酢酸エチル５０部を加え、重量平均分子量７２万のアクリル系共重合体溶液を得た。
(Composition example 2)
In a reaction vessel, 88 parts of butyl acrylate, 4 parts of acrylic acid, 8 parts of butyl methacrylate, 150 parts of ethyl acetate and 0.03 parts of AIBN were charged under a nitrogen atmosphere. The mixture was heated with stirring to confirm the start of the polymerization reaction, and reacted at reflux temperature for 2 hours. Then, 0.03 parts of AIBN was added to the reaction solution, and the reaction was continued for 6 hours. Thereafter, the reaction vessel was cooled and 50 parts of ethyl acetate was added to obtain an acrylic copolymer solution having a weight average molecular weight of 720,000.
（合成例２〜１８）
モノマーの種類及び配合量を表１の記載に従った他は、合成例２と同様に行うことで合成例２〜１８の重合体を得た。
(Composition examples 2 to 18)
The polymers of Synthesis Examples 2 to 18 were obtained in the same manner as in Synthesis Example 2 except that the types and blending amounts of the monomers were as described in Table 1.
得られた共重合体溶液について、溶液の外観、重量平均分子量を以下の方法に従って求めた。その結果を表１に示す。 The appearance and weight average molecular weight of the obtained copolymer solution were determined according to the following method. The results are shown in Table 1.
＜溶液外観＞
得られたアクリル系共重合体溶液の外観を目視で評価した。
<Solution appearance>
The appearance of the obtained acrylic copolymer solution was visually evaluated.
＜重量平均分子量の測定＞
重量平均分子量の測定はＧＰＣを用いた。ＧＰＣは溶媒（ＴＨＦ；テトラヒドロフラン）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り、重量平均分子量の決定はポリスチレン換算で行った。
装置名 ： 島津製作所製、ＬＣ−ＧＰＣシステム「Ｐｒｏｍｉｎｅｎｃｅ」
カラム ： 東ソー社製ＧＭＨＸＬ ４本、東ソー（株）製ＨＸＬ-Ｈ １本を直列に連
結した。
移動相溶媒 ： テトラヒドロフラン
流量 ： １．０ｍｌ／ｍｉｎ
カラム温度 ： ４０℃
<Measurement of weight average molecular weight>
GPC was used to measure the weight average molecular weight. GPC is a liquid chromatography that separates and quantifies a substance dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size thereof, and the weight average molecular weight was determined in terms of polystyrene.
Device name: Shimadzu Corporation LC-GPC system "Prominence"
Column: Four Tosoh GMHXLs and one Tosoh HXL-H were connected in series.
Mobile phase solvent: tetrahydrofuran flow rate: 1.0 ml / min
Column temperature: 40 ° C
表１の略号を以下に記載する。
ＢＡ ： アクリル酸ブチル
ＡＡ ： アクリル酸
ＢＭＡ ： メタクリル酸ブチル
ＣＨＭＡ ： メタクリル酸シクロヘキシル
ＩＢＸＡ ： アクリル酸イソボルニル
ＳＴ ： スチレン
２ＥＨＡ ： アクリル酸２−エチルヘキシル
ＭＭＡ ： メタクリル酸メチル
ＨＥＡ ： アクリル酸２−ヒドロキシエチル
ＨＥＭＡ ： メタクリル酸２−ヒドロキシエチル
ＣＨＤＭＭＡ ： シクロヘキサンジメタノールモノアクリル酸エステル
The abbreviations of Table 1 are listed below.
BA: butyl acrylate AA: acrylic acid BMA: butyl methacrylate CHMA: cyclohexyl methacrylate IBXA: isobornyl acrylate ST: styrene 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate HEMA: methacrylate Acid 2-Hydroxyethyl CHDMMA: Cyclohexane dimethanol monoacrylate
（実施例１）
合成例１で得られた共重合体溶液中の共重合体１００部に対して、硬化剤としてエポキシ化合物であるＴＥＴＲＡＤ−Ｘ（三菱ガス化学社製） ０．０３部（不揮発分換算）、粘着付与剤としてロジン系樹脂であるＡ−７５（荒川化学社製）を３５部配合し、更に溶剤として酢酸エチルを加えて不揮発分を３０％に調整して粘着剤を得た。
前記粘着剤を、厚さ３８μｍの剥離性シート（ポリエチレンテレフタレート製）上に、乾燥後の厚さが２５μｍになるようにコンマコーターで塗工を行い、１００℃で２分間乾燥することで粘着剤層を形成した。次いで、この粘着剤層に、厚さ５０μｍの基材（ポリエチレンテレフタレート製、以下、ＰＥＴシートという）を貼り合せ、温度２３℃相対湿度５０％の条件で１週間熟成することで「剥離性シート／粘着剤層／ＰＥＴシート」という構成の粘着シートを得た。
Example 1
To 100 parts of the copolymer in the copolymer solution obtained in Synthesis Example 1, 0.03 part (nonvolatile matter equivalent) of TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as an epoxy compound as a curing agent, adhesive As a imparting agent, 35 parts of a rosin resin A-75 (manufactured by Arakawa Chemical Co., Ltd.) was blended, and ethyl acetate was further added as a solvent to adjust the nonvolatile content to 30% to obtain a pressure sensitive adhesive.
The pressure-sensitive adhesive is applied on a 38 μm-thick peelable sheet (made of polyethylene terephthalate) by a comma coater so that the thickness after drying is 25 μm, and dried at 100 ° C. for 2 minutes. A layer was formed. Next, a 50 μm thick substrate (made of polyethylene terephthalate, hereinafter referred to as PET sheet) is attached to this pressure-sensitive adhesive layer, and it is aged for 1 week at 23 ° C. and 50% relative humidity. A pressure-sensitive adhesive sheet having a structure of "pressure-sensitive adhesive layer / PET sheet" was obtained.
（実施例２〜１８、比較例１〜１２）
原料を表２、３の配合に従って変更した以外は実施例１と同様に行うことで実施例２〜１８および比較例１〜１２粘着シートを得た。
(Examples 2 to 18, Comparative Examples 1 to 12)
Examples 2 to 18 and Comparative Examples 1 to 12 were obtained in the same manner as in Example 1 except that the raw materials were changed according to the formulations in Tables 2 and 3.
得られた粘着シートを以下の方法で評価した。結果を表２および表３に示す。 The obtained adhesive sheet was evaluated by the following method. The results are shown in Tables 2 and 3.
（１）粘着力
得られた粘着シートを幅２５ｍｍ・縦１５０ｍｍの大きさに準備した。２３℃、相対湿度５０％雰囲気下、前記粘着シートから剥離性シートを剥がして露出した粘着剤層をポリプロピレン（ＰＰ）板に貼り付け、２ｋｇロールで１往復圧着した２４時間放置した後に引張試験機を用いて１８０度方向に３００ｍｍ／分の速度で引き剥がす１８０°ピール試験において粘着力を測定し、下記の評価基準に基づいて評価を行った。（ＪＩＳ Ｚ０２３７：２０００に準拠）
◎：「粘着力が１６Ｎ以上であり、非常に良好。」
○：「粘着力が１３Ｎ以上１６Ｎ未満であり、良好。」
×：「粘着力が１３Ｎ未満であり、実用不可。」
上記同様にステンレス（ＳＵＳ）板に対して粘着力を測定し、下記の評価基準に基づいて評価を行った。
◎：「粘着力が１８Ｎ以上であり、非常に良好。」
○：「粘着力が１５Ｎ以上１８Ｎ未満であり、良好。」
×：「粘着力が１５Ｎ未満であり、実用不可。」
(1) Adhesive force The obtained adhesive sheet was prepared in the magnitude | size of width 25 mm and length 150 mm. The pressure-sensitive adhesive layer is peeled off from the pressure-sensitive adhesive sheet and attached to a polypropylene (PP) plate under an atmosphere of 23 ° C. and a relative humidity of 50%, and left for 24 hours with 1 kg of pressure with a 2 kg roll. The adhesive force was measured in a 180 ° peel test in which peeling was performed at a speed of 300 mm / min in a direction of 180 ° using an adhesive, and evaluation was performed based on the following evaluation criteria. (JIS Z0237: 2000)
:: “The adhesive strength is 16 N or more, very good.”
:: “Adhesive strength is 13 N or more and less than 16 N, good.”
X: "Adhesive force is less than 13 N, and it is not practical."
The adhesive strength was measured with respect to the stainless steel (SUS) board in the same manner as described above, and the evaluation was performed based on the following evaluation criteria.
:: "The adhesive strength is 18 N or more, very good."
:: “Adhesive strength is 15 N or more and less than 18 N, and is good.”
X: "Adhesive force is less than 15 N, and it is not practical."
（２）保持力
得られた粘着シートを幅２５ｍｍ・縦１５０ｍｍの大きさに準備した。前記粘着シートから剥離性シートを剥がして露出した粘着剤層を研磨した幅３０ｍｍ・縦１５０ｍｍのステンレス板の下端部幅２５ｍｍ・横２５ｍｍの部分に貼着し、２ｋｇロールで１往復圧着した後、８０℃雰囲気で粘着シートの下端部に１ｋｇの荷重をかけ、７万秒放置することで保持力を測定した（ＪＩＳ Ｚ０２３７：２０００に準拠）。評価は、粘着シート貼付面上端部が元の位置から下にずれた長さを測定した。
評価基準
○：「ずれた長さが０．５ｍｍ未満である。良好。」
×：「ずれた長さが０．５ｍｍ以上である。実用不可。」
(2) Holding power The obtained adhesive sheet was prepared in the size of width 25 mm and length 150 mm. The peelable sheet is peeled off from the pressure-sensitive adhesive sheet, and the exposed pressure-sensitive adhesive layer is attached to a polished 30 mm wide × 150 mm long stainless steel plate at the lower end 25 mm wide × 25 mm wide and crimped once with a 2 kg roll A holding force was measured by applying a load of 1 kg to the lower end portion of the pressure-sensitive adhesive sheet in an atmosphere at 80 ° C. and leaving it for 70,000 seconds (in accordance with JIS Z0237: 2000). Evaluation evaluated the length which the adhesive sheet sticking surface upper end part shifted below from the original position.
Evaluation criteria ○: "The shifted length is less than 0.5 mm. Good."
X: "The shifted length is 0.5 mm or more. It is not practical."
（３）透明性
得られた粘着シートの粘着剤層の透明性を目視で評価した。粘着剤層の外観に関しては、下記 の３段階の評価基準に基づいて評価を行った。
○：「透明で良好である」
×：「粘着剤層は白化しており、実用不可である」
(3) Transparency The transparency of the pressure-sensitive adhesive layer of the obtained pressure-sensitive adhesive sheet was evaluated visually. The appearance of the pressure-sensitive adhesive layer was evaluated based on the following three evaluation criteria.
○: "transparent and good"
X: "The adhesive layer is whitened and is not practical"
（４）耐白化性
得られた粘着シートを幅２５ｍｍ・縦５０ｍｍの大きさに準備した。次いで２３℃、相対湿度 ５０％雰囲気下、前記粘着シートから剥離性シートを剥がしてガラス板に貼り付け、２ｋｇロー ルで１往復圧着し、「ガラス／粘着剤層／ＰＥＴシート」の積層体を得た。この積層体を２４時 間放置した後、６０℃相対湿度９５％の雰囲気下で１０日間放置した。その後、取り出した直後 の積層体の透明性を目視にて評価した。外観に関しては、下記の３段階の評価基準に基づいて評 価を行った。
○：「透明で良好である」
×：「粘着剤層は白化しており、実用不可」
(4) Whitening resistance The obtained adhesive sheet was prepared in the size of width 25 mm and length 50 mm. Then peel off the peelable sheet from the pressure-sensitive adhesive sheet at 23 ° C. and an atmosphere of relative humidity of 50% and stick it to a glass plate, and press reciprocate with a 2 kg roll for 1 cycle to obtain a laminate of “glass / adhesive layer / PET sheet” Obtained. The laminate was allowed to stand for 24 hours and then for 10 days in an atmosphere of 60 ° C. and 95% relative humidity. Thereafter, the transparency of the laminate immediately after taking it out was visually evaluated. The appearance was evaluated on the basis of the following three evaluation criteria.
○: "transparent and good"
X: "The adhesive layer is whitened and not practical"
表２および表３の略号を以下に記載する。
ＴＥＴＲＡＤ−Ｘ ： Ｎ,Ｎ,Ｎ',Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン
（三菱ガス化学社製）
Ａｌキレート ： アルミニウムトリスアセチルアセトネート
アジリジン化合物 ： ２，２’−ビスヒドロキシメチルブタノール−トリス［３−（１−アジリジニル）プロピオネート］
ＴＤＩ／ＴＭＰ ： トリレンジイソシアネートのトリメチロールプロパンアダクト体
Ａ−７５ ： スーパーエステルＡ−７５（不均化ロジンのグリセリン及びジエチレングリコールエステル、軟化点７５℃、荒川化学社製）
ＰＨ ： ハリタックＰＨ（水添ロジンのペンタエリスリトールエステル、軟化点９７℃、ハリマ化成社製）
ＰＣＪ ： ハリタックＰＣＪ（重合ロジンのペンタエリスリトールエステル、軟化点１２３℃、ハリマ化成社製）
Ｔ−１３０ ： ＹＳポリスターＴ−１３０（ポリテルペン樹脂、軟化点１３０℃、ヤスハラケミカル社製）
Ｐ−１００ ： アルコンＰ−１００（脂環族炭化水素樹脂、軟化点１００℃、荒川化学社製）
The abbreviations of Table 2 and Table 3 are described below.
TETRAD-X: N, N, N ', N'-tetraglycidyl-m-xylylenediamine (made by Mitsubishi Gas Chemical Co., Ltd.)
Al chelate: Aluminum trisacetylacetonate Aziridine compound: 2,2'-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate]
TDI / TMP: trimethylolpropane adduct of tolylene diisocyanate A-75: super ester A-75 (glycerin and diethylene glycol ester of disproportionated rosin, softening point 75 ° C., manufactured by Arakawa Chemical Co., Ltd.)
PH: Haritac PH (pentaerythritol ester of hydrogenated rosin, softening point 97 ° C, manufactured by Harima Chemicals)
PCJ: Haritac PCJ (pentaerythritol ester of polymerized rosin, softening point 123 ° C, manufactured by Harima Chemicals, Inc.)
T-130: YS Polystar T-130 (polyterpene resin, softening point 130 ° C., manufactured by Yasuhara Chemical Co., Ltd.)
P-100: Alcon P-100 (alicyclic hydrocarbon resin, softening point 100 ° C., Arakawa Chemical Co., Ltd.)
表２の実施例１〜１８に示すように本発明の粘着剤は、ポリオレフィン樹脂であるＰＰに対する粘着力、保持力、透明性、耐白化性に優れていることが分かる。これに対し、表３の比較例１〜１２では、いずれかの項目が不良となっており、実用上問題があったり、実用不可であることがわかる。 As shown in Examples 1 to 18 in Table 2, it can be seen that the pressure-sensitive adhesive of the present invention is excellent in the adhesion to a polyolefin resin PP, retention, transparency, and whitening resistance. On the other hand, in Comparative Examples 1 to 12 in Table 3, it is understood that one of the items is defective, and there is a problem in practical use or it is not practical.
本発明の粘着剤は、透明性が良好で、ポリオレフィン樹脂に対して良好な粘着力を有しているために、特に透明ラベル用粘着剤として特に有用である。
The pressure-sensitive adhesive of the present invention is particularly useful as a pressure-sensitive adhesive for transparent labels, because it has good transparency and good adhesion to polyolefin resins.
Claims (4)
前記アクリル系共重合体が、アクリル酸ブチル６０〜９８．５重量％と、カルボキシル基含有モノマー１〜９．９重量％と、モノマー（Ｘ）０．５〜２０重量％とを含むモノマー混合物を溶液重合してなり、
前記モノマー（Ｘ）が、ホモポリマーのガラス転移温度が１５℃以上、かつ２５℃の水１００ｍｌに対する溶解度が１ｇ未満であり、かつ
前記モノマー（Ｘ）は、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸ブチル、アクリル酸ｔ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸フェノキシエチル、メタクリル酸ベンジル、アクリル酸シクロヘキシル、メタクリル酸シクロヘキシル、アクリル酸イソボルニル、メタクリル酸イソボルニル、スチレン、およびα−メチルスチレンからなる群より選ばれるいずれかである、粘着剤。 Containing an acrylic copolymer, a rosin resin, and a curing agent,
A monomer mixture in which the acrylic copolymer comprises 60 to 98.5% by weight of butyl acrylate, 1 to 9.9% by weight of a carboxyl group-containing monomer, and 0.5 to 20% by weight of a monomer (X) Solution polymerization,
The monomer (X) is the glass transition temperature of the homopolymer 15 ℃ or higher, and Ri der less solubility 1g to water 100ml of 25 ° C., and
The monomer (X) may be ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, phenoxyethyl methacrylate, benzyl methacrylate, cyclohexyl acrylate, methacrylate cyclohexyl, isobornyl acrylate, isobornyl methacrylate, Ru der either styrene, and selected from the group consisting of α- methylstyrene, adhesive.
A pressure-sensitive adhesive sheet comprising a substrate and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive according to any one of claims 1 to 3.
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