JP5842394B2 - Composition for aqueous adhesive, aqueous adhesive, adhesive sheet and laminate - Google Patents
Composition for aqueous adhesive, aqueous adhesive, adhesive sheet and laminate Download PDFInfo
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- JP5842394B2 JP5842394B2 JP2011132139A JP2011132139A JP5842394B2 JP 5842394 B2 JP5842394 B2 JP 5842394B2 JP 2011132139 A JP2011132139 A JP 2011132139A JP 2011132139 A JP2011132139 A JP 2011132139A JP 5842394 B2 JP5842394 B2 JP 5842394B2
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- aqueous
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- 230000001070 adhesive effect Effects 0.000 title claims description 81
- 239000000853 adhesive Substances 0.000 title claims description 80
- 239000000203 mixture Substances 0.000 title claims description 67
- 229920002554 vinyl polymer Polymers 0.000 claims description 128
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 47
- -1 2-ethylhexyl Chemical group 0.000 claims description 43
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000004593 Epoxy Substances 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000012736 aqueous medium Substances 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 12
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 claims description 11
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 claims description 11
- 229940118781 dehydroabietic acid Drugs 0.000 claims description 11
- 150000003951 lactams Chemical group 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 description 51
- 238000006116 polymerization reaction Methods 0.000 description 32
- 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 31
- 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 31
- 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 31
- 239000007787 solid Substances 0.000 description 28
- 238000004873 anchoring Methods 0.000 description 21
- 239000010410 layer Substances 0.000 description 21
- 239000004094 surface-active agent Substances 0.000 description 21
- 229940048053 acrylate Drugs 0.000 description 19
- 239000006260 foam Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 229940114077 acrylic acid Drugs 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000012986 chain transfer agent Substances 0.000 description 9
- 239000004745 nonwoven fabric Substances 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000012462 polypropylene substrate Substances 0.000 description 4
- 239000002964 rayon Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-UHFFFAOYSA-N 0.000 description 2
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
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- NTINFTOOVNKGIU-UHFFFAOYSA-N 2-(2-hydroxyethoxycarbonyl)benzoic acid Chemical compound OCCOC(=O)C1=CC=CC=C1C(O)=O NTINFTOOVNKGIU-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KWTKVFXDPKATDW-UHFFFAOYSA-N 2-methyl-3-oxopent-4-enoic acid Chemical compound OC(=O)C(C)C(=O)C=C KWTKVFXDPKATDW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、様々な被着体の貼り合わせに使用できる水性粘着剤、該水性粘着剤の製造に使用する水性粘着剤用組成物、ならびにそれを用いてなる粘着シート及び積層体に関する。 The present invention relates to an aqueous pressure-sensitive adhesive that can be used for bonding various adherends, an aqueous pressure-sensitive adhesive composition that is used for producing the aqueous pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet and a laminate using the same.
近年、粘着剤は、自動車部品や家電製品をはじめとする様々な工業製品の製造に使用されている。 In recent years, pressure-sensitive adhesives have been used in the manufacture of various industrial products such as automobile parts and home appliances.
前記工業製品を製造する際に使用される粘着シートとしては、一般に、ウレタンフォーム等の多孔体や不織布等の支持体の片面または両面に粘着剤層が設けられたものが知られている。
前記多孔体や不織布等の支持体は、粘着剤層と接触する面積が小さいため、いわゆる投錨性が十分でなく、その結果、粘着シートを被着体の表面に貼付し、次いで剥離する際に、前記粘着剤層と支持体との間で界面剥離を引き起こす場合が問題とされていた。
As the pressure-sensitive adhesive sheet used for producing the industrial product, a sheet in which a pressure-sensitive adhesive layer is provided on one side or both sides of a porous body such as urethane foam or a support such as nonwoven fabric is generally known.
Since the support body such as the porous body or the nonwoven fabric has a small area in contact with the pressure-sensitive adhesive layer, the so-called anchoring property is not sufficient, and as a result, the adhesive sheet is attached to the surface of the adherend and then peeled off. The case where interfacial peeling occurs between the pressure-sensitive adhesive layer and the support has been a problem.
一方、前記したような粘着シートは、工業製品の高機能化等に伴って様々な被着体の貼り合わせに使用される場合がある。前記被着体としては、例えば前記したような多孔体や、ポリオレフィン(ポリエチレン、ポリプロピレン等)やゴム等からなる表面極性の低い基材が挙げられ、また、近年は、曲面部等の複雑な形状を備えた被着体が使用される場合もある。 On the other hand, the pressure-sensitive adhesive sheet as described above may be used for bonding various adherends with the enhancement of the functionality of industrial products. Examples of the adherend include a porous body as described above, and a substrate having a low surface polarity made of polyolefin (polyethylene, polypropylene, etc.), rubber, and the like, and recently, a complicated shape such as a curved surface portion. In some cases, an adherend provided with is used.
しかし、従来の粘着シート等を前記表面極性の低い基材等の接着に使用しても、優れた接着強度を長期間維持できず、経時的に剥離を引き起こす場合があった。また、曲面部等の複雑な形状を備えた被着体の接着に従来の粘着シートを使用した場合も、被着体の反発力等によって、粘着シートの経時的な剥がれを引き起こす場合があった。 However, even if a conventional pressure-sensitive adhesive sheet or the like is used for bonding the substrate having a low surface polarity, the excellent adhesive strength cannot be maintained for a long time, and peeling may occur over time. In addition, even when a conventional pressure-sensitive adhesive sheet is used for bonding an adherend having a complicated shape such as a curved surface portion, the pressure-sensitive adhesive sheet may peel off over time due to the repulsive force of the adherend. .
前記したような被着体に対して優れた接着力を有し、かつ、多孔体等の支持体に対して優れた投錨性を備えた粘着剤としては、従来、有機溶剤系の粘着剤が使用されていた。
しかし、近年の環境負荷低減の観点から、前記粘着剤に対しても有機溶剤系から水系への転換が求められており、近年は前記接着力や投錨性に優れた水系の粘着剤の開発が進められている。
As a pressure-sensitive adhesive having excellent adhesion to the adherend as described above and having excellent anchoring properties to a support such as a porous body, conventionally, an organic solvent-based pressure-sensitive adhesive is used. It was used.
However, from the viewpoint of reducing environmental impact in recent years, the adhesive is also required to be converted from an organic solvent system to an aqueous system. In recent years, the development of aqueous adhesives with excellent adhesive strength and anchoring properties has been made. It is being advanced.
前記水性粘着剤としては、例えば（メタ）アクリル酸アルキル又は脂環式エステルを主単量体成分とするアクリル系ポリマーを含み、かつ全固形分中の溶液可溶分が２０〜９０質量％である水系感圧性接着剤組成物であって、溶液可溶分としてガラス転移温度が−２０℃以下で重量平均分子量が１０万以上のアクリル系ポリマー及びガラス転移温度が４０℃以上で重量平均分子量が３００〜５００００のアクリル系ポリマーを含有する水系感圧性接着剤組成物が知られている（例えば特許文献１参照。）。 The aqueous pressure-sensitive adhesive includes, for example, an acrylic polymer having an alkyl (meth) acrylate or an alicyclic ester as a main monomer component, and the solution-soluble content in the total solid content is 20 to 90% by mass. An aqueous pressure-sensitive adhesive composition having an acrylic polymer having a glass transition temperature of −20 ° C. or lower and a weight average molecular weight of 100,000 or higher as a solution-soluble component, and a weight average molecular weight of 40 ° C. or higher. An aqueous pressure-sensitive adhesive composition containing 300 to 50000 acrylic polymer is known (see, for example, Patent Document 1).
しかし、前記水系感圧性接着剤組成物では、依然として多孔体に対する投錨性の点で十分でなく、また、表面極性の低い被着体や複雑形状の被着体に対して実用上十分な接着力を発現できず、その結果、経時的に被着体の剥がれを引き起こす場合があった。 However, the water-based pressure-sensitive adhesive composition is still not sufficient in terms of anchoring properties to the porous body, and has a practically sufficient adhesive force for adherends with low surface polarity and adherends with complex shapes. As a result, the adherend may peel off over time.
一方、粘着剤の分野では、前記したとおり優れた投錨性や様々な被着体に対する優れた接着力とともに、優れた再剥離性を両立した粘着剤が求められている。
具体的には、多孔体や不織布等からなる支持体表面に粘着剤層が設けられた粘着シートを、各種被着体の表面に貼付し、次いで、該粘着シートを被着体表面から剥離しようと力を加えた場合に、支持体と粘着剤層との界面剥離を引き起こすことなく、かつ、被着体に対してはその表面に糊残りを生じることなく剥離可能なレベルの再剥離性を備えた粘着剤が求められている。
しかし、前記文献１記載の水系感圧性接着剤組成物では、前記したとおり投錨性の点で十分でないため、支持体と粘着剤層との界面剥離を引き起こす場合があった。
On the other hand, in the field of pressure-sensitive adhesives, pressure-sensitive adhesives that have both excellent removability as well as excellent anchoring properties and excellent adhesion to various adherends are required.
Specifically, a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer on the surface of a support made of porous material or nonwoven fabric is attached to the surface of various adherends, and then the pressure-sensitive adhesive sheet is peeled off from the surface of the adherend. When the force is applied, it does not cause the interface peeling between the support and the pressure-sensitive adhesive layer. There is a need for a pressure-sensitive adhesive.
However, the water-based pressure-sensitive adhesive composition described in Document 1 is not sufficient in terms of anchoring properties as described above, and thus may cause interfacial peeling between the support and the pressure-sensitive adhesive layer.
本発明が解決しようとする課題は、粘着剤との接触面積が小さい多孔体に対して優れた投錨性を有し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を有し、かつ、再剥離性にも優れた水性粘着剤用組成物、及びそれを用いた水性粘着剤を提供することである。 The problem to be solved by the present invention is that it has excellent anchoring property for a porous body having a small contact area with an adhesive, and is excellent for an adherend having a low surface polarity and an adherend having a complicated shape. It is providing the composition for aqueous adhesives which has the outstanding adhesive force, and was excellent also in removability, and the aqueous adhesive using the same.
本発明者等は、前記課題を解決すべく検討を進めるなかで、従来、水系の粘着剤に使用されているビニル系粘着剤をベースとして検討を進めた。具体的には、従来の水性ビニル系粘着剤に、様々な添加剤を併用することを検討した。 While proceeding with studies to solve the above-mentioned problems, the present inventors proceeded with studies based on vinyl-based pressure-sensitive adhesives that have been conventionally used for water-based pressure-sensitive adhesives. Specifically, the use of various additives in combination with conventional aqueous vinyl adhesives was investigated.
例えば添加剤としてテキサノール、ブチルセロソルブ等の造膜助剤、ブチルポリグルコシド等の乾燥遅延剤、低ガラス転移温度を有するアクリル樹脂（ＡＲＵＦＯＮ ＵＣ−３５１０、Ｔｇ−５０℃、東亜合成（株）製）等を混合した粘着剤を検討したが、前記被着体に対する接着力は低下する傾向にあった。 For example, film forming aids such as texanol and butyl cellosolve as additives, drying retarders such as butyl polyglucoside, acrylic resins having a low glass transition temperature (ARUFON UC-3510, Tg-50 ° C., manufactured by Toa Gosei Co., Ltd.), etc. However, the adhesive strength to the adherend tended to decrease.
本発明者等は、上記のように様々な種類の添加剤とビニル系粘着剤とを組み合わせ検討するなかで、下記一般式（１）で示される構造を有する不均化ロジン酸のエステル化物をビニル重合体と組み合わせ使用した場合に、多孔体等の支持体に対する優れた投錨性と、表面極性の低い被着体等に対する優れた接着力とを備えた水性粘着剤が得られることを見いだした。 As described above, the present inventors studied various combinations of various types of additives and vinyl-based pressure-sensitive adhesives, and obtained an esterified product of disproportionated rosin acid having a structure represented by the following general formula (1). It has been found that when used in combination with a vinyl polymer, an aqueous pressure-sensitive adhesive having excellent anchoring property to a support such as a porous body and excellent adhesion to an adherend having a low surface polarity can be obtained. .
また、本発明者等は、前記水性粘着剤の製造方法の検討を進めるなかで、前記粘着剤を構成するビニル重合体（Ａ）中に、特定の窒素原子含有構造を導入した場合に、更に再剥離性をも付与できることを見出した。 In addition, the inventors of the present invention have further studied the method for producing the aqueous pressure-sensitive adhesive, and when the specific nitrogen atom-containing structure is introduced into the vinyl polymer (A) constituting the pressure-sensitive adhesive, It has been found that removability can also be imparted.
即ち、本発明は、Ｎ−アルキルアミド構造、ラクタム構造及びモルホリン構造からなる群より選ばれる１種以上を有するビニル重合体（Ａ）、不均化ロジン酸のエステル化物（Ｂ）、及び、水系媒体（Ｃ）を含有し、前記不均化ロジン酸のエステル化物（Ｂ）が、下記一般式（１）で示される構造を有するものであることを特徴とする水性粘着剤用組成物、それを含む水性粘着剤及びそれを用いた粘着シートに関するものである。 That is, the present invention relates to a vinyl polymer (A) having at least one selected from the group consisting of an N-alkylamide structure, a lactam structure and a morpholine structure, an esterified product of disproportionated rosin acid (B), and an aqueous system. An aqueous pressure-sensitive adhesive composition comprising a medium (C), wherein the esterified product of disproportionated rosin acid (B) has a structure represented by the following general formula (1): And an adhesive sheet using the same.
（前記一般式（１）中のｎは、１０〜３０の整数を示す。） (In the general formula (1), n represents an integer of 10 to 30.)
本発明の水性粘着剤用組成物を用いることによって、従来の水性粘着剤では達成することができなかった、粘着剤との接触面積が小さい多孔体に対して優れた投錨性を有し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を有し、かつ、再剥離性にも優れた水性粘着剤を得ることができる。前記水性粘着剤及びそれを用いて得られる粘着シートは、例えば、自動車内装材の固着、具体的には自動車天井材やドアトリムの固着をはじめ、クッション剤、シール剤、更には家具、タッチパネル等のＩＴＯ用途での製造場面で使用することができる。 By using the composition for an aqueous pressure-sensitive adhesive of the present invention, the surface has excellent anchoring properties for a porous body having a small contact area with the pressure-sensitive adhesive, which cannot be achieved by a conventional water-based pressure-sensitive adhesive. It is possible to obtain an aqueous pressure-sensitive adhesive having excellent adhesion to an adherend having a low polarity or an adherend having a complicated shape and excellent in removability. The water-based pressure-sensitive adhesive and the pressure-sensitive adhesive sheet obtained using the water-based pressure-sensitive adhesive include, for example, fixing of automobile interior materials, specifically fixing of automobile ceiling materials and door trims, cushioning agents, sealing agents, furniture, touch panels, etc. It can be used in production situations for ITO applications.
本発明の水性粘着剤用組成物は、Ｎ−アルキルアミド構造、ラクタム構造及びモルホリン構造からなる群より選ばれる１種以上を有するビニル重合体（Ａ）、下記一般式（１）で示される構造を有する不均化ロジン酸のエステル化物（Ｂ）、水系媒体（Ｃ）、及び必要に応じてその他の添加剤を含有するものである。 The composition for aqueous pressure-sensitive adhesives of the present invention has a vinyl polymer (A) having at least one selected from the group consisting of an N-alkylamide structure, a lactam structure and a morpholine structure, and a structure represented by the following general formula (1) Containing an esterified product of disproportionated rosin acid (B), an aqueous medium (C), and other additives as required.
前記ビニル重合体（Ａ）及び前記不均化ロジン酸のエステル化物（Ｂ）は、前記水系媒体（Ｃ）中に溶解または分散しうるものである。具体的には、前記ビニル重合体（Ａ）は、重合体（Ａ）中に存在しても良い親水性基や、後述する反応性界面活性剤によって水系媒体（Ｃ）中に安定して分散または溶解されて存在する。 The vinyl polymer (A) and the esterified product (B) of the disproportionated rosin acid can be dissolved or dispersed in the aqueous medium (C). Specifically, the vinyl polymer (A) is stably dispersed in the aqueous medium (C) by a hydrophilic group that may be present in the polymer (A) or a reactive surfactant described later. Or it is dissolved.
また、前記不均化ロジン酸のエステル化物（Ｂ）は、前記一般式（１）で示されるノニオン構造によって水系媒体（Ｃ）中に溶解または分散することができる。 The esterified product (B) of the disproportionated rosin acid can be dissolved or dispersed in the aqueous medium (C) by the nonionic structure represented by the general formula (1).
また、後述するように反応性界面活性剤及び前記不均化ロジン酸のエステル化物（Ｂ）の存在下でビニル単量体を重合しビニル重合体（Ａ）を製造した場合、前記不均化ロジン酸のエステル化物（Ｂ）は、ビニル重合体（Ａ）粒子の外殻に存在し、該ビニル重合体（Ａ）粒子の分散安定性に寄与する。 Further, as described later, when a vinyl monomer (A) is produced by polymerizing a vinyl monomer in the presence of a reactive surfactant and an esterified product (B) of the disproportionated rosin acid, the disproportionation is performed. The esterified product of rosin acid (B) is present in the outer shell of the vinyl polymer (A) particles and contributes to the dispersion stability of the vinyl polymer (A) particles.
本発明では、前記ビニル重合体（Ａ）と前記不均化ロジン酸のエステル化物（Ｂ）とを組み合わせて使用することが、粘着剤との接触面積が少ない多孔体表面等に対して優れた接着力有する水性粘着剤用組成物を得るうえで重要である。 In the present invention, the use of the vinyl polymer (A) and the esterified product of disproportionated rosin acid (B) in combination is excellent for a porous body surface having a small contact area with the pressure-sensitive adhesive. This is important in obtaining a composition for an aqueous pressure-sensitive adhesive having adhesive strength.
はじめに、前記ビニル重合体（Ａ）について説明する。
前記ビニル重合体（Ａ）としては、Ｎ−アルキルアミド構造、ラクタム構造及びモルホリン構造からなる群より選ばれる１種以上を有するものを使用することが、粘着剤に良好な再剥離性を付与するうえで必須である。
前記Ｎ−アルキルアミド構造は、アミド基を構成する窒素原子にアルキル基が結合した構造である。より具体的には、Ｎ−アルキル（メタ)アクリルアミドを重合した際にビニル重合体中に導入されうる構造である。
前記Ｎ−アルキルアミド構造としては、例えばＮ−メチルアミド構造、Ｎ−エチルアミド構造、Ｎ−プロピルアミド構造、Ｎ−イソプロピルアミド構造、Ｎ−ブチルアミド構造等が挙げられる。
また、前記ラクタム構造は、アミド基を構成する窒素原子を含む原子が形成した環状構造である。具体的には、ビニルピロリドンを重合した際にビニル重合体中に導入されうる構造である。
前記ラクタム構造としては、例えばβ-ラクタム、γ-ラクタム、δ-ラクタム等が挙げられる。
また、前記モルホリン構造は、一般にモルホリンといわれるテトラヒドロ−１，４−オキサジンで示される構造である。具体的には、（メタ）アクリロイルモルホリンを重合した際にビニル重合体中に導入されうる構造である。
前記構造のなかでも、Ｎ−アルキルアミド構造を使用することが、前記優れた投錨性や接着力を損なうことなく優れた再剥離性を付与できるため好ましい。
前記Ｎ−アルキルアミド構造、ラクタム構造及びモルホリン構造からなる群より選ばれる構造は、前記ビニル重合体（Ａ）の全体に対して、合計０．３〜２０質量％の範囲で存在することが、前記優れた投錨性や接着力を損なうことなく優れた再剥離性を付与できるため好ましい。
First, the vinyl polymer (A) will be described.
As the vinyl polymer (A), use of a polymer having at least one selected from the group consisting of an N-alkylamide structure, a lactam structure and a morpholine structure imparts good removability to the pressure-sensitive adhesive. It is essential.
The N-alkylamide structure is a structure in which an alkyl group is bonded to a nitrogen atom constituting the amide group. More specifically, it is a structure that can be introduced into a vinyl polymer when N-alkyl (meth) acrylamide is polymerized.
Examples of the N-alkylamide structure include an N-methylamide structure, an N-ethylamide structure, an N-propylamide structure, an N-isopropylamide structure, and an N-butylamide structure.
The lactam structure is a cyclic structure formed by an atom including a nitrogen atom constituting an amide group. Specifically, it is a structure that can be introduced into a vinyl polymer when vinylpyrrolidone is polymerized.
Examples of the lactam structure include β-lactam, γ-lactam, and δ-lactam.
The morpholine structure is a structure represented by tetrahydro-1,4-oxazine generally called morpholine. Specifically, it is a structure that can be introduced into a vinyl polymer when (meth) acryloylmorpholine is polymerized.
Among these structures, it is preferable to use an N-alkylamide structure because it can provide excellent removability without impairing the excellent anchoring property and adhesive strength.
The structure selected from the group consisting of the N-alkylamide structure, lactam structure and morpholine structure is present in a total range of 0.3 to 20% by mass with respect to the whole vinyl polymer (A). This is preferable because excellent removability can be imparted without impairing the excellent anchoring property and adhesive strength.
前記ビニル重合体（Ａ）としては、例えば５０万〜１００万の範囲の重量平均分子量を有するものを使用することが好ましく、５０万〜８０万のものを使用することが、粘着剤との接触面積が小さい多孔体に対して優れた投錨性を有し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を有し、かつ、再剥離性にも優れた水性粘着剤用組成物を得るうえで好ましい。なお、前記ビニル重合体（Ａ）の重量平均分子量とは、前記ビニル重合体（Ａ）と２５℃のテトラヒドラフランとを混合し、２４時間攪拌した場合に、前記テトラヒドロフランに溶解したビニル重合体（Ａ）を、ゲルパーミションクロマトグラフィー（ＧＰＣ）を用いて測定して得られる値を指す。 As said vinyl polymer (A), it is preferable to use what has a weight average molecular weight of the range of 500,000-1 million, for example, and using 500,000-800,000 thing is a contact with an adhesive. It has excellent anchoring properties for porous bodies with a small area, has excellent adhesion to adherends with low surface polarity and adherends with complex shapes, and has excellent removability It is preferable for obtaining a water-based pressure-sensitive adhesive composition. The weight average molecular weight of the vinyl polymer (A) is a vinyl polymer dissolved in the tetrahydrofuran when the vinyl polymer (A) and tetrahydrafuran at 25 ° C. are mixed and stirred for 24 hours. (A) refers to the value obtained by measuring using gel permeation chromatography (GPC).
また、前記ビニル重合体（Ａ）としては、−１０〜−６０℃のガラス転移温度を有するものを使用することが好ましく、−３０〜−６０℃のものを使用することが、粘着剤との接触面積が小さい多孔体に対して優れた投錨性を有し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を備えた水性粘着剤用組成物を得るうえで好ましい。なお、前記ガラス転移温度は、ＦＯＸの式によって導かれた計算値を指す。 Moreover, as said vinyl polymer (A), it is preferable to use what has a glass transition temperature of -10-60 degreeC, and using a -30--60 degreeC thing is with an adhesive. An aqueous pressure-sensitive adhesive composition having excellent anchoring properties with respect to a porous body having a small contact area and having excellent adhesion to an adherend having a low surface polarity or an adherend having a complicated shape is obtained. In addition, it is preferable. The glass transition temperature refers to a calculated value derived by the FOX equation.
ＦＯＸの式によるポリマーのガラス転移温度を計算するための各重合性単量体のガラス転移温度は、例えば、「ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ，ＴＨＩＲＤ ＥＤＩＴＩＯＮ」のVI／２１３〜２５８項や「新高分子文庫・第７巻・塗料用合成樹脂入門（北岡協三著、高分子刊行会、京都、１９７４年）」の１６８〜１６９頁に記載されている数値を採用することができる。なお、上記計算にはラジカル重合性不飽和基を有する反応性界面活性剤は重合性単量体に含めないものとする。 The glass transition temperature of each polymerizable monomer for calculating the glass transition temperature of the polymer according to the FOX formula is, for example, VI / 213-258 of “POLYMER HANDBOOK, THIRD EDITION” or “New Polymer Bunko / No. 7 The numerical values described in pages 168 to 169 of “Introduction to Synthetic Resins for Rolls and Paints” (Kyozo Kitaoka, Polymer Publishing Society, Kyoto, 1974) ”can be employed. In the above calculation, a reactive surfactant having a radically polymerizable unsaturated group is not included in the polymerizable monomer.
また、前記ビニル重合体（Ａ）としては、多孔体等に対する優れた投錨性と、表面極性の低い被着体に対する優れた接着力とを両立する観点から、１５０〜５００ｎｍの平均粒子径を有するものを使用することが好ましく、２００〜４００ｎｍの範囲がより好ましい。ここで、前記平均粒子径は、動的光散乱法によって測定した値を指す。 In addition, the vinyl polymer (A) has an average particle diameter of 150 to 500 nm from the viewpoint of achieving both excellent anchoring properties for porous bodies and the like and excellent adhesion to adherends having low surface polarity. It is preferable to use a thing, and the range of 200-400 nm is more preferable. Here, the average particle diameter refers to a value measured by a dynamic light scattering method.
また、前記ビニル重合体（Ａ）としては、粘着剤との接触面積の小さい多孔体等に対する優れた投錨性と、表面極性の低い被着体に対する優れた接着力とを両立する観点から、できるだけ分岐構造を有さない直鎖脂肪族ビニル重合体を使用することが好ましい。 Moreover, as said vinyl polymer (A), from the viewpoint of satisfying both the excellent anchoring property for a porous body having a small contact area with the pressure-sensitive adhesive and the excellent adhesive force for an adherend having a low surface polarity, as much as possible. It is preferable to use a linear aliphatic vinyl polymer having no branched structure.
前記ビニル重合体（Ａ）としては、具体的には、Ｎ−アクリルアミド構造含有化合物、ラクタム構造含有化合物及びモルホリン構造含有化合物からなる群より選ばれる１種以上のビニル単量体と、必要に応じてその他のビニル単量体とを重合することによって製造することができる。 As the vinyl polymer (A), specifically, one or more vinyl monomers selected from the group consisting of an N-acrylamide structure-containing compound, a lactam structure-containing compound, and a morpholine structure-containing compound, and as necessary Can be produced by polymerizing with other vinyl monomers.
前記Ｎ−アルキルアミド構造含有化合物としては、例えばＮ−メチル（メタ)アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−プロピル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ)アクリルアミド、Ｎ−ブチル（メタ)アクリルアミド等を使用することができる。なかでもＮ−イソプロピル（メタ）アクリルアミドを使用することが好ましい。
また、前記ラクタム構造含有化合物としては、ビニルピロリドンを使用することができる。
また、前記モルホリン構造含有化合物としては、（メタ）アクリロイルモルホリンを使用することができる。
また、前記その他のビニル単量体としては、例えば（メタ）アクリル酸アルキルエステル、カルボキシル基含有ビニル単量体、水酸基含有ビニル単量体等を使用することができる。
Examples of the N-alkylamide structure-containing compound include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-butyl (meth). Acrylamide or the like can be used. Of these, N-isopropyl (meth) acrylamide is preferably used.
As the lactam structure-containing compound, vinyl pyrrolidone can be used.
As the morpholine structure-containing compound, (meth) acryloylmorpholine can be used.
Moreover, as said other vinyl monomer, (meth) acrylic-acid alkylester, a carboxyl group containing vinyl monomer, a hydroxyl group containing vinyl monomer, etc. can be used, for example.
前記（メタ）アクリル酸アルキルエステルとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（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）アクリル酸ノニル、（メタ）アクリル酸シクロヘキシル等を使用することができる。なかでも、アクリル酸ノニル、アクリル酸２−エチルヘキシル、アクリル酸ブチルを使用することが、得られるビニル重合体（Ａ）のガラス転移温度を低くでき、その結果、粘着剤との接触面積が小さい多孔体に対して優れた投錨性を有し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を付与できるため好ましい。 Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, ( 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like can be used. Among these, the use of nonyl acrylate, 2-ethylhexyl acrylate, and butyl acrylate can lower the glass transition temperature of the resulting vinyl polymer (A), and as a result, the porous contact area is small with the adhesive. It is preferable because it has excellent anchoring properties with respect to the body and can provide excellent adhesion to adherends with low surface polarity and adherends with complex shapes.
また、前記（メタ）アクリル酸アクリルエステルとして（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸メチル、アクリル酸エチルを使用することによって、水性粘着剤に優れた耐熱接着力や接着保持力等の粘着性能を付与することが可能である。 In addition, by using cyclohexyl (meth) acrylate, methyl (meth) acrylate, and ethyl acrylate as the (meth) acrylic acid acrylic ester, the adhesive such as heat-resistant adhesive force and adhesive retention force excellent in aqueous adhesives Performance can be imparted.
また、前記カルボキシル基含有ビニル単量体としては、例えば、（メタ）アクリル酸、（メタ）アクリル酸β−カルボキシエチル、２−（メタ）アクリロイルプロピオン酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、イタコン酸ハーフエステル、マレイン酸ハーフエステル、無水マレイン酸、無水イタコン酸、β−（メタ）アクリロイルオキシエチルハイドロゲンサクシネート、β−（メタ）ヒドロキシエチルハイドロゲンフタレート、及びこれらの塩等を、単独または２種以上を併用して使用することができる。なかでも、前記カルボキシル基含有ビニル単量体としては、（メタ）アクリル酸を使用することが好ましい。 Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, β-carboxyethyl (meth) acrylate, 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) hydroxyethyl hydrogen phthalate, and salts thereof alone Alternatively, two or more kinds can be used in combination. Especially, it is preferable to use (meth) acrylic acid as said carboxyl group-containing vinyl monomer.
前記カルボキシル基含有ビニル単量体は、得られるビニル重合体（Ａ）にカルボキシル基やカルボキシレート基を導入し、良好な水分散安定性を付与するうえで使用することが好ましい。また、本発明の水性粘着剤用組成物に後述する油溶性エポキシ化合物（Ｄ）を併用する場合には、該化合物（Ｄ）の有するエポキシ基と前記ビニル重合体（Ａ）中のカルボキシル基とが架橋することで、耐熱接着力や接着保持力等の粘着性能に優れた粘着層を形成することができる。 The carboxyl group-containing vinyl monomer is preferably used for imparting good water dispersion stability by introducing a carboxyl group or a carboxylate group into the resulting vinyl polymer (A). Moreover, when using together the oil-soluble epoxy compound (D) mentioned later to the composition for aqueous | water-based adhesives of this invention, the epoxy group which this compound (D) has, the carboxyl group in the said vinyl polymer (A), By cross-linking, it is possible to form a pressure-sensitive adhesive layer excellent in pressure-sensitive adhesive properties such as heat-resistant adhesive force and adhesive holding force.
また、前記水酸基含有ビニル単量体としては、（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、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート等を使用することができる。 Further, as the hydroxyl group-containing vinyl monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, or the like is used. be able to.
前記水酸基含有ビニル単量体を使用することによって、ビニル重合体（Ａ）中に水酸基を導入することができる。かかる水酸基は、例えばポリイソシアネート架橋剤等を組み合わせ使用する場合に、該架橋剤が有するイソシアネート基と反応する。これにより、耐熱接着力や接着保持力保持力等の粘着性能に優れた粘着層を形成することができる。 By using the hydroxyl group-containing vinyl monomer, a hydroxyl group can be introduced into the vinyl polymer (A). Such a hydroxyl group reacts with an isocyanate group of the crosslinking agent when, for example, a polyisocyanate crosslinking agent is used in combination. Thereby, the adhesion layer excellent in adhesion performance, such as heat-resistant adhesive force and adhesion retention strength retention force, can be formed.
前記ビニル重合体（Ａ）の製造に使用するその他のビニル単量体としては、前記した以外に、例えば（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ−モノアルキルアミノアルキル、（メタ）アクリル酸Ｎ，Ｎ−ジアルキルアミノアルキル、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；（メタ）アクリロニトリル等のビニル系ニトリル類；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン等の芳香族環を有するビニル系単量体；イソプレン、ブタジエン、エチレン等の官能基を有しないビニル系単量体等を使用することもできる。 Other vinyl monomers used for the production of the vinyl polymer (A) include, in addition to those described above, for example, aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, (meth) Vinyl esters such as N, N-dialkylaminoalkyl acrylate, vinyl acetate, vinyl propionate, vinyl versatate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether; ) Vinyl nitriles such as acrylonitrile; vinyl monomers having an aromatic ring such as styrene, α-methylstyrene, vinyl toluene, vinyl anisole, α-halostyrene, vinyl naphthalene; isoprene, butadiene, ethylene A vinyl monomer having no functional group such as can also be used.
本発明で使用するビニル重合体（Ａ）としては、前記ビニル単量体からなる混合物の全量に対して、Ｎ−アクリルアミド構造含有化合物、ラクタム構造含有化合物及びモルホリン構造含有化合物からなる群より選ばれる１種以上のビニル単量体を合計０．３〜２０質量％、前記（メタ）アクリル酸アルキルエステルを４５〜８５質量％、カルボキシル基含有ビニル単量体を１〜５質量％含むビニル単量体混合物を重合して得られたものを使用することが好ましい。なかでも、Ｎ−アルキル（メタ)アクリルアミド、Ｎ−ビニルピロリドン及び（メタ）アクリロイルモルホリンを合計０．３〜２０質量％と、４５〜８５質量％のアクリル酸２−エチルヘキシルと、１〜５質量％のカルボキシル基含有ビニル単量体とを含むビニル単量体混合物を重合して得られるものを使用することが、粘着剤との接触面積が小さい多孔体に対して優れた投錨性を有し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を有し、かつ、再剥離性にも優れた水性粘着剤用組成物を得るうえで好ましい。 The vinyl polymer (A) used in the present invention is selected from the group consisting of an N-acrylamide structure-containing compound, a lactam structure-containing compound, and a morpholine structure-containing compound with respect to the total amount of the mixture composed of the vinyl monomers. A vinyl monomer containing a total of 0.3 to 20% by mass of one or more vinyl monomers, 45 to 85% by mass of the (meth) acrylic acid alkyl ester, and 1 to 5% by mass of a carboxyl group-containing vinyl monomer. It is preferable to use a product obtained by polymerizing the body mixture. Among them, N-alkyl (meth) acrylamide, N-vinylpyrrolidone and (meth) acryloylmorpholine are combined in a total of 0.3 to 20% by mass, 45 to 85% by mass of 2-ethylhexyl acrylate, and 1 to 5% by mass. The use of a polymer obtained by polymerizing a vinyl monomer mixture containing a carboxyl group-containing vinyl monomer has excellent anchoring properties for a porous body having a small contact area with the adhesive, It is preferable for obtaining a composition for an aqueous pressure-sensitive adhesive having excellent adhesion to an adherend having a low surface polarity and an adherend having a complicated shape and also excellent in removability.
前記ビニル重合体（Ａ）は、例えば、前記ビニル単量体を、重合開始剤と水系媒体（Ｃ）と必要に応じて界面活性剤の存在下で乳化重合することによって製造することができる。 The vinyl polymer (A) can be produced, for example, by subjecting the vinyl monomer to emulsion polymerization in the presence of a polymerization initiator, an aqueous medium (C), and optionally a surfactant.
ここで、前記ビニル単量体としてアクリル酸２−エチルヘキシルを使用する場合、得られるビニル重合体が分岐構造を形成しやすい。また、前記アクリル酸２−エチルヘキシルを概ね７０質量％以上使用する場合には、一層、多分岐化したビニル重合体が得られる傾向にある。本願発明では、前記したとおりできる限り分岐していない直鎖状の脂肪族ビニル重合体を使用することが好ましいため、前記分岐を最小限に抑制する製造方法によってビニル重合体（Ａ）を製造することが好ましい。 Here, when 2-ethylhexyl acrylate is used as the vinyl monomer, the resulting vinyl polymer tends to form a branched structure. Further, when 2-ethylhexyl acrylate is used in an amount of about 70% by mass or more, a more branched vinyl polymer tends to be obtained. In the present invention, since it is preferable to use a linear aliphatic vinyl polymer that is not branched as much as possible as described above, the vinyl polymer (A) is produced by a production method that minimizes the branching. It is preferable.
前記分岐構造形成の抑制には、乳化重合温度を前記４５〜６０℃の範囲に調整し、かつ重合開始剤としてアゾ開始剤を使用し、該アゾ開始剤の使用量を前記ビニル単量体の全量に対して０．０１〜０．１０質量％の範囲に調整することが有効である。 In order to suppress the formation of the branched structure, an emulsion polymerization temperature is adjusted to the range of 45 to 60 ° C., and an azo initiator is used as a polymerization initiator. It is effective to adjust to the range of 0.01 to 0.10% by mass with respect to the total amount.
前記アゾ開始剤としては、前記ビニル重合体（Ａ）の分岐構造の形成を抑制し、かつ前記ビニル重合体（Ａ）の生産効率低下を防止する観点から、１０時間半減期温度が「前記乳化重合温度−５℃」以下であるアゾ開始剤を使用することが好ましい。具体的には、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン二塩酸塩及び２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン二硫酸塩からなる群より選ばれる１種以上のものを使用することが好ましい。 The azo initiator has a 10-hour half-life temperature of “the emulsification” from the viewpoint of suppressing the formation of the branched structure of the vinyl polymer (A) and preventing the production efficiency of the vinyl polymer (A) from decreasing. It is preferable to use an azo initiator having a “polymerization temperature of −5 ° C.” or lower. Specifically, 2,2′-azobis [2- (2-imidazolin-2-yl) propane dihydrochloride and 2,2′-azobis [2- (2-imidazolin-2-yl) propane disulfate It is preferable to use one or more selected from the group consisting of:
前記アゾ開始剤の市販品としては、例えば、「ＶＡ−０４４(和光純薬工業、１０時間半減期温度４４℃、２，２−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド)」、「ＶＡ−０４６Ｂ(和光純薬工業、１０時間半減期温度４６℃、２，２−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジスルフェートジハイドレート)」等を使用することができる。 Examples of commercially available products of the azo initiator include, for example, “VA-044 (Wako Pure Chemical Industries, 10 hours half-life temperature: 44 ° C., 2,2-azobis [2- (2-imidazolin-2-yl) propane] dioxide”. Hydrochloride) "," VA-046B (Wako Pure Chemical Industries, 10-hour half-life temperature 46 ° C, 2,2-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate) " Etc. can be used.
また、前記ビニル重合体（Ａ）の製造に使用可能な界面活性剤としては、例えば陰イオン性界面活性剤、非イオン性界面活性剤、陽イオン性界面活性剤、両イオン性界面活性剤等を使用できる。なかでも、陰イオン性界面活性剤を使用することが、粘着剤の機械的安定性を向上する上で好ましい。 Examples of the surfactant that can be used for the production of the vinyl polymer (A) include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Can be used. Among these, the use of an anionic surfactant is preferable for improving the mechanical stability of the pressure-sensitive adhesive.
前記陰イオン性界面活性剤としては、例えば、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルフェニルスルホン酸塩等を単独または２種以上を併用して使用することができる。 As the anionic surfactant, for example, a higher alcohol sulfate, alkylbenzene sulfonate, polyoxyethylene alkylphenyl sulfonate, or the like can be used alone or in combination of two or more.
前記界面活性剤としては、前記ビニル単量体とともに乳化重合しうるラジカル重合性不飽和二重結合を有する界面活性剤、いわゆる反応性界面活性剤を使用することが、該界面活性剤のブリードアウトに起因した接着力等の低下を防止するうえで好ましい。 As the surfactant, it is possible to use a surfactant having a radically polymerizable unsaturated double bond that can be emulsion-polymerized with the vinyl monomer, a so-called reactive surfactant. It is preferable for preventing a decrease in adhesive strength or the like due to the above.
前記反応性界面活性剤としては、例えば、スルホン酸基及びその塩を有する「ラテムルＳ−１８０、ＰＤ−１０４」〔商標；花王株式会社製〕、「エレミノールＪＳ−２、ＲＳ−３０」〔商標；三洋化成工業株式会社製〕等；硫酸基及びその塩を有する「アクアロンＫＨ−０５、ＫＨ−１０」〔商標；第一工業製薬株式会社製〕、「アデカリアソープＳＥ−１０、ＳＥ−２０」〔商標；旭電化工業株式会社製〕等；リン酸基を有する「ニューフロンティアＡ−２２９Ｅ」〔商標；第一工業製薬株式会社製〕等；非イオン性親水基を有する「アクアロンＲＮ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０」〔商標；第一工業製薬株式会社製〕、「ラテムルＰＤ−４２０、ＰＤ−４３０、ＰＤ−４５０」〔商標；花王株式会社製〕等が挙げられ、これらは単独使用でもよく２種以上を併用してもよい。 Examples of the reactive surfactant include “Latemul S-180, PD-104” (trademark; manufactured by Kao Corporation) and “Eleminol JS-2, RS-30” (trademark) having a sulfonic acid group and a salt thereof. Manufactured by Sanyo Chemical Industries Co., Ltd.], etc .; “Aqualon KH-05, KH-10” [trademark; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] having sulfate groups and salts thereof, “Adekaria soap SE-10, SE-20” "Trademark; manufactured by Asahi Denka Kogyo Co., Ltd.", etc .; "New Frontier A-229E" having a phosphate group [Trademark; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], etc .; "Aqualon RN-10 having a nonionic hydrophilic group" , RN-20, RN-30, RN-50 "[trademark; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]," Latemul PD-420, PD-430, PD-450 "[trademark; manufactured by Kao Corporation] and the like. And These may be used in combination of well 2 or more types may be used alone.
前記界面活性剤の使用量は、界面活性剤の種類等によって相違するが、例えば前記非イオン性界面活性剤の場合には、前記ビニル単量体混合物の全量に対して１．０〜５．０質量％の範囲であることが好ましく、１．５〜３．５質量％の範囲がより好ましい。 The amount of the surfactant used varies depending on the type of the surfactant and the like. For example, in the case of the nonionic surfactant, the amount used is 1.0 to 5.5 with respect to the total amount of the vinyl monomer mixture. The range is preferably 0% by mass, and more preferably in the range of 1.5 to 3.5% by mass.
また、前記界面活性剤が陰イオン性界面活性剤、陽イオン性界面活性剤、両イオン性界面活性剤である場合には、前記界面活性剤の使用量は０．５〜３．０質量％の範囲であることが好ましく、１．０〜２．５質量％の範囲がより好ましい。 When the surfactant is an anionic surfactant, a cationic surfactant, or an amphoteric surfactant, the amount of the surfactant used is 0.5 to 3.0% by mass. It is preferable that it is the range of 1.0-2.5 mass%.
次に、本発明で使用する不均化ロジン酸のエステル化物（Ｂ）について説明する。 Next, the esterified product (B) of disproportionated rosin acid used in the present invention will be described.
前記不均化ロジン酸のエステル化物（Ｂ）は、不均化ロジン酸と、下記一般式（１）で示される構造を有するポリオールとをエステル化反応して得られるものであって、下記一般式（１）で示されるエチレンオキサイド構造の繰り返し単位（一般式（１）中のｎ）が１０〜３０の範囲の整数であることを特徴とする。 The esterified product (B) of the disproportionated rosin acid is obtained by esterifying a disproportionated rosin acid and a polyol having a structure represented by the following general formula (1). The repeating unit of the ethylene oxide structure represented by the formula (1) (n in the general formula (1)) is an integer in the range of 10-30.
（前記一般式（１）中のｎは、１０〜３０の整数を示す。）
ここで、前記不均化ロジン酸のエステル化物（Ｂ）の代わりに、前記ｎが８である不均化ロジン酸のエステル化物を使用して得られた水性粘着剤では、該水性粘着剤の軟化点が低下し、多孔体に対する投錨性や、該多孔体及び低表面極性の被着体に対する接着力、耐熱接着力の低下を引き起こす場合がある。一方、前記ｎが４０の不均化ロジン酸のエステル化物を使用して得られた水性粘着剤も、多孔体に対する投錨性や、該多孔体及び低表面極性の被着体に対する接着力、耐熱接着力の低下を引き起こす場合がある。
(In the general formula (1), n represents an integer of 10 to 30.)
Here, in place of the esterified product of disproportionated rosin acid (B), the aqueous adhesive obtained by using the esterified product of disproportionated rosin acid in which n is 8, The softening point may be lowered, which may cause a decrease in anchoring property to the porous body, adhesion force to the porous body and a low surface polarity adherend, and heat resistant adhesive force. On the other hand, the aqueous pressure-sensitive adhesive obtained by using the esterified product of disproportionated rosin acid having n of 40 is also suitable for anchoring to a porous body, adhesion to the porous body and a low surface polarity adherend, and heat resistance. It may cause a decrease in adhesive strength.
水性粘着剤との接触面積が小さい多孔体や、表面極性の低い被着体に対する、より一層優れた接着力を備えた水性粘着剤用組成物を得るためには、前記ｎが好ましくは１０〜２０、より好ましくは１４〜１６の整数である不均化ロジン酸のエステル化物を使用することが好適である。 In order to obtain a composition for an aqueous pressure-sensitive adhesive having a further excellent adhesion to a porous body having a small contact area with the water-based pressure-sensitive adhesive or an adherend having a low surface polarity, n is preferably 10 to 10. It is preferred to use an esterified product of disproportionated rosin acid which is an integer of 20, more preferably an integer of 14-16.
前記不均化ロジン酸のエステル化物（Ｂ）の製造に使用する不均化ロジン酸としては、例えばデヒドロアビエチン酸、ピマール酸、イソピマール酸、サンダラコピマール酸等を使用することができ、なかでもデヒドロアビエチン酸を使用することが好ましい。 As the disproportionated rosin acid used for the production of the esterified product (B) of the disproportionated rosin acid, for example, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, etc. can be used. It is preferred to use dehydroabietic acid.
また、前記不均化ロジン酸と反応するポリオールとしては、例えばエチレンオキサイド構造からなる繰り返し単位が１０〜３０の範囲であるポリオキシエチレングリコールを使用することが好ましく、より好ましくは１０〜２０、特に好ましくは１４〜１６の範囲の繰り返し単位を有するポリオキシエチレングリコールを使用することができる。 Further, as the polyol that reacts with the disproportionated rosin acid, it is preferable to use, for example, polyoxyethylene glycol having a repeating unit having an ethylene oxide structure in the range of 10 to 30, more preferably 10 to 20, particularly Preferably, polyoxyethylene glycol having a repeating unit in the range of 14 to 16 can be used.
前記不均化ロジン酸のエステル化物（Ｂ）は、例えば前記不均化ロジン酸の有するカルボキシル基と、前記ポリオールの有する水酸基とを周知慣用の方法で縮合させることによって製造することができる。得られた不均化ロジン酸のエステル化物（Ｂ）の末端は、水酸基や、メトキシ基やエトキシ基等のアルコキシ基であることが、粘着剤との接触面積が小さい多孔体に対して、特に優れた投錨性を付与し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を付与するうえで好ましい。 The esterified product (B) of the disproportionated rosin acid can be produced, for example, by condensing the carboxyl group possessed by the disproportionated rosin acid and the hydroxyl group possessed by the polyol by a known and conventional method. The end of the esterified product (B) of the obtained disproportionated rosin acid is a hydroxyl group or an alkoxy group such as a methoxy group or an ethoxy group, especially for a porous body having a small contact area with the adhesive. It is preferable for imparting excellent anchoring properties and imparting excellent adhesive force to adherends with low surface polarity and adherends having complex shapes.
前記不均化ロジン酸のエステル化物（Ｂ）は、前記ビニル重合体（Ａ）の全量に対して、０．１質量％〜５質量％の範囲で使用することが好ましく、０．５質量％〜３質量％の範囲で使用することが、粘着剤との接触面積が小さい多孔体に対して、特に優れた投錨性を付与し、表面極性の低い被着体や複雑形状をした被着体に対して優れた接着力を付与し、かつ、不均化ロジン酸エステル化物（Ｂ）の被着体表面へのブリードを抑制できるため好ましい。 The esterified product (B) of the disproportionated rosin acid is preferably used in the range of 0.1% by mass to 5% by mass with respect to the total amount of the vinyl polymer (A), and 0.5% by mass. Use in a range of ˜3% by mass gives a particularly excellent anchoring property to a porous body having a small contact area with the pressure-sensitive adhesive, and an adherend having a low surface polarity or a complicated shape It is preferable because it can impart an excellent adhesive force to the surface and suppress bleeding of the disproportionated rosin acid ester (B) to the adherend surface.
次に、本発明で使用する水系媒体（Ｃ）について説明する。
前記水系媒体（Ｃ）としては、水、水と混和する親水性有機溶剤、及び、これらの混合物を使用することができる。前記親水性有機溶剤としては、例えば、メタノール、エタノール、ｎ−及びイソプロパノール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール類；ポリアルキレングリコールのアルキルエーテル類;Ｎ-メチル-２-ピロリドン等のラクタム類等の、一般に高沸点溶剤として知られるものを使用することができる。本発明では、水のみを用いても良く、また水及び水と混和する有機溶剤との混合物を用いても良く、水と混和する有機溶剤のみを用いても良い。安全性や環境に対する負荷の点から、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみが特に好ましい。
Next, the aqueous medium (C) used in the present invention will be described.
As the aqueous medium (C), water, a hydrophilic organic solvent miscible with water, and a mixture thereof can be used. Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyls of polyalkylene glycol Ethers; those generally known as high-boiling solvents such as lactams such as N-methyl-2-pyrrolidone can be used. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
前記水系媒体（Ｃ）は、本発明の水性粘着剤用組成物の全量に対して３０〜７０質量％含まれることが好ましく、４０〜６０質量％含まれることがより好ましい。 It is preferable that 30-70 mass% is contained with respect to the whole quantity of the composition for aqueous adhesives of this invention, and the said aqueous medium (C) contains 40-60 mass% more preferably.
次に、本発明で使用することができる油溶性エポキシ化合物（Ｄ）について説明する。 Next, the oil-soluble epoxy compound (D) that can be used in the present invention will be described.
油溶性エポキシ化合物（Ｄ）は、加熱等により前記ビニル重合体（Ａ）が有していてもよいカルボキシル基と反応し架橋構造を形成しうるエポキシ基を有するものである。 The oil-soluble epoxy compound (D) has an epoxy group that can react with a carboxyl group that the vinyl polymer (A) may have by heating or the like to form a crosslinked structure.
前記油溶性エポキシ化合物（Ｄ）としては、例えば、デナコールＥＸ−６２２〔ナガセ化成工業株式会社製〕、デナコールＥＸ−２０１〔同社製〕、デナコールＥＸ−２１２〔同社製〕、デナコールＥＸ−９２２〔同社製〕、デナコールＥＸ−２０００〔同社製〕、デナコールＥＸ−４０００〔同社製〕、デナコールＥＸ−７２１〔同社製〕、デナコールＥＸ−２２１〔同社製〕、ＴＥＴＲＡＤ−Ｃ〔三菱ガス化学株式会社製〕、ＴＥＴＲＡＤ−Ｘ〔同社製〕などを使用することができる。なかでもアミン基を有するＴＥＴＲＡＤ−Ｘ、ＴＥＴＲＡＤ−Ｃを使用することが、架橋反応をより促進できるため好ましい。 Examples of the oil-soluble epoxy compound (D) include Denacol EX-622 (manufactured by Nagase Kasei Kogyo Co., Ltd.), Denacol EX-201 (manufactured by the company), Denacol EX-212 (manufactured by the company), and Denacol EX-922 (the company). , Denacol EX-2000 (manufactured by the company), Denacol EX-4000 (manufactured by the company), Denacol EX-721 (manufactured by the company), Denacol EX-221 (manufactured by the company), TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) , TETRAD-X (manufactured by the same company) can be used. Among these, use of TETRAD-X and TETRAD-C having an amine group is preferable because the crosslinking reaction can be further accelerated.
前記油溶性エポキシ化合物（Ｄ）は、粘着剤層のゲル分率を調整し、多孔体や表面極性の低い被着体に対する優れた接着力を付与する観点から、前記ビニル重合体（Ａ）の全量に対して０．０１〜３質量％の範囲で使用することが好ましい。 The oil-soluble epoxy compound (D) adjusts the gel fraction of the pressure-sensitive adhesive layer, and from the viewpoint of imparting excellent adhesion to a porous body and an adherend having a low surface polarity, the vinyl polymer (A) It is preferable to use in the range of 0.01-3 mass% with respect to the whole quantity.
次に、本発明で使用できるロジン系樹脂（Ｅ）について説明する。
本発明では、１５０〜２００℃の軟化点を有するロジン系樹脂（Ｅ）を、前記不均化ロジン酸のエステル化物（Ｂ）と組み合わせ使用することが、多孔体や表面極性の低い被着体に対する耐熱接着力を向上させるうえで特に好ましい。
Next, the rosin resin (E) that can be used in the present invention will be described.
In the present invention, it is possible to use a rosin resin (E) having a softening point of 150 to 200 ° C. in combination with the esterified product (B) of disproportionated rosin acid in a porous body or a low surface polarity adherend. It is particularly preferable for improving the heat-resistant adhesive strength against.
前記耐熱接着力としては、具体的には、被着体を本発明の水性粘着剤を用いて貼り合わせて得られた積層体を、概ね８０℃程度の高温環境下に長期間放置した場合であっても被着体の剥離等を引き起こさないレベルの特性が求められる。なお、前記ロジン系樹脂（Ｅ）の軟化点は、ＪＩＳ Ｋ−５９０２方法で測定された値を指す。 Specifically, the heat-resistant adhesive strength is obtained when a laminate obtained by bonding an adherend using the aqueous pressure-sensitive adhesive of the present invention is left in a high temperature environment of about 80 ° C. for a long period of time. Even if it exists, the characteristic of the level which does not cause peeling of a to-be-adhered body etc. is calculated | required. In addition, the softening point of the rosin resin (E) indicates a value measured by the JIS K-5902 method.
前記ロジン系樹脂（Ｅ）としては、例えば天然ロジン、ロジンエステル、重合ロジン、重合ロジンエステル、水添ロジン、水添ロジンエステル、不均化ロジン、不均化ロジンエステル等のうち、１５０〜２００℃の軟化点を有するものを使用することができる。なかでも重合ロジンエステル等を使用することが好ましい。 Examples of the rosin resin (E) include natural rosin, rosin ester, polymerized rosin, polymerized rosin ester, hydrogenated rosin, hydrogenated rosin ester, disproportionated rosin, disproportionated rosin ester, and the like. Those having a softening point of ° C. can be used. Among these, it is preferable to use a polymerized rosin ester or the like.
前記ロジン系樹脂（Ｅ）は、粘着剤との接触面積が小さい多孔体や、表面極性の低い被着体に対する優れた接着力と、優れた耐熱接着力とを両立する観点から、前記ビニル重合体（Ａ）の全量に対して１０〜３５質量％の範囲で使用することが好ましく、２０〜３０質量％がより好ましい。 The rosin-based resin (E) is a vinyl resin that has both excellent adhesion to a porous body having a small contact area with the pressure-sensitive adhesive and an adherend having a low surface polarity and excellent heat-resistant adhesion. It is preferable to use in the range of 10-35 mass% with respect to the whole quantity of a coalescence (A), and 20-30 mass% is more preferable.
また、本発明では、上記に加え、更にその他のロジン系樹脂を使用することができる。具体的には、天然ロジン、ロジンエステル、重合ロジン、重合ロジンエステル、水添ロジン、水添ロジンエステル、不均化ロジン、不均化ロジンエステル等のうち１５０℃未満の軟化点を有するものを使用することができる。 In the present invention, in addition to the above, other rosin resins can be used. Specifically, natural rosin, rosin ester, polymerized rosin, polymerized rosin ester, hydrogenated rosin, hydrogenated rosin ester, disproportionated rosin, disproportionated rosin ester, etc. having a softening point of less than 150 ° C. Can be used.
また、本発明の水性粘着剤用組成物は、前記ビニル重合体（Ａ）や不均化ロジン酸のエステル化物（Ｂ）や水系媒体（Ｃ）や油溶性エポキシ化合物（Ｄ）やロジン系樹脂（Ｅ）の他に、必要に応じてその他の添加剤等を含有していても良い。 Moreover, the composition for aqueous pressure-sensitive adhesives of the present invention includes the vinyl polymer (A), an esterified product of disproportionated rosin acid (B), an aqueous medium (C), an oil-soluble epoxy compound (D), and a rosin resin. In addition to (E), other additives and the like may be contained as necessary.
前記その他の添加剤としては、例えばα−ピネン樹脂、β−ピネン樹脂、テルペンフェノール樹脂、水添テルペンフェノール樹脂等のテルペン系粘着付与剤樹脂を使用することができる。 As said other additive, terpene type tackifier resin, such as (alpha) -pinene resin, (beta) -pinene resin, terpene phenol resin, hydrogenated terpene phenol resin, can be used, for example.
また、前記添加剤としては、脂肪族炭化水素系樹脂や脂肪族環式構造含有樹脂等の性基油系樹脂を使用することができる。例えば、一般にＣ５系樹脂やＣ９系樹脂、ジシクロペンタジエン系樹脂等として知られる石油系樹脂を併用することもできる。 In addition, as the additive, sex base oil-based resins such as aliphatic hydrocarbon resins and aliphatic cyclic structure-containing resins can be used. For example, petroleum resins generally known as C5 resins, C9 resins, dicyclopentadiene resins, and the like can be used in combination.
次に、本発明の水性接着剤用組成物の製造方法について説明する。
本発明の水性接着剤用組成物は、例えば前記したように予め製造したビニル重合体（Ａ）の水系分散体と、不均化ロジン酸のエステル化物（Ｂ）と必要に応じて油溶性エポキシ化合物（Ｄ）及び前記ロジン系樹脂（Ｅ）とを混合、攪拌することによって製造することができる。
Next, the manufacturing method of the composition for water-based adhesives of this invention is demonstrated.
The aqueous adhesive composition of the present invention comprises, for example, an aqueous dispersion of vinyl polymer (A) prepared in advance as described above, an esterified product of disproportionated rosin acid (B), and an oil-soluble epoxy as required. It can be produced by mixing and stirring the compound (D) and the rosin resin (E).
また、粘着剤との接触面積が小さい多孔体や、表面極性の低い被着体に対する、より一層優れた接着力を備えた水性粘着剤用組成物を得るためには、例えば前記と同様の反応性界面活性剤と前記不均化ロジン酸のエステル化物（Ｂ）と水系媒体（Ｃ）との混合物中に、前記ビニル単量体の混合物と重合開始剤と必要に応じて連鎖移動剤とを一括または別々に供給し、前記ビニル単量体混合物を乳化重合法により反応させることによって、ビニル重合体（Ａ）を含む水性粘着剤用組成物を製造する方法を採用することが好ましい。 In addition, in order to obtain a composition for an aqueous pressure-sensitive adhesive having a further excellent adhesion to a porous body having a small contact area with the pressure-sensitive adhesive or an adherend having a low surface polarity, for example, the same reaction as described above A mixture of the vinyl monomer, a polymerization initiator, and, if necessary, a chain transfer agent in a mixture of the neutral surfactant, the esterified product of disproportionated rosin acid (B) and the aqueous medium (C). It is preferable to employ a method for producing an aqueous pressure-sensitive adhesive composition containing the vinyl polymer (A) by supplying them all at once or separately and reacting the vinyl monomer mixture by an emulsion polymerization method.
具体的には、前記反応性界面活性剤と前記不均化ロジン酸のエステル化物（Ｂ）と水系媒体（Ｃ）との混合物へのビニル単量体混合物や重合開始剤等の供給は、一括供給または逐次供給であることが好ましい。 Specifically, the supply of the vinyl monomer mixture, the polymerization initiator and the like to the mixture of the reactive surfactant, the esterified product of disproportionated rosin acid (B) and the aqueous medium (C) is performed at once. Supply or sequential supply is preferred.
前記供給後、概ね０℃〜８０℃程度の温度範囲で約３〜１０時間程度反応させ、前記ビニル単量体混合物のラジカル重合を乳化重合法により行うことが好ましい。前記供給後の反応温度は、ビニル重合体（Ａ）が分岐構造となるのを抑制する観点から、概ね６５℃以下の比較的低温で行うことが好ましい。 It is preferable that after the supply, the reaction is carried out in a temperature range of about 0 ° C. to 80 ° C. for about 3 to 10 hours, and radical polymerization of the vinyl monomer mixture is carried out by an emulsion polymerization method. The reaction temperature after the supply is preferably performed at a relatively low temperature of about 65 ° C. or less from the viewpoint of suppressing the vinyl polymer (A) from having a branched structure.
前記したように、前記不均化ロジン酸のエステル化物（Ｂ）等の存在下でビニル重合体（Ａ）を製造し本発明の水性粘着剤用組成物を得ることによって、ビニル重合体（Ａ）の粒子の外殻に前記不均化ロジン酸のエステル化物（Ｂ）が局在化し、その結果、粘着剤との接触面積が小さい多孔体や表面極性の低い被着体に対する、より一層優れた接着力を発現することが可能な水性粘着剤用組成物を得ることができる。 As described above, the vinyl polymer (A) is produced by producing the vinyl polymer (A) in the presence of the esterified product (B) of the disproportionated rosin acid to obtain the aqueous adhesive composition of the present invention. The esterified product (B) of the disproportionated rosin acid is localized in the outer shell of the particles of), and as a result, it is more excellent for porous bodies having a small contact area with the adhesive and adherends having low surface polarity. It is possible to obtain a composition for an aqueous pressure-sensitive adhesive that can exhibit high adhesive strength.
前記方法で得られた水性粘着剤用組成物にも、必要に応じて前記油溶性エポキシ化合物（Ｄ）や前記ロジン系樹脂（Ｅ）を併用することができる。具体的には、前記方法で得た水性粘着剤用組成物と前記油溶性エポキシ化合物（Ｄ）や前記ロジン系樹脂（Ｅ）とを混合、攪拌することによって得ることができる。 The oil-soluble epoxy compound (D) and the rosin resin (E) can be used in combination with the aqueous pressure-sensitive adhesive composition obtained by the above method as necessary. Specifically, it can be obtained by mixing and stirring the composition for an aqueous pressure-sensitive adhesive obtained by the above method, the oil-soluble epoxy compound (D) and the rosin resin (E).
前記製法で使用する連鎖移動剤としては、例えばラウリルメルカプタン等のメルカプタン系化合物、α−ピネン、リモネン、ターピノーレン等のテルペン系化合物、アリルアルコール、α−メチルスチレンダイマー等を使用することができる。 Examples of the chain transfer agent used in the production method include mercaptan compounds such as lauryl mercaptan, terpene compounds such as α-pinene, limonene, and terpinolene, allyl alcohol, α-methylstyrene dimer, and the like.
前記連鎖移動剤は、前記ビニル単量体の全量に対して好ましくは０．０１〜０．５質量％、より好ましくは０．０１〜０．２質量％の範囲で使用することができる。
The chain transfer agent can be used in an amount of preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.2% by mass, based on the total amount of the vinyl monomer.
前記方法等で得られた本発明の水性接着剤用組成物は、もっぱら水性粘着剤に使用することができる。 The composition for aqueous adhesives of the present invention obtained by the above method can be used exclusively for aqueous adhesives.
また、前記水性粘着剤は、例えば支持体の片面または両面に粘着層を有する粘着シートの製造に使用することができる。 Moreover, the said water-based adhesive can be used for manufacture of the adhesive sheet which has an adhesion layer in the single side | surface or both surfaces of a support body, for example.
前記粘着シートは、例えば支持体の片面または両面に、前記水性粘着剤を塗工し、水系媒体（Ｃ）を除去するとともに、塗工層のゲル分率が概ね２５〜５５％程度になるまで硬化し粘着層を形成することによって製造することができる。 For example, the pressure-sensitive adhesive sheet is coated with the aqueous pressure-sensitive adhesive on one side or both sides of the support to remove the aqueous medium (C), and the gel fraction of the coating layer is about 25 to 55%. It can be produced by curing to form an adhesive layer.
前記支持体としては、例えばポリエステル、ポリプロピレン、ポリエチレン、ポリビニルカーボネート及びこれらのラミネート体などを使用することができる。なかでもポリエチレンテレフタレートからなるフィルムを使用することが好ましい。 As the support, for example, polyester, polypropylene, polyethylene, polyvinyl carbonate, and laminates thereof can be used. Among them, it is preferable to use a film made of polyethylene terephthalate.
前記支持体の表面は、前記粘着層との密着性を向上する観点から、予めコロナ処理等による易接着表面処理が施されていても良い。 The surface of the support may be subjected to an easy adhesion surface treatment by corona treatment or the like in advance from the viewpoint of improving the adhesion with the adhesive layer.
また、前記支持体としては、一般に、両面粘着テープの芯材に使用される例えば、綿、麻、レーヨン、または、ポリエステルと綿、麻、レーヨンとの混紡品からなる不織布や織布を使用することもできる。 Further, as the support, for example, cotton, hemp, rayon, or a non-woven fabric or woven fabric made of a blend of polyester and cotton, hemp, rayon, which is used as a core material of a double-sided adhesive tape, is used. You can also.
前記支持体表面に水性粘着剤を塗工する方法としては、例えばロールコーター、グラビアコーター、リバースコーター、リップコーター、スプレーコーター、エアーナイフコーター、ダイコーター等を用いる方法が挙げられる。 Examples of the method of applying the aqueous pressure-sensitive adhesive to the surface of the support include methods using a roll coater, gravure coater, reverse coater, lip coater, spray coater, air knife coater, die coater and the like.
前記支持体表面に形成される粘着層の厚みは、特に制限はないが、１〜１００μｍの範囲であることが好ましく、１０〜６０μｍの範囲であることがより好ましい。 Although there is no restriction | limiting in particular in the thickness of the adhesion layer formed in the said support body surface, It is preferable that it is the range of 1-100 micrometers, and it is more preferable that it is the range of 10-60 micrometers.
前記で得られた粘着シートは、とりわけ発泡体等の多孔体の表面に対しても優れた接着力を有することから、例えばウレタンフォーム等の多孔体からなる被着体の接着や積層体の形成に好適に使用することができる。 The pressure-sensitive adhesive sheet obtained above has an excellent adhesive force especially to the surface of a porous body such as a foam, so that, for example, adhesion of an adherend composed of a porous body such as urethane foam or formation of a laminate Can be suitably used.
また、本発明の粘着シートは、表面極性の低い被着体に対して優れた接着力を有することから、例えばポリプロピレンやポリエチレン等のポリオレフィンや、クロロプレンやＥＰＤＭゴム等、及び金属などからなる被着体の接着に使用することができる。 In addition, since the pressure-sensitive adhesive sheet of the present invention has an excellent adhesion to an adherend having a low surface polarity, for example, an adhesion made of polyolefin such as polypropylene or polyethylene, chloroprene, EPDM rubber, or the like, and metal. Can be used for body bonding.
以下、本発明を実施例及び比較例により、一層具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
［ビニル重合体の調製］
（合成例１）
容器に反応性界面活性剤としてラテムルＰＤ−１０４（花王株式会社製、固形分２０質量％）を３０質量部及びアクアロンＫＨ−１０２５（第一工業製薬株式会社製、固形分２５質量％）を２４質量部と、アクリル酸２−エチルヘキシルを４３５質量部、アクリル酸ブチルを１２０質量部、メタクリル酸メチルを２４質量部、Ｎ−イソプロピルアクリルアミド６質量部及びアクリル酸を１５質量部と、連鎖移動剤としてラウリルメルカプタン０．２１質量部と、イオン交換水９０質量部とを仕込み、攪拌することによって、乳化液を調製した。
[Preparation of vinyl polymer]
(Synthesis Example 1)
In the container, 30 parts by mass of Latemul PD-104 (manufactured by Kao Corporation, solid content of 20% by mass) as a reactive surfactant and 24 parts of Aqualon KH-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content of 25% by mass) are used. As a chain transfer agent, 435 parts by mass of 2-ethylhexyl acrylate, 120 parts by mass of butyl acrylate, 24 parts by mass of methyl methacrylate, 6 parts by mass of N-isopropylacrylamide and 15 parts by mass of acrylic acid An emulsion was prepared by charging 0.21 parts by mass of lauryl mercaptan and 90 parts by mass of ion-exchanged water and stirring.
温度計、滴下ロート、還流冷却管及び攪拌装置を備えた重合容器内を窒素ガスで置換し、イオン交換水３７３．２質量部を仕込み、内温５２．５℃に昇温した。 The inside of the polymerization vessel equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with nitrogen gas, charged with 373.2 parts by mass of ion-exchanged water, and the internal temperature was raised to 52.5 ° C.
前記重合容器に、前記乳化液の全量に対して１質量％の乳化液を仕込んだ後、ピロ亜硫酸ナトリウムを０．１５質量部及び過硫酸アンモニウムを０．１８質量部添加し、重合を開始した。 After charging 1% by mass of the emulsion in the polymerization vessel with respect to the total amount of the emulsion, 0.15 parts by mass of sodium pyrosulfite and 0.18 parts by mass of ammonium persulfate were added to initiate polymerization.
３０分間ホールドした後、残りの乳化液（９９質量％）と、２，２’−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド水溶液（不揮発分０．５質量％）１０質量部とを、前記重合容器内に６時間かけて滴下した。 After holding for 30 minutes, the remaining emulsion (99% by mass) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (nonvolatile content 0.5% by mass) 10 mass parts was dripped in the said polymerization container over 6 hours.
滴下終了後、重合容器を内温５２．５℃にて１時間保持し、次いで、重合容器を約２５℃に冷却した後、内容物を２００メッシュ濾布（ポリエステル）で濾過することによって、固形分５３．０質量％、粘度２５０ｍＰａ・ｓ、ｐＨ２．５、粒子径２８０ｎｍ、分子量７０万のビニル重合体エマルジョン１を得た。 After completion of the dropping, the polymerization vessel is kept at an internal temperature of 52.5 ° C. for 1 hour, and then the polymerization vessel is cooled to about 25 ° C., and then the content is filtered through a 200 mesh filter cloth (polyester) to obtain a solid. A vinyl polymer emulsion 1 having a weight of 53.0% by mass, a viscosity of 250 mPa · s, a pH of 2.5, a particle diameter of 280 nm, and a molecular weight of 700,000 was obtained.
（実施例１）
前記合成例１で得たビニル重合体１エマルジョンの固形分１００質量部に対して、不均化ロジン酸のエステル化物（Ｂ）としてエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：１５モル、末端構造は水酸基）１質量部を混合した後、更に１２．５質量％のアンモニア水を４．２質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）１．５質量部とイオン交換水２質量部とを混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン１−１を得た。
(Example 1)
With respect to 100 parts by mass of the solid content of the vinyl polymer 1 emulsion obtained in Synthesis Example 1, as an esterified product (B) of disproportionated rosin acid, ethylene glycol dehydroabietic acid ester (EO addition mole number: 15 mol, terminal) After mixing 1 part by mass of a hydroxyl group), further 4.2 parts by mass of 12.5% by mass of ammonia water and Boncoat 3750-E (a thickener manufactured by DIC Corporation, nonvolatile content 23% by mass) 1 By mixing 5 parts by mass and 2 parts by mass of ion-exchanged water, a vinyl polymer emulsion 1-1 having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 was obtained.
次いで、前記ビニル重合体エマルジョン１−１と油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、２００メッシュの濾布（ポリエステル製）を用いて濾過することにより、水性粘着剤用組成物１を得た。 Next, the vinyl polymer emulsion 1-1 and 0.02 parts by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) which is an oil-soluble epoxy compound are mixed, and a 200 mesh filter cloth (made of polyester) is used. By filtering, the composition 1 for aqueous adhesives was obtained.
（実施例２）
容器に反応性界面活性剤としてラテムルＰＤ−１０４（花王株式会社製、固形分２０質量％）を４５質量部と、不均化ロジン酸のエステル化物（Ｂ）としてエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：１５モル、末端構造は水酸基）を６質量部と、アクリル酸２−エチルヘキシルを４３５質量部、アクリル酸ブチルを１２０質量部、メタクリル酸メチルを２４質量部、Ｎ−イソプロピルアクリルアミド６質量部及びアクリル酸を１５質量部と、連鎖移動剤としてラウリルメルカプタン０．２１質量部と、イオン交換水１０８質量部とを仕込み、攪拌することによって、乳化液を調製した。
(Example 2)
Latem PD-104 (made by Kao Corporation, solid content 20% by mass) as a reactive surfactant in a container and 45 parts by mass of ethylene glycol dehydroabietic acid ester (EO) as an esterified product of disproportionated rosin acid (B) Addition mole number: 15 mol, terminal structure is hydroxyl group) 6 parts by mass, 435 parts by mass of 2-ethylhexyl acrylate, 120 parts by mass of butyl acrylate, 24 parts by mass of methyl methacrylate, 6 parts by mass of N-isopropylacrylamide An emulsion was prepared by charging 15 parts by weight of acrylic acid and 15 parts by weight of acrylic acid, 0.21 part by weight of lauryl mercaptan as a chain transfer agent, and 108 parts by weight of ion-exchanged water.
温度計、滴下ロート、還流冷却管及び攪拌装置を備えた重合容器内を窒素ガスで置換し、イオン交換水３６４．８質量部を仕込み、内温５２．５℃に昇温した。 The inside of the polymerization vessel equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with nitrogen gas, charged with 364.8 parts by mass of ion-exchanged water and heated to an internal temperature of 52.5 ° C.
前記重合容器に、前記乳化液の全量に対して１質量％の乳化液を仕込んだ後、ピロ亜硫酸ナトリウムを０．１５質量部及び過硫酸アンモニウムを０．１８質量部添加し、重合を開始した。 After charging 1% by mass of the emulsion in the polymerization vessel with respect to the total amount of the emulsion, 0.15 parts by mass of sodium pyrosulfite and 0.18 parts by mass of ammonium persulfate were added to initiate polymerization.
３０分間ホールドした後、残りの乳化液（９９質量％）と、２，２’−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド水溶液（不揮発分０．５質量％）１０質量部とを、前記重合容器内に６時間かけて滴下し、更に重合容器を内温５２．５℃にて１時間保持した後、約２５℃に冷却することで、ビニル重合体エマルジョン２−１を得た。 After holding for 30 minutes, the remaining emulsion (99% by mass) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (nonvolatile content 0.5% by mass) 10 parts by mass are dropped into the polymerization vessel over 6 hours, and the polymerization vessel is kept at an internal temperature of 52.5 ° C. for 1 hour, and then cooled to about 25 ° C. -1 was obtained.
前記ビニル重合体エマルジョン２−１の固形分１００質量部に対して、１２．５質量％のアンモニア水を２．０質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．５質量部とイオン交換水１．８質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン２−２を得た。 2.0 mass parts of 12.5 mass% ammonia water with respect to 100 mass parts of solid content of the vinyl polymer emulsion 2-1, Boncoat 3750-E (a thickener manufactured by DIC Corporation, nonvolatile content) 23 parts by mass) is mixed with 1.5 parts by mass of ion exchanged water and 1.8 parts by mass of ion-exchanged water, whereby a vinyl polymer emulsion 2-2 having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 is obtained. Got.
次いで、前記ビニル重合体エマルジョン２−２と、油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、該混合物を２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５２．５質量％、粘度２４２ｍＰａ・ｓ、ｐＨ２．６、粒子径２８５ｎｍ、分子量６５万のビニル重合体と不均化ロジン酸のエステル化物とイオン交換水と油溶性エポキシ化合物とを含む水性粘着剤用組成物２を得た。 Next, the vinyl polymer emulsion 2-2 and 0.02 parts by mass of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is an oil-soluble epoxy compound, are mixed, and the mixture is mixed with a 200 mesh filter cloth (polyester). And filtered to give a vinyl polymer having a solid content of 52.5% by mass, a viscosity of 242 mPa · s, a pH of 2.6, a particle size of 285 nm, and a molecular weight of 650,000, an esterified product of disproportionated rosin acid, ion-exchanged water and oil. A composition 2 for an aqueous pressure-sensitive adhesive containing a soluble epoxy compound was obtained.
（実施例３）
前記実施例２で使用したものと同様のビニル重合体エマルジョン２−１の固形分１００質量部に対して、ロジン系樹脂（Ｅ）としてスーパーエステル Ｅ−８６５−ＮＴ（荒川化学工業株式会社製、軟化点１６０℃、不揮発分５０質量％、重合ロジンエステル）３０質量部とを混合し、次いで、該混合物に１２．５質量％のアンモニア水１．９質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）０．６質量部とイオン交換水０．６質量部とを混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン３−１を得た。
(Example 3)
Superester E-865-NT (made by Arakawa Chemical Industries, Ltd.) as rosin resin (E) with respect to 100 parts by mass of the solid content of vinyl polymer emulsion 2-1 similar to that used in Example 2 above. 30 parts by mass of softening point 160 ° C., non-volatile content 50% by mass, polymerized rosin ester), and then 1.9 parts by mass of 12.5% by mass ammonia water and Boncoat 3750-E (DIC stock) By mixing 0.6 parts by mass of a thickener (non-volatile content 23% by mass) and 0.6 parts by mass of ion-exchanged water, a BM viscosity is 10,000 mPa · s (# 4 × 12) and a pH is 8 A vinyl polymer emulsion 3-1 was obtained.
前記ビニル重合体エマルジョン３−１と、油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、該混合物を２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５２．５質量％、粘度２４２ｍＰａ・ｓ、ｐＨ２．６、粒子径２８５ｎｍ、分子量６５万のビニル重合体と不均化ロジン酸のエステル化物とイオン交換水と油溶性エポキシ化合物とを含む水性粘着剤用組成物３を得た。 The vinyl polymer emulsion 3-1 and 0.02 parts by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), which is an oil-soluble epoxy compound, are mixed, and the mixture is used with a 200 mesh filter cloth (polyester). By filtering, a vinyl polymer having a solid content of 52.5% by mass, a viscosity of 242 mPa · s, a pH of 2.6, a particle size of 285 nm, a molecular weight of 650,000, an esterified product of disproportionated rosin acid, ion-exchanged water, and an oil-soluble epoxy A composition 3 for an aqueous pressure-sensitive adhesive containing the compound was obtained.
（実施例４）
容器に反応性界面活性剤としてラテムルＰＤ−１０４（花王株式会社製、固形分２０質量％）を４５質量部と、不均化ロジン酸のエステル化物（Ｂ）としてエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：１５モル、末端構造は水酸基）を６質量部と、アクリル酸２−エチルヘキシルを４３５質量部、アクリル酸ブチルを９０質量部、アクリル酸エチル３０質量部、メタクリル酸メチルを２４質量部、Ｎ−イソプロピルアクリルアミド６質量部及びアクリル酸を１５質量部と、連鎖移動剤としてラウリルメルカプタン０．２１質量部と、イオン交換水１０８質量部とを仕込み、攪拌することによって、乳化液を調製した。
Example 4
Latem PD-104 (made by Kao Corporation, solid content 20% by mass) as a reactive surfactant in a container and 45 parts by mass of ethylene glycol dehydroabietic acid ester (EO) as an esterified product of disproportionated rosin acid (B) Number of added moles: 15 mol, terminal structure is hydroxyl group) 6 parts by mass, 435 parts by mass of 2-ethylhexyl acrylate, 90 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 24 parts by mass of methyl methacrylate , N-isopropylacrylamide 6 parts by mass and acrylic acid 15 parts by mass, lauryl mercaptan 0.21 part by mass as a chain transfer agent, and ion-exchanged water 108 parts by mass were prepared and stirred to prepare an emulsion. .
温度計、滴下ロート、還流冷却管及び攪拌装置を備えた重合容器内を窒素ガスで置換し、イオン交換水３６４．８質量部を仕込み、内温５２．５℃に昇温した。 The inside of the polymerization vessel equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with nitrogen gas, charged with 364.8 parts by mass of ion-exchanged water and heated to an internal temperature of 52.5 ° C.
前記重合容器に、前記乳化液の全量に対して１質量％の乳化液を仕込んだ後、ピロ亜硫酸ナトリウムを０．１５質量部及び過硫酸アンモニウムを０．１８質量部添加し、重合を開始した。 After charging 1% by mass of the emulsion in the polymerization vessel with respect to the total amount of the emulsion, 0.15 parts by mass of sodium pyrosulfite and 0.18 parts by mass of ammonium persulfate were added to initiate polymerization.
３０分間ホールドした後、残りの乳化液（９９質量％）と、２，２’−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド水溶液（不揮発分０．５質量％）１０質量部とを、前記重合容器内に６時間かけて滴下し、更に重合容器を内温５２．５℃にて１時間保持した後、約２５℃に冷却することで、ビニル重合体エマルジョン４−１を得た。 After holding for 30 minutes, the remaining emulsion (99% by mass) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (nonvolatile content 0.5% by mass) 10 parts by mass was dropped into the polymerization vessel over 6 hours, and the polymerization vessel was held at an internal temperature of 52.5 ° C. for 1 hour, and then cooled to about 25 ° C. -1 was obtained.
前記ビニル重合体エマルジョン４−１の固形分１００質量部に対して、ロジン系樹脂（Ｅ）としてスーパーエステル Ｅ−８６５−ＮＴ（荒川化学工業株式会社製、軟化点１６０℃、不揮発分５０質量％、重合ロジンエステル）固型分３０質量部とを混合し、更に１２．５質量％のアンモニア水を２．１質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．６質量部とイオン交換水１．１質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン４−２を得た。 Superester E-865-NT (manufactured by Arakawa Chemical Industries, softening point 160 ° C., non-volatile content 50% by mass as rosin resin (E) with respect to 100 parts by mass of the solid content of the vinyl polymer emulsion 4-1. , Polymerized rosin ester) 30 parts by mass of solid component, and further 2.1 parts by mass of 12.5% by mass of aqueous ammonia, Boncoat 3750-E (a thickener manufactured by DIC Corporation, nonvolatile content 23) The vinyl polymer emulsion 4-2 having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 is obtained by mixing 1.6 parts by mass) and 1.1 parts by mass of ion-exchanged water. Obtained.
前記ビニル重合体エマルジョン４−２と、油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５２．２質量％、粘度２０８ｍＰａ・ｓ、ｐＨ２．６、粒子径３１８ｎｍ、分子量６２万のビニル重合体と不均化ロジン酸のエステル化物とイオン交換水と油溶性エポキシ化合物とを含む水性粘着剤用組成物４を得た。 Mixing the vinyl polymer emulsion 4-2 with 0.02 parts by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) which is an oil-soluble epoxy compound, and filtering using 200 mesh filter cloth (polyester). A vinyl polymer having a solid content of 52.2% by mass, a viscosity of 208 mPa · s, a pH of 2.6, a particle size of 318 nm, a molecular weight of 620,000, an esterified product of disproportionated rosin acid, ion-exchanged water, and an oil-soluble epoxy compound. An aqueous pressure-sensitive adhesive composition 4 was obtained.
（実施例５）
エチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：１５モル、末端構造は水酸基）の代わりにエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：１８モル、末端構造は水酸基）を使用すること以外は、実施例１と同様の方法により水性粘着剤用組成物５を得た。
(Example 5)
Except for using ethylene glycol dehydroabietic acid ester (EO addition mole number: 18 mol, terminal structure is hydroxyl group) instead of ethylene glycol dehydroabietic acid ester (EO addition mole number: 15 mol, terminal structure is hydroxyl group), An aqueous pressure-sensitive adhesive composition 5 was obtained in the same manner as in Example 1.
（実施例６）
容器に反応性界面活性剤としてラテムルＰＤ−１０４（花王株式会社製、固形分２０質量％）を４５質量部と、不均化ロジン酸のエステル化物（Ｂ）としてエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：１８モル、末端構造は水酸基）を６質量部と、アクリル酸２−エチルヘキシルを４３５質量部、アクリル酸ブチルを１２０質量部、メタクリル酸メチルを２４質量部、Ｎ−イソプロピルアクリルアミド６質量部及びアクリル酸を１５質量部と、連鎖移動剤としてラウリルメルカプタン０．２１質量部と、イオン交換水１０８質量部とを仕込み、攪拌することによって、乳化液を調製した。
(Example 6)
Latem PD-104 (made by Kao Corporation, solid content 20% by mass) as a reactive surfactant in a container and 45 parts by mass of ethylene glycol dehydroabietic acid ester (EO) as an esterified product of disproportionated rosin acid (B) Number of added moles: 18 mol, terminal structure is hydroxyl group) 6 parts by mass, 435 parts by mass of 2-ethylhexyl acrylate, 120 parts by mass of butyl acrylate, 24 parts by mass of methyl methacrylate, 6 parts by mass of N-isopropylacrylamide An emulsion was prepared by charging 15 parts by weight of acrylic acid and 15 parts by weight of acrylic acid, 0.21 part by weight of lauryl mercaptan as a chain transfer agent, and 108 parts by weight of ion-exchanged water.
温度計、滴下ロート、還流冷却管及び攪拌装置を備えた重合容器内を窒素ガスで置換し、イオン交換水３６４．８質量部を仕込み、内温５２．５℃に昇温した。 The inside of the polymerization vessel equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with nitrogen gas, charged with 364.8 parts by mass of ion-exchanged water and heated to an internal temperature of 52.5 ° C.
前記重合容器に、前記乳化液の全量に対して１質量％の乳化液を仕込んだ後、ピロ亜硫酸ナトリウムを０．１５質量部及び過硫酸アンモニウムを０．１８質量部添加し、重合を開始した。 After charging 1% by mass of the emulsion in the polymerization vessel with respect to the total amount of the emulsion, 0.15 parts by mass of sodium pyrosulfite and 0.18 parts by mass of ammonium persulfate were added to initiate polymerization.
３０分間ホールドした後、残りの乳化液（９９質量％）と、２，２’−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド水溶液（不揮発分０．５質量％）１０質量部とを、前記重合容器内に６時間かけて滴下し、更に重合容器を内温５２．５℃にて１時間保持した後、約２５℃に冷却することで、ビニル重合体エマルジョン６−１を得た。 After holding for 30 minutes, the remaining emulsion (99% by mass) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (nonvolatile content 0.5% by mass) 10 parts by mass are dropped into the polymerization vessel over 6 hours, and the polymerization vessel is kept at an internal temperature of 52.5 ° C. for 1 hour, and then cooled to about 25 ° C. -1 was obtained.
前記ビニル重合体エマルジョン６−１の固形分１００質量部に対して、更に１２．５質量％のアンモニア水を２．２質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．２質量部とイオン交換水０．８質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン６−２を得た。 With respect to 100 parts by mass of the solid content of the vinyl polymer emulsion 6-1, 2.2 parts by mass of 12.5% by mass of ammonia water, Boncoat 3750-E (a thickener manufactured by DIC Corporation, non-volatile) A vinyl polymer emulsion 6 having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 by mixing 1.2 parts by mass of 23 parts by mass) and 0.8 parts by mass of ion-exchanged water. 2 was obtained.
前記ビニル重合体エマルジョン６−２と油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５２．４質量％、粘度３１４ｍＰａ・ｓ、ｐＨ２．８、粒子径２９７ｎｍ、分子量６４万のビニル重合体と不均化ロジン酸のエステル化物とイオン交換水と油溶性エポキシ化合物とを含む水性粘着剤用組成物６を得た。 By mixing the vinyl polymer emulsion 6-2 and 0.02 parts by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) which is an oil-soluble epoxy compound, and filtering using a 200 mesh filter cloth (polyester) , Solid content 52.4 mass%, viscosity 314 mPa · s, pH 2.8, particle size 297 nm, molecular weight 640,000 vinyl polymer, disproportionated rosin acid esterified product, ion-exchanged water, and oil-soluble epoxy compound A composition 6 for an aqueous pressure-sensitive adhesive was obtained.
（実施例７）
容器に反応性界面活性剤としてラテムルＰＤ−１０４（花王株式会社製、固形分２０質量％）を４５質量部と、不均化ロジン酸のエステル化物（Ｂ）としてエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：３０モル、末端構造は水酸基）を６質量部と、アクリル酸２−エチルヘキシルを４３５質量部、アクリル酸ブチルを１２０質量部、メタクリル酸メチルを２４質量部、Ｎ−イソプロピルアクリルアミド６質量部及びアクリル酸を１５質量部と、連鎖移動剤としてラウリルメルカプタン０．２１質量部と、イオン交換水１０８質量部とを仕込み、攪拌することによって、乳化液を調製した。
(Example 7)
Latem PD-104 (made by Kao Corporation, solid content 20% by mass) as a reactive surfactant in a container and 45 parts by mass of ethylene glycol dehydroabietic acid ester (EO) as an esterified product of disproportionated rosin acid (B) Addition mole number: 30 mol, terminal structure is hydroxyl group) 6 parts by mass, 435 parts by mass of 2-ethylhexyl acrylate, 120 parts by mass of butyl acrylate, 24 parts by mass of methyl methacrylate, 6 parts by mass of N-isopropylacrylamide An emulsion was prepared by charging 15 parts by weight of acrylic acid and 15 parts by weight of acrylic acid, 0.21 part by weight of lauryl mercaptan as a chain transfer agent, and 108 parts by weight of ion-exchanged water.
温度計、滴下ロート、還流冷却管及び攪拌装置を備えた重合容器内を窒素ガスで置換し、イオン交換水３６４．８質量部を仕込み、内温５２．５℃に昇温した。 The inside of the polymerization vessel equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with nitrogen gas, charged with 364.8 parts by mass of ion-exchanged water and heated to an internal temperature of 52.5 ° C.
前記重合容器に、前記乳化液の全量に対して１質量％の乳化液を仕込んだ後、ピロ亜硫酸ナトリウムを０．１５質量部及び過硫酸アンモニウムを０．１８質量部添加し、重合を開始した。 After charging 1% by mass of the emulsion in the polymerization vessel with respect to the total amount of the emulsion, 0.15 parts by mass of sodium pyrosulfite and 0.18 parts by mass of ammonium persulfate were added to initiate polymerization.
３０分間ホールドした後、残りの乳化液（９９質量％）と、２，２’−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド水溶液（不揮発分０．５質量％）１０質量部とを、前記重合容器内に６時間かけて滴下し、更に重合容器を内温５２．５℃にて１時間保持した後、約２５℃に冷却することで、ビニル重合体エマルジョン７−１を得た。 After holding for 30 minutes, the remaining emulsion (99% by mass) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (nonvolatile content 0.5% by mass) 10 parts by mass are dropped into the polymerization vessel over 6 hours, and the polymerization vessel is kept at an internal temperature of 52.5 ° C. for 1 hour, and then cooled to about 25 ° C. -1 was obtained.
前記ビニル重合体エマルジョン７−１の固形分１００質量部に対して、更に１２．５質量％のアンモニア水を２．２質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．２質量部とイオン交換水１．８質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン７−２を得た。 With respect to 100 parts by mass of the solid content of the vinyl polymer emulsion 7-1, 2.2 parts by mass of 12.5% by mass of ammonia water, Boncoat 3750-E (a thickener manufactured by DIC Corporation, non-volatile) A vinyl polymer emulsion 7- having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 by mixing 1.2 parts by mass of 23 parts by mass) and 1.8 parts by mass of ion-exchanged water. 2 was obtained.
前記ビニル重合体エマルジョン７−２と、油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部と混合し、２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５２．１質量％、粘度６２０ｍＰａ・ｓ、ｐＨ２．８、粒子径２８１ｎｍ、分子量６４万のビニル重合体と不均化ロジン酸のエステル化物とイオン交換水と油溶性エポキシ化合物とを含む水性粘着剤用組成物７を得た。 By mixing the vinyl polymer emulsion 7-2 with 0.02 part by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) which is an oil-soluble epoxy compound, and filtering using 200 mesh filter cloth (polyester). , Including a vinyl polymer having a solid content of 52.1% by mass, a viscosity of 620 mPa · s, a pH of 2.8, a particle diameter of 281 nm, a molecular weight of 640,000, a disproportionated rosin acid, ion-exchanged water, and an oil-soluble epoxy compound. A composition 7 for an aqueous pressure-sensitive adhesive was obtained.
（比較例１）
前記合成例１で得られたビニル重合体エマルジョン１の固形分１００質量部に対して、更に１２．５質量％のアンモニア水を２．２質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．０質量部とイオン交換水０．８質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン８−１を得た。
(Comparative Example 1)
With respect to 100 parts by mass of the solid content of the vinyl polymer emulsion 1 obtained in Synthesis Example 1, 2.2 parts by mass of 12.5% by mass of ammonia water and Boncoat 3750-E (manufactured by DIC Corporation) A vinyl having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 by mixing 1.0 part by weight of a thickener and a nonvolatile content of 23% by weight with 0.8 part by weight of ion-exchanged water. A polymer emulsion 8-1 was obtained.
前記ビニル重合体エマルジョン８−１と油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５３．０質量％、粘度２５０ｍＰａ・ｓ、ｐＨ２．５、粒子径２８０ｎｍ、分子量７０万のビニル重合体とイオン交換水と油溶性エポキシ化合物とを含む水性粘着剤用組成物８を得た。 By mixing the vinyl polymer emulsion 8-1 and 0.02 parts by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) which is an oil-soluble epoxy compound, and filtering using 200 mesh filter cloth (polyester) An aqueous pressure-sensitive adhesive composition 8 containing a vinyl polymer having a solid content of 53.0% by mass, a viscosity of 250 mPa · s, a pH of 2.5, a particle size of 280 nm, and a molecular weight of 700,000, ion-exchanged water, and an oil-soluble epoxy compound is obtained. It was.
（比較例２）
前記合成例１で得られたビニル重合体エマルジョン１の固形分１００質量部に対して、乾燥遅延剤としてノニオシド Ｂ−１５（ブチルポリグルコシド、第一工業製薬株式会社製、固形分５０質量％）１質量部とを混合した後、更に１２．５質量％のアンモニア水を２．５質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．１質量部とイオン交換水０．９質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン９−１を得た。
(Comparative Example 2)
Nonioside B-15 (butyl polyglucoside, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content 50% by mass) as a drying retarder with respect to 100 parts by mass of the solid content of the vinyl polymer emulsion 1 obtained in Synthesis Example 1 After mixing 1 part by mass, 2.5 parts by mass of 12.5% by mass of aqueous ammonia and Boncoat 3750-E (a thickener manufactured by DIC Corporation, nonvolatile content 23% by mass) were added 1.1. A vinyl polymer emulsion 9-1 having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8 was obtained by mixing parts by mass with 0.9 parts by mass of ion-exchanged water.
前記ビニル重合体エマルジョン９−１と、油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０２質量部とを混合し、２００メッシュ濾布（ポリエステル）を用いて濾過することによって、固形分５３．０質量％、粘度２５０ｍＰａ・ｓ、ｐＨ２．５、粒子径２８０ｎｍ、分子量７０万のビニル重合体とイオン交換水と油溶性エポキシ化合物と乾燥遅延剤とを含む水性粘着剤用組成物９を得た。 Mixing the vinyl polymer emulsion 9-1 and 0.02 parts by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) which is an oil-soluble epoxy compound, and filtering using 200 mesh filter cloth (polyester). For aqueous adhesives containing a vinyl polymer having a solid content of 53.0% by mass, a viscosity of 250 mPa · s, a pH of 2.5, a particle size of 280 nm, and a molecular weight of 700,000, ion-exchanged water, an oil-soluble epoxy compound, and a drying retarder. Composition 9 was obtained.
（比較例３）
容器に反応性界面活性剤としてラテムルＰＤ−１０４（花王株式会社製、固形分２０質量％）を４５質量部と、不均化ロジン酸のエステル化物（Ｂ）としてエチレングリコールデヒドロアビエチン酸エステル（ＥＯ付加モル数：８モル、末端構造は水酸基）を６質量部と、アクリル酸２−エチルヘキシルを４３５質量部、アクリル酸ブチルを１２０質量部、メタクリル酸メチルを２４質量部、Ｎ−イソプロピルアクリルアミド６質量部及びアクリル酸を１５質量部と、連鎖移動剤としてラウリルメルカプタン０．２１質量部と、イオン交換水１０８質量部とを仕込み、攪拌することによって、乳化液を調製した。
(Comparative Example 3)
Latem PD-104 (made by Kao Corporation, solid content 20% by mass) as a reactive surfactant in a container and 45 parts by mass of ethylene glycol dehydroabietic acid ester (EO) as an esterified product of disproportionated rosin acid (B) Addition mole number: 8 mol, terminal structure is hydroxyl group) 6 parts by mass, 435 parts by mass of 2-ethylhexyl acrylate, 120 parts by mass of butyl acrylate, 24 parts by mass of methyl methacrylate, 6 parts by mass of N-isopropylacrylamide An emulsion was prepared by charging 15 parts by weight of acrylic acid and 15 parts by weight of acrylic acid, 0.21 part by weight of lauryl mercaptan as a chain transfer agent, and 108 parts by weight of ion-exchanged water.
温度計、滴下ロート、還流冷却管及び攪拌装置を備えた重合容器内を窒素ガスで置換し、イオン交換水３６４．８質量部を仕込み、内温５２．５℃に昇温した。 The inside of the polymerization vessel equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with nitrogen gas, charged with 364.8 parts by mass of ion-exchanged water and heated to an internal temperature of 52.5 ° C.
前記重合容器に、前記乳化液の全量に対して１質量％の乳化液を仕込んだ後、ピロ亜硫酸ナトリウムを０．１５質量部及び過硫酸アンモニウムを０．１８質量部添加し、重合を開始した。 After charging 1% by mass of the emulsion in the polymerization vessel with respect to the total amount of the emulsion, 0.15 parts by mass of sodium pyrosulfite and 0.18 parts by mass of ammonium persulfate were added to initiate polymerization.
３０分間ホールドした後、残りの乳化液（９９質量％）と、２，２’−アゾビス[２−（２−イミダゾリン−２−イル）プロパン]ジハイドロクロライド水溶液（不揮発分０．５質量％）１０質量部とを、前記重合容器内に６時間かけて滴下し、次いで重合容器を内温５２．５℃にて１時間保持した後、約２５℃に冷却した。 After holding for 30 minutes, the remaining emulsion (99% by mass) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (nonvolatile content 0.5% by mass) 10 parts by mass was dropped into the polymerization vessel over 6 hours, and then the polymerization vessel was held at an internal temperature of 52.5 ° C. for 1 hour, and then cooled to about 25 ° C.
前記重合物の固形分１００質量部に対して、更に１２．５質量％のアンモニア水を２．２質量部と、ボンコート３７５０−Ｅ（ＤＩＣ株式会社製の増粘剤、不揮発分２３質量％）を１．４質量部とイオン交換水１．０質量部を混合することによって、ＢＭ粘度が１００００ｍＰａ・ｓ（＃４×１２）、ｐＨが８であるビニル重合体エマルジョン１０−１を得た。 With respect to 100 parts by mass of the solid content of the polymer, 2.2 parts by mass of 12.5% by mass of ammonia water and Boncoat 3750-E (thickener manufactured by DIC Corporation, nonvolatile content 23% by mass) Was mixed with 1.0 part by mass of ion-exchanged water to obtain a vinyl polymer emulsion 10-1 having a BM viscosity of 10,000 mPa · s (# 4 × 12) and a pH of 8.
前記ビニル重合体エマルジョン１０−１と油溶性エポキシ化合物であるＴＥＴＲＡＤ−Ｃ（三菱ガス化学株式会社製）０．０１質量部とを混合し、内容物を２００メッシュ濾布（ポリエステル）で濾過することによって、固形分５２．１質量％、粘度２３４ｍＰａ・ｓ、ｐＨ２．７、粒子径２８７ｎｍ、分子量６０万のビニル重合体と不均化ロジン酸のエステル化物とイオン交換水とを含む水性粘着剤用組成物１０を得た。 Mixing the vinyl polymer emulsion 10-1 and 0.01 part by mass of TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), which is an oil-soluble epoxy compound, and filtering the contents with a 200 mesh filter cloth (polyester). For aqueous adhesives containing a vinyl polymer having a solid content of 52.1% by mass, a viscosity of 234 mPa · s, a pH of 2.7, a particle size of 287 nm, a molecular weight of 600,000, an esterified product of disproportionated rosin acid, and ion-exchanged water Composition 10 was obtained.
［粘着シートの作製］
前記水性粘着剤用組成物を用いて得られた水性粘着剤を、アプリケーターを用いて離型紙上に、乾燥膜厚が６０μｍとなるように塗工した。
[Production of adhesive sheet]
The aqueous pressure-sensitive adhesive obtained using the composition for water-based pressure-sensitive adhesive was coated on a release paper using an applicator so that the dry film thickness was 60 μm.
次いで、前記塗工物を１００℃の乾燥オーブン中で３分間乾燥し、該塗工表面に、厚さ５ｍｍのウレタンフォーム（イノアックコーポレーション株式会社製、ＥＣＳウレタンフォーム）を載置し、該ウレタンフォームの厚さが２．５ｍｍとなるまで加圧し前記塗工表面と前記ウレタンフォームとを接着することによって積層体を得た。 Next, the coated product is dried in a drying oven at 100 ° C. for 3 minutes, and a urethane foam having a thickness of 5 mm (ECS urethane foam, manufactured by INOAC Corporation) is placed on the coated surface. The laminate was obtained by pressurizing until the thickness became 2.5 mm and bonding the coated surface and the urethane foam.
得られた積層体を４０℃の雰囲気下に４８時間以上放置しエージングすることによって、本発明の粘着シートを得た。 The obtained laminate was allowed to stand for 48 hours or more in an atmosphere at 40 ° C. for aging to obtain an adhesive sheet of the present invention.
［両面粘着シートの作製］
前記水性粘着剤用組成物を用いて得られた水性粘着剤を、アプリケーターを用いて２枚の離型紙上に、それぞれ、乾燥膜厚が６０μｍとなるように塗工した。
[Production of double-sided PSA sheet]
The aqueous adhesive obtained using the composition for aqueous adhesives was applied onto two release papers using an applicator so that the dry film thickness was 60 μm.
次いで、前記塗工物を１００℃の乾燥オーブン中で３分間乾燥した後、一方の塗工物の塗工面にレーヨン不織布（秤量１４ｇ／ｍ２）を載置し、次いで該レーヨン不織布上に他方の塗工物の塗工面を載置したものを、１００℃に調整したロールを用い４０００ｇｆ／ｃｍの圧力で圧着し、４０℃×５０ＲＨ％の高温高湿室で２日間放置することによって両面粘着シートを得た。 Next, after the coated product was dried in a drying oven at 100 ° C. for 3 minutes, a rayon nonwoven fabric (weighing 14 g / m 2 ) was placed on the coated surface of one coated product, and then the other on the rayon nonwoven fabric. The coated surface of the coated product is pressure-bonded at a pressure of 4000 gf / cm using a roll adjusted to 100 ° C. and left in a high-temperature and high-humidity chamber of 40 ° C. × 50 RH% for 2 days. A sheet was obtained.
［多孔体に対する接着力（投錨性）の評価方法］
＜目視による評価方法＞
前記方法で得られた粘着シートを裁断し、その断面をマイクロスコープ（キーエンス株式会社、倍率５０倍）を用いて、粘着剤層とウレタンフォームとの接触部位（接着部位）の状態を目視で観察した。
[Evaluation Method of Adhesive Strength (Positioning Property) to Porous Material]
<Visual evaluation method>
The pressure-sensitive adhesive sheet obtained by the above method is cut, and the cross section of the pressure-sensitive adhesive sheet is visually observed using a microscope (Keyence Co., Ltd., 50 times magnification) at the contact part (adhesion part) between the pressure-sensitive adhesive layer and the urethane foam. did.
［判定基準］
◎；ウレタンフォームと粘着剤層との間に空隙や明確な界面がない。
○；ウレタンフォームと粘着剤層との接触部位全体の１０％未満の範囲で、空隙や明確な界面が確認された。
△；ウレタンフォームと粘着剤層との接触部位全体の１０以上３０％未満の範囲で、空隙や明確な界面が確認された。
×；ウレタンフォームと粘着剤層との接触部位全体の３０％以上の範囲で、空隙や明確な界面が確認された。
[Criteria]
A: There is no void or clear interface between the urethane foam and the pressure-sensitive adhesive layer.
A: Gaps and clear interfaces were confirmed within a range of less than 10% of the entire contact area between the urethane foam and the pressure-sensitive adhesive layer.
(Triangle | delta); The space | gap and a clear interface were confirmed in 10 to less than 30% of the whole contact site | part of a urethane foam and an adhesive layer.
X: The void | clearance and the clear interface were confirmed in the range of 30% or more of the whole contact site | part of a urethane foam and an adhesive layer.
［表面極性の低い被着体に対する接着力の評価方法］
前記方法で得られた両面粘着シートの一方の面側のみ離型紙を除去し、その粘着剤層表面に、厚さ２５μｍのポリエステルフィルムを載置し、その上部から、２ｋｇのロールを２往復させ荷重をかけることにより、それらを圧着させた。
[Method for evaluating adhesion to adherends with low surface polarity]
The release paper was removed only on one side of the double-sided pressure-sensitive adhesive sheet obtained by the above method, a 25 μm thick polyester film was placed on the surface of the pressure-sensitive adhesive layer, and a 2 kg roll was reciprocated twice from the top. They were crimped by applying a load.
次いで前記両面粘着シートと前記ポリエステルフィルムとからなる積層体を幅２０ｍｍ×長さ１００ｍｍの大きさに切り取って得た試験片の、他方の面側の離型紙を除去し、その粘着剤層表面にポリプロピレン基材を載置し、その上部から２ｋｇロール１往復の荷重をかけることにより、それらを貼り合わせた。 Next, the release paper on the other side of the test piece obtained by cutting the laminate composed of the double-sided pressure-sensitive adhesive sheet and the polyester film into a size of 20 mm wide × 100 mm long is removed, and the pressure-sensitive adhesive layer surface is removed. The polypropylene base material was mounted, and the 2 kg roll 1 reciprocating load was applied from the upper part, and they were bonded together.
次いで、前記粘着層とポリプロピレン基材との間の接着強度を、ＪＩＳＺ０２３７に準拠し、１８０度方向３００ｍｍ／ｍｉｎの速度で剥離しようとした際の剥離強度に基づき評価した。 Next, the adhesive strength between the pressure-sensitive adhesive layer and the polypropylene base material was evaluated based on the peel strength when attempting to peel at a speed of 300 mm / min in the 180 degree direction in accordance with JISZ0237.
また、前記ポリプロピレン基材の代わりにステンレス（ＳＵＳ）基材を用いる以外は前記と同様の方法で、粘着剤層とステンレス基材との間の接着強度を評価した。
前記剥離強度が、いずれの基材に対しても概ね１４Ｎ／２０ｍｍ以上のものを、表面極性の低い被着体に対する接着力に優れると評価した。
Moreover, the adhesive strength between an adhesive layer and a stainless steel base material was evaluated by the same method as the above except that a stainless steel (SUS) base material was used instead of the polypropylene base material.
The peel strength of about 14 N / 20 mm or more for any of the substrates was evaluated as being excellent in adhesion to an adherend having a low surface polarity.
［耐熱接着力の評価方法］
＜耐熱クリープ試験による評価＞
離型紙を除去した前記粘着シートを、幅２５ｍｍ×長さ５０ｍｍの面積のポリプロピレン基材に貼付し、５ｋｇのロールを用いて１往復圧着することにより積層体を得た。
[Evaluation method for heat-resistant adhesive strength]
<Evaluation by heat-resistant creep test>
The pressure-sensitive adhesive sheet from which the release paper was removed was attached to a polypropylene base material having an area of 25 mm width × 50 mm length, and was subjected to one reciprocal pressure bonding using a 5 kg roll to obtain a laminate.
８０℃の環境下で簡易型保持力試験機（テスター産業株式会社製）を用い、前記積層体を構成する粘着シートの支持体であるウレタンフォーム部分に、サンドペーパー＃３６０番手を介して１００ｇのおもりをつけ、前記ウレタンフォーム部分が下になる状態で３０分間放置した。 Using a simple holding force tester (manufactured by Tester Sangyo Co., Ltd.) in an environment of 80 ° C., 100 g of sandpaper # 360 is placed on the urethane foam part that is the support of the pressure-sensitive adhesive sheet constituting the laminate. A weight was attached, and the urethane foam part was left for 30 minutes with the part facing down.
３０分後、粘着シートがポリプロピレン基材から剥離（ｍｍ）した距離を測定した。なお、３０分経過前に、粘着シートを構成する支持体であるウレタンフォームと粘着剤層とが剥離し、前記ウレタンフォームが落下した場合には、落下までに要した時間（分）を測定した。 After 30 minutes, the distance at which the pressure-sensitive adhesive sheet peeled (mm) from the polypropylene substrate was measured. In addition, before 30 minutes passed, the urethane foam and the pressure-sensitive adhesive layer as the support constituting the pressure-sensitive adhesive sheet were peeled off, and when the urethane foam was dropped, the time (minutes) required until dropping was measured. .
また、前記ポリプロピレン基材の代わりにステンレス基材を使用すること以外は前記と同様の方法により、耐熱接着力の評価を行った。
前記３０分以内に落下することがなく、または、落下した場合であっても落下までに要した時間が１０分以上であるものを、耐熱接着力に優れると評価した。
Moreover, the heat resistant adhesive force was evaluated by the same method as described above except that a stainless steel substrate was used instead of the polypropylene substrate.
Those that did not fall within the 30 minutes, or those that took 10 minutes or more to fall even when dropped, were evaluated as having excellent heat-resistant adhesive strength.
＜軟化点による評価＞
離型紙を除去した前記粘着シートを、幅２５ｍｍ×長さ２５ｍｍの面積のポリプロピレンからなる被着体に貼付し、５ｋｇのロールを用いて１往復圧着することにより積層体を得た。
<Evaluation by softening point>
The pressure-sensitive adhesive sheet from which the release paper had been removed was affixed to an adherend made of polypropylene having a width of 25 mm × length of 25 mm, and was subjected to one reciprocal pressure bonding using a 5 kg roll to obtain a laminate.
２３℃の環境下、簡易型保持力試験機（テスター産業株式会社製）を用い、前記積層体を構成する粘着シートの支持体であるウレタンフォーム部分に、サンドペーパー＃３６０番手を介して３１０ｇのおもりをつけ、前記ウレタンフォーム部分が下になる状態で、２３℃から３℃／５分の速度で昇温し、粘着シートがポリプロピレン基材から落下した温度を測定した。 In an environment of 23 ° C., a simple holding force tester (manufactured by Tester Sangyo Co., Ltd.) was used, and 310 g of sandpaper # 360 was placed on the urethane foam portion that was a support for the pressure-sensitive adhesive sheet constituting the laminate. A weight was applied, and the temperature was increased from 23 ° C. to 3 ° C./5 minutes with the urethane foam part facing down, and the temperature at which the adhesive sheet dropped from the polypropylene substrate was measured.
また、前記ポリプロピレン基材の代わりにステンレス基材を使用すること以外は前記と同様の方法により、軟化点の測定を行った。
前記軟化点がいずれの基材に対しても６０℃以上であるものを、耐熱接着力に優れると評価した。
Moreover, the softening point was measured by the same method as described above except that a stainless steel substrate was used instead of the polypropylene substrate.
Those having a softening point of 60 ° C. or higher with respect to any of the substrates were evaluated as having excellent heat-resistant adhesive strength.
［再剥離性の評価方法］
離型紙を除去した前記粘着シートの、幅２０ｍｍ×長さ５０ｍｍの面積をステンレス基材に貼付し、５ｋｇのロールを用いて１往復圧着することにより積層体を得た。この積層体を６０℃の乾燥オーブン中で５００時間保存した後、２３℃下に取出し、１時間放置した。
次いで、前記積層体から前記ステンレス基材を手で剥離し、ステンレス基材への糊残りの状態を目視にて観察を行った。ステンレス基材と粘着面の界面で剥離し、ステンレスに糊残り無い状態であったものを「○界面」と評価し、ステンレス基材に粘着剤が糊残りしたものを「×糊残り」と評価した。
[Evaluation method of removability]
The pressure-sensitive adhesive sheet from which the release paper had been removed was pasted on a stainless steel substrate with an area of 20 mm width × 50 mm length, and a laminate was obtained by reciprocating once using a 5 kg roll. The laminate was stored in a drying oven at 60 ° C. for 500 hours, then taken out at 23 ° C. and left for 1 hour.
Next, the stainless steel substrate was peeled off from the laminate by hand, and the state of the adhesive residue on the stainless steel substrate was visually observed. Evaluated as “○ interface” when the adhesive was peeled off at the interface between the stainless steel substrate and the adhesive surface, leaving no adhesive residue on the stainless steel, and evaluated as “x adhesive residue” when the adhesive remained on the stainless steel substrate. did.
［ゲル分率の評価方法］
前記方法で作製した両面粘着シートを縦２０ｍｍ及び横１００ｍｍの大きさに切り取ったものを試験片とした。前記試験片から離型紙を除去した粘着剤層の質量を、精密天秤を用いて測定した（Ｗ１）。
[Evaluation method of gel fraction]
A test piece was prepared by cutting the double-sided PSA sheet produced by the above method into a size of 20 mm in length and 100 mm in width. The mass of the pressure-sensitive adhesive layer from which the release paper was removed from the test piece was measured using a precision balance (W1).
次に、前記粘着剤層を５０ｃｃのトルエン中に２４時間浸漬した後、１００℃の乾燥オーブン中で２時間乾燥した。乾燥後の粘着剤層の質量（Ｗ２）を、精密天秤を用いて測定した。 Next, the pressure-sensitive adhesive layer was immersed in 50 cc of toluene for 24 hours and then dried in a drying oven at 100 ° C. for 2 hours. The mass (W2) of the pressure-sensitive adhesive layer after drying was measured using a precision balance.
ゲル分率は、（質量（Ｗ２）−不織布の質量）／（質量（Ｗ１）−不織布の質量）×１００に基づいて算出した。 The gel fraction was calculated based on (mass (W2) −mass of nonwoven fabric) / (mass (W1) −mass of nonwoven fabric) × 100.
なお、前記不織布の質量は、０．０２８ｇである。 In addition, the mass of the said nonwoven fabric is 0.028g.
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