JP5231821B2 - Adhesive and adhesive sheet - Google Patents
Adhesive and adhesive sheet Download PDFInfo
- Publication number
- JP5231821B2 JP5231821B2 JP2008011475A JP2008011475A JP5231821B2 JP 5231821 B2 JP5231821 B2 JP 5231821B2 JP 2008011475 A JP2008011475 A JP 2008011475A JP 2008011475 A JP2008011475 A JP 2008011475A JP 5231821 B2 JP5231821 B2 JP 5231821B2
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- sensitive adhesive
- mass
- pressure
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims description 34
- 230000001070 adhesive effect Effects 0.000 title claims description 34
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 81
- 239000000839 emulsion Substances 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 238000009833 condensation Methods 0.000 claims description 16
- 230000005494 condensation Effects 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 21
- 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 17
- 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 17
- 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 17
- -1 2-ethylhexyl group Chemical group 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000000344 soap Substances 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000123 paper Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011086 glassine Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、各種の被着体、特に結露または湿潤した被着体に対する粘着性に優れ、さらに機械安定性（高速塗工安定性）に優れた水性エマルション型粘着剤および同粘着剤を使用した粘着シートに関するものである。 The present invention uses an aqueous emulsion-type pressure-sensitive adhesive and the same pressure-sensitive adhesive that are excellent in adhesiveness to various adherends, in particular, condensate or wet adherends, and excellent in mechanical stability (high-speed coating stability). The present invention relates to an adhesive sheet.
粘着シートは、通常の接着剤のように実用的な接着力を得る場合でも高い圧力又はエネルギーを必要とせず、指圧程度の圧力で貼り合わせると直ちに実用に耐える接着力を発揮するという使用上の簡便さや、使用に当たり良好な作業性を有することから、近年、多くの分野において用いられている。
この粘着シートの用途としては、例えば包装・結束用、事務・家庭用、接合用、塗装マスキング用、表面保護用、防食・装飾用、ラベル用などを挙げることができる。
この粘着シートは、一般に基材シートとその表面に形成された粘着剤層と、必要に応じて粘着剤層上に設けられる剥離シートから構成されており、使用に際しては、剥離シートが設けられている場合には、該剥離シートを剥がし、粘着剤層を被着体に当接させて貼付することが行われている。前記粘着剤層を構成する粘着剤としては、例えばアクリル系、ウレタン系、ゴム系、シリコーン系などがあるが、これらの中で、粘着力、保持力、耐候性、耐熱性などの性能および経済性の点から、アクリル系粘着剤が多用されている。このアクリル系粘着剤としては、従来、溶剤型のものが主として用いられてきたが、近年、粘着剤層形成時における有機溶剤の揮発が環境衛生や安全面で問題となっており、また、粘着シートにした場合でも、粘着剤層には僅かながら有機溶剤が残存しており、それが使用中に徐々に揮発し、環境衛生面で問題となっていた。
これに対し、水系のエマルション型粘着剤は、環境衛生、安全面については特に問題はなく、又高濃度化による高速塗工及び有機溶剤を使用しないことによる低コスト化が可能であることから、最近では、溶剤型に代えて、水系のエマルション型のものが使用されるようになってきた。特に、食品関係に使用されるラベルには、無溶剤型の粘着剤を用いたラベルが好んで使用されている。
しかしながら、水系のエマルション型粘着剤においては、乳化剤などの親水性成分が多く含まれているため、結露または湿潤した被着体への粘着力や耐水粘着力に乏しいという問題があった。例えば、水系のエマルション型粘着剤を用いて作製された粘着シートを結露または湿潤した状態の被着体に貼付した場合、あるいは該粘着シート貼付後に水などに浸漬した場合に、粘着シートの浮きや剥れが生じたり、基材シートと粘着剤層との界面で剥がれが生じたりしていた。結露面や湿潤面への粘着力や耐水粘着力を重視し、乳化剤などの親水性成分の使用量を少なくしたエマルション型粘着剤は、エマルション粒子の粒子安定性が劣るものとなり、高い剪断力のかかる環境下ではエマルション粒子の凝集が起こりやすい。
一方、耐水性に優れた水系のアクリル系エマルション型粘着剤としては、特定の単量体を、反応性ノニオン乳化剤の存在下に乳化重合してなる粘着剤が開示（例えば、特許文献１、２参照）されており、また、結露面や湿潤面に対する良好な初期粘着力を発現する水分散型粘着剤組成物として、アクリル系又はゴム系の水分散型粘着剤と、重量平均分子量２０，０００〜５，０００，０００のポリアルキレングリコールとを特定の割合で含む組成物（例えば、特許文献３参照）、特定の軟化温度を有するロジンを添加した組成物（例えば、特許文献４参照）、親水性ポリマーを含有させた組成物（例えば、特許文献５参照）等が開示されている。
しかしながら、これらの粘着剤や粘着剤組成物は、低温粘着力、結露面または湿潤面粘着力、耐水粘着力及び粘着シートに用いた場合の曲面貼付性のすべてを十分に満足し得るものではない上、機械的安定性の点でも十分ではない。
一般的に、界面活性剤などの親水性成分の添加量が少ないエマルション粒子は粒子安定性が低く、親水性成分の添加量が多い粘着剤は、結露面または湿潤面への粘着力が低い。
The pressure-sensitive adhesive sheet does not require high pressure or energy even when a practical adhesive force is obtained like a normal adhesive, and when it is bonded with a pressure of about a finger pressure, it immediately exhibits a practical adhesive force. In recent years, it has been used in many fields because of its simplicity and good workability in use.
Examples of uses of the pressure-sensitive adhesive sheet include packaging / bundling, office / household use, bonding, coating masking, surface protection, anticorrosion / decoration, and labeling.
This pressure-sensitive adhesive sheet is generally composed of a base sheet, a pressure-sensitive adhesive layer formed on the surface thereof, and a release sheet provided on the pressure-sensitive adhesive layer as necessary. In use, the release sheet is provided. When it is, the release sheet is peeled off, and the pressure-sensitive adhesive layer is adhered to the adherend and applied. Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acrylic, urethane-based, rubber-based, and silicone-based materials. Among these, performance and economy such as adhesive strength, holding power, weather resistance, and heat resistance are included. From the viewpoint of properties, acrylic pressure-sensitive adhesives are frequently used. Conventionally, as this acrylic adhesive, a solvent-type adhesive has been mainly used. However, in recent years, volatilization of an organic solvent at the time of forming an adhesive layer has been a problem in terms of environmental hygiene and safety. Even when the sheet is used, a slight amount of organic solvent remains in the pressure-sensitive adhesive layer, and it gradually evaporates during use, causing a problem in terms of environmental hygiene.
On the other hand, the water-based emulsion-type pressure-sensitive adhesive has no particular problems with respect to environmental hygiene and safety, and high-speed coating due to high concentration and cost reduction by not using an organic solvent are possible. Recently, a water-based emulsion type has been used instead of the solvent type. In particular, labels using solvent-free pressure-sensitive adhesives are preferably used for labels used in food products.
However, the water-based emulsion-type pressure-sensitive adhesive contains a large amount of hydrophilic components such as an emulsifier, and thus has a problem that it has poor adhesion or water-resistant adhesion to a condensed or wet adherend. For example, when a pressure-sensitive adhesive sheet prepared using a water-based emulsion-type pressure-sensitive adhesive is affixed to an adherend in a condensed or wet state, or when the pressure-sensitive adhesive sheet is immersed in water after application of the pressure-sensitive adhesive sheet, Peeling occurred, or peeling occurred at the interface between the base sheet and the pressure-sensitive adhesive layer. Emulsion-type adhesives that emphasize the adhesiveness to dew and wet surfaces and water-resistant adhesive strength, and reduce the amount of hydrophilic components such as emulsifiers, are poor in particle stability of emulsion particles and have high shearing force. In such an environment, aggregation of emulsion particles tends to occur.
On the other hand, as an aqueous acrylic emulsion-type pressure-sensitive adhesive having excellent water resistance, a pressure-sensitive adhesive obtained by emulsion polymerization of a specific monomer in the presence of a reactive nonionic emulsifier is disclosed (for example, Patent Documents 1 and 2). In addition, as a water-dispersed pressure-sensitive adhesive composition exhibiting a good initial adhesive force on a dew condensation surface or a wet surface, an acrylic or rubber-based water-dispersed pressure-sensitive adhesive and a weight average molecular weight of 20,000 A composition containing ˜5,000,000 polyalkylene glycol in a specific ratio (for example, see Patent Document 3), a composition containing a rosin having a specific softening temperature (for example, see Patent Document 4), hydrophilic A composition containing a functional polymer (see, for example, Patent Document 5) is disclosed.
However, these pressure-sensitive adhesives and pressure-sensitive adhesive compositions do not sufficiently satisfy all of low-temperature pressure-sensitive adhesive strength, condensation surface or wet surface pressure-sensitive adhesive strength, water-resistant pressure-sensitive adhesive strength, and curved surface stickiness when used for pressure-sensitive adhesive sheets. In addition, the mechanical stability is not sufficient.
In general, emulsion particles with a small amount of addition of a hydrophilic component such as a surfactant have low particle stability, and pressure-sensitive adhesives with a large amount of addition of a hydrophilic component have low adhesion to a condensation surface or a wet surface.
本発明は、このような背景の下、共重合させる際のカルボキシル基含有不飽和単量体の含有量及び界面活性剤の含有量、アルカリ可溶型またはアルカリ膨潤型エマルションの添加量を最適化することにより、粒子安定性、すなわち、機械安定性（高速塗工安定性）と、結露面または湿潤面に対する粘着力の両立を図った粘着剤およびそれを使用した粘着シートを提供することを目的とする。 In this background, the present invention optimizes the carboxyl group-containing unsaturated monomer content, surfactant content, and alkali-soluble or alkali-swelled emulsion addition amount during copolymerization. It is an object of the present invention to provide a pressure-sensitive adhesive that achieves both particle stability, that is, mechanical stability (high-speed coating stability) and adhesion to a condensation surface or a wet surface, and a pressure-sensitive adhesive sheet using the same. And
本発明者らは、鋭意検討した結果、カルボキシル基含有不飽和単量体単位を少量含む多量のアクリル系エマルションとカルボキシル基含有不飽和単量体単位を多量に含む少量のアルカリ可溶型またはアルカリ膨潤型エマルションを成分として用いることにより、上記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies, the present inventors have found that a large amount of an acrylic emulsion containing a small amount of a carboxyl group-containing unsaturated monomer unit and a small amount of an alkali-soluble type or alkali containing a large amount of a carboxyl group-containing unsaturated monomer unit. It has been found that the above problems can be solved by using a swelling emulsion as a component, and the present invention has been completed.
すなわち、本発明は、下記
（1）（メタ）アクリル酸アルキルエステルおよびカルボキシル基含有不飽和単量体から本質的になる不飽和単量体混合物（カルボキシル基含有不飽和単量体の含有量０．３〜０．８質量％）１００質量部当たり界面活性剤０．４〜１．２質量部存在下、乳化重合させて得られたアクリル系エマルション［Ａ］と、前記不飽和単量体混合物１００質量部当たりアルカリ可溶型またはアルカリ膨潤型エマルション［Ｂ］を０．０５〜０．９質量部含む水性エマルション型粘着剤であって、マーロン試験による残渣が１g以下であることを特徴とする水性エマルション型粘着剤、
（2）アルカリ可溶型またはアルカリ膨潤型エマルション［Ｂ］がアクリル酸エチルおよび（メタ）アクリル酸を共重合したエマルションである上記（1）記載の水性エマルション型粘着剤、
（3）前記アルカリ可溶型またはアルカリ膨潤型エマルション［Ｂ］が１０〜３０質量％のカルボキシル基含有不飽和単量体単位を含むポリマーエマルションである上記（1）または（2）に記載の水性エマルション型粘着剤、
（4）前記（メタ）アクリル酸アルキルエステルが２−エチルヘキシルアクリレートおよびブチルアクリレートからなるものである上記（1）〜（3）のいずれかに記載の水性エマルション型粘着剤、
（5）さらにタッキファイヤーを含む上記（1）〜（4）のいずれかに記載の水性エマルション型粘着剤、
（6）固形分含有量が４５〜６５質量％である上記（1）〜（5）のいずれかに記載の水性エマルション型粘着剤、
（7）上記（1）〜（6）のいずれかに記載の水性エマルション型粘着剤を基材に塗布して粘着剤層を設けてなる粘着シートおよび
（8）結露面または湿潤面貼付用である上記（7）に記載の粘着シートを提供する。
That is, the present invention provides an unsaturated monomer mixture consisting essentially of the following (1) (meth) acrylic acid alkyl ester and a carboxyl group-containing unsaturated monomer (content of carboxyl group-containing unsaturated monomer is 0 .3 to 0.8% by mass) Acrylic emulsion [A] obtained by emulsion polymerization in the presence of 0.4 to 1.2 parts by mass of a surfactant per 100 parts by mass, and the unsaturated monomer mixture. An aqueous emulsion-type pressure-sensitive adhesive containing 0.05 to 0.9 parts by mass of an alkali-soluble or alkali-swelled emulsion [B] per 100 parts by mass, wherein the residue by Marlon test is 1 g or less. Aqueous emulsion adhesive,
(2) The aqueous emulsion-type pressure-sensitive adhesive according to the above (1), wherein the alkali-soluble or alkali-swelling emulsion [B] is an emulsion obtained by copolymerizing ethyl acrylate and (meth) acrylic acid,
(3) The aqueous solution according to (1) or (2) above, wherein the alkali-soluble or alkali-swelling emulsion [B] is a polymer emulsion containing 10 to 30% by mass of a carboxyl group-containing unsaturated monomer unit. Emulsion-type adhesive,
(4) The aqueous emulsion-type pressure-sensitive adhesive according to any one of the above (1) to (3), wherein the (meth) acrylic acid alkyl ester comprises 2-ethylhexyl acrylate and butyl acrylate,
(5) The aqueous emulsion-type pressure-sensitive adhesive according to any one of (1) to (4), further including a tackifier,
(6) The aqueous emulsion-type pressure-sensitive adhesive according to any one of (1) to (5), wherein the solid content is 45 to 65% by mass,
(7) A pressure-sensitive adhesive sheet in which the water-based emulsion-type pressure-sensitive adhesive according to any one of the above (1) to (6) is applied to a base material to provide a pressure-sensitive adhesive layer, and (8) A pressure-sensitive adhesive sheet according to the above (7) is provided.
本発明の水性エマルション型粘着剤を使用した粘着シートは、各種の被着体、特に結露または湿潤した被着体に対する粘着性に優れ、さらに、高速度（１５０〜５００ｍ/分程度）で塗工した場合でも、塗工欠陥が少なく、機械安定性（高速塗工安定性）に優れている。 The pressure-sensitive adhesive sheet using the water-based emulsion-type pressure-sensitive adhesive of the present invention is excellent in adhesiveness to various adherends, in particular, a condensed or wet adherend, and is coated at a high speed (about 150 to 500 m / min). Even in this case, there are few coating defects and excellent mechanical stability (high-speed coating stability).
以下、本発明の水性エマルション型粘着剤および粘着シートについて詳細に説明する。
まず、［Ａ］成分であるアクリル系エマルションについて説明する。
本発明の水性エマルション型粘着剤を構成する［Ａ］成分における不飽和単量体混合物中の（メタ）アクリル酸エステルとしては、エステル部分のアルキル基としてメチル基、エチル基、プロピル基、ｎ-ブチル基、イソブチル基、イソアミル基、ヘキシル基、ヘプチル基、２−エチルヘキシル基、イソオクチル基、イソノニル基、イソデシル基等、炭素数１〜２０程度のアルキル基を有するアクリル酸またはメタクリル酸のアルキルエステルである。
これらの中でも、炭素数４〜１２のものが好ましく、炭素数４〜８のものがさらに好ましい。具体的には、アクリル酸ブチル、アクリル酸２−エチルヘキシル等である。これらの（メタ）アクリル酸エステルは単独または２種以上の混合物として用いてもよいが、性能の観点からアクリル酸ブチルとアクリル酸２−エチルヘキシルの組み合わせが好ましい。
Hereinafter, the water-based emulsion pressure-sensitive adhesive and pressure-sensitive adhesive sheet of the present invention will be described in detail.
First, the acrylic emulsion as the [A] component will be described.
The (meth) acrylic acid ester in the unsaturated monomer mixture in the component [A] constituting the aqueous emulsion-type pressure-sensitive adhesive of the present invention includes a methyl group, an ethyl group, a propyl group, n- It is an alkyl ester of acrylic acid or methacrylic acid having an alkyl group of about 1 to 20 carbon atoms such as butyl group, isobutyl group, isoamyl group, hexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, etc. is there.
Among these, those having 4 to 12 carbon atoms are preferable, and those having 4 to 8 carbon atoms are more preferable. Specific examples include butyl acrylate and 2-ethylhexyl acrylate. These (meth) acrylic acid esters may be used alone or as a mixture of two or more thereof, but a combination of butyl acrylate and 2-ethylhexyl acrylate is preferable from the viewpoint of performance.
不飽和単量体混合物中のカルボキシル基含有不飽和単量体としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、クロトン酸等が挙げられ、入手の容易さ、重合性等の観点からアクリル酸およびメタクリル酸が好ましい。
不飽和単量体混合物（１００質量％）中、カルボキシル基含有不飽和単量体の含有量は０．３〜０．８質量％であり、好ましくは０．３５〜０．７５質量％である。
カルボキシル基含有不飽和単量体の含有量が０．３質量％未満では機械安定性、結露面または湿潤面への粘着力および塗工性に劣り、０．８質量％を超えると機械安定性および塗工性には優れているが、結露面または湿潤面への粘着力が低下する。
なお、本発明における結露面または湿潤面粘着力というのは、０℃環境下に放置したポリエチレン被着体を２３℃、５０％ＲＨ環境下に３０秒放置後、同環境下にて被着体にサンプルを２ｋｇのロールを１往復させて押圧して貼付し、貼付直後にＪＩＳ Ｚ−０２３７の１８０°引き剥がし粘着力測定法に準じて測定したものである。
Examples of the carboxyl group-containing unsaturated monomer in the unsaturated monomer mixture include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, and the like. From the viewpoint of availability, polymerizability, etc. Acid and methacrylic acid are preferred.
In the unsaturated monomer mixture (100% by mass), the content of the carboxyl group-containing unsaturated monomer is 0.3 to 0.8% by mass, preferably 0.35 to 0.75% by mass. .
When the content of the carboxyl group-containing unsaturated monomer is less than 0.3% by mass, the mechanical stability, the adhesion to the condensation surface or the wet surface and the coating property are inferior, and when it exceeds 0.8% by mass, the mechanical stability is obtained. In addition, the coating property is excellent, but the adhesion to the dew condensation surface or the wet surface is reduced.
In the present invention, the dew-bonding surface or the wet surface adhesive force means that the polyethylene adherend left in an environment of 0 ° C. is allowed to stand in an environment of 23 ° C. and 50% RH for 30 seconds, and then the adherend in the same environment. The sample was measured by following a JIS Z-0237 peeling-off adhesive force measuring method of 180 ° immediately after applying the sample to a sample.
不飽和単量体混合物には、必要に応じて、上記以外に（メタ）アクリル酸ヒドロキシエチルのような（メタ）アクリル酸ヒドロキシアルキル等の水酸基含有単量体、酢酸ビニル、スチレン等を１種以上使用することができる。 In addition to the above, the unsaturated monomer mixture includes one kind of hydroxyl group-containing monomer such as hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, vinyl acetate, styrene, etc. It can be used above.
本発明の水性エマルション型粘着剤においては、前記不飽和単量体混合物をその１００質量部に対して０．４〜１．２質量部、好ましくは０．４〜１．０質量部の界面活性剤存在下、水系溶媒中で乳化重合させることにより［Ａ］成分のアクリル系エマルションが得られる。
界面活性剤の量が０．４質量部未満では、結露面または湿潤面への粘着力には優れているが、機械安定性および塗工性に劣る。１．２質量部を超えると機械安定性および塗工性には優れているが、結露面または湿潤面への粘着力が低下する。
In the aqueous emulsion type pressure-sensitive adhesive of the present invention, the unsaturated monomer mixture has a surface activity of 0.4 to 1.2 parts by weight, preferably 0.4 to 1.0 parts by weight, based on 100 parts by weight thereof. An acrylic emulsion of [A] component is obtained by emulsion polymerization in an aqueous solvent in the presence of an agent.
When the amount of the surfactant is less than 0.4 parts by mass, the adhesive strength to the dew condensation surface or the wet surface is excellent, but the mechanical stability and coating property are poor. When the amount exceeds 1.2 parts by mass, the mechanical stability and the coating property are excellent, but the adhesive force to the dew condensation surface or the wet surface decreases.
使用し得る界面活性剤としては、アニオン系やノニオン系乳化剤が挙げられる。アニオン系乳化剤としては、具体的にラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエ―テル硫酸ナトリウム、ポリオキシエチレンアルキルフエニルエ―テル硫酸ナトリウム等が挙げられる。ノニオン系乳化剤としては、ポリオキシエチレンアルキルエ―テル、ポリオキシエチレンアルキルフエニルエ―テル等が挙げられる。また、プロペニル基、アクリロイル基等を導入したラジカル重合性の反応性乳化剤も使用することができる。これらの乳化剤を単独又は併用して使用することもできる。
反応性乳化剤としては、反応性を有する乳化剤であれば特に限定されないが、例えば、アニオン型、ノニオン型の反応性乳化剤が使用される。具体的には、アニオン型反応性乳化剤として「アデカリアソープＳＥ−２０Ｎ」、「アデカリアソープＳＥ−１０Ｎ」、「アデカリアソープＰＰ−７０」、「アデカリアソープＰＰ−７１０」、「アデカリアソープＳＲ−１０」、「アデカリアソープＳＲ−２０」〔以上、旭電化工業社製〕、「エレミノールＪＳ−２」、「エレミノールＲＳ−３０」〔以上、三洋化成工業社製〕、「ラテムルＥ−１１８Ｂ」、「ラテムルＳ−１８０Ａ」、「ラテムルＳ−１８０」、「ラテムルＰＤ−１０４」〔以上、花王社製〕、「アクアロンＢＣ−０５」、「アクアロンＢＣ−１０」、「アクアロンＢＣ−２０」、「アクアロンＨＳ−０５」、「アクアロンＨＳ−１０」、「アクアロンＨＳ−２０」、「ニューフロンティアＳ−５１０」、「アクアロンＫＨ−０５」、「アクアロンＫＨ−１０」〔以上、第一工業製薬社製〕、「フォスフィノ−ルＴＸ」〔東邦化学工業社製〕、ノニオン型反応性乳化剤として「アデカリアソープＮＥ−１０」、「アデカリアソープＮＥ−２０」、「アデカリアソープＮＥ−３０」、「アデカリアソープＮＥ−４０」、「アデカリアソープＥＲ−１０」、「アデカリアソープＥＲ−２０」、「アデカリアソープＥＲ−３０」、「アデカリアソープＥＲ−４０」〔以上、旭電化工業社製〕、「アクアロンＲＮ−１０」、「アクアロンＲＮ−２０」、「アクアロンＲＮ−３０」、「アクアロンＲＮ−５０」〔以上、第一工業製薬社製〕等の市販品が挙げられる。
Examples of the surfactant that can be used include anionic and nonionic emulsifiers. Specific examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and the like. Examples of nonionic emulsifiers include polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. A radical polymerizable reactive emulsifier into which a propenyl group, an acryloyl group or the like is introduced can also be used. These emulsifiers can be used alone or in combination.
The reactive emulsifier is not particularly limited as long as it is a reactive emulsifier. For example, anionic and nonionic reactive emulsifiers are used. Specifically, as an anionic reactive emulsifier, “Adekalia Soap SE-20N”, “Adekalia Soap SE-10N”, “Adekalia Soap PP-70”, “Adekalia Soap PP-710”, “Adekalia” “Soap SR-10”, “Adekaria Soap SR-20” (manufactured by Asahi Denka Kogyo Co., Ltd.), “Eleminol JS-2”, “Eleminol RS-30” (manufactured by Sanyo Kasei Kogyo Co., Ltd.), “Latemle E -118B "," Latemul S-180A "," Latemul S-180 "," Latemul PD-104 "(manufactured by Kao Corporation)," Aqualon BC-05 "," Aqualon BC-10 "," Aqualon BC- 20 "," Aqualon HS-05 "," Aquaron HS-10 "," Aquaron HS-20 "," New Frontier S-510 "," Aquaron K " -05 "," Aqualon KH-10 "(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)," Phosfinol TX "(manufactured by Toho Chemical Co., Ltd.)," Adekalia Soap NE-10 "as a nonionic reactive emulsifier, “Adekaria soap NE-20”, “Adekaria soap NE-30”, “Adekaria soap NE-40”, “Adekaria soap ER-10”, “Adekaria soap ER-20”, “Adekaria soap ER” -30 "," Adekaria Soap ER-40 "(manufactured by Asahi Denka Kogyo Co., Ltd.)," Aqualon RN-10 "," Aquaron RN-20 "," Aquaron RN-30 "," Aquaron RN-50 "[ As mentioned above, commercial products such as those manufactured by Daiichi Kogyo Seiyaku Co., Ltd. may be mentioned.
アクリル系エマルション［Ａ］の乳化重合の条件としては、特に限定されず、通常の乳化重合で適用される条件をそのまま適用することができる。一般的には、反応器内を不活性ガスで置換した後、還流下撹拌しながら昇温を開始し４０〜１００℃程度の温度範囲で昇温開始後１〜８時間程度重合を行う。 The conditions for the emulsion polymerization of the acrylic emulsion [A] are not particularly limited, and the conditions applied in normal emulsion polymerization can be applied as they are. In general, after replacing the inside of the reactor with an inert gas, the temperature is increased while stirring under reflux, and the polymerization is carried out for about 1 to 8 hours after starting the temperature increase in a temperature range of about 40 to 100 ° C.
アクリル系エマルション［Ａ］を乳化重合法で調製する際、通常、重合開始剤が用いられる。重合開始剤として、２，２´−アゾビス（２−メチルプロピオンアミジン）二塩酸塩、２，２´−アゾビス（２−アミジノプロパン）ジヒドロクロライド等のアゾ系、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、ベンゾイルパ―オキサイド、ｔ−ブチルハイドロパ―オキサイド、過酸化水素等の過酸化物を使用することができる。又過硫酸塩と亜硫酸水素ナトリウムとの組み合わせや過酸化物とアスコルビン酸ナトリウムとの組み合わせ等からなるレドックス開始剤も使用することができる。これらの重合開始剤は、通常は、乳化重合の各段階ごとに所定量を添加して、重合反応を行わせるようにすればよい。 When the acrylic emulsion [A] is prepared by an emulsion polymerization method, a polymerization initiator is usually used. As polymerization initiators, azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-amidinopropane) dihydrochloride, potassium persulfate, ammonium persulfate and the like Peroxides such as sulfate, benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide can be used. A redox initiator comprising a combination of persulfate and sodium bisulfite or a combination of peroxide and sodium ascorbate can also be used. These polymerization initiators are usually added in a predetermined amount at each stage of the emulsion polymerization to cause the polymerization reaction.
アクリル系エマルション［Ａ］を乳化重合法で調製する際、さらに、タッキファイヤー（粘着付与剤）を使用してもよい。タッキファイヤーを使用することにより、結露面または湿潤面への粘着力が優れた粘着剤が得られる。
タッキファイヤーの使用量は、不飽和単量体混合物１００質量部に対して１〜１５質量部（固形分換算）程度、好ましくは３〜１０質量部（同）である。タッキファイヤーの使用量１質量部未満では結露面または湿潤面への粘着力が劣り、１５質量部を超える量使用すると高速塗工安定性が劣るようになる。
タッキファイヤーとしては、ロジン系樹脂、石油系樹脂、テルペン系樹脂、アルキルフェノール樹脂、クマロン樹脂、クマロンインデン樹脂、スチレン樹脂、キシレン樹脂等が用いられる。
ロジン系樹脂とは、ロジンとロジン誘導体をいう。ロジンはガムロジン、ウッドロジン、トール油ロジンである。ロジン誘導体としては、重合ロジン、不均化ロジン、水素化ロジン、強化ロジン、ロジンエステル、重合ロジンエステル、ロジンフェノールの形態が挙げられ、エステル化に使用する多価アルコールとしてはエチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール等が使用できる。
石油系樹脂としては、Ｃ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５−Ｃ９共重合系石油樹脂、クマロン樹脂、クマロン−インデン系樹脂、ピュアモノマー樹脂、ジシクロペンタジエン系石油樹脂およびこれらの水素化物等が挙げられる。
テルペン系樹脂としては、テルペン重合体、β−ピネン重合体、テルペンフェノール樹脂及び芳香族変性テルペン重合体等が挙げられる。アルキルフェノール樹脂およびキシレン樹脂としては、アルキルフェノール変性キシレン樹脂、ロジン変性キシレン樹脂等が挙げられる。
When the acrylic emulsion [A] is prepared by an emulsion polymerization method, a tackifier (tackifier) may be further used. By using a tackifier, it is possible to obtain an adhesive having excellent adhesion to a dew condensation surface or a wet surface.
The amount of tackifier used is about 1 to 15 parts by mass (in terms of solid content), preferably 3 to 10 parts by mass (same as above) with respect to 100 parts by mass of the unsaturated monomer mixture. When the amount of tackifier used is less than 1 part by mass, the adhesive force on the dew condensation surface or wet surface is inferior.
As the tackifier, rosin resin, petroleum resin, terpene resin, alkylphenol resin, coumarone resin, coumarone indene resin, styrene resin, xylene resin and the like are used.
The rosin resin refers to rosin and rosin derivatives. Rosin is gum rosin, wood rosin, tall oil rosin. Examples of rosin derivatives include polymerized rosin, disproportionated rosin, hydrogenated rosin, reinforced rosin, rosin ester, polymerized rosin ester, rosin phenol, and polyhydric alcohols used for esterification include ethylene glycol, diethylene glycol, Glycerin, pentaerythritol, etc. can be used.
Examples of petroleum resins include C5 petroleum resins, C9 petroleum resins, C5-C9 copolymer petroleum resins, coumarone resins, coumarone-indene resins, pure monomer resins, dicyclopentadiene petroleum resins, and hydrides thereof. Is mentioned.
Examples of the terpene resin include a terpene polymer, a β-pinene polymer, a terpene phenol resin, and an aromatic modified terpene polymer. Examples of the alkylphenol resin and xylene resin include alkylphenol-modified xylene resin and rosin-modified xylene resin.
次に、本発明の水性エマルション型粘着剤中の［Ｂ］成分であるアルカリ可溶型またはアルカリ膨潤型エマルションについて説明する。
［Ｂ］成分は、カルボキシル基を多量に有するポリマーを含有するエマルションで、水に分散されているポリマー粒子が、アンモニア水のようなアルカリの添加により溶解または膨潤して著しく増粘するため、一般的には水系の塗料、紙の塗工液、水性インク等の用途に粘性改良剤、ゲル化剤、チクソトロピー添加剤等として利用されている。
本発明の水性エマルション型粘着剤においては、このアルカリ可溶型またはアルカリ膨潤型エマルションを従来のような粘性改良剤として用いるのではなく、エマルション粒子の安定性向上を目的として用いる。
この［Ｂ］成分であるアルカリ可溶型またはアルカリ膨潤型エマルションは、一般に（メタ）アクリル酸エチルのような（メタ）アクリル酸アルキルエステルを主成分とし、これにアクリル酸、メタクリル酸などの（メタ）アクリル酸のようなカルボキシル基を有する単量体を多量に加え、さらに、必要に応じて多官能性単量体のようなモノマーを少量加えて乳化重合により製造することができる。
多官能性単量体としては、（ポリ）エチレングリコールジ（メタ）アクリレート、メチレンビスアクリルアミド、１，６−ヘキサンジオ―ルジ（メタ）アクリレート、トリメチロ―ルプロパントリ（メタ）アクリレート、ジビニルベンゼン等の多官能性単量体が挙げられ、これらの群より選ばれる１種以上を使用することができる。多官能性単量体由来の単位の含有量は、［Ｂ］成分を構成する全単量体単位中０〜２質量％がよい。その含有量が２質量％を超える場合には、結露面または湿潤面への粘着力が低下する。
Next, the alkali-soluble or alkali-swelling emulsion that is the [B] component in the aqueous emulsion-type pressure-sensitive adhesive of the present invention will be described.
Component [B] is an emulsion containing a polymer having a large amount of carboxyl groups, and polymer particles dispersed in water are dissolved or swelled by the addition of an alkali such as aqueous ammonia, so that the viscosity is significantly increased. Specifically, it is used as a viscosity improver, a gelling agent, a thixotropic additive, etc. for uses such as water-based paints, paper coating liquids, and water-based inks.
In the aqueous emulsion type pressure-sensitive adhesive of the present invention, this alkali-soluble type or alkali-swelling type emulsion is not used as a conventional viscosity improver, but is used for the purpose of improving the stability of emulsion particles.
The [B] component, an alkali-soluble or alkali-swelled emulsion, generally contains a (meth) acrylic acid alkyl ester such as ethyl (meth) acrylate as the main component, and includes acrylic acid and methacrylic acid ( It can be prepared by emulsion polymerization by adding a large amount of a monomer having a carboxyl group such as (meth) acrylic acid and further adding a small amount of a monomer such as a polyfunctional monomer as required.
Polyfunctional monomers such as (poly) ethylene glycol di (meth) acrylate, methylenebisacrylamide, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, etc. And one or more selected from these groups can be used. The content of the unit derived from the polyfunctional monomer is preferably 0 to 2% by mass in all monomer units constituting the [B] component. When the content exceeds 2% by mass, the adhesive strength to the dew condensation surface or the wet surface decreases.
また、アルコキシポリエチレングリコール（メタ）アクリレート等の会合性モノマーを乳化共重合する場合もある。（メタ）アクリル酸のようなカルボキシル基を有する単量体と（メタ）アクリル酸エチルのような（メタ）アクリル酸アルキルエステルを主成分とすることは、乳化重合時の安定性とエマルションポリマーのアルカリ可溶型またはアルカリ膨潤型とが優れるためで、乳化重合の工程としては、重合性単量体滴下やプレエマルション滴下法により、有効成分２０〜４０質量％程度のものが製造され販売されている。（メタ）アクリル酸のようなカルボキシル基を有する単量体の使用量は１０〜３０質量％、好ましくは２０質量％前後である。１０質量％未満であると、重合安定性は向上するが、得られるカルボキシル基を多く持つポリマーのアルカリ可溶性またはアルカリ膨潤性が低下するおそれがある。３０質量％を超えると、重合安定性が低下すると共に、アルカリ環境下において粘度上昇が大きくなるので好ましくない。
このアルカリ可溶型またはアルカリ膨潤型エマルションは、多官能性単量体の量や種類、得られるポリマーの分子量、会合性モノマーの種類によって、架橋性を調整することができ、それによって目的とする機械安定性や結露面または湿潤面への粘着力を調製することができる。
［Ｂ］成分であるアルカリ可溶型またはアルカリ膨潤型エマルションは市販されており、例えば、東亜合成（株）製「アロンＢ−３００Ｋ」、同「アロンＡ−７０７５」、ローム・アンド・ハース（株）製「プライマルＴＴ−６１５」等が挙げられる。
In some cases, an associative monomer such as alkoxy polyethylene glycol (meth) acrylate is emulsion-copolymerized. The main component is a monomer having a carboxyl group such as (meth) acrylic acid and a (meth) acrylic acid alkyl ester such as ethyl (meth) acrylate. Since the alkali-soluble type or the alkali-swelling type is excellent, as the emulsion polymerization step, about 20 to 40% by mass of an active ingredient is produced and sold by a polymerizable monomer dropping method or a pre-emulsion dropping method. Yes. The amount of the monomer having a carboxyl group such as (meth) acrylic acid is 10 to 30% by mass, preferably about 20% by mass. When the content is less than 10% by mass, the polymerization stability is improved, but the alkali-soluble or alkali-swelling property of the resulting polymer having many carboxyl groups may be lowered. If it exceeds 30% by mass, the polymerization stability is lowered, and the increase in viscosity is increased in an alkaline environment, which is not preferable.
This alkali-soluble or alkali-swelled emulsion can be adjusted in cross-linkability depending on the amount and type of the polyfunctional monomer, the molecular weight of the resulting polymer, and the type of the associative monomer, and is thus intended. It is possible to adjust the mechanical stability and the adhesive force to the dew condensation surface or the wet surface.
[B] Component-soluble alkali-soluble or alkali-swelled emulsions are commercially available. For example, “Aron B-300K”, “Aron A-7075” manufactured by Toa Gosei Co., Ltd., Rohm and Haas ( "Primal TT-615" manufactured by Co., Ltd.
本発明の水性エマルション型粘着剤においては、［Ａ］成分と［Ｂ］成分の配合割合は、［Ａ］成分中の不飽和単量体混合物１００質量部当たり［Ｂ］成分が０．０５〜０．９質量部である。
［Ｂ］成分の配合量が０．０５質量部未満および０．９質量部を超える場合は、いずれも結露面または湿潤面への粘着力には優れているが、機械安定性および塗工性が低下する。
In the aqueous emulsion type pressure-sensitive adhesive of the present invention, the blending ratio of the [A] component and the [B] component is such that the [B] component is 0.05 to 100 parts by mass of the unsaturated monomer mixture in the [A] component. 0.9 parts by mass.
When the blending amount of the component [B] is less than 0.05 parts by weight and more than 0.9 parts by weight, both have excellent adhesion to the condensation surface or wet surface, but mechanical stability and coatability Decreases.
本発明の水性エマルション型粘着剤はマーロン試験による残渣が１g以下であることを特徴としている。
前記のように、高速度（１５０〜５００ｍ/分程度）で塗工した場合でも、マーロン試験による残渣が１g以下であれば凝集物発生による塗工筋の発生が減少し、塗工機の機械安定性が良好であると判断することができる。
本発明におけるマーロン試験は、マーロン型機械安定性試験機〔テスター産業（株）社製〕により、水性エマルション型粘着剤５０ｇを試料とし、荷重２９４Ｎ（３０ｋｇ）、回転数１０００ｒｐｍ、シェア印加時間３０分の条件にて行う機械安定性試験であり、試験後に凝集物を３００メッシュのＳＵＳフィルターで濾別し、残渣の乾燥（１０５℃で６０分間）重量を測ることにより求めた量（ｇ）である。
The aqueous emulsion-type pressure-sensitive adhesive of the present invention is characterized in that the residue by the Marlon test is 1 g or less.
As described above, even when coating is performed at a high speed (about 150 to 500 m / min), if the residue by the Marlon test is 1 g or less, the generation of coating streaks due to the generation of aggregates is reduced, and the machine of the coating machine It can be determined that the stability is good.
The Marlon test in the present invention was carried out using a Marlon mechanical stability tester (manufactured by Tester Sangyo Co., Ltd.), using 50 g of an aqueous emulsion adhesive as a sample, a load of 294 N (30 kg), a rotation speed of 1000 rpm, and a share application time of 30 minutes. This is a mechanical stability test conducted under the conditions of (1): the amount (g) obtained by filtering the aggregates with a 300 mesh SUS filter after the test and measuring the dry weight of the residue (105 ° C. for 60 minutes). .
本発明の水性エマルション型粘着剤においては、必要に応じて本発明の効果に影響しない範囲で、各種の添加剤、例えば、可塑剤、軟化剤、充填剤、顔料、染料、老化防止剤、増粘剤、消泡剤、防腐剤等を配合することができる。 In the aqueous emulsion type pressure-sensitive adhesive of the present invention, various additives such as a plasticizer, a softener, a filler, a pigment, a dye, an anti-aging agent, an increase agent are used as long as they do not affect the effects of the present invention. A sticking agent, an antifoaming agent, a preservative, etc. can be mix | blended.
また、本発明の水性エマルション型粘着剤においては、固形分濃度は、好ましくは４５〜６５質量％、より好ましくは５０〜６０質量％である。
また、粘度は５０〜５，０００ｍＰａ・ｓ、好ましくは１００〜２，０００ｍＰａ・ｓ（ＢＭ型粘度計、６０回転、２５℃）である。さらに、ｐＨは７.２〜９.０の範囲にある。
Moreover, in the aqueous | water-based emulsion type adhesive of this invention, solid content concentration becomes like this. Preferably it is 45-65 mass%, More preferably, it is 50-60 mass%.
The viscosity is 50 to 5,000 mPa · s, preferably 100 to 2,000 mPa · s (BM type viscometer, 60 rotations, 25 ° C.). Furthermore, the pH is in the range of 7.2 to 9.0.
次に、本発明の粘着シートにおける基材について詳細に説明する。
基材としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリイミド、ポリエーテルイミド、ポリアラミド、ポリエーテルケトン、ポリエーテル・エーテルケトン、ポリフェニレンサルファイド、ポリ（４−メチルペンテン−１）等の樹脂製のシートやフィルム、上質紙、コート紙、グラシン紙、ラミネート紙等の紙基材等が用いられる。
基材の厚さは、使用する材料によって多少異なるが、通常は、５〜３００μｍ程度であり、好ましくは、１０〜１００μｍ程度である。
Next, the base material in the adhesive sheet of this invention is demonstrated in detail.
As a base material, polyethylene terephthalate, polyethylene naphthalate, polyimide, polyetherimide, polyaramid, polyetherketone, polyetheretherketone, polyphenylene sulfide, poly (4-methylpentene-1) and other resin sheets and films Paper substrates such as fine paper, coated paper, glassine paper, and laminate paper are used.
Although the thickness of a base material changes a little with materials to be used, it is about 5-300 micrometers normally, Preferably, it is about 10-100 micrometers.
水性エマルション型粘着剤を基材または後記する剥離シートに塗布するには、同粘着剤のエマルションを調製して、それを、通常行われているグラビアコート法、バーコート法、スプレーコート法、スピンコート法、ロールコート法、ダイコート法、ナイフコート法、エアナイフコート法、リップコート法、カーテンコート法等を用いて行うことができる。 In order to apply an aqueous emulsion type adhesive to a substrate or a release sheet to be described later, an emulsion of the same adhesive is prepared and applied to a gravure coating method, a bar coating method, a spray coating method, a spin method, or the like. The coating method, roll coating method, die coating method, knife coating method, air knife coating method, lip coating method, curtain coating method and the like can be used.
基材上に形成させる粘着剤層の乾燥・硬化後の厚さは通常は、３〜５０μｍ程度、好ましくは、５〜４０μｍ程度である。粘着剤層の厚さを３μｍ以上とすることにより、本発明の粘着シートに必要な結露または湿潤粘着力を確保することができ、５０μｍ以下とすることにより、コストアップを防ぐとともに、粘着剤層が端部からはみ出すのを防止する。 The thickness of the pressure-sensitive adhesive layer formed on the substrate after drying and curing is usually about 3 to 50 μm, and preferably about 5 to 40 μm. By setting the thickness of the pressure-sensitive adhesive layer to 3 μm or more, it is possible to ensure the condensation or wet pressure-sensitive adhesive force necessary for the pressure-sensitive adhesive sheet of the present invention. Is prevented from protruding from the end.
次に、剥離シートについて詳細に説明する。
基材上に形成された粘着剤層の保護用の剥離シートとしては、フッ素系樹脂、シリコーン系樹脂、長鎖アルキル基含有カルバメート等の剥離剤をコーティングしたポリエチレンテレフタレート、ポリエチレン、ポリプロピレン等の樹脂フィルムや上質紙、グラシン紙、ラミネート紙等の紙基材に上記剥離剤をコーティングした剥離シートを用いることができる。剥離シートの厚さは使用する材料によって多少異なるが、通常は、１０〜２５０μｍ、好ましくは、２０〜２００μｍである。剥離剤層の厚さは、通常は、０．１〜５μｍ、好ましくは、０．５〜２μｍ程度である。
Next, the release sheet will be described in detail.
As a release sheet for protecting the pressure-sensitive adhesive layer formed on the substrate, a resin film such as polyethylene terephthalate, polyethylene, or polypropylene coated with a release agent such as a fluororesin, a silicone resin, or a long-chain alkyl group-containing carbamate Alternatively, a release sheet obtained by coating the release agent on a paper substrate such as high-quality paper, glassine paper, or laminate paper can be used. The thickness of the release sheet varies somewhat depending on the material used, but is usually 10 to 250 μm, preferably 20 to 200 μm. The thickness of the release agent layer is usually about 0.1 to 5 μm, preferably about 0.5 to 2 μm.
本発明の粘着シートは、通常の感圧性接着シ―ト類の製造方法にしたがって、前記の基材上に水性エマルション型粘着剤を直接塗工後乾燥することにより、あるいは前記の剥離シートの剥離剤層上に塗工後乾燥したのち、前記の基材上に転写することにより粘着剤層を形成させ、シ―ト状やテ―プ状等のロールや積層体、または単葉で剥離シートと貼付された形態とされた粘着シ―ト類とすることができる。 The pressure-sensitive adhesive sheet of the present invention is obtained by directly applying an aqueous emulsion-type pressure-sensitive adhesive on the base material and then drying it according to a conventional method for producing pressure-sensitive adhesive sheets, or by peeling the release sheet. After coating on the adhesive layer and drying, an adhesive layer is formed by transferring onto the base material, and a sheet or tape-like roll or laminate, or a single sheet and a release sheet. Adhesive sheets in the form of affixed can be used.
以下、本発明を実施例により具体的に説明するが、本発明は以下の実施例のみに限定されるものではない。また、以下において、単に部あるいは％とある場合はすべて質量部あるいは質量％を意味するものである。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to a following example. Further, in the following description, the term “parts” or “%” means all parts by mass or mass%.
＜実施例１〜８＞
（1）粘着剤の調製
２−エチルヘキシルアクリレート（表中の略号２−ＥＨＡ）４０質量部、ブチルアクリレート（表中の略号ＢＡ）６０質量部、表１に記載した各部数のアクリル酸（カルボキシル基含有不飽和単量体、表中の略号ＡＡ）からなる不飽和単量体混合物にタッキファイアー（表中の略号ＴＦ）であるテルペンフェノール樹脂［荒川化学工業社製、商品名「タマノル９０１」］６質量部を攪拌機、温度計、還流冷却器、滴下ロートを有する反応容器に投入して約３０℃に保ちながら、３０分間攪拌し溶解させた。
上記成分を均質に溶解させた後、同温度で表1に記載した部数のアニオン系界面活性剤［第一工業製薬社製、商品名「ニューフロンティアＡ−２２９Ｅ」］をイオン交換水５７質量部に分散させた分散液を加え、３０分間攪拌して不飽和単量体混合物等を含む乳化物を作製した。
別途、攪拌機、還流冷却器、温度計、窒素導入管及び滴下ロートを備えた反応容器に脱イオン水４０部を投入し、窒素を流入させながら、反応容器内の温度を８０℃まで昇温させ、濃度が５質量％になるように過硫酸カリウム４部を仕込んで溶解させた。この中に予め調製した前記不飽和単量体混合物等を含む溶液を約８０℃に保ちながら３時間かけて滴下した。
乳化物の滴下と並行して濃度５質量％の過硫酸カリウム水溶液４部を滴下して反応容器内の温度を８０〜８３℃に保持しながら３時間攪拌して乳化重合を行なった。
滴下終了後、１時間目および２時間目に、それぞれ過硫酸カリウム１質量部ずつ添加して重合を完結させ、同温度で３時間熟成した後室温に冷却して［Ａ］成分であるアクリル系エマルションを調製した。
次いで、ｐＨが８．０になるように２５質量％アンモニア水を加えて調整し、さらに表１に記載した部数の［Ｂ］成分であるアルカリ可溶型またはアルカリ膨潤型エマルション[アクリル酸エチル１００質量部およびメタクリル酸２０質量部をドデシルメルカプタン０．２質量部存在下で乳化共重合したもの、固形分濃度２５質量％]を添加して水性エマルション型粘着剤（固形分濃度５５質量％）を得た。
<Examples 1-8>
(1) Preparation of pressure-sensitive adhesive 40 parts by mass of 2-ethylhexyl acrylate (abbreviation 2-EHA in the table), 60 parts by mass of butyl acrylate (abbreviation BA in the table), acrylic acid (carboxyl group) of each part described in Table 1 A terpene phenol resin [trade name “Tamanol 901” manufactured by Arakawa Chemical Industries, Ltd.] which is a tackifier (abbreviation TF in the table) to an unsaturated monomer mixture comprising the unsaturated monomer contained, abbreviation AA in the table) 6 parts by mass was put into a reaction vessel having a stirrer, a thermometer, a reflux condenser and a dropping funnel, and stirred and dissolved for 30 minutes while maintaining at about 30 ° C.
After homogeneously dissolving the above components, the anionic surfactant in the number of parts listed in Table 1 at the same temperature [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name “New Frontier A-229E”] was added in 57 parts by mass of ion-exchanged water. The dispersion liquid dispersed in was added and stirred for 30 minutes to prepare an emulsion containing an unsaturated monomer mixture and the like.
Separately, 40 parts of deionized water is put into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel, and the temperature in the reaction vessel is raised to 80 ° C. while introducing nitrogen. Then, 4 parts of potassium persulfate was charged and dissolved so that the concentration became 5% by mass. A solution containing the unsaturated monomer mixture and the like prepared in advance was added dropwise over 3 hours while maintaining the temperature at about 80 ° C.
In parallel with the dropping of the emulsion, 4 parts of an aqueous potassium persulfate solution having a concentration of 5% by mass was dropped, and emulsion polymerization was carried out by stirring for 3 hours while maintaining the temperature in the reaction vessel at 80 to 83 ° C.
After completion of dropping, 1 part by weight of potassium persulfate was added at 1 hour and 2 hours respectively to complete the polymerization. After aging at the same temperature for 3 hours, the mixture was cooled to room temperature and then the acrylic component [A] An emulsion was prepared.
Subsequently, 25 mass% ammonia water was added and adjusted so that pH might be set to 8.0, Furthermore, the alkali-soluble type or alkali swelling type emulsion [ethyl acrylate 100 which is the [B] component of the number of parts described in Table 1) Emulsion copolymerization of 20 parts by mass and 20 parts by mass of methacrylic acid in the presence of 0.2 parts by mass of dodecyl mercaptan, solid content concentration of 25% by mass] to add an aqueous emulsion type adhesive (solid content concentration of 55% by mass) Obtained.
（２）粘着シートの製造および粘着剤面の観察
幅１ｍのグラシン紙の片面にシリコーン系剥離剤で表面処理された剥離シート（長さ５０００ｍ）上に、上記実施例で得られた水性エマルション型粘着剤および下記比較例で得られた比較用の水性エマルション型粘着剤を乾燥後の厚さが２０μmになるようにグラビアコーターを用いて塗工速度２５０ｍ/分で塗工し、１００℃で乾燥後、基材として坪量５５ｇ/ｍ2の上質紙に貼り合わせ、形成された粘着剤層を上質紙側に転写させ粘着シートを製造した。製造された粘着シート（１０ｍ）の剥離シートを剥離して上質紙側に転写された粘着剤層面の状態を観察した。
表１における粘着剤層面の状態（高速塗工性）の評価基準は以下の通りである。
○：塗工筋が観察されない。
△：塗工筋が１ｍ幅に１〜３本観察される。
×：塗工筋が１ｍ幅に４本以上観察される。
(2) Manufacture of pressure-sensitive adhesive sheet and observation of pressure-sensitive adhesive surface Aqueous emulsion type obtained in the above example on a release sheet (length 5000 m) surface-treated with a silicone-based release agent on one side of glassine paper having a width of 1 m The pressure-sensitive adhesive and the comparative aqueous emulsion-type pressure-sensitive adhesive obtained in the following comparative examples were coated at a coating speed of 250 m / min using a gravure coater so that the thickness after drying was 20 μm, and dried at 100 ° C. Then, it was bonded to a high-quality paper having a basis weight of 55 g / m 2 as a base material, and the formed pressure-sensitive adhesive layer was transferred to the high-quality paper side to produce a pressure-sensitive adhesive sheet. The state of the pressure-sensitive adhesive layer surface, which was peeled off from the produced pressure-sensitive adhesive sheet (10 m) and transferred to the high-quality paper, was observed.
The evaluation criteria of the state (high-speed coating property) of the pressure-sensitive adhesive layer surface in Table 1 are as follows.
○: No coating streaks are observed.
Δ: 1 to 3 coating stripes are observed in 1 m width.
X: Four or more coating stripes are observed in 1 m width.
〔比較例１〜６〕
表１に示す量のアクリル酸およびアニオン系乳化剤を不飽和単量体混合物に混合して乳化重合し、乳化重合後、表１に示す量のアルカリ可溶型またはアルカリ膨潤型エマルションを添加した以外は実施例と同様に行い、比較用の水性エマルション型粘着剤を得た。
比較用の水性エマルション型粘着剤及び粘着シートの性能評価結果を併せて表１に示す。
[Comparative Examples 1-6]
Acrylic acid and an anionic emulsifier in the amounts shown in Table 1 were mixed with an unsaturated monomer mixture and subjected to emulsion polymerization. After the emulsion polymerization, an alkali-soluble or alkali-swelling emulsion in the amount shown in Table 1 was added. Was carried out in the same manner as in Example, and a comparative water-based emulsion type pressure-sensitive adhesive was obtained.
The performance evaluation results of the comparative aqueous emulsion-type pressure-sensitive adhesive and pressure-sensitive adhesive sheet are shown together in Table 1.
表１中の［Ａ］を除く成分量の数値は［Ａ］の単量体成分合計１００質量部に対する有効成分量を示す。
使用した［Ａ］成分における略号は下記の通りである。
２ＥＨＡ：２−エチルヘキシルアクリレート
ＢＡ：ｎ−ブチルアクリレート
ＭＡＡ：メタクリル酸
The numerical value of the component amount excluding [A] in Table 1 indicates the effective component amount with respect to 100 parts by mass of the total monomer components of [A].
The abbreviations in the used [A] component are as follows.
2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate MAA: methacrylic acid
表１から以下のことが明らかである。
（1）実施例１〜９における水性エマルション型粘着剤は機械安定性が高く塗工性が良好であり、結露（湿潤）面に対する粘着力も高い。
（2）比較例1では［Ａ］成分中のアクリル酸の量が少ないため、水性エマルション型粘着剤の機械安定性が低く、凝集物の発生量が多い。しかも、結露（湿潤）面に対する粘着力も低い。
（3）比較例２では［Ａ］成分中のアクリル酸の量が多いため、水性エマルション型粘着剤の機械安定性は良いが、結露（湿潤）面に対する粘着力が低い。
（4）比較例３では［Ａ］成分中の乳化剤の使用量が少ないため、結露（湿潤）面に対する粘着力は実施例並みであるが、機械安定性が低く凝集物の発生量が多い。
（5）比較例４では［Ａ］成分中の乳化剤の使用量が多いため、機械安定性が高く凝集物の発生量が少ないが、結露（湿潤）面に対する粘着力は低い。
（6）比較例５では［Ｂ］成分の使用量が０のため、結露（湿潤）面に対する粘着力は実施例並みであるが、機械安定性が低く凝集物の発生量が多い。
（7）比較例６では［Ｂ］成分の使用量が多いため、結露（湿潤）面に対する粘着力は実施例並みであるが、機械安定性は低く凝集物の発生量が多い。
From Table 1, the following is clear.
(1) The water-based emulsion type adhesives in Examples 1 to 9 have high mechanical stability and good coatability, and also have high adhesion to the dew (wet) surface.
(2) In Comparative Example 1, since the amount of acrylic acid in the [A] component is small, the mechanical stability of the aqueous emulsion-type pressure-sensitive adhesive is low, and the amount of aggregates generated is large. In addition, the adhesion to the dew condensation (wet) surface is low.
(3) In Comparative Example 2, since the amount of acrylic acid in the [A] component is large, the mechanical stability of the water-based emulsion-type adhesive is good, but the adhesion to the dew (wet) surface is low.
(4) In Comparative Example 3, since the amount of emulsifier used in the component [A] is small, the adhesion to the dew (wet) surface is similar to that in the example, but the mechanical stability is low and the amount of aggregates generated is large.
(5) In Comparative Example 4, since the amount of the emulsifier used in the component [A] is large, the mechanical stability is high and the amount of aggregates is small, but the adhesion to the dew (wet) surface is low.
(6) In Comparative Example 5, since the amount of the [B] component used is 0, the adhesion to the dew (wet) surface is the same as in the examples, but the mechanical stability is low and the amount of aggregates generated is large.
(7) In Comparative Example 6, since the amount of the [B] component used is large, the adhesion to the dew (wet) surface is the same as in the examples, but the mechanical stability is low and the amount of aggregates generated is large.
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