JP2020002307A - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JP2020002307A JP2020002307A JP2018124885A JP2018124885A JP2020002307A JP 2020002307 A JP2020002307 A JP 2020002307A JP 2018124885 A JP2018124885 A JP 2018124885A JP 2018124885 A JP2018124885 A JP 2018124885A JP 2020002307 A JP2020002307 A JP 2020002307A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- component
- mass
- parts
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000000853 adhesive Substances 0.000 title abstract description 51
- 230000001070 adhesive effect Effects 0.000 title abstract description 51
- -1 alkyl ether phosphoric acid ester Chemical class 0.000 claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 163
- 239000010410 layer Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 52
- 239000011248 coating agent Substances 0.000 abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011737 fluorine Substances 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011241 protective layer Substances 0.000 description 13
- 229920001296 polysiloxane Polymers 0.000 description 11
- 239000003505 polymerization initiator Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002562 thickening agent Substances 0.000 description 9
- 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 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 230000000873 masking effect Effects 0.000 description 6
- 239000003002 pH adjusting agent Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000001846 repelling effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007883 water-soluble azo polymerization initiator Substances 0.000 description 2
- 125000004814 1,1-dimethylethylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- PBYIFPWEHGSUEY-UHFFFAOYSA-N 2-ethenyl-4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C=C)=N1 PBYIFPWEHGSUEY-UHFFFAOYSA-N 0.000 description 1
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- MBLQIMSKMPEILU-UHFFFAOYSA-N 4-methyl-2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C(C)=C)=N1 MBLQIMSKMPEILU-UHFFFAOYSA-N 0.000 description 1
- IRHWINGBSHBXAD-UHFFFAOYSA-N 5-ethyl-2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CCC1CN=C(C(C)=C)O1 IRHWINGBSHBXAD-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000007880 VA-057 Substances 0.000 description 1
- 239000007881 VA-086 Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 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
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-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
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Abstract
Description
本発明は、粘着剤組成物および粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet.
粘着剤組成物およびそれを用いた粘着シートは、産業上の種々の分野において広範に用いられている（特許文献１等）。 BACKGROUND ART Pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets using the same are widely used in various industrial fields (Patent Document 1, etc.).
粘着剤組成物およびそれを用いた粘着シートに要求される特性として、初期接着力、耐ハガレ性、および塗工適性の３つの特性がある。 There are three characteristics required for the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet using the same, such as initial adhesive strength, peeling resistance, and coating suitability.
初期接着力が低すぎると、粘着シートが被着体に接着しないおそれ、または被着体から剥離してしまうおそれがある。逆に、初期接着量が高すぎると、粘着シートが被着体から剥離しにくく、粘着剤組成物が被着体表面に残留（糊残り）してしまうおそれがある。 If the initial adhesive strength is too low, the pressure-sensitive adhesive sheet may not adhere to the adherend, or may peel from the adherend. Conversely, if the initial adhesion amount is too high, the pressure-sensitive adhesive sheet is less likely to peel from the adherend, and the pressure-sensitive adhesive composition may remain on the surface of the adherend (adhesive residue).
耐ハガレ性が低いと、粘着シートが、意図しない外力により被着体から剥離してしまうおそれがある。 If the peel resistance is low, the pressure-sensitive adhesive sheet may peel off from the adherend due to an unintended external force.
塗工適性が良好でないと、粘着剤組成物を基材に塗工して粘着シートを製造する際に、均一な塗工が困難であったり、クレーター状の欠点（ハジキ）を生じたりするおそれがある。 If the coating aptitude is not good, uniform coating may be difficult or a crater-like defect (repelling) may occur when a pressure-sensitive adhesive composition is applied to a substrate to produce a pressure-sensitive adhesive sheet. There is.
しかしながら、粘着剤組成物およびそれを用いた粘着シートにおいて、初期接着力、耐ハガレ性、および塗工適性の３つの特性を全て良好とすることは困難である。 However, in the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet using the same, it is difficult to improve all three properties of initial adhesive strength, peel resistance and coating suitability.
そこで、本発明は、初期接着力、耐ハガレ性、および塗工適性の３つの特性が全て良好な粘着剤組成物および粘着シートを提供することを目的とする。 Then, an object of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having all three properties of good initial adhesive strength, peeling resistance, and coating suitability.
前記目的を達成するために、本発明の粘着剤組成物は、
下記成分（Ａ）〜（Ｃ）を含み、
下記成分（Ａ）における重合体は、少なくとも下記成分（ａ１）５０〜９９．９質量部および（ａ２）０．１〜１０質量部の共重合体であり、
下記成分（Ｃ）は、下記成分（ｃ１）および（ｃ２）を含む
ことを特徴とする。
（Ａ）重合体のエマルション
（Ｂ）アルキル基の炭素数が１０〜１６であるポリオキシアルキレンアルキルエーテルリン酸エステル系化合物
（Ｃ）界面活性剤
（ａ１）アルキル基の炭素数が２〜１２のアクリル酸アルキルエステル、およびアルキル基の炭素数が２〜１２のメタクリル酸アルキルエステルの少なくとも一方
（ａ２）カルボキシ基含有不飽和単量体
（ｃ１）フッ素系界面活性剤
（ｃ２）分子中にフッ素原子を含まないアニオン性界面活性剤
To achieve the above object, the pressure-sensitive adhesive composition of the present invention,
It contains the following components (A) to (C),
The polymer in the following component (A) is a copolymer of at least the following component (a1) 50 to 99.9 parts by mass and (a2) 0.1 to 10 parts by mass,
The following component (C) is characterized by containing the following components (c1) and (c2).
(A) Emulsion of polymer (B) Polyoxyalkylene alkyl ether phosphate ester compound having 10 to 16 carbon atoms in alkyl group (C) Surfactant
(A1) at least one of an alkyl acrylate having 2 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 2 to 12 carbon atoms in an alkyl group (a2) a carboxy group-containing unsaturated monomer (c1) Fluorinated surfactant (c2) Anionic surfactant containing no fluorine atom in the molecule
本発明の粘着シートは、基材と、粘着剤層とを含み、前記粘着剤層が、前記本発明の粘着剤組成物を含むことを特徴とする。 The pressure-sensitive adhesive sheet of the present invention includes a substrate and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer includes the pressure-sensitive adhesive composition of the present invention.
本発明によれば、初期接着力、耐ハガレ性、および塗工適性の３つの特性が全て良好な粘着剤組成物および粘着シートを提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having all three favorable properties of initial adhesive strength, peel resistance, and coating suitability.
以下、本発明について、例を挙げて説明する。ただし、本発明は、以下の説明により限定されない。 Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited by the following description.
本発明の粘着剤組成物は、例えば、さらに、架橋剤（Ｄ）を含んでいてもよい。 The pressure-sensitive adhesive composition of the present invention may further contain, for example, a crosslinking agent (D).
本発明の粘着剤組成物は、例えば、前記成分（Ｃ）が、さらに、下記成分（ｃ３）を含んでいてもよい。
（ｃ３）ノニオン性界面活性剤
In the pressure-sensitive adhesive composition of the present invention, for example, the component (C) may further include the following component (c3).
(C3) Nonionic surfactant
本発明の粘着剤組成物は、例えば、前記成分（Ａ）中の不揮発成分１００質量部に対し、前記成分（Ｂ）の不揮発成分を０．０１〜０．６質量部、前記成分（Ｃ）の不揮発成分を合計０．５質量部〜３質量部含んでいてもよい。 The pressure-sensitive adhesive composition of the present invention comprises, for example, 0.01 to 0.6 parts by mass of the non-volatile component of the component (B) and 100 parts by mass of the non-volatile component in the component (A). May be contained in a total amount of 0.5 parts by mass to 3 parts by mass.
本発明の粘着シートは、例えば、前記基材が紙製の基材であってもよい。 In the pressure-sensitive adhesive sheet of the present invention, for example, the substrate may be a paper substrate.
本発明において、「初期接着力」は、粘着シートを被着体に接着させた直後の接着力をいい、すなわち、接着後の接着力の経時変化を考慮しない接着力をいう。本発明において、粘着剤または粘着シートの初期接着力の測定方法は、特に限定されないが、例えば、後述する実施例に記載の測定方法で測定できる。 In the present invention, the “initial adhesive strength” refers to the adhesive strength immediately after the pressure-sensitive adhesive sheet is adhered to the adherend, that is, the adhesive strength without considering the change over time in the adhesive strength after bonding. In the present invention, the method for measuring the initial adhesive force of the pressure-sensitive adhesive or the pressure-sensitive adhesive sheet is not particularly limited, but can be measured, for example, by the measurement method described in Examples described later.
本発明において、「接着力」と「粘着力」とは、特に区別はなく、同義であるものとする。本発明において、「接着剤」と「粘着剤」とは、特に区別はなく、同義であるものとする。本発明において、「粘着剤組成物」は、粘着剤のうち、組成物であるものをいう。 In the present invention, "adhesive strength" and "adhesive strength" are not particularly distinguished and have the same meaning. In the present invention, “adhesive” and “adhesive” are not particularly distinguished and have the same meaning. In the present invention, the “pressure-sensitive adhesive composition” refers to a pressure-sensitive adhesive that is a composition.
本発明において、「アルキル」は、例えば、直鎖状または分枝状のアルキルを含む。本発明において、アルキル基は、特に限定されないが、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基およびtert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等が挙げられる。 In the present invention, “alkyl” includes, for example, linear or branched alkyl. In the present invention, the alkyl group is not particularly limited, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group, pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like.
本発明において、「アルキレン」は、例えば、直鎖状アルキレン（メチレンもしくはポリメチレン）または分枝状のアルキレンを含む。本発明において、アルキレン基は、特に限定されないが、例えば、メチレン基、ジメチレン基（エチレン基）、エチリデン基、トリメチレン基、１−メチルエチレン基（プロピレン基）、テトラメチレン基、１−メチルトリメチレン基、２−メチルトリメチレン基、１，１−ジメチルエチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基等が挙げられる。 In the present invention, "alkylene" includes, for example, linear alkylene (methylene or polymethylene) or branched alkylene. In the present invention, the alkylene group is not particularly limited. Examples thereof include a methylene group, a dimethylene group (ethylene group), an ethylidene group, a trimethylene group, a 1-methylethylene group (propylene group), a tetramethylene group, and 1-methyltrimethylene. Groups, 2-methyltrimethylene group, 1,1-dimethylethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and the like.
以下、本発明の実施形態について、さらに具体的に説明する。ただし、本発明は、以下の実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described more specifically. However, the present invention is not limited to the following embodiments.
［１．粘着剤組成物］
本発明の粘着剤組成物は、前述のとおり、
下記成分（Ａ）〜（Ｃ）を含み、
下記成分（Ａ）における重合体は、少なくとも下記成分（ａ１）５０〜９９．９質量部および（ａ２）０．１〜１０質量部の共重合体であり、
下記成分（Ｃ）は、下記成分（ｃ１）および（ｃ２）を含む
ことを特徴とする。
（Ａ）重合体のエマルション
（Ｂ）アルキル基の炭素数が１０〜１６であるポリオキシアルキレンアルキルエーテルリン酸エステル系化合物
（Ｃ）界面活性剤
（ａ１）アルキル基の炭素数が２〜１２のアクリル酸アルキルエステル、およびアルキル基の炭素数が２〜１２のメタクリル酸アルキルエステルの少なくとも一方
（ａ２）カルボキシ基含有不飽和単量体
（ｃ１）フッ素系界面活性剤
（ｃ２）分子中にフッ素原子を含まないアニオン性界面活性剤
[1. Adhesive composition]
The pressure-sensitive adhesive composition of the present invention, as described above,
It contains the following components (A) to (C),
The polymer in the following component (A) is a copolymer of at least the following component (a1) 50 to 99.9 parts by mass and (a2) 0.1 to 10 parts by mass,
The following component (C) is characterized by containing the following components (c1) and (c2).
(A) Emulsion of polymer (B) Polyoxyalkylene alkyl ether phosphate ester compound having 10 to 16 carbon atoms in alkyl group (C) Surfactant
(A1) at least one of an alkyl acrylate having 2 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 2 to 12 carbon atoms in an alkyl group (a2) a carboxy group-containing unsaturated monomer (c1) Fluorinated surfactant (c2) Anionic surfactant containing no fluorine atom in the molecule
［１−１．成分（Ａ）］
成分（Ａ）は、前述のとおり、重合体のエマルションであり、前記重合体は、少なくとも下記成分（ａ１）５０〜９９．９質量部および（ａ２）０．１〜１０質量部の共重合体である。
（ａ１）アルキル基の炭素数が２〜１２のアクリル酸アルキルエステル、およびアルキル基の炭素数が２〜１２のメタクリル酸アルキルエステルの少なくとも一方
（ａ２）カルボキシ基含有不飽和単量体
[1-1. Component (A)]
The component (A) is an emulsion of a polymer as described above, and the polymer is a copolymer of at least the following components (a1) 50 to 99.9 parts by mass and (a2) 0.1 to 10 parts by mass. It is.
(A1) at least one of an alkyl acrylate having 2 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 2 to 12 carbon atoms in an alkyl group (a2) a carboxy group-containing unsaturated monomer
成分（Ａ）は、例えば、前記重合体が水中に分散したエマルション（水系エマルション）であってもよい。 The component (A) may be, for example, an emulsion in which the polymer is dispersed in water (aqueous emulsion).
成分（ａ１）および（ａ２）の質量部は、例えば、前記重合体の共重合成分（モノマー）全ての質量を１００質量部とした場合の質量部であってもよい。なお、前記重合体の共重合成分は、後述するように、成分（ａ１）および（ａ２）以外の他の共重合成分を含んでいてもよいし、含んでいなくてもよい。 The parts by mass of the components (a1) and (a2) may be, for example, parts by mass when all the components of the copolymer (monomer) of the polymer are 100 parts by mass. The copolymer component of the polymer may or may not contain other copolymer components other than the components (a1) and (a2), as described later.
成分（ａ１）は、前述のとおり、アルキル基の炭素数が２〜１２のアクリル酸アルキルエステル、およびアルキル基の炭素数が２〜１２のメタクリル酸アルキルエステルの少なくとも一方である。前記アルキル基は、前述のとおり、直鎖アルキル基でも分枝アルキル基でもよい。前記アルキル基の炭素数は、例えば、２以上、３以上、または４以上であり、例えば、１２以下、または１０以下である。成分（ａ１）としては、例えば、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ブチルアクリレート、イソブチルアクリレート、イソアミルアクリレート、ヘキシルアクリレート、ヘプチルアクリレート、２−エチルヘキシルアクリレート、イソオクチルアクリレート、ｎ−オクチルアクリレート、イソノニルアクリレート、イソデシルアクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、イソブチルメタクリレート、イソアミルメタクリレート、ヘキシルメタクリレート、ヘプチルメタクリレート、２−エチルヘキシルメタクリレート、イソオクチルメタクリレート、ｎ−オクチルメタクリレート、イソノニルメタクリレート、イソデシルメタクリレート等があげられ、１種類のみ用いても２種類以上併用してもよい。 As described above, the component (a1) is at least one of an alkyl acrylate having 2 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 2 to 12 carbon atoms in an alkyl group. As described above, the alkyl group may be a linear alkyl group or a branched alkyl group. The alkyl group has, for example, 2 or more, 3 or more, or 4 or more, for example, 12 or less, or 10 or less. As the component (a1), for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, n-octyl acrylate, iso- Nonyl acrylate, isodecyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, isoamyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, isononyl methacrylate , Iso Sill methacrylate and the like, may be used in combination of two or more types be used only one type.
前記重合体の共重合成分中における成分（ａ１）の含有量は、前述のとおり、５０〜９９．９質量部であり、例えば、５５質量部以上、６０質量部以上、７０質量部以上、８０質量部以上、または９０質量部以上であり、例えば、９９質量部以下、９８質量部以下、９６質量部以下、９４質量部以下、または９２質量部以下である。成分（ａ１）の含有量が５０質量部以上であることで、高い粘着性が得られる。また、成分（ａ１）の含有量は、再剥離性の観点からは多すぎないことが好ましい。 The content of the component (a1) in the copolymerization component of the polymer is 50 to 99.9 parts by mass, as described above, and is, for example, 55 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more. It is at least 90 parts by mass, for example, at most 99 parts by mass, at most 98 parts by mass, at most 96 parts by mass, at most 94 parts by mass, or at most 92 parts by mass. When the content of the component (a1) is 50 parts by mass or more, high tackiness can be obtained. Further, the content of the component (a1) is preferably not too large from the viewpoint of removability.
成分（ａ２）は、前述のとおり、カルボキシ基含有不飽和単量体である。成分（ａ２）は、特に限定されず、例えば、一般的なカルボキシ基含有不飽和単量体でもよい。成分（ａ２）としては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、クロトン酸等があげられ、１種類のみ用いても２種類以上併用してもよい。 Component (a2) is a carboxy group-containing unsaturated monomer as described above. The component (a2) is not particularly limited, and may be, for example, a general carboxy group-containing unsaturated monomer. Examples of the component (a2) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, and the like. One type may be used alone, or two or more types may be used in combination.
成分（Ａ）の共重合成分中における成分（ａ２）の含有量は、前述のとおり、０．１〜１０質量部であり、例えば、０．５質量部以上、または１．０質量部以上であり、例えば、７．０質量部以下、５．０質量部以下、または３．０質量部以下である。成分（ａ２）の含有量は、粘着剤組成物の凝集力および基材に対する密着性の観点からは少なすぎないことが好ましく、粘着力の観点からは多すぎないことが好ましい。 As described above, the content of the component (a2) in the copolymerization component of the component (A) is 0.1 to 10 parts by mass, for example, 0.5 parts by mass or more, or 1.0 part by mass or more. Yes, for example, 7.0 parts by mass or less, 5.0 parts by mass or less, or 3.0 parts by mass or less. The content of the component (a2) is preferably not too small from the viewpoint of the cohesive force of the pressure-sensitive adhesive composition and the adhesion to the substrate, and is preferably not too high from the viewpoint of the adhesive force.
また、成分（Ａ）の共重合成分は、前述のとおり、成分（ａ１）および（ａ２）以外の他の共重合成分を含んでいてもよいし、含んでいなくてもよい。前記他の共重合成分は、特に限定されないが、例えば、メタクリル酸メチル、アクリル酸メチル等があげられ、１種類のみ用いても２種類以上併用してもよい。 Further, as described above, the copolymer component of the component (A) may or may not include other copolymer components other than the components (a1) and (a2). The other copolymerization component is not particularly limited, and examples thereof include methyl methacrylate, methyl acrylate, and the like. One type may be used alone, or two or more types may be used in combination.
成分（Ａ）の製造方法は、特に限定されない。例えば、前記重合体の共重合成分全てを乳化重合させることで、前記重合体を製造するとともに、前記重合体のエマルションを形成させて成分（Ａ）としてもよい。 The method for producing the component (A) is not particularly limited. For example, the copolymer may be produced by emulsion-polymerizing all of the copolymer components of the polymer, and an emulsion of the polymer may be formed to be the component (A).
前記乳化重合の方法は、特に限定されず、例えば、一般的な乳化重合の方法と同様もしくはそれに準じてもよいし、または、それに適宜変更を加えてもよい。前記乳化重合の方法は、具体的には、例えば、（１）水および全ての共重合成分を一括混合して乳化重合する方法、（２）水および全ての共重合成分の混合物のうち、一部を反応器に加え、残りを前記反応器中に滴下して乳化重合する方法（プレエマルション法）、（３）モノマー滴下法、等があげられる。これらの中でも、乳化重合反応の安定性の点から（２）のプレエマルション法が好ましい。また、水および前記共重合成分に加え、必要に応じ、重合開始剤、乳化剤、分散安定剤等を混合して乳化重合を行ってもよい。 The method of the emulsion polymerization is not particularly limited. For example, the method may be the same as or similar to a general emulsion polymerization method, or may be appropriately modified. Specifically, the emulsion polymerization method includes, for example, (1) a method in which water and all the copolymerization components are mixed at once and emulsion polymerization is performed, and (2) a mixture of water and all the copolymerization components. A part is added to the reactor, and the remainder is dropped into the reactor to perform emulsion polymerization (pre-emulsion method), (3) a monomer dropping method, and the like. Among these, the pre-emulsion method (2) is preferred from the viewpoint of the stability of the emulsion polymerization reaction. Further, in addition to water and the above-mentioned copolymerization component, if necessary, a polymerization initiator, an emulsifier, a dispersion stabilizer and the like may be mixed to carry out emulsion polymerization.
前記重合開始剤は、特に限定されないが、例えば、水溶性アゾ重合開始剤、過硫酸塩類、有機過酸化物類、過酸化水素等があげられ、１種類のみ用いても２種類以上併用してもよい。前記水溶性アゾ重合開始剤は、例えば、富士フイルム和光純薬株式会社の商品名Ｖ−５０、Ｖ−５０１、ＶＡ−０８６、ＶＡ−０５７、ＶＡ−０６１等があげられ、１種類のみ用いても２種類以上併用してもよい。 The polymerization initiator is not particularly limited, for example, a water-soluble azo polymerization initiator, persulfates, organic peroxides, hydrogen peroxide, and the like. Is also good. Examples of the water-soluble azo polymerization initiator include, for example, trade names V-50, V-501, VA-086, VA-057, VA-061 and the like of Fujifilm Wako Pure Chemical Industries, Ltd. May be used in combination of two or more.
前記乳化剤は、特に限定されないが、例えば、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤等があげられ、１種類のみ用いても２種類以上併用してもよい。前記アニオン性界面活性剤は、例えば、アルキル硫酸エステル、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩、商品名アデカリアソープＳＲ−１０、アデカリアソープＳＲ−２０（いずれも株式会社ＡＤＥＫＡ製）、商品名アクアロンＨＳ−１０、アクアロンＨＳ−２０（いずれも第一工業製薬株式会社製）、商品名エレミノールＪＳ−２０、エレミノールＲＳ−３０００（いずれも三洋化成工業株式会社製）、商品名ラテムルＰＤ−１０４（花王株式会社製）、商品名テイカパワーＢＮ−２０６０（テイカ株式会社）等があげられ、１種類のみ用いても２種類以上併用してもよい。前記ノニオン性界面活性剤は、例えば、ポリオキシエチレンアルキルエーテル、商品名アデカリアソープＥＲ−１０、アデカリアソープＥＲ−２０（いずれも株式会社ＡＤＥＫＡ製）、商品名アクアロンＲＮ−１０、アクアロンＲＮ−２０（いずれも第一工業製薬株式会社製）、商品名ラテムルＰＤ−４２０、ラテムルＰＤ−４３０（いずれも花王株式会社製）等があげられ、１種類のみ用いても２種類以上併用してもよい。 The emulsifier is not particularly limited, and examples thereof include an anionic surfactant, a nonionic surfactant, and a cationic surfactant. One type may be used alone, or two or more types may be used in combination. Examples of the anionic surfactant include alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, trade names Adecaria Soap SR-10, and Adecaria Soap SR-20 (all stocks). Adeka Co., Ltd.), trade names Aqualon HS-10, Aqualon HS-20 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), trade names Eleminol JS-20, Eleminol RS-3000 (all manufactured by Sanyo Chemical Industry Co., Ltd.), Trade name LATERMUL PD-104 (manufactured by Kao Corporation), trade name Takeka Power BN-2060 (TAYCA Corporation), etc., may be used alone, or two or more kinds may be used in combination. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, trade names Adekaria Soap ER-10 and Adekaria Soap ER-20 (all manufactured by ADEKA Corporation), trade names Aqualon RN-10, Aqualon RN- 20 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), trade names Latemul PD-420, Latemul PD-430 (all manufactured by Kao Corporation), and the like. Good.
前記分散安定剤は、特に限定されないが、例えば、ポリビニルアルコール、デンプン、ポリアクリル酸、ポリアクリルアミド、水溶性アクリル樹脂、水溶性ポリエステル樹脂、水溶性ポリアミド樹脂、水溶性ポリウレタン樹脂等があげられ、１種類のみ用いても２種類以上併用してもよい。 The dispersion stabilizer is not particularly limited, and examples thereof include polyvinyl alcohol, starch, polyacrylic acid, polyacrylamide, a water-soluble acrylic resin, a water-soluble polyester resin, a water-soluble polyamide resin, and a water-soluble polyurethane resin. Only one type may be used, or two or more types may be used in combination.
前記（２）のプレエマルション法は、特に限定されないが、例えば、以下のようにして行うことができる。まず、水および全ての共重合成分を混合し、プレエマルションを得る。このプレエマルションには、前記重合開始剤、前記乳化剤、前記分散安定剤等を混合してもよい。また、例えば、必要に応じ、親水性溶剤、疎水性溶剤等を混合してもよい。つぎに、前記プレエマルションの一部を重合反応させる（第１の重合工程）。このとき、必要に応じ、加熱、攪拌等をしてもよい。反応系は、開放系であってもよいが、窒素等の不活性ガスで置換されていてもよい。前記第１の重合工程における反応温度は特に限定されないが、例えば、３０〜９０℃、または４０〜８５℃である。前記第１の重合工程における反応時間も特に限定されず、適宜設定可能である。つぎに、残りのプレエマルションを滴下し、さらに重合反応させる（第２の重合工程）。前記第２の重合工程は、滴下終了後、さらに重合反応を継続してもよい。前記第２の重合工程における反応温度は特に限定されないが、例えば、前記第１の重合工程と同じである。前記残りのプレエマルションの滴下時間も特に限定されず、適宜設定可能である。前記滴下終了後における反応時間も特に限定されず、適宜設定可能である。以上のようにして、前記重合体を製造できる。 The pre-emulsion method (2) is not particularly limited, and can be performed, for example, as follows. First, water and all copolymer components are mixed to obtain a pre-emulsion. The pre-emulsion may be mixed with the polymerization initiator, the emulsifier, the dispersion stabilizer, and the like. Further, for example, a hydrophilic solvent, a hydrophobic solvent, and the like may be mixed as necessary. Next, a part of the pre-emulsion is subjected to a polymerization reaction (first polymerization step). At this time, heating, stirring, and the like may be performed as necessary. The reaction system may be an open system, but may be replaced by an inert gas such as nitrogen. The reaction temperature in the first polymerization step is not particularly limited, but is, for example, 30 to 90 ° C or 40 to 85 ° C. The reaction time in the first polymerization step is not particularly limited and can be set as appropriate. Next, the remaining pre-emulsion is dropped, and a polymerization reaction is further performed (second polymerization step). In the second polymerization step, the polymerization reaction may be continued after the completion of the dropwise addition. The reaction temperature in the second polymerization step is not particularly limited, but is, for example, the same as that in the first polymerization step. The dripping time of the remaining pre-emulsion is not particularly limited and can be set as appropriate. The reaction time after completion of the dropping is not particularly limited, and can be set as appropriate. As described above, the polymer can be produced.
前記乳化重合は、例えば、重合反応の途中で前記重合開始剤を追加する工程を含んでいてもよい。これにより、例えば、臭気の原因となる残留モノマー（共重合成分）を抑制できる。例えば、前記第２の重合工程における前記滴下終了後に、前記重合開始剤を追加してもよい。前記重合開始剤の追加は、１回で行ってもよいし、複数回に分けてもよい。 The emulsion polymerization may include, for example, a step of adding the polymerization initiator during the polymerization reaction. Thereby, for example, the residual monomer (copolymer component) that causes odor can be suppressed. For example, the polymerization initiator may be added after the completion of the dropping in the second polymerization step. The addition of the polymerization initiator may be performed once or may be performed a plurality of times.
［１−２．成分（Ｂ）］
成分（Ｂ）は、前述のとおり、アルキル基の炭素数が１０〜１６であるポリオキシアルキレンアルキルエーテルリン酸エステル系化合物である。アルキル基およびアルキレン基は、前述のとおり、直鎖状でも分枝状でもよい。前記アルキレン基の炭素数は、例えば、１以上、または２以上であり、例えば、６以下、５以下、または４以下である。また、成分（Ｂ）において、前記ポリオキシアルキレンアルキルエーテルリン酸エステル系化合物は、例えば、アルキル基が分枝構造を有し、かつエチレンオキサイド鎖を有していてもよい。成分（Ｂ）は、特に限定されないが、セスキオクチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリス（β−クロロエチル）ホスフェート、トリス（β−クロロプロピル）ホスフェート、トリス（ジクロロプロピル）ホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリス（ｉ−プロペルフェニル）ホスフェート、クレジルジフェニルホスフェート、オクチルジフェニルホスフェート、トリブトキシエチルホスフェート、アルキルポリオキシエチレンリン酸エステル、アルキルフェノールポリオキシエチレンリン酸エステルおよびこれらのナトリウム，カリウム，アンモニアおよびアミン等の中和塩があげられ、１種類のみ用いても２種類以上併用してもよい。粘着剤組成物の耐水性の観点からは、前記中和塩が好ましい。
[1-2. Component (B)]
As described above, the component (B) is a polyoxyalkylene alkyl ether phosphate compound having 10 to 16 carbon atoms in the alkyl group. As described above, the alkyl group and the alkylene group may be linear or branched. The alkylene group has, for example, 1 or more, or 2 or more, for example, 6 or less, 5 or less, or 4 or less. In the component (B), the polyoxyalkylene alkyl ether phosphate compound may have, for example, an alkyl group having a branched structure and an ethylene oxide chain. Component (B) is not particularly limited, but sesquioctyl phosphate, tributyl phosphate, trioctyl phosphate, tris (β-chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, triphenylphosphate, Tricresyl phosphate, tris (i-properphenyl) phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tributoxyethyl phosphate, alkyl polyoxyethylene phosphate, alkyl phenol polyoxyethylene phosphate and their sodium and potassium , Ammonia and amines, etc., and may be used alone or in combination of two or more. From the viewpoint of the water resistance of the pressure-sensitive adhesive composition, the neutralized salt is preferable.
成分（Ｂ）の含有量は、特に限定されないが、成分（Ａ）中の不揮発成分１００質量部に対し、成分（Ｂ）中の不揮発成分が、例えば、０．０１質量部以上、０．０５質量部以上、または０．１０質量部以上であり、例えば、０．６質量部以下、０．５５質量部以下、または０．５０質量部以下である。粘着シートの再剥離性（糊残り防止）の観点からは、成分（Ｂ）の含有量が少なすぎないことが好ましく、曲面接着性および耐水接着性の観点からは、成分（Ｂ）の含有量が多すぎないことが好ましい。 The content of the component (B) is not particularly limited, but the non-volatile component in the component (B) is, for example, 0.01 part by mass or more and 0.05 part by mass with respect to 100 parts by mass of the non-volatile component in the component (A). It is at least 0.6 parts by mass, at most 0.50 parts by mass, or at most 0.50 parts by mass. The content of the component (B) is preferably not too small from the viewpoint of the removability (prevention of adhesive residue) of the pressure-sensitive adhesive sheet, and the content of the component (B) is preferable from the viewpoint of the curved surface adhesion and the water-resistant adhesion. Is preferably not too much.
なお、成分（Ｂ）は、例えば、その一部または全部が界面活性剤であってもよいが、界面活性剤でなくてもよい。成分（Ｂ）の一部または全部が界面活性剤である場合は、成分（Ｂ）中の界面活性剤は、成分（Ｃ）（界面活性剤）の含有量には含まれないものとする。 The component (B) may be, for example, part or all of a surfactant but not necessarily a surfactant. When part or all of the component (B) is a surfactant, the surfactant in the component (B) is not included in the content of the component (C) (surfactant).
［１−３．成分（Ｃ）］
成分（Ｃ）は、前述のとおり、界面活性剤であり、下記成分（ｃ１）および（ｃ２）を含む。
（ｃ１）フッ素系界面活性剤
（ｃ２）分子中にフッ素原子を含まないアニオン性界面活性剤
[1-3. Component (C)]
The component (C) is a surfactant as described above, and includes the following components (c1) and (c2).
(C1) fluorinated surfactant (c2) anionic surfactant containing no fluorine atom in the molecule
本発明において、「フッ素系界面活性剤」は、分子中にフッ素原子を含む界面活性剤である。前記フッ素系界面活性剤は、例えば、アルキル鎖中の少なくとも一つの水素原子をフッ素原子に置換した界面活性剤でもよい。前記フッ素系界面活性剤は、例えば、パーフルオロ基を有する界面活性剤でもよい。前記フッ素系界面活性剤は、例えば、親水部および疎水部を有する。前記フッ素系界面活性剤は、例えば、前記疎水部がパーフルオロ基であってもよい。本発明において、「パーフルオロ基」は、例えば、炭化水素中の全ての水素原子または大部分の水素原子がフッ素原子で置換された基である。前記パーフルオロ基は、例えば、アルキル基中の全ての水素原子または大部分の水素原子がフッ素原子で置換されたパーフルオロアルキル基でもよい。 In the present invention, the “fluorinated surfactant” is a surfactant containing a fluorine atom in a molecule. The fluorine-based surfactant may be, for example, a surfactant in which at least one hydrogen atom in an alkyl chain has been replaced with a fluorine atom. The fluorine-based surfactant may be, for example, a surfactant having a perfluoro group. The fluorine-based surfactant has, for example, a hydrophilic part and a hydrophobic part. In the fluorinated surfactant, for example, the hydrophobic portion may be a perfluoro group. In the present invention, the “perfluoro group” is, for example, a group in which all or most of the hydrogen atoms in a hydrocarbon are replaced with fluorine atoms. The perfluoro group may be, for example, a perfluoroalkyl group in which all or most of the hydrogen atoms in an alkyl group are substituted with fluorine atoms.
なお、成分（Ｃ）が、フッ素系界面活性剤でありアニオン性界面活性剤でもある界面活性剤を含む場合、その界面活性剤は成分（ｃ１）であり、成分（ｃ２）ではないものとする。また、本発明の粘着剤組成物中に、成分（Ａ）における重合体の合成に用いた界面活性剤（例えば乳化剤）が残留している場合、その残留界面活性剤は、成分（Ｃ）には含まれないものとする。すなわち、成分（Ａ）合成の際に乳化剤として働きうる界面活性剤が本発明の粘着剤組成物中に残留していた場合、その界面活性剤は成分（Ｃ）には含まれないものとする。 When the component (C) contains a surfactant that is both a fluorine-based surfactant and an anionic surfactant, the surfactant is the component (c1) and not the component (c2). . When the surfactant (for example, emulsifier) used for the synthesis of the polymer in the component (A) remains in the pressure-sensitive adhesive composition of the present invention, the residual surfactant is added to the component (C). Shall not be included. That is, when a surfactant capable of acting as an emulsifier during the synthesis of the component (A) remains in the pressure-sensitive adhesive composition of the present invention, the surfactant is not included in the component (C). .
成分（ｃ１）のフッ素系界面活性剤は、特に限定されないが、例えば、商品名メガファックＦ−１４２Ｄ、メガファックＦ−１４０５（いずれもＤＩＣ株式会社製）、商品名ＣａｐｓｔｏｎｅＦＳ−３１（いずれもデュポン社ケマーズ社製）、商品名サーフロンＳ−２４２、サーフロンＳ−２４３（いずれもＡＧＣセイミケミカル株式会社製）等のパーフルオロアルキルエチレンオキサイド付加物等があげられ、１種類のみ用いても２種類以上併用してもよい。 Although the fluorine-based surfactant of the component (c1) is not particularly limited, for example, Megafac F-142D and Megafac F-1405 (both are manufactured by DIC Corporation), and Capstone FS-31 (both are manufactured by DuPont) And perfluoroalkylethylene oxide adducts such as Surflon S-242 and Surflon S-243 (all manufactured by AGC Seimi Chemical Co., Ltd.). You may use together.
成分（ｃ２）のアニオン性界面活性剤は、特に限定されないが、例えば、高級アルコールの硫酸エステル及びその塩、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、ポリオキシエチレンアルキルジフェニルエーテルスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、コハク酸ジアルキルエステルスルホン酸塩等があげられ、１種類のみ用いても２種類以上併用してもよい。成分（ｃ２）としては、具体的には、例えば、商品名エアロゾルＯＴ−７５（サイテックインダストリー社製）、商品名サーフィノール４２０、サーフィノール４４０（日信化学工業株式会社製）等があげられる。 The anionic surfactant of the component (c2) is not particularly limited, and examples thereof include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, and polyoxyethylene alkyl diphenyl ether sulfonates. And alkyl diphenyl ether disulfonic acid salts, dialkyl succinic acid ester sulfonates, and the like. One type may be used alone, or two or more types may be used in combination. Specific examples of the component (c2) include Aerosol OT-75 (trade name, manufactured by Cytec Industries), Surfynol 420, and Surfynol 440 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.).
成分（Ｃ）の含有量は、特に限定されないが、成分（Ａ）中の不揮発成分１００質量部に対し、成分（Ｃ）中の不揮発成分が、例えば、０．５質量部以上、または０．６質量部以上であり、例えば、３質量部以下、または２．８質量部以下である。塗工適性の観点からは、成分（Ｃ）の含有量が少なすぎないことが好ましく、耐ハガレ性の観点からは、成分（Ｃ）の含有量が多すぎないことが好ましい。 The content of the component (C) is not particularly limited, but the non-volatile component in the component (C) is, for example, 0.5 parts by mass or more or 100 parts by mass of the non-volatile component in the component (A). It is at least 6 parts by mass, for example, at most 3 parts by mass or at most 2.8 parts by mass. It is preferable that the content of the component (C) is not too small from the viewpoint of coating suitability, and it is preferable that the content of the component (C) is not too large from the viewpoint of peel resistance.
成分（ｃ１）の含有量は、特に限定されないが、成分（Ａ）中の不揮発成分１００質量部に対し、成分（ｃ１）中の不揮発成分が、例えば、０．０１質量部以上、０．０３質量部以上、または０．０５質量部以上であり、例えば、１．０質量部以下、または０．８質量部以下である。塗工適性の観点からは、成分（ｃ１）の含有量が少なすぎないことが好ましく、塗工適性（最適量）の観点からは、成分（ｃ１）の含有量が多すぎないことが好ましい。 The content of the component (c1) is not particularly limited, but the non-volatile component in the component (c1) is, for example, 0.01 part by mass or more and 0.03 parts by mass with respect to 100 parts by mass of the non-volatile component in the component (A). It is at least 1.0 part by mass, or, for example, at most 1.0 part by mass, or at most 0.8 part by mass. It is preferable that the content of the component (c1) is not too small from the viewpoint of coating suitability, and it is preferable that the content of the component (c1) is not too large from the viewpoint of coating suitability (optimum amount).
成分（ｃ２）の含有量は、特に限定されないが、成分（Ａ）中の不揮発成分１００質量部に対し、成分（ｃ２）中の不揮発成分が、例えば、０．１質量部以上、０．２質量部以上、または０．３質量部以上であり、例えば、３．０質量部以下、２．０質量部以下、または１．０質量部以下である。塗工適性の観点からは、成分（ｃ２）の含有量が少なすぎないことが好ましく、耐ハガレ性の観点からは、成分（ｃ２）の含有量が多すぎないことが好ましい。 The content of the component (c2) is not particularly limited, but the non-volatile component in the component (c2) is, for example, 0.1 part by mass or more and 0.2 part by mass with respect to 100 parts by mass of the non-volatile component in the component (A). It is at least 3.0 parts by mass, at most 3.0 parts by mass, at most 2.0 parts by mass, or at most 1.0 part by mass. It is preferable that the content of the component (c2) is not too small from the viewpoint of coating suitability, and it is preferable that the content of the component (c2) is not too large from the viewpoint of peel resistance.
また、成分（Ｃ）は、成分（ｃ１）および（ｃ２）以外の他の界面活性剤を含んでいてもよいし、含んでいなくてもよい。前記他の界面活性剤は、例えば、下記成分（ｃ３）があげられる。
（ｃ３）ノニオン性界面活性剤
Further, the component (C) may or may not contain a surfactant other than the components (c1) and (c2). Examples of the other surfactant include the following component (c3).
(C3) Nonionic surfactant
成分（ｃ３）のノニオン性界面活性剤は、特に限定されないが、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンジフェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体等があげられ、１種類のみ用いても２種類以上併用してもよい。成分（ｃ３）としては、具体的には、例えば、商品名レオコールＳＣ−５０、レオコールＳＣ−１２０、レオコールＳＣ−１５０（いずれもライオン・スペシャリティ・ケミカルズ株式会社製）等があげられる。 The nonionic surfactant of the component (c3) is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene diphenyl ether, and polyoxyethylene-polyoxypropylene block copolymer. One type may be used alone, or two or more types may be used in combination. Specific examples of component (c3) include Leocoal SC-50, Leocoal SC-120, and Leocoal SC-150 (all manufactured by Lion Specialty Chemicals Co., Ltd.).
成分（ｃ３）の含有量は、特に限定されないが、成分（Ａ）中の不揮発成分１００質量部に対し、成分（ｃ３）中の不揮発成分が、例えば、０．１質量部以上、または０．２質量部以上であり、例えば、１．０質量部以下、または０．９質量部以下である。塗工適性の観点からは、成分（ｃ３）の含有量が少なすぎないことが好ましく、初期接着力の観点からは、成分（ｃ３）の含有量が多すぎないことが好ましい。 The content of the component (c3) is not particularly limited, but the non-volatile component in the component (c3) is, for example, 0.1 part by mass or more or 100 parts by mass with respect to 100 parts by mass of the non-volatile component in the component (A). It is at least 2 parts by mass, for example, at most 1.0 part by mass or at most 0.9 part by mass. It is preferable that the content of the component (c3) is not too small from the viewpoint of coating suitability, and it is preferable that the content of the component (c3) is not too large from the viewpoint of initial adhesion.
成分（Ｃ）（界面活性剤）は、例えば、本発明の粘着剤組成物において、濡れ性を担保する成分（濡れ剤）として働くと考えられる。本発明の粘着剤組成物は、成分（Ｃ）を含むことで、例えば、良好な塗工適性が得られる。また、本発明の粘着剤組成物は、成分（Ｂ）および（Ｃ）を含むことで、例えば、適度な初期接着力が得られる。 The component (C) (surfactant) is considered to function as, for example, a component (wetting agent) that ensures wettability in the pressure-sensitive adhesive composition of the present invention. When the pressure-sensitive adhesive composition of the present invention contains the component (C), for example, good coating suitability is obtained. Further, by including the components (B) and (C) in the pressure-sensitive adhesive composition of the present invention, for example, an appropriate initial adhesive strength can be obtained.
［１−４．成分（Ａ）〜（Ｃ）以外の成分］
本発明の粘着剤組成物は、成分（Ａ）〜（Ｃ）以外の他の成分を含んでいてもよいし、含んでいなくてもよい。前記他の成分としては、例えば、前記架橋剤（Ｄ）（以下、成分（Ｄ）または単に架橋剤ということがある。）があげられる。
[1-4. Components other than components (A) to (C)]
The pressure-sensitive adhesive composition of the present invention may or may not contain other components other than the components (A) to (C). Examples of the other component include the cross-linking agent (D) (hereinafter, sometimes referred to as component (D) or simply a cross-linking agent).
成分（Ｄ）（架橋剤（Ｄ））は、特に限定されないが、例えば、分子内にオキサゾリン基を有し、かつ水分散体の架橋剤である。架橋剤（Ｄ）は、例えば、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−エチル−２−オキサゾリン等の付加重合性オキサゾリンを１種類または２種類以上用いて乳化重合等により得られた水分散系架橋剤等があげられ、１種類のみ用いても２種類以上併用してもよい。そのような架橋剤（Ｄ）は、例えば、商品名エポクロスＫ−２０１０Ｅ、エポクロスＫ−２０２０Ｅ、エポクロスＫ−２０３０Ｅ、エポクロスＷＳ−７００（いずれも株式会社日本触媒）等があげられる。 The component (D) (crosslinking agent (D)) is not particularly limited, and is, for example, a crosslinking agent having an oxazoline group in a molecule and of an aqueous dispersion. The crosslinking agent (D) is, for example, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Aqueous dispersion obtained by emulsion polymerization or the like using one or more addition polymerizable oxazolines such as 2-isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline. A crosslinking agent may be used, and one kind may be used alone or two or more kinds may be used in combination. Examples of such a crosslinking agent (D) include Epocross K-2010E, Epocross K-2020E, Epocross K-2030E, and Epocross WS-700 (all of which are Nippon Shokubai Co., Ltd.).
成分（Ｄ）の含有量は、特に限定されないが、成分（Ａ）中の不揮発成分１００質量部に対し、成分（Ｄ）中の不揮発成分が、例えば、０．３質量部以上、または０．４質量部以上であり、例えば、２．０質量部以下、または１．８質量部以下である。粘着剤組成物の耐熱性、凝集力および基材に対する密着性の観点からは、成分（Ｄ）の含有量が少なすぎないことが好ましく、粘着剤組成物の耐ハガレ性、耐水性および接着力の観点からは、成分（Ｄ）の含有量が多すぎないことが好ましい。 The content of the component (D) is not particularly limited, but the non-volatile component in the component (D) is, for example, 0.3 parts by mass or more, or 100 parts by mass of the non-volatile component in the component (A). It is 4 parts by mass or more, for example, 2.0 parts by mass or less, or 1.8 parts by mass or less. It is preferable that the content of the component (D) is not too small from the viewpoints of heat resistance, cohesive force, and adhesion to the substrate of the pressure-sensitive adhesive composition, and peeling resistance, water resistance, and adhesion of the pressure-sensitive adhesive composition are preferable. In light of the above, it is preferable that the content of the component (D) is not too large.
成分（Ａ）〜（Ｃ）以外の他の成分としては、架橋剤（Ｄ）以外に、例えば、増粘剤、ｐＨ調整剤、溶媒、酸化防止剤、架橋防止剤、充填剤、着色剤、紫外線吸収剤、消泡剤、光安定剤、帯電防止剤等があげられ、１種類のみ用いても２種類以上併用してもよい。前記他の成分は、具体的には、特に限定されず、例えば、一般的な粘着剤と同様またはそれに準じてもよい。前記増粘剤としては、例えば、アクリルポリマー製増粘剤、ウレタンポリマー製増粘剤等があげられる。前記アクリルポリマー製増粘剤としては、例えば、商品名アロンＢ−３００Ｋ（東亞合成株式会社）等があげられる。前記ｐＨ調整剤としては、例えば、アンモニア水、水酸化ナトリウム水溶液、希塩酸、希硫酸等があげられ、１種類のみ用いても２種類以上併用してもよい。前記紫外線吸収剤としては、特に限定されないが、例えば、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系等の紫外線吸収剤が挙げられる。前記消泡剤としては、特に限定されないが、例えば、シリコーン系、鉱物油系等の消泡剤が挙げられる。前記光安定剤としては、特に限定されないが、例えば、ヒンダードアミン系等の光安定剤が挙げられる。前記帯電防止剤としては、無機塩類、有機塩類等のイオン性化合物、ノニオン性界面活性剤等の非イオン性化合物が挙げられる。前記溶媒、前記酸化防止剤および前記架橋防止剤については、特に限定されないが、例えば、一般的な粘着剤と同様またはそれに準じてもよい。 Other components other than the components (A) to (C) include, in addition to the crosslinking agent (D), for example, a thickener, a pH adjuster, a solvent, an antioxidant, a crosslinking inhibitor, a filler, a coloring agent, Examples thereof include an ultraviolet absorber, an antifoaming agent, a light stabilizer, and an antistatic agent. One type may be used alone, or two or more types may be used in combination. The other components are not specifically limited, and may be, for example, the same as or similar to general adhesives. Examples of the thickener include an acrylic polymer thickener, a urethane polymer thickener, and the like. Examples of the acrylic polymer thickener include Alon B-300K (trade name) (Toagosei Co., Ltd.). Examples of the pH adjuster include ammonia water, an aqueous solution of sodium hydroxide, dilute hydrochloric acid, dilute sulfuric acid and the like. One type may be used alone, or two or more types may be used in combination. The ultraviolet absorber is not particularly limited, and examples thereof include a benzophenone-based, benzotriazole-based, and triazine-based ultraviolet absorber. The defoaming agent is not particularly limited, and examples thereof include silicone-based and mineral oil-based defoaming agents. The light stabilizer is not particularly limited, and includes, for example, a hindered amine-based light stabilizer. Examples of the antistatic agent include ionic compounds such as inorganic salts and organic salts, and nonionic compounds such as nonionic surfactants. The solvent, the antioxidant, and the cross-linking inhibitor are not particularly limited, but may be, for example, the same as or similar to a general adhesive.
［１−５．粘着剤組成物の製造方法および用途］
本発明の粘着剤組成物の製造方法は、特に限定されず、例えば、本発明の粘着剤組成物を構成する全成分を単に混合するのみでもよい。混合する順序は特に限定されないが、例えば、重合体のエマルションである成分（Ａ）中に、他の成分を順次混合してもよい。例えば、増粘剤およびｐＨ調整剤（アンモニア水等）を用いる場合、凝集物の生成等を防止する観点から、成分（Ｂ）および増粘剤は、ｐＨ調整剤よりも先に、またはｐＨ調整剤と同時に成分（Ａ）中に混合することが好ましい。成分（Ｃ）は、どの順序で混合しても凝集物の生成等を起こしにくい。
[1-5. Production method and use of pressure-sensitive adhesive composition]
The method for producing the pressure-sensitive adhesive composition of the present invention is not particularly limited, and for example, may be simply mixing all components constituting the pressure-sensitive adhesive composition of the present invention. The order of mixing is not particularly limited. For example, other components may be sequentially mixed into the component (A) which is an emulsion of the polymer. For example, when a thickener and a pH adjuster (aqueous ammonia, etc.) are used, the component (B) and the thickener are added prior to the pH adjuster or from the viewpoint of preventing the formation of aggregates and the like. It is preferable to mix it with component (A) simultaneously with the agent. The component (C) hardly causes generation of aggregates and the like, even if mixed in any order.
本発明の粘着剤組成物の用途も特に限定されないが、例えば、一般的な粘着剤組成物と同様の用途に用いることができる。本発明の粘着剤組成物は、例えば、本発明の粘着シートにおける前記粘着剤層に用いることができる。 Although the use of the pressure-sensitive adhesive composition of the present invention is not particularly limited, for example, it can be used for the same use as a general pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition of the present invention can be used, for example, in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention.
［２．粘着シート］
つぎに、本発明の粘着シートおよびその製造方法、用途等について、例をあげて説明する。
[2. Adhesive sheet]
Next, the pressure-sensitive adhesive sheet of the present invention, its production method, applications, and the like will be described with reference to examples.
本発明の粘着シートは、前述のとおり、基材と、粘着剤層とを含み、前記粘着剤層が、前記本発明の粘着剤組成物を含むことを特徴とする。前記粘着剤層は、本発明の粘着剤組成物のみからなっていてもよいし、本発明の粘着剤組成物以外の成分を含んでいてもよい。 As described above, the pressure-sensitive adhesive sheet of the present invention includes a substrate and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer includes the pressure-sensitive adhesive composition of the present invention. The pressure-sensitive adhesive layer may be composed only of the pressure-sensitive adhesive composition of the present invention, or may include components other than the pressure-sensitive adhesive composition of the present invention.
本発明の粘着シートは、前記基材および前記粘着剤層以外の他の構成要素を含んでいてもよいし、含んでいなくてもよい。本発明の粘着シートは、例えば、前記粘着剤層における前記基材と反対側に、保護層（剥離シート、セパレーター、またはリリースライナーともいう。）が積層されていてもよい。 The pressure-sensitive adhesive sheet of the present invention may or may not include other components other than the base and the pressure-sensitive adhesive layer. In the pressure-sensitive adhesive sheet of the present invention, for example, a protective layer (also referred to as a release sheet, a separator, or a release liner) may be laminated on the side of the pressure-sensitive adhesive layer opposite to the base material.
前記基材は、特に限定されず、例えば、一般的な粘着シートの基材と同様でもよい。前記基材は、例えば、プラスチック、ポリウレタン、紙、金属箔等があげられる。前記プラスチックとしては、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）、ＰＣ（ポリカーボネート）等があげられる。前記紙としては、例えば、和紙、洋紙等があげられる。 The substrate is not particularly limited, and may be, for example, the same as the substrate of a general pressure-sensitive adhesive sheet. Examples of the substrate include plastic, polyurethane, paper, and metal foil. Examples of the plastic include PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene), and PC (polycarbonate). Examples of the paper include Japanese paper and Western paper.
前記基材の形状も特に限定されず、例えば、シート、フィルム、発泡体等が挙げられる。前記基材は、製造後の粘着シートの取扱いやすさ、保存のしやすさ等の観点から、例えば、巻き取り可能な長尺のテープ状であることが好ましい。 The shape of the substrate is not particularly limited, and examples thereof include a sheet, a film, and a foam. The base material is preferably in the form of a long tape that can be wound, for example, from the viewpoint of ease of handling and preservation of the manufactured pressure-sensitive adhesive sheet.
また、前記基材は、例えば、必要に応じて、前記基材の粘着剤層形成面に、易接着処理を施した基材であってもよい。前記易接着処理は、特に限定されないが、具体的には、例えば、コロナ放電を処理する方法、アンカーコート剤を塗布する方法等が挙げられる。 Further, the base material may be, for example, a base material on which an adhesive layer forming surface of the base material has been subjected to an easy-adhesion treatment, if necessary. The easy adhesion treatment is not particularly limited, but specific examples include a method of treating corona discharge, a method of applying an anchor coat agent, and the like.
前記保護層は、特に限定されず、例えば、一般的な粘着シートの保護層と同様でもよい。前記保護層は、プラスチック、ポリウレタン、紙、金属箔等があげられる。前記プラスチックとしては、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）、ＰＣ（ポリカーボネート）等があげられる。前記紙としては、例えば、和紙、洋紙等があげられる。また、前記保護層は、例えば、前記粘着剤層と接する側に、前記粘着剤層に対する剥離性を高めるための剥離処理がされていてもよい。前記剥離処理は、特に限定されないが、例えば、シリコーンによるコーティング（シリコーン処理）等でもよい。前記保護層（剥離シート）は、例えば、シリコーン処理された剥離紙、またはシリコーン処理された剥離フィルムであってもよい。 The protective layer is not particularly limited, and may be, for example, the same as the protective layer of a general pressure-sensitive adhesive sheet. Examples of the protective layer include plastic, polyurethane, paper, and metal foil. Examples of the plastic include PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene), and PC (polycarbonate). Examples of the paper include Japanese paper and Western paper. Further, the protective layer may be subjected to, for example, a release treatment on the side in contact with the pressure-sensitive adhesive layer to enhance the releasability from the pressure-sensitive adhesive layer. The release treatment is not particularly limited, but may be, for example, coating with silicone (silicone treatment). The protective layer (release sheet) may be, for example, a silicone-treated release paper or a silicone-treated release film.
本発明の粘着シートの製造方法は、特に限定されず、例えば、一般的な粘着シートの製造方法と同様でもよい。本発明の粘着シートは、例えば、前記基材に本発明の粘着剤組成物を塗工して前記粘着剤層を形成することにより製造できる。また、本発明の粘着シートは、例えば、前記保護層に本発明の粘着剤組成物を塗工して前記粘着剤層を形成し、さらに、前記粘着剤層に前記基材を積層させることにより製造できる。例えば、基材が和紙等の場合は、張力に強く凹凸が少ない前記保護層（例えば、シリコーン処理された剥離紙、またはシリコーン処理された剥離フィルム）に粘着剤組成物を塗工して乾燥させた後、和紙基材に転写することが好ましい。 The method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and for example, may be the same as the method for producing a general pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet of the present invention can be produced, for example, by applying the pressure-sensitive adhesive composition of the present invention to the base material to form the pressure-sensitive adhesive layer. Further, the pressure-sensitive adhesive sheet of the present invention, for example, by applying the pressure-sensitive adhesive composition of the present invention to the protective layer to form the pressure-sensitive adhesive layer, further by laminating the base material on the pressure-sensitive adhesive layer Can be manufactured. For example, when the base material is Japanese paper or the like, the pressure-sensitive adhesive composition is applied to the protective layer having high tension and having few irregularities (for example, a silicone-treated release paper or a silicone-treated release film) and dried. After that, it is preferable to transfer to a Japanese paper base material.
本発明の粘着シートは、具体的には、例えば、以下のようにして製造できる。まず、前記保護層に本発明の粘着剤組成物を塗工して前記粘着剤層を形成する（塗工工程）。前記塗工工程における塗工方法は、特に限定されず、公知の方法でもよい。前記塗工方法としては、例えば、ロールコーター法、コンマコーター法、ダイコーター法、リバースコーター法、シルクスクリーン法、グラビアコーター法等が挙げられる。前記塗工工程における前記粘着剤組成物の塗工量（塗布量）は、特に限定されないが、前記粘着剤層の厚みが、例えば、５μｍ以上、または１０μｍ以上、例えば、１００μｍ以下、または８０μｍ以下となるようにする。 Specifically, the pressure-sensitive adhesive sheet of the present invention can be produced, for example, as follows. First, the pressure-sensitive adhesive composition of the present invention is applied to the protective layer to form the pressure-sensitive adhesive layer (coating step). The coating method in the coating step is not particularly limited, and may be a known method. Examples of the coating method include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method. The coating amount (coating amount) of the pressure-sensitive adhesive composition in the coating step is not particularly limited, but the thickness of the pressure-sensitive adhesive layer is, for example, 5 μm or more, or 10 μm or more, for example, 100 μm or less, or 80 μm or less. So that
なお、例えば、本発明の粘着剤組成物が架橋剤（Ｄ）を含まない場合は、前記塗工工程に先立ち、架橋剤（Ｄ）を混合してもよい。 In addition, for example, when the pressure-sensitive adhesive composition of the present invention does not contain a crosslinking agent (D), the crosslinking agent (D) may be mixed before the coating step.
前記塗工工程により形成された前記粘着剤組成物は、そのまま前記粘着剤層としてもよい。また、前記塗工工程後、前記塗工面上において前記粘着剤組成物を加熱し（第１の加熱工程）、架橋反応をさらに進行させて前記粘着剤層としてもよい。前記第１の加熱工程における加熱温度は、特に限定されないが、例えば、６０℃以上であり、例えば、１８０℃以下である。前記第１の加熱工程における加熱時間は、特に限定されず、適宜設定可能である。 The pressure-sensitive adhesive composition formed in the coating step may be used as the pressure-sensitive adhesive layer as it is. Further, after the coating step, the pressure-sensitive adhesive composition may be heated on the coating surface (first heating step), and a crosslinking reaction may be further advanced to form the pressure-sensitive adhesive layer. The heating temperature in the first heating step is not particularly limited, but is, for example, 60 ° C. or more, for example, 180 ° C. or less. The heating time in the first heating step is not particularly limited, and can be set as appropriate.
さらに、前記塗工工程後、前記粘着剤層上の、前記保護層と反対側に前記基材を積層させる（基材積層工程）。前記基材積層工程において、例えば、前記基材と前記粘着剤層との密着性を高めるために、ローラー等で圧着してもよい。また、その後さらに加熱して、前記粘着剤層中における架橋反応をさらに進行させてもよい（第２の加熱工程）。前記第２の加熱工程における加熱温度は、特に限定されないが、例えば、６０℃以上であり、例えば、１８０℃以下である。前記第２の加熱工程における加熱時間は、特に限定されず、適宜設定可能である。以上のようにして本発明の粘着シートを製造できるが、前述のとおり、本発明の粘着シートの製造方法はこれに限定されない。 Further, after the coating step, the base material is laminated on the pressure-sensitive adhesive layer on the side opposite to the protective layer (base material laminating step). In the base material laminating step, for example, pressure may be applied by a roller or the like in order to increase the adhesion between the base material and the pressure-sensitive adhesive layer. Further, after that, further heating may be performed to further advance the crosslinking reaction in the pressure-sensitive adhesive layer (second heating step). The heating temperature in the second heating step is not particularly limited, but is, for example, 60 ° C. or more, for example, 180 ° C. or less. The heating time in the second heating step is not particularly limited, and can be set as appropriate. As described above, the pressure-sensitive adhesive sheet of the present invention can be produced, but as described above, the method for producing the pressure-sensitive adhesive sheet of the present invention is not limited to this.
本発明の粘着シートの用途は、特に限定されず、例えば、一般的な粘着シートと同様の用途において、広く使用可能である。 The application of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and can be widely used, for example, in the same applications as general pressure-sensitive adhesive sheets.
本発明の粘着シートは、例えば、マスキングテープ等に用いてもよい。前記マスキングテープの基材は、例えば、和紙等でもよい。 The pressure-sensitive adhesive sheet of the present invention may be used for, for example, a masking tape. The base material of the masking tape may be, for example, Japanese paper.
本発明の粘着シートは、前述のとおり、初期接着力、耐ハガレ性、および塗工適性の３つの特性が全て良好である。初期接着力、耐ハガレ性、および塗工適性の測定方法は、特に限定されないが、例えば、後述する実施例に記載の測定方法により測定できる。 As described above, the pressure-sensitive adhesive sheet of the present invention has all three favorable properties of initial adhesive strength, peel resistance, and coating suitability. The method for measuring the initial adhesive strength, peeling resistance, and coating suitability is not particularly limited, but can be measured, for example, by the measurement methods described in Examples described later.
前述のとおり、初期接着力が低すぎると、粘着シートが被着体に接着しないおそれ、または被着体から剥離してしまうおそれがある。逆に、初期接着力が高すぎると、粘着シートが被着体から剥離しにくく、粘着剤が被着体表面に残留（糊残り）してしまうおそれがある。本発明の粘着シートは、例えば、初期接着力が適正であることにより、これらの問題を抑制または防止できる。例えば、マスキングテープの場合、初期接着力が低すぎないことで、被着体（紙、樹脂シート等）からの粘着シートの剥離を抑制または防止できる。また、初期接着力が高すぎないことで、前記被着体から粘着シートを剥離する際に、基材（例えば和紙）ごと被着体に残留したり、粘着剤層だけが前記被着体に残留（糊残り）したりすることを、抑制または防止できる。 As described above, if the initial adhesive strength is too low, the pressure-sensitive adhesive sheet may not adhere to the adherend or may peel off from the adherend. Conversely, if the initial adhesive strength is too high, the pressure-sensitive adhesive sheet is difficult to peel off from the adherend, and the pressure-sensitive adhesive may remain on the surface of the adherend (adhesive residue). The pressure-sensitive adhesive sheet of the present invention can suppress or prevent these problems, for example, when the initial adhesive force is appropriate. For example, in the case of a masking tape, the peeling of the pressure-sensitive adhesive sheet from the adherend (paper, resin sheet, etc.) can be suppressed or prevented because the initial adhesive strength is not too low. In addition, since the initial adhesive force is not too high, when the pressure-sensitive adhesive sheet is peeled from the adherend, the base material (for example, Japanese paper) remains on the adherend, or only the pressure-sensitive adhesive layer adheres to the adherend. Residual (adhesive residue) can be suppressed or prevented.
また、例えば、耐ハガレ性が適正であることにより、例えば、粘着シート（例えばマスキングテープ）が、意図しない外力により被着体から剥離してしまう現象を抑制または防止できる。 Further, for example, by having appropriate peel resistance, it is possible to suppress or prevent a phenomenon in which, for example, an adhesive sheet (for example, a masking tape) peels off from an adherend due to an unintended external force.
また、例えば、塗工適性が良好であることにより、例えば、シリコーン処理された保護層に粘着剤組成物を塗工しても、粘着剤組成物がシリコーンによって弾かれ、前記保護層の中央部に偏在してしまう等の現象を抑制または防止できる。これによって、粘着剤組成物を均一に塗工できる。また、例えば、塗工適性が良好であることにより、クレーター状の欠点（ハジキ）等を抑制または防止できる。 Further, for example, due to good coating suitability, for example, even if the pressure-sensitive adhesive composition is applied to the silicone-treated protective layer, the pressure-sensitive adhesive composition is repelled by the silicone and the central portion of the protective layer Phenomena such as uneven distribution can be suppressed or prevented. Thereby, the pressure-sensitive adhesive composition can be uniformly applied. In addition, for example, crater-shaped defects (repelling) can be suppressed or prevented due to good coating suitability.
本発明の粘着シートの形態も特に限定されないが、例えば、保管時には、前記粘着剤層上に前記保護層を貼付して前記粘着剤層を保護し、使用直前に前記セパレータを剥離することが好ましい。また、例えば、本発明の粘着シートが、巻き取り可能な長尺のテープ状であり、巻き取って保管することが好ましい。 Although the form of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, for example, during storage, it is preferable that the protective layer is stuck on the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive layer, and the separator is peeled off immediately before use. . In addition, for example, the pressure-sensitive adhesive sheet of the present invention is preferably in the form of a long tape that can be wound up, and is preferably wound up and stored.
さらに、本発明の粘着シートは、例えば、前述のとおり、マスキングテープに限定されず広い用途に使用可能であり、例えば、粘着ラベル、粘着テープ、表面保護フィルム等に用いることができる。 Further, the pressure-sensitive adhesive sheet of the present invention is not limited to a masking tape and can be used for a wide range of applications as described above, and can be used for a pressure-sensitive adhesive label, a pressure-sensitive adhesive tape, a surface protection film, and the like.
以下、本発明の実施例について説明する。なお、本発明はこれらの実施例に限定されるものではない。 Hereinafter, examples of the present invention will be described. Note that the present invention is not limited to these examples.
以下の実施例において製造した粘着剤組成物には、下記の成分を使用した。
成分（Ａ）：下記合成例１で製造した重合体のエマルション
成分（Ｂ）：商品名フォスファノールＲＳ−７１０（東邦化学工業株式会社、ポリオキシアルキレンアルキルエーテルリン酸／ポリオキシアルキレンアルキルエーテル、アルキル基炭素数１３（分枝構造を有する）およびエチレンオキサイド構造を有する。）
成分（Ｃ）：下記成分（ｃ１）〜（ｃ３）
成分（ｃ１）：商品名ＣａｐｓｔｏｎｅＦＳ−３１（ケマーズ社、部分フッ素化アルコール置換グリコール）
成分（ｃ２）：商品名エアロゾルＯＴ−７５（サイテックインダストリーズ株式会社、ジオクチルスルホコハク酸ナトリウム）
成分（ｃ３）：商品名レオコールＳＣ−５０（ライオン株式会社、ポリオキシアルキレンアルキルエーテル）
成分（Ｄ）：商品名エポクロスＷＳ−７００（株式会社日本触媒、オキサゾリン基含有ポリマー）
ｐＨ調整剤：２５質量％アンモニア水
増粘剤：商品名アロンＢ−３００Ｋ（東亞合成株式会社、アクリル酸系重合物）
The following components were used in the pressure-sensitive adhesive composition manufactured in the following Examples.
Component (A): Emulsion component of polymer produced in Synthesis Example 1 below (B): Trade name Phosphanol RS-710 (Toho Chemical Industry Co., Ltd., polyoxyalkylene alkyl ether phosphate / polyoxyalkylene alkyl ether, (The alkyl group has 13 carbon atoms (has a branched structure) and has an ethylene oxide structure.)
Component (C): The following components (c1) to (c3)
Ingredient (c1): trade name Capstone FS-31 (Kemers, partially fluorinated alcohol-substituted glycol)
Ingredient (c2): trade name aerosol OT-75 (Sytec Industries Co., Ltd., sodium dioctyl sulfosuccinate)
Ingredient (c3): trade name Leocol SC-50 (Lion Corporation, polyoxyalkylene alkyl ether)
Component (D): Epocross WS-700 (trade name) (Nippon Shokubai Co., Ltd., oxazoline group-containing polymer)
pH adjuster: 25% by mass aqueous ammonia thickener: Alon B-300K (trade name, Toagosei Co., Ltd., acrylic acid polymer)
（合成例１）
以下のようにして成分（Ａ）（重合体のエマルション）を製造した。
(Synthesis example 1)
Component (A) (polymer emulsion) was produced as follows.
ビーカーＡにアクリル酸２−エチルヘキシル（成分（ａ１））３６２．５質量部、アクリル酸ｎ−ブチル（成分（ａ１））１２５質量部、アクリル酸（成分（ａ２））２．５質量部、およびメタクリル酸（成分（ａ２））１０質量部を量り取り、均一に攪拌した。別のビーカーＢに、イオン交換水１４８質量部、乳化剤（商品名テイカパワーＢＮ−２０６０、テイカ株式会社）１２．５質量部、重合開始剤（商品名Ｖ−５０、富士フイルム和光純薬株式会社）０．５０質量部を量り取り、均一に撹拌した。その後、ビーカーＢにビーカーＡの内容物を加え、ディスパーで混合してプレエマルションを得た。 In a beaker A, 362.5 parts by mass of 2-ethylhexyl acrylate (component (a1)), 125 parts by mass of n-butyl acrylate (component (a1)), 2.5 parts by mass of acrylic acid (component (a2)), and 10 parts by mass of methacrylic acid (component (a2)) was weighed out and stirred uniformly. In another beaker B, 148 parts by mass of ion-exchanged water, 12.5 parts by mass of an emulsifier (trade name: Takeka Power BN-2060, Teika Co., Ltd.), a polymerization initiator (trade name: V-50, Fujifilm Wako Pure Chemical Industries, Ltd.) ) 0.50 parts by weight was weighed out and stirred uniformly. Thereafter, the contents of beaker A were added to beaker B, and mixed with a disper to obtain a pre-emulsion.
撹拌機、冷却管、温度計、滴下ロートを備えたセパラブルフラスコにイオン交換水１８７質量部を量り取り、撹拌しながら６５〜７５℃まで加熱した。つぎに、前記プレエマルション７．５質量部および重合開始剤（商品名Ｖ−５０、富士フイルム和光純薬株式会社）の１質量％水溶液０．８５質量部を前記セパラブルフラスコに投入し、前記温度で３０分間加熱攪拌して重合反応（第１の重合工程）を行った。その後、前記温度で加熱攪拌を継続しながら、滴下ロートを用いて残りのプレエマルションを２時間かけて滴下した。前記プレエマルションの滴下終了時において、残留モノマー（共重合成分）の量は、６．８質量部（８０００ｐｐｍ）であった。さらに、前記プレエマルションの滴下終了後、前記温度で３時間加熱攪拌を継続し、さらに重合反応を行った（第２の重合工程）。この第２の重合工程において、前記プレエマルションの滴下終了から１時間後および２時間後に、それぞれ、重合開始剤（商品名Ｖ−５０、富士フイルム和光純薬株式会社）の１質量％水溶液５質量部とを前記セパラブルフラスコ内に添加した。前記プレエマルションの滴下終了から３時間後に、加熱を停止して放冷し、重合反応を終了させた。このようにして、重合体のエマルションである成分（Ａ）を得た。得られた成分（Ａ）において、エマルションの不揮発成分は６０質量％であり、成分（Ａ）の２０倍希釈水溶液のｐＨは４．０であった。また、得られた成分（Ａ）中の残留モノマー（共重合成分）の量は、２．５質量部（３０００ｐｐｍ）となっていた。すなわち、前記第２の重合工程における前記重合開始剤の追加により、残留モノマーが抑制されたことが確認できた。 In a separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a dropping funnel, 187 parts by mass of ion-exchanged water was weighed, and heated to 65 to 75 ° C while stirring. Next, 7.5 parts by mass of the pre-emulsion and 0.85 parts by mass of a 1% by mass aqueous solution of a polymerization initiator (trade name: V-50, Fujifilm Wako Pure Chemical Industries, Ltd.) were charged into the separable flask. The polymerization reaction (first polymerization step) was performed by heating and stirring at a temperature for 30 minutes. Thereafter, the remaining pre-emulsion was dropped over 2 hours using a dropping funnel while heating and stirring at the above temperature. At the end of the dropping of the pre-emulsion, the amount of the residual monomer (copolymer component) was 6.8 parts by mass (8000 ppm). Further, after the completion of the dropping of the pre-emulsion, heating and stirring were continued at the above temperature for 3 hours to further carry out a polymerization reaction (second polymerization step). In the second polymerization step, 1 hour and 2 hours after the completion of dropping of the pre-emulsion, 5% by weight of a 1% by weight aqueous solution of a polymerization initiator (trade name: V-50, Fujifilm Wako Pure Chemical Industries, Ltd.) Parts were added to the separable flask. After 3 hours from the completion of the dropping of the pre-emulsion, heating was stopped and the mixture was allowed to cool to terminate the polymerization reaction. Thus, the component (A) which is an emulsion of the polymer was obtained. In the obtained component (A), the nonvolatile component of the emulsion was 60% by mass, and the pH of the 20-fold diluted aqueous solution of the component (A) was 4.0. Further, the amount of the residual monomer (copolymer component) in the obtained component (A) was 2.5 parts by mass (3000 ppm). That is, it was confirmed that the addition of the polymerization initiator in the second polymerization step suppressed the residual monomer.
（実施例１）
合成例１で得たエマルション（成分（Ａ））９１．５質量部（不揮発成分６０質量％［５４．９質量部］含有）中に、前記フォスファノールＲＳ−７１０（成分（Ｂ））０．２質量部（不揮発成分１００質量％［０．２質量部］含有）、前記エアロゾルＯＴ−７５（成分（ｃ２）、アニオン性界面活性剤）０．３質量部（不揮発成分７５質量％［０．２２５質量部］含有、前記ＣａｐｓｔｏｎｅＦＳ−３１（成分（ｃ１）、フッ素系界面活性剤）０．２４質量部（不揮発成分２５質量％［０．０６質量部］含有）、前記レオコールＳＣ−５０（成分（ｃ３）、ノニオン性界面活性剤）０．３１質量部（不揮発成分１００質量％［０．３１質量部］含有）、前記アロンＢ−３００Ｋ（増粘剤）０．３質量部（不揮発成分４４質量％［０．１３２質量部］含有）、濃度２５質量％アンモニア水（ｐＨ調整剤）０．２９質量部、および前記エポクロスＷＳ−７００（成分（Ｄ）、内部架橋剤）２．５４質量部（不揮発成分２５質量％［０．６３５質量部］含有）を前記順序で添加して混合し、本実施例の粘着剤組成物を得た。なお、各成分の含有量（質量部）は、全て、各成分中の固形分（不揮発成分）および揮発成分を全て含めた全体の含有量（質量部）で示している。下記表１に示す他の全ての実施例および比較例においても、同様である。各成分における固形分（不揮発成分）のみの含有量（質量部）は、前記かっこ書きで示している。
(Example 1)
In 91.5 parts by mass of the emulsion (component (A)) obtained in Synthesis Example 1 (containing 60% by mass [54.9 parts by mass] of a nonvolatile component), the phosphanol RS-710 (component (B)) 0.2 parts by mass (containing 100% by mass [0.2 parts by mass] of a nonvolatile component), 0.3 parts by mass of the aerosol OT-75 (component (c2), anionic surfactant) (75% by mass of a non-volatile component [0 .225 parts by mass], 0.24 parts by mass of the Capstone FS-31 (component (c1), a fluorine-based surfactant) (containing 25% by mass [0.06 parts by mass] of a non-volatile component), and the above-mentioned Leocol SC-50 ( Component (c3), nonionic surfactant) 0.31 part by mass (contains 100% by mass [0.31 part by mass] of non-volatile component), 0.3 part by mass of Aron B-300K (thickener) (non-volatile component) 44% by mass [0.132 Parts), a concentration of 25% by mass of aqueous ammonia (pH adjuster) 0.29 parts by mass, and the above-mentioned Epocross WS-700 (component (D), an internal crosslinking agent) 2.54 parts by mass (nonvolatile components 25% by mass) [0.635 parts by mass] were added in the above order and mixed to obtain a pressure-sensitive adhesive composition of this example. The contents (parts by mass) of each component were all It is indicated by the total content (parts by mass) including all solid components (non-volatile components) and volatile components, and is the same in all other Examples and Comparative Examples shown in Table 1 below. The content (parts by mass) of only the solid content (non-volatile components) is shown in parentheses.
つぎに、前記本実施例の粘着剤組成物を、塗工幅１００ｍｍのアプリケーターを用いて、シリコーン処理が施された剥離紙（商品名ＳＰ−８Ｅ、リンテック株式会社）に塗工した（塗工工程）。つぎに、前記剥離紙を、塗工した前記粘着剤組成物とともに、１００℃の熱風循環式乾燥機内に２分間放置して加熱し、乾燥させた（第１の加熱工程）。このようにして、前記剥離紙上に粘着剤層を形成した。さらに、前記粘着剤層上に、目止め処理が施された和紙基材を貼り合わせ、重量５ｋｇのゴムローラーを２往復させて前記粘着剤層を前記和紙基材に圧着した。これを４０℃の熱風循環式乾燥機内に３日間放置して架橋反応をさらに進行させ、本実施例の粘着シート（感圧式粘着シート）を得た。この粘着シートにおける前記粘着剤層の厚みは、約４０μｍであった。 Next, the pressure-sensitive adhesive composition of this example was applied to a silicone-treated release paper (trade name: SP-8E, Lintec Co., Ltd.) using an applicator having a coating width of 100 mm (coating). Process). Next, the release paper, together with the coated pressure-sensitive adhesive composition, was left in a hot air circulating dryer at 100 ° C. for 2 minutes to be heated and dried (first heating step). Thus, an adhesive layer was formed on the release paper. Further, a Japanese paper base material subjected to a sealing treatment was bonded on the pressure-sensitive adhesive layer, and the rubber layer having a weight of 5 kg was reciprocated two times to pressure-bond the pressure-sensitive adhesive layer to the Japanese paper base material. This was left in a hot air circulating drier at 40 ° C. for 3 days to further advance the crosslinking reaction, and the pressure-sensitive adhesive sheet (pressure-sensitive pressure-sensitive adhesive sheet) of this example was obtained. The thickness of the pressure-sensitive adhesive layer in this pressure-sensitive adhesive sheet was about 40 μm.
（実施例２〜５、比較例１〜６）
粘着剤組成物を構成する各成分の種類および分量を、下記表１の通りとしたことを除いては、実施例１と同様の方法で粘着剤組成物および粘着シート（感圧式粘着シート）を得た。ただし、比較例５の粘着剤組成物は、後述するように、塗工適性が良くないため、粘着シートを製造することができなかった。
(Examples 2 to 5, Comparative Examples 1 to 6)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet (pressure-sensitive pressure-sensitive adhesive sheet) were prepared in the same manner as in Example 1 except that the types and amounts of the components constituting the pressure-sensitive adhesive composition were as shown in Table 1 below. Obtained. However, as described later, the pressure-sensitive adhesive composition of Comparative Example 5 could not produce a pressure-sensitive adhesive sheet because of poor coating suitability.
以上のようにして製造した実施例１〜５および比較例１〜６の粘着シートまたは粘着剤組成物について、下記の方法で、初期接着力、耐ハガレ性および塗工適性を測定した。測定結果は、下記表１に併せて示す。 With respect to the pressure-sensitive adhesive sheets or pressure-sensitive adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 6 produced as described above, initial adhesive strength, peeling resistance, and coating suitability were measured by the following methods. The measurement results are shown in Table 1 below.
（初期接着力）
測定対象の粘着シートを幅２５ｍｍにカットし、剥離紙を取り除いて研磨ステンレス板に重量２ｋｇのゴムローラーを１往復させて貼り合わせた。これを２３℃、湿度５０％ＲＨの環境下に１時間静置後、前記粘着シートの一端を引張試験機に取り付け、１８０°方向（前記一端と反対側の端に向かう方向）に引張速度３００ｍｍ／分で引き剥がした時の剥離力（Ｎ／２５ｍｍ）を初期接着力とした。初期接着力が１〜２Ｎ／２５ｍｍの範囲内であった場合に、合格と評価した。
(Initial adhesive strength)
The pressure-sensitive adhesive sheet to be measured was cut into a width of 25 mm, the release paper was removed, and a rubber roller having a weight of 2 kg was reciprocated once on the polished stainless steel plate and bonded. This was left to stand in an environment of 23 ° C. and 50% RH for 1 hour, and one end of the pressure-sensitive adhesive sheet was attached to a tensile tester. The peeling force (N / 25 mm) at the time of peeling at a rate of / min was defined as the initial adhesive force. When the initial adhesive force was in the range of 1 to 2 N / 25 mm, it was evaluated as acceptable.
（耐ハガレ性）
測定対象の粘着シートを幅１５ｍｍにカットし、剥離紙を取り除いて研磨ステンレス板に重量２ｋｇのゴムローラーを１往復させて貼り合わせた。これを２３℃、湿度５０％ＲＨの環境下に１時間静置後、前記粘着シートの一端に重量１０ｇの重りを取り付け、９０°方向（前記粘着シートを貼り合わせた平面に対し垂直な方向）に垂らした。その状態で、室温下５時間放置後に、前記ステンレス板から剥がれた前記粘着シートの長さを測定し、耐ハガレ性の指標とした。剥がれた前記粘着シートの長さが短いほど、耐ハガレ性が高いと評価できる。剥がれた前記粘着シートの長さが８０ｍｍ以下であった場合に、実用上問題ないと判断し、合格と評価した。
(Removal resistance)
The pressure-sensitive adhesive sheet to be measured was cut to a width of 15 mm, the release paper was removed, and a rubber roller having a weight of 2 kg was reciprocated once to the polished stainless steel plate and bonded. This was allowed to stand for 1 hour in an environment of 23 ° C. and a humidity of 50% RH. A weight having a weight of 10 g was attached to one end of the pressure-sensitive adhesive sheet, and a 90 ° direction (a direction perpendicular to the plane on which the pressure-sensitive adhesive sheet was bonded) was attached. I dropped it. In this state, after standing at room temperature for 5 hours, the length of the pressure-sensitive adhesive sheet peeled off from the stainless steel plate was measured and used as an index of peel resistance. The shorter the length of the peeled pressure-sensitive adhesive sheet, the higher the peel resistance can be evaluated. When the length of the peeled pressure-sensitive adhesive sheet was 80 mm or less, it was judged that there was no problem in practical use, and the pass was evaluated.
（塗工適性）
前記粘着シートの製造工程と同じ方法で、前記塗工工程および前記第１の加熱工程を行った。すなわち、測定対象の粘着剤組成物を、塗工幅１００ｍｍのアプリケーターを用いて、シリコーン処理が施された剥離紙（商品名ＳＰ−８Ｅ、リンテック株式会社）に塗工した（塗工工程）。つぎに、前記剥離紙を、塗工した前記粘着剤組成物とともに、１００℃の熱風循環式乾燥機内に２分間放置して加熱し、乾燥させた（第１の加熱工程）。そして、乾燥直後の前記粘着剤組成物の塗工幅を測定し、かつ、乾燥直後の粘着剤層の外観を目視で観測した。この測定および観測結果を、下記の基準により、○、△または×と評価した。
〇：塗工幅は９５ｍｍ〜１００ｍｍで、ハジキ（クレーター状の欠点）は見られなかった。
△：塗工幅は９０ｍｍ〜９４ｍｍで、ハジキがみられる場合があった。
×：塗工幅は９０ｍｍ未満で、ハジキがみられる場合があった。
(Coating suitability)
The coating step and the first heating step were performed in the same manner as in the step of manufacturing the pressure-sensitive adhesive sheet. That is, the pressure-sensitive adhesive composition to be measured was applied to a silicone-treated release paper (trade name: SP-8E, Lintec Corporation) using an applicator having a coating width of 100 mm (coating step). Next, the release paper, together with the coated pressure-sensitive adhesive composition, was left in a hot air circulating dryer at 100 ° C. for 2 minutes to be heated and dried (first heating step). Then, the coating width of the pressure-sensitive adhesive composition immediately after drying was measured, and the appearance of the pressure-sensitive adhesive layer immediately after drying was visually observed. The measurement and observation results were evaluated as ○, Δ or × according to the following criteria.
〇: The coating width was 95 mm to 100 mm, and no cissing (crater-like defect) was observed.
Δ: The coating width was 90 mm to 94 mm, and repelling was sometimes observed.
X: The coating width was less than 90 mm, and repelling was sometimes observed.
表１に示したとおり、実施例１〜５の粘着剤組成物は、初期接着力、耐ハガレ性、および塗工適性の３つの特性が全て良好であった。これに対し、成分（Ｂ）を含まない比較例１は、耐ハガレ性および塗工適性は良好であるものの、初期接着力が２．２５Ｎ／２５ｍｍ（２Ｎ／２５ｍｍを超える数値）で高すぎた。成分（ｃ１）を含まない比較例２は、初期接着力および耐ハガレ性は良好であるものの、塗工適性が良くなかった。具体的には、比較例２では、粘着シートを製造することはできたものの、塗工幅は９０ｍｍ未満で、ハジキがみられる場合があった。このように塗工ムラがあると、経時変化により、接着力、耐ハガレ性等が悪化するおそれがある。同様に成分（ｃ１）を含まない比較例３は、成分（ｃ２）の量を比較例２よりも増やしたことで、初期接着力および塗工適性は良好であったものの、耐ハガレ性が良くなかった。成分（ｃ２）を含まない比較例４は、初期接着力および耐ハガレ性は良好であるものの、比較例２と同じく塗工適性が良くなかった。成分（ｃ２）を含まない比較例５は、成分（ｃ１）の量を比較例４よりも増やしたが、塗工適性がさらに悪化し、粘着シートを製造することができなかった。このため、比較例５については、初期接着力および耐ハガレ性の測定もできなかった。成分（ｃ１）および（ｃ２）をいずれも含まない比較例６は、塗工適性も悪く、初期接着力も高すぎた。 As shown in Table 1, the pressure-sensitive adhesive compositions of Examples 1 to 5 were all good in the three properties of initial adhesive strength, peel resistance, and coating suitability. On the other hand, Comparative Example 1, which did not contain the component (B), had good peeling resistance and coating suitability, but had an initial adhesive strength of 2.25 N / 25 mm (a value exceeding 2 N / 25 mm), which was too high. . Comparative Example 2 containing no component (c1) had good initial adhesive strength and peel resistance, but poor coating suitability. Specifically, in Comparative Example 2, although the pressure-sensitive adhesive sheet could be produced, the coating width was less than 90 mm, and repelling was sometimes observed. Such coating unevenness may deteriorate the adhesive strength, peeling resistance, and the like due to aging. Similarly, Comparative Example 3 containing no component (c1) had good initial adhesive strength and coating suitability, but good peeling resistance, by increasing the amount of component (c2) compared to Comparative Example 2. Did not. Comparative Example 4, which did not contain the component (c2), had good initial adhesive strength and peel resistance, but poor coating suitability as in Comparative Example 2. In Comparative Example 5 containing no component (c2), although the amount of the component (c1) was increased as compared with Comparative Example 4, the coating suitability was further deteriorated, and a pressure-sensitive adhesive sheet could not be produced. For this reason, the initial adhesive strength and peeling resistance of Comparative Example 5 could not be measured. Comparative Example 6, which did not contain any of the components (c1) and (c2), was poor in coating suitability and too high in initial adhesive strength.
以上、説明したとおり、本発明によれば、初期接着力、耐ハガレ性、および塗工適性の３つの特性が全て良好な粘着剤および粘着シートを提供することができる。本発明の粘着剤組成物および粘着シートは、例えば、マスキングテープ等に用いることができるが、これに限定されず、例えば、一般的な粘着剤組成物および粘着シートと同様の用途において、広く使用可能である。 As described above, according to the present invention, it is possible to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet having all three favorable properties of initial adhesive strength, peel resistance, and coating suitability. The pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of the present invention can be used, for example, for a masking tape, but are not limited thereto.For example, they are widely used in the same applications as general pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets. It is possible.
Claims (6)
下記成分（Ａ）における重合体は、少なくとも下記成分（ａ１）５０〜９９．９質量部および（ａ２）０．１〜１０質量部の共重合体であり、
下記成分（Ｃ）は、下記成分（ｃ１）および（ｃ２）を含む
ことを特徴とする粘着剤組成物。
（Ａ）重合体のエマルション
（Ｂ）アルキル基の炭素数が１０〜１６であるポリオキシアルキレンアルキルエーテルリン酸エステル系化合物
（Ｃ）界面活性剤
（ａ１）アルキル基の炭素数が２〜１２のアクリル酸アルキルエステル、およびアルキル基の炭素数が２〜１２のメタクリル酸アルキルエステルの少なくとも一方
（ａ２）カルボキシ基含有不飽和単量体
（ｃ１）フッ素系界面活性剤
（ｃ２）分子中にフッ素原子を含まないアニオン性界面活性剤 It contains the following components (A) to (C),
The polymer in the following component (A) is a copolymer of at least the following component (a1) 50 to 99.9 parts by mass and (a2) 0.1 to 10 parts by mass,
The pressure-sensitive adhesive composition, wherein the following component (C) includes the following components (c1) and (c2).
(A) Emulsion of polymer (B) Polyoxyalkylene alkyl ether phosphate ester compound having 10 to 16 carbon atoms in alkyl group (C) Surfactant
(A1) at least one of an alkyl acrylate having 2 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 2 to 12 carbon atoms in an alkyl group (a2) a carboxy group-containing unsaturated monomer (c1) Fluorinated surfactant (c2) Anionic surfactant containing no fluorine atom in the molecule
（ｃ３）ノニオン性界面活性剤 The pressure-sensitive adhesive composition according to claim 1, wherein the component (C) further includes the following component (c3).
(C3) Nonionic surfactant
前記粘着剤層が、請求項１から４のいずれか一項に記載の粘着剤組成物を含むことを特徴とする粘着シート。 Including a base material and an adhesive layer,
A pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer contains the pressure-sensitive adhesive composition according to any one of claims 1 to 4.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171120A (en) * | 1991-12-24 | 1993-07-09 | Mitsui Toatsu Chem Inc | Surface protecting film |
| JPH0677194A (en) * | 1992-08-28 | 1994-03-18 | Mitsui Toatsu Chem Inc | Wafer working tape and its usage method |
| JPH09316407A (en) * | 1996-05-30 | 1997-12-09 | Nitto Denko Corp | Rereleasable pressure-sensitive adhesive sheet |
| JP2006241419A (en) * | 2005-03-07 | 2006-09-14 | Nippon Synthetic Chem Ind Co Ltd:The | Removable aqueous adhesive composition and decoration sheet |
-
2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171120A (en) * | 1991-12-24 | 1993-07-09 | Mitsui Toatsu Chem Inc | Surface protecting film |
| JPH0677194A (en) * | 1992-08-28 | 1994-03-18 | Mitsui Toatsu Chem Inc | Wafer working tape and its usage method |
| JPH09316407A (en) * | 1996-05-30 | 1997-12-09 | Nitto Denko Corp | Rereleasable pressure-sensitive adhesive sheet |
| JP2006241419A (en) * | 2005-03-07 | 2006-09-14 | Nippon Synthetic Chem Ind Co Ltd:The | Removable aqueous adhesive composition and decoration sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022508414A (en) * | 2019-07-10 | 2022-01-19 | Dic株式会社 | Adhesive composition and surface protective film |
| JP7060165B2 (en) | 2019-07-10 | 2022-04-26 | Dic株式会社 | Adhesive composition and surface protective film |
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| JP7100512B2 (en) | 2022-07-13 |
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