JP2010116474A - Uv-polymerizable self-adhesive composition, pressure-sensitive adhesive using the same, and adhesive sheet using pressure-sensitive adhesive - Google Patents
Uv-polymerizable self-adhesive composition, pressure-sensitive adhesive using the same, and adhesive sheet using pressure-sensitive adhesive Download PDFInfo
- Publication number
- JP2010116474A JP2010116474A JP2008290264A JP2008290264A JP2010116474A JP 2010116474 A JP2010116474 A JP 2010116474A JP 2008290264 A JP2008290264 A JP 2008290264A JP 2008290264 A JP2008290264 A JP 2008290264A JP 2010116474 A JP2010116474 A JP 2010116474A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomer
- pressure
- sensitive adhesive
- adhesive composition
- 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 73
- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 66
- 230000001070 adhesive effect Effects 0.000 title claims description 52
- 239000000178 monomer Substances 0.000 claims abstract description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 25
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 25
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 25
- 150000003505 terpenes Chemical class 0.000 claims description 23
- 235000007586 terpenes Nutrition 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- -1 aromatic hydroxy ester Chemical class 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 239000002390 adhesive tape Substances 0.000 abstract description 6
- 238000003848 UV Light-Curing Methods 0.000 abstract description 3
- 239000004971 Cross linker Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 15
- 239000006260 foam Substances 0.000 description 13
- 239000000123 paper Substances 0.000 description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000006188 syrup Substances 0.000 description 9
- 235000020357 syrup Nutrition 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 5
- 239000003522 acrylic cement Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- ZQTOUKNMSGUNJK-UHFFFAOYSA-N (2-hydroxy-3-phenylpropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)CC1=CC=CC=C1 ZQTOUKNMSGUNJK-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-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
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 150000002773 monoterpene derivatives Chemical class 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- TUHHNZDBGKJLMZ-UHFFFAOYSA-N 10-methylundecyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCCCOC(=O)C(C)=C TUHHNZDBGKJLMZ-UHFFFAOYSA-N 0.000 description 1
- BVQFZORZFCJQGB-UHFFFAOYSA-N 10-methylundecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCOC(=O)C=C BVQFZORZFCJQGB-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- IUPSARVXBUSQKA-UHFFFAOYSA-N 2-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CCCCC(O)COC(=O)C(C)=C IUPSARVXBUSQKA-UHFFFAOYSA-N 0.000 description 1
- FYAWPPXBNNWJRK-UHFFFAOYSA-N 2-hydroxyhexyl prop-2-enoate Chemical compound CCCCC(O)COC(=O)C=C FYAWPPXBNNWJRK-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- LANHEKZGKDEWLK-UHFFFAOYSA-N 2-methylideneheptanoic acid Chemical compound CCCCCC(=C)C(O)=O LANHEKZGKDEWLK-UHFFFAOYSA-N 0.000 description 1
- HEBDGRTWECSNNT-UHFFFAOYSA-N 2-methylidenepentanoic acid Chemical compound CCCC(=C)C(O)=O HEBDGRTWECSNNT-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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- TZCGFWIYMJNJIO-UHFFFAOYSA-N 4-methylpentyl 2-methylprop-2-enoate Chemical compound CC(C)CCCOC(=O)C(C)=C TZCGFWIYMJNJIO-UHFFFAOYSA-N 0.000 description 1
- BDMYQVMQTKUZNB-UHFFFAOYSA-N 4-methylpentyl prop-2-enoate Chemical compound CC(C)CCCOC(=O)C=C BDMYQVMQTKUZNB-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
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000011344 liquid material Substances 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 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
- 229940065472 octyl acrylate Drugs 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
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 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
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012545 processing Methods 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
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、紫外線重合性粘着剤組成物、紫外線重合性粘着剤組成物を用いた紫外線重合性感圧接着剤及びこの紫外線重合性感圧接着剤を用いた接着シ―トに関するものである。 The present invention relates to an ultraviolet polymerizable pressure-sensitive adhesive composition, an ultraviolet polymerizable pressure-sensitive adhesive using the ultraviolet polymerizable pressure-sensitive adhesive composition, and an adhesive sheet using the ultraviolet polymerizable pressure-sensitive adhesive.
従来から、粘着剤には、ゴム系粘着剤、アクリル系粘着剤、ビニルエーテル系粘着剤、シリコーン系粘着剤などが使用されてきた。中でも、（メタ）アクリル系ポリマーを主成分とするアクリル系粘着剤は、耐候性や酸化劣化に優れているという理由で様々な分野で使用されている。
（メタ）アクリルポリマーはそれ自体に粘着性がある。低表面エネルギー材料に対する粘着特性は十分でないという理由で、（メタ）アクリル系ポリマーに粘着付与樹脂を添加したアクリル系粘着剤が利用されている。粘着付与樹脂には、ロジンやテルペン樹脂などの天然樹脂系粘着付与樹脂、キシレン樹脂等の合成樹脂系粘着付与樹脂が知られている。しながら、これらの粘着付与樹脂は粘着力は増加させるものの、凝集力を減少させることも知られており、これらを総合的に判断して検討されている。
Conventionally, rubber adhesives, acrylic adhesives, vinyl ether adhesives, silicone adhesives, and the like have been used as adhesives. Among them, acrylic pressure-sensitive adhesives mainly composed of (meth) acrylic polymers are used in various fields because they are excellent in weather resistance and oxidative deterioration.
The (meth) acrylic polymer itself is sticky. An acrylic pressure-sensitive adhesive in which a tackifying resin is added to a (meth) acrylic polymer is used because the adhesive property to a low surface energy material is not sufficient. Known tackifying resins include natural resin tackifying resins such as rosin and terpene resins, and synthetic resin tackifying resins such as xylene resins. However, these tackifier resins are known to reduce cohesive force while increasing adhesive strength, and these are comprehensively judged and studied.
一般に、アクリル系の感圧性接着剤は、アルキルアクリレ―ト単量体を主成分とした単量体を溶液重合することにより調製されてきたが、有機溶剤の安全性や環境衛生上の制約から、最近では、エマルジヨン重合や光重合が多く用いられつつある。中でも、光重合した感圧性接着剤は、その製造工程で溶剤を全く使用しないため、安全性と環境改善の面で、特に有利である。
光重合の例として、アクリル酸アルキルエステルを主成分とするビニル系モノマーに光重合開始剤を添加した液状物を、基材に塗布又は含浸し、強度１〜３００Ｗ／ｍ２の紫外線を照射して少なくとも９０重量％を重合反応させ、次にその強度以上の紫外線を照射して重合反応を完結させるアクリル系粘着テープの製造方法が開発されている（特許文献２特開平２−６０９８１号公報）。
特許文献３特許第２９２２０３６号公報には、特定の単量体混合物と光重合開始剤を含む組成物に特定の強度の紫外線を照射した後、加熱乾燥を行う感圧接着剤の製造方法が開示されている。
一方、粘着剤はその利便性から現在ラベル、シート、テープ等多くの粘着製品をはじめ、各種被着体の貼り合せ等に利用されている。この様に粘着剤の用途が拡大するにつれて、粘着剤に求められる性能もより広範になっている。かかる要求性能として、基材及び被着材の多様化により各種プラスチック材料などに対する接着性が重視されている。
アクリル系粘着剤のプラスチック材料に対する接着性等の改善のため、粘着付与樹脂を配合することが一般的である。
一般に粘着付与樹脂として好適に用いられる粘着付与樹脂は、ラジカル重合反応の連鎖移動・停止剤として作用するため、重合が阻害されるので十分な凝集力の接着性能を有する粘着剤層を形成できない。
In general, acrylic pressure-sensitive adhesives have been prepared by solution polymerization of monomers based on alkyl acrylate monomers, but there are restrictions on the safety and environmental health of organic solvents. Therefore, in recent years, emulsion polymerization and photopolymerization are often used. Among these, the photopolymerized pressure-sensitive adhesive is particularly advantageous in terms of safety and environmental improvement because no solvent is used in the production process.
As an example of photopolymerization, a liquid material obtained by adding a photopolymerization initiator to a vinyl monomer mainly composed of an acrylic acid alkyl ester is applied or impregnated on a base material, and irradiated with ultraviolet rays having an intensity of 1 to 300 W / m 2. A method for producing an acrylic pressure-sensitive adhesive tape has been developed in which at least 90% by weight is subjected to a polymerization reaction, and then the polymerization reaction is completed by irradiating with ultraviolet rays having a strength higher than that (Patent Document 2 Japanese Patent Laid-Open No. 2-60981). .
Patent Document 3 Japanese Patent No. 2922036 discloses a method for producing a pressure-sensitive adhesive in which a composition containing a specific monomer mixture and a photopolymerization initiator is irradiated with ultraviolet rays having a specific strength and then dried by heating. Has been.
On the other hand, pressure-sensitive adhesives are currently used for laminating various adherends as well as many pressure-sensitive adhesive products such as labels, sheets and tapes. Thus, as the application of the pressure-sensitive adhesive expands, the performance required for the pressure-sensitive adhesive has become wider. As this required performance, importance is attached to the adhesiveness with respect to various plastic materials by diversification of a base material and a to-be-adhered material.
In order to improve the adhesiveness of an acrylic pressure-sensitive adhesive to a plastic material, it is common to add a tackifying resin.
In general, a tackifying resin suitably used as a tackifying resin acts as a chain transfer / termination agent for a radical polymerization reaction, and thus polymerization is inhibited, so that a pressure-sensitive adhesive layer having sufficient cohesive strength adhesive performance cannot be formed.
かかる問題を解決する手段として、特許文献１特開平４−３２０４７１号公報（特許３１５４７３９号）は、光重合させるべき接着剤組成物として、アクリル酸の炭素数１〜１４のアルキルエステル又はメタクリル酸の炭素数１〜１４のアルキルエステル単量体（以下、単にアルキルアクリレ―ト単量体と総称する）を主成分とする主単量体７０〜９９重量％）中に、極性基含有の共重合性単量体（（メタ）アクリル酸、イタコン酸、２−アクリルアミドプロパンスルホン酸などの不飽和酸、２−ヒドロキシエチル（メタ）アクリレ―ト、２−ヒドロキシプロピル（メタ）アクリレ―トなどの水酸基含有単量体）３０〜１重量％を含む単量体混合物１００重量部に対して、特定の粘着付与剤である（フエノ―ル変性ロジン系粘着付与剤）２〜４０重量部及び（ｃ）光重合開始剤０．１〜５重量部、ｄ）多官能アクリレ―ト単量体０．２〜５重量部を含む光重合性接着剤組成物である。このフエノ―ル変性ロジン系粘着付与剤であれば重合阻害が少なく、高い粘着力と充分な凝集力を得られると提案されている。しかしながら、両面テープのように粘着剤の厚さが0.1mmを超えるような場合には、重合率も低く、粘着力も低くなってしまう。 As means for solving such a problem, Patent Document 1 Japanese Patent Application Laid-Open No. 4-320471 (Patent No. 315439) discloses an adhesive composition to be photopolymerized as an alkyl ester of acrylic acid having 1 to 14 carbon atoms or methacrylic acid. A main group monomer (mainly 70 to 99% by weight) mainly composed of an alkyl ester monomer having 1 to 14 carbon atoms (hereinafter, simply referred to as an alkyl acrylate monomer). Polymerizable monomers (unsaturated acids such as (meth) acrylic acid, itaconic acid, 2-acrylamidopropanesulfonic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. It is a specific tackifier (phenol-modified rosin tackifier) 2 to 100 parts by weight of a monomer mixture containing 30 to 1% by weight of a hydroxyl group-containing monomer. 0 parts by weight and (c) a photopolymerization initiator 0.1 to 5 parts by weight, d) a polyfunctional acrylate - is a photopolymerizable adhesive composition comprising a preparative monomer 0.2 to 5 parts by weight. It has been proposed that this phenol-modified rosin tackifier has little polymerization inhibition and can provide high adhesive strength and sufficient cohesive strength. However, when the thickness of the pressure-sensitive adhesive exceeds 0.1 mm as in a double-sided tape, the polymerization rate is low and the adhesive strength is also low.
また、特許文献４特開平２−１８４８５号公報には、水素化ロジンエステル系粘着付与剤を、それぞれ用いることが提案されているが、水素化ロジンエステル系粘着付与剤でもラジカル重合の連鎖移動剤としての効果はなくなってはおらず、モノマー転化率は非水素化ロジンエステル系粘着付与剤よりも向上するが、生成するアクリルポリマーは低分子量化され、十分な凝集力を得ることはできない。 Further, Patent Document 4 Japanese Patent Application Laid-Open No. 2-18485 proposes to use hydrogenated rosin ester tackifiers, respectively. However, hydrogenated rosin ester tackifiers are chain transfer agents for radical polymerization. As a result, the monomer conversion rate is improved as compared with the non-hydrogenated rosin ester tackifier, but the resulting acrylic polymer has a low molecular weight and cannot obtain a sufficient cohesive force.
以上のことから、十分な接着性、及び凝集力、具体的には、保持力、定荷重剥離性、ウレタンフォーム耐反発性、曲面接着性を有している紫外線重合性粘着剤組成物、紫外線重合性粘着剤組成物を用いた感圧性接着剤及びこの感圧性接着剤を用いた接着シ―トが求められている。
本発明が解決しようとする課題は、十分な接着性、及び凝集力、具体的には、保持力、定荷重剥離性、ウレタンフォーム耐反発性及び曲面接着性を有している新規なアクリル系粘着剤を含む紫外線重合性接着剤組成物を提供することである。 The problem to be solved by the present invention is a novel acrylic system having sufficient adhesiveness and cohesive strength, specifically, holding power, constant load peelability, urethane foam rebound resistance and curved surface adhesiveness. It is providing the ultraviolet-polymerizable adhesive composition containing an adhesive.
又、これを用いた紫外線重合性感圧性接着剤及びこれを用いた接着シートを提供することである。 Moreover, it is providing the ultraviolet-ray polymerizable pressure sensitive adhesive using this, and an adhesive sheet using the same.
本発明者らは、本発明の課題について鋭意研究し、以下の点を新たに見出して、前記課題を解決した。
１. 本発明者は、樹脂成分として従来から用いられてきた単量体成分に着目し、特定割合で含有する（ａ）、（ｂ）及び（ｃ）成分に分けて、特定量とし、これに（ｅ）及び（ｆ）組み合わせた紫外線重合性接着剤組成物を有効であるとするものである。具体的には（ｃ）成分について注目して独立した成分として含有量も多くしている。従来から水酸基含有モノマーは架橋剤(特にイソシアネート系架橋剤)との反応部位や、若干のTg調整剤として、アクリル系粘着剤ポリマーには0.1〜1％程度含有されることが周知の事実であるが、本発明では水酸基自身の効果を見出し、従来とは全くことなる量を含有させることにより、効果とをもたらすことを発見した。
下記（ａ）、（ｂ）、（ｃ）、（ｅ）、（ｆ）の５成分、
（ａ）アクリル酸の炭素数１〜１４のアルキルエステル又はメタクリル酸の炭素数１〜１４のアルキルエステル単量体を主成分とする主単量体７０〜９７重量％、
（ｂ）不飽和カルボン酸単量体１5〜１重量％、
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体１5〜1重量％からなる構成される単量体混合物（（ａ）+（ｂ）＋（ｃ）１００重量部）、
（ｅ）光重合開始剤０．１〜５重量部及び
（ｆ）架橋剤０．０１〜５重量部
を含むことを特徴とする紫外線重合性接着剤組成物。
２. 本発明者は、樹脂成分として従来から用いられてきた、樹脂成分として従来から用いられてきた単量体成分に着目し、特定割合で含有する（ａ）、（ｂ）及び（ｃ）成分に分けて、特定量とし、これに（ｅ）及び（ｆ）組み合わせた紫外線重合性接着剤組成物を有効であるとするものである。具体的には（ｃ）成分について注目して独立した成分として含有量も多くしている。このことにより（ｄ）成分を添加しても、従来の発明より優れた粘着物性と凝集力とのバランスを保つことが可能となり、多種の部材への粘着性が求められる各種基材の両面テープとして用いるときなどに有用である。
（ａ）アクリル酸と炭素数１〜１４のアルキルエステル又はメタクリル酸と炭素数１〜１４のアルキルエステル単量体を主成分とする主単量体７０〜９７重量％、
（ｂ）不飽和カルボン酸単量体１5〜１重量％、
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体単量体１5〜1重量％からなる構成される単量体混合物（（ａ）+（ｂ）＋（ｃ）１００重量部）、
（ｄ）粘着付与剤２〜３０重量部、（ｅ）光重合開始剤０．１〜５重量部及び（ｆ）架橋剤０．０１〜５重量部からなる紫外線重合性接着剤組成物とし、これを紫外線重合して得られる紫外線重合性接着剤組成物は、従来の同種の従来知られている紫外線重合性接着剤組成物と比較して、粘着性を有していることを見出した。
３. 前記２の（ｄ）の粘着付与剤として水添ロジン系粘着付与剤及びこの混合物、テルペンフェノール共重合体系粘着付与剤及びこの混合物、水添テルペンフェノール共重合体系粘着付与剤、及びこの混合物若しくはこれらの混合物を用いると、他のロジン系粘着付与剤を用いる場合と比較して凝集力の点でも良好な結果を得ることができることを見出した。
The present inventors diligently studied the problems of the present invention, and found the following points newly to solve the problems.
1. The present inventor pays attention to a monomer component that has been conventionally used as a resin component, and divides the component into (a), (b), and (c) components that are contained in a specific ratio to obtain a specific amount. And (e) and (f) the ultraviolet polymerizable adhesive composition in combination is effective. Specifically, the content is also increased as an independent component by paying attention to the component (c). Conventionally, it is a well-known fact that a hydroxyl group-containing monomer is contained in an acrylic pressure-sensitive adhesive polymer as a reaction site with a crosslinking agent (particularly an isocyanate-based crosslinking agent) or a slight Tg adjusting agent in an amount of about 0.1 to 1%. However, in the present invention, the effect of the hydroxyl group itself has been found, and it has been found that the effect is brought about by containing an amount completely different from the conventional one.
The following five components (a), (b), (c), (e), (f),
(A) 70 to 97% by weight of a main monomer mainly composed of an alkyl ester having 1 to 14 carbon atoms of acrylic acid or an alkyl ester monomer having 1 to 14 carbon atoms of methacrylic acid,
(B) 15 to 1% by weight of unsaturated carboxylic acid monomer,
(C) a monomer mixture composed of 15 to 1% by weight of a copolymerizable monomer containing at least one hydroxyl group ((a) + (b) + (c) 100 parts by weight),
(E) 0.1 to 5 parts by weight of a photopolymerization initiator and (f) 0.01 to 5 parts by weight of a crosslinking agent.
2. The present inventor pays attention to a monomer component that has been conventionally used as a resin component and has been conventionally used as a resin component, and contains (a), (b), and (c) in a specific ratio. The component is divided into the components to make specific amounts, and the ultraviolet polymerizable adhesive composition combined with (e) and (f) is considered to be effective. Specifically, the content is also increased as an independent component by paying attention to the component (c). Thus, even when the component (d) is added, it is possible to maintain a balance between adhesive physical properties and cohesive force superior to those of the conventional invention, and double-sided tapes of various base materials that require adhesiveness to various members. Useful when used as
(A) 70 to 97% by weight of a main monomer mainly composed of acrylic acid and an alkyl ester having 1 to 14 carbon atoms or methacrylic acid and an alkyl ester monomer having 1 to 14 carbon atoms,
(B) 15 to 1% by weight of unsaturated carboxylic acid monomer,
(C) a monomer mixture composed of 15 to 1% by weight of a copolymerizable monomer monomer containing at least one hydroxyl group ((a) + (b) + (c) 100 parts by weight),
(D) An ultraviolet polymerizable adhesive composition comprising 2 to 30 parts by weight of a tackifier, (e) 0.1 to 5 parts by weight of a photopolymerization initiator, and (f) 0.01 to 5 parts by weight of a crosslinking agent, It has been found that an ultraviolet polymerizable adhesive composition obtained by ultraviolet polymerization of this has tackiness as compared with a conventionally known ultraviolet polymerizable adhesive composition of the same type.
3. A hydrogenated rosin tackifier and a mixture thereof, a terpene phenol copolymer tackifier and a mixture thereof, a hydrogenated terpene phenol copolymer tackifier, and a mixture thereof as the tackifier of (2) above Or when these mixtures were used, it discovered that a favorable result could be obtained also in the point of cohesion force compared with the case where other rosin type tackifiers are used.
本発明により得られる、紫外線重合性接着剤組成物は、従来の同種の従来知られている紫外線重合性接着剤組成物と比較して、粘着性を有しており、その際に用いる粘着付与剤として水添ロジン系粘着付与剤及びこの混合物、テルペンフェノール共重合体系粘着付与剤、水添テルペンフェノール共重合体系粘着付与剤、及びこの混合物、若しくはこれらの混合物を用いると、他のロジン系粘着付与剤を用いる場合と比較して凝集力の点でも良好な結果を得ることができる。 The ultraviolet-polymerizable adhesive composition obtained by the present invention has tackiness as compared with the conventional ultraviolet-polymerizable adhesive composition of the same type as that of the prior art, and the tackifier used in that case. When a hydrogenated rosin tackifier and a mixture thereof, a terpene phenol copolymer tackifier, a hydrogenated terpene phenol copolymer tackifier, and a mixture thereof, or a mixture thereof are used as agents, other rosin tackifiers are used. Good results can be obtained in terms of cohesive strength as compared with the case of using an imparting agent.
樹脂成分として従来から用いられてきた単量体成分に着目し、特定割合で含有する（ａ）、（ｂ）及び（ｃ）成分に分けて、特定量とし、これに（ｅ）及び（ｆ）組み合わせた紫外線重合性接着剤組成物を有効であるとするものである。具体的には（ｃ）成分について注目して独立した成分として含有量も多くしている。
下記（ａ）、（ｂ）、（ｃ）、（ｅ）、（ｆ）の５成分、
（ａ）アクリル酸の炭素数１〜１４のアルキルエステル又はメタクリル酸の炭素数１〜１４のアルキルエステル単量体を主成分とする主単量体７０〜９７重量％、
（ｂ）不飽和カルボン酸単量体１5〜１重量％、
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体１5〜1重量％からなる構成される単量体混合物（（ａ）+（ｂ）＋（ｃ）１００重量部）
（ｅ）光重合開始剤０．１〜５重量部及び
（ｆ）架橋剤０．０１〜５重量部
を含むことを特徴とする紫外線重合性接着剤組成物。
Focusing on the monomer component conventionally used as the resin component, it is divided into the components (a), (b), and (c) contained in a specific ratio, and the specific amount is added to these components (e) and (f ) The combined UV-polymerizable adhesive composition is effective. Specifically, the content is also increased as an independent component by paying attention to the component (c).
The following five components (a), (b), (c), (e), (f),
(A) 70 to 97% by weight of a main monomer mainly composed of an alkyl ester having 1 to 14 carbon atoms of acrylic acid or an alkyl ester monomer having 1 to 14 carbon atoms of methacrylic acid,
(B) 15 to 1% by weight of unsaturated carboxylic acid monomer,
(C) A monomer mixture composed of 15 to 1% by weight of a copolymerizable monomer containing at least one hydroxyl group ((a) + (b) + (c) 100 parts by weight)
(E) 0.1 to 5 parts by weight of a photopolymerization initiator and (f) 0.01 to 5 parts by weight of a crosslinking agent.
本発明者は、樹脂成分として従来から用いられてきた、樹脂成分として従来から用いられてきた単量体成分に着目し、特定割合で含有する（ａ）、（ｂ）及び（ｃ）成分に分けて、特定量とし、これに（ｅ）及び（ｆ）組み合わせた紫外線重合性接着剤組成物を有効であるとするものである。具体的には（ｃ）成分について注目して独立した成分として含有量も多くしている。
紫外線重合性接着剤組成物及び紫外線重合性感圧性接着剤として用いるときに有用である。
本発明は、下記（ａ）〜（ｆ）の６成分からなる光重合性接着剤組成物である。具体的には以下の通りである。
下記（ａ）〜（ｆ）の６成分、
（ａ）アルキル基が１〜１４個の炭素原子を有するアルキルアクリレ―トまたはアルキルメタクリレ―ト単量体を主成分とする主単量体70〜９７重量％、
（ｂ）不飽和カルボン酸単量体１5〜１重量％、
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体１5〜1重量％からなる構成される単量体混合物（（ａ）+（ｂ）＋（ｃ）１００重量部）、
（ｄ）粘着付与剤２〜３０重量部、
（ｅ）光重合開始剤０．１〜５重量部及び
（ｆ）架橋剤０．０１〜５重量部
含む紫外線重合性接着剤組成物。
This inventor pays attention to the monomer component conventionally used as a resin component, and has been conventionally used as a resin component, and contains (a), (b), and (c) component contained in a specific ratio. Separately, a specific amount is used, and the ultraviolet polymerizable adhesive composition combined with (e) and (f) is effective. Specifically, the content is also increased as an independent component by paying attention to the component (c).
It is useful when used as an ultraviolet polymerizable adhesive composition and an ultraviolet polymerizable pressure sensitive adhesive.
The present invention is a photopolymerizable adhesive composition comprising the following six components (a) to (f). Specifically, it is as follows.
6 components of the following (a) to (f),
(A) 70 to 97% by weight of a main monomer based on an alkyl acrylate or alkyl methacrylate monomer having an alkyl group having 1 to 14 carbon atoms,
(B) 15 to 1% by weight of unsaturated carboxylic acid monomer,
(C) a monomer mixture composed of 15 to 1% by weight of a copolymerizable monomer containing at least one hydroxyl group ((a) + (b) + (c) 100 parts by weight),
(D) 2 to 30 parts by weight of a tackifier,
(E) 0.1 to 5 parts by weight of a photopolymerization initiator and (f) 0.01 to 5 parts by weight of a crosslinking agent.
以下に前記の二つの場合の（ａ）から（ｆ）の各成分について説明する。 The components (a) to (f) in the above two cases will be described below.
（ａ）アクリル酸と炭素数１〜１４のアルキルエステル又はメタクリル酸と炭素数１〜１４のアルキルエステル単量体は以下の通りである。
具体的には以下の通りである。
アクリル酸と炭素数１〜１４のアルキルエステルは、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸ヘキシル、アクリル酸イソヘキシル、アクリル酸オクチル、アクリル酸イソオクチル、アクリル酸ノニル、アクリル酸イソノニル、アクリル酸デシル、アクリル酸イソデシル、アクリル酸ドデシル、アクリル酸イソドデシルを挙げることができる。
メタクリル酸と炭素数１〜１４のアルキルエステル単量体は、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタアクリル酸イソブチル、メタアクリル酸ヘキシル、メタアクリル酸イソヘキシル、メタアクリル酸オクチル、メタアクリル酸イソオクチル、メタクリル酸ノニル、メタクリル酸イソノニル、メタアクリル酸デシル、メタアクリル酸イソデシル、メタアクリル酸ドデシル、メタアクリル酸イソドデシル等を挙げることができる。
これらのほかに、窒素含有ビニル単量体、たとえば、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、アクリロイルモルホリン、ジメチルアミノエチルアクリレート、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド等を用いることもできる。
(A) Acrylic acid and an alkyl ester having 1 to 14 carbon atoms or methacrylic acid and an alkyl ester monomer having 1 to 14 carbon atoms are as follows.
Specifically, it is as follows.
Acrylic acid and alkyl ester having 1 to 14 carbon atoms are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isohexyl acrylate, octyl acrylate, isooctyl acrylate, acrylic Examples include acid nonyl, isononyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and isododecyl acrylate.
Methacrylic acid and alkyl ester monomer having 1 to 14 carbon atoms are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isohexyl methacrylate, methacrylic acid Examples include octyl, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, isododecyl methacrylate, and the like.
In addition to these, nitrogen-containing vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, dimethylaminoethyl acrylate, acrylamide, N, N-dimethylacrylamide and the like can also be used.
（ｂ）不飽和カルボン酸単量体は、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、2-カルボキシ-1-ブテン、2-カルボキシ-1-ペンテン、2-カルボキシ-1-ヘキセン、2-カルボキシ-1-ヘプテンを挙げることができる。 (B) Unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, 2-carboxy- Mention may be made of 1-hexene and 2-carboxy-1-heptene.
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体はビニルアルコール、アリルアルコール、3-メチルアリルアルコール、2-ブテン-1-オール、2−ブテン-1,4-ジオール、アクリル酸又はメタクリル酸のヒドロキシアルキルエステル、アクリル酸又はメタクリル酸と多価アルコールのモノエステルなどをあげることができる。
アクリル酸又はメタクリル酸のヒドロキシアルキルエステルは、アクリル酸−２−ヒドロキシエチル、アクリル酸−２−ヒドロキシプロピル、アクリル酸−２−ヒドロキシブチル、アクリル酸−２−ヒドロキヘキシル、メタクリル酸-2-ヒドロキシエチル、メタクリル酸-2-ヒドロキシプロピル、メタクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシプロピル、メタクリル酸−２−ヒドロキシブチル、メタクリル酸−２−ヒドロキヘキシルを挙げることができる。
アクリル酸又はメタクリル酸と多価アルコールのモノエステルは、アクリル酸又はメタクリル酸とポリエチレングリジコール又はポリプロピレングリコールとのモノエステルを挙げることができる。
中でも、２-ヒドロキシ−３−フェノキシプロピルアクリレート、ならびに２−ヒドロキシエチルアクリレート、4-ヒドロキシブチルアクリレートを用いることが望ましい。
(C) The copolymerizable monomer containing at least one hydroxyl group is vinyl alcohol, allyl alcohol, 3-methylallyl alcohol, 2-buten-1-ol, 2-butene-1,4-diol, acrylic acid or Examples thereof include hydroxyalkyl esters of methacrylic acid, acrylic acid or monoesters of methacrylic acid and polyhydric alcohols.
Hydroxyalkyl esters of acrylic acid or methacrylic acid are: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyhexyl acrylate, 2-hydroxyethyl methacrylate And 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate and 2-hydroxyhexyl methacrylate.
Examples of monoesters of acrylic acid or methacrylic acid and polyhydric alcohols include monoesters of acrylic acid or methacrylic acid and polyethylene glycolicol or polypropylene glycol.
Among these, it is desirable to use 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate.
（ｄ）の成分の粘着付与剤は、ロジン、水添ロジン、テルペン樹脂、テルペンフェノール共重合体系樹脂、又は水添テルペンフェノール共重合体系樹脂をあげることができる。
水添ロジン及びテルペンフェノール共重合体系樹脂、水添テルペンフェノール共重合体系粘着付与剤、を用いる場合が好ましい結果を得ることができる。
水添ロジン系粘着付与剤とは、ロジンの分子骨格内に存在する脂肪族性の二重結合を水素添加により減少させたものや、その誘導体(エステル化、グリシジルエステル化など)を示し、色相、加熱安定性、耐候性に優れたものである。
本発明で使用される水添ロジン系粘着付与剤は、市販されている水素化されたロジン、またはその誘導体を使用することができる。たとえばパインクリスタルKE-100、311、359、604(何れも荒川化学社製)、リカタックF-85、105(理化ファインテク社製)などを挙げることができる。
テルペンフェノール共重合体系粘着付与剤は、モノテルペン(α-ピネン、β-ピネン、リモネン)とフェノールとの共重合体を指し、そのフェノール含有量や分子量を変化させ、SP値や軟化点を調整することができる。水添テルペンフェノール系粘着付与剤は、上記のテルペンフェノール共重合体中のモノテルペンに由来する不飽和結合を水素添加で減少させることにより、色相、耐熱性、耐薬品性を改良したものである。
本発明で使用されるテルペンフェノール共重合体系粘着付与剤は、市販されているテルペンフェノール共重合体系粘着付与剤、またはその誘導体を使用することができる。例えばYSポリスターTシリーズ、「THシリーズ」→削除、Sシリーズ、Nシリーズ、マイティーエースGシリーズ、Kシリーズ(何れもヤスハラケミカル社製)などがあげられる。
本発明で使用される水添テルペンフェノール系粘着付与剤は、市販されている水添テルペンフェノール系粘着付与剤、またはその誘導体を使用することができる。例えばYSポリスター THシリーズ、UHシリーズ(何れもヤスハラケミカル社製)などがあげられる。
Examples of the tackifier of the component (d) include rosin, hydrogenated rosin, terpene resin, terpene phenol copolymer resin, or hydrogenated terpene phenol copolymer resin.
Preferred results can be obtained when using hydrogenated rosin and terpene phenol copolymer resin, or hydrogenated terpene phenol copolymer tackifier.
Hydrogenated rosin tackifiers are those in which aliphatic double bonds existing in the molecular skeleton of rosin are reduced by hydrogenation or derivatives thereof (esterification, glycidyl esterification, etc.) It is excellent in heat stability and weather resistance.
As the hydrogenated rosin tackifier used in the present invention, a commercially available hydrogenated rosin or a derivative thereof can be used. Examples thereof include pine crystals KE-100, 311, 359, and 604 (all manufactured by Arakawa Chemical Co., Ltd.) and Ricacac F-85 and 105 (manufactured by Rika Finetech).
A terpene phenol copolymer tackifier is a copolymer of monoterpene (α-pinene, β-pinene, limonene) and phenol, changing its phenol content and molecular weight, adjusting SP value and softening point. can do. The hydrogenated terpene phenol tackifier has improved hue, heat resistance and chemical resistance by reducing unsaturated bonds derived from monoterpenes in the terpene phenol copolymer by hydrogenation. .
As the terpene phenol copolymer tackifier used in the present invention, a commercially available terpene phenol copolymer tackifier or a derivative thereof can be used. For example, YS Polystar T series, “TH series” → deletion, S series, N series, Mighty Ace G series, K series (all manufactured by Yasuhara Chemical Co., Ltd.) and the like.
As the hydrogenated terpene phenol tackifier used in the present invention, a commercially available hydrogenated terpene phenol tackifier or a derivative thereof can be used. For example, YS Polystar TH series, UH series (both manufactured by Yasuhara Chemical Co., Ltd.) and the like can be mentioned.
（ｅ）成分の光重合開始剤は以下の通りである。
光重合開始剤は以下の通りである。
光開始剤としては、アセトフェノン系、ベンゾインエーテル系、ケタール系、フォスフィンオキシド系、ベンゾフェノン系、ベンゾイン系、ハロゲン化ケトン系、アシルフォスフォナート系など、従来公知のものが使用できる。
(E) The photoinitiator of a component is as follows.
The photopolymerization initiator is as follows.
As the photoinitiator, conventionally known photoinitiators such as acetophenone series, benzoin ether series, ketal series, phosphine oxide series, benzophenone series, benzoin series, halogenated ketone series and acyl phosphonate series can be used.
（ｅ）の架橋剤は以下の通りである。
本発明のUV硬化型アクリル系粘着剤組成物を使用したアクリル系粘着剤や、これを使用した粘着テープ又は粘着シートの耐熱性や凝集性を向上させたい場合には、UV硬化型アクリル系粘着剤組成物中に共重合可能なビニル基を一分子中に2個以上有する化合物を配合してもよい。また、UV硬化型粘着剤組成物中にヒドロキシル基やカルボキシル基などを有するモノマーを含有する場合は、ポリイソシアネート化合物、ポリアミン化合物、メラミン樹脂、尿素樹脂、エポキシ樹脂、カルボジイミド化合物等の、従来公知の熱活性型架橋剤を使用してもよい。
The crosslinking agent of (e) is as follows.
When it is desired to improve the heat resistance and cohesiveness of the acrylic adhesive using the UV curable acrylic adhesive composition of the present invention, and the adhesive tape or adhesive sheet using the same, the UV curable acrylic adhesive A compound having two or more copolymerizable vinyl groups in one molecule may be blended in the agent composition. Further, when the UV curable pressure-sensitive adhesive composition contains a monomer having a hydroxyl group or a carboxyl group, such as a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, an epoxy resin, and a carbodiimide compound are conventionally known. A thermally activated crosslinking agent may be used.
この紫外線重合性接着剤組成物には、前記６成分のほかに、任意成分として、難燃剤、発泡剤、熱伝導性フィラ−、導電性フィラ−、中空フィラ−などの各種フィラ−や顔料、染料などの従来公知の各種の添加剤がある。紫外重合反応を阻害しない範囲内でこれらの任意成分を適宜配合、使用することができる。 In addition to the above six components, the ultraviolet polymerizable adhesive composition includes, as optional components, various fillers and pigments such as a flame retardant, a foaming agent, a heat conductive filler, a conductive filler, and a hollow filler, There are various conventionally known additives such as dyes. These optional components can be appropriately blended and used within a range not inhibiting the ultraviolet polymerization reaction.
本発明においては、このような紫外線重合性接着剤組成物を、被着体上に直接塗工するか、または一旦剥離紙上に塗工したうえで、紫外線を照射して、光重合させることにより、それ自体感圧接着性を有する、粘着化されたアクリル系感圧性接着剤とすることができる。
UV光の発生源としては、蛍光ケミカルランプ、ブラックライト、低圧、高圧、超高圧水銀ランプ、メタルハライドランプ、太陽光線などがある。UV光の照射強度は、終始一定の強度でも行って良いし、硬化途中で強度を変化させることにより、硬化後の物性を微調整することもできる。
In the present invention, such an ultraviolet polymerizable adhesive composition is directly applied on an adherend, or once applied on a release paper, and then irradiated with ultraviolet rays to be photopolymerized. It can be a tackified acrylic pressure sensitive adhesive which itself has pressure sensitive adhesive properties.
Sources of UV light include fluorescent chemical lamps, black light, low pressure, high pressure, ultrahigh pressure mercury lamps, metal halide lamps, and sunlight. The irradiation intensity of UV light may be constant throughout, or the physical properties after curing can be finely adjusted by changing the intensity during curing.
粘着テープ及び粘着シート
本発明のＵＶ硬化型アクリル系粘着剤組成物を使用したアクリル系粘着剤は、粘着テープ又は粘着シートとして用いる。粘着剤層の厚みは特に限定されないが、好ましくは10μm〜3mmである。
Adhesive Tape and Adhesive Sheet The acrylic adhesive using the UV curable acrylic adhesive composition of the present invention is used as an adhesive tape or an adhesive sheet. Although the thickness of an adhesive layer is not specifically limited, Preferably it is 10 micrometers-3 mm.
支持体としては、不織布、化学繊維などの布類、和紙、クラフト紙、クルパック紙、クレープ紙等の紙類、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリ塩化ビニル系樹脂フィルム、ポリスチレンフィルム等のプラスチックフィルム類、銅箔、アルミ箔、鉄箔等の金属箔類、ウレタンフォーム、ポリエチレンフォーム、アクリルフォーム等の発泡体類など、一般に粘着テープの基材として使用されている全ての基材が用いることができる。 Supports include non-woven fabrics, fabrics such as chemical fibers, papers such as Japanese paper, kraft paper, kurpack paper, crepe paper, plastics such as polyester film, polyethylene film, polypropylene film, polyvinyl chloride resin film, polystyrene film, etc. All base materials generally used as base materials for adhesive tapes, such as films, copper foil, aluminum foil, metal foil such as iron foil, foams such as urethane foam, polyethylene foam, and acrylic foam should be used. Can do.
粘着剤組成物のテープ又はシート状への加工は、通常ロールツーロール等の流れ作業で行われるため、短い時間での十分な硬化が必要とされる。この観点から要求されるUV硬化時間は、15分以内である。好ましくは10分以内である。 Since the processing of the pressure-sensitive adhesive composition into a tape or sheet is usually performed by a flow operation such as roll-to-roll, sufficient curing in a short time is required. The UV curing time required from this viewpoint is within 15 minutes. Preferably it is within 10 minutes.
UV硬化型アクリル系粘着剤組成物を基材や剥離紙に塗布又は含浸後にUV硬化する際は、空気中の酸素で硬化が阻害されるため、これを防止する手段を実施しなければならない。例えば、UV硬化型アクリル系粘着剤組成物を塗工後、ポリエチレンテレフタレート製フィルムなどのUV光の透過性が高いフィルムで覆い酸素を遮蔽する方法や、窒素や炭酸ガス、ヘリウムガスのような不活性なガスを用いて酸素濃度0.1質量%以下、好ましくは0.03質量%以下の雰囲気中で硬化させる方法がある。 When UV curing is carried out after applying or impregnating a UV curable acrylic pressure-sensitive adhesive composition to a substrate or release paper, the curing is inhibited by oxygen in the air, and means for preventing this must be implemented. For example, after applying a UV curable acrylic pressure-sensitive adhesive composition, cover it with a film with high UV light transmittance such as a polyethylene terephthalate film to shield oxygen, or use nitrogen, carbon dioxide or helium gas. There is a method of curing using an active gas in an atmosphere having an oxygen concentration of 0.1% by mass or less, preferably 0.03% by mass or less.
本発明で得られる結果の評価試験方法は以下の通りである。 The evaluation test method for the results obtained in the present invention is as follows.
180°粘着力評価試験方法
JIS-Z-1528に準じ、被着体としてSUS304(表面BA処理)板、ABS板およびポリプロピレン板を用いて、粘着力（N/1０mm幅）を測定した。
180 ° adhesive strength evaluation test method
In accordance with JIS-Z-1528, SUS304 (surface BA treatment) plate, ABS plate and polypropylene plate were used as adherends, and the adhesive strength (N / 10 mm width) was measured.
保持力評価試験方法
JIS-Z-1528に準じ、２８０番耐水研磨紙で研磨したステンレス板を被着体とし、貼り付け面積を20ｍｍ×20ｍｍとし、70℃雰囲気で4.9Nの荷重を垂直にかけ1時間放置後の落下の有無、ズレ距離を測定した。
Holding power evaluation test method
In accordance with JIS-Z-1528, a stainless steel plate polished with No. 280 water-resistant abrasive paper is used as the adherend, the application area is 20 mm x 20 mm, a load of 4.9 N is applied vertically at 70 ° C, and the unit drops for 1 hour. The presence or absence and the deviation distance were measured.
定荷重剥離性評価試験方法
２８０番耐水研磨紙で研磨したステンレス板に、厚さ２５μｍのポリエステルフィルムで裏打ちした2０ｍｍ幅×50ｍｍ長の両面粘着テープ試料を、２．０ｋｇローラ１往復で加圧貼付し、30分間常温で放置後、70℃雰囲気で2.9N、2.0Nの荷重をかけて９０度方向に剥離させ、１時間放置後の落下の有無、剥がれた距離を測定した。
Constant load peelability evaluation test method A 20 mm x 50 mm double-sided adhesive tape sample lined with a 25 µm thick polyester film is pressed onto a stainless steel plate polished with No. 280 water-resistant abrasive paper with one reciprocating 2.0 kg roller. Then, after leaving at room temperature for 30 minutes, it was peeled in the direction of 90 ° under a load of 2.9N and 2.0N in a 70 ° C. atmosphere, and the presence or absence of dropping after leaving for 1 hour and the peeled distance were measured.
ウレタンフォーム耐反発性評価試験方法
厚さ10ｍｍ、20ｍｍ×70ｍｍのウレタンフォームの片面に両面テープを全面に貼り付け、厚さ2ｍｍのステンレス板の端に20ｍｍ×20ｍｍを貼り、残りのウレタンフォームをステンレス板の反対側に折り返して貼り付けた。２．０ｋｇローラ１往復で加圧貼付し、常温30分放置後、70℃雰囲気に72時間放置し、剥がれた距離を測定した。
評価基準 〇：剥がれなし ×：全面剥がれ
Urethane foam resilience evaluation test method Double-sided tape is affixed to one side of a 10 mm thick, 20 mm x 70 mm urethane foam, 20 mm x 20 mm is affixed to the edge of a 2 mm thick stainless steel plate, and the remaining urethane foam is stainless steel It was folded and pasted on the opposite side of the board. The pressure was applied with one reciprocating 2.0 kg roller, left at room temperature for 30 minutes, then left in a 70 ° C. atmosphere for 72 hours, and the peeled distance was measured.
Evaluation criteria 〇: No peeling ×: Full peeling
曲面接着性評価試験方法
厚さ、0.5ｍｍ、幅30ｍｍ、長さ180ｍｍのアルミ板に両面テープを20ｍｍ×180ｍｍ貼り付け、厚さ2ｍｍ、長さ200ｍｍのABS板に貼り、5.0ｋｇローラ１往復で加圧貼付し、30分間常温で放置した。
その200ｍｍ長のABS板を70℃雰囲気で190ｍｍになるように湾曲させ72間放置後剥がれた距離を測定した。両端から剥がれが生じている場合には剥れた距離が大きいほうを評価結果とした。
評価基準 〇：剥がれなし ×：全面剥がれ
Curved surface adhesiveness evaluation test method Double-sided tape 20mm x 180mm affixed to an aluminum plate with a thickness of 0.5mm, width 30mm, length 180mm, affixed to an ABS plate with a thickness of 2mm and length 200mm, and a 5.0kg roller with one reciprocation Affixed under pressure and left at room temperature for 30 minutes.
The 200 mm long ABS plate was bent to 190 mm in an atmosphere of 70 ° C., and the distance peeled after standing for 72 hours was measured. When peeling occurred from both ends, the larger peeling distance was taken as the evaluation result.
Evaluation criteria 〇: No peeling ×: Full peeling
アクリルシロップ1の調製について
攪拌機、還流冷却器、温度計、UVランプ及び窒素ガス導入口を備えた反応容器に、2-エチルヘキシルアクリレート89部、アクリル酸6部、2-ヒドロキシ-3-フェニルプロピルアクリレート(新中村化学工業社製：NKエステル702A)５部、光重合開始剤としてダロキュア1173(チバスペシャリティーケミカル社製)0.01部、ｎ-ドデシルメルカプタン0.001部を添加し、窒素雰囲気下でＵＶ光を照射してアクリルシロップを調製した。
Preparation of acrylic syrup 1 In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, UV lamp and nitrogen gas inlet, 89 parts of 2-ethylhexyl acrylate, 6 parts of acrylic acid, 2-hydroxy-3-phenylpropyl acrylate (Shin Nakamura Chemical Co., Ltd .: NK Ester 702A) 5 parts, Darocur 1173 (manufactured by Ciba Specialty Chemicals) as photopolymerization initiator, 0.01 part, n-dodecyl mercaptan 0.001 part are added, and UV light is applied in a nitrogen atmosphere. Acrylic syrup was prepared by irradiation.
ＵＶ硬化型アクリル系粘着剤組成物1の調製について
上記アクリルシロップ100部に対して、水添ロジン系粘着付与樹脂パインクリスタルKE-100を10部(荒川化学社製)、架橋剤としてヘキサンジオールジアクリレート (新中村化学工業社製：NKエステルA-HD-N)0.06部、追加の光重合開始剤ダロキュア1173(チバスペシャリティーケミカル社製)0.3部を添加して均一に撹拌した。撹拌混合時に混入した空気泡を脱泡操作により除去して、UV硬化型アクリル系粘着剤組成物1を調製した。
Preparation of UV curable acrylic pressure-sensitive adhesive composition 1 10 parts of hydrogenated rosin-based tackifying resin pine crystal KE-100 (manufactured by Arakawa Chemical Co., Ltd.) and 100 parts of the above acrylic syrup 0.06 part of acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-HD-N) and 0.3 part of an additional photopolymerization initiator Darocur 1173 (manufactured by Ciba Specialty Chemicals) were added and stirred uniformly. The air bubbles mixed during the stirring and mixing were removed by a defoaming operation to prepare a UV curable acrylic pressure-sensitive adhesive composition 1.
粘着シート1の調製について
上記UV硬化型アクリル系粘着剤組成物1を、表面を離型剤処理した厚さ50μmのポリエチレンテレフタレート(PET)フィルム上にレーヨン紙14ｇ/ｍ２(MR原紙：三木特殊製紙社製)を基材とし、その両面に硬化後の厚さが0.15mmになるように塗工し、その上に厚さ50μmのPETフィルムで被覆した後、紫外線を照射して粘着シート1を得た。
Preparation of pressure-sensitive adhesive sheet 1 Rayon paper 14 g / m 2 (MR base paper: Miki Special) on a 50 μm thick polyethylene terephthalate (PET) film with the above UV curable acrylic pressure-sensitive adhesive composition 1 treated with a release agent (Made by Paper Industries Co., Ltd.) as a base material, coated on both sides so that the thickness after curing is 0.15 mm, coated with a 50 μm thick PET film on it, and then irradiated with ultraviolet rays to give an adhesive sheet 1 Got.
ＵＶ硬化型アクリル系粘着剤組成物２の調製について
粘着剤組成物1の水添ロジン系粘着付与樹脂の変わりにテルペンフェノール系粘着付与樹脂マイティーエースG125(ヤスハラケミカル社製)を用い、架橋剤としてのヘキサンジオールジアクリレート (新中村化学工業社製：NKエステルA-HD-N)を0.04部とした。
Preparation of UV curable acrylic pressure-sensitive adhesive composition 2 A terpene phenol-based tackifying resin Mighty Ace G125 (manufactured by Yasuhara Chemical Co., Ltd.) was used in place of the hydrogenated rosin-based tackifying resin of pressure-sensitive adhesive composition 1 as a crosslinking agent. Hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-HD-N) was made 0.04 part.
粘着シート２の調製について
粘着剤組成物２を用い粘着シート1と同様の操作で粘着シートを得た。
Preparation of pressure-sensitive adhesive sheet 2 A pressure-sensitive adhesive sheet was obtained in the same manner as pressure-sensitive adhesive sheet 1 using pressure-sensitive adhesive composition 2.
ＵＶ硬化型アクリル系粘着剤組成物3の調製について
粘着剤組成物1の水添ロジン系粘着付与樹脂の変わりに水添テルペンフェノール系粘着付与樹脂YSポリスターUH115(ヤスハラケミカル社製)を15部添加、架橋剤としてのヘキサンジオールジアクリレート (新中村化学工業社製：NKエステルA-HD-N)を0.02部とした。
About preparation of UV curable acrylic pressure-sensitive adhesive composition 3 Instead of hydrogenated rosin-based tackifying resin of pressure-sensitive adhesive composition 1, 15 parts of hydrogenated terpene phenol-based tackifying resin YS Polystar UH115 (manufactured by Yasuhara Chemical Co., Ltd.) were added. Hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-HD-N) as a crosslinking agent was 0.02 part.
粘着シート3の調製について
粘着剤組成物2を用い粘着シート1と同様の操作で粘着シートを得た。
Preparation of pressure-sensitive adhesive sheet 3 A pressure-sensitive adhesive sheet was obtained in the same manner as pressure-sensitive adhesive sheet 1 using pressure-sensitive adhesive composition 2.
アクリルシロップ2の調製について
アクリルシロップ1の2-ヒドロキシ-3-フェニルプロピルアクリレートの変わりに２−ヒドロキシエチルアクリレート2.7部添加した。
Preparation of acrylic syrup 2 Instead of 2-hydroxy-3-phenylpropyl acrylate of acrylic syrup 1, 2.7 parts of 2-hydroxyethyl acrylate was added.
ＵＶ硬化型アクリル系粘着剤組成物4の調製について
アクリルシロップ２において粘着剤組成物1と同様に調整した。
Preparation of UV curable acrylic pressure-sensitive adhesive composition 4 was carried out in the same manner as pressure-sensitive adhesive composition 1 in acrylic syrup 2.
粘着シート４の調製について
粘着剤組成物４を用い粘着シート1と同様の操作で粘着シートを得た。
About the preparation of the adhesive sheet 4, the adhesive composition 4 was used and the adhesive sheet was obtained by operation similar to the adhesive sheet 1. FIG.
比較例１
アクリルシロップ３の調製について
攪拌機、還流冷却器、温度計、UVランプ及び窒素ガス導入口を備えた反応容器に、2-エチルヘキシルアクリレート93.8部、アクリル酸6部、2-ヒドロキシアクリレート0.2部、光重合開始剤としてダロキュア1173(チバスペシャリティーケミカル社製)0.01部、ｎ-ドデシルメルカプタン0.001部を添加し、窒素雰囲気下でＵＶ光を照射してアクリルシロップを調製した。
Comparative Example 1
Preparation of acrylic syrup 3 In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, UV lamp and nitrogen gas inlet, 93.8 parts 2-ethylhexyl acrylate, 6 parts acrylic acid, 0.2 parts 2-hydroxy acrylate, photopolymerization As an initiator, 0.01 part of Darocur 1173 (manufactured by Ciba Specialty Chemicals) and 0.001 part of n-dodecyl mercaptan were added, and UV light was irradiated in a nitrogen atmosphere to prepare an acrylic syrup.
ＵＶ硬化型アクリル系粘着剤組成物5の調製について
上記アクリルシロップ100部に対して、水添ロジン系粘着付与樹脂パインクリスタルKE-100を10部(荒川化学社製)、ヘキサンジオールジアクリレート (新中村化学工業社製：NKエステルA-HD-N)0.06部、追加の光重合開始剤ダロキュア1173(チバスペシャリティーケミカル社製)0.3部を添加して均一に撹拌した。撹拌混合時に混入した空気泡を脱泡操作により除去して、UV硬化型アクリル系粘着剤組成物を調製した。
Preparation of UV curable acrylic pressure-sensitive adhesive composition 5 To 100 parts of the above acrylic syrup, 10 parts of hydrogenated rosin-based tackifier resin Pine Crystal KE-100 (manufactured by Arakawa Chemical Co., Ltd.), hexanediol diacrylate (new) Nakamura Chemical Co., Ltd .: NK Ester A-HD-N) 0.06 part and additional photopolymerization initiator Darocur 1173 (Ciba Specialty Chemical Co.) 0.3 part were added and stirred uniformly. Air bubbles mixed during stirring and mixing were removed by a defoaming operation to prepare a UV curable acrylic pressure-sensitive adhesive composition.
粘着シート５の調製について
上記組成物を用い粘着シート1と同様の操作で粘着シートを得た。
比較例２
Preparation of pressure-sensitive adhesive sheet 5 A pressure-sensitive adhesive sheet was obtained in the same manner as pressure-sensitive adhesive sheet 1 using the above composition.
Comparative Example 2
ＵＶ硬化型アクリル系粘着剤組成物6の調製について
粘着剤組成物1の水添ロジン系粘着付与樹脂の変わりにフェノール変性ロジンエステル樹脂タマノル803L(荒川化学社製)を用い、架橋剤としてのヘキサンジオールジアクリレート (新中村化学工業社製：NKエステルA-HD-N)を0.5部とした。
粘着シート6の調製について
粘着剤組成物6を用い粘着シート5と同様の操作で粘着シート6を得た。
Preparation of UV curable acrylic pressure-sensitive adhesive composition 6 Instead of the hydrogenated rosin-based tackifying resin of pressure-sensitive adhesive composition 1, phenol-modified rosin ester resin Tamanol 803L (Arakawa Chemical Co., Ltd.) was used and hexane as a crosslinking agent. Diol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-HD-N) was 0.5 part.
Preparation of pressure-sensitive adhesive sheet 6 A pressure-sensitive adhesive sheet 6 was obtained using the pressure-sensitive adhesive composition 6 in the same manner as the pressure-sensitive adhesive sheet 5.
実施例１から４及び比較例１から２について前記の試験方法を行って評価を行った。用いた原料を表１に示した。
評価結果について表２に示した。
Examples 1 to 4 and Comparative Examples 1 to 2 were evaluated using the above test methods. The raw materials used are shown in Table 1.
The evaluation results are shown in Table 2.
結果について
実施例1では粘着付与剤を添加しても保持力、定荷重剥離性が良好で、尚且つ、ウレタンフォーム耐反発性、曲面接着性も良好な結果を示している。
実施例2においてはテルペンフェノール共重合体系粘着付与剤を添加しているが、保持力、定荷重剥離性が良好で、尚且つ、ウレタンフォーム耐反発性、曲面接着性も良好な結果を示している。
実施例3においては水添テルペンフェノール共重合体系粘着付与剤を添加しているが、保持力、定荷重剥離性が良好で、尚且つ、ウレタンフォーム耐反発性、曲面接着性も良好な結果を示している。
実施例4では水酸基含有モノマーを変更しているが保持力、定荷重剥離性が良好で、尚且つ、ウレタンフォーム耐反発性、曲面接着性も良好な結果を示している。
比較例1のように粘着剤組成物の水酸基含有共重合性単量体含有量が少ない場合には、粘着力は得られているものの充分な凝集力が得られず、保持力、定荷重剥離性で粘着剤の凝集破壊により落下が生じている。
比較例2では水酸基含有モノマーを多く含むが、粘着付与樹脂にフェノール変性ロジンエステル樹脂を用いたもので、この粘着付与樹脂では重合率も低く、粘着力も低い。さらには定荷重剥離性でも落下が生じ、耐反発性や曲面接着性も得ることができなかった。
Results In Example 1, even when a tackifier is added, the holding power and constant load peelability are good, and the urethane foam resilience resistance and curved surface adhesion are also good.
In Example 2, a terpene phenol copolymer tackifier was added, but the holding power and constant load peelability were good, and the urethane foam resilience resistance and curved surface adhesion were also good. Yes.
In Example 3, a hydrogenated terpene phenol copolymer tackifier was added, but the holding power and constant load peelability were good, and the urethane foam resilience resistance and curved surface adhesion were also good. Show.
In Example 4, the hydroxyl group-containing monomer was changed, but the holding power and constant load peelability were good, and the urethane foam resilience resistance and curved surface adhesion were also good.
When the content of the hydroxyl group-containing copolymerizable monomer in the pressure-sensitive adhesive composition is small as in Comparative Example 1, the adhesive force is obtained, but sufficient cohesive force cannot be obtained, holding force, constant load peeling It has fallen due to cohesive failure of the adhesive.
Comparative Example 2 contains a large amount of a hydroxyl group-containing monomer, but a phenol-modified rosin ester resin is used as the tackifier resin. This tackifier resin has a low polymerization rate and a low adhesive strength. Furthermore, even when the load was peeled off at a constant load, a drop occurred, and the resilience resistance and curved surface adhesion could not be obtained.
Claims (8)
（ａ）アクリル酸の炭素数１〜１４のアルキルエステル又はメタクリル酸の炭素数１〜１４のアルキルエステル単量体、少なくとも１つを主成分とする主単量体７０〜９７重量％、
（ｂ）不飽和カルボン酸単量体１5〜１重量％、
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体１5〜1重量％からなる構成される単量体混合物（（ａ）+（ｂ）＋（ｃ）１００重量部）、
（ｅ）光重合開始剤０．１〜５重量部及び
（ｆ）架橋剤０．０１〜５重量部
を含むことを特徴とする紫外線重合性接着剤組成物。 The following five components (a), (b), (c), (e), (f),
(A) C1-C14 alkyl ester of acrylic acid or C1-C14 alkyl ester monomer of methacrylic acid, main monomer 70-97 wt% based on at least one,
(B) 15 to 1% by weight of unsaturated carboxylic acid monomer,
(C) a monomer mixture composed of 15 to 1% by weight of a copolymerizable monomer containing at least one hydroxyl group ((a) + (b) + (c) 100 parts by weight),
(E) 0.1 to 5 parts by weight of a photopolymerization initiator and (f) 0.01 to 5 parts by weight of a crosslinking agent.
（ａ）アクリル酸と炭素数１〜１４のアルキルエステル又はメタクリル酸と炭素数１〜１４のアルキルエステル単量体を主成分とする主単量体７０〜９７重量％、
（ｂ）不飽和カルボン酸単量体１５〜１重量％、
（ｃ）水酸基を少なくとも１つ含有する共重合性単量体１5〜1重量％からなる構成される単量体混合物（（ａ）+（ｂ）＋（ｃ）１００重量部）、
（ｄ）粘着付与剤２〜３０重量部、
（ｅ）光重合開始剤０．１〜５重量部及び
（ｆ）架橋剤０．０１〜５重量部
含むことを特徴とする紫外線重合性接着剤組成物。 6 components of the following (a) to (f),
(A) 70 to 97% by weight of a main monomer mainly composed of acrylic acid and an alkyl ester having 1 to 14 carbon atoms or methacrylic acid and an alkyl ester monomer having 1 to 14 carbon atoms,
(B) 15 to 1% by weight of an unsaturated carboxylic acid monomer,
(C) a monomer mixture composed of 15 to 1% by weight of a copolymerizable monomer containing at least one hydroxyl group ((a) + (b) + (c) 100 parts by weight),
(D) 2 to 30 parts by weight of a tackifier,
(E) 0.1 to 5 parts by weight of a photopolymerization initiator and (f) 0.01 to 5 parts by weight of a crosslinking agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008290264A JP5530621B2 (en) | 2008-11-12 | 2008-11-12 | UV-polymerizable pressure-sensitive adhesive composition, pressure-sensitive adhesive using UV-polymerizable pressure-sensitive adhesive composition, and adhesive sheet using this pressure-sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008290264A JP5530621B2 (en) | 2008-11-12 | 2008-11-12 | UV-polymerizable pressure-sensitive adhesive composition, pressure-sensitive adhesive using UV-polymerizable pressure-sensitive adhesive composition, and adhesive sheet using this pressure-sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010116474A true JP2010116474A (en) | 2010-05-27 |
| JP5530621B2 JP5530621B2 (en) | 2014-06-25 |
Family
ID=42304325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008290264A Active JP5530621B2 (en) | 2008-11-12 | 2008-11-12 | UV-polymerizable pressure-sensitive adhesive composition, pressure-sensitive adhesive using UV-polymerizable pressure-sensitive adhesive composition, and adhesive sheet using this pressure-sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5530621B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014503640A (en) * | 2010-12-13 | 2014-02-13 | スリーエム イノベイティブ プロパティズ カンパニー | Pressure sensitive adhesive for low surface energy substrates |
| JP2014040593A (en) * | 2011-12-22 | 2014-03-06 | Sekisui Chem Co Ltd | Surface protective film |
| JPWO2013115250A1 (en) * | 2012-02-03 | 2015-05-11 | 昭和電工株式会社 | Photocurable transparent adhesive sheet composition, optical adhesive sheet |
| JPWO2013105455A1 (en) * | 2012-01-12 | 2015-05-11 | 電気化学工業株式会社 | Method for manufacturing adhesive sheet and electronic component |
| WO2015079902A1 (en) * | 2013-11-26 | 2015-06-04 | リンテック株式会社 | Double-sided adhesive sheet and method for producing double-sided adhesive sheet |
| WO2017098972A1 (en) * | 2015-12-08 | 2017-06-15 | セメダイン株式会社 | Bonding method using photocurable adhesive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09111195A (en) * | 1995-10-18 | 1997-04-28 | Sekisui Chem Co Ltd | Production of viscoelastic sheet |
| JP3154739B2 (en) * | 1991-04-19 | 2001-04-09 | 日東電工株式会社 | Photopolymerizable adhesive composition, pressure-sensitive adhesive using the same, and adhesive sheets thereof |
| JP2003013028A (en) * | 2001-06-29 | 2003-01-15 | Sekisui Chem Co Ltd | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| JP2004508442A (en) * | 2000-09-08 | 2004-03-18 | テサ・アクチエンゲゼルシヤフト | Method for crosslinking polyacrylate |
-
2008
- 2008-11-12 JP JP2008290264A patent/JP5530621B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3154739B2 (en) * | 1991-04-19 | 2001-04-09 | 日東電工株式会社 | Photopolymerizable adhesive composition, pressure-sensitive adhesive using the same, and adhesive sheets thereof |
| JPH09111195A (en) * | 1995-10-18 | 1997-04-28 | Sekisui Chem Co Ltd | Production of viscoelastic sheet |
| JP2004508442A (en) * | 2000-09-08 | 2004-03-18 | テサ・アクチエンゲゼルシヤフト | Method for crosslinking polyacrylate |
| JP2003013028A (en) * | 2001-06-29 | 2003-01-15 | Sekisui Chem Co Ltd | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014503640A (en) * | 2010-12-13 | 2014-02-13 | スリーエム イノベイティブ プロパティズ カンパニー | Pressure sensitive adhesive for low surface energy substrates |
| JP2014040593A (en) * | 2011-12-22 | 2014-03-06 | Sekisui Chem Co Ltd | Surface protective film |
| JPWO2013105455A1 (en) * | 2012-01-12 | 2015-05-11 | 電気化学工業株式会社 | Method for manufacturing adhesive sheet and electronic component |
| JPWO2013115250A1 (en) * | 2012-02-03 | 2015-05-11 | 昭和電工株式会社 | Photocurable transparent adhesive sheet composition, optical adhesive sheet |
| WO2015079902A1 (en) * | 2013-11-26 | 2015-06-04 | リンテック株式会社 | Double-sided adhesive sheet and method for producing double-sided adhesive sheet |
| JP5901044B2 (en) * | 2013-11-26 | 2016-04-06 | リンテック株式会社 | Double-sided pressure-sensitive adhesive sheet and method for producing double-sided pressure-sensitive adhesive sheet |
| CN105745293A (en) * | 2013-11-26 | 2016-07-06 | 琳得科株式会社 | Double-sided adhesive sheet and method for producing double-sided adhesive sheet |
| JPWO2015079902A1 (en) * | 2013-11-26 | 2017-03-16 | リンテック株式会社 | Double-sided pressure-sensitive adhesive sheet and method for producing double-sided pressure-sensitive adhesive sheet |
| WO2017098972A1 (en) * | 2015-12-08 | 2017-06-15 | セメダイン株式会社 | Bonding method using photocurable adhesive |
| JP6156607B1 (en) * | 2015-12-08 | 2017-07-05 | セメダイン株式会社 | Adhesion method using photocurable adhesive |
| CN108431157A (en) * | 2015-12-08 | 2018-08-21 | 思美定株式会社 | Use the adhering method of photo-curable sticker |
| CN108431157B (en) * | 2015-12-08 | 2021-02-05 | 思美定株式会社 | Bonding method using photocurable adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5530621B2 (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107532042B (en) | UV curable adhesive based on acrylic polymers | |
| CN102449094B (en) | ultraviolet radiation curable pressure sensitive acrylic adhesive | |
| CN104797671B (en) | Height adhesion promoting acrylate contact adhesive | |
| JP5530621B2 (en) | UV-polymerizable pressure-sensitive adhesive composition, pressure-sensitive adhesive using UV-polymerizable pressure-sensitive adhesive composition, and adhesive sheet using this pressure-sensitive adhesive | |
| KR101600686B1 (en) | Manufacturing method of heat-peelable adhesive sheet or adhesive tape using uv curing system | |
| JP4936908B2 (en) | Active energy ray polymerizable composition, pressure-sensitive adhesive, and pressure-sensitive adhesive tape | |
| CN101855310A (en) | Composition for forming contact-bonding coating film of actinic-energy-ray curable type and strippable adhesive-coated paper employing the same | |
| JPH09324164A (en) | Acrylic tacky agent | |
| JP3797628B2 (en) | Pressure sensitive adhesive and adhesive sheet thereof | |
| JPH11152457A (en) | Acrylic self-adhesive tape or sheet | |
| JP7166052B2 (en) | Adhesive sheet | |
| JP2003128714A (en) | Method for producing partially polymerized acrylic polymer composition, partially polymerized acrylic polymer composition produced by the production method and adhesive composition produced by ultraviolet polymerization of the composition | |
| JPH11140406A (en) | Adhesive composition | |
| JPWO2016158413A1 (en) | Temperature-sensitive adhesive composition | |
| JP2000303045A (en) | Pressure-sensitive acrylic adhesive composition, and adhesive tape, or the like, coated therewith | |
| JPH03292379A (en) | Pressure-sensitive adhesive tape or sheet | |
| JP3053693B2 (en) | Method and apparatus for manufacturing double-sided tape | |
| JP3510722B2 (en) | Method for manufacturing viscoelastic sheet | |
| JP2004010835A (en) | Ultraviolet-curable acrylic pressure sensitive adhesive, process for producing it and pressure sensitive adhesive sheet | |
| JP2873352B2 (en) | Pressure sensitive adhesive | |
| JP2000303046A (en) | Pressure-sensitive acrylic adhesive composition and adhesive tape, or the like, coated therewith | |
| JPH09263744A (en) | Acrylic adhesive composition and adhesive tape | |
| JP5258466B2 (en) | Thermosetting adhesive composition, thermosetting adhesive tape or sheet, and flexible circuit board | |
| JP2005239875A (en) | Adhesiveness-improving agent, (meth)acrylic adhesive composition containing the same, and adhesive sheet | |
| JPH11335649A (en) | Thermosetting adhesive composition and its adhesive sheets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20110624 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20110707 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20111108 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130426 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130528 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130725 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140415 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140421 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5530621 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |