JP4942171B2 - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JP4942171B2 JP4942171B2 JP2006249061A JP2006249061A JP4942171B2 JP 4942171 B2 JP4942171 B2 JP 4942171B2 JP 2006249061 A JP2006249061 A JP 2006249061A JP 2006249061 A JP2006249061 A JP 2006249061A JP 4942171 B2 JP4942171 B2 JP 4942171B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- pressure
- sensitive adhesive
- component
- cation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title description 43
- 230000001070 adhesive effect Effects 0.000 title description 43
- 239000000203 mixture Substances 0.000 title description 33
- -1 isocyanate compound Chemical class 0.000 description 78
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 229920000058 polyacrylate Polymers 0.000 description 35
- 239000000178 monomer Substances 0.000 description 34
- 239000007788 liquid Substances 0.000 description 20
- 125000002947 alkylene group Chemical group 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 11
- 150000002892 organic cations Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000001449 anionic compounds Chemical class 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910001412 inorganic anion Inorganic materials 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-UHFFFAOYSA-N 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 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 239000002904 solvent Substances 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
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- NNLHWTTWXYBJBQ-UHFFFAOYSA-N 1-butyl-4-methylpyridin-1-ium Chemical compound CCCC[N+]1=CC=C(C)C=C1 NNLHWTTWXYBJBQ-UHFFFAOYSA-N 0.000 description 1
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- BGSUDDILQRFOKZ-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C)=C1 BGSUDDILQRFOKZ-UHFFFAOYSA-M 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- ZHCHRKVXJJJZFX-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCC(O)OC1=CC=CC=C1 ZHCHRKVXJJJZFX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent 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
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GVXHSMAJJFVLGD-UHFFFAOYSA-N methyl 5-chloro-7-(trifluoromethyl)thieno[3,2-b]pyridine-3-carboxylate Chemical compound C1=C(Cl)N=C2C(C(=O)OC)=CSC2=C1C(F)(F)F GVXHSMAJJFVLGD-UHFFFAOYSA-N 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
- 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
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、粘着剤組成物に関し、より詳しくは、偏光板などの光学部材の表面保護シートにおける粘着剤層に用いられ、帯電防止性に優れるとともに、被着体の表面の形状及び極性や剥離速度による粘着力の差を小さくすることが可能な粘着剤組成物に関する。 The present invention relates to a pressure-sensitive adhesive composition. More specifically, the present invention is used for a pressure-sensitive adhesive layer in a surface protective sheet of an optical member such as a polarizing plate, and has excellent antistatic properties, and the shape, polarity and peeling of the surface of an adherend. The present invention relates to a pressure-sensitive adhesive composition capable of reducing a difference in adhesive strength due to speed.
従来より、電子機器等に貼付される粘着シートとして、基材、剥離紙等を帯電防止処理したり、粘着剤層の下塗り層として帯電防止層を積層した帯電防止粘着シートが使用されている。 Conventionally, as a pressure-sensitive adhesive sheet attached to an electronic device or the like, an antistatic pressure-sensitive adhesive sheet obtained by subjecting a base material, release paper, or the like to an antistatic treatment or laminating an antistatic layer as an undercoat layer of a pressure-sensitive adhesive layer has been used.
近年では、粘着剤層そのものに帯電防止機能を付与する要求が高まっており、粘着剤層に帯電防止剤を添加した帯電防止粘着剤が開発されている。例えば、イオン性液体及び（メタ）アクリル酸アルキレンオキサイドを有する(メタ)アクリル系ポリマーを含有する粘着剤組成物が報告されている（特許文献１参照）。 In recent years, there has been an increasing demand for imparting an antistatic function to the adhesive layer itself, and an antistatic adhesive in which an antistatic agent is added to the adhesive layer has been developed. For example, a pressure-sensitive adhesive composition containing a (meth) acrylic polymer having an ionic liquid and an alkylene oxide (meth) acrylate has been reported (see Patent Document 1).
しかしながら、上記粘着剤組成物を利用した粘着シートを、例えば、低極性で表面に凹凸のあるアンチグレア（ＡＧ）偏光板に貼付した場合と、高極性で表面が平滑なプレーン（ｐｌａｎｅ）偏光板に貼付した場合とでは、その表面形状及び極性の相違により粘着力に差が生じてしまうため、偏光板の種類に合わせて設計した粘着シートをそれぞれ使用する必要があった。このことは、ＡＧ偏光板を利用した電子機器とプレーン偏光板を利用した電子機器を並行して取り扱うラインでは、両者に適した粘着シートを利用しなければならないことを意味し、コストや作業効率の面で問題があった。 However, the pressure-sensitive adhesive sheet using the above-mentioned pressure-sensitive adhesive composition is applied, for example, to an anti-glare (AG) polarizing plate having low polarity and unevenness on the surface, and to a plain polarizing plate having a high polarity and smooth surface. In the case of pasting, since the difference in adhesive force is caused by the difference in surface shape and polarity, it was necessary to use an adhesive sheet designed according to the type of polarizing plate. This means that a line that handles an electronic device using an AG polarizing plate and an electronic device using a plain polarizing plate must use a pressure-sensitive adhesive sheet suitable for both. Cost and work efficiency There was a problem in terms of.
一方、表面を保護する役目を終えた粘着シートは剥離して廃棄されるが、この剥離を高速で行うと、粘着力の関係から剥離時に要する力が大きくなるため、作業効率の低下、汚染などが生じるという問題があり、これらを改善するために粘着力を低く抑えると、部材の密着性が悪くなり粘着シートに浮きやハガレが生じるという問題があった。 On the other hand, the adhesive sheet that has finished the role of protecting the surface is peeled off and discarded, but if this peeling is performed at a high speed, the force required for peeling increases due to the adhesive force, resulting in reduced work efficiency, contamination, etc. In order to improve these problems, if the adhesive force is kept low, there is a problem that the adhesiveness of the member is deteriorated and the adhesive sheet is lifted or peeled off.
この問題を解決するため、ヒドロキシル基およびカルボキシル基を含有し、特定範囲のガラス転移温度を有するアクリル系共重合体と芳香族多官能性イソシアネート化合物を用いることにより、剥離力の速度依存性を少なくした感圧接着剤組成物が報告されている（特許文献２参照）。 In order to solve this problem, by using an acrylic copolymer containing a hydroxyl group and a carboxyl group and having a glass transition temperature in a specific range and an aromatic polyfunctional isocyanate compound, the speed dependency of the peeling force is reduced. A pressure-sensitive adhesive composition has been reported (see Patent Document 2).
しかしながら、上記接着剤組成物は帯電防止機能を有さず、さらに、被着体の表面形状及び極性の相違により生じる粘着力の差を小さくすることはできなかった。 However, the adhesive composition does not have an antistatic function, and further, it has not been possible to reduce the difference in adhesive force caused by the difference in surface shape and polarity of the adherend.
したがって、帯電防止性に優れるとともに、被着体の表面状態の相違による粘着力の差を小さくすることができ、さらに、高速剥離と低速剥離とにおける粘着力の差も小さい粘着剤組成物の開発が求められており、本発明は、このような粘着剤組成物を提供することをその課題とする。 Therefore, it is possible to reduce the difference in adhesive force due to the difference in the surface state of the adherend while having excellent antistatic properties, and furthermore, the development of an adhesive composition having a small difference in adhesive force between high-speed peeling and low-speed peeling. Therefore, an object of the present invention is to provide such a pressure-sensitive adhesive composition.
本発明者は、上記課題を解決すべく鋭意研究を行った結果、アルキレンオキサイド構造を有する（メタ）アクリル系モノマー、特定の官能基を有する２種のモノマーおよび（メタ）アクリル酸アルキルエステルを共重合して得られる(メタ)アクリル系ポリマーに、有機カチオンと無機アニオンからなる液体イオン塩およびイソシアネート架橋剤を配合することにより得られる粘着剤組成物は、帯電防止効果に優れるとともに、剥離速度に関わらず被着体の表面形状及び極性の相違による粘着力の差を小さくすることができ、かつ、剥離速度による粘着力の差をも小さくし得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has jointly used a (meth) acrylic monomer having an alkylene oxide structure, two types of monomers having a specific functional group, and a (meth) acrylic acid alkyl ester. The pressure-sensitive adhesive composition obtained by blending a liquid ion salt composed of an organic cation and an inorganic anion and an isocyanate crosslinking agent into a (meth) acrylic polymer obtained by polymerization is excellent in antistatic effect and has a peeling rate. Regardless of the surface shape and polarity of the adherend, the difference in adhesive force can be reduced, and the difference in adhesive force due to the peeling speed can be reduced, and the present invention has been completed. .
すなわち本発明は、
次の成分（Ａ）ないし（Ｃ）
（Ａ）次の成分（ａ１）ないし（ａ４）を共重合することにより得られる（メタ）アク
リル系ポリマー（但し、（ａ１）〜（ａ４）の合計が１００質量％）
（ａ１）アルキレンオキサイド構造を有する（メタ）アクリル系モノマー
１０〜７０質量％
（ａ２）水酸基含有モノマー １〜 ８質量％
（ａ３）カルボキシル基、アミド基、又はアミノ基のいずれかの官能基を含有するモ
ノマー ０．０５〜０．５質量％
（ａ４）（メタ）アクリル酸アルキルエステル ２５〜８５質量％
（Ｂ）有機カチオンおよび無機アニオンとからなる液体イオン塩
（Ｃ）イソシアネート架橋剤
を含有することを特徴とする粘着剤組成物である。
That is, the present invention
Next component (A) thru | or (C)
(A) (Meth) acrylic polymer obtained by copolymerizing the following components (a1) to (a4) (however, the total of (a1) to (a4) is 100% by mass)
(A1) A (meth) acrylic monomer having an alkylene oxide structure
10-70% by mass
(A2) Hydroxyl group-containing monomer 1 to 8% by mass
(A3) A module containing any functional group of a carboxyl group, an amide group, or an amino group
Nomer 0.05-0.5% by mass
(A4) (meth) acrylic acid alkyl ester 25-85 mass%
(B) Liquid ion salt comprising an organic cation and an inorganic anion
(C) A pressure-sensitive adhesive composition containing an isocyanate crosslinking agent.
さらに本発明は、上記の粘着剤組成物を架橋して得られる粘着シートである。 Furthermore, this invention is an adhesive sheet obtained by bridge | crosslinking said adhesive composition.
本発明の粘着剤組成物は、優れた帯電防止効果を有するとともに、被着体の表面の形状及び極性や剥離速度により生じる粘着力の差を小さくすることができるため、適用可能な被着体の範囲が広く、機械的特性に優れ作業効率を向上させることができるものである。 The pressure-sensitive adhesive composition of the present invention has an excellent antistatic effect and can reduce the difference in pressure-sensitive adhesive force caused by the shape and polarity of the surface of the adherend and the peeling speed. Is excellent in mechanical characteristics and can improve working efficiency.
本発明の粘着剤組成物は、構成成分として後記成分（ａ１）ないし（ａ４）を共重合して得られる（メタ）アクリル系ポリマー（成分（Ａ））、有機カチオンおよび無機アニオンとからなる液体イオン塩（成分（Ｂ））およびイソシアネート架橋剤（成分（Ｃ））を含有するものである。 The pressure-sensitive adhesive composition of the present invention is a liquid comprising a (meth) acrylic polymer (component (A)) obtained by copolymerizing components (a1) to (a4) described later as constituent components, an organic cation and an inorganic anion. An ionic salt (component (B)) and an isocyanate crosslinking agent (component (C)) are contained.
上記（メタ）アクリル系ポリマーを構成する成分は、アルキレンオキサイド構造を有する（メタ）アクリル系モノマー（成分（ａ１））、水酸基含有モノマー（成分（ａ２））、カルボキシル基、アミド基またはアミノ基のいずれかの官能基を含有するモノマー（成分（ａ３））および（メタ）アクリル酸アルキルエステル（成分（ａ４））である。 The component constituting the (meth) acrylic polymer is a (meth) acrylic monomer having an alkylene oxide structure (component (a1)), a hydroxyl group-containing monomer (component (a2)), a carboxyl group, an amide group or an amino group. A monomer (component (a3)) containing any functional group and a (meth) acrylic acid alkyl ester (component (a4)).
成分（Ａ）を構成する成分（ａ１）は、アルキレンオキサイド構造を分子中に有するものであり、アルキレンオキサイド構造としては、例えば、オキシメチレン基、オキシエチレン基、オキシプロピレン基、オキシブチレン基などが挙げられ、また（メタ）アクリル酸に対するアルキレンオキサイド構造の付加モル数は特に限定されないが、１〜３が好ましい。 The component (a1) constituting the component (A) has an alkylene oxide structure in the molecule, and examples of the alkylene oxide structure include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. The number of added moles of the alkylene oxide structure to (meth) acrylic acid is not particularly limited, but is preferably 1 to 3.
上記アルキレンオキサイド構造を有する（メタ）アクリル系モノマーの具体例としては、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレートなどのメトキシポリエチレングリコール（メタ）アクリレート；エトキシジエチレングリコール（メタ）アクリレート、エトキシトリエチレングリコール（メタ）アクリレートなどのエトキシポリエチレングリコール（メタ）アクリレート；ブトキシジエチレングリコール（メタ）アクリレート、ブトキシトリエチレングリコール（メタ）アクリレートなどのブトキシポリエチレングリコール（メタ）アクリレート；フェノキシジエチレングリコール（メタ）アクリレート、フェノキシトリエチレングリコール（メタ）アクリレートなどのフェノキシポリエチレングリコール（メタ）アクリレート；メトキシジプロピレングリコール（メタ）アクリレートなどのメトキシポリプロピレングリコール（メタ）アクリレートなどがあげられる。なかでも、エトキシジエチレングリコールアクリレート、メトキシエチルアクリレートなどが好ましく用いられる。 Specific examples of the (meth) acrylic monomer having an alkylene oxide structure include methoxypolyethylene glycol (meth) acrylate such as methoxydiethylene glycol (meth) acrylate and methoxytriethylene glycol (meth) acrylate; ethoxydiethylene glycol (meth) acrylate, Ethoxypolyethylene glycol (meth) acrylate such as ethoxytriethylene glycol (meth) acrylate; butoxypolyethylene glycol (meth) acrylate such as butoxydiethylene glycol (meth) acrylate; butoxytriethylene glycol (meth) acrylate; phenoxydiethylene glycol (meth) acrylate, Phenoxytriethylene glycol (meth) acrylate Roh carboxymethyl polyethylene glycol (meth) acrylate; and methoxy polypropylene glycol (meth) acrylates such as methoxy dipropylene glycol (meth) acrylate. Of these, ethoxydiethylene glycol acrylate and methoxyethyl acrylate are preferably used.
上記成分（ａ１）のアルキレンオキサイド構造を有する（メタ）アクリル系モノマーは、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は成分（Ａ）の（メタ）アクリル系ポリマーのモノマー成分中１０〜７０質量％であり、好ましくは２０〜６０質量％である。この含有量が１０質量％よりも少ない場合や７０質量％よりも大きい場合には、被着体の表面形状及び極性による粘着力の差が大きくなったり、剥離時に被着体への汚染が生じる場合がある。 The (meth) acrylic monomer having an alkylene oxide structure as the component (a1) may be used singly or in combination of two or more. It is 10-70 mass% in the monomer component of the (meth) acrylic polymer of A), Preferably it is 20-60 mass%. When the content is less than 10% by mass or greater than 70% by mass, the difference in the adhesive force due to the surface shape and polarity of the adherend becomes large, or the adherend is contaminated during peeling. There is a case.
また、成分（Ａ）を構成する成分（ａ２）の水酸基含有モノマーとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート等のようなアルキレンジオールのモノ（メタ）アクリレート類；Ｎ−ヒドロキシエチル（メタ）アクリルアミド、Ｎ−ヒドロキシプロピル（メタ）アクリルアミド等のような（メタ）アクリルアミド類などが挙げられ、このうち４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレートなどが好ましく用いられる。 Moreover, as a hydroxyl-containing monomer of the component (a2) which comprises a component (A), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4 is mentioned, for example. -Mono (meth) acrylates of alkylene diols such as hydroxybutyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, etc .; N-hydroxyethyl (meth) acrylamide, Examples include (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, among which 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like are preferably used.
上記成分（ａ２）の水酸基含有モノマーは、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は成分（Ａ）の（メタ）アクリル系ポリマーのモノマー成分中１〜８質量％であることが好ましく、さらに、３〜６質量％であることがより好ましい。 The hydroxyl group-containing monomer of the component (a2) may be used alone or in combination of two or more, but the total content is the (meth) acrylic component of the component (A) It is preferable that it is 1-8 mass% in the monomer component of a polymer, and it is more preferable that it is 3-6 mass%.
更に、成分（Ａ）を構成する成分（ａ３）のカルボキシル基、アミド基、又はアミノ基のいずれかの官能基を含有するモノマーは、例えば、カルボキシル基含有モノマーとして、（メタ）アクリル酸、（メタ）アクリル酸βカルボキシエチル、イタコン酸、クロトン酸、マレイン酸、フマル酸などを挙げることができ、また、アミド基含有モノマーとしては、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−（１，１−ジメチル−３−オキソブチル）アクリルアミド、tert-ブチルアクリルアミドスルホン酸などが挙げられ、さらにアミノ基含有モノマーとしては、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレートなどが例示できる。これらのうち、アクリル酸、アクリルアミド、ジメチルアミノエチルメタクリレートなどが好ましく用いられる。また、この成分（ａ３）には、Ｎ‐（Ｎ′，Ｎ′‐ジメチルアミノメチル）アクリルアミドなどの、カルボキシル基、アミド基又はアミノ基を２つ以上有するモノマーも含まれる。 Furthermore, the monomer containing any functional group of carboxyl group, amide group or amino group of component (a3) constituting component (A) is, for example, (meth) acrylic acid, ( (Meth) acrylic acid β-carboxyethyl, itaconic acid, crotonic acid, maleic acid, fumaric acid and the like can be mentioned. Examples of amide group-containing monomers include acrylamide, N, N-dimethylacrylamide, N- (1,1 -Dimethyl-3-oxobutyl) acrylamide, tert-butylacrylamidesulfonic acid and the like, and examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate. N, N-dimethylaminopropyl (meth) acrylate, N , N-diethylaminopropyl (meth) acrylate and the like. Of these, acrylic acid, acrylamide, dimethylaminoethyl methacrylate and the like are preferably used. The component (a3) also includes a monomer having two or more carboxyl groups, amide groups or amino groups, such as N- (N ′, N′-dimethylaminomethyl) acrylamide.
上記成分（ａ３）のカルボキシル基、アミド基、又はアミノ基のいずれかの官能基を含有するモノマーは、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は成分（Ａ）の（メタ）アクリル系ポリマーのモノマー成分中０．０５〜０．５質量％であることが好ましく、０．１〜０．３質量％がより好ましい。この範囲であると剥離速度による粘着力の差を小さくすることができ、（ａ３）モノマーが０．０５質量％未満では剥離力の速度依存性を少なくすることが困難であり、０．５質量％より多い場合は、高速剥離時に停止と瞬間剥離が交互に繰り返される現象（ジッピング）が生じてしまう。また、（ａ３）モノマーは（メタ）アクリル系ポリマーの極性を微調整するという作用効果も有する。 The monomer containing any functional group of the carboxyl group, amide group, or amino group of the component (a3) may be used alone or in combination of two or more. The total content is preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.3% by mass in the monomer component of the (meth) acrylic polymer of component (A). Within this range, the difference in adhesive force due to the peeling speed can be reduced, and if the amount of the monomer (a3) is less than 0.05% by mass, it is difficult to reduce the speed dependency of the peeling force. If it is more than%, a phenomenon (zipping) in which stopping and instantaneous peeling are alternately repeated during high-speed peeling occurs. Further, the (a3) monomer also has an effect of finely adjusting the polarity of the (meth) acrylic polymer.
さらにまた、成分（Ａ）を構成する成分（ａ４）の（メタ）アクリル酸アルキルエステルとしては、具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｎ−ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチルなどが挙げられ、このうち（メタ）アクリル酸２−エチルヘキシルが好ましく用いられる。 Furthermore, specific examples of the (meth) acrylic acid alkyl ester of the component (a4) constituting the component (A) include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid n. -Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and the like, among which 2-ethylhexyl (meth) acrylate is preferably used.
上記成分（ａ４）の（メタ）アクリル酸アルキルエステルは、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は（メタ）アクリル系ポリマーのモノマー成分中２５〜８５質量％であることが好ましく、さらに、３５〜７５質量％であることがより好ましい。 The (meth) acrylic acid alkyl ester of the component (a4) may be used singly or as a mixture of two or more, but the total content is a (meth) acrylic polymer. It is preferable that it is 25-85 mass% in the monomer component of this, and it is more preferable that it is 35-75 mass%.
本発明に用いられる成分（Ａ）の（メタ）アクリル系ポリマーは、上記成分（ａ１）ないし（ａ４）のモノマーを、例えば、溶液重合、乳化重合、塊状重合など（メタ）アクリル系ポリマーの合成に通常用いられる方法によって共重合させることにより得ることができるものである。この成分（Ａ）のメタ）アクリル系ポリマーの分子量は特に制限されるものではないが、好ましくは２０万〜７０万である。 The (meth) acrylic polymer of the component (A) used in the present invention is prepared by synthesizing the (meth) acrylic polymer such as solution polymerization, emulsion polymerization, bulk polymerization or the like from the monomers of the above components (a1) to (a4). It can be obtained by copolymerizing by a method usually used in the above. The molecular weight of the component (A) meth) acrylic polymer is not particularly limited, but is preferably 200,000 to 700,000.
また、本発明に用いられる成分（Ａ）の（メタ）アクリル系ポリマーの製造にあたっては、上記成分のほか、必要に応じ、重合開始剤、重合調整剤を使用することができる。 Moreover, in the manufacture of the (meth) acrylic polymer of the component (A) used in the present invention, a polymerization initiator and a polymerization regulator can be used as necessary in addition to the above components.
上記重合開始剤としては、例えば、アゾビスイソブチロニトリル等のアゾ系重合開始剤、過酸化ベンゾイル等の過酸化物系重合開始剤などが挙げられ、上記成分（ａ１）〜（ａ４）のモノマーの混合物１００重量部に対して、０．０１〜１重量部の範囲で用いることができる。 Examples of the polymerization initiator include azo polymerization initiators such as azobisisobutyronitrile, peroxide polymerization initiators such as benzoyl peroxide, and the like, and the above components (a1) to (a4). It can be used in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer mixture.
一方、本発明の成分（Ｂ）は、有機カチオンと無機アニオンの組み合わせからなる液体イオン塩である。なお、本明細書において液体イオン塩とは室温（２５℃）において液体である塩を意味する。 On the other hand, the component (B) of the present invention is a liquid ion salt comprising a combination of an organic cation and an inorganic anion. In the present specification, the liquid ionic salt means a salt that is liquid at room temperature (25 ° C.).
上記成分（Ｂ）を構成する有機カチオンとしては、たとえば、イミダゾリウムカチオン、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオンなどが挙げられるが、このうちイミダゾリウムカチオン、ピリジニウムカチオンが好ましく用いられ、特にピリジニウムカチオンが好ましい。 Examples of the organic cation constituting the component (B) include imidazolium cation, pyridinium cation, piperidinium cation, pyrrolidinium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, tetraalkylammonium cation, Examples include alkylsulfonium cations, among which imidazolium cations and pyridinium cations are preferably used, and pyridinium cations are particularly preferable.
上記イミダゾリウムカチオンの具体例としては、例えば、１，３−ジメチルイミダゾリウムカチオン、１，３−ジエチルイミダゾリウムカチオン、１−エチル−３−メチルイミダゾリウムカチオン、１−ブチル−３−メチルイミダゾリウムカチオン、１−へキシル−３−メチルイミダゾリウムカチオン、１−オクチル−３−メチルイミダゾリウムカチオン、１−デシル−３−メチルイミダゾリウムカチオン、１−ドデシル−３−メチルイミダゾリウムカチオン、１−テトラデシル−３−メチルイミダゾリウムカチオン、１，２−ジメチル−３−プロピルイミダゾリウムカチオン、１−エチル−２，３−ジメチルイミダゾリウムカチオン、１−ブチル−２，３−ジメチルイミダゾリウムカチオン、１−へキシル−２，３−ジメチルイミダゾリウムカチオンなどが挙げられ、このうち、１−ブチル−３−メチルイミダゾリウムカチオン、１−へキシル−３−メチルイミダゾリウムカチオンなどが好ましく用いられる。 Specific examples of the imidazolium cation include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl-3-methylimidazolium. Cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl -3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-he Xyl-2,3-dimethylimidazolium Cation and the like, of which 1-butyl-3-methylimidazolium cation, and hexyl-3-methylimidazolium cation to 1 are preferably used.
また、上記ピリジニウムカチオンの具体例としては、例えば、１−エチルピリジニウムカチオン、１−ブチルピリジニウムカチオン、１−へキシルピリジニウムカチオン、１−ブチル−３−メチルピリジニウムカチオン、１−ブチル−４−メチルピリジニウムカチオン、１−へキシル−３−メチルピリジニウムカチオン、１−へキシル−４−メチルピリジニウムカチオン、１−ブチル−３，４−ジメチルピリジニウムカチオンなどが挙げられ、このうち、１−へキシル−４−メチルピリジニウムカチオンなどが好ましく用いられる。 Specific examples of the pyridinium cation include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, and 1-butyl-4-methylpyridinium. Cations, 1-hexyl-3-methylpyridinium cation, 1-hexyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, etc., among which 1-hexyl-4- A methylpyridinium cation or the like is preferably used.
また、上記成分（Ｂ）を構成する無機アニオンとしては、例えば、Ｃｌ−、Ｂｒ−、Ｉ−、ＡｌＣｌ４ −、Ａｌ２Ｃｌ７ −、ＢＦ４ −、ＰＦ６ −、ＣｌＯ４ −、ＮＯ３ −、ＡｓＦ６ −、ＳｂＦ６ −、ＮｂＦ６ −、ＴａＦ６ −、Ｆ（ＨＦ）ｎ −などが例示でき、このうち、ＰＦ６ −、ＢＦ４ −などが好ましく用いられる。 Examples of the inorganic anion constituting the component (B) include Cl − , Br − , I − , AlCl 4 − , Al 2 Cl 7 − , BF 4 − , PF 6 − , ClO 4 − , and NO 3. -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n - , etc. can be exemplified, of which, PF 6 -, BF 4 -, etc. are preferably used.
本発明の成分（Ｂ）は、上記有機カチオンおよび無機アニオンから適宜選択される組み合わせからなる塩であり、具体的には、１−エチル−３−メチルイミダゾリウムテトラフルオロボレート、１−エチル−３−メチルイミダゾリウムヘキサフルオロホスフェ−ト、１−ブチル−３−メチルピリジニウムテトラフルオロボレート、１−ブチル−３−メチルピリジニウムヘキサフルオロホスフェート、１−ヘキシル−３−メチルイミダゾリウムテトラフルオロボレート、１−ヘキシル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−オクチル−３−メチルイミダゾリウムテトラフルオロボレート、１−オクチル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−へキシル−３−メチルイミダゾリウムブロミド、１−へキシル−３−メチルイミダゾリウムクロライド、１−へキシル−２，３−ジメチルイミダゾリウムテトラフルオロボレート、１−へキシル−２，３−ジメチルイミダゾリウムヘキサフルオロホスフェート；１−ブチルピリジニウムテトラフルオロボレート、１−ブチルピリジニウムヘキサフルオロホスフェート、１−へキシルピリジニウムテトラフルオロボレート、１−へキシルピリジニウムヘキサフルオロホスフェート、１−ブチル−３−メチルピリジニウムテトラフルオロボレート、１−ブチル−３−メチルピリジニウムヘキサフルオロホスフェート、１−ヘキシル−４−メチルピリジニウムテトラフルオロボレート、１−ヘキシル−４−メチルピリジニウムヘキサフルオロホスフェートなどが挙げられ、このうち、１−ブチル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−ヘキシル−３−メチルイミダゾリウムテトラフルオロボレート、１−ヘキシル−４−メチルピリジニウムヘキサフルオロホスフェートなどが好ましく用いられる。 Component (B) of the present invention is a salt comprising a combination appropriately selected from the above organic cations and inorganic anions. Specifically, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3 -Methylimidazolium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1- Hexyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium bromide, 1 − Xyl-3-methylimidazolium chloride, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1-hexyl-2,3-dimethylimidazolium hexafluorophosphate; 1-butylpyridinium tetrafluoroborate, 1 -Butylpyridinium hexafluorophosphate, 1-hexylpyridinium tetrafluoroborate, 1-hexylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium hexafluorophosphate, 1 -Hexyl-4-methylpyridinium tetrafluoroborate, 1-hexyl-4-methylpyridinium hexafluorophosphate, etc., among which 1-butyl-3- Chill hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-4-methylpyridinium hexafluorophosphate are preferred.
この成分（Ｂ）の配合量は、前記成分（Ａ）１００重量部に対して、通常０．０５〜３重量部の範囲であり、好ましくは、０．３〜１．５重量部の範囲である。 The amount of component (B) is usually in the range of 0.05 to 3 parts by weight, preferably in the range of 0.3 to 1.5 parts by weight, relative to 100 parts by weight of component (A). is there.
さらに、本発明の成分（Ｃ）のイソシアネート架橋剤は、分子中に水酸基と架橋し得るイソシアネート基を有する化合物であり、具体的には、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマーや、それらをトリメチロールプロパンなどの２価以上のアルコール化合物等に付加反応させたイソシアネート化合物ないしイソシアヌレート化物等が例示される。また、公知のポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどにイソシアネート化合物を付加反応させたウレタンプレポリマー型のイソシアネート等も挙げられる。これらのうち、ヘキサジメチレンイソシアネートなどが好ましく用いられる。 Furthermore, the isocyanate crosslinking agent of component (C) of the present invention is a compound having an isocyanate group capable of crosslinking with a hydroxyl group in the molecule, and specifically, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene. Illustrative examples include isocyanate monomers such as diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and isocyanate compounds or isocyanurates obtained by addition reaction of them with dihydric or higher alcohol compounds such as trimethylolpropane. . Moreover, the urethane prepolymer type isocyanate etc. which made the isocyanate compound addition reaction to well-known polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. are mentioned. Of these, hexadimethylene isocyanate is preferably used.
この成分（Ｃ）の配合量は、成分（Ａ）１００重量部に対して、通常０．５〜１０重量部の範囲であり、好ましくは、２〜５重量部の範囲である。 The amount of component (C) is usually in the range of 0.5 to 10 parts by weight, preferably in the range of 2 to 5 parts by weight, relative to 100 parts by weight of component (A).
本発明の粘着剤組成物は、上記成分（Ａ）ないし（Ｃ）に、必要に応じその他の添加剤を添加して、常法により混合することによって得られる。またその際に、上記成分を溶解又は分散させるために有機溶媒等の溶剤を含有させても良いが、溶剤を用いずにそのまま混合することが好ましい。 The pressure-sensitive adhesive composition of the present invention can be obtained by adding other additives to the components (A) to (C) as necessary and mixing them by a conventional method. Further, in this case, a solvent such as an organic solvent may be contained in order to dissolve or disperse the above components, but it is preferable to mix as it is without using a solvent.
本発明の帯電防止粘着剤組成物には、前記各成分のほか、本発明の効果を損なわない範囲で必要に応じ、粘着付与剤、可塑剤、酸化防止剤、防腐剤等を配合することができる。 In addition to the components described above, the antistatic pressure-sensitive adhesive composition of the present invention may contain a tackifier, a plasticizer, an antioxidant, a preservative, etc., as necessary within the range that does not impair the effects of the present invention. it can.
以上のようにして得られた本発明の粘着剤組成物を、常法により、支持体の表面に塗布し、乾燥させることによって、本発明の粘着シートを得ることができる。 The pressure-sensitive adhesive composition of the present invention obtained as described above can be applied to the surface of a support by a conventional method and dried to obtain the pressure-sensitive adhesive sheet of the present invention.
粘着シートの製造において、上記支持体としては、例えば、ポリエステル、ポリエチレンなどの樹脂フィルムを用いることができ、また、粘着剤組成物の塗布厚さは、通常２〜３０μｍであり、好ましくは１０〜２０μｍである。 In the production of the pressure-sensitive adhesive sheet, for example, a resin film such as polyester or polyethylene can be used as the support, and the coating thickness of the pressure-sensitive adhesive composition is usually 2 to 30 μm, preferably 10 to 10 μm. 20 μm.
上記のようにして得られた本発明の粘着シートは、剥離速度に関わらず、ＡＧ偏光板やプレーン偏光板など表面の形状及び極性が相違する被着体に貼付した場合の粘着力の差が小さく、また低速剥離における粘着力と高速剥離における粘着力との差も小さいものである。 The pressure-sensitive adhesive sheet of the present invention obtained as described above has a difference in adhesive strength when applied to an adherend having a different surface shape and polarity, such as an AG polarizing plate or a plain polarizing plate, regardless of the peeling speed. In addition, the difference between the adhesive strength at low speed peeling and the adhesive strength at high speed peeling is small.
次に製造例及び実施例によって、本発明をさらに詳細に説明するが、本発明はこれら実施例等に何ら制約されるものではない。 Next, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these examples.
製 造 例 １
成分（ａ１）としてエトキシジエチレングリコールアクリレート（ＥＣＡ、共栄社製）６０重量部、成分（ａ２）として４−ヒドロキシブチルアクリレート（４ＨＢＡ）５重量部、成分（ａ３）としてアクリル酸０．１５重量部、成分（ａ４）として２−エチルヘキシルアクリレート（２ＥＨＡ）３４．８５重量部、酢酸エチル１２０重量部およびアゾビスイソブチロニトリル（ＡＩＢＮ）０．１重量部を反応容器に入れ、この反応容器内の空気を窒素ガスで置換した。その後、窒素雰囲気中で攪拌しながら、この反応容器を７０℃に昇温させ、６時間反応させた。反応終了後、酢酸エチルで希釈し、分子量５０万のアクリル系ポリマー溶液Ａ１を得た。
Manufacturing example 1
60 parts by weight of ethoxydiethylene glycol acrylate (ECA, manufactured by Kyoeisha) as component (a1), 5 parts by weight of 4-hydroxybutyl acrylate (4HBA) as component (a2), 0.15 parts by weight of acrylic acid as component (a3), component ( As a4), 34.85 parts by weight of 2-ethylhexyl acrylate (2EHA), 120 parts by weight of ethyl acetate and 0.1 part by weight of azobisisobutyronitrile (AIBN) are placed in a reaction vessel, and the air in the reaction vessel is purged with nitrogen. Replaced with gas. Thereafter, while stirring in a nitrogen atmosphere, the reaction vessel was heated to 70 ° C. and reacted for 6 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain an acrylic polymer solution A1 having a molecular weight of 500,000.
製 造 例 ２ 〜 ３
成分（ａ１）ないし（ａ４）を下記表２のように代えた以外は製造例１と同様にしてアクリル系ポリマー溶液Ａ２およびＡ３を得た。その分子量も表１に併記する。
Production examples 2 to 3
Acrylic polymer solutions A2 and A3 were obtained in the same manner as in Production Example 1 except that components (a1) to (a4) were changed as shown in Table 2 below. The molecular weight is also shown in Table 1.
製造比較例 １ 〜 １５
成分（ａ１）ないし（ａ４）を下記表２のように代えた以外は製造例１と同様にしてアクリル系ポリマー溶液Ｂ１ないしＢ１５を得た。その分子量も表１に併記する。
Production Comparative Examples 1 to 15
Acrylic polymer solutions B1 to B15 were obtained in the same manner as in Production Example 1 except that the components (a1) to (a4) were changed as shown in Table 2 below. The molecular weight is also shown in Table 1.
なお、表中の略記は次のとおりである。
ＭＥＡ：メトキシエチルアクリレート
ＥＣＡ：エトキシジエチレングルコールアクリレート
４ＨＢＡ：４−ヒドロキシブチルアクリレート
２ＨＥＡ：２−ヒドロキシエチルアクリレート
ＡＡ：アクリル酸
ＡＭ：アクリルアミド
ＤＭ：ジメチルアミノエチルメタクリレート
２ＥＨＡ：２−エチルヘキシルアクリレート
Abbreviations in the table are as follows.
MEA: methoxyethyl acrylate ECA: ethoxydiethylene glycol acrylate 4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate AA: acrylic acid AM: acrylamide DM: dimethylaminoethyl methacrylate 2EHA: 2-ethylhexyl acrylate
実 施 例 １
製造例１で得られたアクリル系ポリマー溶液Ａ１の固形分１００重量部に対し、液体イオン塩として１−ヘキシル−４−メチルピリジニウムヘキサフルオロホスフェート１重量部と、イソシアネート架橋剤としてヘキサメチレンジイソシアネート（ＨＭＤＩ）３重量部とを加え、これを混合して、粘着剤組成物を得た。
Example 1
1 part by weight of 1-hexyl-4-methylpyridinium hexafluorophosphate as a liquid ionic salt and hexamethylene diisocyanate (HMDI) as an isocyanate crosslinking agent with respect to 100 parts by weight of the solid content of the acrylic polymer solution A1 obtained in Production Example 1. ) 3 parts by weight were added and mixed to obtain an adhesive composition.
この粘着剤組成物を、ポリエステルフィルム上に乾燥後の厚さが２０μｍになるように塗工し、８０℃で２分間乾燥させた後、粘着剤層側に剥離処理されたポリエステルフィルム（ＰＥＴ３８１１、リンテック社製）を貼り合わせ、２３℃、湿度６５％の条件下で７日間熟成させて粘着シートを得た。 The pressure-sensitive adhesive composition was coated on a polyester film so that the thickness after drying was 20 μm, dried at 80 ° C. for 2 minutes, and then peeled to the pressure-sensitive adhesive layer side (PET 3811, And aged for 7 days under conditions of 23 ° C. and 65% humidity to obtain an adhesive sheet.
実 施 例 ２ 〜 ３
アクリル系ポリマー溶液と液体イオン塩を下記表２のように代えた以外は実施例１と同様にして粘着剤組成物および粘着シートを得た。なお、液体イオン塩のカチオンとアニオンがそれぞれ有機又は無機のいずれであるか表２中に記載した。
Examples 2 to 3
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1 except that the acrylic polymer solution and the liquid ion salt were changed as shown in Table 2 below. Table 2 shows whether the cation and anion of the liquid ion salt are organic or inorganic.
比 較 例 １ 〜 １５
アクリルポリマー溶液とイオン性液体を下記表２のように代えた以外は実施例１と同様にして粘着剤組成物および粘着シートを得た。なお、イオン塩のカチオンとアニオンがそれぞれ有機又は無機のいずれであるか、またイオン塩の室温における状態を併記した。
Comparative Examples 1-15
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1 except that the acrylic polymer solution and the ionic liquid were changed as shown in Table 2 below. The cation and anion of the ionic salt are either organic or inorganic, and the state of the ionic salt at room temperature is also shown.
実施例１ないし３及び比較例１ないし１５で得られた粘着シートについて、下記評価方法及び基準によって、剥離力、帯電防止性について評価した。結果を表３に示す。 The pressure-sensitive adhesive sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 15 were evaluated for peel strength and antistatic properties by the following evaluation methods and standards. The results are shown in Table 3.
（評価方法及び基準）
＜剥離力＞
粘着シートを１５０ｍｍ×２５０ｍｍのサイズに裁断した後、剥離処理されたポリエステルフィルムを剥離し、ＡＧ偏光板、Ｐｌａｎｅ偏光板の片面にそれぞれ転写した。２３℃、６５％条件で１日放置した後、貼付した粘着シートを引き剥がし速度３００ｍｍ／ｍｉｎ（低速）、３０ｍ／ｍｉｎ（高速）で１８０°方向に剥離したときの粘着力を測定し、それぞれ低速剥離力、高速剥離力とした。
(Evaluation methods and standards)
<Peeling force>
After the pressure-sensitive adhesive sheet was cut into a size of 150 mm × 250 mm, the peeled polyester film was peeled off and transferred to one side of the AG polarizing plate and the Plane polarizing plate, respectively. After leaving at 23 ° C. and 65% for 1 day, the adhesive sheet was peeled off at a peeling speed of 300 mm / min (low speed) and 30 m / min (high speed) to measure the adhesive strength when peeled in the 180 ° direction. Low-speed peeling force and high-speed peeling force were used.
＜帯電防止性＞
（評価方法）
アクリル板（７０ｍｍ×１５０ｍｍ×１ｍｍ）と偏光板（ＡＧ偏光板、プレーン偏光板）とを、偏光板のＡＧ面、プレーン面が外側になるように貼り合わせた積層体を作成し除電器（ＫＥＹＥＮＣＥ社製 ＳＪ−Ｆ３００）により除電した。
上記実施例、比較例で得られた粘着シートを４０ｍｍ×１５０ｍｍに裁断した後、あらかじめ除電しておいた積層体のＡＧ面、プレーン面に２ｋｇゴムローラーを用いて圧着した。２５℃、６５％条件下で１日放置した後、再度除電を行い、引き剥がし速度３０ｍ／ｍｉｎ、剥離角度１８０°で剥離したときの偏光板表面電位を電位測定器（ＫＥＹＥＮＣＥ社製 ＳＫ）で測定した。
（評価基準）
評価 剥離帯電圧
○ ： ±０．５ｋＶ未満
△ ： ±０．５〜１．０ｋＶ
× ： ±１．０ｋＶ以上
<Antistatic property>
(Evaluation methods)
A laminate is prepared by bonding an acrylic plate (70 mm x 150 mm x 1 mm) and a polarizing plate (AG polarizing plate, plain polarizing plate) so that the AG surface and plain surface of the polarizing plate are on the outside, and a static eliminator (KEYENCE). The electricity was removed by SJ-F300 manufactured by the company.
The pressure-sensitive adhesive sheets obtained in the above Examples and Comparative Examples were cut into 40 mm × 150 mm, and then pressure-bonded using a 2 kg rubber roller to the AG surface and the plain surface of the laminate that had been previously neutralized. After leaving at 25 ° C. and 65% for 1 day, the charge was removed again, and the surface potential of the polarizing plate when peeled at a peeling speed of 30 m / min and a peeling angle of 180 ° was measured with a potential meter (SK manufactured by KEYENCE). It was measured.
(Evaluation criteria)
Evaluation Peeling voltage ○: Less than ± 0.5kV △: ± 0.5-1.0kV
×: ± 1.0 kV or more
※2 剥離時に粘着剤層で破壊が起こり、精確に測定できなかった。
* 2 When peeling, the adhesive layer was broken and could not be measured accurately.
この結果から明らかなように、本発明の粘着剤組成物を使用して製造した粘着テープは、帯電防止性に優れるとともに、高速剥離および低速剥離のいずれにおいても、ＡＧ偏光板とプレーン偏光板に対し同等の粘着力を示し、さらには、高速剥離における粘着力と低速剥離における粘着力の差も小さいものであった。 As is clear from this result, the pressure-sensitive adhesive tape produced using the pressure-sensitive adhesive composition of the present invention is excellent in antistatic properties, and can be used as an AG polarizing plate and a plain polarizing plate in both high-speed peeling and low-speed peeling. On the other hand, the adhesive strength was the same, and the difference between the adhesive strength at high speed peeling and the adhesive strength at low speed peeling was small.
これに対し、アクリル系ポリマーのモノマー組成やイオン塩が本発明のものと相違する比較例では、ＡＧ偏光板とプレーン偏光板とで粘着力の差が大きかったり、被着体への汚染が生じたりして十分な性能のものが得られなかった。例えば、前記特許文献１（特開２００６−６３３１１号公報）の実施例１に用いられるアクリル系ポリマーと同様のモノマー組成によるアクリル系ポリマーと、同じ有機カチオンと有機アニオンとからなる液体イオン塩を用いた比較例１５では、低速剥離、高速剥離のいずれにおいてもＡＧ偏光板とプレーン偏光板とに対する粘着力の差は大きく、また、低速剥離における粘着力と高速剥離における粘着力の差も実施例１ないし３と比較して大きいものであった。 On the other hand, in the comparative example in which the monomer composition and ionic salt of the acrylic polymer are different from those of the present invention, there is a large difference in adhesive force between the AG polarizing plate and the plain polarizing plate, or contamination of the adherend occurs. As a result, a product with sufficient performance could not be obtained. For example, an acrylic polymer having the same monomer composition as the acrylic polymer used in Example 1 of Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-63311), and a liquid ion salt composed of the same organic cation and organic anion are used. In Comparative Example 15, the difference in adhesive strength between the AG polarizing plate and the plain polarizing plate was large in both low-speed peeling and high-speed peeling, and the difference in adhesive strength in low-speed peeling and in high-speed peeling was also in Example 1. Or larger than 3.
本発明の粘着シートが、ＡＧ偏光板でもプレーン偏光板でも同等の粘着力を示す理由は明らかではないが、次のように考えられている。すなわち、ＡＧ偏光板は低極性で表面に凹凸があるのに対し、プレーン偏光板は高極性で平滑である。アルキレンオキサイド構造を有する（メタ）アクリル系モノマーやその他水酸基含有モノマーなどの官能基含有モノマーの含有量が多いほど成分（Ａ）の（メタ）アクリル系ポリマーは高極性となり、（メタ）アクリル系ポリマーの極性が高くなるほど、低極性のＡＧ偏光板に対する粘着力は低下し、高極性のプレーン偏光板に対する粘着力は増大する。 The reason why the pressure-sensitive adhesive sheet of the present invention exhibits the same pressure-sensitive adhesive strength for both AG polarizing plates and plain polarizing plates is not clear, but is considered as follows. That is, the AG polarizing plate is low in polarity and has irregularities on the surface, whereas the plain polarizing plate is high in polarity and smooth. The higher the content of the functional group-containing monomer such as a (meth) acrylic monomer having an alkylene oxide structure or other hydroxyl group-containing monomer, the higher the polarity of the (meth) acrylic polymer of the component (A), and the (meth) acrylic polymer The higher the polarity, the lower the adhesion to the low-polarity AG polarizing plate and the adhesion to the high-polarity plain polarizing plate.
一方、ＡＧ偏光板の表面の凹凸の隙間は小さいため、通常粘着剤は全面に付着するのではなく、凹部には接触していない。したがって、（メタ）アクリル系ポリマーのＡＧ偏光板とプレーン偏光板に対する親和性が同等の場合には、接触面積が少ない分、（メタ）アクリル系ポリマーとの粘着力はプレーン偏光板の方がＡＧ偏光板よりも大きくなる。 On the other hand, since the gap between the concaves and convexes on the surface of the AG polarizing plate is small, the pressure-sensitive adhesive does not usually adhere to the entire surface and does not contact the concave portions. Therefore, if the affinity of the (meth) acrylic polymer for the AG polarizing plate and that of the plain polarizing plate are the same, the adhesive strength with the (meth) acrylic polymer is smaller for the plain polarizing plate due to the smaller contact area. It becomes larger than the polarizing plate.
しかしながら、成分（Ｂ）の液体イオン塩のアクリル系ポリマーに対する相溶性が適度なものである（完全に相溶せず僅かに局在化が生じる）場合には、液体イオン塩がブリードすることなく粘着剤表面で僅かに局在化してＡＧ偏光板の凹凸面へ穴埋めするため粘着力が増大する。 However, when the compatibility of the liquid ion salt of the component (B) with the acrylic polymer is appropriate (not completely compatible and slightly localized), the liquid ion salt does not bleed. Adhesive strength increases because it is slightly localized on the surface of the adhesive and fills the concave and convex surfaces of the AG polarizing plate.
この液体イオン塩と（メタ）アクリル系ポリマーの相溶性は、液体イオン塩のカチオンとアニオンの組み合わせと（メタ）アクリル系ポリマー中のアルキレンオキサイド構造を有するモノマーの含有量に関係する。まず、液体イオン塩のイオン結合力は、カチオン／アニオンの組み合わせが、無機／無機、有機／無機、有機／有機の順で大きいため、高極性である成分（Ａ）の（メタ）アクリル系ポリマーへの相溶性は、有機／有機、有機／無機、無機／無機の順で高くなる。一方、アルキレンオキサイド構造を有するモノマーの含有量が多いほど極性が高くなり液体イオン塩に対する相溶性が高くなる。 The compatibility of the liquid ionic salt and the (meth) acrylic polymer is related to the combination of the cation and anion of the liquid ionic salt and the content of the monomer having an alkylene oxide structure in the (meth) acrylic polymer. First, the ionic / bonding strength of the liquid ion salt is such that the combination of cation / anion is large in the order of inorganic / inorganic, organic / inorganic, and organic / organic, so the (meth) acrylic polymer of component (A) that is highly polar The compatibility in the order of organic / organic, organic / inorganic, and inorganic / inorganic increases. On the other hand, the higher the content of the monomer having an alkylene oxide structure, the higher the polarity and the higher the compatibility with the liquid ion salt.
そこで、液体イオン塩として、有機カチオンと無機アニオンの組み合わせを選択し、（メタ）アクリル系ポリマー中のアルキレンオキサイド構造を有するモノマーの含有量を１０〜７０質量％とすることによって、その相溶性が高すぎることなく適度なものとなって、上記凹凸面への穴埋め効果が得られ、ＡＧ偏光板、プレーン偏光板の表面形状、極性の違いに拘わらず同様の粘着力を有する粘着剤組成物が得られるのである。これに対し、アルキレンオキサイド構造を有するモノマーを７０質量％以上含有した場合や、液体イオン塩として有機カチオンと有機アニオンとの組み合わせを用いた場合には、粘着剤組成物の極性が高くなるため、表面の極性の低いＡＧ偏光板との密着性が悪くなったり、また、アクリル系ポリマーと液体イオン塩との相溶性が高くイオン塩の局在化が起こらない為、ＡＧ偏光板に対する粘着力は低いままとなってしまうのである。 Therefore, by selecting a combination of an organic cation and an inorganic anion as the liquid ion salt and setting the content of the monomer having an alkylene oxide structure in the (meth) acrylic polymer to 10 to 70% by mass, the compatibility is improved. The pressure-sensitive adhesive composition is suitable without being too high, has a filling effect on the uneven surface, and has the same adhesive force regardless of the surface shape and polarity of the AG polarizing plate and the plain polarizing plate. It is obtained. On the other hand, when the monomer having an alkylene oxide structure is contained by 70% by mass or more, or when a combination of an organic cation and an organic anion is used as the liquid ion salt, the polarity of the pressure-sensitive adhesive composition is increased. The adhesion to the AG polarizing plate is low because the adhesion to the AG polarizing plate with low surface polarity is poor, and the compatibility between the acrylic polymer and the liquid ionic salt is high and the ionic salt is not localized. It will remain low.
このように、ＡＧ偏光板に対しては、（メタ）アクリル系ポリマーの極性を低下させることによって、また、穴埋め効果の高い有機カチオンと無機アニオンの組み合わせの液体イオン塩を選択することによって粘着力は増大し、一方、プレーン偏光板に対しては、（メタ）アクリル系ポリマーの極性を高くすると粘着力が増大するが、本願発明では、この（メタ）アクリル系ポリマーの極性と穴埋め効果の両方を調整することによって、表面状態の異なる偏光板に対して同等の粘着力を発揮する粘着剤組成物を得ることができるのである。 Thus, for the AG polarizing plate, the adhesive strength is reduced by reducing the polarity of the (meth) acrylic polymer, and by selecting a liquid ion salt of a combination of an organic cation and an inorganic anion that has a high filling effect. On the other hand, for a plain polarizing plate, the adhesive strength increases when the polarity of the (meth) acrylic polymer is increased. In the present invention, both the polarity of this (meth) acrylic polymer and the hole filling effect are obtained. By adjusting the pressure-sensitive adhesive composition, it is possible to obtain a pressure-sensitive adhesive composition that exhibits the same adhesive strength to polarizing plates having different surface states.
本発明の粘着剤組成物は、帯電防止効果に優れるとともに、低速、高速剥離のいずれにおいても、被着体表面の形状及び極性の相違による粘着力の差が小さく、かつ、剥離速度による粘着力の差も小さいため、機械的特性に優れ作業効率を向上できるものである。 The pressure-sensitive adhesive composition of the present invention is excellent in the antistatic effect, has a small difference in adhesive force due to the difference in shape and polarity of the adherend surface in both low speed and high speed peeling, and adhesive strength due to the peeling speed. Since the difference is small, the mechanical efficiency is excellent and the working efficiency can be improved.
したがって、本発明の粘着剤組成物を用いた粘着シートは、偏光板などの光学部材の表面保護用粘着シートとして、有利に用いられるものである。
以 上
Therefore, the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition of the present invention is advantageously used as a surface-protective pressure-sensitive adhesive sheet for optical members such as polarizing plates.
that's all
Claims (5)
（Ａ）次の成分（ａ１）ないし（ａ４）を共重合することにより得られる（メタ）アク
リル系ポリマー（但し、（ａ１）〜（ａ４）の合計が１００質量％）
（ａ１）アルキレンオキサイド構造を有する（メタ）アクリル系モノマー
１０〜７０質量％
（ａ２）水酸基含有モノマー １〜 ８質量％
（ａ３）カルボキシル基、アミド基、又はアミノ基のいずれかの官能基を含有するモ
ノマー ０．０５〜０．５質量％
（ａ４）（メタ）アクリル酸アルキルエステル ２５〜８５質量％
（Ｂ）有機カチオンおよび無機アニオンとからなる液体イオン塩
（Ｃ）イソシアネート架橋剤
を含有することを特徴とする粘着剤組成物。 Next component (A) thru | or (C)
(A) (Meth) acrylic polymer obtained by copolymerizing the following components (a1) to (a4) (however, the total of (a1) to (a4) is 100% by mass)
(A1) A (meth) acrylic monomer having an alkylene oxide structure
10-70% by mass
(A2) Hydroxyl group-containing monomer 1 to 8% by mass
(A3) A module containing any functional group of a carboxyl group, an amide group, or an amino group
Nomer 0.05-0.5% by mass
(A4) (meth) acrylic acid alkyl ester 25-85 mass%
(B) Liquid ion salt comprising an organic cation and an inorganic anion
(C) A pressure-sensitive adhesive composition containing an isocyanate crosslinking agent.
A pressure-sensitive adhesive sheet obtained by crosslinking the pressure-sensitive adhesive composition according to claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006249061A JP4942171B2 (en) | 2006-09-14 | 2006-09-14 | Adhesive composition and adhesive sheet |
| KR1020097005446A KR101092952B1 (en) | 2006-09-14 | 2007-09-13 | Adhesive composition and adhesive sheet |
| PCT/JP2007/067790 WO2008032762A1 (en) | 2006-09-14 | 2007-09-13 | Adhesive composition and adhesive sheet |
| CN2007800341574A CN101553548B (en) | 2006-09-14 | 2007-09-13 | Adhesive composition and adhesive sheet |
| TW096134536A TWI458796B (en) | 2006-09-14 | 2007-09-14 | Adhesive composition and adhesive sheet |
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|---|---|---|---|
| JP2006249061A JP4942171B2 (en) | 2006-09-14 | 2006-09-14 | Adhesive composition and adhesive sheet |
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| JP2008069261A JP2008069261A (en) | 2008-03-27 |
| JP4942171B2 true JP4942171B2 (en) | 2012-05-30 |
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| JP (1) | JP4942171B2 (en) |
| KR (1) | KR101092952B1 (en) |
| CN (1) | CN101553548B (en) |
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| WO (1) | WO2008032762A1 (en) |
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| JP4096209B2 (en) * | 1996-02-02 | 2008-06-04 | 綜研化学株式会社 | Adhesive composition and surface protective film formed by applying the same |
| JP2000129235A (en) * | 1998-10-27 | 2000-05-09 | Minnesota Mining & Mfg Co <3M> | Antistatic pressure-sensitive adhesive composition |
| JP2001146581A (en) * | 1999-11-19 | 2001-05-29 | Nippon Nsc Ltd | Water-redispersible pressure-sensitive adhesive emulsion composition and pressure-sensitive adhesive article obtained by using the same |
| ATE286936T1 (en) * | 2001-08-02 | 2005-01-15 | 3M Innovative Properties Co | OPTICALLY CLEAR AND ANTISTATIC ADHESIVES |
| JP5422091B2 (en) * | 2003-12-26 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Antistatic acrylic adhesive |
| JP2005314579A (en) * | 2004-04-30 | 2005-11-10 | Nitto Denko Corp | Adhesive composition and adhesive sheets |
| JP5030251B2 (en) * | 2004-07-26 | 2012-09-19 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
| TWI387629B (en) * | 2004-07-26 | 2013-03-01 | Nitto Denko Corp | Pressure sensitive adhesive composition, pressure sensitive adhesive sheet and surface protective film |
| JP4917267B2 (en) * | 2004-09-16 | 2012-04-18 | 日東電工株式会社 | Adhesive composition, adhesive sheet, and surface protective film |
| JP2007002112A (en) * | 2005-06-24 | 2007-01-11 | Toyo Ink Mfg Co Ltd | Method for decreasing surface resistance value of insulation substrate |
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| KR101092952B1 (en) | 2011-12-12 |
| CN101553548B (en) | 2011-07-27 |
| TW200829668A (en) | 2008-07-16 |
| KR20090055576A (en) | 2009-06-02 |
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| TWI458796B (en) | 2014-11-01 |
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