JPWO2019194047A1 - Copolymerized Polymers, Adhesive Compositions, and Optical Components Containing them - Google Patents
Copolymerized Polymers, Adhesive Compositions, and Optical Components Containing them Download PDFInfo
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- JPWO2019194047A1 JPWO2019194047A1 JP2020511718A JP2020511718A JPWO2019194047A1 JP WO2019194047 A1 JPWO2019194047 A1 JP WO2019194047A1 JP 2020511718 A JP2020511718 A JP 2020511718A JP 2020511718 A JP2020511718 A JP 2020511718A JP WO2019194047 A1 JPWO2019194047 A1 JP WO2019194047A1
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- Prior art keywords
- monomer
- meth
- sensitive adhesive
- copolymerized polymer
- weight
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 230000003287 optical effect Effects 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 title claims description 30
- 239000000853 adhesive Substances 0.000 title description 21
- 230000001070 adhesive effect Effects 0.000 title description 21
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 abstract 1
- -1 3,4-dihydroxyphenyl Chemical group 0.000 description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 238000001723 curing Methods 0.000 description 23
- 239000010410 layer Substances 0.000 description 18
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 15
- 239000012790 adhesive layer Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229960003638 dopamine Drugs 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 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 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- FBTSUTGMWBDAAC-UHFFFAOYSA-N 3,4-Dihydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1O FBTSUTGMWBDAAC-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- NVPXEWPKAICFCQ-UHFFFAOYSA-N ethyl acetate;titanium Chemical compound [Ti].CCOC(C)=O NVPXEWPKAICFCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012788 optical film Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MMEJYPZZFYTVLJ-WAYWQWQTSA-N (z)-2-(2-prop-2-enoyloxyethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCOC(=O)C=C MMEJYPZZFYTVLJ-WAYWQWQTSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- PWMLMBQHHBLIQM-UHFFFAOYSA-N 1-(3-prop-2-enoyloxypropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCCOC(=O)C=C)C(O)=O PWMLMBQHHBLIQM-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- YDRQKFSCVSLQKI-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1(CCOC(=O)C=C)C(O)=O YDRQKFSCVSLQKI-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
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- ZWZSYZJMMCLLGF-UHFFFAOYSA-N 4-(2-methylprop-2-enyl)benzene-1,2-diol Chemical compound CC(=C)CC1=CC=C(O)C(O)=C1 ZWZSYZJMMCLLGF-UHFFFAOYSA-N 0.000 description 1
- NEYLBGHJWMKEJO-UHFFFAOYSA-N 4-(3-methylbut-3-enyl)benzene-1,2-diol Chemical compound CC(=C)CCC1=CC=C(O)C(O)=C1 NEYLBGHJWMKEJO-UHFFFAOYSA-N 0.000 description 1
- PXZVPBVQUZCKHM-UHFFFAOYSA-N 4-(7-methyloct-7-enyl)benzene-1,2-diol Chemical compound OC=1C=C(C=CC=1O)CCCCCCC(=C)C PXZVPBVQUZCKHM-UHFFFAOYSA-N 0.000 description 1
- HCUVEECYVSXERA-UHFFFAOYSA-N 4-but-3-enylbenzene-1,2-diol Chemical compound Oc1ccc(CCC=C)cc1O HCUVEECYVSXERA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FHEHIXJLCWUPCZ-UHFFFAOYSA-N 4-prop-2-enylbenzene-1,2-diol Chemical compound OC1=CC=C(CC=C)C=C1O FHEHIXJLCWUPCZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PBHKZGYWHVXIRY-UHFFFAOYSA-K aluminum 2,2-diacetyl-3-oxobutanoate Chemical compound [Al+3].CC(=O)C(C(C)=O)(C(C)=O)C([O-])=O.CC(=O)C(C(C)=O)(C(C)=O)C([O-])=O.CC(=O)C(C(C)=O)(C(C)=O)C([O-])=O PBHKZGYWHVXIRY-UHFFFAOYSA-K 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- BCTOVGWZAFCYBA-UHFFFAOYSA-N dodecyl benzenesulfonate titanium Chemical compound [Ti].C1(=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCC BCTOVGWZAFCYBA-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-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
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000010069 protein adhesion Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
-
- 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
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C09J157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
構成要素として、下記式（１）で表されるカテコール基を有するモノマーＡ及びモノマーＡと共重合可能なモノマーＢ、を含む共重合ポリマー：（式中、Ｒ１〜Ｒ４は水素原子又は炭素数１〜２０のアルキル基を表す。Ｙはアミド結合又はエステル結合を表すが直接結合であってもよい。ｎは０又は１〜１０の整数を表す）。A copolymerized polymer containing a monomer A having a catechol group represented by the following formula (1) and a monomer B copolymerizable with the monomer A as constituent elements: (In the formula, R1 to R4 are hydrogen atoms or carbon atoms 1). Represents an alkyl group of ~ 20; Y represents an amide or ester bond but may be a direct bond; n represents an integer of 0 or 1-10).
Description
本発明は、カテコール基を含む共重合ポリマーに関する。より詳細には、偏光板、位相差板等の光学部材に用いられる粘着剤として有用な共重合ポリマー、粘着剤組成物及びそれを含む光学部材に関する。 The present invention relates to a copolymerized polymer containing a catechol group. More specifically, the present invention relates to a copolymerized polymer useful as an adhesive used for an optical member such as a polarizing plate and a retardation plate, an adhesive composition, and an optical member containing the same.
カテコール基は多様な材料表面に強固な接着性を発現する。近年、その物性を利用して、様々な応用が盛んに研究されている。例えば、非特許文献１にはドーパミンのアミノ基部分に開始剤を導入し、ポリエチレングリコール鎖をグラフトすることにより、タンパク質の接着を抑制できることが開示されている。非特許文献２にはドーパミンメタアクリルアミド（以下、ＤＭＡと略記する）モノマーと疎水性モノマーとのフリーラジカル重合による、カテコール基含有両親媒性ランダム共重合体の合成方法が開示されている。 Catechol groups exhibit strong adhesiveness on various material surfaces. In recent years, various applications have been actively studied by utilizing its physical characteristics. For example, Non-Patent Document 1 discloses that protein adhesion can be suppressed by introducing an initiator into the amino group portion of dopamine and grafting a polyethylene glycol chain. Non-Patent Document 2 discloses a method for synthesizing a catechol group-containing amphipathic random copolymer by free radical polymerization of a dopamine metaacrylamide (hereinafter abbreviated as DMA) monomer and a hydrophobic monomer.
また、特許文献１には、水溶性主鎖モノマー、架橋剤、重合開始剤、及び側鎖にカテコール基を有する接着性モノマー、を構成要素とする接着性ハイドロゲルが医療用接着剤、生体用接着剤に有用であることが開示されている。特許文献２には、カテコールセグメントを含むブロック共重合体が無機ナノ粒子の分散剤として有用であることが開示されている。 Further, in Patent Document 1, an adhesive hydrogel containing a water-soluble main chain monomer, a cross-linking agent, a polymerization initiator, and an adhesive monomer having a catechol group in the side chain as constituent elements is used as a medical adhesive and for living organisms. It has been disclosed that it is useful for adhesives. Patent Document 2 discloses that a block copolymer containing a catechol segment is useful as a dispersant for inorganic nanoparticles.
しかしながら、特許文献１に記載のハイドロゲルは水を内部に含んでおり、光学フィルムの粘接着剤には適さない。またウェットコーティングなどの加工性に劣る。特許文献２に記載のポリマーは分子量１０万程度の共重合ポリマーであり、分散剤としての使用は可能であるが、光学フィルムの粘接着剤には適さない。
一方、現在、一般に偏光板は、延伸配向したポリビニルアルコール（以下、ＰＶＡと略記する）又はその誘導体のフィルムに、ヨウ素や二色性染料を含有させて偏光素子とし、少なくともその片面に酢酸セルロース系フィルム（以下、ＴＡＣと略記する）等の保護フィルムを積層して製造される。前記積層にはＰＶＡ樹脂を含む水溶液が接着剤として用いられる。偏光板の利用に際しては、例えば、この偏光板を液晶セルのガラス板表面に感圧性接着剤層を介して貼り合わせて液晶表示装置が製造される。
そこで、本発明の目的は、接着力に優れる共重合ポリマー、粘着剤組成物、及びそれを含む光学部材を提供することにある。However, the hydrogel described in Patent Document 1 contains water inside and is not suitable as an adhesive for an optical film. Moreover, it is inferior in processability such as wet coating. The polymer described in Patent Document 2 is a copolymer polymer having a molecular weight of about 100,000, and although it can be used as a dispersant, it is not suitable as an adhesive for an optical film.
On the other hand, at present, in general, a polarizing plate is made into a polarizing element by adding iodine or a dichroic dye to a film of stretch-oriented polyvinyl alcohol (hereinafter abbreviated as PVA) or a derivative thereof, and at least one side thereof is based on cellulose acetate. It is manufactured by laminating a protective film such as a film (hereinafter abbreviated as TAC). An aqueous solution containing PVA resin is used as an adhesive for the lamination. When using a polarizing plate, for example, a liquid crystal display device is manufactured by bonding this polarizing plate to the surface of a glass plate of a liquid crystal cell via a pressure-sensitive adhesive layer.
Therefore, an object of the present invention is to provide a copolymerized polymer having excellent adhesive strength, a pressure-sensitive adhesive composition, and an optical member containing the same.
上記目的は、下記の［１］〜［９］に記載の本発明により達成される。
すなわち、本発明は以下に関する。
［発明１］構成要素として、下記式（１）で表されるカテコール基を有するモノマーＡと、モノマーＡと共重合可能なモノマーＢ、を含む共重合ポリマー：
（式中、Ｒ１〜Ｒ４は水素原子又は炭素数１〜２０のアルキル基を表し、Ｙはアミド結合、エステル結合、又は直接結合を表し、ｎは０又は１〜１０の整数を表す）。
［発明２］モノマーＢが炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルのモノマー、ヒドロキシル基を有する（メタ）アクリル酸アルキルエステルのモノマー、及びカルボキシル基を有する（メタ）アクリル酸アルキルエステルのモノマーからなる群から選択される少なくとも１種を含む発明１に記載の共重合ポリマー。
［発明３］モノマーＢが炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルのモノマーの少なくとも１種、及びカルボキシル基又はヒドロキシル基を有する（メタ）アクリル酸アルキルエステルのモノマーの少なくとも１種を含む発明１に記載の共重合ポリマー。
［発明４］前記炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルの含有量が全モノマー中の６０〜９９．９９重量％である発明２又は３に記載の共重合ポリマー。
［発明５］前記ヒドロキシル基又はカルボキシル基を有する（メタ）アクリル酸アルキルエステルの含有量が全モノマー中の０〜１０重量％（０重量％を含まず）である発明２乃至４のいずれか一項に記載の共重合ポリマー。
［発明６］重量平均分子量（Ｍｗ）が３０万〜２００万である発明１乃至５ のいずれか一項に記載の共重合ポリマー。
［発明７］モノマーＡの含有量が全モノマー中の０．０１〜２０重量％である発明１乃至６のいずれか一項に記載の共重合ポリマー。
［発明８］発明１乃至７のいずれか一項に記載の共重合ポリマーと硬化剤を含む粘着剤組成物。
［発明９］さらに添加剤を含有する発明８に記載の粘着剤組成物。
［発明１０］発明８又は９に記載の粘着剤組成物を含む光学部材。The above object is achieved by the present invention described in the following [1] to [9].
That is, the present invention relates to the following.
[Invention 1] A copolymerized polymer containing a monomer A having a catechol group represented by the following formula (1) and a monomer B copolymerizable with the monomer A as constituent elements:
(In the formula, R 1 to R 4 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, Y represents an amide bond, an ester bond, or a direct bond, and n represents an integer of 0 or 1 to 10). ..
[Invention 2] A monomer of a (meth) acrylic acid alkyl ester in which monomer B has an alkyl group having 1 to 20 carbon atoms, a monomer of a (meth) acrylic acid alkyl ester having a hydroxyl group, and a (meth) acrylic having a carboxyl group. The copolymerized polymer according to Invention 1, which comprises at least one selected from the group consisting of monomers of an acid alkyl ester.
[Invention 3] At least one monomer of a (meth) acrylic acid alkyl ester in which monomer B has an alkyl group having 1 to 20 carbon atoms, and at least one of a (meth) acrylic acid alkyl ester monomer having a carboxyl group or a hydroxyl group. The copolymerized polymer according to Invention 1, which comprises one type.
[Invention 4] The copolymerized polymer according to Invention 2 or 3, wherein the content of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is 60 to 99.99% by weight in all the monomers.
[Invention 5] Any one of Inventions 2 to 4, wherein the content of the (meth) acrylic acid alkyl ester having a hydroxyl group or a carboxyl group is 0 to 10% by weight (not including 0% by weight) in all the monomers. The copolymerized polymer according to the section.
[Invention 6] The copolymerized polymer according to any one of Inventions 1 to 5, which has a weight average molecular weight (Mw) of 300,000 to 2,000,000.
[Invention 7] The copolymerized polymer according to any one of Inventions 1 to 6, wherein the content of the monomer A is 0.01 to 20% by weight in all the monomers.
[Invention 8] A pressure-sensitive adhesive composition containing the copolymerization polymer according to any one of Inventions 1 to 7 and a curing agent.
[Invention 9] The pressure-sensitive adhesive composition according to Invention 8, further containing an additive.
[Invention 10] An optical member containing the pressure-sensitive adhesive composition according to Invention 8 or 9.
本発明によれば、ガラス等の無機材料、ＴＡＣ、アクリル、ポリカーボネート（以下、ＰＣと略記する）、シクロオレフィンポリマー（以下、ＣＯＰと略記する）等の有機材料などの基材に対する接着力に優れる共重合ポリマー、粘着剤組成物及びそれを含む光学部材を提供することができる。 According to the present invention, the adhesive strength to a base material such as an inorganic material such as glass, an organic material such as TAC, acrylic, polycarbonate (hereinafter abbreviated as PC), and a cycloolefin polymer (hereinafter abbreviated as COP) is excellent. Copolymerized polymers, pressure-sensitive adhesive compositions and optical members containing them can be provided.
本発明の共重合ポリマーは、構成要素として、下記式（１）で表されるカテコール基を有するモノマーＡ及びモノマーＡと共重合可能なモノマーＢ、を含む。
前記一般式（１）中、Ｒ１〜Ｒ４は水素原子又は炭素数１〜２０のアルキル基を表し、Ｒ１〜Ｒ３は好ましくは水素であり、Ｒ４は好ましくは水素又はメチル基である。Ｙは、アミド結合又はエステル結合を表すが、直接結合であってもよい。ｎは０又は１〜１０の整数を表し、好ましくは０又は１〜５の整数であり、より好ましくは０又は１〜３の整数であり、さらに好ましくは２である。In the general formula (1), R 1 to R 4 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 1 to R 3 are preferably hydrogen, and R 4 is preferably a hydrogen or methyl group. is there. Y represents an amide bond or an ester bond, but may be a direct bond. n represents an integer of 0 or 1 to 10, preferably an integer of 0 or 1 to 5, more preferably an integer of 0 or 1 to 3, and even more preferably 2.
Ｙがアミド結合の場合、好ましくはモノマーＡは（メタ）アクリルアミドである。その例として、Ｎ−［２−（３，４−ジヒドロキシフェニル）メチル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）エチル］（メタ）アクリルアミド（以下で「ドーパミン（メタ）アクリルアミド」ということがあり、単にＤＭＡと略記することがある。）、Ｎ−［２−（３，４−ジヒドロキシフェニル）プロピル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）ブチル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）ペンチル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）ヘキシル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）ヘプチル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）オクチル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）ノニル］（メタ）アクリルアミド、Ｎ−［２−（３，４−ジヒドロキシフェニル）デシル］（メタ）アクリルアミドなどが挙げられる。 When Y is an amide bond, the monomer A is preferably (meth) acrylamide. Examples are N- [2- (3,4-dihydroxyphenyl) methyl] (meth) acrylamide, N- [2- (3,4-dihydroxyphenyl) ethyl] (meth) acrylamide (hereinafter referred to as "dopamine (meth)". ) Acrylamide, sometimes simply abbreviated as DMA), N- [2- (3,4-dihydroxyphenyl) propyl] (meth) acrylamide, N- [2- (3,4-dihydroxy) Phenyl) butyl] (meth) acrylamide, N- [2- (3,4-dihydroxyphenyl) pentyl] (meth) acrylamide, N- [2- (3,4-dihydroxyphenyl) hexyl] (meth) acrylamide, N -[2- (3,4-dihydroxyphenyl) heptyl] (meth) acrylamide, N- [2- (3,4-dihydroxyphenyl) octyl] (meth) acrylamide, N- [2- (3,4-dihydroxyphenyl) heptyl] Phenyl) nonyl] (meth) acrylamide, N- [2- (3,4-dihydroxyphenyl) decyl] (meth) acrylamide and the like can be mentioned.
また、Ｙがエステル結合の場合、好ましくはモノマーＡは（メタ）アクリル酸エステルである。その例として、Ｎ−［２−（３，４−ジヒドロキシフェニル）メチル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）エチル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）プロピル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）ブチル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）ペンチル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）ヘキシル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）ヘプチル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）オクチル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）ノニル］（メタ）アクリレート、Ｎ−［２−（３，４−ジヒドロキシフェニル）デシル］（メタ）アクリレートなどが挙げられる。 When Y is an ester bond, the monomer A is preferably a (meth) acrylic acid ester. Examples are N- [2- (3,4-dihydroxyphenyl) methyl] (meth) acrylate, N- [2- (3,4-dihydroxyphenyl) ethyl] (meth) acrylate, N- [2- ( 3,4-Dihydroxyphenyl) propyl] (meth) acrylate, N- [2- (3,4-dihydroxyphenyl) butyl] (meth) acrylate, N- [2- (3,4-dihydroxyphenyl) pentyl] ( Meta) acrylate, N- [2- (3,4-dihydroxyphenyl) hexyl] (meth) acrylate, N- [2- (3,4-dihydroxyphenyl) heptyl] (meth) acrylate, N- [2-( 3,4-Dihydroxyphenyl) octyl] (meth) acrylate, N- [2- (3,4-dihydroxyphenyl) nonyl] (meth) acrylate, N- [2- (3,4-dihydroxyphenyl) decyl] ( Meta) acrylate and the like can be mentioned.
また、Ｙが含まれない場合、３，４−ジヒドロキシスチレン、３−（３，４−ジヒドロキシフェニル）−１−プロペン、４−（３，４−ジヒドロキシフェニル）−１−ブテン、５−（３，４−ジヒドロキシフェニル）−１−ペンテン、６−（３，４−ジヒドロキシフェニル）−１−ヘキセン、７−（３，４−ジヒドロキシフェニル）−１−ヘプテン、８−（３，４−ジヒドロキシフェニル）−１−オクテン、９−（３，４−ジヒドロキシフェニル）−１−ノネン、１０−（３，４−ジヒドロキシフェニル）−１−デセン、３−（３，４−ジヒドロキシフェニル）−２−メチル−１−プロペン、４−（３，４−ジヒドロキシフェニル）−２−メチル−１−ブテン、５−（３，４−ジヒドロキシフェニル）−２−メチル−１−ペンテン、６−（３，４−ジヒドロキシフェニル）−２−メチル−１−ヘキセン、７−（３，４−ジヒドロキシフェニル）−２メチル−１−ヘプテン、８−（３，４−ジヒドロキシフェニル）−２メチル−１−オクテン、９−（３，４−ジヒドロキシフェニル）−２メチル−１−ノネン、１０−（３，４−ジヒドロキシフェニル）−２メチル−１−デセンなどが挙げられる。 When Y is not contained, 3,4-dihydroxystyrene, 3- (3,4-dihydroxyphenyl) -1-propene, 4- (3,4-dihydroxyphenyl) -1-butene, 5- (3) , 4-Dihydroxyphenyl) -1-pentene, 6- (3,4-dihydroxyphenyl) -1-hexene, 7- (3,4-dihydroxyphenyl) -1-heptene, 8- (3,4-dihydroxyphenyl) ) -1-octene, 9- (3,4-dihydroxyphenyl) -1-nonene, 10- (3,4-dihydroxyphenyl) -1-decene, 3- (3,4-dihydroxyphenyl) -2-methyl -1-Propene, 4- (3,4-dihydroxyphenyl) -2-methyl-1-butene, 5- (3,4-dihydroxyphenyl) -2-methyl-1-pentene, 6- (3,4-) Dihydroxyphenyl) -2-methyl-1-hexene, 7- (3,4-dihydroxyphenyl) -2methyl-1-heptene, 8- (3,4-dihydroxyphenyl) -2methyl-1-octene, 9- Examples thereof include (3,4-dihydroxyphenyl) -2methyl-1-nonene, 10- (3,4-dihydroxyphenyl) -2methyl-1-decene and the like.
本発明の共重合ポリマーを用いた粘着剤組成物の接着性は、共重合ポリマーに含有されるカテコール基の数に比例する。したがって、強固な接着性を要する場合には、側鎖にモノマーＡの量を増加させればよい。すなわち該モノマーの量を調節することによって、所望の接着強度を得ることができる。 The adhesiveness of the pressure-sensitive adhesive composition using the copolymerized polymer of the present invention is proportional to the number of catechol groups contained in the copolymerized polymer. Therefore, if strong adhesiveness is required, the amount of monomer A in the side chain may be increased. That is, the desired adhesive strength can be obtained by adjusting the amount of the monomer.
モノマーＡとしては、ドーパ（３，４−ジヒドロキシフェニルアラニン）又はその誘導体に由来するものが、性能や製造の容易さの点で好ましく、容易に入手可能な点で、ドーパに由来するものがより好ましい。ここでいうドーパ又はその誘導体に由来するものとは、上記一般式（１）で表わされるもののうち、ｎ＝２で表わされるものをいう。好ましくは製造のしやすさから前記モノマーはドーパに由来するものであり、具体的にはドーパから合成することができるものであり、より好ましくはドーパミン（メタ）アクリルアミド、ドーパミン（メタ）アクリレートであり、製造のしやすさからドーパミン（メタ）アクリルアミドが更に好ましい。 As the monomer A, those derived from dopa (3,4-dihydroxyphenylalanine) or a derivative thereof are preferable in terms of performance and ease of production, and those derived from dopa are more preferable in terms of being easily available. .. The term "derived from dopa or a derivative thereof" as used herein refers to a substance represented by the above general formula (1), which is represented by n = 2. Preferably, the monomer is derived from dopamine because of ease of production, and specifically, it can be synthesized from dopamine, and more preferably dopamine (meth) acrylamide and dopamine (meth) acrylate. , Dopamine (meth) acrylamide is more preferable from the viewpoint of ease of production.
モノマーＡは、非特許文献２に記載の方法によって製造することができる。具体的には、無水メタクリル酸及びドーパミン塩酸塩からモノマーＡを作製することが可能である。 Monomer A can be produced by the method described in Non-Patent Document 2. Specifically, it is possible to prepare the monomer A from methacrylic anhydride and dopamine hydrochloride.
モノマーＡの含有量は、全モノマー中の０．０１〜２０重量％が好ましく、０．０１〜１０重量％がより好ましく、１〜７重量％がさらに好ましい。 The content of the monomer A is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, still more preferably 1 to 7% by weight in all the monomers.
本発明で用いられる、モノマーＡと共重合可能なモノマーＢとしては、後記する硬化剤と反応して架橋点などとして機能するものが用いられ、その種類について特に限定はない。例えば、炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルのモノマー、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマーを用いることができる。 As the monomer B copolymerizable with the monomer A used in the present invention, a monomer B that reacts with a curing agent described later and functions as a cross-linking point or the like is used, and the type thereof is not particularly limited. For example, a monomer of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms, a monomer having a hydroxyl group, and a monomer having a carboxyl group can be used.
モノマーＢとしては、優れた粘着性が得られることから、炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルのモノマーの少なくとも１種、及びヒドロキシル基又はカルボキシル基を有するモノマーの少なくとも１種を用いることが好ましい。 As the monomer B, at least one of the (meth) acrylic acid alkyl ester monomers having an alkyl group having 1 to 20 carbon atoms and at least one of the monomers having a hydroxyl group or a carboxyl group can obtain excellent adhesiveness. It is preferable to use one type.
炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルモノマーの具体例としては、ｎ−ブチル（メタ）アクリレート、ｓ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、へキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、ｎ−トリデシル（メタ）アクリレート、ｎ−テトラデシル（メタ）アクリレートなどが挙げられる。炭素数は４〜１２が好ましい。炭素数４〜１２のアルキル基を有する（メタ）アクリル酸アルキルエステルモノマーを用いることにより、被着体への粘着力を制御することが容易となり、再剥離性に優れたものが得られやすくなる。 Specific examples of the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 20 carbon atoms include n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (. Meta) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl Examples thereof include (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate. The number of carbon atoms is preferably 4 to 12. By using a (meth) acrylic acid alkyl ester monomer having an alkyl group having 4 to 12 carbon atoms, it becomes easy to control the adhesive force to the adherend, and it becomes easy to obtain a product having excellent removability. ..
前記炭素数１〜２０のアルキル基を有する（メタ）アクリル酸アルキルエステルモノマーが含有される場合、その含有量は、全モノマー中の６０〜９９．９９重量％が好ましく、８３〜９９重量％がより好ましい。前記範囲内にあると、粘着剤組成物の濡れ性と凝集力のバランスを制御しやすくなる。 When the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 20 carbon atoms is contained, the content thereof is preferably 60 to 99.99% by weight, preferably 83 to 99% by weight, based on the total monomer. More preferred. When it is within the above range, it becomes easy to control the balance between the wettability and the cohesive force of the pressure-sensitive adhesive composition.
モノマーＢとして、ヒドロキシル基を有するモノマーを含有することが好ましい。ヒドロキシル基含有モノマーを用いることにより、粘着剤組成物の架橋などを制御しやすくなり、ひいては流動による濡れ性の改善と剥離における粘着（接着）力の低減とのバランスを制御しやすくなる。さらに、ヒドロキシル基は、帯電防止剤として使用できるイオン性化合物及びオキシアルキレン鎖を有するオルガノポリシロキサンと適度な相互作用を有するため、帯電防止性の面においても好適に用いることができる。 As the monomer B, it is preferable to contain a monomer having a hydroxyl group. By using the hydroxyl group-containing monomer, it becomes easy to control the cross-linking of the pressure-sensitive adhesive composition, and it becomes easy to control the balance between the improvement of the wettability due to the flow and the reduction of the adhesive (adhesive) force in the peeling. Further, since the hydroxyl group has an appropriate interaction with an ionic compound that can be used as an antistatic agent and an organopolysiloxane having an oxyalkylene chain, it can be suitably used in terms of antistatic properties.
前記ヒドロキシル基を有するモノマーとしては、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、４−ヒドロキシブチル（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、８−ヒドロキシオクチル（メタ）アクリレート、１０−ヒドロキシデシル（メタ）アクリレート、１２−ヒドロキシラウリル（メタ）アクリレート、（４−ヒドロキシメチルシクロヘキシル）メチルアクリレート、Ｎ−メチロール（メタ）アクリルアミドなどが挙げられる。 Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxy. Examples thereof include octyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, and N-methylol (meth) acrylamide.
前記ヒドロキシル基を有するモノマーが含有される場合、その含有量は、全モノマー中の０〜１０重量％（０重量％を含まず）が好ましく、０．５〜５重量％がより好ましい。前記範囲内にあると、粘着剤組成物の濡れ性と凝集力のバランスを制御しやすくなるため、好ましい。 When the monomer having a hydroxyl group is contained, the content thereof is preferably 0 to 10% by weight (not including 0% by weight), more preferably 0.5 to 5% by weight, based on the total amount of the monomers. When it is within the above range, it becomes easy to control the balance between the wettability and the cohesive force of the pressure-sensitive adhesive composition, which is preferable.
また、モノマーＢとして、カルボキシル基を有するモノマーを含有することが好ましい。粘着力向上や架橋下基点として働く官能基を有するモノマーを用いることができる。 Further, it is preferable that the monomer B contains a monomer having a carboxyl group. A monomer having a functional group that acts as a base point for improving adhesive strength and cross-linking can be used.
前記カルボキシル基を有するモノマーとしては、例えば、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、２−（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシエチルフタル酸、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２−（メタ）アクリロイロキシエチルテトラヒドロフタル酸などが挙げられる。 Examples of the monomer having a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2- (meth). Acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono ( Examples thereof include meta) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.
前記カルボキシル基を有するモノマーが含有される場合、その含有量は、全モノマー中の０〜１０重量％（０重量％を含まず）が好ましく、０．５〜５重量％がより好ましい。 When the monomer having a carboxyl group is contained, the content thereof is preferably 0 to 10% by weight (not including 0% by weight), more preferably 0.5 to 5% by weight, based on the total amount of the monomers.
本発明の共重合ポリマーの重合方法は、特に制限されるものではなく、溶液重合、乳化重合、塊状重合、懸濁重合、放射線硬化(放射線エネルギー)重合等の共重合ポリマーの合成手法として、一般的に用いられる各種の重合方法を適用することができる。特に、作業性の観点や、被着体への低汚染性など特性面から、溶液重合が好ましい態様である。また、得られる共重合ポリマーは、ランダム共重合体、ブロック共重合体、交互共重合体、グラフト共重合体などいずれでもよい。 The polymerization method of the copolymerization polymer of the present invention is not particularly limited, and is generally used as a method for synthesizing a copolymerization polymer such as solution polymerization, emulsification polymerization, massive polymerization, suspension polymerization, and radiation curing (radio energy) polymerization. Various polymerization methods can be applied. In particular, solution polymerization is a preferred embodiment from the viewpoint of workability and characteristics such as low contamination of the adherend. Further, the obtained copolymer polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.
溶液重合は、水又は有機溶媒中で行われる。有機溶媒としては、例えば、トルエン、キシレン、ベンゼン、ヘキサン、ヘプタン、酢酸エチル、酢酸ブチル、メチルイソブチルケトン、メチルエチルケトン、アセトン、１，４−ジオキサン、ジメチルスルフォシキド（ＤＭＳＯ）、メタノール、Ｎ−メチルピロリドン（ＮＭＰ）、イオン性液体等を用いることができるが、１，４−ジオキサン又はＤＭＳＯが好ましい。 Solution polymerization is carried out in water or an organic solvent. Examples of the organic solvent include toluene, xylene, benzene, hexane, heptane, ethyl acetate, butyl acetate, methyl isobutyl ketone, methyl ethyl ketone, acetone, 1,4-dioxane, dimethyl sulfoxide (DMSO), methanol, N-. Methylpyrrolidone (NMP), ionic liquids and the like can be used, but 1,4-dioxane or DMSO is preferable.
重合には重合開始剤を用いてもよい。重合開始剤としては、無機系又は有機系のいずれの重合開始剤であってもよいが、例えばアゾビスイソブチロニトリル（以下、ＡＩＢＮと略記する）、ベンジルパーオキサド等の有機系重合開始剤を使用することが好ましい。重合開始剤の使用量は、通常の使用量であれば良く、例えば、全モノマー成分１００重量部に対して０．０１〜１重量部程度の範囲から選択することができる。 A polymerization initiator may be used for the polymerization. The polymerization initiator may be either an inorganic or organic polymerization initiator, and for example, an organic polymerization initiator such as azobisisobutyronitrile (hereinafter abbreviated as AIBN) or benzyl peroxide is used. It is preferable to use an agent. The amount of the polymerization initiator used may be a normal amount, and can be selected from, for example, about 0.01 to 1 part by weight with respect to 100 parts by weight of all the monomer components.
本発明の共重合ポリマーは、粘着力、凝集力に優れると共に、ポリマー中に不飽和結合がないため光や酸素に対する安定性が高く、また、モノマーの種類や分子量の選択の自由度が高いという点でも優れている。 The copolymerized polymer of the present invention has excellent adhesive strength and cohesive strength, is highly stable against light and oxygen because there are no unsaturated bonds in the polymer, and has a high degree of freedom in selecting the type and molecular weight of the monomer. It is also excellent in terms of points.
エージング作業の前後でも十分な架橋密度を持った高分子とするためには、該重量平均分子量（Ｍｗ）は３０万〜２００万であることが好ましく、５０万〜１３０万であることがより好ましい。 In order to obtain a polymer having a sufficient crosslink density even before and after the aging operation, the weight average molecular weight (Mw) is preferably 300,000 to 2 million, more preferably 500,000 to 1.3 million. ..
本発明の共重合ポリマーは、硬化剤を含有することにより粘着剤組成物として使用することができる。硬化剤としては、例えば、ポリイソシアネート系硬化剤、メラミン系硬化剤、ジアミン系硬化剤、エポキシ系硬化剤、尿素系硬化剤、金属キレート系硬化剤などが挙げられる。 The copolymerized polymer of the present invention can be used as a pressure-sensitive adhesive composition by containing a curing agent. Examples of the curing agent include polyisocyanate-based curing agents, melamine-based curing agents, diamine-based curing agents, epoxy-based curing agents, urea-based curing agents, metal chelate-based curing agents, and the like.
金属キレート系硬化剤にはアルミニウム系硬化剤、チタニウム系硬化剤やジルコニウム系硬化剤等があり、例えば、アルミニウムトリスアセチルアセトネート、アルミニウムビスエチルアセトアセテートモノアセチルアセトネート、アルミニウムトリスエチルアセトアセテート、チタンアセチルアセトネート、チタンテトラアセチルアセトネート、チタンエチルアセトアセテート、ドデシルベンゼンスルホン酸チタン化合物、リン酸チタン化合物、チタンオクチレングリコレート、チタンエチルアセトアセテート、ジルコニウムテトラアセチルアセトネート、ジルコニウムテトラアセチルアセトネート、ジルコニウムモノアセチルアセトネート、ジルコニウムテトラアセチルアセトネートなどが挙げられる。 Metal chelate-based curing agents include aluminum-based curing agents, titanium-based curing agents, zirconium-based curing agents, and the like. For example, aluminum trisacetylacetate, aluminum bisethylacetate monoacetylacetate, aluminumtrisethylacetate, and titanium. Acetylacetate, Titanium Tetraacetylacetate, Titanium Ethylacetate, Titanium Dodecylbenzenesulfonate, Titanium Phosphate, Titanium Octylene Glycolate, Titanium Ethylacetate, Zirconium Tetraacetylacetate, Zirconium Tetraacetylacetate Examples thereof include zirconium monoacetylacetonate and zirconium tetraacetylacetonate.
ポリイソシアネート系硬化剤には、例えば、ヘキサメチ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のトリメチロールプロパン付加物などの脂肪族ジイソシアネート、トリレンジイソシアネート又はトリレンジイソシアネートのトリメチロールプロパン付加物等の芳香族ジイソシアネートの如きポリイソシアネート化合物、オキシム系ブロック型ポリイソシアネート、活性メチレン系ブロック型ポリイソシアネートなどが挙げられる。 Polyisocyanate-based curing agents include polyisocyanates such as aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylolpropane adduct of hexamethylene diisocyanate, and aromatic diisocyanates such as tolylene diisocyanate or trimethylolpropane adduct of tolylene diisocyanate. Examples thereof include isocyanate compounds, oxime-based block-type polyisocyanates, and active methylene-based block-type polyisocyanates.
硬化剤の使用量は前記共重合ポリマーに対して０．０５〜０．１５重量部の範囲から選択することが好ましい。また、必要に応じてスズ化合物などの触媒を使用しても良い。 The amount of the curing agent used is preferably selected from the range of 0.05 to 0.15 parts by weight with respect to the copolymerized polymer. Further, a catalyst such as a tin compound may be used if necessary.
本発明の粘着剤組成物は、さらに添加剤を含有して使用することができる。添加剤としては、硬化補助剤、色調整色素、レベリング剤、帯電防止剤、酸化防止剤、分散剤、難燃剤、滑剤、可塑剤、紫外線吸収剤、シランカップリング剤その他添加剤等がある。被着体への接着性を良好に保つためにシランカップリング剤が好適に使用できる。シランカップリング剤には、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシランなどが挙げられ、エポキシ系シランカップリング剤が好ましい。 The pressure-sensitive adhesive composition of the present invention can be used by further containing an additive. Additives include curing aids, color adjusting dyes, leveling agents, antistatic agents, antioxidants, dispersants, flame retardants, lubricants, plasticizers, UV absorbers, silane coupling agents and other additives. A silane coupling agent can be preferably used in order to maintain good adhesion to the adherend. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, methacrypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3). , 4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3- Examples of aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyandiapropyltriethoxysilane, etc. include epoxy-based silane coupling agents. preferable.
添加剤の添加量は前記共重合ポリマーに対して０．０５〜０．１５重量部の範囲から選択することが好ましい。 The amount of the additive added is preferably selected from the range of 0.05 to 0.15 parts by weight with respect to the copolymerized polymer.
本発明の粘着剤組成物は、フローコート法、スプレー法、バーコート法、グラビアコート法、ロールコート法、ブレードコート法、エアーナイフコート法、リップコート法、ダイコーター法等の公知の塗工方法で塗付され得る。仕上がりの粘着剤組成物層の膜厚が通常２〜１００μｍ、好ましくは１０〜４０μｍとなるように塗付される。塗布後の粘着剤組成物を５０〜１４０℃、好ましくは６０〜１１０℃で乾燥することによって硬化が進む。通常、この後エージング処理が行われる。エージング処理の条件は使用する粘着剤組成物によって条件が異なるが、本発明の粘着剤組成物については２０〜６０℃の恒温槽中、１日〜１週間程度保管するのが好ましい。 The pressure-sensitive adhesive composition of the present invention has known coating methods such as a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, an air knife coating method, a lip coating method, and a die coater method. Can be applied by method. The finished pressure-sensitive adhesive composition layer is usually applied so that the film thickness is 2 to 100 μm, preferably 10 to 40 μm. Curing proceeds by drying the pressure-sensitive adhesive composition after coating at 50 to 140 ° C., preferably 60 to 110 ° C. Usually, the aging process is performed after this. The conditions for the aging treatment differ depending on the pressure-sensitive adhesive composition used, but the pressure-sensitive adhesive composition of the present invention is preferably stored in a constant temperature bath at 20 to 60 ° C. for about 1 day to 1 week.
本発明の粘着剤組成物を硬化させた粘着剤層は、多様な材料面に強固に接着することができる。例えば、ガラスのような無機物、ＴＡＣ、アクリル、ＰＣ、ＣＯＰ等の有機物に対して優れた接着性を有する。したがって、本発明の粘着剤組成物を硬化させた粘着剤層は、偏光板などの光学部材の貼り合せに好適に使用することができる。 The pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition of the present invention can be firmly adhered to various material surfaces. For example, it has excellent adhesiveness to inorganic substances such as glass and organic substances such as TAC, acrylic, PC, and COP. Therefore, the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition of the present invention can be suitably used for bonding optical members such as polarizing plates.
本発明の粘着剤組成物を硬化させた粘着剤層は、偏光板を主とする液晶表示装置の周辺の各種光学部材、タッチパネル用の各種光学部材、電子ペーパー用の各種光学部材、有機ＥＬ用の各種光学部材等の貼り合せに用いることができる。
また、これらの光学部材の少なくとも一方の面に、前記粘着剤組成物を硬化させた粘着剤層が積層されている粘着剤層付き光学部材とすることができる。具体的には、「光学部材／粘着剤層／光学部材」、「光学部材／粘着剤層／離型フィルム」、「光学部材／粘着剤層」、「光学部材／粘着剤層／光学部材／粘着剤層／光学部材」、「光学部材／粘着剤層／光学部材／粘着剤層／離型フィルム」、「離型フィルム／粘着剤層／光学部材／粘着剤層／離型フィルム」等の構成が挙げられる。
例えば、「光学部材／粘着剤層／離型フィルム」のように、離型フィルムで保護された粘着剤層を有する場合、離型フィルムを剥がして、「光学部材／粘着剤層」のように粘着剤層を表出させ、他の光学部材と貼合することにより、粘着剤層が層間の貼合に用いられた「光学部材／粘着剤層／光学部材」のような構成が得られる。The pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition of the present invention includes various optical members around a liquid crystal display device mainly a polarizing plate, various optical members for a touch panel, various optical members for electronic paper, and organic EL. It can be used for bonding various optical members and the like.
Further, the optical member with a pressure-sensitive adhesive layer may be formed by laminating a pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition on at least one surface of these optical members. Specifically, "optical member / adhesive layer / optical member", "optical member / adhesive layer / release film", "optical member / adhesive layer", "optical member / adhesive layer / optical member / "Adhesive layer / optical member", "optical member / adhesive layer / optical member / adhesive layer / release film", "release film / adhesive layer / optical member / adhesive layer / release film", etc. The configuration can be mentioned.
For example, when having an adhesive layer protected by a release film such as "optical member / adhesive layer / release film", the release film is peeled off to form "optical member / adhesive layer". By exposing the pressure-sensitive adhesive layer and bonding it with another optical member, a configuration such as "optical member / pressure-sensitive adhesive layer / optical member" in which the pressure-sensitive adhesive layer is used for bonding between layers can be obtained.
以下、実施例を用いて、本発明を説明するが、これらに限定されるものではない。尚、実施例において部は重量部を、％は重量％をそれぞれ意味する。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight" and "%" means% by weight.
共重合ポリマーの重量平均分子量（Ｍｗ）は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法の下記条件にて測定した。
分析装置：東ソー社製、ＧＰＣ ＨＬＣ−８３２０ＧＰＣ
カラム：東ソー社製、ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ−Ｈ（２連）
カラム温度：４０℃
流速：０．３５ｍｌ／ｍｉｎ
溶離液：テトラヒドロフラン
検出器：示差屈折計
標準試料：ポリスチレンThe weight average molecular weight (Mw) of the copolymerized polymer was measured under the following conditions by the GPC (gel permeation chromatography) method.
Analyzer: GPC HLC-8320GPC manufactured by Tosoh Corporation
Column: Super Multipore HZ-H (2 stations) manufactured by Tosoh Corporation
Column temperature: 40 ° C
Flow velocity: 0.35 ml / min
Eluent: Tetrahydrofuran Detector: Differential Refractometer Standard Sample: Polystyrene
＜合成例１＞
（ＤＭＡの合成）
水６００ｇに炭酸水素ナトリウムウム１２ｇ、ホウ酸ナトリウム６０ｇを溶解して緩衝液を作製した。次いで、この緩衝液に出発原料としてドーパミン塩酸塩を加え、この溶液を攪拌しながら、メタクリル酸無水物２２％のテトラヒドロフラン溶液を滴下した。その際、ＮａＯＨ水溶液を適宜加えて溶液をｐＨ８以上に保った。この溶液を一晩攪拌した後、ＨＣｌ水溶液を加えて溶液をｐＨ２以下に調整後、酢酸エチルを加えて生成物を抽出した。この有機溶液を硫酸ナトリウムで乾燥後、エバポレーターで濃縮した。得られた粗生成物に対してヘキサンを用いて再結晶を行った。次に、減圧濾過により得られた個体を回収し、乾燥を行うことで、式（２）の化合物（ＤＭＡ）を１５ｇ得た。化合物の同定は薄層クロマトグラフィー及び１Ｈ ＮＭＲで行った。<Synthesis example 1>
(Composition of DMA)
A buffer solution was prepared by dissolving 12 g of sodium hydrogen carbonate and 60 g of sodium borate in 600 g of water. Next, dopamine hydrochloride was added to this buffer as a starting material, and a solution of 22% methacrylic anhydride in tetrahydrofuran was added dropwise while stirring the solution. At that time, an aqueous NaOH solution was appropriately added to keep the solution at pH 8 or higher. After stirring this solution overnight, hydrochloric acid aqueous solution was added to adjust the solution to pH 2 or less, and ethyl acetate was added to extract the product. This organic solution was dried over sodium sulfate and then concentrated on an evaporator. The obtained crude product was recrystallized using hexane. Next, the solid obtained by vacuum filtration was collected and dried to obtain 15 g of the compound (DMA) of the formula (2). Compounds were identified by thin layer chromatography and 1 1 H NMR.
＜実施例１＞
（共重合ポリマーの作製）
重合容器に、アクリル酸ｎ‐ブチル９６部、アクリル酸２−ヒドロキシエチル１部、ＤＭＡ３部、１，４−ジオキサン１５０部を仕込み、室温で1時間窒素置換を行った。その後、攪拌下で６８℃に昇温し、重合開始剤としてアゾビスイソブチルニトリル（ＡＩＢＮ）０．０３部を添加し、６８℃にて７．０時間反応させ本発明の共重合ポリマーを作製した。該共重合ポリマーの重量平均分子量（Ｍｗ）は５５万で、固形分は２２％であった。<Example 1>
(Preparation of copolymer polymer)
96 parts of n-butyl acrylate, 1 part of 2-hydroxyethyl acrylate, 3 parts of DMA, and 150 parts of 1,4-dioxane were charged in a polymerization vessel, and nitrogen substitution was carried out at room temperature for 1 hour. Then, the temperature was raised to 68 ° C. with stirring, 0.03 part of azobisisobutynitrile (AIBN) was added as a polymerization initiator, and the reaction was carried out at 68 ° C. for 7.0 hours to prepare the copolymerized polymer of the present invention. .. The weight average molecular weight (Mw) of the copolymerized polymer was 550,000, and the solid content was 22%.
＜実施例２＞
アクリル酸ｎ‐ブチル部の量を９５部、アクリル酸２−ヒドロキシエチルの量を２部とする以外は実施例１と同様の方法で本発明の共重合ポリマーを作製した。該共重合ポリマーの重量平均分子量（Ｍｗ）は６７万で、固形分は１９％であった。<Example 2>
The copolymerized polymer of the present invention was prepared in the same manner as in Example 1 except that the amount of n-butyl acrylate was 95 and the amount of 2-hydroxyethyl acrylate was 2. The weight average molecular weight (Mw) of the copolymerized polymer was 670,000, and the solid content was 19%.
＜実施例３＞
アクリル酸ｎ‐ブチル部の量を９０部、アクリル酸２−ヒドロキシエチルの量を２部、ＤＭＡの量を８部とする以外は実施例１と同様の方法で本発明の共重合ポリマーを作製した。該共重合ポリマーの重量平均分子量（Ｍｗ）は７２万で、固形分は１９％であった。<Example 3>
The copolymerized polymer of the present invention was prepared in the same manner as in Example 1 except that the amount of n-butyl acrylate was 90 parts, the amount of 2-hydroxyethyl acrylate was 2 parts, and the amount of DMA was 8 parts. did. The weight average molecular weight (Mw) of the copolymerized polymer was 720,000, and the solid content was 19%.
＜比較例１＞
アクリル酸ｎ‐ブチル部の量を９９部、アクリル酸２−ヒドロキシエチルの量を１部、ＤＭＡの量を０部とする以外は実施例１と同様の方法で本発明の共重合ポリマーを作製した。該共重合ポリマーの重量平均分子量（Ｍｗ）は１２１万で、固形分は２１％であった。<Comparative example 1>
The copolymerized polymer of the present invention was prepared in the same manner as in Example 1 except that the amount of n-butyl acrylate was 99 parts, the amount of 2-hydroxyethyl acrylate was 1 part, and the amount of DMA was 0. did. The weight average molecular weight (Mw) of the copolymerized polymer was 1.21 million, and the solid content was 21%.
＜比較例２＞
アクリル酸ｎ‐ブチル部の量を９８部、アクリル酸２−ヒドロキシエチルの量を２部、ＤＭＡの量を０部とする以外は実施例１と同様の方法で本発明の共重合ポリマーを作製した。該共重合ポリマーの重量平均分子量（Ｍｗ）は１２０万で、固形分は２２％であった。<Comparative example 2>
The copolymerized polymer of the present invention was prepared in the same manner as in Example 1 except that the amount of n-butyl acrylate was 98 parts, the amount of 2-hydroxyethyl acrylate was 2 parts, and the amount of DMA was 0. did. The weight average molecular weight (Mw) of the copolymerized polymer was 1.2 million, and the solid content was 22%.
＜実施例４〜６並びに比較例３及び４＞
（粘着剤組成物の作製及びそれを硬化させた粘着剤層の作製）
実施例１〜３並びに比較例１及び２で得られた共重合ポリマーを使用し、表１に示す各材料を均一になるように混合し、各粘着剤組成物を作製した（それぞれ、実施例４〜６並びに比較例３及び４）。該粘着剤組成物を溶解した塗工液を、ＰＥＴ５０１１（商品名：剥離ＰＥＴフィルム、リンテック社製）上にコンマコーターで１．５ｍ／分の塗工速度、乾燥温度１００℃により、粘着剤層の厚さが２５μｍになるように塗工して粘着剤層を形成した。該粘着剤層を３５℃の恒温槽中に１週間保管してエージング処理を行った。<Examples 4 to 6 and Comparative Examples 3 and 4>
(Preparation of Adhesive Composition and Preparation of Cured Adhesive Layer)
Using the copolymerized polymers obtained in Examples 1 to 3 and Comparative Examples 1 and 2, each material shown in Table 1 was mixed so as to be uniform to prepare each pressure-sensitive adhesive composition (each in Example). 4 to 6 and Comparative Examples 3 and 4). A coating liquid in which the pressure-sensitive adhesive composition is dissolved is applied onto PET5011 (trade name: peeling PET film, manufactured by Lintec Corporation) with a comma coater at a coating speed of 1.5 m / min and a drying temperature of 100 ° C. to apply a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer was formed by coating so that the thickness of the adhesive layer was 25 μm. The pressure-sensitive adhesive layer was stored in a constant temperature bath at 35 ° C. for 1 week for aging treatment.
（接着性評価）
実施例４〜６並びに比較例３及び４により得られた粘着剤組成物を硬化させた粘着剤層をＴＡＣフィルム（厚み８０μｍ）に貼合して２５ｍｍ幅にカットし、評価サンプルを作製した。該評価サンプルをガラス板（厚み１ｍｍ）、アクリル板（厚み１ｍｍ）、ＰＣ板（厚み１ｍｍ）に貼合し、下記条件にて接着強度を測定した。
測定方法：ＪＩＳ Ｚ０２３７「粘着テープ・粘着シート試験方法」に準拠
測定条件：１８０度ピール、引張り速度３００ｍｍ／ｍｉｎ(Adhesion evaluation)
The pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive compositions obtained in Examples 4 to 6 and Comparative Examples 3 and 4 was attached to a TAC film (thickness 80 μm) and cut into a width of 25 mm to prepare an evaluation sample. The evaluation sample was attached to a glass plate (thickness 1 mm), an acrylic plate (thickness 1 mm), and a PC plate (thickness 1 mm), and the adhesive strength was measured under the following conditions.
Measurement method: Compliant with JIS Z0237 "Adhesive tape / adhesive sheet test method" Measurement conditions: 180 degree peel, tensile speed 300 mm / min
表２より、本発明の共重合ポリマーを使用した粘着剤層はガラス板、アクリル板、ＰＣ板に対する接着性が著しく向上していることが確認できた。 From Table 2, it was confirmed that the pressure-sensitive adhesive layer using the copolymerized polymer of the present invention had significantly improved adhesiveness to the glass plate, acrylic plate, and PC plate.
（光学部材の耐久性試験）
耐久性評価を行うサンプルは下記方法にて作製した。
（偏光板の作製）
ポリビニルアルコール（クラレ社製、商品名：クラレビニロン＃７５０）をクロランチンファストレッド（Ｃ．Ｉ．２８１６０）０．２５ｇ／Ｌ、クリソフェニン（Ｃ．Ｉ．２４８９５）０．１８ｇ／Ｌ、ソロフェニルブルー４ＧＬ（Ｃ．Ｉ．３４２００）１．０ｇ／Ｌ及び硫酸ナトリウム１０ｇ／Ｌを含む水溶液中で、３５℃３分間染色した後、溶液中で４倍に延伸した。ついでこの染色シートを酢酸ニッケル２．５ｇ／Ｌ及びほう酸６．６ｇ／Ｌを含む水溶液中３５℃で３分浸漬した。ついでそのシートを緊張状態が保持された状態で、室温で３分間乾燥を行った後、７０℃で３分間加熱処理し、偏光素子を得た。
トリアセチルセルロースフィルム（富士フイルム社製 ＺＲＤ-６０）及びアクリル（大倉工業社製 ＯＸＩＳ ＦＺ−Ｔ１３−Ｗ１−４０）、得られた偏光素子の両面にそれぞれ４％のポリビニルアルコール樹脂（日本酢ビ・ポバール社製 ＮＨ−２６）を含む水溶液を介してラミネートして、７０℃で１０分乾燥させ、偏光板を得た。(Durability test of optical members)
Samples for durability evaluation were prepared by the following method.
(Preparation of polarizing plate)
Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: Kuraray Vinylon # 750), chloranthin fast red (CI 28160) 0.25 g / L, chrysophenin (CI 24895) 0.18 g / L, solophenyl After staining in an aqueous solution containing 1.0 g / L of blue 4GL (CI34200) and 10 g / L of sodium sulfate for 3 minutes at 35 ° C., the product was stretched 4-fold in the solution. Then, this dyeing sheet was immersed in an aqueous solution containing 2.5 g / L of nickel acetate and 6.6 g / L of boric acid at 35 ° C. for 3 minutes. Then, the sheet was dried at room temperature for 3 minutes in a tense state, and then heat-treated at 70 ° C. for 3 minutes to obtain a polarizing element.
Triacetyl cellulose film (ZRD-60 manufactured by Fujifilm) and acrylic (OXIS FZ-T13-W1-40 manufactured by Okura Industrial Co., Ltd.), and 4% polyvinyl alcohol resin (Japan Vam & Poval) on both sides of the obtained polarizing element. It was laminated with an aqueous solution containing NH-26) manufactured by Poval Co., Ltd. and dried at 70 ° C. for 10 minutes to obtain a polarizing plate.
（偏光板製品の作製）
前述より得られた偏光板のアクリル面に、本発明及び比較例の粘着剤層を貼り合わせて光学部材を作製し、１６０ｍｍ×９０ｍｍの長方形にカットする。カットした該偏光板製品の該粘着剤層を亜州社製青板ガラスに貼り合わせて、オートクレーブ処理（６０℃、０．５ＭＰa、１５分）を行い、耐久性評価用サンプルとした。耐久性評価は１１５℃の環境に該評価用サンプルを５００時間保管して行った。
耐久性評価は、耐久性試験後のサンプルを下記の基準で確認して行った。
＜剥がれ＞
◎：偏光板端部の剥がれが１．０ｍｍ未満であった。
〇：偏光板端部の剥がれが１．０ｍｍ以上１０ｍｍ未満であった。
×：偏光板端部の剥がれが１０ｍｍ以上であった。(Manufacturing of polarizing plate products)
An optical member is prepared by laminating the pressure-sensitive adhesive layer of the present invention and the comparative example on the acrylic surface of the polarizing plate obtained from the above, and cut into a rectangle of 160 mm × 90 mm. The adhesive layer of the cut polarizing plate product was attached to a blue plate glass manufactured by Ashu Co., Ltd. and autoclaved (60 ° C., 0.5 MPa, 15 minutes) to prepare a sample for durability evaluation. The durability evaluation was carried out by storing the evaluation sample in an environment of 115 ° C. for 500 hours.
Durability evaluation was performed by confirming the sample after the durability test according to the following criteria.
<Peeling>
⊚: The peeling of the edge of the polarizing plate was less than 1.0 mm.
◯: The peeling of the end of the polarizing plate was 1.0 mm or more and less than 10 mm.
X: The peeling of the end of the polarizing plate was 10 mm or more.
表３より、本発明の共重合ポリマーを使用した粘着剤層を用いた偏光板の耐久性は、比較例に比べて、向上していることが確認できた。
From Table 3, it was confirmed that the durability of the polarizing plate using the pressure-sensitive adhesive layer using the copolymerized polymer of the present invention was improved as compared with the comparative example.
Claims (10)
（式中、Ｒ１〜Ｒ４は水素原子又は炭素数１〜２０のアルキル基を表し、Ｙはアミド結合、エステル結合、又は直接結合を表し、ｎは０又は１〜１０の整数を表す）。A copolymerized polymer containing a monomer A having a catechol group represented by the following formula (1) and a monomer B copolymerizable with the monomer A as constituent elements:
(In the formula, R 1 to R 4 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, Y represents an amide bond, an ester bond, or a direct bond, and n represents an integer of 0 or 1 to 10). ..
An optical member comprising the pressure-sensitive adhesive composition according to claim 8 or 9.
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| JP2018072449 | 2018-04-04 | ||
| JP2018072449 | 2018-04-04 | ||
| PCT/JP2019/013220 WO2019194047A1 (en) | 2018-04-04 | 2019-03-27 | Copolymerization polymer, adhesive agent composition, and optical member containing same |
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| JP2019183078A (en) * | 2018-04-17 | 2019-10-24 | 日立化成株式会社 | Adhesive |
| JP7521241B2 (en) | 2020-04-06 | 2024-07-24 | Ａｇｃ株式会社 | Curable composition and cured product |
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