WO2022265074A1 - 粘着フィルム、及び積層体 - Google Patents
粘着フィルム、及び積層体 Download PDFInfo
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- WO2022265074A1 WO2022265074A1 PCT/JP2022/024191 JP2022024191W WO2022265074A1 WO 2022265074 A1 WO2022265074 A1 WO 2022265074A1 JP 2022024191 W JP2022024191 W JP 2022024191W WO 2022265074 A1 WO2022265074 A1 WO 2022265074A1
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- WIPO (PCT)
- Prior art keywords
- adhesive film
- resin
- polyvinyl acetal
- group
- film
- Prior art date
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 177
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims description 133
- 239000011347 resin Substances 0.000 claims description 133
- 229920002554 vinyl polymer Polymers 0.000 claims description 129
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 114
- 239000004014 plasticizer Substances 0.000 claims description 68
- -1 oxypropylene group Chemical group 0.000 claims description 66
- 239000011354 acetal resin Substances 0.000 claims description 60
- 150000001241 acetals Chemical class 0.000 claims description 60
- 229920006324 polyoxymethylene Polymers 0.000 claims description 60
- 239000011521 glass Substances 0.000 claims description 52
- 239000005340 laminated glass Substances 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 38
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 36
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 17
- 125000006353 oxyethylene group Chemical group 0.000 claims description 14
- 238000006359 acetalization reaction Methods 0.000 claims description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000010408 film Substances 0.000 description 139
- 239000010410 layer Substances 0.000 description 53
- 239000000178 monomer Substances 0.000 description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 description 28
- 239000002585 base Substances 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 22
- 239000011342 resin composition Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 239000011368 organic material Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 238000006640 acetylation reaction Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 13
- 239000005357 flat glass Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 150000007524 organic acids Chemical class 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 229910010272 inorganic material Inorganic materials 0.000 description 12
- 239000011147 inorganic material Substances 0.000 description 12
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 12
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 10
- 150000003384 small molecules Chemical class 0.000 description 10
- 125000004036 acetal group Chemical group 0.000 description 9
- 230000021736 acetylation Effects 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 8
- 239000012634 fragment Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 235000005985 organic acids Nutrition 0.000 description 8
- 230000002087 whitening effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 150000002895 organic esters Chemical class 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 229910052753 mercury Inorganic materials 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
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- GCDUWJFWXVRGSM-UHFFFAOYSA-N 2-[2-(2-heptanoyloxyethoxy)ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCC GCDUWJFWXVRGSM-UHFFFAOYSA-N 0.000 description 2
- YJGHMLJGPSVSLF-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC YJGHMLJGPSVSLF-UHFFFAOYSA-N 0.000 description 2
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 2
- SSKNCQWPZQCABD-UHFFFAOYSA-N 2-[2-[2-(2-heptanoyloxyethoxy)ethoxy]ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOCCOC(=O)CCCCCC SSKNCQWPZQCABD-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- 101100029848 Arabidopsis thaliana PIP1-2 gene Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
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- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
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- FSRKEDYWZHGEGG-UHFFFAOYSA-N [2-(8-methylnonyl)phenyl] dihydrogen phosphate Chemical compound CC(C)CCCCCCCC1=CC=CC=C1OP(O)(O)=O FSRKEDYWZHGEGG-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 239000005341 toughened glass Substances 0.000 description 1
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Images
Classifications
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- 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
- C09J129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/38—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
-
- 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]
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- 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
- C09J2459/00—Presence of polyacetal
Definitions
- the present invention relates to an adhesive film and a laminate provided with an adhesive film.
- adhesive films are widely used to superimpose and fix surface protection panels, polarizing plates, films with touch sensors, glass with touch sensors, etc. .
- (meth)acrylic resins have been widely used as adhesive films from the viewpoints of transparency, adhesiveness, and the like.
- polyvinyl acetal resins has also been investigated.
- Plasticized polyvinyl acetal resins are also widely used as interlayer films for laminated glass.
- the interlayer film for laminated glass constitutes laminated glass, for example, by bonding two laminated glass members.
- Laminated glass is safe because it does not scatter glass fragments even if it is damaged by an external impact, so it is widely used as window glass for vehicles such as automobiles, aircraft, buildings, and the like.
- the laminated glass is formed by, for example, placing the light control film between two glass plates, and bonding the light control film and each glass plate via a resin film as an intermediate film for laminated glass.
- Configurations are known that allow The use of an adhesive film containing a plasticized polyvinyl acetal-based resin as the resin film is being studied.
- adhesive films containing plasticized polyvinyl acetal-based resins and interlayer films for laminated glasses used in the above-mentioned displays and laminated glasses may not be used for a long time under high temperature and high humidity because the plasticizer and the polyvinyl acetal-based resin absorb moisture.
- plasticizer and the polyvinyl acetal-based resin absorb moisture.
- conventional (meth)acrylic resin films which are widely used as adhesive films in liquid crystal displays and the like, have high moisture and heat resistance and are less likely to cause whitening problems, but it is difficult to increase impact resistance. Therefore, when it is used for laminated glass or display applications, when it is broken by an external impact, glass fragments scatter and safety becomes low, making it difficult to use it for vehicle applications, for example.
- an object of the present invention is to improve both impact resistance and moist heat resistance in an adhesive film containing a thermoplastic resin.
- the present inventors have found that, in an adhesive film containing a thermoplastic resin, the maximum peak temperature of tan ⁇ is within a predetermined temperature range, the shear storage modulus is a certain value or more, and the ratio of undissolved components to isopropanol is set to a certain value or less, the above problems can be solved, and the following invention has been completed. That is, the present invention provides the following [1] to [31]. [1] An adhesive film containing a thermoplastic resin, The maximum peak temperature of tan ⁇ is 0° C. or higher and 52° C. or lower, the shear storage modulus at 20° C.
- a 1 O is an oxyalkylene group having 2 to 6 carbon atoms, m is the average number of repetitions, and is 4 to 200.
- R 1 is an alkyl group having 1 to 8 carbon atoms or It is a hydrogen atom.
- the oxyalkylene group may be of one type alone, or two or more types may be mixed.* indicates the bonding position with another group.
- the polyalkylene oxide structure is linked to the main chain via either a single bond, or an ether bond, an ester bond, an amide bond, or a hydrocarbon group which may have at least one of these bonds.
- the pressure-sensitive adhesive film according to any one of [4] to [9] above.
- thermoplastic resin Adhesive film as described.
- the plasticizer is at least one selected from the group consisting of organic ester plasticizers, organic phosphorus plasticizers, organic ether plasticizers, and alcohol plasticizers.
- the adhesive film contains, as a plasticizer, an ester of a glycol and a monobasic organic acid, an ester compound of a dibasic organic acid having 4 to 12 carbon atoms and an alcohol having 4 to 10 carbon atoms, or polyalkylene glycol.
- the pressure-sensitive adhesive film according to any one of [1] to [17] above, which contains at least one selected from the group consisting of plasticizers and polyoxyalkylene ether plasticizers.
- a laminate comprising the adhesive film according to any one of [1] to [19] above and a pair of substrates, wherein the adhesive film is arranged between the pair of substrates.
- the base material constitutes at least part of a touch panel, a light modulating element, and a display element.
- An intermediate member disposed between the pair of base materials and an adhesive film disposed between each base material and the intermediate member, wherein at least one of the adhesive films is the adhesive film The laminate according to any one of [20] to [23] above.
- the intermediate member is either a touch panel or a light control element.
- a liquid crystal display comprising the laminate according to any one of [20] to [26] above.
- a laminated glass comprising the laminate according to any one of [20] to [26] above.
- a display comprising the laminate according to any one of [20] to [26] above.
- both impact resistance and moist heat resistance can be improved in an adhesive film containing a thermoplastic resin.
- FIG. 5 is a cross-sectional view showing a laminate according to a second embodiment; It is a sectional view showing a layered product concerning a 3rd embodiment. It is a sectional view showing a layered product concerning a 4th embodiment.
- the pressure-sensitive adhesive film of the present invention contains a thermoplastic resin, has a maximum peak temperature of tan ⁇ of 0° C. or more and 52° C. or less, and has a shear storage modulus of 3 ⁇ 10 5 Pa or more at 20° C., and pressure-sensitive adhesive film 1
- 0 g is dissolved in 10 g of isopropyl alcohol
- the undissolved component is 35% by mass or more and 100% by mass or less.
- the pressure-sensitive adhesive film of the present invention can be made excellent in both impact resistance and moist heat resistance by having the above configuration.
- the maximum peak temperature of tan ⁇ of the adhesive film is 0°C or higher and 52°C or lower. If the maximum peak temperature of tan ⁇ is less than 0°C, impact resistance may not be sufficiently improved. Therefore, when a laminate obtained by bonding with an adhesive film is subjected to an impact, it is likely to be damaged, and when it is damaged, fragments are likely to scatter. Further, when the maximum peak temperature of tan ⁇ is higher than 52° C., the flexibility of the resin film becomes insufficient, and the adhesiveness to various resin materials and inorganic glass may not be improved.
- the maximum peak temperature of tan ⁇ of the adhesive film is preferably 50° C. or less, more preferably 44° C. or less.
- the maximum peak temperature of tan ⁇ is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher.
- the maximum peak temperature of tan ⁇ of the adhesive film is detected by performing viscoelasticity measurement using a dynamic viscoelasticity measuring device and reading the peak temperature at which the loss tangent tan ⁇ obtained from the viscoelasticity measurement result is the maximum value. can.
- the pressure-sensitive adhesive film of the present invention has a shear storage modulus of 3 ⁇ 10 5 Pa or more at 20°C. If the shear storage elastic modulus is less than 3 ⁇ 10 5 Pa, the impact resistance will be low, and the laminate obtained by bonding with the adhesive film will be easily damaged when impact is applied, and when it is damaged, it will be broken into pieces. becomes easier to disperse.
- the shear storage modulus at 20° C. is preferably 1 ⁇ 10 6 Pa or more, more preferably 5 ⁇ 10 6 Pa or more, further preferably 1 ⁇ 10 7 Pa or more, and 2 ⁇ 10 7 . More preferably Pa or higher.
- the shear storage modulus of the pressure-sensitive adhesive film at 20°C is preferably high from the viewpoint of impact resistance, but from the viewpoint of improving other physical properties in a well-balanced manner, for example, 5 ⁇ 10 9 Pa or less, preferably 1 ⁇ 10 9 Pa or less, more preferably 8 ⁇ 10 8 Pa or less.
- the adhesive film of the present invention has a ratio of undissolved components of 35% by mass or more and 100% by mass or less when 1.0 g of the adhesive film is dissolved in 10 g of isopropyl alcohol. If the undissolved component is less than 35% by mass, the moisture and heat resistance is lowered, and when used for a long time in a high-temperature and high-humidity environment, whitening may occur at the periphery of the adhesive film, resulting in poor appearance. From the viewpoint of further improving moist heat resistance, the content of undissolved components is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.
- the shear storage modulus, the maximum peak temperature of tan ⁇ , and the proportion of undissolved components described above can be adjusted by appropriately selecting the type of resin, the molecular weight of the resin, the presence or absence of a plasticizer, and its content. .
- thermoplastic resins used for adhesive films include (meth)acrylic resins, polyvinyl acetal resins, polyvinyl alcohol resins (PVA), polyurethane resins (PU), ethylene-vinyl acetate copolymer resins (EVA ), saponified ethylene-vinyl acetate copolymer (EVOH), ethylene-methacrylic acid copolymer resin, ionomer resin, isobutylene resin, styrene-isoprene copolymer resin, styrene-butadiene copolymer resin, and the like.
- the thermoplastic resin may be used singly or in combination of two or more.
- polyvinyl acetal resin polyurethane resin (PU), ethylene-vinyl acetate copolymer resin (EVA), and ethylene-vinyl acetate copolymer string are used from the viewpoint of achieving both moist heat resistance and impact resistance.
- compounds (EVOH), ethylene-methacrylic acid copolymer resins, ionomer resins, isobutylene resins, styrene-isoprene copolymer resins, and styrene-butadiene copolymer resins are preferred.
- thermoplastic resins described above polyvinyl acetal-based resins are more preferable.
- thermoplastic resin By using a polyvinyl acetal-based resin, it becomes easier to achieve excellent impact resistance. In addition, it becomes easy to improve the adhesive force to various resin materials and inorganic glass.
- the polyvinyl acetal-based resin used for the thermoplastic resin will be described in detail below.
- the thermoplastic resin is more preferably a polyvinyl acetal resin.
- the polyvinyl acetal resin may be a modified polyvinyl acetal resin or an unmodified polyvinyl acetal resin.
- the modified polyvinyl acetal resin may have a structure (modifying group) other than an acetal group, a hydroxyl group, and an acetyl group, and preferably has a modifying group in a side chain, as will be described later. Hydrophobicity of the modified polyvinyl acetal resin is increased by appropriately changing the type of modifying group, and the proportion of the above-described undissolved components can be easily increased.
- a polyvinyl acetal-based resin is obtained by acetalizing polyvinyl alcohol with an aldehyde, and optionally reacting it with a modifier or re-acetylating it. Moreover, in order to obtain a modified polyvinyl acetal resin, modified polyvinyl alcohol may be used as the raw material polyvinyl alcohol.
- the structure other than the above acetal group, hydroxyl group, and acetyl group is preferably a polyalkylene oxide structure.
- a polyalkylene oxide structure by having a polyalkylene oxide structure, the hydrophobicity increases and the ratio of the above-described undissolved components increases, thereby facilitating improvement in resistance to heat and humidity. In addition, it becomes easy to improve the impact resistance and the adhesiveness to resin materials.
- the polyalkylene oxide structure is as represented by the following formula (1).
- a 1 O is an oxyalkylene group having 2 to 6 carbon atoms, m is the average number of repetitions, and is 4 to 200.
- R 1 is an alkyl group having 1 to 8 carbon atoms or It is a hydrogen atom.
- the oxyalkylene group may be of one type alone, or two or more types may be mixed.* indicates the bonding position with another group.
- the oxyalkylene group for A 1 O is an oxyalkylene group having 2 to 6 carbon atoms, preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably an oxyalkylene group having 2 or 3 carbon atoms.
- the alkylene group in the oxyalkylene group may be linear or may have a branched structure.
- the oxyalkylene group includes, for example, an oxyethylene group, an oxypropylene group, or an oxybutylene group, preferably an oxyethylene group or an oxypropylene group.
- One type of oxyalkylene group may be used alone, but two or more types may be used in combination. When two or more types are used in combination, each oxyalkylene group may be added at random or may be added in blocks, but is more preferably added at random.
- the oxyalkylene group in the polyalkylene oxide structure preferably contains at least one of an oxyethylene group and an oxypropylene group, and preferably contains both an oxyethylene group and an oxypropylene group.
- both an oxyethylene group and an oxypropylene group may form a block structure, but more preferably a random structure.
- the ratio (PO/EO) of the oxypropylene group to the oxyethylene group is, for example, 1/9 or more and 9/1 or less, preferably 2 /8 or more and 8/2 or less, more preferably 3/7 or more and 7/3 or less.
- m represents the average number of repeating oxyalkylene groups, and is 4-200, preferably 5-100, more preferably 10-80, and still more preferably 15-50.
- the alkyl group for R 1 may be linear or may have a branched structure.
- alkyl groups for R 1 include branched butyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl and t-butyl groups, n-pentyl group, branched pentyl group, n branched heptyl groups such as -hexyl group, branched hexyl group, n-heptyl group, isoheptyl group and 3-heptyl group; branched octyl groups such as n-octyl group, isooctyl group and 2-ethylhexyl group; R 1 may be either an alkyl group or a hydrogen atom, but an alkyl group is preferred.
- the polyalkylene oxide structure preferably has an alkyl group at the end. If the polyalkylene oxide structure has an alkyl group at its terminal, the hydrophobicity of the structure increases, and the resistance to moist heat of the adhesive film is more likely to be improved.
- the alkyl group may have 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
- the above polyalkylene oxide structure may be linked to the main chain via a single bond, but is preferably linked to the main chain via a linking group other than a single bond.
- Linking groups other than single bonds include ether bond (-O-), ester bond (-COO-), amide bond (-CONR-: R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom ), or a hydrocarbon group which may have at least one of these bonds.
- R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom
- a hydrocarbon group which may have at least one of these bonds is more preferable.
- the number of carbon atoms in the hydrocarbon group is not particularly limited, but may be, for example, about 1-10, preferably 1-4.
- the polyalkylene oxide structure is bonded to the main chain via either an ether bond or —CH 2 O—.
- the polyalkylene oxide structure is attached to the main chain through any of these to facilitate its manufacture.
- an oxygen atom is preferably bonded to the polyalkylene oxide structure.
- a polyvinyl acetal-based resin typically has an acetal group, a hydroxyl group, and an acetyl group.
- the polyvinyl acetal-based resin does not have to contain hydroxyl groups by being modified with functional groups or undergoing a re-acetylation reaction.
- the acetal group, hydroxyl group, and acetyl group are groups bonded directly to the main chain or via an oxygen atom, as shown in formulas (3-1) to (3-3) described later.
- a hydroxyl group, etc., possessed by the polyalkylene oxide structure is not included.
- the polyvinyl acetal-based resin is preferably modified to have a polyalkylene oxide structure represented by the above formula (1) as described above.
- the polyvinyl acetal resin having a polyalkylene oxide structure is sometimes described as a modified polyvinyl acetal resin (A) in order to distinguish it from other polyvinyl acetal resins.
- the modified polyvinyl acetal resin (A) preferably has a modification amount of 0.1 mol % or more and 10 mol % or less with the polyalkylene oxide structure (that is, the functional group represented by formula (1)).
- the amount of modification is within the above range, the maximum peak temperature of tan ⁇ becomes an appropriate temperature, the shear storage elastic modulus at 20° C. tends to increase, and the impact resistance tends to improve. Moreover, it becomes easy to improve the adhesive force with respect to various resin materials. Furthermore, by making it more than the said lower limit, the ratio of the above-described undissolved component becomes high, and heat-and-moisture resistance tends to become favorable.
- the amount modified by the polyalkylene oxide structure is preferably 0.2 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.4 mol% or more, and particularly 0.5 mol% or more. 8 mol % or less is preferable, 6 mol % or less is more preferable, and 4 mol % or less is even more preferable.
- the amount of modification by the functional group represents the ratio of the functional group to all the vinyl monomer units that constitute the polyvinyl acetal-based resin.
- the amount of modification can be calculated from the spectrum obtained by subjecting the polyvinyl acetal-based resin to proton NMR measurement.
- the degree of acetalization, the amount of hydroxyl groups, and the degree of acetylation, which will be described later, can be calculated from the spectrum obtained by performing proton NMR measurement.
- the polyvinyl acetal-based resin does not have to have the polyalkylene oxide structure described above.
- a polyvinyl acetal resin may be a modified polyvinyl acetal resin having a modifying group other than the functional group represented by formula (1), or may be an unmodified polyvinyl acetal resin. Even with an unmodified polyvinyl acetal resin, the maximum peak temperature of tan ⁇ can be lowered by reducing the amount of hydroxyl groups as will be described later by a re-acetylation reaction or the like, thereby making it easier to increase the impact resistance.
- Examples of modifying groups other than the functional groups represented by formula (1) include alkyl groups.
- the alkyl group may be linear or may have a branched structure.
- the number of carbon atoms in the alkyl group is, for example, 2-30, preferably 3-24, more preferably 5-20, still more preferably 7-18, still more preferably 11-18.
- the alkyl group may be directly bonded to the main chain, preferably a structural unit derived from a vinyl group constituting the main chain, but preferably an ether bond (-O-) or an ester bond (*-COO-**). , through a urethane bond (*-NHCOO-**), more preferably through an ester bond or a urethane bond.
- the polyvinyl acetal-based resin has a vinyl group-derived structural unit as a main chain, and the functional group represented by formula (1) is bonded to the vinyl group-derived structural unit that constitutes the main chain. good. Therefore, the polyvinyl acetal-based resin preferably has a structural unit represented by the following formula (2). It is more preferable to have
- R 2 is a single bond or a hydrocarbon group which may have at least one of an ester bond and an ether bond. or.
- a 1 O, R 1 , and m in the formulas (2), (2-1), and (2-2) are as described above, so description thereof will be omitted.
- the carbon number of R 2 in formula (2) is, for example, 1-10, preferably 1-4.
- the hydrocarbon group of R 2 may have an ester bond or an ether bond as described above, but preferably does not have an ester bond or an ether bond.
- Polyvinyl acetal-based resins typically have an acetal group, a hydroxyl group, and an acetyl group. ) and structural units represented by formula (3-3). Therefore, the modified polyvinyl acetal resin is composed of structural units represented by the following formulas (3-1), (3-2) and (3-3) and structural units represented by the above formula (2). It is preferable to have However, when the polyvinyl acetal-based resin is, for example, an unmodified polyvinyl acetal resin, as described above, the polyvinyl acetal-based resin may not have a hydroxyl group and may not have the structural unit represented by formula (3-2). That is, the unmodified polyvinyl acetal resin has structural units represented by the following formulas (3-1) and (3-3), and optionally further a structural unit represented by the following formula (3-2). may have.
- R represents a hydrogen atom or a hydrocarbon group having 1 to 19 carbon atoms.
- Polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol or modified polyvinyl alcohol obtained by modifying polyvinyl alcohol with aldehyde as described above, and then modifying it as necessary. 80-99.8 mole % polyvinyl alcohol is commonly used.
- the number of carbon atoms in the acetal group contained in the polyvinyl acetal-based resin is not particularly limited. ⁇ 6 is more preferred, and 2, 3 or 4 is even more preferred. Accordingly, the number of carbon atoms in R represented by formula (3-1) is preferably 1 to 9, more preferably 1 to 5, even more preferably 1 to 3.
- the acetal group is particularly preferably a butyral group, and therefore, the polyvinyl acetal-based resin is preferably a polyvinyl butyral-based resin.
- the degree of acetalization (that is, the amount of acetal) of the polyvinyl acetal-based resin is, for example, 40 mol % or more and 90 mol % or less.
- the degree of acetalization is preferably 60 mol % or more, more preferably 63 mol % or more, and even more preferably 65 mol % or more. As the degree of acetalization increases, the ratio of the above-described undissolved components tends to increase, and resistance to moist heat tends to improve. Also, the degree of acetalization is more preferably 88 mol % or less, and still more preferably 85 mol % or less. By setting the degree of acetalization within these ranges, it becomes easier to contain a certain amount of the functional group represented by formula (1) while maintaining an appropriate amount of hydroxyl groups.
- the degree of acetalization means the degree of acetoacetalization when the acetal group of the polyvinyl acetal-based resin is an acetoacetal group, and the degree of butyralization when the acetal group is a butyral group. . Further, the degree of acetalization represents the ratio of acetalized vinyl alcohol units to all vinyl monomer units constituting the polyvinyl acetal-based resin.
- the hydroxyl group content of the polyvinyl acetal resin is preferably 35 mol % or less, more preferably 33 mol % or less, still more preferably 30 mol % or less, and even more preferably 25 mol % or less.
- amount of hydroxyl groups is set to the above upper limit or less, the maximum peak temperature of tan ⁇ can be easily adjusted to a suitable value, and the adhesive strength to low-polarity resin materials such as polycarbonate can be easily increased. Furthermore, it becomes easier to increase the proportion of the undissolved portion described above.
- the hydroxyl group content of the polyvinyl acetal resin is preferably 0 mol% or more, but in the case of the modified polyvinyl acetal resin (A), from the viewpoint of preventing the adhesive film from becoming too flexible, a certain amount is preferably 5 mol % or more, preferably 9 mol % or more, more preferably 10 mol % or more, still more preferably 12 mol % or more.
- the hydroxyl group content is lowered in order to lower the maximum peak temperature of tan ⁇ and increase the adhesive strength to resins with low polarity such as polycarbonate.
- the amount of hydroxyl groups in the unmodified polyvinyl acetal resin is preferably 15 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, even more preferably 3 mol% or less, and most preferably 0 mol%. is.
- the amount of hydroxyl groups represents the ratio of hydroxyl groups to all vinyl monomer units constituting the polyvinyl acetal-based resin.
- the degree of acetylation (acetyl group content) of the polyvinyl acetal resin is, for example, 0.01 mol % or more and 50 mol % or less. In order to keep the amount of modification by the functional group above a certain value, the degree of acetylation should also be below a certain value. Therefore, the degree of acetylation of the modified polyvinyl acetal resin (A) is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 12 mol% or less, and even more preferably 5 mol% or less. The degree of acetylation of the modified polyvinyl acetal resin (A) is, for example, 0.01 mol % or more as described above, preferably 0.1 mol % or more, and more preferably 0.3 mol % or more.
- the acetyl The degree of conversion is preferably a certain value or more, preferably 15 mol % or more, more preferably 25 mol % or more, and still more preferably 30 mol % or more.
- the degree of acetylation of the unmodified polyvinyl acetal resin is, for example, 50 mol % or less, preferably 45 mol % or less, and more preferably 42 mol % or less.
- the degree of acetylation represents the ratio of acetyl groups to all vinyl monomer units constituting the polyvinyl acetal-based resin.
- the weight average molecular weight (Mw) of the polyvinyl acetal resin is preferably 50,000 or more and 800,000 or less.
- the weight-average molecular weight within the above range, the shear storage modulus, the maximum peak temperature of tan ⁇ , and the like are set within the desired range, and the impact resistance, adhesiveness, etc. are easily improved.
- the weight average molecular weight (Mw) of the polyvinyl acetal resin is more preferably 100,000 or more, still more preferably 120,000 or more, and even more preferably 150,000 or more.
- the weight average molecular weight (Mw) is more preferably 600,000 or less, even more preferably 500,000 or less, and even more preferably 400,000 or less.
- the weight average molecular weight (Mw) is measured by gel permeation chromatography.
- Aldehydes used in producing polyvinyl acetal resins are not particularly limited, and are, for example, aldehydes having 1 to 20 carbon atoms, but generally aldehydes having 2 to 10 carbon atoms are preferably used.
- the aldehyde having 2 to 10 carbon atoms is not particularly limited, and examples thereof include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, and n-octylaldehyde.
- aldehydes having 2 to 6 carbon atoms such as acetaldehyde, n-butyraldehyde, n-hexylaldehyde and n-valeraldehyde are preferable, aldehydes having 2, 3 and 4 carbon atoms are more preferable, and n-butyraldehyde is further preferable. preferable.
- aldehydes may be used alone or in combination of two or more.
- the polyvinyl acetal-based resins used in the present invention may be used singly or in combination of two or more.
- the pressure-sensitive adhesive film of the present invention may have a thermoplastic resin other than the polyvinyl acetal-based resin as long as the effects of the present invention are exhibited.
- the main component is a polyvinyl acetal-based resin.
- Thermoplastic resins other than polyvinyl acetal resins are as described above.
- the content of the polyvinyl acetal-based resin is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, based on the total amount of the thermoplastic resin contained in the adhesive film. Most preferably it is 100% by mass. Therefore, the thermoplastic resin contained in the pressure-sensitive adhesive film of the present invention may consist only of a polyvinyl acetal-based resin.
- the adhesive film of the present invention may contain a plasticizer.
- the adhesive film becomes flexible by containing a plasticizer, and by lowering the maximum peak temperature of tan ⁇ of the adhesive film, it is possible to increase the adhesiveness to various adherends such as various resin materials such as polycarbonate and inorganic glass. can.
- the adhesive film of the present invention does not contain a plasticizer or contains a small amount of the plasticizer. By containing only a small amount of plasticizer or not containing it, it is possible to prevent the ratio of the undissolved components from decreasing, and the wet heat resistance tends to be improved.
- the adhesive film of the present invention contains a small amount of plasticizer or does not contain a plasticizer, by using the above-described predetermined thermoplastic resin, the adhesion to various resin materials such as polycarbonate can be improved.
- the content of the plasticizer in the adhesive film is preferably less than 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the adhesive film.
- the content of the plasticizer is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less.
- the lower limit of the plasticizer content is 0 parts by mass.
- the resin composition of the present invention may not contain a plasticizer, but the inclusion of a plasticizer makes it easier to improve the adhesiveness of the resin film.
- the resin composition preferably contains a plasticizer from the viewpoint of improving the adhesiveness of the resin film.
- plasticizers examples include organic ester plasticizers and organic phosphorous plasticizers such as organic phosphate plasticizers and organic phosphite plasticizers.
- organic ether plasticizers such as polyalkylene glycol plasticizers and polyoxyalkylene ether plasticizers, and alcohol plasticizers are also included.
- a plasticizer may be used individually by 1 type, and may use 2 or more types together. Among them, organic ester plasticizers are preferred.
- Preferred organic ester plasticizers include monobasic organic acid esters and polybasic organic acid esters.
- Monobasic organic acid esters include esters of glycols with monobasic organic acids.
- Glycols include polyalkylene glycols in which each alkylene unit has 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and the number of repeating alkylene units is 2 to 10, preferably 2 to 4.
- the glycol may also be a monoalkylene glycol having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms (that is, 1 repeating unit).
- Specific examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and butylene glycol.
- Examples of monobasic organic acids include organic acids having 3 to 10 carbon atoms, and specific examples include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, and 2-ethylhexylic acid. , n-nonylic acid and decylic acid.
- Specific monobasic organic acids include triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, di Propylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, triethylene glycol di-n-heptanoate, tetraethylene glycol Di-n-heptanoate, triethylene glycol di-2-ethylbutyrate,
- polybasic organic acid esters examples include ester compounds of dibasic organic acids having 4 to 12 carbon atoms such as adipic acid, sebacic acid and azelaic acid and alcohols having 4 to 10 carbon atoms. .
- the alcohol having 4 to 10 carbon atoms may be linear, branched, or cyclic. Specific examples include dibutyl sebacate, dioctyl azelate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptyl nonyl adipate, dibutyl carbitol adipate, and mixed adipates.
- oil-modified alkyd sebacic acid may be used.
- Mixed adipates include adipates prepared from two or more alcohols selected from alkyl alcohols having 4 to 9 carbon atoms and cyclic alcohols having 4 to 9 carbon atoms.
- the organic phosphorus plasticizer include phosphoric acid esters such as tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphate.
- the organic ester plasticizer is not limited to the complete ester of each ester described above, and may be a partial ester.
- it may be a partial ester between a glycol and a monobasic organic acid, or a partial ester between a dibasic organic acid and an alcohol.
- Specific examples include triethylene glycol-mono-2-ethylhexanoate.
- it may be a trihydric or higher alcohol such as glycerin and a partial ester of a monobasic organic acid.
- Monobasic organic acids include monobasic organic acids having 3 to 24 carbon atoms, preferably 6 to 18 carbon atoms.
- partial esters of trihydric or higher alcohols and monobasic organic acids include mono- or diesters of glycerin and stearic acid and mono- or diesters of glycerin and 2-ethylhexyl acid.
- organic ester plasticizers triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferably used.
- Polyalkylene glycol-based plasticizers include polyethylene glycol, polypropylene glycol, poly(ethylene oxide/propylene oxide) block copolymer, poly(ethylene oxide/propylene oxide) random copolymer, polytetramethylene glycol and the like. Among them, polypropylene glycol is preferred.
- a polyoxyalkylene ether-based plasticizer is an ether compound of a monohydric or polyhydric alcohol and polyoxyalkylene.
- Specific polyoxyalkylene ether plasticizers include, for example, polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene nonyl ether, polyoxyethylene Ethylene decyl ether, polyoxyethylene allyl ether, polyoxypropylene allyl ether, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyalkylene pentaerythritol ether, etc.
- the polyoxyalkylene ether plasticizer is preferably an ether compound of polyhydric alcohol and polyoxyalkylene, more preferably an ether compound of glycerin or diglycerin and polyoxyalkylene, still more preferably glycerin or diglycerin. and polyoxypropylene.
- Alcohol-based plasticizers include various polyhydric alcohols such as butanediol, hexanediol, trimethylolpropane, and pentaerythritol. Among these, trimethylolpropane is preferred.
- the adhesive film may appropriately contain known additives used in combination with the thermoplastic resin, in addition to the plasticizer. That is, the adhesive film may be made of a thermoplastic resin such as a polyvinyl acetal-based resin. good too. Additives other than the plasticizer specifically include ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, adhesion modifiers, pigments, dyes, fluorescent brighteners, crystal nucleating agents, and the like. . Moreover, the resin composition of the present invention may be diluted with a solvent and used in the form of a diluent.
- the adhesive film does not contain a low-molecular-weight compound, or if it does contain a small amount.
- the low-molecular-weight compound refers to a compound having a molecular weight of less than 1,000, and includes the above-described plasticizers and reactive diluents that are cured by light irradiation.
- reactive diluents include (meth)acrylic reactive diluents such as (meth)acrylic monomers and (meth)acrylic oligomers, epoxy reactive diluents such as epoxy monomers and epoxy oligomers, and alkoxysilanes. Silicone-based reactive diluents such as monomers and alkoxysilane oligomers may be used.
- the content of the low molecular weight compound in the adhesive film is, for example, less than 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the adhesive film. When the content of the low-molecular-weight compound is reduced, the ratio of undissolved components increases, and the resistance to moist heat tends to be improved.
- the content of the low-molecular-weight compound is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, from the viewpoint of moist heat resistance.
- the lower limit of the content of the low molecular weight compound is 0 parts by mass.
- the polyvinyl acetal resin used in the adhesive film of the present invention is obtained by acetalizing polyvinyl alcohol (also referred to as "raw material polyvinyl alcohol") with aldehyde, and then reacting with a modifier as necessary, or re-acetylating. It is obtained by As raw material polyvinyl alcohol, unmodified polyvinyl alcohol may be used, but in the case of obtaining a modified polyvinyl acetal resin, modified polyvinyl alcohol may be used as raw material polyvinyl alcohol. For example, when producing a modified polyvinyl acetal resin (A) having a polyalkylene oxide structure, it is preferable to use the following production method (1).
- polyoxyalkylene-modified polyvinyl alcohol is produced as raw material polyvinyl alcohol. Specifically, it is obtained by polymerizing a vinyl ester and a monomer containing a vinyl monomer having a polyoxyalkylene group to obtain a polymer, and then saponifying the polymer. Alkali or acid is generally used for saponification, and alkali is preferably used.
- the polyoxyalkylene-modified polyvinyl alcohol only one type may be used, or two or more types may be used in combination.
- the polyoxyalkylene-modified polyvinyl alcohol obtained above is acetalized with an aldehyde to obtain a modified polyvinyl acetal resin (A).
- the method of acetalization is preferably carried out by a known method.
- Vinyl esters used in production method (1) include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isoformate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid.
- Vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, and the like can be used. Among these, vinyl acetate is preferred.
- vinyl monomers having a polyoxyalkylene group used in production method (1) include compounds represented by the following formula (4).
- a polyoxyalkylene vinyl ether represented by the following formula (4-1) and a polyoxyalkylene allyl ether represented by the following formula (4-2) are preferable.
- vinyl monomers having a polyoxyalkylene group include polyoxyethylene monovinyl ether, polyoxyethylene polyoxypropylene monovinyl ether, polyoxypropylene monovinyl ether, polyoxyethylene monoallyl ether, polyoxyethylene polyoxypropylene mono Allyl ether, polyoxypropylene monoallyl ether, polyoxyethylene alkyl vinyl ether, polyoxyethylene polyoxypropylene alkyl vinyl ether, polyoxypropylene alkyl vinyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether, polyoxy and propylene alkyl allyl ether.
- an unmodified polyvinyl acetal resin it is preferable to manufacture it by the following manufacturing methods (2).
- Manufacturing method (2) raw polyvinyl alcohol is acetalized with aldehyde to obtain a polyvinyl acetal-based resin (hereinafter also referred to as raw polyvinyl acetal-based resin).
- raw polyvinyl acetal-based resin a polyvinyl acetal-based resin
- undenatured polyvinyl alcohol obtained by saponifying polyvinyl ester is used as raw material polyvinyl alcohol.
- the raw material polyvinyl acetal resin is preferably subjected to a re-acetylation treatment to obtain an unmodified polyvinyl acetal resin.
- the re-acetylation treatment may be performed by a conventionally known method using acetic anhydride in the presence of a base such as pyridine.
- the re-acetylation treatment may be carried out by heating at, for example, 50° C. or higher and 100° C. or lower, preferably 70° C. or higher and 90° C. or lower.
- the modified polyvinyl acetal resin having an alkyl group in its side chain may be produced, for example, by the following production method.
- a raw material polyvinyl alcohol is acetalized with an aldehyde to obtain a polyvinyl acetal-based resin (hereinafter also referred to as a raw material polyvinyl acetal-based resin).
- the raw material polyvinyl alcohol used here is obtained by saponifying a polyvinyl ester, and is preferably unmodified polyvinyl alcohol.
- the raw material polyvinyl acetal resin is reacted with a modifying agent having an alkyl group to introduce an alkyl group into the raw material polyvinyl acetal resin.
- the modifying agent is preferably a compound having a reactive group that forms a urethane bond or an ester bond by reacting with the hydroxyl group of the raw material polyvinyl acetal resin.
- alkyl isocyanates having an alkyl group having 2 to 30 carbon atoms such as n-octadecyl isocyanate.
- carboxylic acids having 3 to 31 carbon atoms, or carboxylic acid derivatives such as anhydrides, carboxylic acid esters and carboxylic acid halides of the above carboxylic acids are also included.
- Preferred carboxylic acid derivatives are carboxylic acid chlorides such as 2-ethylhexanoyl chloride, lauroyl chloride, myristyl chloride, palmitoyl chloride and stearoyl chloride.
- the pressure-sensitive adhesive film of the present invention is not only a single pressure-sensitive adhesive film, but also a layered or film-like form obtained by laminating or coating on another member. Sheets, which are relatively thick, are also called adhesive films.
- the thickness of the adhesive film is not particularly limited, it is, for example, 100 ⁇ m or more and 2000 ⁇ m or less, preferably 100 ⁇ m or more and 1000 ⁇ m or less.
- the thickness of the adhesive film is preferably as large as possible, more preferably 200 ⁇ m or more, and still more preferably 300 ⁇ m or more.
- the thickness of the adhesive film is more preferably 500 ⁇ m or less.
- the adhesive film of the present invention may consist of a single layer.
- the layers constituting the single-layer film preferably have the same composition as described for the adhesive film. That is, the layer constituting the single-layer film preferably contains a thermoplastic resin and does not contain a plasticizer, or contains a plasticizer in the above-described content. Furthermore, additives may be appropriately added as described above.
- the adhesive film of the present invention may be a multilayer film having two or more layers.
- the composition of the entire film should be as described for the adhesive film, but each layer (hereinafter also referred to as "first layer") may have the composition as described for the adhesive film.
- each first layer preferably contains a thermoplastic resin and does not contain a plasticizer, or contains a plasticizer in the amount described above, as described for the adhesive film.
- additives may be appropriately added as described above.
- the details of the thermoplastic resin, plasticizer, and additives in each first layer of the multilayer film and the details of the content of each component are as described for the adhesive film above.
- the thermoplastic resin used as the reference for the content is the thermoplastic resin contained in each first layer.
- each first layer may have the same composition or different compositions.
- the multilayer film may be a laminate of the above-described first layer and a layer other than the first layer (hereinafter also referred to as "second layer"). Specifically, for example, a three-layer structure of first layer/second layer/first layer may be used.
- each layer preferably has the same composition as described for the adhesive film.
- the adhesive film of the present invention can be produced by forming a resin composition containing a thermoplastic resin such as a polyvinyl acetal resin into a film by a known method.
- the resin composition contains at least a thermoplastic resin such as a polyvinyl acetal-based resin produced as described above, and may be prepared by adding a plasticizer, an additive, and the like, if necessary.
- the resin composition may be used by diluting it with a solvent as appropriate.
- a single-layer pressure-sensitive adhesive film is formed by coating a resin composition on a support such as a release sheet, or by pouring it into a mold, heating and drying as necessary, and forming a film. It may be molded into a thin film, or may be molded into a film by extrusion molding, press molding, or the like. Further, as described above, when the polyvinyl acetal-based resin is reacted with the modifier to obtain the polyvinyl acetal-based resin, the molding may be performed as follows.
- composition containing a raw material polyvinyl acetal resin, a modifier, and other optional additives such as a plasticizer is coated on a support such as a release sheet, or a mold and then heated to react the modifying agent with the raw material polyvinyl acetal-based resin to form a film.
- the adhesive film is a multilayer film
- each layer may be suitably laminated, and the multi-layer structure may be formed by co-extrusion or the like.
- the pressure-sensitive adhesive film of the present invention is not particularly limited and can be used for various applications, but is preferably used for various display applications, laminated glass applications, and the like.
- the display is not particularly limited, it is preferably for vehicle use.
- the display includes a liquid crystal display, an organic EL display, and the like, and among them, a liquid crystal display is preferable.
- Laminated glass is used in vehicles such as automobiles, trains, ships, airplanes, and other vehicles, buildings, condominiums, detached houses, halls, and gymnasiums, as well as machine tools for cutting and polishing, excavators, and cranes. It is used for window glass of construction machines and the like, and is preferably used for vehicles such as automobiles.
- the pressure-sensitive adhesive film of the present invention has high impact resistance and is less likely to cause damage to laminates and the like described later, and even if damage occurs, the fragments are less likely to scatter, so it is used for in-vehicle displays and vehicle window glasses. It is suitable to
- the laminated glass and display to which the pressure-sensitive adhesive film of the present invention is applied preferably include a laminate described below.
- the pressure-sensitive adhesive film of the present invention is not particularly limited, it is preferably used together with a substrate such as an organic material substrate or an inorganic material substrate, and used as part of a laminate.
- the laminate of the present invention preferably includes the adhesive film described above and a base material selected from at least one of an inorganic material base material and an organic material base material.
- the adhesive film is preferably arranged so as to adhere to at least one of the inorganic material substrate and the organic material substrate.
- the adhesive film can have high adhesive strength to various resin materials, so that it can be attached to the base material with high adhesive strength by arranging it at a position where it adheres to the organic material base material.
- organic material substrates include organic resin plates and resin films.
- the organic resin plate is also called an organic glass plate.
- organic resin plates include, but are not limited to, polycarbonate plates, (meth)acrylic plates such as polymethylmethacrylate plates, acrylonitrile-styrene copolymer plates, acrylonitrile-butadiene-styrene copolymer plates, polyester plates such as polyethylene terephthalate plates, Various organic glass plates such as fluorine resin plate, polyvinyl chloride plate, chlorinated polyvinyl chloride plate, polypropylene plate, polystyrene plate, polysulfone plate, epoxy resin plate, phenol resin plate, unsaturated polyester resin plate, polyimide resin plate, etc. mentioned.
- the organic resin plate may be appropriately subjected to surface treatment or the like.
- a polycarbonate plate is preferable from the viewpoint of excellent transparency and impact resistance
- a (meth)acrylic plate is preferable from the viewpoint of high transparency, excellent weather resistance, and mechanical strength. is more preferred.
- the thickness of the organic resin plate is not particularly limited, it is preferably 0.1 mm or more, more preferably 0.4 mm or more, and preferably 5.0 mm or less, further preferably 3.0 mm or less.
- the resin film is not particularly limited, but includes polyester resin films such as (meth)acrylic resin films, polycarbonate films, polyethylene terephthalate (PET) films and polyethylene naphthalate (PEN) films, polyolefin resin films such as polyethylene films and polypropylene films, A cyclic polyolefin (COP) film, a triacetyl cellulose (TAC) film, a polyether sulfone (PES) resin film, a polyimide resin film, and the like are included.
- a surface layer such as a hard coat layer made of (meth)acrylic resin may be provided on the surface of the resin film.
- the resin film may consist of a single layer, or may be a laminate of two or more layers.
- the organic material substrate may be a functional film containing the above resin film.
- functional films include polarizing films (polarizing plates) and light control films. The structures of the polarizing film and the light control film are as described later.
- the thickness of the resin film or functional film in the laminate is not particularly limited, it is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more, and preferably 500 ⁇ m or less, further preferably 450 ⁇ m or less. It should be noted that while the organic resin plate is relatively thick, has low flexibility, and cannot be generally bent, it is generally referred to as a resin film, which is relatively thin and generally bendable. are not clearly distinguished.
- An inorganic glass plate can be mentioned as an inorganic material base material.
- the inorganic glass plate is not particularly limited, but examples thereof include float plate glass, tempered glass, colored glass, polished plate glass, figured glass, wired plate glass, lined plate glass, ultraviolet absorbing plate glass, infrared reflecting plate glass, and infrared absorbing plate glass. , various glass plates such as green glass.
- the inorganic glass may be subjected to surface treatment or the like.
- the thickness of the inorganic glass is not particularly limited, it is preferably 0.1 mm or more, more preferably 1.0 mm or more, and preferably 5.0 mm or less, further preferably 3.0 mm or less.
- the organic material base material or the inorganic material base material may be appropriately attached with an electrode, a sensor, or the like.
- the electrode is composed of a conductive layer laminated on each base material.
- a touch sensor is mentioned as a sensor.
- a touch sensor is a sensor that detects a touch input when a finger, touch pen, or other object approaches or touches a base material, and is composed of a conductive layer laminated on the base material.
- a touch sensor causes an electrical change such as capacitance, current, or voltage to occur in the conductive layer. Detect touch input.
- the conductive layer is not particularly limited, and conventionally known transparent electrode materials can be used without particular limitation.
- Examples include indium tin oxide (ITO) conductive films, tin oxide conductive films, and zinc oxide conductive films. , polymer conductive films, and the like.
- the organic material substrate (especially, film) on which a conductive layer such as an electrode or sensor is laminated may have the above-described hard coat layer formed on the surface opposite to the surface on which the conductive layer is provided.
- the surface opposite to the surface on which the conductive layer is provided is usually the surface to be adhered to the adhesive film, but the adhesive film of the present invention has good adhesion even to the surface provided with the hard coat layer. Easy to use.
- the adhesive film of the present invention is not particularly limited, it is preferably used for bonding a pair of substrates. Therefore, the laminate of the present invention specifically includes the adhesive film and a pair of substrates, and preferably the adhesive film is arranged between the pair of substrates. And it is preferable that a pair of base material is joined through an adhesive film.
- both of the pair of substrates are preferably glass.
- the glass may be an inorganic glass plate or an organic glass plate.
- one of the pair of substrates may be glass and the other may be a film. In this case, the glass may be an inorganic glass plate or an organic glass plate.
- the film may be a resin film, but is preferably a functional film such as a polarizing film (polarizing plate) or a light control film.
- the pressure-sensitive adhesive sheet of the present invention has high impact resistance, even if it is used for bonding glass to glass or glass to another member, the glass is less likely to break, and even if the glass is broken, the fragments is less likely to scatter and safety is enhanced.
- the laminate is not particularly limited, but includes a pair of substrates selected from inorganic material substrates and organic material substrates, and an adhesive film disposed between the pair of substrates, and has three or more layers. It preferably has a multilayer structure. In such a multilayer structure, for example, the adhesive film may be adhered to both of the pair of substrates, thereby joining the pair of substrates via the adhesive film. In this case, the adhesive film is preferably the adhesive film of the present invention described above.
- the laminate may have a structure in which another intermediate member is arranged between the pair of base materials.
- an adhesive film is provided between each base material and the intermediate member.
- the adhesive film is preferably adhered to each base material and the intermediate member, so that the base material and the intermediate member are bonded via the adhesive film.
- the adhesive film between the substrate and the intermediate member may be a resin film, and at least one of them may be the pressure-sensitive adhesive film of the present invention.
- An adhesive film is preferred.
- the intermediate member preferably has at least one of the inorganic material substrate and the organic material substrate described above, and at least one of the inorganic material substrate and the organic material substrate is arranged at a position where the pressure-sensitive adhesive film of the present invention adheres. good.
- the laminate described above may constitute a display, laminated glass, etc., but is not limited to these.
- the intermediate member may be a touch panel, a light control element, or the like, but is not limited to these.
- the inorganic material base material and the organic material base material may constitute a part of a touch panel, a light control element, a display element constituting a display, and the like.
- the laminate of the present invention can be produced, for example, by preparing an adhesive film and crimping each member through the prepared adhesive film.
- it can be produced by laminating a base material, an adhesive film, and a base material in this order and pressing them together.
- an intermediate member it can be produced by stacking the base material, the adhesive film, the intermediate member, the adhesive film, and the base material in this order and pressing them together.
- Crimping is not particularly limited, but it is preferable to crimp while heating.
- final bonding may be performed with a higher pressure, temperature, or both than the temporary pressure bonding.
- FIG. 1 shows a laminate according to a first embodiment.
- 30 A of laminated bodies are applied to a display with a touch panel.
- the display with a touch panel is preferably an in-vehicle display.
- a laminate 30A according to the present embodiment includes a display element 31, a surface protection panel 32, and a touch panel 33 arranged between the display element 31 and the surface protection panel 32. , and between the surface protection panel 32 and the touch panel 33, adhesive films 34A and 34B are arranged, respectively.
- the surface protection panel 32 is preferably an organic resin plate or an inorganic glass plate, and preferably an inorganic glass plate.
- the display element 31 may be an organic EL display element or a liquid crystal display element.
- a polarizing plate (polarizing film) is preferably provided on the outermost surface of the display element 31 .
- the outermost surface on the front side is the outermost surface on the surface protection panel side, and the opposite side is also called the back side.
- a polarizing plate (polarizing film) generally has a structure in which protective films are provided on both sides of a polarizer such as a polyvinyl alcohol resin film.
- the protective film is composed of the resin film described above, preferably a PET film, a COP film, or a TAC film.
- a hard coat layer made of (meth)acrylic resin or the like may be provided on the surface of the protective film as a surface layer of the substrate.
- a protective film is provided on the outermost surface on the front surface side. Therefore, in either case, the outermost surface on the front side of the display element 31 is composed of the organic material base material.
- the touch panel 33 may be composed of any one of inorganic glass, organic resin plate, or resin film with a touch sensor attached, but inorganic glass or resin film with a touch sensor is preferable. Further, in the touch panel 33, two or more of the inorganic glass, the organic resin plate, or the resin film may be laminated to form a multilayer structure. Also in this case, the touch sensor may be attached to any one of the inorganic glass, the organic resin plate, and the resin film in the touch panel 33 . Further, the touch panel 33 may have a protective film made of a resin film on either the outermost surface on the front side or the outermost surface on the back side. Therefore, in the touch panel 33, the bonding surface with the bonding films 34A and 34B is any one of inorganic glass, organic glass, and resin film.
- the adhesive films 34A and 34B are adhered to the display element 31, the touch panel 33, the touch panel 33 and the surface protection panel 32 to join them together.
- Either one of the adhesive films 34A and 34B may be the adhesive film of the present invention, but both are preferably the adhesive film of the present invention.
- the pressure-sensitive adhesive film of the present invention can have high adhesive strength not only to inorganic material substrates but also to various resin materials (that is, organic material substrates). Therefore, in the display element 33, the surface protection panel 32, and the touch panel 33, the adhesive surfaces of the adhesive films 34A and 34B may be composed of an organic material base material. , the display element 31 and the touch panel 33, and the surface protection panel 32 and the touch panel 33 can be joined.
- the pressure-sensitive adhesive film of the present invention has high impact resistance, even when the display with a touch panel is an in-vehicle display, it is possible to prevent the display with a touch panel from being damaged and causing serious damage. Furthermore, since the laminate has good moist heat resistance, the laminate can be used for a long period of time in a high-temperature and high-humidity environment.
- FIG. 2 shows a laminate according to a second embodiment.
- the laminate according to the second embodiment is also applied to a display, but the touch panel 33 is omitted in the laminate 30B. , with an adhesive film 34 disposed therebetween.
- the adhesive film 34 is made of the adhesive film of the present invention.
- the adhesive film 34 (adhesive film) is adhered to the display element 31 and the surface protection panel 32 to join them. Therefore, as in the first embodiment, the display element 31 and the surface protection panel 32 They are joined with high adhesive strength.
- the adhesive film has high impact resistance and high humidity and heat resistance, even if the laminate 30B is applied to an in-vehicle display, the display is less likely to suffer serious damage due to breakage. can be used for a long period of time.
- the surface protection panel 32 may be an OGS (one glass solution) panel, and the surface protection panel 32 may be provided with a sensor such as a touch sensor. Therefore, the surface protection panel 32 may be made of inorganic glass or the like with a sensor attached.
- OGS one glass solution
- FIG. 3 shows a laminate according to a third embodiment.
- a laminated body 30C according to the third embodiment is applied to a laminated glass with a light control function.
- a laminate 30C according to the present embodiment includes a pair of laminated glass members (base materials) 41 and 42 and a light control element 43 disposed between the pair of laminated glass members 41 and 42.
- Adhesive films 34A and 34B are arranged between 41 and the light control element 43 and between the other laminated glass member 42 and the light control element 43, respectively.
- the laminated glass members 41 and 42 may be inorganic glass plates or organic resin plates, and the details thereof are as described above.
- the light control element 43 is preferably a light control film including two resin films and a light control layer arranged between the two resin films. Therefore, the adhesive surfaces of the light control element 43 and the adhesive films 34A and 34B are made of a resin material.
- resin films included in the light modulating element 43 include polyester resin films such as PET films and PEN films, (meth)acrylic resin films, TAC films, PES resin films, and polyimide resin films. Among these, polyester resin films are preferred, and PET films are more preferred, from the viewpoint of handleability and the like.
- a conductive layer forming an electrode is provided on each of the two resin films on the light control layer side.
- the light control layer changes the visible light transmittance by switching between the application and non-application of a voltage between the conductive layers of the two resin films.
- the light control layer is preferably composed of a liquid crystal layer such as polymer dispersed liquid crystal (PDLC).
- the light control film may be an SPD (Suspended Particle Device) film, an electrochromic film, an electrophoretic film device, or the like.
- the light-modulating layer may be an SPD layer comprising a resin matrix and a light-modulating suspension dispersed in the resin matrix, or it may be an electrochromic material layer.
- it may be an electrophoretic layer including electrophoretic particles and a dispersing agent for dispersing the electrophoretic particles.
- the adhesive films 34A and 34B are respectively adhered to the laminated glass member 41 and the light control element 43, and the laminated glass member 42 and the light control element 43 to join them.
- the adhesive films 34A and 34B are resin films, and one of them is preferably the adhesive film of the present invention, but both are preferably the adhesive film of the present invention.
- the pressure-sensitive adhesive film of the present invention has high adhesive strength not only to inorganic material substrates but also to various resin materials. be able to.
- the adhesive film of the present invention has high impact resistance and high moist heat resistance, even when the laminated glass according to the third embodiment is used as a vehicle window glass, serious damage due to breakage occurs. can be prevented, and long-term use under high temperature and high humidity is also possible.
- FIG. 4 shows a laminate according to a fourth embodiment.
- a laminate 30D according to the present embodiment is applied to laminated glass.
- a laminate 30D according to the present embodiment includes a pair of laminated glass members 41 and 42 and an adhesive film 34 disposed between the pair of laminated glass members 41 and 42, and the adhesive film 34 is the above-described book. It is preferable to consist of the adhesive film of the invention.
- a pair of laminated glass members 41 and 42 are as described in the third embodiment. Since the adhesive film 34 (adhesive film) is adhered to both of the laminated glass members 41 and 42 to join them together, the laminated glass members 41 and 42 can be joined with high adhesive strength.
- the adhesive film of the present invention has high impact resistance and high moisture and heat resistance, even when the laminated glass according to the fourth embodiment is used as a vehicle window glass, damage due to breakage occurs. can be prevented, and long-term use under high temperature and high humidity is also possible.
- the present invention will be described in more detail by way of examples, the present invention is not limited by these examples.
- the measuring method of each physical-property value in this invention, and the evaluation method are as follows.
- Weight average molecular weight (Mw) was calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples. Shodex GPC KF-806L (manufactured by Showa Denko) was used as a column, and tetrahydrofuran was used as an eluent.
- ⁇ Shear storage modulus and maximum peak temperature of tan ⁇ > The pressure-sensitive adhesive films obtained in Examples and Comparative Examples were cut into a length of 10 mm and a width of 5 mm, and a dynamic viscoelasticity measuring device (manufactured by IT Instrument Control Co., Ltd., trade name "DVA-200") was used to measure the following: , and the 20° C. shear storage modulus (G′) was detected. Also, the peak temperature of the loss tangent tan ⁇ obtained from the results of the viscoelasticity measurement was read. Among the above peak temperatures in the temperature range of ⁇ 50 to 150° C., the peak temperature at which tan ⁇ has the maximum value was defined as the maximum peak temperature of tan ⁇ . (Measurement condition) Deformation mode: shear mode, measurement temperature: -50°C to 200°C, heating rate: 5°C/min, measurement frequency: 1 Hz, strain: 1%
- ⁇ Proportion of undissolved components> 1.0 g of the adhesive film of each example and comparative example is immersed in 10.0 g of isopropyl alcohol, and shaken at 50 rpm, 15 ° C., 48 hours with a mix rotor (product name “Mix Rotor Variable VMR-5R”, manufactured by AS ONE). did. After that, the undissolved components were taken out on a 200-mesh wire mesh and dried by heating at 110° C. for 1 hour. Assuming that the weight of the undissolved component after drying was W1, and the weight of the adhesive film before being immersed in isopropyl alcohol was W2, the ratio of the undissolved component was determined by the following formula. Undissolved component (% by mass) W1/W2 x 100
- the pressure-sensitive adhesive films obtained in each example and comparative example were cut into a size of 11.0 cm long ⁇ 11.0 cm wide.
- two glass plates (clear float glass, length 10 cm ⁇ width 10 cm ⁇ thickness 2.5 mm) were prepared.
- An adhesive film was sandwiched between two glass plates, and a pressure of 80° C. and 100 kPa was applied for 10 minutes for temporary pressure bonding. After that, it was pressurized to 1.3 MPa over 10 minutes, heated to 140° C. over 30 minutes, and then pressure-bonded under conditions of 1.3 MPa and 140° C. for 20 minutes. Then, the temperature was lowered to 32° C. over 40 minutes under a pressure condition of 1.3 MPa, and the pressure condition was further reduced to 0 MPa over 10 minutes to obtain a laminated glass.
- the adhesive film protruding from the edge of the glass was cut.
- the laminated glass was vertically placed in a thermo-hygrostat adjusted to 50° C. and 95% RH and held for 12 weeks. After 12 weeks, the laminated glass was taken out, the whitening distances from the outer edges and corners of the laminated glass were measured, and the largest whitening distance was used for evaluation according to the following evaluation criteria.
- AA Whitening distance less than 5 mm
- A Whitening distance is 5 mm or more and less than 12 mm
- B Whitening distance is 12 mm or more
- the obtained adhesive film was cut into a size of 31.0 cm long ⁇ 31.0 cm wide.
- two glass plates (clear float glass, 30.5 cm long ⁇ 30.5 cm wide ⁇ 1.0 mm thick) were prepared.
- An adhesive film was sandwiched between two glass plates, and a pressure of 80° C. and 100 kPa was applied for 10 minutes for temporary pressure bonding. After that, it was pressurized to 1.3 MPa over 10 minutes, heated to 140° C. over 30 minutes, and then pressure-bonded under conditions of 1.3 MPa and 140° C. for 20 minutes. After that, the temperature was lowered to 32° C.
- Allyl ether monomer (1) shown in Table 1 was prepared. Allyl ether monomer (1) is a compound represented by formula (4-2), A 1 O is an oxyethylene group (EO), and its average number of repetitions and terminal group (R 1 ) are shown in Table 1. It is shown. 834 parts by mass of vinyl acetate, 147 parts by mass of allyl ether monomer (1), and 20 parts by mass of methanol were added to a flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, and the system was purged with nitrogen. After that, the temperature was raised to 52°C.
- Allyl ether monomer (1) shown in Table 1 was prepared. Allyl ether monomer (1) is a compound represented by formula (4-2), A 1 O is an oxyethylene group (EO), and its average number of repetitions and terminal group (R 1 ) are shown in Table 1. It is shown. 834 parts by mass of vinyl acetate, 147 parts by mass of allyl ether monomer (1), and 20
- the obtained polyvinyl acetal-based resin (PVB1) was press-molded at a temperature of 160° C. and a pressure of 20 MPa to obtain an adhesive film having a thickness of 380 ⁇ m.
- the maximum peak temperature of tan ⁇ , the shear storage modulus (G′) at 20 ° C. and 85 ° C., and the proportion of undissolved components were measured for the resulting adhesive film, and the impact resistance and moist heat resistance were evaluated. did.
- Example 2 For 100 parts by mass of PVB1, a plasticizer (triethylene glycol-di-2-ethylhexanoate: 3GO) is mixed in the amount shown in Table 3 to obtain a resin composition, and the obtained resin Using the composition, press molding was performed in the same manner as in Example 1 to prepare an adhesive film. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- a plasticizer triethylene glycol-di-2-ethylhexanoate: 3GO
- Example 4 After adding the allyl ether monomer (1) and methanol, the temperature in the system was raised to 60 ° C., 2,2-azobisisobutyronitrile was added at 60 ° C., and polymerization was performed.
- Example 1 In the same manner as above, PVB2 was obtained, and an adhesive film was produced in the same manner as in Example 1 using PVB2. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- Example 5 The allyl ether monomer used was changed to allyl ether monomer (2), and 794 parts by mass of vinyl acetate, 186 parts by mass of allyl ether monomer (2), and 20 parts by mass of methanol, 2,2-azobisisobutyro PVB3 was obtained in the same manner as in Example 1 except that the nitrile was changed to 0.5 parts by mass, and a pressure-sensitive adhesive film was produced in the same manner as in Example 1 using PVB3. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- the allyl ether monomer (2) is a compound represented by formula (4-2), in which A 1 O is a mixture of an oxypropylene group (PO) and an oxyethylene group (EO), and the average number of repetitions is and terminal groups (R 1 ) are as shown in Table 1.
- Example 6 The allyl ether monomer used was changed to allyl ether monomer (3), and 572 parts by mass of vinyl acetate, 143 parts by mass of allyl ether monomer (3), and 286 parts by mass of methanol, 2,2-azobisisobutyro Nitrile was changed to 0.7 parts by mass. Furthermore, after adding the allyl ether monomer (3) and methanol, the temperature in the system was raised to 60 ° C., 2,2-azobisisobutyronitrile was added at 60 ° C., and polymerization was performed. 1 was carried out in the same manner as in Example 1 to obtain PVB4, and an adhesive film was produced in the same manner as in Example 1 using PVB4.
- the physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- the allyl ether monomer (3) is a compound represented by formula (4-2), in which A 1 O is a mixture of an oxypropylene group (PO) and an oxyethylene group (EO), and the average number of repetitions is and terminal groups (R 1 ) are as shown in Table 1.
- Example 7 PVB7 was obtained in the same manner as in Example 1 except that the allyl ether monomer (1) used was changed to 74 parts by mass, and the plasticizer was polypropylene glycol ("PPG1000", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter sometimes referred to as "PPG1000") was changed to prepare an adhesive film in the same manner as in Example 3. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- PPG1000 polypropylene glycol
- Example 8 Polyoxypropylene diglyceryl ether (“Unilube DGP-700” manufactured by NOF Corporation, hereinafter sometimes referred to as "DGP700") having a number average molecular weight of 700 as the plasticizer using PVB7 Example except that An adhesive film was produced in the same manner as in 3. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- DGP700 Polyoxypropylene diglyceryl ether
- Example 9 Polyoxypropylene glyceryl ether (“Uniol TG-1000R” manufactured by NOF Corporation, hereinafter sometimes referred to as "TG1000R") having a number average molecular weight of 1000 was used as the plasticizer using PVB7.
- An adhesive film was produced in the same manner as in 3. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- the polyvinyl acetal-based resin to be used is PVB5, which is unmodified polyvinyl butyral, and 100 parts by mass of PVB5 is mixed with 40 parts by mass of a plasticizer (3GO) to obtain a resin composition, Using the obtained resin composition, press molding was performed in the same manner as in Example 1 to obtain an adhesive film. The physical properties of the resulting adhesive film were measured and evaluated in the same manner as in Example 1.
- the polyvinyl acetal-based resin to be used is PVB6, which is unmodified polyvinyl butyral, and 100 parts by mass of PVB6 is mixed with 25 parts by mass of a plasticizer (3GO) to obtain a resin composition, Using the obtained resin composition, press molding was performed in the same manner as in Example 1 to obtain an adhesive film. The obtained adhesive film was evaluated in the same manner as in Example 1.
- PVB5 which is unmodified polyvinyl butyral, was used as the polyvinyl acetal resin.
- a plasticizer 3GO
- 10 parts by weight of a reactive diluent trimethylolpropane triacrylate: TMPA
- BP benzophenone
- the shear storage modulus (G'), the maximum peak temperature of tan ⁇ , and the proportion of undissolved components were measured. Furthermore, in the evaluation of impact resistance and moist heat resistance, a laminate was produced using the adhesive film produced in Comparative Example 3 as described in each evaluation method above, and an ultra-high pressure mercury lamp was applied to the laminate. was used to irradiate 4000 mJ/cm 2 of light with a wavelength of 365 nm. After that, impact resistance and moist heat resistance were evaluated.
- PVB6 which is unmodified polyvinyl butyral, was used as the polyvinyl acetal resin. 13 parts by mass of a plasticizer (3GO), 4 parts by mass of a reactive diluent (TMPA), and 0.04 parts by mass of benzophenone as a photopolymerization initiator are mixed with 100 parts by mass of PVB6 to form a resin. A composition was obtained, and the resulting resin composition was press-molded in the same manner as in Example 1 to obtain an adhesive film. Also, the adhesive film was irradiated with 4000 mJ/cm 2 of light having a wavelength of 365 nm using an ultra-high pressure mercury lamp.
- the shear storage modulus (G'), the maximum peak temperature of tan ⁇ , and the proportion of undissolved components were measured. And impact resistance and moist heat resistance were evaluated. Furthermore, in the evaluation of impact resistance and moist heat resistance, laminated glass was produced using the adhesive film produced in Comparative Example 4 as described in each evaluation method above, and an ultra-high pressure mercury lamp was applied to the laminated glass. was used to irradiate 4000 mJ/cm 2 of light with a wavelength of 365 nm. After that, impact resistance and moist heat resistance were evaluated.
- PVB1 to PVB7 used in Examples and Comparative Examples are shown in Table 2 below.
- the (meth)acrylic polymers used in Comparative Examples are shown in Table 3 below.
- Table 4 shows the working conditions, physical properties and evaluation results of each example and comparative example. *1 Shows parts by mass for 100 parts by mass of thermoplastic resin. *2 Shows parts by mass for 100 parts by mass of reactive diluent.
- the adhesive film of each of the above examples has a maximum peak temperature of tan ⁇ within a predetermined range, a high shear storage modulus at 20 ° C., and a ratio of undissolved components Also, both the impact resistance and the wet heat resistance were improved.
- Comparative Examples 1 to 4 although the maximum peak temperature of tan ⁇ was within a predetermined range and the shear storage elastic modulus at 20 ° C. was high, the proportion of undissolved components was low, so the wet heat resistance was improved. I could't do it.
- the shear storage elastic modulus (G') at 20°C was low, so the impact resistance was insufficient.
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Abstract
Description
また、液晶ディスプレイなどにおいて粘着フィルムとして広く使用されている従来の(メタ)アクリル系樹脂フィルムは、耐湿熱性が高く、白化の問題が生じにくいが、耐衝撃性は高くすることは難しい。そのため、合わせガラスやディスプレイ用途で使用すると、外部衝撃を受けて破損した際にガラスの破片が飛散して安全性が低くなり、例えば車両用途に使用することが難しくなる。
すなわち、本発明は、以下の[1]~[31]を提供する。
[1]熱可塑性樹脂を含む粘着フィルムであって、
tanδの最大ピーク温度が0℃以上52℃以下であり、20℃のせん断貯蔵弾性率が3×105Pa以上であり、かつ、前期粘着フィルム1.0gをイソプロピルアルコール10gに溶解させた場合の未溶解成分の割合が35質量%以上100質量%以下である、粘着フィルム。
[2]可塑剤を含まない、若しくは前記熱可塑性樹脂100重量部に対して可塑剤を20重量部未満で含む、上記[1]に記載の粘着フィルム。
[3]前記熱可塑性樹脂がポリビニルアセタール系樹脂である、上記[1]又は[2]に記載の粘着フィルム。
[4]前記ポリビニルアセタール系樹脂が、以下の式(1)で示すポリアルキレンオキサイド構造を有する上記[3]に記載の粘着フィルム。
(式(1)において、A1Oは炭素数2~6のオキシアルキレン基であり、mは平均繰り返し数であり、4~200である。R1は炭素数が1~8のアルキル基又は水素原子である。なお、オキシアルキレン基は1種単独でもよいし、2種類以上が混在していてもよい。*は他の基との結合位置である。)
[5]前記ポリビニルアセタール系樹脂が、前記ポリアルキレンオキサイド構造を0.1モル%以上10モル%以下の割合で含む、上記[4]に記載の粘着フィルム。
[6]前記ポリアルキレンオキサイド構造が、オキシエチレン基及びオキシプロピレン基の少なくともいずれかを含む、上記[4]又は[5]に記載の粘着フィルム。
[7]前記ポリアルキレンオキサイド構造が、オキシエチレン基及びオキシプロピレン基の両方を含み、これらがランダム構造を有する上記[6]に記載の粘着フィルム。
[8]前記ポリアルキレンオキサイド構造の末端がアルキル基である上記[4]~[7]のいずれか1項に記載の粘着フィルム。
[9]前記ポリビニルアセタール系樹脂のアセタール化度が60モル%以上である上記[3]~[8]のいずれか1項に記載の粘着フィルム。
[10]前記ポリアルキレンオキサイド構造が、単結合、またはエーテル結合、エステル結合、アミド結合、及びこれら結合のうち少なくともいずれかを有してもよい炭化水素基のいずれかを介して主鎖に連結される、上記[4]~[9]のいずれか1項に記載の粘着フィルム。
[11]前記ポリビニルアセタール系樹脂の水酸基量が、5モル%以上35モル%以下である、上記[3]~[10]のいずれか1項に記載の粘着フィルム。
[12]前記ポリビニルアセタール系樹脂のアセチル化度が、0.01モル%以上50モル%以下である、上記[3]~[11]のいずれか1項に記載の粘着フィルム。
[13]前記ポリビニルアセタール系樹脂が、ポリビニルブチラール系樹脂である、上記[3]~[12]のいずれか1項に記載の粘着フィルム。
[14]前記ポリビニルアセタール系樹脂の重量平均分子量(Mw)が、50,000以上800,000以下である、上記[3]~[13]のいずれか1項に記載の粘着フィルム。
[15]前記ポリビニルアセタール系樹脂の含有量は、粘着フィルムに含有される熱可塑性樹脂全量基準で、50質量%以上100質量%以下である、上記[3]~[14]のいずれか1項に記載の粘着フィルム。
[16]分子量1000未満の低分子量化合物を含有しないか、または、前記熱可塑性樹脂100質量部に対して、20質量部未満で含有する、上記[1]~[15]のいずれか1項に記載の粘着フィルム。
[17]前記可塑剤が、有機エステル可塑剤、有機リン系可塑剤、有機エーテル系可塑剤、及びアルコール系可塑剤からなる群から選択される少なくとも1種である、上記[2]~[16]のいずれか1項に記載の粘着フィルム。
[18]前記粘着フィルムが、可塑剤として、グリコールと一塩基性有機酸とのエステル、炭素数4~12の二塩基性有機酸と炭素数4~10のアルコールとのエステル化合物、ポリアルキレングリコール系可塑剤、及びポリオキシアルキレンエーテル系可塑剤からなる群から選択される少なくとも1種を含む、上記[1]~[17]のいずれか1項に記載の粘着フィルム。
[19]厚みが100μm以上2000μm以下である、上記[1]~[18]のいずれか1項に記載の粘着フィルム。
[20]上記[1]~[19]のいずれか1項に記載の粘着フィルムと、一対の基材とを備え、前記一対の基材の間に前記粘着フィルムが配置される、積層体。
[21]前記一対の基材のいずれもがガラスである上記[20]に記載の積層体。
[22]前記一対の基材の一方がガラス、他方が調光フィルム及び偏光フィルムのいずれかである上記[20]に記載の積層体。
[23]前記基材が、タッチパネル、調光素子、及び表示素子の少なくとも一部を構成する、上記[20]~[22]のいずれか1項に記載の積層体。
[24]前記一対の基材の間に配置される中間部材と、各基材と前記中間部材の間に配置される接着用フィルムを備え、前記接着用フィルムの少なくともいずれかが、前記粘着フィルムである、上記[20]~[23]のいずれか1項に記載の積層体。
[25]前記中間部材の前記粘着フィルムが接着する位置に無機材料基材、及び有機材料基材の少なくともいずれかが配置される、上記[24]に記載の積層体。
[26]前記中間部材が、タッチパネル及び調光素子のいずれかである、上記[24]又は[25]に記載の積層体。
[27]上記[20]~[26]のいずれか1項に記載の積層体を含む液晶ディスプレイ。
[28]上記[20]~[26]のいずれか1項に記載の積層体を含む合わせガラス。
[29]上記[20]~[26]のいずれか1項に記載の積層体を含むディスプレイ。
[30]上記[1]~[19]のいずれか1項に記載の粘着フィルムのディスプレイにおける使用。
[31]上記[1]~[19]のいずれか1項に記載の粘着フィルムの合わせガラスにおける使用。
本発明の粘着フィルムは、熱可塑性樹脂を含み、tanδの最大ピーク温度が0℃以上52℃以下であり、20℃のせん断貯蔵弾性率が3×105Pa以上であり、かつ、粘着フィルム1.0gをイソプロピルアルコール10gに溶解させた場合の未溶解成分が35質量%以上100質量%以下となるものである。
本発明の粘着フィルムは、以上の構成を有することで、耐衝撃性及び耐湿熱性の両方を優れたものにできる。
[tanδの最大ピーク温度]
本発明において、粘着フィルムのtanδの最大ピーク温度が、0℃以上52℃以下である。tanδの最大ピーク温度が0℃未満となると、耐衝撃性が十分に向上しないことがある。そのため、粘着フィルムにより接着させて得られた積層体に衝撃が加わると破損しやすくなり、さらに破損した際に破片が飛散しやすくなる。また、tanδの最大ピーク温度が52℃より高くなると、樹脂フィルムの柔軟性が不十分となり、各種樹脂材料や、無機ガラスに対する接着性を良好にできないことがある。一方で、tanδの最大ピーク温度が0℃未満となると、粘着性が必要以上に高くなって取扱い性が低下することがある。
以上の観点から、粘着フィルムのtanδの最大ピーク温度は、50℃以下が好ましく、44℃以下がより好ましい。また、tanδの最大ピーク温度は、好ましくは5℃以上、より好ましくは10℃以上、さらに好ましくは20℃以上である。
なお、粘着フィルムのtanδの最大ピーク温度は、動的粘弾性測定装置を用いて粘弾性測定を行い、粘弾性測定の結果から得られる損失正接tanδが最大値となるピーク温度を読み取ることで検出できる。
本発明の粘着フィルムは、20℃におけるせん断貯蔵弾性率が3×105Pa以上である。せん断貯蔵弾性率が3×105Pa未満となると、耐衝撃性が低くなり、粘着フィルムにより接着させて得られた積層体などに衝撃が加わると破損しやすくなり、また、破損した際に破片が飛散しやすくなる。
耐衝撃性の観点から、上記した20℃におけるせん断貯蔵弾性率は1×106Pa以上が好ましく、5×106Pa以上がより好ましく、1×107Pa以上がさらに好ましく、2×107Pa以上がよりさらに好ましい。
粘着フィルムの20℃におけるせん断貯蔵弾性率は、耐衝撃性の観点からは高いほうがよいが、他の物性などをバランスよく良好にする観点から、例えば5×109Pa以下、好ましくは1×109Pa以下、さらに好ましくは8×108Pa以下である。
本発明の粘着フィルムは、粘着フィルム1.0gをイソプロピルアルコール10gに溶解させた場合の未溶解成分の割合が35質量%以上100質量%以下である。未溶解成分が35質量%未満であると、耐湿熱性が低下して、高温高湿環境下で長期間しようすると、粘着フィルムの周辺部に白化が生じて外観不良などが生じることがある。
耐湿熱性をより向上させる観点から、未溶解成分は、45質量%以上が好ましく、50質量%以上がより好ましく、60質量%以上がさらに好ましい。
粘着フィルムに使用される熱可塑性樹脂としては、例えば(メタ)アクリル系樹脂、ポリビニルアセタール系樹脂、ポリビニルアルコール系樹脂(PVA)、ポリウレタン系樹脂(PU)、エチレン-酢酸ビニル共重合体樹脂(EVA)、エチレン-酢酸ビニル共重合体けん化物(EVOH)、エチレン-メタクリル酸共重合体樹脂、アイオノマー樹脂、イソブチレン樹脂、スチレン-イソプレン共重合体樹脂、スチレン-ブタジエン共重合体樹脂などが挙げられる。
粘着フィルムにおいて、熱可塑性樹脂は1種単独で用いてもよく、2種以上を併用してもよい。
上記の通り熱可塑性樹脂は、ポリビニルアセタール系樹脂であることがより好ましい。ポリビニルアセタール系樹脂は、変性ポリビニルアセタール樹脂であってもよいし、未変性ポリビニルアセタール樹脂であってもよい。変性ポリビニルアセタール樹脂は、後述する通り、アセタール基、水酸基、及びアセチル基以外の構造(変性基)を有すればよく、好ましくは変性基を側鎖に有する。変性ポリビニルアセタール樹脂は、変性基の種類を適宜変更することで疎水性が高まり、上記した未溶解成分の割合を高くしやすくなる。
ポリビニルアセタール系樹脂は、ポリビニルアルコールをアルデヒドでアセタール化し、さらに必要に応じて変性剤と反応させたり、再酢化処理したりすることで得られるものである。また、変性ポリビニルアセタール樹脂を得るには、原料となるポリビニルアルコールとして変性ポリビニルアルコールを使用してもよい。
(式(1)において、A1Oは炭素数2~6のオキシアルキレン基であり、mは平均繰り返し数であり、4~200である。R1は炭素数が1~8のアルキル基又は水素原子である。なお、オキシアルキレン基は1種単独でもよいし、2種類以上が混在していてもよい。*は他の基との結合位置である。)
オキシアルキレン基におけるアルキレン基は、直鎖であってもよいし、分岐構造を有してもよい。オキシアルキレン基としては、例えばオキシエチレン基、オキシプロピレン基、又はオキシブチレン基が挙げられ、好ましくはオキシエチレン基、オキシプロピレン基である。オキシアルキレン基は1種単独で使用してよいが、2種以上を併用してもよい。2種以上を併用する場合、各オキシアルキレン基は、ランダムに付加してもよいし、ブロックで付加してもよいが、ランダムに付加されることがより好ましい。
オキシエチレン基(EO)及びオキシプロピレン基(PO)を含む場合、オキシプロピレン基のオキシエチレン基に対する比(PO/EO)は、モル比で、例えば1/9以上9/1以下、好ましくは2/8以上8/2以下であり、より好ましくは3/7以上7/3以下である。
また、R1におけるアルキル基は、直鎖であってもよいし、分岐構造を有していてもよい。
R1におけるアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、s-ブチル、t-ブチル基どの分岐ブチル基、n-ペンチル基、分岐ペンチル基、n-ヘキシル基、分岐ヘキシル基、n-ヘプチル基、イソヘプチル基、3-ヘプチル基などの分岐ヘプチル基、n-オクチル基、イソオクチル基、2-エチルヘキシル基などの分岐オクチル基などが挙げられる。
R1は、アルキル基及び水素原子のいずれでもよいが、アルキル基が好ましい。したがって、ポリアルキレンオキサイド構造は、末端がアルキル基であることが好ましい。ポリアルキレンオキサイド構造は、末端にアルキル基を有すると、疎水性が高まり、粘着フィルムの耐湿熱性がより向上しやすくなる。アルキル基の炭素数は、上記のとおり、炭素数1~8であればよいが、好ましくは炭素数1~6、より好ましは炭素数1~4である。
単結合以外の連結基としては、エーテル結合(-O-)、エステル結合(-COO-)、アミド結合(-CONR-:Rは水素原子又は炭素数1~4のアルキル基、好ましくは水素原子)、又はこれら結合のうち少なくともいずれかを有してもよい炭化水素基が挙げられる。これらの中では、エーテル結合(-O-)、エステル結合(-COO-)、又はこれら結合のうち少なくともいずれかを有してもよい炭化水素基がより好ましい。該炭化水素基の炭素数は、特に限定されないが、例えば1~10程度であればよく、好ましくは1~4である。また、これらの中では、上記ポリアルキレンオキサイド構造は、エーテル結合又は-CH2O-のいずれかを介して、主鎖に結合されることがより好ましい。ポリアルキレンオキサイド構造は、これらのいずれかを介して主鎖に結合することで、その製造が容易になる。なお、-CH2O-においては、酸素原子が上記ポリアルキレンオキサイド構造に結合するとよい。
また、ポリビニルアセタール系樹脂は、変性することで、上記の通り、上記式(1)で示されるポリアルキレンオキサイド構造を有することが好ましい。なお、以下では、ポリアルキレンオキサイド構造を有するポリビニルアセタール系樹脂は、他のポリビニルアセタール系樹脂と区別して説明するために、変性ポリビニルアセタール樹脂(A)として説明することがある。
これら観点から、ポリアルキレンオキサイド構造による変性量は、0.2モル%以上が好ましく、0.3モル%以上がより好ましく、0.4モル%以上がさらに好ましく、0.5モル%以上が特に好ましく、また、8モル%以下が好ましく、6モル%以下がより好ましく、4モル%以下がさらに好ましい。
なお、エステル結合、ウレタン結合において、「*」及び「**」は、アルキル基又は主鎖に対する結合位置であり、各結合において「*」がアルキル基に対する結合位置で、「**」が主鎖に対する結合位置であることが好ましい。
ただし、ポリビニルアセタール系樹脂は、例えば未変性ポリビニルアセタール樹脂などである場合、上記のとおり水酸基を有さず、式(3-2)で示される構成単位を有さなくてもよい。すなわち、未変性ポリビニルアセタール樹脂は、以下の式(3-1)及び式(3-3)で示される構成単位を有し、さらに任意で以下の式(3-2)で示される構成単位を有してもよい。
アセタール基としては、具体的にはブチラール基が特に好ましく、したがって、ポリビニルアセタール系樹脂としては、ポリビニルブチラール系樹脂が好ましい。ポリビニルアセタール系樹脂のアセタール化度(すなわち、アセタール量)は、例えば40モル%以上90モル%以下である。また、アセタール化度は、60モル%以上が好ましく、63モル%以上がより好ましく、65モル%以上がさらに好ましい。アセタール化度が高くなることで、上記した未溶解成分の割合が高くなりやすく、耐湿熱性が向上しやすくなる。
また、アセタール化度は、より好ましくは88モル%以下であり、さらに好ましくは85モル%以下である。アセタール化度をこれら範囲内とすることで、水酸基の量を適度な量としつつ、式(1)で示される官能基を一定量含有させやすくなる。
なお、アセタール化度とは、ポリビニルアセタール系樹脂のアセタール基がアセトアセタール基である場合には、アセトアセタール化度を意味し、アセタール基がブチラール基である場合には、ブチラール化度を意味する。
また、アセタール化度は、ポリビニルアセタール系樹脂を構成する全ビニル単量体単位に対する、アセタール化されたビニルアルコール単位の割合を表す。
また、ポリビニルアセタール系樹脂の水酸基量は、0モル%以上であるとよいが、変性ポリビニルアセタール樹脂(A)である場合には、粘着フィルムが柔軟になりすぎることを防止する観点から、一定量の水酸基量を含有するとよく、例えば5モル%以上、好ましくは9モル%以上、より好ましくは10モル%以上、さらに好ましくは12モル%以上である。
なお、水酸基量は、ポリビニルアセタール系樹脂を構成する全ビニル単量体単位に対する、水酸基の割合を表す。
また、変性ポリビニルアセタール樹脂(A)のアセチル化度は、上記のとおり例えば0.01モル%以上であるが、好ましくは0.1モル%以上、より好ましくは0.3モル%以上である。
なお、アセチル化度は、ポリビニルアセタール系樹脂を構成する全ビニル単量体単位に対する、アセチル基の割合を表す。
なお、重量平均分子量(Mw)は、ゲル浸透クロマトグラフィーにより測定されるものである。
本発明で使用するポリビニルアセタール系樹脂は、1種単独で使用してもよいし、2種以上を併用してもよい。
具体的には、ポリビニルアセタール系樹脂の含有量は、粘着フィルムに含有される熱可塑性樹脂全量基準で、例えば50質量%以上であり、好ましくは70質量%以上、より好ましくは90質量%以上、最も好ましくは100質量%である。したがって、本発明の粘着フィルムに含まれる熱可塑性樹脂は、ポリビニルアセタール系樹脂のみからなるものでもよい。
本発明の粘着フィルムは、可塑剤を含有してもよい。粘着フィルムは、可塑剤を含有することにより柔軟となり、粘着フィルムのtanδの最大ピーク温度を低くして、ポリカーボネートなどの各種樹脂材料や無機ガラスなどの各種被着体に対する接着性を高くすることができる。ただし、本発明の粘着フィルムは、可塑剤を含有しないか、含有していても少量であることが好ましい。可塑剤を少量のみ含有し又は含有させないことで、上記した未溶解成分の割合が低下するのを防止して、耐湿熱性が良好になりやすい。
また、本発明の粘着フィルムは、可塑剤が少量であり又は含有しなくても、上記した所定の熱可塑性樹脂を使用することで、ポリカーボネートなどの各種の樹脂材料に対する接着性を良好にできる。
耐湿熱性の観点から、可塑剤の上記含有量は、好ましくは15質量部以下であり、より好ましくは10質量部以下、さらに好ましくは5質量部以下、よりさらに好ましくは1質量部以下である。可塑剤の含有量の下限は、0質量部である。
本発明の樹脂組成物は、変性ポリビニルアセタール樹脂(A)を使用する場合には、可塑剤を含有しなくてもよいが、可塑剤を含有することで樹脂フィルムの接着性を向上しやすくなる。一方で、樹脂組成物は、未変性ポリビニルアセタール樹脂を使用する場合には、樹脂フィルムの接着性を向上させる観点から、可塑剤を含有したほうがよい。
可塑剤は1種単独で使用してもよいし、2種以上を併用してもよい。上記したなかでも、有機エステル可塑剤が好ましい。好ましい有機エステル可塑剤としては、一塩基性有機酸エステル及び多塩基性有機酸エステル等が挙げられる。
グリコールとしては、具体的には、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、ブチレングリコールなどが挙げられる。
一塩基性有機酸としては、炭素数3~10の有機酸が挙げられ、具体的には、酪酸、イソ酪酸、カプロン酸、2-エチル酪酸、ヘプチル酸、n-オクチル酸、2-エチルヘキシル酸、n-ノニル酸及びデシル酸などが挙げられる。
具体的には、セバシン酸ジブチル、アゼライン酸ジオクチル、アジピン酸ジヘキシル、アジピン酸ジオクチル、アジピン酸ヘキシルシクロヘキシル、アジピン酸ジイソノニル、アジピン酸ヘプチルノニル、ジブチルカルビトールアジペート、混合型アジピン酸エステルなどが挙げられる。また、油変性セバシン酸アルキドなどでもよい。混合型アジピン酸エステルとしては、炭素数4~9のアルキルアルコール及び炭素数4~9の環状アルコールから選択される2種以上のアルコールから作製されたアジピン酸エステルが挙げられる。
上記有機リン系可塑剤としては、トリブトキシエチルホスフェート、イソデシルフェニルホスフェート及びトリイソプロピルホスフェート等のリン酸エステルなどが挙げられる。
さらに、グリセリンなどの3価以上のアルコールと、一塩基性有機酸の部分エステルなどであってよい。一塩基性有機酸としては、炭素数3~24、好ましくは炭素数6~18の一塩基性有機酸が挙げられる。3価以上のアルコールと、一塩基性有機酸の部分エステルの具体例としては、グリセリンとステアリン酸のモノ又はジエステル、グリセリンと2-エチルヘキシル酸とのモノ又はジエステルなどが挙げられる。
有機エステル可塑剤としては、上記したなかでも、トリエチレングリコール-ジ-2-エチルヘキサノエート(3GO)が特に好適に用いられる。
具体的なポリオキシアルキレンエーテル系可塑剤としては、例えば、ポリオキシエチレンヘキシルエーテル、ポリオキシエチレンヘプチルエーテル、ポリオキシエチレンオクチルエーテル、ポリオキシエチレン-2-エチルヘキシルエーテル、ポリオキシエチレンノニルエーテル、ポリオキシエチレンデシルエーテル、ポリオキシエチレンアリルエーテル、ポリオキシプロピレンアリルエーテル、ポリオキシエチレングリセリルエーテル、ポリオキシプロピレングリセリルエーテル、ポリオキシエチレンジグリセリルエーテル、ポリオキシプロピレンジグリセリルエーテル、ポリオキシアルキレンペンタエリスリトールエーテルなどが挙げられる。
ポリオキシアルキレンエーテル系可塑剤は、好ましくは多価アルコールとポリオキシアルキレンとのエーテル化合物であり、より好ましくはグリセリン又はジグリセリンとポリオキシアルキレンとのエーテル化合物であり、更に好ましくはグリセリン又はジグリセリンとポリオキシプロピレンとのエーテル化合物である。
アルコール系可塑剤としては、ブタンジオール、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトールなどの各種の多価アルコールが挙げられる。これらの中では、トリメチロールプロパンが好ましい。
可塑剤以外の添加剤は、具体的には、紫外線吸収剤、赤外線吸収剤、酸化防止剤、光安定剤、接着力調整剤、顔料、染料、蛍光増白剤、結晶核剤等が挙げられる。また、本発明の樹脂組成物は、溶媒により希釈されて希釈液の形態で使用されてもよい。
なお、低分子量化合物は、分子量1000未満の化合物をいい、上記した可塑剤や、光照射による硬化する反応性希釈剤などが挙げられる。反応性希釈剤としては、例えば、(メタ)アクリルモノマーや(メタ)アクリルオリゴマー等の(メタ)アクリル系反応性希釈剤や、エポキシモノマー、エポキシオリゴマー等のエポキシ系反応性希釈剤や、アルコキシシランモノマー、アルコキシシランオリゴマー等のシリコーン系反応性希釈剤等が挙げられる。
粘着フィルムにおける低分子量化合物の含有量は、粘着フィルムに含まれる熱可塑性樹脂100質量部に対して、例えば20質量部未満である。低分子量化合物の含有量を少なくすると、未溶解成分の割合が高くなり、耐湿熱性が向上しやすくなる。低分子量化合物の含有量は、耐湿熱性の観点から、好ましくは15質量部以下であり、より好ましくは10質量部以下、さらに好ましくは5質量部以下、よりさらに好ましくは1質量部以下である。低分子量化合物の含有量の下限は、0質量部である。
本発明の粘着フィルムで使用されるポリビニルアセタール系樹脂は、ポリビニルアルコール(「原料ポリビニルアルコール」ともいう)をアルデヒドでアセタール化し、その後、必要に応じて変性剤と反応させ、または再酢化処理をすることで得られるものである。原料ポリビニルアルコールとしては、未変性ポリビニルアルコールでもよいが、変性ポリビニルアセタール樹脂を得る場合には、原料ポリビニルアルコールとして変性ポリビニルアルコールを使用してもよい。
例えば、ポリアルキレンオキサイド構造を有する変性ポリビニルアセタール樹脂(A)を製造する際には、以下の製造方法(1)により製造することが好ましい。
本製造方法(1)では、まず、原料ポリビニルアルコールとしてポリオキシアルキレン変性ポリビニルアルコールを製造する。具体的には、ビニルエステルと、ポリオキシアルキレン基を有するビニルモノマーを含むモノマーを重合してポリマーを得た後、ポリマーをけん化することにより得られる。ケン化には、一般に、アルカリ又は酸が用いられるが、アルカリを用いることが好ましい。ポリオキシアルキレン変性ポリビニルアルコールとしては、1種のみが用いられてもよく、2種以上が併用されてもよい。
次いで、上記で得られたポリオキシアルキレン変性ポリビニルアルコールに対して、アルデヒドでアセタール化して、変性ポリビニルアセタール樹脂(A)を得るとよい。アセタール化の方法は、公知の方法で行うとよい。
(製造方法(2))
本製造方法(2)では、原料ポリビニルアルコールをアルデヒドでアセタール化して、ポリビニルアセタール系樹脂(以下、原料ポリビニルアセタール系樹脂ともいう)を得る。ここで、原料ポリビニルアルコールとしては、ポリビニルエステルをケン化して得られた未変性ポリビニルアルコールを使用する。次いで、原料ポリビニルアセタール系樹脂に対して、再酢化処理して、未変性ポリビニルアセタール樹脂を得るとよい。再酢化処理としては、従来公知の方法で行えばよいが、無水酢酸を用いてピリジンなどの塩基存在下で行えばよい。また、再酢化処理は、例えば50℃以上100℃以下、好ましくは70℃以上90℃以下程度に加熱して行うとよい。ポリビニルアセタール系樹脂は、再酢化処理されることで、水酸基量が少なくなり、tanδの最大ピーク温度を低くしやすくなり、ポリカーボネートなどの各種樹脂材料に対する接着性が良好となる。
まず、原料ポリビニルアルコールをアルデヒドでアセタール化して、ポリビニルアセタール系樹脂(以下、原料ポリビニルアセタール系樹脂ともいう)を得る。ここで使用される原料ポリビニルアルコールは、ポリビニルエステルをケン化して得られたものであり、未変性ポリビニルアルコールであることが好ましい。
次に、上記原料ポリビニルアセタール系樹脂に対して、アルキル基を有する変性剤を反応させて、原料ポリビニルアセタール系樹脂にアルキル基を導入する。変性剤としては、原料ポリビニルアセタール系樹脂が有する水酸基に反応して、ウレタン結合やエステル結合を形成する反応性基を有する化合物であるとよい。具体的には、n-オクタデシルイソシアネートなどのアルキル基の炭素数が2~30であるアルキルイソシアネートが挙げられる。また、炭素数3~31のカルボン酸、又は上記カルボン酸の無水物、カルボン酸エステル、カルボン酸ハライドなどのカルボン酸誘導体が挙げられる。カルボン酸誘導体としては、2-エチルヘキサノイルクロリド、ラウロイルクロリド、ミリスチルクロリド、パルミトイルクロリド、ステアロイルクロリドなどのカルボン酸クロリドが好ましい。
また、多層フィルムは、上記した第1の層と、第1の層以外の層(以下、「第2の層」ともいう)との積層体であってもよい。具体的には、例えば第1の層/第2の層/第1の層の3層構造などが挙げられる。
なお、本発明の粘着フィルムが2層以上の多層フィルムである場合、各層がそれぞれ上記粘着フィルムで述べたとおりの組成であることが好ましい。
本発明の粘着フィルムは、ポリビニルアセタール系樹脂などの熱可塑性樹脂を含む樹脂組成物を公知の方法でフィルム状に成形することで製造することができる。樹脂組成物は、上記の通り製造されたポリビニルアセタール系樹脂などの熱可塑性樹脂を少なくとも含み、必要に応じて、可塑剤、添加剤などを添加して調製するとよい。また、樹脂組成物は、適宜溶媒に希釈して使用してもよい。
また、上記の通り、原料ポリビニルアセタール系樹脂を変性剤と反応させて、ポリビニルアセタール系樹脂を得る場合には、以下のように成形してもよい。すなわち、原料ポリビニルアセタール系樹脂と、変性剤と、その他の必要に応じて配合される可塑剤などの添加剤を含む組成物を、剥離シートなどの支持体上に塗布して、あるいは、型枠に流し込んで、その後、加熱することで変性剤を原料ポリビニルアセタール系樹脂に反応させつつフィルム状に成形してもよい。
合わせガラスは、自動車、電車などの車両、船舶、飛行機などの各種乗り物、あるいは、ビル、マンション、一戸建て、ホール、体育館などの各種建築物、あるいは切削、研磨などの工作機械、ショベルやクレーンなどの建設機械等の窓ガラスに使用されるが、中でも自動車などの車両用途が好ましい。本発明の粘着フィルムは、耐衝撃性が高く、後述する積層体などに破損を生じさせにくく、また、破損が生じてもその破片が飛散しにくいので、車載用ディスプレイや車両用窓ガラスに使用することが適している。
なお、本発明の粘着フィルムが適用される合わせガラス及びディスプレイは、後述する積層体を備えるとよい。
本発明の粘着フィルムは、特に限定されないが、有機材料基材、無機材料基材などの基材とともに使用され、積層体の一部として使用されることが好ましい。本発明の積層体は、具体的には、上記粘着フィルムと、無機材料基材、及び有機材料基材の少なくともいずれかから選択される基材を備えるとよい。また、粘着フィルムは、無機材料基材、及び有機材料基材の少なくともいずれに接着するように配置されることが好ましい。なお、粘着フィルムは、各種樹脂材料に対する接着力を高くでき、そのため、有機材料基材に接着する位置に配置されることで、高い接着力で基材に接着させることができる。
上記した中では、透明性、耐衝撃性に優れる点から、ポリカーボネート板が好ましく、透明性が高く、耐候性、機械強度に優れる点から、(メタ)アクリル板が好ましく、これらの中ではポリカーボネート板がより好ましい。
有機樹脂板の厚さは、特に限定されないが、好ましくは0.1mm以上、さらに好ましくは0.4mm以上であり、また、好ましくは5.0mm以下、さらに好ましくは3.0mm以下である。
樹脂フィルムは、1層単層からなるもでもよいが、2層以上が積層されたものでもよい。
また、有機材料基材は、上記樹脂フィルムを含む機能フィルムであってもよい。機能フィルムとしては、偏光フィルム(偏光板)、調光フィルムなどが挙げられる。偏光フィルム及び調光フィルムの構成は後述するとおりである。
積層体における樹脂フィルムや機能フィルムの厚さは、特に限定されないが、好ましくは30μm以上、さらに好ましくは50μm以上であり、また、好ましくは500μm以下、さらに好ましくは450μm以下である。
なお、厚みが比較的大きく、柔軟性が低くて、一般的に折り曲げできないようなものを有機樹脂板という一方、厚みが比較的小さく、一般的に折り曲げ可能なものを概ね樹脂フィルムというが、これらは明確に区別されるものでない。
センサーとしては、タッチセンサーが挙げられる。タッチセンサーとは、指、タッチペン、その他の物体が基材に近づき、又は接触するタッチ入力を検知するセンサーであり、上記基材に積層される導電層により構成される。タッチセンサーは、指、タッチペン、その他の物体が、基材に近づき、又は接触することで、静電容量、電流、電圧などの電気的な変化が導電層に生じ、その電気的な変化により、タッチ入力を検知する。
導電層は、特に限定されず、従来公知の透明性を有する電極材料であれば特に限定なく用いることができ、例えば、インジウム錫酸化物(ITO)導電膜、酸化錫導電膜、酸化亜鉛導電膜、高分子導電膜などが挙げられる。
また、電極、センサーなどの導電層が積層された有機材料基材(特に、フィルム)は、導電層が設けられた面とは反対側の面に上記したハードコート層が形成されてもよい。導電層が設けられた面とは反対側の面は、通常、粘着フィルムとの接着面となるが、本発明の粘着フィルムは、ハードコート層が設けられた面に対しても接着力を良好にしやすい。
ここで、一対の基材は、両方がガラスであることが好ましい。ガラスとしては、無機ガラス板であってもよいし、有機ガラス板であってもよい。
また、一対の基材は、一方がガラスで他方がフィルムであってもよい。この場合、ガラスとしては、無機ガラス板であってもよいし、有機ガラス板であってもよい。また、フィルムは、樹脂フィルムであってもよいが、偏光フィルム(偏光板)、調光フィルムなどの機能フィルムが好ましい。
本発明の粘着シートは、耐衝撃性が高いので、ガラス同士、又はガラスと他の部材を接合するために使用されても、ガラスが破損しにくく、また、ガラスが破損された場合でもその破片が飛散しにくくなり安全性などが高められる。
このような多層構造において、接着用フィルムは、例えば、一対の基材の両方に接着され、それにより、一対の基材が接着用フィルムを介して接合されるとよい。この場合、接着用フィルムは、上記した本発明の粘着フィルムであるとよい。
中間部材は、上記した無機材料基材、及び有機材料基材の少なくともいずれを有するとよく、本発明の粘着フィルムが接着する位置に無機材料基材、及び有機材料基材の少なくともいずれが配置されるとよい。
圧着は、特に限定されないが、加熱しながら圧着させることが好ましい。また、比較的低い圧力及び温度で仮接着した後に、圧力、温度又はこれらの両方を仮圧着よりも高くして本接着してもよい。
また、表示素子31としては、有機EL表示素子、液晶表示素子が挙げられる。表示素子31は、その表面側の最外面に偏光板(偏光フィルム)が設けられることが好ましい。なお、表面側の最外面とは、表面保護パネル側の最外面であり、その反対側を裏面側ともいう。
偏光板(偏光フィルム)は、一般的にポリビニルアルコール樹脂フィルムなどの偏光子の両面に保護フィルムが設けられた構成を有する。保護フィルムは、上記した樹脂フィルムから構成され、好ましくは、PETフィルム、COPフィルム、又はTACフィルムのいずれかである。なお、保護フィルムの表面には、基材の表面層として、(メタ)アクリル系樹脂などからなるハードコート層が設けられてもよい。また、表示素子31は、その表面側の面に偏光板が設けられない場合でも、表面側の最外面には保護フィルムが設けられるとよい。したがって、いずれの場合でも、表示素子31の表面側の最表面は有機材料基材により構成されることになる。
また、タッチパネル33において、無機ガラス、有機樹脂板、又は樹脂フィルムは、これらのうちから2以上が積層されて多層構造体であってもよい。その場合も、タッチパネル33において、無機ガラス、有機樹脂板、又は樹脂フィルムのいずれかにタッチセンサーが付されるとよい。
また、タッチパネル33は、表面側の最表面、裏面側の最表面のいずれかに樹脂フィルムからなる保護フィルムが配置されてもよい。したがって、タッチパネル33は、接着用フィルム34A、34Bとの接着面が、無機ガラス、有機ガラス、及び樹脂フィルムのいずれかとなる。
本発明の粘着フィルムは、無機材料基材のみならず、各種樹脂材料(すなわち、有機材料基材)に対しても、高い接着力を有することができる。したがって、表示素子33、表面保護パネル32、及びタッチパネル33は、接着用フィルム34A、34Bとの接着面が、有機材料基材により構成されることがあるが、そのような場合でも、高い接着力で、表示素子31とタッチパネル33、及び表面保護パネル32とタッチパネル33とを接合させることができる。
また、本発明の粘着フィルムは、耐衝撃性が高いので、タッチパネル付きディスプレイが車載用ディスプレイである場合でも、タッチパネル付きディスプレイの破損による甚大な被害が発生することが防止できる。さらに、耐湿熱性が良好であるので、積層体は高温高湿環境下で長期使用が可能になる。
表示素子31と、表面保護パネル32の詳細は、第1の実施形態で述べたとおりである。
本実施形態では接着用フィルム34が本発明の粘着フィルムからなる。接着用フィルム34(粘着フィルム)は、表示素子31及び表面保護パネル32に接着されて、これらを接合し、したがって、第1の実施形態と同様に、表示素子31と表面保護パネル32とは、高い接着力で接合されることになる。また、粘着フィルムは、耐衝撃性及び耐湿熱性が高いので、積層体30Bが車載用ディスプレイに適用されたとしても、ディスプレイの破損におり甚大な被害が発生にくくなり、また、高温高湿下での長期使用も可能となる。
合わせガラス部材41、42は、無機ガラス板、有機樹脂板のいずれでもよく、これらの詳細は上記で説明したとおりである。
調光素子43が備える樹脂フィルムとしては、PETフィルム、PENフィルムなどのポリエステル樹脂フィルム、(メタ)アクリル樹脂フィルム、TACフィルム、PES樹脂フィルム、ポリイミド樹脂フィルムなどが挙げられる。これらの中では、取扱い性などの観点から、ポリエステル樹脂フィルムが好ましく、中でもPETフィルムがより好ましい。
また、2枚の樹脂フィルムそれぞれには調光層側の面に電極を構成する導電層が設けられる。
本発明の粘着フィルムは、無機材料基材のみならず、各種樹脂材料に対しても、高い接着力を有するので、高い接着力で、合わせガラス部材41、42と、偏光素子43とを接合させることができる。
また、本発明の粘着フィルムは、耐衝撃性及び耐湿熱性が高いので、第3の実施形態に係る合わせガラスが車両用窓ガラスに使用されるような場合でも、破損による甚大な被害が発生することが防止でき、また、高温高湿下での長期使用も可能となる。
一対の合わせガラス部材41、42は、第3の実施形態において説明したとおりである。接着用フィルム34(粘着フィルム)は、合わせガラス部材41、42の両方に接着されて、これらを接合するので、合わせガラス部材41、42を高い接着力で接合することができる。
また、本発明の粘着フィルムは、耐衝撃性及び耐湿熱性が高いので、第4の実施形態に係る合わせガラスが車両用窓ガラスに使用されるような場合でも、破損による甚大な被害が発生することが防止でき、また、高温高湿下での長期使用も可能となる。
粘着フィルムをテトラヒドロフランに0.05重量%の濃度に溶解させ、シリンジフィルター(メルク社製、Millex-LH 0.45μm)を用いてろ過した後、ゲル浸透クロマトグラフィー(Waters社製、e2690)を用いて、分子量を測定した。重量平均分子量(Mw)は、単分散ポリスチレン標準試料により作成した分子量校正曲線を使用して算出した。また、カラムはShodex GPC KF-806L(昭和電工社製)を用い、溶離液としてテトラヒドロフランを用いた。
実施例、比較例で得られた粘着フィルムを、長さ10mm、幅5mmで切り出し、動的粘弾性測定装置(アイティー計測制御株式会社製、商品名「DVA-200」)を用いて、以下の測定条件で粘弾性を測定し、20℃せん断貯蔵弾性率(G’)を検出した。
また、粘弾性測定の結果から得られる損失正接tanδのピーク温度を読みとった。-50~150℃の温度領域において上記ピーク温度のうち、tanδが最大値となるピーク温度をtanδの最大ピーク温度とした。
(測定条件)
変形様式:せん断モード、測定温度:-50℃~200℃、昇温速度:5℃/分、測定周波数:1Hz、歪:1%
ポリビニルアセタール系樹脂をクロロホルム-dに溶解し、1H-NMR(核磁気共鳴スペクトル)を用いて測定し、各ユニットのモル比を分析することで求めた。
イソプロピルアルコール10.0gに、各実施例、比較例の粘着フィルム1.0gを浸漬し、ミックスローター(製品名「ミックスローターバリアブル VMR-5R」、アズワン社製)で50rpm、15℃、48時間振盪した。その後、未溶解成分を200メッシュの金網上に取出し、110℃で1時間加熱して乾燥させた。乾燥後の未溶解成分の重量をW1、粘着フィルムのイソプロピルアルコールに浸漬する前の重量をW2とすると以下の式により、未溶解成分の割合を求めた。
未溶解成分(質量%)=W1/W2×100
各実施例、比較例で得られた粘着フィルムを縦11.0cm×横11.0cmの大きさに切断した。一対の合わせガラス部材として、2枚のガラス板(クリアフロートガラス、縦10cm×横10cm×厚み2.5mm)を用意した。2枚のガラス板の間に、粘着フィルムを挟み込み、10分間、80℃、及び100kPaの圧力をかけて仮圧着を行った。その後10分かけて1.3MPaまで加圧、及び、30分かけて140℃まで加熱し、その後20分間1.3MPa・140℃の条件で圧着した。次いで、1.3MPaの加圧条件下にて、40分かけて32℃まで降温し、さらにその後10分かけて加圧条件を0MPaとし、合わせガラスを得た。ガラス端部にはみ出した粘着フィルムに関してはカットした。
AA:白化距離が5mm未満
A:白化距離が5mm以上12mm未満
B:白化距離が12mm以上
得られた粘着フィルムを縦31.0cm×横31.0cmの大きさに切断した。一対の合わせガラス部材として、2枚のガラス板(クリアフロートガラス、縦30.5cm×横30.5cm×厚み1.0mm)を用意した。2枚のガラス板の間に、粘着フィルムを挟み込み、10分間、80℃、及び100kPaの圧力をかけて仮圧着を行った。その後10分かけて1.3MPaまで加圧、及び、30分かけて140℃まで加熱し、次いで20分間1.3MPa・140℃の条件で圧着した。その後1.3MPaの加圧条件下にて、40分かけて32℃まで降温し、さらにその後10分かけて加圧条件を0MPaとし、合わせガラスを得た。ガラス端部にはみ出した粘着フィルムに関してはカットした。
得られた合わせガラスを、表面温度が23℃となるように調整した。次いで、5.0mの高さから、6枚の合わせガラスに対してそれぞれ、質量227g及び直径38mmの鋼球を、合わせガラスの中心部分に落下させた。まず、鋼球が合わせガラスを貫通していないか確認した。貫通していない合わせガラスに関しては、衝撃面の反対側からの剥離破片の総重量を測定して、耐衝撃性について以下の評価基準で評価した。
A:剥離破片の総重量10g未満
B:剥離破片の総重量が10g以上であるか、又は、鋼球が合わせガラスを貫通
[エチレンオキサイド変性ポリビニルアルコールの合成]
表1に記載のアリルエーテルモノマー(1)を用意した。アリルエーテルモノマー(1)は、式(4-2)に示す化合物であり、A1Oがオキシエチレン基(EO)であり、その平均繰り返し数、及び末端基(R1)は、表1に示すとおりである。
攪拌機、温度計、滴下ロートおよび還流冷却器を付したフラスコ中に、酢酸ビニル834質量部、アリルエーテルモノマー(1)147質量部、及びメタノール20質量部を添加し、系内の窒素置換を行った後、温度を52℃まで昇温した。温度を52℃に維持した状態で、この系に2,2-アゾビスイソブチロニトリル0.5質量部を添加し、重合を開始した。重合開始から5時間で重合を停止した。オーブンで加熱を行い、未反応のモノマーとメタノールを除去した後、共重合体の40質量%メタノール溶液を調製した。
得られた共重合体のメタノール溶液100質量部を40℃で攪拌しながら、3質量%のNaOHメタノール溶液7.4質量部を添加して、よく混合した後に放置した。2時間後、固化したポリマーを粉砕機で粉砕し、メタノールで洗浄後、乾燥してポリマー粉末(エチレンオキサイド変性ポリビニルアルコール)を得た。
得られたポリマー粉末280gを純水2100gに加え、90℃の温度で約2時間攪拌し溶解させた。この溶液を40℃に冷却し、濃度35質量%の塩酸160質量部とn-ブチルアルデヒド150質量部を添加し、液温を20℃まで下げ、温度を保持してアセタール化反応を行い、反応生成物を析出させた。その後、液温を40℃として3時間保持して反応を完了させ、常法により中和、水洗及び乾燥を経て、ポリビニルアセタール系樹脂(PVB1)の白色粉末を得た。
得られたポリビニルアセタール系樹脂(PVB1)を、温度160℃、圧力20MPaでプレス成形して厚み380μmの粘着フィルムを得た。得られた粘着フィルムに対して、tanδの最大ピーク温度、20℃及び85℃におけるせん断貯蔵弾性率(G’)、及び未溶解成分の割合を測定し、また、耐衝撃性及び耐湿熱性を評価した。
100質量部のPVB1に対して、表3に記載の量で可塑剤(トリエチレングリコール-ジ-2-エチルヘキサノエート:3GO)を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形し、粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
アリルエーテルモノマー(1)、及びメタノール添加後に、系内の温度を60℃に上昇させ、60℃で2,2-アゾビスイソブチロニトリルを添加して、重合を行った以外は実施例1と同様に実施して、PVB2を得て、PVB2を用いて実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
使用するアリルエーテルモノマーを、アリルエーテルモノマー(2)に変更して、かつ酢酸ビニル794質量部、アリルエーテルモノマー(2)186質量部、及びメタノール20質量部、2,2-アゾビスイソブチロニトリルを0.5質量部に変更した以外は実施例1と同様に実施して、PVB3を得て、PVB3を用いて実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
なお、アリルエーテルモノマー(2)は、式(4-2)に示す化合物であり、A1Oがオキシプロピレン基(PO)とオキシエチレン基(EO)が混在しており、その平均繰り返し数、及び末端基(R1)は、表1に示すとおりである。
使用するアリルエーテルモノマーを、アリルエーテルモノマー(3)に変更して、かつ酢酸ビニル572質量部、アリルエーテルモノマー(3)143質量部、及びメタノール286質量部、2,2-アゾビスイソブチロニトリルを0.7質量部に変更した。さらに、アリルエーテルモノマー(3)及びメタノール添加後に、系内の温度を60℃に上昇させ、60℃で2,2-アゾビスイソブチロニトリルを添加して、重合を行った以外は実施例1と同様に実施して、PVB4を得て、PVB4を用いて実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
なお、アリルエーテルモノマー(3)は、式(4-2)に示す化合物であり、A1Oがオキシプロピレン基(PO)とオキシエチレン基(EO)が混在しており、その平均繰り返し数、及び末端基(R1)は、表1に示すとおりである。
使用するアリルエーテルモノマー(1)を74質量部に変更した以外は実施例1と同様に実施して、PVB7を得て、PVB7を用いて可塑剤を数平均分子量が1000であるポリプロピレングリコール(「PPG1000」、富士フィルム和光純薬社製、以下「PPG1000」と呼ぶことがある)に変更した以外は実施例3と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
PVB7を用いて可塑剤を数平均分子量が700であるポリオキシプロピレンジグリセリルエーテル(「ユニルーブDGP-700」、日油株式会社製,以下「DGP700」と呼ぶことがある)にした以外は実施例3と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
PVB7を用いて可塑剤を数平均分子量が1000であるポリオキシプロピレングリセリルエーテル(「ユニーオールTG-1000R」、日油株式会社製,以下「TG1000R」と呼ぶことがある)にした以外は実施例3と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
使用するポリビニルアセタール系樹脂を、未変性ポリビニルブチラールであるPVB5を使用し、かつ100質量部のPVB5に対して、40質量部の可塑剤(3GO)を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、かつ評価を行った。
使用するポリビニルアセタール系樹脂を、未変性ポリビニルブチラールであるPVB6を使用し、かつ100質量部のPVB6に対して、25質量部の可塑剤(3GO)を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、実施例1と同様に評価した。
ポリビニルアセタール系樹脂として、未変性ポリビニルブチラールであるPVB5を使用した。100質量部のPVB5に対して、30質量部の可塑剤(3GO)、10質量部の反応性希釈剤(トリメチロールプロパントリアクリレート:TMPA)、及び光重合開始剤としてのベンゾフェノン(BP)0.1質量部を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。
また、粘着フィルムに対して、超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。光照射後にせん断貯蔵弾性率(G’)、tanδの最大ピーク温度、及び未溶解成分の割合を測定した。
さらに、耐衝撃性及び耐湿熱性の評価においては、比較例3で作製した粘着フィルムを用いて上記各評価方法で述べたとおりに積層体を製造して、その積層体に対して超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。その後、耐衝撃性及び耐湿熱性を評価した。
ポリビニルアセタール系樹脂として、未変性ポリビニルブチラールであるPVB6を使用した。100質量部のPVB6に対して、13質量部の可塑剤(3GO)、4質量部の反応性希釈剤(TMPA)、及び光重合開始剤としてのベンゾフェノン0.04質量部を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。 また、粘着フィルムに対して、超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。光照射後にせん断貯蔵弾性率(G’)、tanδの最大ピーク温度、及び未溶解成分の割合を測定した。かつ耐衝撃性及び耐湿熱性を評価した。
さらに、耐衝撃性及び耐湿熱性の評価においては、比較例4で作製した粘着フィルムを用いて上記各評価方法で述べたとおりに合わせガラスを製造して、その合わせガラスに対して超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。その後、耐衝撃性及び耐湿熱性を評価した。
表3に示すモノマー比でモノマーを重合して得た(メタ)アクリル系重合体(Ac1)100質量部を固形分量45質量%になるように酢酸エチルで希釈して、固形分基準で、イソシアネート系架橋剤(日本ポリウレタン社製「コロネートL-45」、固形分量45質量%)を1質量部添加して、樹脂組成物を得た。得られた樹脂組成物を、離型PETフィルムの離型処理面に乾燥後の厚さが150μmになるように塗工して、80℃で15分間乾燥して、粘着フィルムを得た。得られた粘着フィルムに対して、23℃で5日間養生した後、実施例1と同様に評価した。
(メタ)アクリル系重合体(Ac1)を(メタ)アクリル系重合体(Ac2)に変更した点を除いて比較例5と同様に実施した。
それに対して、比較例1~4では、tanδの最大ピーク温度が所定の範囲内であり、20℃のせん断貯蔵弾性率が高かったものの、未溶解成分の割合が低かったため、耐湿熱性を良好にでできなかった。また、比較例5、6では、20℃におけるせん断貯蔵弾性率(G’)が低いため、耐衝撃性が不十分であった。
31 表示素子
32 表面保護パネル
34、34A、34B 接着用フィルム(粘着フィルム)
32 第2の層
41、42 合わせガラス部材
43 調光素子(調光フィルム)
Claims (14)
- 熱可塑性樹脂を含む粘着フィルムであって、
tanδの最大ピーク温度が0℃以上52℃以下であり、20℃のせん断貯蔵弾性率が3×105Pa以上であり、かつ、前期粘着フィルム1.0gをイソプロピルアルコール10gに溶解させた場合の未溶解成分の割合が35質量%以上100質量%以下である、粘着フィルム。 - 可塑剤を含まない、若しくは前記熱可塑性樹脂100重量部に対して可塑剤を20重量部未満で含む、請求項1に記載の粘着フィルム。
- 前記熱可塑性樹脂がポリビニルアセタール系樹脂である、請求項1又は2に記載の粘着フィルム。
- 前記ポリビニルアセタール系樹脂が、前記ポリアルキレンオキサイド構造を0.1モル%以上10モル%以下の割合で含む、請求項4に記載の粘着フィルム。
- 前記ポリアルキレンオキサイド構造が、オキシエチレン基及びオキシプロピレン基の少なくともいずれかを含む、請求項4又は5に記載の粘着フィルム。
- 前記ポリアルキレンオキサイド構造が、オキシエチレン基及びオキシプロピレン基の両方を含み、これらがランダム構造を有する請求項6に記載の粘着フィルム。
- 前記ポリアルキレンオキサイド構造の末端がアルキル基である請求項4~7のいずれか1項に記載の粘着フィルム。
- 前記ポリビニルアセタール系樹脂のアセタール化度が60モル%以上である請求項3~8のいずれか1項に記載の粘着フィルム。
- 請求項1~9のいずれか1項に記載の粘着フィルムと、一対の基材とを備え、前記一対の基材の間に前記粘着フィルムが配置される、積層体。
- 前記一対の基材のいずれもがガラスである請求項10に記載の積層体。
- 前記一対の基材の一方がガラス、他方が調光フィルム及び偏光フィルムのいずれかである請求項10に記載の積層体。
- 請求項10~12のいずれか1項に記載の積層体を含む液晶ディスプレイ。
- 請求項10~12のいずれか1項に記載の積層体を含む合わせガラス。
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JP2015025042A (ja) * | 2013-07-25 | 2015-02-05 | 積水化学工業株式会社 | 接着剤用ポリビニルアセタール樹脂 |
WO2016158694A1 (ja) * | 2015-03-31 | 2016-10-06 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
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JP2015025042A (ja) * | 2013-07-25 | 2015-02-05 | 積水化学工業株式会社 | 接着剤用ポリビニルアセタール樹脂 |
WO2016158694A1 (ja) * | 2015-03-31 | 2016-10-06 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
WO2017061545A1 (ja) * | 2015-10-07 | 2017-04-13 | 積水化学工業株式会社 | ポリビニルアセタール樹脂組成物、接着シート、タッチパネル用層間充填材料及び積層体 |
JP2017149956A (ja) * | 2015-10-07 | 2017-08-31 | 積水化学工業株式会社 | タッチパネル用層間充填材料及びタッチパネル積層体 |
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