WO2020158176A1 - Layered body - Google Patents
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- Publication number
- WO2020158176A1 WO2020158176A1 PCT/JP2019/047249 JP2019047249W WO2020158176A1 WO 2020158176 A1 WO2020158176 A1 WO 2020158176A1 JP 2019047249 W JP2019047249 W JP 2019047249W WO 2020158176 A1 WO2020158176 A1 WO 2020158176A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- resin film
- adhesive layer
- meth
- pressure
- Prior art date
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- 229920005989 resin Polymers 0.000 claims abstract description 240
- 239000011347 resin Substances 0.000 claims abstract description 232
- 239000010410 layer Substances 0.000 claims abstract description 204
- 239000012790 adhesive layer Substances 0.000 claims abstract description 75
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 170
- 238000000034 method Methods 0.000 abstract description 65
- 239000000463 material Substances 0.000 abstract description 43
- 230000003014 reinforcing effect Effects 0.000 abstract description 18
- 230000001681 protective effect Effects 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 236
- -1 polyethylene terephthalate Polymers 0.000 description 178
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 96
- 230000000694 effects Effects 0.000 description 95
- 239000003431 cross linking reagent Substances 0.000 description 94
- 239000000203 mixture Substances 0.000 description 71
- 230000001771 impaired effect Effects 0.000 description 60
- 239000002253 acid Substances 0.000 description 59
- 238000004519 manufacturing process Methods 0.000 description 58
- 239000000178 monomer Substances 0.000 description 51
- 229920001940 conductive polymer Polymers 0.000 description 49
- 239000003999 initiator Substances 0.000 description 48
- 229920000058 polyacrylate Polymers 0.000 description 44
- 239000000758 substrate Substances 0.000 description 42
- 238000000576 coating method Methods 0.000 description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 40
- 239000000853 adhesive Substances 0.000 description 36
- 230000001070 adhesive effect Effects 0.000 description 36
- 229920001296 polysiloxane Polymers 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 32
- 239000002985 plastic film Substances 0.000 description 32
- 229920006255 plastic film Polymers 0.000 description 32
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 31
- 229920001225 polyester resin Polymers 0.000 description 31
- 239000004645 polyester resin Substances 0.000 description 31
- 150000001768 cations Chemical class 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 29
- 239000003505 polymerization initiator Substances 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000001035 drying Methods 0.000 description 21
- 239000002608 ionic liquid Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 238000011282 treatment Methods 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 17
- 150000002148 esters Chemical class 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 12
- 125000005907 alkyl ester group Chemical group 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 10
- 150000004820 halides Chemical class 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000005846 sugar alcohols Polymers 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 239000004840 adhesive resin Substances 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 8
- 229940059574 pentaerithrityl Drugs 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 238000012719 thermal polymerization Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000004696 Poly ether ether ketone Substances 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 6
- 244000028419 Styrax benzoin Species 0.000 description 6
- 235000000126 Styrax benzoin Nutrition 0.000 description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 229960002130 benzoin Drugs 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 235000019382 gum benzoic Nutrition 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
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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 6
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 6
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 4
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- 239000006087 Silane Coupling Agent Substances 0.000 description 4
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- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
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- 239000003963 antioxidant agent Substances 0.000 description 4
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- 229920005601 base polymer Polymers 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
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- 239000003086 colorant Substances 0.000 description 4
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- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000007756 gravure coating Methods 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
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- PIODCVYLDQEZFW-UHFFFAOYSA-N diethyl-heptyl-methylazanium Chemical compound CCCCCCC[N+](C)(CC)CC PIODCVYLDQEZFW-UHFFFAOYSA-N 0.000 description 1
- OBRWMJNKKIMAPZ-UHFFFAOYSA-N diethyl-methyl-pentylazanium Chemical compound CCCCC[N+](C)(CC)CC OBRWMJNKKIMAPZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MEJYOZOPFBOWNM-UHFFFAOYSA-N triethyl(heptyl)azanium Chemical compound CCCCCCC[N+](CC)(CC)CC MEJYOZOPFBOWNM-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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]
Definitions
- the present invention relates to a laminated body.
- the present invention relates to a laminate that can be suitably used in the manufacturing process of optical members and electronic members.
- a surface protective film SPV
- a reinforcing film RF
- Patent Document 1 a surface protective film
- a continuous roll-to-roll method is used rather than the step of pasting the surface protection film and the reinforcing film one by one. The process is effective.
- the substrate surface of the surface protective film or the reinforcing film is a laminate pasted on the light release adhesive layer surface of the carrier sheet having a base material and a light release adhesive layer, a roll-to-roll method,
- the surface protection film and the reinforcing film can be continuously attached to the member.
- the carrier sheet is peeled off after the attachment.
- the light release adhesive layer of the carrier sheet is used to remove the surface protection film or the base material surface of the reinforcing film (particularly the end portion). ) May appear to float.
- Such a phenomenon is often seen particularly when the above-mentioned laminated body is unrolled, when it passes through a roll, or when the surface protective film or the separator of the reinforcing film is peeled off.
- An object of the present invention is a laminate in which a surface protective film and a reinforcing film are laminated on a carrier sheet, and when continuously attached to a member by roll-to-roll, from a pressure-sensitive adhesive layer included in the carrier sheet.
- An object of the present invention is to provide a laminate in which the base material surface of a surface protection film or a reinforcing film is hard to float.
- the laminate of the present invention is A laminate having five or more layers, which has a resin film (1), a pressure-sensitive adhesive layer (1), a resin film (2), a pressure-sensitive adhesive layer (2), and a resin film (3) in this order,
- the pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated
- the resin film (2) and the adhesive layer (2) are directly laminated
- the laminated portion of the adhesive layer (1) and the resin film (2) is divided into a plurality of through holes having a width of 0.5 mm to 10 mm in a direction substantially orthogonal to the longitudinal direction,
- the length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is 1 mm to 2000 mm,
- a laminated portion of a plurality of the adhesive layers (1) and the resin film (2) divided by the through holes Is the maximum amount of floating from the pressure-sensitive adhesive layer (2), the width of the through
- the total area of the resin film (2) in the plane direction is smaller than the total area of the adhesive layer (2) in the plane direction.
- weight When the expression “weight” is used in this specification, it may be read as “mass” which is commonly used as an SI system unit indicating weight.
- the expression “(meth)acrylic” means “acrylic and/or methacrylic
- the expression “(meth)acrylate” means “acrylate and/or methacrylate”.
- the expression “(meth)allyl” means “allyl and/or methallyl
- the expression “(meth)acrolein” means “acrolein and/or methacrolein”. Means "rain”.
- the laminate of the present invention is a laminate of 5 or more layers having the resin film (1), the pressure-sensitive adhesive layer (1), the resin film (2), the pressure-sensitive adhesive layer (2), and the resin film (3) in this order. Therefore, the pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated, and the resin film (2) and the pressure-sensitive adhesive layer (2) are directly laminated.
- the laminate of the present invention has a resin film (1), a pressure-sensitive adhesive layer (1), a resin film (2), a pressure-sensitive adhesive layer (2) and a resin film (3) in this order, and the pressure-sensitive adhesive layer (1 ) And the resin film (2) are directly laminated, and the resin film (2) and the pressure-sensitive adhesive layer (2) are directly laminated, as long as the effects of the present invention are not impaired. It may have other suitable layers.
- the number of layers of the laminate of the present invention is preferably 5 to 10 layers, more preferably 5 to 8 layers, and further preferably 5 to 7 layers, depending on the number of other layers described above. , Particularly preferably 5 to 6 layers, most preferably 5 layers.
- the laminated portion of the pressure-sensitive adhesive layer (1) and the resin film (2) is divided into a plurality of through holes having a width of 0.5 mm to 10 mm in a direction substantially orthogonal to the longitudinal direction.
- the width of such a through hole is preferably 0.6 mm to 8 mm, more preferably 0.7 mm to 6 mm, further preferably 0.8 mm to 5 mm, and particularly preferably 0.9 mm to 4 mm. Yes, and most preferably 1 mm to 3 mm.
- Such a through hole is preferably substantially rectangular parallelepiped-shaped.
- the laminated portion of the pressure-sensitive adhesive layer (1) and the resin film (2) is divided into a plurality of through holes each having a predetermined length in a direction substantially orthogonal to the longitudinal direction.
- the surface of the surface protective film or the reinforcing film of the carrier sheet may not easily float from the pressure-sensitive adhesive layer of the carrier sheet.
- the laminated portion of the pressure-sensitive adhesive layer (1) and the resin film (2) is divided into a plurality of parts by the above-mentioned through holes.
- the length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is 1 mm to 2000 mm, preferably 1 mm to 1000 mm, more preferably 1 mm to 500 mm. And more preferably 2 mm to 500 mm, particularly preferably 2 mm to 400 mm, and most preferably 2 mm to 300 mm.
- the laminate of the present invention is roll-to-roll.
- the surface of the base material of the surface protection film or the reinforcing film may be hardly floated from the pressure-sensitive adhesive layer of the carrier sheet to form a laminate.
- the total area of the resin film (2) in the plane direction is preferably smaller than the total area of the adhesive layer (2) in the plane direction.
- the ratio of the total area of the resin film (2) in the plane direction to the total area of the adhesive layer (2) in the plane direction is preferably 20% to 99.9%, more preferably 50% to 99%. %, more preferably 60% to 98%, particularly preferably 70% to 97%, and most preferably 80% to 96%. Since the total area of the resin film (2) in the plane direction is smaller than the total area of the pressure-sensitive adhesive layer (2) in the plane direction, the laminate of the present invention is roll-to-roll continuous to the member. When it is attached to, the base material surface of the surface protection film or the reinforcing film may become a laminate more difficult to float from the pressure-sensitive adhesive layer of the carrier sheet.
- the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, and the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) adheres to each other.
- the maximum amount floating from the agent layer (2) is that the width of the through hole is 5 mm, and the length in the longitudinal direction of the laminated portion of the plurality of adhesive layers (1) and the resin film (2) divided by the through hole is When it is 50 mm, it is 0.5 mm or less, preferably 0.3 mm or less, more preferably 0.2 mm or less, still more preferably 0.1 mm or less, and particularly preferably 0.08 mm or less. , And most preferably 0 mm.
- the method for measuring the above-mentioned floating will be described later.
- the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, and the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) adheres to each other.
- the maximum amount floating from the agent layer (2) is that the width of the through hole is 3 mm, and the length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through hole is When it is 50 mm, it is preferably 0.7 mm or less, more preferably 0.5 mm or less, further preferably 0.3 mm or less, particularly preferably 0.2 mm or less, and most preferably 0 mm. .. The method for measuring the above-mentioned floating will be described later.
- the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, and the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) adheres to each other.
- the maximum amount floating from the agent layer (2) is that the width of the through hole is 1 mm, and the length in the longitudinal direction of the laminated portion of the plurality of adhesive layer (1) and the resin film (2) divided by the through hole is When it is 50 mm, it is preferably 1.2 mm or less, more preferably 1.0 mm or less, further preferably 0.5 mm or less, particularly preferably 0.2 mm or less, and most preferably 0.1 mm. It is as follows. The method for measuring the above-mentioned floating will be described later.
- the laminate 100 of the present invention comprises a resin film (1) 10, an adhesive layer (1) 20, a resin film (2) 30, and an adhesive.
- the agent layer (2) 40 and the resin film (3) 50 are directly laminated in this order.
- the laminated portion of the pressure-sensitive adhesive layer (1) 20 and the resin film (2) 30 is divided into a plurality of portions by a through hole 60 having a predetermined length in a direction substantially orthogonal to the longitudinal direction, and is divided. It constitutes a laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2).
- the laminate portion of the resin film (1), the adhesive layer (1) and the resin film (2) can be a surface protection film or a reinforcing film.
- the resin film (1) can serve as a separator.
- the laminate portion of the pressure-sensitive adhesive layer (2) and the resin film (3) can be a carrier sheet.
- the carrier sheet can also be treated as a surface protective film.
- the laminate of the present invention is obtained when the pressure-sensitive adhesive layer (2) is peeled from the resin film (2) at a peeling angle of 180° and a peeling speed of 30 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the adhesive strength is preferably 1 gf/25 mm or more, more preferably 1 gf/25 mm to 10 gf/25 mm, further preferably 1.2 gf/25 mm to 8 gf/25 mm, and further preferably 1.4 gf/25 mm- It is 7 gf/25 mm, particularly preferably 1.6 gf/25 mm to 5 gf/25 mm, and most preferably 1.8 gf/25 mm to 3 gf/25 mm.
- the laminate of the present invention makes it possible to prevent the resin film (2) from being lifted from the adhesive layer (2) when continuously attached to a member by roll-to-roll. Can be suppressed.
- the method for measuring the adhesive strength will be described later.
- the laminate of the present invention is obtained when the pressure-sensitive adhesive layer (2) is peeled from the resin film (2) at a peeling angle of 180° and a peeling speed of 300 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the adhesive force is preferably 2 gf/25 mm or more, more preferably 2 gf/25 mm to 20 gf/25 mm, further preferably 2.5 gf/25 mm to 10 gf/25 mm, further preferably 3 gf/25 mm to 9 gf/ It is 25 mm, particularly preferably 3 gf/25 mm to 8 gf/25 mm, and most preferably 3.5 gf/25 mm to 7 gf/25 mm.
- the laminate of the present invention makes it possible to prevent the resin film (2) from being lifted from the adhesive layer (2) when continuously attached to a member by roll-to-roll. Can be suppressed.
- the method for measuring the adhesive strength will be described later.
- the laminate of the present invention is obtained when the pressure-sensitive adhesive layer (2) is peeled from the resin film (2) at a peeling angle of 180° and a peeling speed of 2400 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the adhesive strength is preferably 5 gf/25 mm or more, more preferably 5 gf/25 mm to 100 gf/25 mm, further preferably 7 gf/25 mm to 60 gf/25 mm, further preferably 8 gf/25 mm to 40 gf/25 mm.
- the laminate of the present invention makes it possible to prevent the resin film (2) from being lifted from the adhesive layer (2) when continuously attached to a member by roll-to-roll. Can be suppressed.
- the method for measuring the adhesive strength will be described later.
- the laminate of the present invention peels the pressure-sensitive adhesive layer (1) from glass at a peeling angle of 180 degrees and a peeling speed of 300 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the adhesive force (2) when peeled from the adhesive layer is preferably adhesive force (1)>adhesive force (2). When the adhesive strength (1)>the adhesive strength (2), the effect of the present invention can be more exhibited. The method for measuring the adhesive strength will be described later.
- the laminate of the present invention has a total light transmittance of preferably 60% or more, more preferably 70% to 100%, further preferably 80% to 100%, particularly preferably 83% to 100%. %, and most preferably 85% to 100%.
- the method for measuring the total light transmittance will be described later.
- the haze of the laminate of the present invention is preferably 15% or less, more preferably 0% to 10%, further preferably 0% to 8%, and particularly preferably 0% to 7%. , And most preferably 0% to 6%.
- the method for measuring the haze will be described later.
- the thickness of the resin film (1) is preferably from 1 ⁇ m to 300 ⁇ m, more preferably from 10 ⁇ m to 200 ⁇ m, further preferably from 30 ⁇ m to 150 ⁇ m, and particularly preferably from the viewpoint that the effect of the present invention can be further exhibited. Is 40 ⁇ m to 100 ⁇ m, and most preferably 50 ⁇ m to 80 ⁇ m.
- the resin film (1) includes a resin base film (1a).
- the resin substrate film (1a) examples include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBT); polyethylene (PE), polypropylene ( PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other plastic films composed of an olefin resin containing ⁇ -olefin as a monomer component; polyvinyl chloride Plastic film composed of (PVC); plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), all Plastic film composed of amide resin such as aromatic polyamide (aramid); Plastic film composed of polyimide resin; Plastic film composed of polyether ether ketone (PEEK); Polyethylene (PE), polypropylene (PP) ) And other plastic films composed of ole
- the resin base film (1a) may have only one layer, or may have two or more layers.
- the resin substrate film (1a) may be stretched.
- the resin base film (1a) may be surface-treated.
- the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric bombardment exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.
- the resin base film (1a) may contain any appropriate additive as long as the effects of the present invention are not impaired.
- the resin film (1) may have a release layer (1b) in order to enhance the releasability from the adhesive layer (1).
- the release layer (1b) side is directly laminated on the pressure-sensitive adhesive layer (1).
- any appropriate forming material can be adopted as long as the effect of the present invention is not impaired.
- a forming material include a silicone type release agent, a fluorine type release agent, a long chain alkyl type release agent, and a fatty acid amide type release agent. Of these, silicone-based release agents are preferred.
- the release layer (1b) can be formed as a coating layer.
- any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired.
- a thickness is preferably 10 nm to 2000 nm, more preferably 10 nm to 1500 nm, further preferably 10 nm to 1000 nm, and particularly preferably 10 nm to 500 nm.
- the release layer (1b) may be only one layer or two or more layers.
- silicone type release layer examples include addition reaction type silicone resins.
- Specific examples of the addition reaction type silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T manufactured by Shin-Etsu Chemical; TPR- manufactured by Toshiba Silicone. 6700, TPR-6710, TPR-6721; Toray Dow Corning SD7220, SD7226; and the like.
- the coating amount (after drying) of the silicone-based release layer is preferably 0.01 g/m 2 to 2 g/m 2 , more preferably 0.01 g/m 2 to 1 g/m 2 , and further preferably It is 0.01 g/m 2 to 0.5 g/m 2 .
- the release layer (1b) is usually formed by coating the above-mentioned forming material on any appropriate layer by a conventionally known coating method such as reverse gravure coating, bar coating, die coating, etc. It can be performed by heat treatment at about 200° C. to cure. If necessary, heat treatment and irradiation with active energy rays such as ultraviolet irradiation may be used in combination.
- the resin film (1) may have an antistatic layer (1c).
- any appropriate thickness can be adopted as long as the effect of the present invention is not impaired.
- Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
- the antistatic layer (1c) may be a single layer or two or more layers.
- any suitable antistatic layer can be adopted as long as it can exhibit an antistatic effect as long as the effect of the present invention is not impaired.
- Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the resin substrate film (1a). Specific coating methods include a roll coating method, a bar coating method and a gravure coating method.
- any appropriate conductive polymer can be adopted as long as the effect of the present invention is not impaired.
- a conductive polymer include a conductive polymer obtained by doping a ⁇ -conjugated conductive polymer with a polyanion.
- the ⁇ -conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
- polyanion examples include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacryl carboxylic acid.
- the conductive polymer may be only one kind or two or more kinds.
- One embodiment of the resin film (1) includes a resin substrate film (1a), an antistatic layer (1c) and a release layer (1b) in this order.
- this embodiment comprises a resin substrate film (1a), an antistatic layer (1c) and a release layer (1b).
- the resin film (1) includes an antistatic layer (1c), a resin base film (1a), an antistatic layer (1c) and a release layer (1b) in this order.
- this embodiment comprises an antistatic layer (1c), a resin substrate film (1a), an antistatic layer (1c) and a release layer (1b).
- the pressure-sensitive adhesive layer (1) may be a single layer or two or more layers.
- the thickness of the pressure-sensitive adhesive layer (1) is preferably 0.5 ⁇ m to 150 ⁇ m, more preferably 1 ⁇ m to 100 ⁇ m, and further preferably 3 ⁇ m to 80 ⁇ m, from the viewpoint that the effect of the present invention can be further exhibited. Particularly preferred is 5 ⁇ m to 50 ⁇ m, and most preferred is 5 ⁇ m to 30 ⁇ m.
- the pressure-sensitive adhesive layer (1) has a laminated portion with the resin film (2) divided into a plurality of through holes each having a predetermined length in a direction substantially orthogonal to the longitudinal direction.
- the pressure-sensitive adhesive layer (1) is preferably composed of at least one selected from the group consisting of acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, rubber pressure-sensitive adhesives and silicone pressure-sensitive adhesives.
- the adhesive layer (1) can be formed by any appropriate method.
- a method include, for example, at least one selected from the group consisting of a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition, urethane-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive composition, silicone-based pressure-sensitive adhesive composition).
- a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition, urethane-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive composition, silicone-based pressure-sensitive adhesive composition).
- a suitable base material for example, the resin film (2)
- Examples of such a coating method include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater and a roll brush coater. The method of is mentioned.
- the adhesive layer (1) may include a conductive component.
- the conductive component may be only one kind or two or more kinds.
- the acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
- the acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a crosslinking agent from the viewpoint that the effects of the present invention can be more exhibited.
- the acrylic polymer can be called a so-called base polymer in the field of acrylic pressure-sensitive adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.
- the content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 60% by weight to 99.9% by weight, and more preferably 65% by weight to 99.9% by weight, in terms of solid content. It is more preferably 70% to 99.9% by weight, particularly preferably 75% to 99.9% by weight, and most preferably 80% to 99.9% by weight.
- acrylic polymer any suitable acrylic polymer can be adopted as long as the effect of the present invention is not impaired.
- the weight average molecular weight of the acrylic polymer is preferably 300,000 to 2,500,000, more preferably 350,000 to 2,000,000, and further preferably 400,000 to 1800,000, from the viewpoint that the effects of the present invention can be further exhibited. And particularly preferably 500,000 to 1,500,000.
- the acrylic polymer is preferably a (meth)acrylic acid alkyl ester in which the alkyl group of the (a component) alkyl ester moiety has 4 to 12 carbon atoms from the viewpoint that the effect of the present invention can be further exhibited, and (b) It is an acrylic polymer formed by polymerization from a composition (A) containing (component) at least one selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid.
- the acrylic polymer is preferably a (meth)acrylic acid alkyl ester in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms, as the component (a), from the viewpoint that the effects of the present invention can be further exhibited.
- Each of (a component) and (b component) may be independently one type, or two or more types.
- Examples of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include, for example, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate.
- n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable, and n-butyl acrylate and acryl are more preferable, from the viewpoint that the effects of the present invention can be further exhibited.
- It is 2-ethylhexyl acid.
- Examples of at least one component (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples thereof include (meth)acrylic acid ester having an OH group such as hydroxybutyl (meth)acrylate and (meth)acrylic acid. Among these, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, from the viewpoint that the effects of the present invention can be further exhibited.
- the composition (A) may contain a copolymerizable monomer other than the components (a) and (b).
- the copolymerizable monomer may be only one type, or may be two or more types.
- Such copolymerizable monomers include, for example, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride).
- carboxyl group-containing monomers excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide , N-butoxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and other amide group-containing monomers; aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, t-butyl (meth)acrylate Amino group-containing monomers such as aminoethyl; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, Heterocycle-containing vinyl monomers such as (meth)acryloylmorpholine,
- a polyfunctional monomer can also be adopted.
- the polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule.
- the ethylenically unsaturated group any appropriate ethylenically unsaturated group can be adopted as long as the effects of the present invention are not impaired.
- examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group).
- polyfunctional monomer examples include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol.
- examples thereof include (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate and urethane acrylate. Only one kind of such a polyfunctional monomer may be used, or two or more kinds thereof may be used.
- (meth)acrylic acid alkoxyalkyl ester can also be adopted.
- the (meth)acrylic acid alkoxyalkyl ester include 2-(meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, and (meth)acrylic acid 3-methacrylate. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate.
- the (meth)acrylic acid alkoxyalkyl ester may be only one kind, or may be two or more kinds.
- the content of the (meth)acrylic acid alkyl ester (a component) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer that constitutes the acrylic polymer in that the effects of the present invention can be further exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, further preferably 40% by weight to 98% by weight, particularly preferably 50% by weight based on the total amount of the components (100% by weight). % By weight to 95% by weight.
- the content of at least one kind (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is such that the acrylic polymer is added in that the effect of the present invention can be further exhibited. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, further preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 10% by weight.
- composition (A) may contain any appropriate other component as long as the effect of the present invention is not impaired.
- examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent.
- any appropriate content can be adopted as long as the effect of the present invention is not impaired.
- the polymerization initiator a thermal polymerization initiator, a photopolymerization initiator (photoinitiator) or the like can be adopted depending on the type of the polymerization reaction.
- the polymerization initiator may be only one type, or may be two or more types.
- the thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization.
- thermal polymerization initiators include azo-based polymerization initiators, peroxide-based polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox-based polymerization initiators, and the like. ..
- the azo initiators disclosed in JP-A-2002-69411 are particularly preferable.
- Such an azo-based polymerization initiator is preferable in that the decomposed product of the polymerization initiator is unlikely to remain in the acrylic polymer as a portion causing generation of a heat-generated gas (outgas).
- azo-based polymerization initiator examples include 2,2′-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN) and 2,2′-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN). , 2,2′-azobis(2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid and the like.
- the photopolymerization initiator can be preferably used when the acrylic polymer is obtained by active energy ray polymerization.
- the photopolymerization initiator include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime photopolymerization initiators.
- Agents benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole.
- examples include methyl ether.
- examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-(t-butyl). Examples thereof include dichloroacetophenone.
- Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. ..
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalene sulfonyl chloride.
- Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
- Examples of the benzoin-based photopolymerization initiator include benzoin and the like.
- Examples of the benzyl photopolymerization initiator include benzyl and the like.
- benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenylketone, and the like.
- ketal photopolymerization initiator examples include benzyl dimethyl ketal.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and dodecylthioxanthone.
- the acrylic pressure-sensitive adhesive composition may contain a crosslinking agent.
- a crosslinking agent By using the cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited.
- the cross-linking agent may be only one kind or two or more kinds.
- a polyfunctional isocyanate crosslinking agent As the crosslinking agent, a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt.
- examples thereof include a system-based crosslinking agent, a carbodiimide-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, and an amine-based crosslinking agent.
- at least one kind (component (c)) selected from the group consisting of a polyfunctional isocyanate cross-linking agent and an epoxy cross-linking agent is preferable from the viewpoint that the effect of the present invention can be further exhibited.
- polyfunctional isocyanate cross-linking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Aliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.
- lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate
- cyclopentylene diisocyanate cyclohexylene diisocyanate
- Aromatic polyisocyanates of Examples of the polyfunctional isocyanate cross-linking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”), trimethylolpropane/hexamethylene diisocyanate adduct (Japan Polyurethane Industry Co., Ltd. Company name, product name "Coronate HL”), product name "Coronate HX” (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemicals, Inc., product name "Takenate 110N”), etc. Commercial products are also included.
- epoxy cross-linking agent examples include N,N,N′,N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, and 1,3-bis(N,N-diglycidylamino).
- any appropriate content can be adopted as long as the effect of the present invention is not impaired.
- a content is, for example, preferably 0.05 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer, from the viewpoint that the effect of the present invention can be exhibited more. It is more preferably 0.1 part by weight to 18 parts by weight, further preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight.
- the acrylic pressure-sensitive adhesive composition may contain any appropriate other component as long as the effect of the present invention is not impaired.
- other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), Anti-aging agent, inorganic filler, organic filler, metal powder, colorant (pigment or dye, etc.), foil, UV absorber, antioxidant, light stabilizer, chain transfer agent, plasticizer, softener, Examples thereof include surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and catalysts.
- any appropriate urethane-based pressure-sensitive adhesive may be adopted, for example, known urethane-based pressure-sensitive adhesives described in JP-A-2017-039859, etc., within a range that does not impair the effects of the present invention. ..
- a urethane-based pressure-sensitive adhesive for example, a urethane-based pressure-sensitive adhesive formed from a urethane-based pressure-sensitive adhesive composition, wherein the urethane-based pressure-sensitive adhesive composition is selected from the group consisting of a urethane prepolymer and a polyol. It contains at least one kind and a crosslinking agent.
- the urethane-based pressure-sensitive adhesive may be only one kind or two or more kinds.
- the urethane-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
- any suitable rubber-based pressure-sensitive adhesive can be adopted, for example, known rubber-based pressure-sensitive adhesives described in JP-A-2005-074771 and the like, within a range that does not impair the effects of the present invention. .. These may be only one kind or two or more kinds.
- the rubber-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
- silicone-based pressure-sensitive adhesive any appropriate silicone-based pressure-sensitive adhesive may be adopted, for example, known silicone-based pressure-sensitive adhesives described in JP-A-2014-047280 and the like, as long as the effects of the present invention are not impaired. .. These may be only one kind or two or more kinds.
- the silicone-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
- the adhesive layer (1) may contain a conductive component.
- a pressure-sensitive adhesive composition as a material of the pressure-sensitive adhesive layer (1) (a group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive composition At least one selected from the above may contain a conductive component.
- any appropriate conductive component can be adopted as long as the effect of the present invention is not impaired.
- a conductive component is preferably at least one compound selected from an ionic liquid, an ion conductive polymer, an ion conductive filler and an electric conductive polymer.
- the ratio of the base polymer (for example, acrylic polymer, polyol, urethane prepolymer, rubber polymer, silicone polymer) to the conductive component is such that the conductive component is With respect to 100 parts by weight of the base polymer, it is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 9.0 parts by weight, and further preferably 0.075 parts by weight to 8 parts by weight. 0.0 parts by weight, particularly preferably 0.1 parts by weight to 7.0 parts by weight.
- the ionic liquid any appropriate ionic liquid can be adopted as long as the effect of the present invention is not impaired.
- the ionic liquid means a molten salt (ionic compound) which is liquid at 25°C.
- the ionic liquid may be only one kind or two or more kinds.
- Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation.
- any appropriate onium cation can be adopted as long as the effect of the present invention is not impaired.
- Such an onium cation is preferably at least one selected from nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations.
- the onium cation that can form the ionic liquid is preferably at least one selected from cations having a structure represented by any one of the general formulas (1) to (5) from the viewpoint that the effects of the present invention can be further exhibited. Is.
- Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom
- Rb and Rc are the same or different and each represents hydrogen or a carbon atom having 1 to 16 carbon atoms. It represents a hydrogen group and may contain a hetero atom. However, when the nitrogen atom contains a double bond, there is no Rc.
- Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom
- Re, Rf and Rg are the same or different and each represents hydrogen or a carbon number of 1 to It represents 16 hydrocarbon groups and may contain a hetero atom.
- Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may include a hetero atom
- Ri, Rj, and Rk are the same or different and each represents hydrogen or a carbon number of 1 to It represents 16 hydrocarbon groups and may contain a hetero atom.
- Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom
- Rl, Rm, Rn, and Ro are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms; It may contain atoms. However, when Z is a sulfur atom, there is no Ro.
- X represents a Li atom, a Na atom, or a K atom.
- Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton.
- cation represented by the general formula (1) examples include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl.
- Pyridinium cation such as -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrroli Dinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinide Cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation , 1-Ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-
- Examples of the cation represented by the general formula (2) include imidazolium cation, tetrahydropyrimidinium cation, and dihydropyrimidinium cation.
- cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl.
- Examples of the cation represented by the general formula (3) include a pyrazolium cation and a pyrazolinium cation.
- cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl- A pyrazolium cation such as a 2,3,5-trimethylpyrazolium cation, a 1-propyl-2,3,5-trimethylpyrazolium cation, a 1-butyl-2,3,5-trimethylpyrazolium cation; Pyra such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation Zolinium cation; and the like.
- Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the above alkyl group substituted with an alkenyl group, an alkoxyl group, or an epoxy group. Some of them are listed.
- cation represented by the general formula (4) include, for example, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethyl.
- Asymmetric tetraalkylammonium cations such as phosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, N,N-diethyl-N-methyl-N-(2-methoxyethyl) Ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl ammonium cation, N,N-dimethyl-N-ethyl-N-propyl ammonium cation, N,N-dimethyl-N-ethyl-N-butyl ammonium cation, N,N-dimethyl -N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-d
- any appropriate fluoroorganic anion can be adopted as long as the effect of the present invention is not impaired.
- Such a fluoroorganic anion may be completely fluorinated (perfluorinated) or partially fluorinated.
- fluoroorganic anion examples include perfluoroalkyl sulfonate, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl)imide, and more specifically, for example, trifluoromethane sulfonate, pentafluoroethane sulfonate. , Heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide.
- ionic liquid a combination of the above cation component and the above anion component can be appropriately selected and used.
- an ionic liquid include, for example, 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethane sulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethane Sulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-octy
- the ionic liquid As the ionic liquid, a commercially available one may be used, but it is also possible to synthesize it as follows.
- the method for synthesizing an ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained, but in general, the literature "Ionic liquids-the forefront and future of development-" (CMC Publishing Co., Ltd.) Issue), a halide method, a hydroxide method, an acid ester method, a complex formation method, a neutralization method and the like are used.
- the halide method, the hydroxide method, the acid ester method, the complex formation method, and the neutralization method are shown below for the synthesis method using a nitrogen-containing onium salt as an example.
- Other ionic liquids such as the above can be obtained by the same method.
- the halide method is a method performed by the reactions shown in the reaction formulas (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction formula (1), chlorine, bromine, or iodine is used as halogen).
- the obtained halide is an acid (HA) or salt having the anion structure (A ⁇ ) of the desired ionic liquid (MA and M are cations that form a salt with the desired anion such as ammonium, lithium, sodium and potassium). ) And the target ionic liquid (R 4 NA) is obtained.
- the hydroxide method is a method performed by the reactions shown in the reaction formulas (4) to (8).
- a reaction of a halide (R 4 NX) with an ion exchange membrane method electrolysis (reaction formula (4)), an OH type ion exchange resin method (reaction formula (5)), or silver oxide (Ag 2 O) (reaction formula ( In 6)
- a hydroxide (R 4 NOH) is obtained (as halogen, chlorine, bromine or iodine is used).
- the target ionic liquid (R 4 NA) can be obtained.
- the acid ester method is a method performed by the reactions shown in the reaction formulas (9) to (11). First, a tertiary amine (R 3 N) is reacted with an acid ester to obtain an acid ester product (reaction formula (9).
- an acid ester inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid can be used. Esters and methanesulfonic acid, methylphosphonic acid, and organic acid esters such as formic acid are used).
- the target ionic liquid (R 4 NA) is obtained by using the reaction of the reaction formulas (10) to (11) for the obtained acid ester product in the same manner as in the above halogenation method.
- an ionic liquid can be directly obtained by using methyltrifluoromethanesulfonate, methyltrifluoroacetate, or the like as the acid ester.
- the neutralization method is a method performed by the reaction shown in the reaction formula (12).
- Tertiary amine and CF 3 COOH, CF 3 SO 3 H, is reacted (CF 3 SO 2) 2 NH , (CF 3 SO 2) 3 CH, and organic acids such as (C 2 F 5 SO 2) 2 NH Can be obtained.
- R in the above reaction formulas (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms and may contain a hetero atom.
- any appropriate ion conductive polymer can be adopted as long as the effect of the present invention is not impaired.
- examples of such an ion conductive polymer include an ion conductive polymer obtained by polymerizing or copolymerizing a monomer having a quaternary ammonium salt group; polythiophene, polyaniline, polypyrrole, polyethyleneimine, allylamine-based polymer, and the like. Conductive polymer; and the like.
- the ion conductive polymer may be only one kind or two or more kinds.
- any appropriate ion conductive filler can be adopted as long as the effect of the present invention is not impaired.
- examples of such an ion conductive filler include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium and iron. , Cobalt, copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide) and the like.
- the ion conductive filler may be only one kind or two or more kinds.
- any appropriate electrically conductive polymer can be adopted as long as the effect of the present invention is not impaired.
- Examples of such an electrically conductive polymer include (3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid).
- a pressure-sensitive adhesive composition as a material of the pressure-sensitive adhesive layer (1) (at least one selected from the group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, and a silicone pressure-sensitive adhesive composition).
- the seed may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents.
- Inorganic fillers Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), foil materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
- any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired.
- Such a thickness is preferably 25 ⁇ m to 500 ⁇ m, more preferably 25 ⁇ m to 400 ⁇ m, further preferably 25 ⁇ m to 300 ⁇ m, and particularly preferably 25 ⁇ m to the point that the effect of the present invention can be further exhibited. It is 200 ⁇ m, and most preferably 25 ⁇ m to 150 ⁇ m.
- the resin film (2) has a laminated portion with the adhesive layer (1) divided into a plurality of through holes each having a predetermined length in a direction substantially orthogonal to the longitudinal direction.
- the resin film (2) includes a resin base film (2a).
- a plastic film composed of a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyethylene (PE), polypropylene ( PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other plastic films composed of an olefin resin containing ⁇ -olefin as a monomer component; polyvinyl chloride Plastic film composed of (PVC); plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), all Plastic film composed of amide resin such as aromatic polyamide (aramid); Plastic film composed of polyimide resin; Plastic film composed of polyetheretherketone (PEEK); Polyethylene (PE), polypropylene (PP) ) And other plastic films composed of o
- the resin base film (2a) may have only one layer or two or more layers.
- the resin substrate film (2a) may be stretched.
- the resin base film (2a) may be surface-treated.
- the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric bombardment exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.
- the resin substrate film (2a) may contain any appropriate additive depending on the purpose, within a range that does not impair the effects of the present invention.
- the resin film (2) may have a conductive layer (2b).
- the conductive layer (2b) may be arranged between the pressure-sensitive adhesive layer (1) and the resin base film (2a).
- the conductive layer (2b) may be only one layer or two or more layers.
- the conductive layer (2b) can be provided by forming it on any suitable base material.
- a substrate is preferably a resin substrate film (2a).
- the conductive layer (2b) is formed by any suitable thin film forming method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, a chemical plating method, an electroplating method, or a combination thereof.
- the conductive film is formed on any suitable substrate (preferably, the resin substrate film (2a)).
- the vacuum deposition method and the sputtering method are preferable from the viewpoints of the formation speed of the conductive film, the formability of a large-area film, the productivity, and the like.
- metal-based materials such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, alloys thereof; indium oxide, A metal oxide-based material composed of tin oxide, titanium oxide, cadmium oxide, a mixture thereof, or the like; another metal compound composed of copper iodide or the like is used.
- any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention.
- a thickness is, for example, preferably 30 ⁇ to 600 ⁇ when formed of a metal-based material, and preferably 80 ⁇ to 5000 ⁇ when formed of a metal oxide-based material.
- the surface resistance value of the conductive layer (2b) is preferably 1.0 ⁇ 10 10 ⁇ / ⁇ or less, more preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less, further preferably 1.0 ⁇ 10 9. It is 8 ⁇ / ⁇ or less, and particularly preferably 1.0 ⁇ 10 7 ⁇ / ⁇ or less.
- the corona discharge is formed on the surface of the substrate (preferably the resin substrate film (2a)).
- Adhesion between the conductive film and the substrate (preferably the resin substrate film (2a)) after any suitable pretreatment such as treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, and undercoat treatment. Can also be increased.
- the resin film (2) may have an antistatic layer (2c).
- the antistatic layer (2c) may be arranged between the pressure-sensitive adhesive layer (1) and the resin base film (2a) and/or between the resin base film (2a) and the pressure-sensitive adhesive layer (2).
- the antistatic layer (2c) may be a single layer or two or more layers.
- any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired.
- Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
- the surface resistance value of the antistatic layer (2c) is preferably 1.0 ⁇ 10 10 ⁇ / ⁇ or less, more preferably 8.0 ⁇ 10 9 ⁇ / ⁇ or less, further preferably 5.0 ⁇ . It is 10 9 ⁇ / ⁇ or less, and particularly preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less.
- any appropriate antistatic layer can be adopted as long as it can exhibit an antistatic effect as long as the effect of the present invention is not impaired.
- Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate base material layer.
- it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the resin substrate film (2a). After coating, it is dried if necessary and a curing treatment (heat treatment, ultraviolet treatment, etc.) is performed if necessary.
- Specific coating methods include a roll coating method, a bar coating method and a gravure coating method.
- the conductive coating liquid containing a conductive polymer any appropriate conductive coating liquid can be adopted as long as the effect of the present invention is not impaired.
- a conductive coating liquid preferably contains a conductive polymer, a binder, a crosslinking agent and a solvent. The solvent is substantially removed by volatilization, evaporation, etc. due to heating in the process of forming the antistatic layer (2c). Therefore, the antistatic layer (2c) preferably contains a conductive polymer, a binder and a crosslinking agent. ..
- Examples of the solvent include organic solvents, water, and mixed solvents thereof.
- Examples of the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic carbonization such as n-hexane and cyclohexane.
- Hydrogen aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; alkylene glycol monoalkyl ethers (eg ethylene glycol monomethyl ether, Glycol ethers such as ethylene glycol monoethyl ether) and dialkylene glycol monoalkyl ether; and the like.
- the solvent is preferably water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
- the content ratio of the conductive polymer in the antistatic layer (2c) is preferably 3% by weight to 80% by weight, more preferably 5% by weight to 60% by weight.
- any appropriate conductive polymer can be adopted as long as the effect of the present invention is not impaired.
- a conductive polymer include a conductive polymer obtained by doping a ⁇ -conjugated conductive polymer with a polyanion.
- the ⁇ -conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
- polyanion examples include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacryl carboxylic acid.
- the conductive polymer may be only one kind or two or more kinds.
- the content ratio of the binder in the antistatic layer (2c) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 90% by weight.
- any appropriate binder can be adopted as long as the effect of the present invention is not impaired.
- the binder may be only one type or two or more types.
- a resin is preferable, and a polyester resin is more preferable.
- the proportion of the polyester resin in the binder is preferably 90% by weight to 100% by weight, more preferably 98% by weight to 100% by weight.
- the polyester resin contains polyester as a main component (preferably more than 50% by weight, more preferably 75% by weight or more, further preferably 90% by weight or more, particularly preferably substantially 100% by weight). It is preferable to include as.
- any appropriate polyester can be adopted as long as the effect of the present invention is not impaired.
- a polyester is preferably a polyvalent carboxylic acid having two or more carboxyl groups in one molecule (for example, a dicarboxylic acid compound) and a derivative thereof (for example, an anhydride or an esterified product of the polyvalent carboxylic acid).
- it preferably has a structure in which two or more compounds (polyhydric alcohol components) are condensed.
- any suitable polyvalent carboxylic acid can be adopted as long as the effect of the present invention is not impaired.
- polycarboxylic acid components include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, ( ⁇ )-malic acid, meso-tartaric acid, Itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipic acid, Tetramethyl adipic acid, methylene adipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluo
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Alimic dicarboxylic acids such as hymic acid and 1,4-cyclohexanedicarboxylic acid and their acid anhydrides; lower alkyl esters of these dicarboxylic acids (eg, esters with monoalcohols having 1 to 3 carbon atoms);
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Alimic dicarboxylic acids such as hymic acid and 1,4-cyclohexanedicarboxylic acid and their acid an
- any appropriate polyhydric alcohol can be adopted as long as the effect of the present invention is not impaired.
- examples of such polyhydric alcohol components include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propane Diols such as diol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, bisphenol A; these diols Alkylene
- the molecular weight of the polyester resin is preferably 5 ⁇ 10 3 to 1.5 ⁇ 10 5 , and more preferably 1 as the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). ⁇ 10 4 to 6 ⁇ 10 4 .
- the glass transition temperature (Tg) of the polyester resin is preferably 0°C to 120°C, more preferably 10°C to 80°C.
- polyester resin for example, commercially available Toyobo Co., Ltd. product name “Bironard” can be used.
- the conductive coating liquid as long as the effect of the present invention is not impaired, as a binder, a resin other than polyester resin (for example, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, silicone resin, polysilazane resin, polyurethane resin, It may further contain at least one resin selected from a fluororesin and a polyolefin resin.
- a resin other than polyester resin for example, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, silicone resin, polysilazane resin, polyurethane resin.
- any appropriate cross-linking agent can be adopted as long as the effect of the present invention is not impaired.
- the cross-linking agent may be only one kind or two or more kinds.
- a crosslinking agent preferably an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent.
- metal salt-based crosslinking agents metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, amine-based crosslinking agents and the like.
- a melamine-based cross-linking agent is preferable.
- the content ratio of the crosslinking agent in the antistatic layer (2c) is preferably 1% by weight to 30% by weight, more preferably 2% by weight to 20% by weight.
- the antistatic layer (2c) may contain any appropriate other component as long as the effect of the present invention is not impaired.
- the pressure-sensitive adhesive layer (2) may be only one layer or may be two or more layers.
- the thickness of the pressure-sensitive adhesive layer (2) is preferably 0.5 ⁇ m to 150 ⁇ m, more preferably 1 ⁇ m to 100 ⁇ m, and further preferably 2 ⁇ m to 80 ⁇ m, from the viewpoint that the effect of the present invention can be further exhibited. Particularly preferred is 3 ⁇ m to 50 ⁇ m, and most preferred is 5 ⁇ m to 30 ⁇ m.
- the adhesive layer (2) can be formed by any appropriate method.
- a pressure-sensitive adhesive composition that forms a pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (2) is applied onto any appropriate base material (for example, the resin film (3)).
- Examples include a method of forming a pressure-sensitive adhesive layer on the substrate by heating and drying according to need, and curing if necessary.
- Examples of such a coating method include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater and a roll brush coater. The method of is mentioned.
- the pressure-sensitive adhesive layer (2) is preferably composed of an acrylic pressure-sensitive adhesive.
- the acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
- the acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a crosslinking agent from the viewpoint that the effects of the present invention can be more exhibited.
- the acrylic polymer can be called a so-called base polymer in the field of acrylic pressure-sensitive adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.
- the content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 60% by weight to 99.9% by weight, and more preferably 65% by weight to 99.9% by weight, in terms of solid content. It is more preferably 70% to 99.9% by weight, particularly preferably 75% to 99.9% by weight, and most preferably 80% to 99.9% by weight.
- acrylic polymer any suitable acrylic polymer can be adopted as long as the effect of the present invention is not impaired.
- the weight average molecular weight of the acrylic polymer is preferably 300,000 to 2,500,000, more preferably 350,000 to 2,000,000, and further preferably 400,000 to 1800,000, from the viewpoint that the effects of the present invention can be further exhibited. And particularly preferably 500,000 to 1,500,000.
- the acrylic polymer is preferably a (meth)acrylic acid alkyl ester in which the alkyl group of the (a component) alkyl ester moiety has 4 to 12 carbon atoms from the viewpoint that the effect of the present invention can be further exhibited, and (b) It is an acrylic polymer formed by polymerization from a composition (B) containing (component) at least one selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid.
- the (a component) and the (b component) may each independently be only one kind or two or more kinds.
- Examples of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include, for example, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate.
- n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable, and n-butyl acrylate and acryl are more preferable, from the viewpoint that the effects of the present invention can be further exhibited.
- It is 2-ethylhexyl acid.
- Examples of at least one component (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples thereof include (meth)acrylic acid ester having an OH group such as hydroxybutyl (meth)acrylate and (meth)acrylic acid. Among these, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, from the viewpoint that the effects of the present invention can be further exhibited.
- the composition (B) may contain a copolymerizable monomer other than the components (a) and (b).
- the copolymerizable monomer may be only one type, or may be two or more types.
- Such copolymerizable monomers include, for example, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride).
- carboxyl group-containing monomers excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide , N-butoxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and other amide group-containing monomers; aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, t-butyl (meth)acrylate Amino group-containing monomers such as aminoethyl; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, Heterocycle-containing vinyl monomers such as (meth)acryloylmorpholine,
- a polyfunctional monomer can also be adopted.
- the polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule.
- the ethylenically unsaturated group any appropriate ethylenically unsaturated group can be adopted as long as the effects of the present invention are not impaired.
- examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group).
- polyfunctional monomer examples include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol.
- examples thereof include (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate and urethane acrylate. Only one kind of such a polyfunctional monomer may be used, or two or more kinds thereof may be used.
- (meth)acrylic acid alkoxyalkyl ester can also be adopted.
- the (meth)acrylic acid alkoxyalkyl ester include 2-(meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, and (meth)acrylic acid 3-methacrylate. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate.
- the (meth)acrylic acid alkoxyalkyl ester may be only one kind, or may be two or more kinds.
- the content of the (meth)acrylic acid alkyl ester (a component) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer that constitutes the acrylic polymer in that the effects of the present invention can be further exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, further preferably 40% by weight to 98% by weight, particularly preferably 50% by weight based on the total amount of the components (100% by weight). % By weight to 95% by weight.
- the content of at least one kind (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is such that the acrylic polymer is added in that the effect of the present invention can be further exhibited. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, further preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 10% by weight.
- composition (B) may contain any appropriate other component as long as the effect of the present invention is not impaired.
- examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent.
- any appropriate content can be adopted as long as the effect of the present invention is not impaired.
- the polymerization initiator a thermal polymerization initiator, a photopolymerization initiator (photoinitiator) or the like can be adopted depending on the type of the polymerization reaction.
- the polymerization initiator may be only one type, or may be two or more types.
- the thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization.
- thermal polymerization initiators include azo-based polymerization initiators, peroxide-based polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox-based polymerization initiators, and the like. ..
- the azo initiators disclosed in JP-A-2002-69411 are particularly preferable.
- Such an azo-based polymerization initiator is preferable in that the decomposed product of the polymerization initiator is unlikely to remain in the acrylic polymer as a portion causing generation of a heat-generated gas (outgas).
- azo-based polymerization initiator examples include 2,2′-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN) and 2,2′-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN). , 2,2′-azobis(2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid and the like.
- the photopolymerization initiator can be preferably used when the acrylic polymer is obtained by active energy ray polymerization.
- the photopolymerization initiator include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime photopolymerization initiators.
- Agents benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole.
- examples include methyl ether.
- examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-(t-butyl). Examples thereof include dichloroacetophenone.
- Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. ..
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalene sulfonyl chloride.
- Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
- Examples of the benzoin-based photopolymerization initiator include benzoin and the like.
- Examples of the benzyl photopolymerization initiator include benzyl and the like.
- benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenylketone, and the like.
- ketal photopolymerization initiator examples include benzyl dimethyl ketal.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and dodecylthioxanthone.
- the acrylic pressure-sensitive adhesive composition may contain a crosslinking agent.
- a crosslinking agent By using the cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited.
- the cross-linking agent may be only one kind or two or more kinds.
- a polyfunctional isocyanate crosslinking agent As the crosslinking agent, a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt.
- examples thereof include a system-based crosslinking agent, a carbodiimide-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, and an amine-based crosslinking agent.
- at least one kind (component (c)) selected from the group consisting of a polyfunctional isocyanate cross-linking agent and an epoxy cross-linking agent is preferable from the viewpoint that the effect of the present invention can be further exhibited.
- polyfunctional isocyanate cross-linking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Aliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.
- lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate
- cyclopentylene diisocyanate cyclohexylene diisocyanate
- Aromatic polyisocyanates of Examples of the polyfunctional isocyanate cross-linking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”), trimethylolpropane/hexamethylene diisocyanate adduct (Japan Polyurethane Industry Co., Ltd. Company name, product name "Coronate HL”), product name "Coronate HX” (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemicals, Inc., product name "Takenate 110N”), etc. Commercial products are also included.
- epoxy cross-linking agent examples include N,N,N′,N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, and 1,3-bis(N,N-diglycidylamino).
- any appropriate content can be adopted as long as the effect of the present invention is not impaired.
- a content is, for example, preferably 0.05 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer, from the viewpoint that the effect of the present invention can be exhibited more. It is more preferably 0.1 part by weight to 18 parts by weight, further preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight.
- the acrylic pressure-sensitive adhesive composition may contain any appropriate other component as long as the effect of the present invention is not impaired.
- other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), Anti-aging agent, inorganic filler, organic filler, metal powder, colorant (pigment or dye, etc.), foil, UV absorber, antioxidant, light stabilizer, chain transfer agent, plasticizer, softener, Examples thereof include surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and catalysts.
- the adhesive layer (2) may contain a conductive component.
- the conductive component ⁇ 1-2-5. The description in the section of conductive component> can be directly applied.
- the pressure-sensitive adhesive composition (preferably an acrylic pressure-sensitive adhesive composition) that is a material of the pressure-sensitive adhesive layer (2) may contain any appropriate other component as long as the effect of the present invention is not impaired.
- examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents.
- Inorganic fillers Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), foil materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
- Resin film (3) >> The thickness of the resin film (3) is preferably from 4 ⁇ m to 450 ⁇ m, more preferably from 8 ⁇ m to 350 ⁇ m, further preferably from 12 ⁇ m to 250 ⁇ m, and particularly preferably from the viewpoint that the effect of the present invention can be further exhibited. It is 16 ⁇ m to 150 ⁇ m, and most preferably 20 ⁇ m to 100 ⁇ m.
- the resin film (3) includes a resin base film (3a).
- the resin substrate film (3a) examples include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBT); polyethylene (PE), polypropylene ( PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other plastic films composed of an olefin resin containing ⁇ -olefin as a monomer component; polyvinyl chloride Plastic film composed of (PVC); plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), all Plastic film composed of amide resin such as aromatic polyamide (aramid); Plastic film composed of polyimide resin; Plastic film composed of polyetheretherketone (PEEK); Polyethylene (PE), polypropylene (PP) ) And other olefinic resin films; poly
- the resin base film (3a) may have only one layer or two or more layers.
- the resin substrate film (3a) may be stretched.
- the resin base film (3a) may be surface-treated.
- the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric bombardment exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.
- a fatty acid amide or polyethyleneimine is added to the resin film (3) for the purpose of forming a wound body that can be easily rewound. It is possible to add a long-chain alkyl-based additive or the like for release treatment, or to provide a coating layer made of any suitable release agent such as silicone-based, long-chain alkyl-based or fluorine-based release agent.
- the resin film (3) may contain any appropriate additive depending on the purpose, as long as the effects of the present invention are not impaired.
- the resin film (3) may have a conductive layer (3b).
- the conductive layer (3b) may be arranged between the pressure-sensitive adhesive layer (2) and the resin base film (3a).
- the conductive layer (3b) may be only one layer or two or more layers.
- the conductive layer (3b) can be provided by forming it on any appropriate base material.
- a substrate is preferably a resin substrate film (3a).
- the conductive layer (3b) is formed by any suitable thin film forming method such as a vacuum deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, a chemical plating method, an electroplating method, or a combination thereof.
- the conductive film is formed on any suitable base material (preferably, the resin base material film (3a)).
- the vacuum deposition method and the sputtering method are preferable from the viewpoints of the formation speed of the conductive film, the formability of a large-area film, the productivity, and the like.
- metal-based materials such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, alloys thereof; indium oxide, A metal oxide-based material composed of tin oxide, titanium oxide, cadmium oxide, a mixture thereof, or the like; another metal compound composed of copper iodide or the like is used.
- any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired.
- a thickness is, for example, preferably 30 ⁇ to 600 ⁇ when formed of a metal-based material, and preferably 80 ⁇ to 5000 ⁇ when formed of a metal oxide-based material.
- the surface resistance value of the conductive layer (3b) is preferably 1.0 ⁇ 10 10 ⁇ / ⁇ or less, more preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less, and further preferably 1.0 ⁇ 10 9. It is 8 ⁇ / ⁇ or less, and particularly preferably 1.0 ⁇ 10 7 ⁇ / ⁇ or less.
- a corona discharge is formed on the surface of the base material (preferably the resin base film (3a)).
- Adhesion between the conductive film and the substrate (preferably the resin substrate film (3a)) after any suitable pretreatment such as treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, and undercoat treatment. Can also be increased.
- the resin film (3) may have an antistatic layer (3c).
- the antistatic layer (3c) may be disposed between the pressure-sensitive adhesive layer (2) and the resin base film (3a) and/or on the opposite side of the resin base film (3a) from the pressure-sensitive adhesive layer (2). ..
- the antistatic layer (3c) may be a single layer or two or more layers.
- any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired.
- Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
- the surface resistance value of the antistatic layer (3c) is preferably 1.0 ⁇ 10 10 ⁇ / ⁇ or less, more preferably 8.0 ⁇ 10 9 ⁇ / ⁇ or less, and further preferably 5.0 ⁇ . It is 10 9 ⁇ / ⁇ or less, and particularly preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less.
- any suitable antistatic layer can be adopted as long as it is a layer capable of exhibiting an antistatic effect, as long as the effect of the present invention is not impaired.
- Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate base material layer.
- it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the resin substrate film (3a). After coating, it is dried if necessary and a curing treatment (heat treatment, ultraviolet treatment, etc.) is performed if necessary.
- Specific coating methods include a roll coating method, a bar coating method and a gravure coating method.
- the conductive coating liquid containing a conductive polymer any appropriate conductive coating liquid can be adopted as long as the effect of the present invention is not impaired.
- a conductive coating liquid preferably contains a conductive polymer, a binder, a crosslinking agent and a solvent.
- the solvent is substantially eliminated by volatilization or evaporation by heating or the like in the process of forming the antistatic layer (3c). Therefore, the antistatic layer (3c) preferably contains a conductive polymer, a binder and a crosslinking agent. ..
- Examples of the solvent include organic solvents, water, and mixed solvents thereof.
- Examples of the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic carbonization such as n-hexane and cyclohexane.
- Hydrogen aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; alkylene glycol monoalkyl ethers (eg ethylene glycol monomethyl ether, Glycol ethers such as ethylene glycol monoethyl ether) and dialkylene glycol monoalkyl ether; and the like.
- the solvent is preferably water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
- the content ratio of the conductive polymer in the antistatic layer (3c) is preferably 3% by weight to 80% by weight, more preferably 5% by weight to 60% by weight.
- any appropriate conductive polymer can be adopted as long as the effect of the present invention is not impaired.
- a conductive polymer include a conductive polymer obtained by doping a ⁇ -conjugated conductive polymer with a polyanion.
- the ⁇ -conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
- polyanion examples include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacryl carboxylic acid.
- the conductive polymer may be only one kind or two or more kinds.
- the content ratio of the binder in the antistatic layer (3c) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 90% by weight.
- any appropriate binder can be adopted as long as the effect of the present invention is not impaired.
- the binder may be only one type or two or more types.
- a resin is preferable, and a polyester resin is more preferable.
- the proportion of the polyester resin in the binder is preferably 90% by weight to 100% by weight, more preferably 98% by weight to 100% by weight.
- the polyester resin contains polyester as a main component (preferably more than 50% by weight, more preferably 75% by weight or more, further preferably 90% by weight or more, particularly preferably substantially 100% by weight). It is preferable to include as.
- any appropriate polyester can be adopted as long as the effect of the present invention is not impaired.
- a polyester is preferably a polyvalent carboxylic acid having two or more carboxyl groups in one molecule (for example, a dicarboxylic acid compound) and a derivative thereof (for example, an anhydride or an esterified product of the polyvalent carboxylic acid).
- it preferably has a structure in which two or more compounds (polyhydric alcohol components) are condensed.
- any suitable polyvalent carboxylic acid can be adopted as long as the effect of the present invention is not impaired.
- polycarboxylic acid components include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, ( ⁇ )-malic acid, meso-tartaric acid, Itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipic acid, Tetramethyl adipic acid, methylene adipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluo
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Alimic dicarboxylic acids such as hymic acid and 1,4-cyclohexanedicarboxylic acid and their acid anhydrides; lower alkyl esters of these dicarboxylic acids (eg, esters with monoalcohols having 1 to 3 carbon atoms);
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Alimic dicarboxylic acids such as hymic acid and 1,4-cyclohexanedicarboxylic acid and their acid an
- any appropriate polyhydric alcohol can be adopted as long as the effect of the present invention is not impaired.
- examples of such polyhydric alcohol components include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propane Diols such as diol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, bisphenol A; these diols Alkylene
- the molecular weight of the polyester resin is preferably 5 ⁇ 10 3 to 1.5 ⁇ 10 5 , and more preferably 1 as the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). ⁇ 10 4 to 6 ⁇ 10 4 .
- the glass transition temperature (Tg) of the polyester resin is preferably 0°C to 120°C, more preferably 10°C to 80°C.
- polyester resin for example, commercially available Toyobo Co., Ltd. product name “Bironard” can be used.
- the conductive coating liquid as long as the effect of the present invention is not impaired, as a binder, a resin other than polyester resin (for example, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, silicone resin, polysilazane resin, polyurethane resin, It may further contain at least one resin selected from a fluororesin and a polyolefin resin.
- a resin other than polyester resin for example, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, silicone resin, polysilazane resin, polyurethane resin.
- any appropriate cross-linking agent can be adopted as long as the effect of the present invention is not impaired.
- the cross-linking agent may be only one kind or two or more kinds.
- a crosslinking agent preferably an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent.
- metal salt-based crosslinking agents metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, amine-based crosslinking agents and the like.
- a melamine-based cross-linking agent is preferable.
- the content ratio of the cross-linking agent in the antistatic layer (3c) is preferably 1% by weight to 30% by weight, more preferably 2% by weight to 20% by weight.
- the antistatic layer (3c) may contain any appropriate other component as long as the effect of the present invention is not impaired.
- the layered product of the present invention can be manufactured by any appropriate method as long as the effects of the present invention are not impaired.
- the laminate of the present invention comprises a resin film (1), an adhesive layer (1), a resin film (2), an adhesive layer (2) and a resin film (3). ) are provided in this order, and a case of a laminated body composed of these components will be described.
- One embodiment of the method for producing a laminate of the present invention has a resin film (1), a pressure-sensitive adhesive layer (1), and a resin film (2) in this order, and a laminate (I ), a pressure-sensitive adhesive layer (2) and a resin film (3) in this order to produce a laminate (II) composed of these components, and then, the resin film of the laminate (I).
- the surface of (2) and the surface of the pressure-sensitive adhesive layer (2) of the laminate (II) are attached.
- the laminate (I) is, for example, a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition, urethane-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive composition, silicone, which forms a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (1). At least one selected from the group consisting of the adhesive system) is applied on the resin film (2), heated and dried if necessary, and cured as necessary to obtain the resin film (2). The pressure-sensitive adhesive layer (1) is formed thereon, and then the resin film (1) (release layer (1b) is provided on the surface of the pressure-sensitive adhesive layer (1) opposite to the resin film (2). If that is the case, paste that side).
- a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition, urethane-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive composition, silicone, which forms a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (1). At least one selected from the group consisting of the adhesive system) is applied on the resin film (2), heated and dried if necessary, and cured as
- a plurality of portions of the resin film are cut from the resin film (2) side with a CO 2 laser or the like so that the width of the portion to be cut has a predetermined width and the width of the portion that is not cut has a predetermined width.
- Half-cut up to the surface of (1) that is, the resin film (1) is not cut, and the half-cut portion is removed by any appropriate method.
- the laminate (II) is required, for example, by applying a pressure-sensitive adhesive composition (preferably an acrylic pressure-sensitive adhesive composition) forming a pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (2) onto the resin film (3).
- the adhesive layer (2) is formed on the resin film (3) by heating and drying according to the above, and curing as necessary.
- any suitable separator for example, the resin film (1) may be used. A similar film may be attached.
- the weight average molecular weight was measured by the gel permeation chromatograph (GPC) method. Specifically, the product name "HLC-8120GPC” (manufactured by Tosoh Corporation) was used as a GPC measuring device, and the measurement was performed under the following conditions, and the standard polystyrene conversion value was calculated.
- GPC gel permeation chromatograph
- a laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C.
- a universal tensile tester manufactured by Minebea Co., Ltd., product name: TCM-1kNB was used at a peeling angle of 180 degrees and a peeling speed of 30 mm/min.
- the adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
- a laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C.
- a universal tensile tester manufactured by Minebea Co., Ltd., product name: TCM-1kNB was used at a peeling angle of 180 degrees and a peeling speed of 300 mm/min.
- the adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
- a laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH.
- the resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C.
- a universal tensile tester manufactured by Minebea Co., Ltd., product name: TCM-1kNB was used at a peeling angle of 180 degrees and a peeling speed of 2400 mm/min.
- the adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
- the resin film (1) was peeled from the produced evaluation sample, and the glass plate (Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) was used. It was attached by reciprocating once with a 0 kg roller. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester was used to perform peeling at a peeling angle of 180° and a peeling speed of 300 mm/min, and the adhesive strength (1) was measured.
- a laminate (II) with a separator composed of separator/adhesive layer (2)/resin film (3) was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample.
- an adherend prepared by peeling the resin film (1) from the laminate (I) and adhered to a glass plate as described in the section ⁇ Measurement of adhesive strength (1)> is prepared at a temperature of 23° C.
- the separator was peeled from the evaluation sample and attached to the adherend by reciprocating a 2.0 kg roller once.
- a universal tensile tester was used to peel at a peeling angle of 180° and a peeling speed of 300 mm/min, and the adhesive strength (2) was measured.
- the laminate (I) is cut into a width of 50 mm and a length of 300 mm, and is cut from the resin film (2) side by a CO 2 laser at 5 positions so as to be evenly spaced at 1 mm or at 3 mm equally spaced.
- Half-cut to the surface of the resin film (1) that is, the resin film (1) is not cut, and half-cut at 5 positions so that The removed part was removed by hand.
- the sample was manufactured so that the distance between the half-cut/removed portions was 50 mm.
- the surface of the pressure-sensitive adhesive layer (2) of the laminate (II) cut into a width of 60 mm and a length of 400 mm was attached to the surface of the resin film (2) of the laminate (I) to obtain a measurement sample.
- the measurement sample was wound around a roll having a diameter of 6 inches so that the resin film (1) was on the outer side, and the laminated portion of the plurality of divided adhesive layers (1) and the resin film (2) formed an adhesive layer ( The maximum amount floating from 2) was measured with a magnifying glass, and the average value of the measurements at any 5 points was taken as the floating amount.
- a (meth)acrylic polymer (1) solution (40% by weight) having a weight average molecular weight of 700,000.
- TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Inc.
- a cross-linking agent was added as a solid content to 100 parts by weight of the solid content of the (meth)acrylic polymer (1) solution.
- 6 parts by weight in terms of conversion was added, diluted with ethyl acetate so that the total solid content was 20% by weight, and stirred with a disper to obtain a pressure-sensitive adhesive composition (1) containing an acrylic resin.
- a (meth)acrylic polymer (2) solution (40) having a weight average molecular weight of 550,000. Wt%) was prepared.
- Coronate HX manufactured by Tosoh Corporation
- a cross-linking agent was added as solid content to 4 parts by weight per 100 parts by weight of the solid content of the (meth)acrylic polymer (2) solution.
- a silicone-treated surface of a substrate made of a 75 ⁇ m-thick polyester resin “Lumirror S10” (thickness: 75 ⁇ m, manufactured by Toray Industries, Inc.) having a silicone treatment on one surface is bonded to the surface of the adhesive layer to form a resin.
- a laminate (A) having a structure of film (with silicone-treated surface)/adhesive layer/resin film was obtained.
- Example 1 The separator was peeled off from the laminate (B1) obtained in Production Example 8, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (1). The results are shown in Table 1.
- Example 2 The separator was peeled off from the laminate (B2) obtained in Production Example 9, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (2). The results are shown in Table 1.
- Example 3 The separator was peeled off from the laminate (B3) obtained in Production Example 10, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The side was attached to obtain a laminate (3). The results are shown in Table 1.
- Example 4 The separator was peeled off from the laminate (B4) obtained in Production Example 11, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (4). The results are shown in Table 1.
- Example 5 The separator was peeled off from the laminate (B5) obtained in Production Example 12, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (5). The results are shown in Table 1.
- Example 6 The separator was peeled off from the laminate (B6) obtained in Production Example 13, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (6). The results are shown in Table 1.
- the laminated body of the present invention can be suitably used in the manufacturing process of optical members and electronic members.
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Abstract
Provided is a layered body having a surface protective film or a reinforcing film layered on a carrier sheet, wherein the base material surface of the surface protective film or the reinforcing film does not lift readily from the adhesive layer of the carrier sheet, when being adhered continuously onto a member via a roll-to-roll process. This layered body is a layered body of five or more layers comprising a resin film (1), an adhesive layer (1), a resin film (2), an adhesive layer (2), and a resin film (3), in this order, wherein the adhesive layer (1) and the resin film (2) have been layered directly on one another, and the resin film (2) and the adhesive layer (2) have been layered directly on one another. In a direction substantially orthogonal to the length direction, the layered part between the adhesive layer (1) and the resin film (2) is segmented into a plurality by 0.5 mm to 10 mm-wide through-holes. The length of the plurality of layered parts from the adhesive layers (1) and the resin film (2) segmented by the through-holes is 1 mm to 2,000 mm in the length direction. When the layered body is wound around a six-inch diameter roll in such a manner that the resin film (1) is on the outside, the maximum amount by which the plurality of layered parts from the adhesive layer (1) and the resin film (2) segmented by the through-holes are lifted from the adhesive layer (2) is 0.2 mm or less, when the width of the through-holes is 5 mm and the length of the plurality of layered parts from the adhesive layer (1) and the resin film (2) segmented by the through-holes is 50 mm in the length direction.
Description
本発明は積層体に関する。好ましくは、本発明は、光学部材や電子部材の製造工程において好適に用い得る積層体に関する。
The present invention relates to a laminated body. Preferably, the present invention relates to a laminate that can be suitably used in the manufacturing process of optical members and electronic members.
光学部材や電子部材の製造工程においては、加工、組立、検査、輸送などの際の部材の表面の傷付き防止のために表面保護フィルム(SPV)が貼り付けられたり、薄くて脆弱な部材の補強のために補強用フィルム(RF)が貼り付けられたりすることがある(例えば、特許文献1など)。
In the manufacturing process of optical members and electronic members, a surface protective film (SPV) is attached to prevent scratches on the surface of members during processing, assembly, inspection, transportation, etc. A reinforcing film (RF) may be attached for reinforcement (for example, Patent Document 1).
上記のような貼り付け工程における効率を高めるためには、表面保護フィルムや補強用フィルムを枚葉で一枚ずつ貼り付ける工程よりも、ロール・ツー・ロール(Roll-to-Roll)方式による連続工程が有効である。
In order to improve the efficiency in the above-mentioned pasting process, a continuous roll-to-roll method is used rather than the step of pasting the surface protection film and the reinforcing film one by one. The process is effective.
表面保護フィルムや補強用フィルムの基材面を、基材と軽剥離粘着剤層を有するキャリアシートの該軽剥離粘着剤層面に貼り付けた積層体とすれば、ロール・ツー・ロールでの、部材への該表面保護フィルムや該補強用フィルムの連続的な貼り付けが可能となる。この場合、貼り付け後にキャリアシートを剥離することになる。
If the substrate surface of the surface protective film or the reinforcing film is a laminate pasted on the light release adhesive layer surface of the carrier sheet having a base material and a light release adhesive layer, a roll-to-roll method, The surface protection film and the reinforcing film can be continuously attached to the member. In this case, the carrier sheet is peeled off after the attachment.
ところが、上記のような積層体を用いて部材への貼り付け工程を連続的に行う際に、キャリアシートの軽剥離粘着剤層から表面保護フィルムや補強用フィルムの基材面(特に、端部)が浮く現象が見られることがある。このような現象は、特に、上記のような積層体を繰り出しする際や、ロールを通過する際や、表面保護フィルムや補強用フィルムのセパレータを剥離する際に、よく見られる。
However, when the step of attaching to a member using the above-mentioned laminate is continuously performed, the light release adhesive layer of the carrier sheet is used to remove the surface protection film or the base material surface of the reinforcing film (particularly the end portion). ) May appear to float. Such a phenomenon is often seen particularly when the above-mentioned laminated body is unrolled, when it passes through a roll, or when the surface protective film or the separator of the reinforcing film is peeled off.
上記のような現象が起こると、部材への表面保護フィルムや補強用フィルムの貼り付け位置合わせの精度が低下してズレが生じるという問題が生じる。また、上記のような現象が起こると、浮きの箇所をきっかけとして、部材に貼り付ける前に、キャリアシートの軽剥離粘着剤層から表面保護フィルムや補強用フィルムが剥がれてしまうという問題が生じる。
If the above phenomena occur, the accuracy of the attachment position alignment of the surface protection film and the reinforcing film on the member will decrease, causing a problem of deviation. In addition, when the phenomenon as described above occurs, there arises a problem that the surface protection film and the reinforcing film are peeled off from the light release adhesive layer of the carrier sheet before being attached to the member, triggered by the floating portion.
本発明の課題は、表面保護フィルムや補強用フィルムをキャリアシートに積層させた積層体であって、ロール・ツー・ロールで部材に連続的に貼り付ける際に、キャリアシートが有する粘着剤層から表面保護フィルムや補強用フィルムの基材面が浮き難い積層体を提供することにある。
An object of the present invention is a laminate in which a surface protective film and a reinforcing film are laminated on a carrier sheet, and when continuously attached to a member by roll-to-roll, from a pressure-sensitive adhesive layer included in the carrier sheet. An object of the present invention is to provide a laminate in which the base material surface of a surface protection film or a reinforcing film is hard to float.
本発明の積層体は、
樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有する、5層以上の積層体であって、
該粘着剤層(1)と該樹脂フィルム(2)が直接に積層されてなり、
該樹脂フィルム(2)と該粘着剤層(2)が直接に積層されてなり、
該粘着剤層(1)と該樹脂フィルム(2)の積層部分は、長手方向と実質的に直交する方向に、幅0.5mm~10mmの貫通孔によって複数に区分けされてなり、
該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分の長手方向の長さが、1mm~2000mmであり、
直径6インチのロールに対して該樹脂フィルム(1)が外側になるように巻き付けたとき、該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分が該粘着剤層(2)から浮いている最大量が、該貫通孔の幅が5mm、該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分の長手方向の長さが50mmのときに、0.2mm以下である。 The laminate of the present invention is
A laminate having five or more layers, which has a resin film (1), a pressure-sensitive adhesive layer (1), a resin film (2), a pressure-sensitive adhesive layer (2), and a resin film (3) in this order,
The pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated,
The resin film (2) and the adhesive layer (2) are directly laminated,
The laminated portion of the adhesive layer (1) and the resin film (2) is divided into a plurality of through holes having a width of 0.5 mm to 10 mm in a direction substantially orthogonal to the longitudinal direction,
The length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is 1 mm to 2000 mm,
When the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, a laminated portion of a plurality of the adhesive layers (1) and the resin film (2) divided by the through holes Is the maximum amount of floating from the pressure-sensitive adhesive layer (2), the width of the through-hole is 5 mm, the plurality of pressure-sensitive adhesive layer (1) and the resin film (2) laminated portion divided by the through-hole When the length in the longitudinal direction is 50 mm, it is 0.2 mm or less.
樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有する、5層以上の積層体であって、
該粘着剤層(1)と該樹脂フィルム(2)が直接に積層されてなり、
該樹脂フィルム(2)と該粘着剤層(2)が直接に積層されてなり、
該粘着剤層(1)と該樹脂フィルム(2)の積層部分は、長手方向と実質的に直交する方向に、幅0.5mm~10mmの貫通孔によって複数に区分けされてなり、
該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分の長手方向の長さが、1mm~2000mmであり、
直径6インチのロールに対して該樹脂フィルム(1)が外側になるように巻き付けたとき、該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分が該粘着剤層(2)から浮いている最大量が、該貫通孔の幅が5mm、該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分の長手方向の長さが50mmのときに、0.2mm以下である。 The laminate of the present invention is
A laminate having five or more layers, which has a resin film (1), a pressure-sensitive adhesive layer (1), a resin film (2), a pressure-sensitive adhesive layer (2), and a resin film (3) in this order,
The pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated,
The resin film (2) and the adhesive layer (2) are directly laminated,
The laminated portion of the adhesive layer (1) and the resin film (2) is divided into a plurality of through holes having a width of 0.5 mm to 10 mm in a direction substantially orthogonal to the longitudinal direction,
The length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is 1 mm to 2000 mm,
When the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, a laminated portion of a plurality of the adhesive layers (1) and the resin film (2) divided by the through holes Is the maximum amount of floating from the pressure-sensitive adhesive layer (2), the width of the through-hole is 5 mm, the plurality of pressure-sensitive adhesive layer (1) and the resin film (2) laminated portion divided by the through-hole When the length in the longitudinal direction is 50 mm, it is 0.2 mm or less.
一つの実施形態においては、上記樹脂フィルム(2)の平面方向側の総面積が、上記粘着剤層(2)の平面方向側の総面積よりも小さい。
In one embodiment, the total area of the resin film (2) in the plane direction is smaller than the total area of the adhesive layer (2) in the plane direction.
本発明によれば、表面保護フィルムや補強用フィルムをキャリアシートに積層させた積層体であって、ロール・ツー・ロールで部材に連続的に貼り付ける際に、キャリアシートが有する粘着剤層から表面保護フィルムや補強用フィルムの基材面が浮き難い積層体を提供することができる。
According to the present invention, a laminate in which a surface protection film or a reinforcing film is laminated on a carrier sheet, and when continuously attached to a member by roll-to-roll, from a pressure-sensitive adhesive layer included in the carrier sheet. It is possible to provide a laminate in which the base material surface of the surface protection film or the reinforcing film does not easily float.
本明細書中で「重量」との表現がある場合は、重さを示すSI系単位として慣用されている「質量」と読み替えてもよい。
When the expression "weight" is used in this specification, it may be read as "mass" which is commonly used as an SI system unit indicating weight.
本明細書中で「(メタ)アクリル」との表現がある場合は、「アクリルおよび/またはメタクリル」を意味し、「(メタ)アクリレート」との表現がある場合は、「アクリレートおよび/またはメタクリレート」を意味し、「(メタ)アリル」との表現がある場合は、「アリルおよび/またはメタリル」を意味し、「(メタ)アクロレイン」との表現がある場合は、「アクロレインおよび/またはメタクロレイン」を意味する。
In the present specification, the expression "(meth)acrylic" means "acrylic and/or methacrylic", and the expression "(meth)acrylate" means "acrylate and/or methacrylate". And the expression "(meth)allyl" means "allyl and/or methallyl", and the expression "(meth)acrolein" means "acrolein and/or methacrolein". Means "rain".
≪≪1.積層体≫≫
本発明の積層体は、樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有する、5層以上の積層体であって、該粘着剤層(1)と該樹脂フィルム(2)が直接に積層されてなり、該樹脂フィルム(2)と該粘着剤層(2)が直接に積層されてなる。 <<<< 1. Laminate >>
The laminate of the present invention is a laminate of 5 or more layers having the resin film (1), the pressure-sensitive adhesive layer (1), the resin film (2), the pressure-sensitive adhesive layer (2), and the resin film (3) in this order. Therefore, the pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated, and the resin film (2) and the pressure-sensitive adhesive layer (2) are directly laminated.
本発明の積層体は、樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有する、5層以上の積層体であって、該粘着剤層(1)と該樹脂フィルム(2)が直接に積層されてなり、該樹脂フィルム(2)と該粘着剤層(2)が直接に積層されてなる。 <<<< 1. Laminate >>
The laminate of the present invention is a laminate of 5 or more layers having the resin film (1), the pressure-sensitive adhesive layer (1), the resin film (2), the pressure-sensitive adhesive layer (2), and the resin film (3) in this order. Therefore, the pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated, and the resin film (2) and the pressure-sensitive adhesive layer (2) are directly laminated.
本発明の積層体は、樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有し、該粘着剤層(1)と該樹脂フィルム(2)が直接に積層されてなり、該樹脂フィルム(2)と該粘着剤層(2)が直接に積層されてなる限り、本発明の効果を損なわない範囲で、任意の適切な他の層を有していてもよい。
The laminate of the present invention has a resin film (1), a pressure-sensitive adhesive layer (1), a resin film (2), a pressure-sensitive adhesive layer (2) and a resin film (3) in this order, and the pressure-sensitive adhesive layer (1 ) And the resin film (2) are directly laminated, and the resin film (2) and the pressure-sensitive adhesive layer (2) are directly laminated, as long as the effects of the present invention are not impaired. It may have other suitable layers.
本発明の積層体の積層数は、上記の他の層の数により、好ましくは5層~10層であり、より好ましくは5層~8層であり、さらに好ましくは5層~7層であり、特に好ましくは5層~6層であり、最も好ましくは5層である。
The number of layers of the laminate of the present invention is preferably 5 to 10 layers, more preferably 5 to 8 layers, and further preferably 5 to 7 layers, depending on the number of other layers described above. , Particularly preferably 5 to 6 layers, most preferably 5 layers.
本発明の積層体は、粘着剤層(1)と樹脂フィルム(2)の積層部分が、長手方向と実質的に直交する方向に、幅0.5mm~10mmの貫通孔によって複数に区分けされてなる。このような貫通孔の幅は、好ましくは0.6mm~8mmであり、より好ましくは0.7mm~6mmであり、さらに好ましくは0.8mm~5mmであり、特に好ましくは0.9mm~4mmであり、最も好ましくは1mm~3mmである。このような貫通孔は、好ましくは、実質的に直方体形状である。
In the laminate of the present invention, the laminated portion of the pressure-sensitive adhesive layer (1) and the resin film (2) is divided into a plurality of through holes having a width of 0.5 mm to 10 mm in a direction substantially orthogonal to the longitudinal direction. Become. The width of such a through hole is preferably 0.6 mm to 8 mm, more preferably 0.7 mm to 6 mm, further preferably 0.8 mm to 5 mm, and particularly preferably 0.9 mm to 4 mm. Yes, and most preferably 1 mm to 3 mm. Such a through hole is preferably substantially rectangular parallelepiped-shaped.
本発明の積層体は、粘着剤層(1)と樹脂フィルム(2)の積層部分が、長手方向と実質的に直交する方向に所定の長さの貫通孔によって複数に区分けされてなることにより、ロール・ツー・ロールで部材に連続的に貼り付ける際に、キャリアシートが有する粘着剤層から表面保護フィルムや補強用フィルムの基材面が浮き難い積層体となり得る。
In the laminate of the present invention, the laminated portion of the pressure-sensitive adhesive layer (1) and the resin film (2) is divided into a plurality of through holes each having a predetermined length in a direction substantially orthogonal to the longitudinal direction. When a roll-to-roll member is continuously attached to a member, the surface of the surface protective film or the reinforcing film of the carrier sheet may not easily float from the pressure-sensitive adhesive layer of the carrier sheet.
本発明の積層体においては、上記の貫通孔によって、粘着剤層(1)と樹脂フィルム(2)の積層部分が複数に区分けされてなる。貫通孔によって区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分の長手方向の長さは1mm~2000mmであり、好ましくは1mm~1000mmであり、より好ましくは1mm~500mmであり、さらに好ましくは2mm~500mmであり、特に好ましくは2mm~400mmであり、最も好ましくは2mm~300mmである。貫通孔によって区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分の長手方向の長さが所定範囲にあることにより、本発明の積層体は、ロール・ツー・ロールで部材に連続的に貼り付ける際に、キャリアシートが有する粘着剤層から表面保護フィルムや補強用フィルムの基材面が浮き難い積層体となり得る。
In the laminated body of the present invention, the laminated portion of the pressure-sensitive adhesive layer (1) and the resin film (2) is divided into a plurality of parts by the above-mentioned through holes. The length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is 1 mm to 2000 mm, preferably 1 mm to 1000 mm, more preferably 1 mm to 500 mm. And more preferably 2 mm to 500 mm, particularly preferably 2 mm to 400 mm, and most preferably 2 mm to 300 mm. Since the length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is within a predetermined range, the laminate of the present invention is roll-to-roll. When continuously attached to a member, the surface of the base material of the surface protection film or the reinforcing film may be hardly floated from the pressure-sensitive adhesive layer of the carrier sheet to form a laminate.
本発明の積層体は、好ましくは、樹脂フィルム(2)の平面方向側の総面積が、粘着剤層(2)の平面方向側の総面積よりも小さい。粘着剤層(2)の平面方向側の総面積に対する樹脂フィルム(2)の平面方向側の総面積の割合は、好ましくは20%~99.9%であり、より好ましくは50%~99%であり、さらに好ましくは60%~98%であり、特に好ましくは70%~97%であり、最も好ましくは80%~96%である。樹脂フィルム(2)の平面方向側の総面積が、粘着剤層(2)の平面方向側の総面積よりも小さいことにより、本発明の積層体は、ロール・ツー・ロールで部材に連続的に貼り付ける際に、キャリアシートが有する粘着剤層から表面保護フィルムや補強用フィルムの基材面がより浮き難い積層体となり得る。
In the laminate of the present invention, the total area of the resin film (2) in the plane direction is preferably smaller than the total area of the adhesive layer (2) in the plane direction. The ratio of the total area of the resin film (2) in the plane direction to the total area of the adhesive layer (2) in the plane direction is preferably 20% to 99.9%, more preferably 50% to 99%. %, more preferably 60% to 98%, particularly preferably 70% to 97%, and most preferably 80% to 96%. Since the total area of the resin film (2) in the plane direction is smaller than the total area of the pressure-sensitive adhesive layer (2) in the plane direction, the laminate of the present invention is roll-to-roll continuous to the member. When it is attached to, the base material surface of the surface protection film or the reinforcing film may become a laminate more difficult to float from the pressure-sensitive adhesive layer of the carrier sheet.
本発明の積層体は、直径6インチのロールに対して樹脂フィルム(1)が外側になるように巻き付け、区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分が粘着剤層(2)から浮いている最大量が、貫通孔の幅が5mm、貫通孔によって区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分の長手方向の長さが50mmのときに、0.5mm以下であり、好ましくは0.3mm以下であり、より好ましくは0.2mm以下であり、さらに好ましくは0.1mm以下であり、特に好ましくは0.08mm以下であり、最も好ましくは0mmである。上記浮きの測定方法については後述する。
In the laminate of the present invention, the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, and the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) adheres to each other. The maximum amount floating from the agent layer (2) is that the width of the through hole is 5 mm, and the length in the longitudinal direction of the laminated portion of the plurality of adhesive layers (1) and the resin film (2) divided by the through hole is When it is 50 mm, it is 0.5 mm or less, preferably 0.3 mm or less, more preferably 0.2 mm or less, still more preferably 0.1 mm or less, and particularly preferably 0.08 mm or less. , And most preferably 0 mm. The method for measuring the above-mentioned floating will be described later.
本発明の積層体は、直径6インチのロールに対して樹脂フィルム(1)が外側になるように巻き付け、区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分が粘着剤層(2)から浮いている最大量が、貫通孔の幅が3mm、貫通孔によって区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分の長手方向の長さが50mmのときに、好ましくは0.7mm以下であり、より好ましくは0.5mm以下であり、さらに好ましくは0.3mm以下であり、特に好ましくは0.2mm以下であり、最も好ましくは0mmである。上記浮きの測定方法については後述する。
In the laminate of the present invention, the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, and the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) adheres to each other. The maximum amount floating from the agent layer (2) is that the width of the through hole is 3 mm, and the length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through hole is When it is 50 mm, it is preferably 0.7 mm or less, more preferably 0.5 mm or less, further preferably 0.3 mm or less, particularly preferably 0.2 mm or less, and most preferably 0 mm. .. The method for measuring the above-mentioned floating will be described later.
本発明の積層体は、直径6インチのロールに対して樹脂フィルム(1)が外側になるように巻き付け、区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分が粘着剤層(2)から浮いている最大量が、貫通孔の幅が1mm、貫通孔によって区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分の長手方向の長さが50mmのときに、好ましくは1.2mm以下であり、より好ましくは1.0mm以下であり、さらに好ましくは0.5mm以下であり、特に好ましくは0.2mm以下であり、最も好ましくは0.1mm以下である。上記浮きの測定方法については後述する。
In the laminate of the present invention, the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, and the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) adheres to each other. The maximum amount floating from the agent layer (2) is that the width of the through hole is 1 mm, and the length in the longitudinal direction of the laminated portion of the plurality of adhesive layer (1) and the resin film (2) divided by the through hole is When it is 50 mm, it is preferably 1.2 mm or less, more preferably 1.0 mm or less, further preferably 0.5 mm or less, particularly preferably 0.2 mm or less, and most preferably 0.1 mm. It is as follows. The method for measuring the above-mentioned floating will be described later.
本発明の積層体の一つの実施形態は、図1に示すように、本発明の積層体100が、樹脂フィルム(1)10、粘着剤層(1)20、樹脂フィルム(2)30、粘着剤層(2)40、樹脂フィルム(3)50がこの順に直接に積層されてなる。図1において、粘着剤層(1)20と樹脂フィルム(2)30の積層部分は、長手方向と実質的に直交する方向に所定の長さの貫通孔60によって複数に区分けされ、区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分を構成する。
In one embodiment of the laminate of the present invention, as shown in FIG. 1, the laminate 100 of the present invention comprises a resin film (1) 10, an adhesive layer (1) 20, a resin film (2) 30, and an adhesive. The agent layer (2) 40 and the resin film (3) 50 are directly laminated in this order. In FIG. 1, the laminated portion of the pressure-sensitive adhesive layer (1) 20 and the resin film (2) 30 is divided into a plurality of portions by a through hole 60 having a predetermined length in a direction substantially orthogonal to the longitudinal direction, and is divided. It constitutes a laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2).
図1に示す本発明の積層体の一つの実施形態において、樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)の積層体部分は、表面保護フィルムや補強用フィルムとなり得る。この場合、樹脂フィルム(1)はセパレータとなり得る。
In one embodiment of the laminate of the present invention shown in FIG. 1, the laminate portion of the resin film (1), the adhesive layer (1) and the resin film (2) can be a surface protection film or a reinforcing film. In this case, the resin film (1) can serve as a separator.
図1に示す本発明の積層体の一つの実施形態において、粘着剤層(2)、樹脂フィルム(3)の積層体部分は、キャリアシートとなり得る。キャリアシートは表面保護フィルムとしても扱われ得る。
In one embodiment of the laminate of the present invention shown in FIG. 1, the laminate portion of the pressure-sensitive adhesive layer (2) and the resin film (3) can be a carrier sheet. The carrier sheet can also be treated as a surface protective film.
本発明の積層体は、温度23℃、湿度50%RHの雰囲気下における、剥離角度180度、剥離速度30mm/分で該粘着剤層(2)を該樹脂フィルム(2)から剥離するときの粘着力が、好ましくは1gf/25mm以上であり、より好ましくは1gf/25mm~10gf/25mmであり、さらに好ましくは1.2gf/25mm~8gf/25mmであり、さらに好ましくは1.4gf/25mm~7gf/25mmであり、特に好ましくは1.6gf/25mm~5gf/25mmであり、最も好ましくは1.8gf/25mm~3gf/25mmである。上記粘着力が上記範囲内にあれば、本発明の積層体は、ロール・ツー・ロールで部材に連続的に貼り付ける際に、粘着剤層(2)から樹脂フィルム(2)の浮きをより抑制し得る。上記粘着力の測定方法については後述する。
The laminate of the present invention is obtained when the pressure-sensitive adhesive layer (2) is peeled from the resin film (2) at a peeling angle of 180° and a peeling speed of 30 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The adhesive strength is preferably 1 gf/25 mm or more, more preferably 1 gf/25 mm to 10 gf/25 mm, further preferably 1.2 gf/25 mm to 8 gf/25 mm, and further preferably 1.4 gf/25 mm- It is 7 gf/25 mm, particularly preferably 1.6 gf/25 mm to 5 gf/25 mm, and most preferably 1.8 gf/25 mm to 3 gf/25 mm. When the above-mentioned adhesive force is within the above range, the laminate of the present invention makes it possible to prevent the resin film (2) from being lifted from the adhesive layer (2) when continuously attached to a member by roll-to-roll. Can be suppressed. The method for measuring the adhesive strength will be described later.
本発明の積層体は、温度23℃、湿度50%RHの雰囲気下における、剥離角度180度、剥離速度300mm/分で該粘着剤層(2)を該樹脂フィルム(2)から剥離するときの粘着力が、好ましくは2gf/25mm以上であり、より好ましくは2gf/25mm~20gf/25mmであり、さらに好ましくは2.5gf/25mm~10gf/25mmであり、さらに好ましくは3gf/25mm~9gf/25mmであり、特に好ましくは3gf/25mm~8gf/25mmであり、最も好ましくは3.5gf/25mm~7gf/25mmである。上記粘着力が上記範囲内にあれば、本発明の積層体は、ロール・ツー・ロールで部材に連続的に貼り付ける際に、粘着剤層(2)から樹脂フィルム(2)の浮きをより抑制し得る。上記粘着力の測定方法については後述する。
The laminate of the present invention is obtained when the pressure-sensitive adhesive layer (2) is peeled from the resin film (2) at a peeling angle of 180° and a peeling speed of 300 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The adhesive force is preferably 2 gf/25 mm or more, more preferably 2 gf/25 mm to 20 gf/25 mm, further preferably 2.5 gf/25 mm to 10 gf/25 mm, further preferably 3 gf/25 mm to 9 gf/ It is 25 mm, particularly preferably 3 gf/25 mm to 8 gf/25 mm, and most preferably 3.5 gf/25 mm to 7 gf/25 mm. When the above-mentioned adhesive force is within the above range, the laminate of the present invention makes it possible to prevent the resin film (2) from being lifted from the adhesive layer (2) when continuously attached to a member by roll-to-roll. Can be suppressed. The method for measuring the adhesive strength will be described later.
本発明の積層体は、温度23℃、湿度50%RHの雰囲気下における、剥離角度180度、剥離速度2400mm/分で該粘着剤層(2)を該樹脂フィルム(2)から剥離するときの粘着力が、好ましくは5gf/25mm以上であり、より好ましくは5gf/25mm~100gf/25mmであり、さらに好ましくは7gf/25mm~60gf/25mmであり、さらに好ましくは8gf/25mm~40gf/25mmであり、特に好ましくは9gf/25mm~30gf/25mmであり、最も好ましくは10gf/25mm~25gf/25mmである。上記粘着力が上記範囲内にあれば、本発明の積層体は、ロール・ツー・ロールで部材に連続的に貼り付ける際に、粘着剤層(2)から樹脂フィルム(2)の浮きをより抑制し得る。上記粘着力の測定方法については後述する。
The laminate of the present invention is obtained when the pressure-sensitive adhesive layer (2) is peeled from the resin film (2) at a peeling angle of 180° and a peeling speed of 2400 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The adhesive strength is preferably 5 gf/25 mm or more, more preferably 5 gf/25 mm to 100 gf/25 mm, further preferably 7 gf/25 mm to 60 gf/25 mm, further preferably 8 gf/25 mm to 40 gf/25 mm. Yes, particularly preferably 9 gf/25 mm to 30 gf/25 mm, and most preferably 10 gf/25 mm to 25 gf/25 mm. When the above-mentioned adhesive force is within the above range, the laminate of the present invention makes it possible to prevent the resin film (2) from being lifted from the adhesive layer (2) when continuously attached to a member by roll-to-roll. Can be suppressed. The method for measuring the adhesive strength will be described later.
本発明の積層体は、粘着剤層(1)の、温度23℃、湿度50%RHの雰囲気下における、剥離角度180度、剥離速度300mm/分で該粘着剤層(1)をガラスから剥離するときの粘着力(1)と、粘着剤層(2)の温度23℃、湿度50%RHの雰囲気下における、剥離角度180度、剥離速度300mm/分で該粘着剤層(2)をガラスから剥離するときの粘着力(2)とが、好ましくは、粘着力(1)>粘着力(2)である。粘着力(1)>粘着力(2)であることにより、本発明の効果がより発現し得る。上記粘着力の測定方法については後述する。
The laminate of the present invention peels the pressure-sensitive adhesive layer (1) from glass at a peeling angle of 180 degrees and a peeling speed of 300 mm/min in an atmosphere of a temperature of 23° C. and a humidity of 50% RH. Adhesive strength (1) when the temperature of the adhesive layer (2) is 23° C. and humidity is 50% RH, and the peeling angle is 180 degrees and the peeling speed is 300 mm/min. The adhesive force (2) when peeled from the adhesive layer is preferably adhesive force (1)>adhesive force (2). When the adhesive strength (1)>the adhesive strength (2), the effect of the present invention can be more exhibited. The method for measuring the adhesive strength will be described later.
本発明の積層体は、全光線透過率が、好ましくは60%以上であり、より好ましくは70%~100%であり、さらに好ましくは80%~100%であり、特に好ましくは83%~100%であり、最も好ましくは85%~100%である。上記全光線透過率の測定方法については後述する。
The laminate of the present invention has a total light transmittance of preferably 60% or more, more preferably 70% to 100%, further preferably 80% to 100%, particularly preferably 83% to 100%. %, and most preferably 85% to 100%. The method for measuring the total light transmittance will be described later.
本発明の積層体は、ヘイズが、好ましくは15%以下であり、より好ましくは0%~10%であり、さらに好ましくは0%~8%であり、特に好ましくは0%~7%であり、最も好ましくは0%~6%である。上記ヘイズの測定方法については後述する。
The haze of the laminate of the present invention is preferably 15% or less, more preferably 0% to 10%, further preferably 0% to 8%, and particularly preferably 0% to 7%. , And most preferably 0% to 6%. The method for measuring the haze will be described later.
≪1-1.樹脂フィルム(1)≫
樹脂フィルム(1)の厚みとしては、本発明の効果をより発現させ得る点で、好ましくは1μm~300μmであり、より好ましくは10μm~200μmであり、さらに好ましくは30μm~150μmであり、特に好ましくは40μm~100μmであり、最も好ましくは50μm~80μmである。 <<1-1. Resin film (1)>>
The thickness of the resin film (1) is preferably from 1 μm to 300 μm, more preferably from 10 μm to 200 μm, further preferably from 30 μm to 150 μm, and particularly preferably from the viewpoint that the effect of the present invention can be further exhibited. Is 40 μm to 100 μm, and most preferably 50 μm to 80 μm.
樹脂フィルム(1)の厚みとしては、本発明の効果をより発現させ得る点で、好ましくは1μm~300μmであり、より好ましくは10μm~200μmであり、さらに好ましくは30μm~150μmであり、特に好ましくは40μm~100μmであり、最も好ましくは50μm~80μmである。 <<1-1. Resin film (1)>>
The thickness of the resin film (1) is preferably from 1 μm to 300 μm, more preferably from 10 μm to 200 μm, further preferably from 30 μm to 150 μm, and particularly preferably from the viewpoint that the effect of the present invention can be further exhibited. Is 40 μm to 100 μm, and most preferably 50 μm to 80 μm.
樹脂フィルム(1)は、樹脂基材フィルム(1a)を含む。
The resin film (1) includes a resin base film (1a).
樹脂基材フィルム(1a)としては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)等のポリエステル系樹脂から構成されるプラスチックフィルム;ポリエチレン(PE)、ポリプロピレン(PP)、ポリメチルペンテン(PMP)、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体(EVA)等のα-オレフィンをモノマー成分とするオレフィン系樹脂から構成されるプラスチックフィルム;ポリ塩化ビニル(PVC)から構成されるプラスチックフィルム;酢酸ビニル系樹脂から構成されるプラスチックフィルム;ポリカーボネート(PC)から構成されるプラスチックフィルム;ポリフェニレンスルフィド(PPS)から構成されるプラスチックフィルム;ポリアミド(ナイロン)、全芳香族ポリアミド(アラミド)等のアミド系樹脂から構成されるプラスチックフィルム;ポリイミド系樹脂から構成されるプラスチックフィルム;ポリエーテルエーテルケトン(PEEK)から構成されるプラスチックフィルム;ポリエチレン(PE)、ポリプロピレン(PP)等のオレフィン系樹脂から構成されるプラスチックフィルム;ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン-フッ化ビニリデン共重合体などのフッ素系樹脂などから構成されるプラスチックフィルム;などが挙げられる。
Examples of the resin substrate film (1a) include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBT); polyethylene (PE), polypropylene ( PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other plastic films composed of an olefin resin containing α-olefin as a monomer component; polyvinyl chloride Plastic film composed of (PVC); plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), all Plastic film composed of amide resin such as aromatic polyamide (aramid); Plastic film composed of polyimide resin; Plastic film composed of polyether ether ketone (PEEK); Polyethylene (PE), polypropylene (PP) ) And other plastic films composed of olefinic resins; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride And a plastic film composed of a fluororesin such as a copolymer.
樹脂基材フィルム(1a)は、1層のみであってもよいし、2層以上であってもよい。樹脂基材フィルム(1a)は、延伸されたものであってもよい。
The resin base film (1a) may have only one layer, or may have two or more layers. The resin substrate film (1a) may be stretched.
樹脂基材フィルム(1a)は、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理などが挙げられる。
The resin base film (1a) may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric bombardment exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.
樹脂基材フィルム(1a)には、本発明の効果を損なわない範囲で、任意の適切な添加剤が含まれていてもよい。
The resin base film (1a) may contain any appropriate additive as long as the effects of the present invention are not impaired.
樹脂フィルム(1)は、粘着剤層(1)からの剥離性を高めるため、離型層(1b)を有していてもよい。樹脂フィルム(1)が離型層(1b)を有する場合、離型層(1b)の側が、粘着剤層(1)に直接に積層されてなる。
The resin film (1) may have a release layer (1b) in order to enhance the releasability from the adhesive layer (1). When the resin film (1) has the release layer (1b), the release layer (1b) side is directly laminated on the pressure-sensitive adhesive layer (1).
離型層(1b)の形成材料は、本発明の効果を損なわない範囲で、任意の適切な形成材料を採用し得る。このような形成材料としては、例えば、シリコーン系離型剤、フッ素系離型剤、長鎖アルキル系離型剤、脂肪酸アミド系離型剤などが挙げられる。これらのなかでも、シリコーン系離型剤が好ましい。離型層(1b)は、塗布層として形成することができる。
As the forming material of the release layer (1b), any appropriate forming material can be adopted as long as the effect of the present invention is not impaired. Examples of such a forming material include a silicone type release agent, a fluorine type release agent, a long chain alkyl type release agent, and a fatty acid amide type release agent. Of these, silicone-based release agents are preferred. The release layer (1b) can be formed as a coating layer.
離型層(1b)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは10nm~2000nmであり、より好ましくは10nm~1500nmであり、さらに好ましくは10nm~1000nmであり、特に好ましくは10nm~500nmである。
As the thickness of the release layer (1b), any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired. Such a thickness is preferably 10 nm to 2000 nm, more preferably 10 nm to 1500 nm, further preferably 10 nm to 1000 nm, and particularly preferably 10 nm to 500 nm.
離型層(1b)は、1層のみであってもよいし、2層以上であってもよい。
The release layer (1b) may be only one layer or two or more layers.
シリコーン系離型層としては、例えば、付加反応型シリコーン樹脂が挙げられる。付加反応型シリコーン樹脂としては、具体的には、例えば、信越化学工業製のKS-774、KS-775、KS-778、KS-779H、KS-847H、KS-847T;東芝シリコーン製のTPR-6700、TPR-6710、TPR-6721;東レ・ダウ・コーニング製のSD7220、SD7226;などが挙げられる。シリコーン系離型層の塗布量(乾燥後)は、好ましくは0.01g/m2~2g/m2であり、より好ましくは0.01g/m2~1g/m2であり、さらに好ましくは0.01g/m2~0.5g/m2である。
Examples of the silicone type release layer include addition reaction type silicone resins. Specific examples of the addition reaction type silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T manufactured by Shin-Etsu Chemical; TPR- manufactured by Toshiba Silicone. 6700, TPR-6710, TPR-6721; Toray Dow Corning SD7220, SD7226; and the like. The coating amount (after drying) of the silicone-based release layer is preferably 0.01 g/m 2 to 2 g/m 2 , more preferably 0.01 g/m 2 to 1 g/m 2 , and further preferably It is 0.01 g/m 2 to 0.5 g/m 2 .
離型層(1b)の形成は、例えば、上記の形成材料を、任意の適切な層上に、リバースグラビアコート、バーコート、ダイコート等、従来公知の塗布方式により塗布した後に、通常、120~200℃程度で熱処理を施すことにより硬化させることにより行うことができる。また、必要に応じて熱処理と紫外線照射等の活性エネルギー線照射とを併用してもよい。
The release layer (1b) is usually formed by coating the above-mentioned forming material on any appropriate layer by a conventionally known coating method such as reverse gravure coating, bar coating, die coating, etc. It can be performed by heat treatment at about 200° C. to cure. If necessary, heat treatment and irradiation with active energy rays such as ultraviolet irradiation may be used in combination.
樹脂フィルム(1)は、帯電防止層(1c)を有していてもよい。
The resin film (1) may have an antistatic layer (1c).
帯電防止層(1c)の厚みとしては、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは1nm~1000nmであり、より好ましくは5nm~900nmであり、さらに好ましくは7.5nm~800nmであり、特に好ましくは10nm~700nmである。
As the thickness of the antistatic layer (1c), any appropriate thickness can be adopted as long as the effect of the present invention is not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
帯電防止層(1c)は、1層のみであってもよいし、2層以上であってもよい。
The antistatic layer (1c) may be a single layer or two or more layers.
帯電防止層(1c)としては、帯電防止効果を奏することができる層であれば、本発明の効果を損なわない範囲で、任意の適切な帯電防止層を採用し得る。このような帯電防止層としては、好ましくは、導電性ポリマーを含む導電コート液を任意の適切な基材層上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液を樹脂基材フィルム(1a)上にコーティングして形成される帯電防止層である。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。
As the antistatic layer (1c), any suitable antistatic layer can be adopted as long as it can exhibit an antistatic effect as long as the effect of the present invention is not impaired. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the resin substrate film (1a). Specific coating methods include a roll coating method, a bar coating method and a gravure coating method.
導電性ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な導電性ポリマーを採用し得る。このような導電性ポリマーとしては、例えば、π共役系導電性ポリマーにポリアニオンがドープされた導電性ポリマーなどが挙げられる。π共役系導電性ポリマーとしては、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレンなどの鎖状導電性ポリマーが挙げられる。ポリアニオンとしては、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリメタクリルカルボン酸などが挙げられる。導電性ポリマーは、1種のみであってもよいし、2種以上であってもよい。
As the conductive polymer, any appropriate conductive polymer can be adopted as long as the effect of the present invention is not impaired. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacryl carboxylic acid. The conductive polymer may be only one kind or two or more kinds.
樹脂フィルム(1)の一つの実施形態は、樹脂基材フィルム(1a)と帯電防止層(1c)と離型層(1b)をこの順に含む。代表的には、この実施形態は、樹脂基材フィルム(1a)と帯電防止層(1c)と離型層(1b)とからなる。
One embodiment of the resin film (1) includes a resin substrate film (1a), an antistatic layer (1c) and a release layer (1b) in this order. Typically, this embodiment comprises a resin substrate film (1a), an antistatic layer (1c) and a release layer (1b).
樹脂フィルム(1)の別の一つの実施形態は、帯電防止層(1c)と樹脂基材フィルム(1a)と帯電防止層(1c)と離型層(1b)をこの順に含む。代表的には、この実施形態は、帯電防止層(1c)と樹脂基材フィルム(1a)と帯電防止層(1c)と離型層(1b)とからなる。
Another embodiment of the resin film (1) includes an antistatic layer (1c), a resin base film (1a), an antistatic layer (1c) and a release layer (1b) in this order. Typically, this embodiment comprises an antistatic layer (1c), a resin substrate film (1a), an antistatic layer (1c) and a release layer (1b).
≪1-2.粘着剤層(1)≫
粘着剤層(1)は、本発明の効果を損なわない範囲で、任意の適切な粘着剤層を採用し得る。粘着剤層(1)は、1層のみであってもよいし、2層以上であってもよい。 <<1-2. Adhesive layer (1)>>
As the pressure-sensitive adhesive layer (1), any appropriate pressure-sensitive adhesive layer can be adopted as long as the effect of the present invention is not impaired. The pressure-sensitive adhesive layer (1) may be a single layer or two or more layers.
粘着剤層(1)は、本発明の効果を損なわない範囲で、任意の適切な粘着剤層を採用し得る。粘着剤層(1)は、1層のみであってもよいし、2層以上であってもよい。 <<1-2. Adhesive layer (1)>>
As the pressure-sensitive adhesive layer (1), any appropriate pressure-sensitive adhesive layer can be adopted as long as the effect of the present invention is not impaired. The pressure-sensitive adhesive layer (1) may be a single layer or two or more layers.
粘着剤層(1)の厚みは、本発明の効果をより発現させ得る点で、好ましくは0.5μm~150μmであり、より好ましくは1μm~100μmであり、さらに好ましくは3μm~80μmであり、特に好ましくは5μm~50μmであり、最も好ましくは5μm~30μmである。
The thickness of the pressure-sensitive adhesive layer (1) is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, and further preferably 3 μm to 80 μm, from the viewpoint that the effect of the present invention can be further exhibited. Particularly preferred is 5 μm to 50 μm, and most preferred is 5 μm to 30 μm.
粘着剤層(1)は、上述のように、樹脂フィルム(2)との積層部分が、長手方向と実質的に直交する方向に所定の長さの貫通孔によって複数に区分けされてなる。
As described above, the pressure-sensitive adhesive layer (1) has a laminated portion with the resin film (2) divided into a plurality of through holes each having a predetermined length in a direction substantially orthogonal to the longitudinal direction.
粘着剤層(1)は、好ましくは、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤、シリコーン系粘着剤からなる群から選ばれる少なくとも1種から構成される。
The pressure-sensitive adhesive layer (1) is preferably composed of at least one selected from the group consisting of acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, rubber pressure-sensitive adhesives and silicone pressure-sensitive adhesives.
粘着剤層(1)は、任意の適切な方法によって形成し得る。このような方法としては、例えば、粘着剤組成物(アクリル系粘着剤組成物、ウレタン系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物からなる群から選ばれる少なくとも1種)を任意の適切な基材(例えば、樹脂フィルム(2))上に塗布し、必要に応じて加熱・乾燥を行い、必要に応じて硬化させて、該基材上において粘着剤層を形成する方法が挙げられる。このような塗布の方法としては、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、エアーナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーター、ロールブラッシュコーターなどの方法が挙げられる。
The adhesive layer (1) can be formed by any appropriate method. Examples of such a method include, for example, at least one selected from the group consisting of a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition, urethane-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive composition, silicone-based pressure-sensitive adhesive composition). ) Is applied on any suitable base material (for example, the resin film (2)), heated and dried as necessary, and cured as necessary to form a pressure-sensitive adhesive layer on the base material. There is a method of doing. Examples of such a coating method include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater and a roll brush coater. The method of is mentioned.
粘着剤層(1)は、導電成分を含んでいてもよい。導電成分は、1種のみであってもよいし、2種以上であってもよい。
The adhesive layer (1) may include a conductive component. The conductive component may be only one kind or two or more kinds.
<1-2-1.アクリル系粘着剤>
アクリル系粘着剤は、アクリル系粘着剤組成物から形成される。 <1-2-1. Acrylic adhesive>
The acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
アクリル系粘着剤は、アクリル系粘着剤組成物から形成される。 <1-2-1. Acrylic adhesive>
The acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
アクリル系粘着剤組成物は、本発明の効果をより発現させ得る点で、好ましくは、アクリル系ポリマーと架橋剤を含む。
The acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a crosslinking agent from the viewpoint that the effects of the present invention can be more exhibited.
アクリル系ポリマーは、アクリル系粘着剤の分野においていわゆるベースポリマーと称され得るものである。アクリル系ポリマーは、1種のみであってもよいし、2種以上であってもよい。
The acrylic polymer can be called a so-called base polymer in the field of acrylic pressure-sensitive adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.
アクリル系粘着剤組成物中のアクリル系ポリマーの含有割合は、固形分換算で、好ましくは60重量%~99.9重量%であり、より好ましくは65重量%~99.9重量%であり、さらに好ましくは70重量%~99.9重量%であり、特に好ましくは75重量%~99.9重量%であり、最も好ましくは80重量%~99.9重量%である。
The content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 60% by weight to 99.9% by weight, and more preferably 65% by weight to 99.9% by weight, in terms of solid content. It is more preferably 70% to 99.9% by weight, particularly preferably 75% to 99.9% by weight, and most preferably 80% to 99.9% by weight.
アクリル系ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切なアクリル系ポリマーを採用し得る。
As the acrylic polymer, any suitable acrylic polymer can be adopted as long as the effect of the present invention is not impaired.
アクリル系ポリマーの重量平均分子量は、本発明の効果をより発現させ得る点で、好ましくは30万~250万であり、より好ましくは35万~200万であり、さらに好ましくは40万~180万であり、特に好ましくは50万~150万である。
The weight average molecular weight of the acrylic polymer is preferably 300,000 to 2,500,000, more preferably 350,000 to 2,000,000, and further preferably 400,000 to 1800,000, from the viewpoint that the effects of the present invention can be further exhibited. And particularly preferably 500,000 to 1,500,000.
アクリル系ポリマーとしては、本発明の効果をより発現させ得る点で、好ましくは、(a成分)アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステル、(b成分)OH基を有する(メタ)アクリル酸エステルおよび(メタ)アクリル酸からなる群から選ばれる少なくとも1種、を含む組成物(A)から重合によって形成されるアクリル系ポリマーである。
The acrylic polymer is preferably a (meth)acrylic acid alkyl ester in which the alkyl group of the (a component) alkyl ester moiety has 4 to 12 carbon atoms from the viewpoint that the effect of the present invention can be further exhibited, and (b) It is an acrylic polymer formed by polymerization from a composition (A) containing (component) at least one selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid.
アクリル系ポリマーとしては、本発明の効果をより一層発現させ得る点で、好ましくは、(a成分)として、アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステルと、(b成分)として、OH基を有する(メタ)アクリル酸エステルを含まずに(メタ)アクリル酸を含む、組成物(A)から重合によって形成されるアクリル系ポリマーであり、より好ましくは、(a成分)として、アルキルエステル部分のアルキル基の炭素数が4~8である(メタ)アクリル酸アルキルエステルと、(b成分)として、OH基を有する(メタ)アクリル酸エステルを含まずにアクリル酸を含む、組成物(A)から重合によって形成されるアクリル系ポリマーである。
The acrylic polymer is preferably a (meth)acrylic acid alkyl ester in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms, as the component (a), from the viewpoint that the effects of the present invention can be further exhibited. And (acrylic acid) as a component (b), which is formed by polymerization from the composition (A) and contains (meth)acrylic acid without containing (meth)acrylic acid ester having an OH group, and more preferably , (A component) does not include (meth)acrylic acid alkyl ester in which the alkyl group of the alkyl ester moiety has 4 to 8 carbon atoms, and (b component) does not include (meth)acrylic acid ester having an OH group. It is an acrylic polymer formed by polymerization from the composition (A) containing acrylic acid in the composition.
(a成分)、(b成分)は、それぞれ、独立に、1種のみであってもよいし、2種以上であってもよい。
Each of (a component) and (b component) may be independently one type, or two or more types.
アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステル(a成分)としては、例えば、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシルなどが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸2-エチルヘキシルであり、より好ましくは、アクリル酸n-ブチル、アクリル酸2-エチルヘキシルである。
Examples of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include, for example, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate. S-Butyl acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate And so on. Among these, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable, and n-butyl acrylate and acryl are more preferable, from the viewpoint that the effects of the present invention can be further exhibited. It is 2-ethylhexyl acid.
OH基を有する(メタ)アクリル酸エステルおよび(メタ)アクリル酸からなる群から選ばれる少なくとも1種(b成分)としては、例えば、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシブチルなどのOH基を有する(メタ)アクリル酸エステル、(メタ)アクリル酸などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸であり、より好ましくは、アクリル酸ヒドロキシエチル、アクリル酸である。
Examples of at least one component (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples thereof include (meth)acrylic acid ester having an OH group such as hydroxybutyl (meth)acrylate and (meth)acrylic acid. Among these, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, from the viewpoint that the effects of the present invention can be further exhibited.
組成物(A)は、(a)成分および(b)成分以外の、共重合性モノマーを含んでいてもよい。共重合性モノマーは、1種のみであってもよいし、2種以上であってもよい。このような共重合性モノマーとしては、例えば、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸、これらの酸無水物(例えば、無水マレイン酸、無水イタコン酸などの酸無水物基含有モノマー)などのカルボキシル基含有モノマー(ただし、(メタ)アクリル酸を除く);(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-ヒドロキシエチル(メタ)アクリルアミドなどのアミド基含有モノマー;(メタ)アクリル酸アミノエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチルなどのアミノ基含有モノマー;(メタ)アクリル酸グリシジル、(メタ)アクリル酸メチルグリシジルなどのエポキシ基含有モノマー;アクリロニトリルやメタクリロニトリルなどのシアノ基含有モノマー;N-ビニル-2-ピロリドン、(メタ)アクリロイルモルホリン、N-ビニルピペリドン、N-ビニルピペラジン、N-ビニルピロール、N-ビニルイミダゾール、ビニルピリジン、ビニルピリミジン、ビニルオキサゾールなどの複素環含有ビニル系モノマー;ビニルスルホン酸ナトリウムなどのスルホン酸基含有モノマー;2-ヒドロキシエチルアクリロイルフォスフェートなどのリン酸基含有モノマー;シクロヘキシルマレイミド、イソプロピルマレイミドなどのイミド基含有モノマー;2-メタクリロイルオキシエチルイソシアネートなどのイソシアネート基含有モノマー;シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等の脂環式炭化水素基を有する(メタ)アクリル酸エステル;フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレートなどの芳香族炭化水素基を有する(メタ)アクリル酸エステル;酢酸ビニル、プロピオン酸ビニルなどのビニルエステル;スチレン、ビニルトルエンなどの芳香族ビニル化合物;エチレン、ブタジエン、イソプレン、イソブチレンなどのオレフィン類やジエン類;ビニルアルキルエーテルなどのビニルエーテル類;塩化ビニル;などが挙げられる。
The composition (A) may contain a copolymerizable monomer other than the components (a) and (b). The copolymerizable monomer may be only one type, or may be two or more types. Such copolymerizable monomers include, for example, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). ) And other carboxyl group-containing monomers (excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide , N-butoxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and other amide group-containing monomers; aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, t-butyl (meth)acrylate Amino group-containing monomers such as aminoethyl; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, Heterocycle-containing vinyl monomers such as (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole; sulfonic acids such as sodium vinylsulfonate Group-containing monomer; phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate; imide group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomer such as 2-methacryloyloxyethylisocyanate; cyclopentyl (meth)acrylate, (Meth)acrylic acid ester having an alicyclic hydrocarbon group such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; aromatic such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate and benzyl (meth)acrylate (Meth)acrylic ester having a hydrocarbon group; vinyl ester such as vinyl acetate and vinyl propionate; aromatic vinyl compound such as styrene and vinyltoluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl Vinyl ethers such as alkyl ethers; vinyl chloride; and the like.
共重合性モノマーとしては、多官能性モノマーも採用し得る。多官能性モノマーとは、1分子中に2以上のエチレン性不飽和基を有するモノマーをいう。エチレン性不飽和基としては、本発明の効果を損なわない範囲で、任意の適切なエチレン性不飽和基を採用し得る。このようなエチレン性不飽和基としては、例えば、ビニル基、プロペニル基、イソプロペニル基、ビニルエーテル基(ビニルオキシ基)、アリルエーテル基(アリルオキシ基)などのラジカル重合性官能基が挙げられる。多官能性モノマーとしては、例えば、ヘキサンジオールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、(ポリ)エチレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどが挙げられる。このような多官能性モノマーは、1種のみであってもよいし、2種以上であってもよい。
As the copolymerizable monomer, a polyfunctional monomer can also be adopted. The polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any appropriate ethylenically unsaturated group can be adopted as long as the effects of the present invention are not impaired. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol. Di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl Examples thereof include (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate and urethane acrylate. Only one kind of such a polyfunctional monomer may be used, or two or more kinds thereof may be used.
共重合性モノマーとしては、(メタ)アクリル酸アルコキシアルキルエステルも採用し得る。(メタ)アクリル酸アルコキシアルキルエステルとしては、例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸メトキシトリエチレングリコール、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸3-エトキシプロピル、(メタ)アクリル酸4-メトキシブチル、(メタ)アクリル酸4-エトキシブチルなどが挙げられる。(メタ)アクリル酸アルコキシアルキルエステルは、1種のみであってもよいし、2種以上であってもよい。
As a copolymerizable monomer, (meth)acrylic acid alkoxyalkyl ester can also be adopted. Examples of the (meth)acrylic acid alkoxyalkyl ester include 2-(meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, and (meth)acrylic acid 3-methacrylate. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate. The (meth)acrylic acid alkoxyalkyl ester may be only one kind, or may be two or more kinds.
アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステル(a成分)の含有量は、本発明の効果をより発現させ得る点で、アクリル系ポリマーを構成するモノマー成分全量(100重量%)に対して、好ましくは30重量%以上であり、より好ましくは35重量%~99重量%であり、さらに好ましくは40重量%~98重量%であり、特に好ましくは50重量%~95重量%である。
The content of the (meth)acrylic acid alkyl ester (a component) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer that constitutes the acrylic polymer in that the effects of the present invention can be further exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, further preferably 40% by weight to 98% by weight, particularly preferably 50% by weight based on the total amount of the components (100% by weight). % By weight to 95% by weight.
OH基を有する(メタ)アクリル酸エステルおよび(メタ)アクリル酸からなる群から選ばれる少なくとも1種(b成分)の含有量は、本発明の効果をより発現させ得る点で、アクリル系ポリマーを構成するモノマー成分全量(100重量%)に対して、好ましくは1重量%以上であり、より好ましくは1重量%~30重量%であり、さらに好ましくは2重量%~20重量%であり、特に好ましくは3重量%~10重量%である。
The content of at least one kind (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is such that the acrylic polymer is added in that the effect of the present invention can be further exhibited. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, further preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 10% by weight.
組成物(A)は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、重合開始剤、連鎖移動剤、溶剤などが挙げられる。これらの他の成分の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。
The composition (A) may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent. As the content of these other components, any appropriate content can be adopted as long as the effect of the present invention is not impaired.
重合開始剤は、重合反応の種類に応じて、熱重合開始剤や光重合開始剤(光開始剤)などを採用し得る。重合開始剤は、1種のみであってもよいし、2種以上であってもよい。
As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator (photoinitiator) or the like can be adopted depending on the type of the polymerization reaction. The polymerization initiator may be only one type, or may be two or more types.
熱重合開始剤は、好ましくは、アクリル系ポリマーを溶液重合によって得る際に採用され得る。このような熱重合開始剤としては、例えば、アゾ系重合開始剤、過酸化物系重合開始剤(例えば、ジベンゾイルペルオキシド、tert-ブチルペルマレエートなど)、レドックス系重合開始剤などが挙げられる。これらの熱重合開始剤の中でも、特開2002-69411号公報に開示されたアゾ系開始剤が特に好ましい。このようなアゾ系重合開始剤は、重合開始剤の分解物が加熱発生ガス(アウトガス)の発生原因となる部分としてアクリル系ポリマー中に残留しにくい点で好ましい。アゾ系重合開始剤としては、2,2’-アゾビスイソブチロニトリル(以下、AIBNと称する場合がある)、2,2’-アゾビス-2-メチルブチロニトリル(以下、AMBNと称する場合がある)、2,2’-アゾビス(2-メチルプロピオン酸)ジメチル、4,4’-アゾビス-4-シアノバレリアン酸などが挙げられる。
The thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization. Examples of such thermal polymerization initiators include azo-based polymerization initiators, peroxide-based polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox-based polymerization initiators, and the like. .. Among these thermal polymerization initiators, the azo initiators disclosed in JP-A-2002-69411 are particularly preferable. Such an azo-based polymerization initiator is preferable in that the decomposed product of the polymerization initiator is unlikely to remain in the acrylic polymer as a portion causing generation of a heat-generated gas (outgas). Examples of the azo-based polymerization initiator include 2,2′-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN) and 2,2′-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN). , 2,2′-azobis(2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid and the like.
光重合開始剤は、好ましくは、アクリル系ポリマーを活性エネルギー線重合によって得る際に採用され得る。光重合開始剤としては、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α-ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤等などが挙げられる。
The photopolymerization initiator can be preferably used when the acrylic polymer is obtained by active energy ray polymerization. Examples of the photopolymerization initiator include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime photopolymerization initiators. Agents, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like.
ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、アニソールメチルエーテルなどが挙げられる。アセトフェノン系光重合開始剤としては、例えば、2,2-ジエトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、4-フェノキシジクロロアセトフェノン、4-(t-ブチル)ジクロロアセトフェノンなどが挙げられる。α-ケトール系光重合開始剤としては、例えば、2-メチル-2-ヒドロキシプロピオフェノン、1-[4-(2-ヒドロキシエチル)フェニル]-2-メチルプロパン-1-オンなどが挙げられる。芳香族スルホニルクロリド系光重合開始剤としては、例えば、2-ナフタレンスルホニルクロライドなどが挙げられる。光活性オキシム系光重合開始剤としては、例えば、1-フェニル-1,1-プロパンジオン-2-(o-エトキシカルボニル)-オキシムなどが挙げられる。ベンゾイン系光重合開始剤としては、例えば、ベンゾインなどが挙げられる。ベンジル系光重合開始剤としては、例えば、ベンジルなどが挙げられる。ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、3,3'-ジメチル-4-メトキシベンゾフェノン、ポリビニルベンゾフェノン、α-ヒドロキシシクロヘキシルフェニルケトンなどが挙げられる。ケタール系光重合開始剤としては、例えば、ベンジルジメチルケタールなどが挙げられる。チオキサントン系光重合開始剤としては、例えば、チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジイソプロピルチオキサントン、ドデシルチオキサントンなどが挙げられる。
Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. Examples include methyl ether. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-(t-butyl). Examples thereof include dichloroacetophenone. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. .. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalene sulfonyl chloride. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzyl photopolymerization initiator include benzyl and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone, and the like. Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and dodecylthioxanthone.
アクリル系粘着剤組成物は、架橋剤を含んでいてもよい。架橋剤を用いることにより、アクリル系粘着剤の凝集力を向上でき、本発明の効果をより発現させ得る。架橋剤は、1種のみであってもよいし、2種以上であってもよい。
The acrylic pressure-sensitive adhesive composition may contain a crosslinking agent. By using the cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited. The cross-linking agent may be only one kind or two or more kinds.
架橋剤としては、多官能イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、多官能イソシアネート系架橋剤およびエポキシ系架橋剤からなる群から選ばれる少なくとも1種(c成分)である。
As the crosslinking agent, a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt. Examples thereof include a system-based crosslinking agent, a carbodiimide-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, and an amine-based crosslinking agent. Among these, at least one kind (component (c)) selected from the group consisting of a polyfunctional isocyanate cross-linking agent and an epoxy cross-linking agent is preferable from the viewpoint that the effect of the present invention can be further exhibited.
多官能イソシアネート系架橋剤としては、例えば、1,2-エチレンジイソシアネート、1,4-ブチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネートなどの低級脂肪族ポリイソシアネート類;シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネートなどの脂環族ポリイソシアネート類;2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、4,4'-ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート類などが挙げられる。多官能イソシアネート系架橋剤としては、例えば、トリメチロールプロパン/トリレンジイソシアネート付加物(日本ポリウレタン工業株式会社製、商品名「コロネートL」)、トリメチロールプロパン/ヘキサメチレンジイソシアネート付加物(日本ポリウレタン工業株式会社製、商品名「コロネートHL」)、商品名「コロネートHX」(日本ポリウレタン工業株式会社)、トリメチロールプロパン/キシリレンジイソシアネート付加物(三井化学株式会社製、商品名「タケネート110N」)などの市販品も挙げられる。
Examples of the polyfunctional isocyanate cross-linking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Aliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Aromatic polyisocyanates of Examples of the polyfunctional isocyanate cross-linking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”), trimethylolpropane/hexamethylene diisocyanate adduct (Japan Polyurethane Industry Co., Ltd. Company name, product name "Coronate HL"), product name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemicals, Inc., product name "Takenate 110N"), etc. Commercial products are also included.
エポキシ系架橋剤(多官能エポキシ化合物)としては、例えば、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン、ジグリシジルアニリン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、1,6-ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、o-フタル酸ジグリシジルエステル、トリグリシジル-トリス(2-ヒドロキシエチル)イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール-S-ジグリシジルエーテルの他、分子内にエポキシ基を2つ以上有するエポキシ系樹脂などが挙げられる。エポキシ系架橋剤としては、商品名「テトラッドC」(三菱ガス化学株式会社製)などの市販品も挙げられる。
Examples of the epoxy cross-linking agent (polyfunctional epoxy compound) include N,N,N′,N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, and 1,3-bis(N,N-diglycidylamino). Methyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, Glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2- Examples thereof include hydroxyethyl)isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. As the epoxy-based cross-linking agent, commercially available products such as trade name “Tetrad C” (manufactured by Mitsubishi Gas Chemical Co., Inc.) can also be mentioned.
アクリル系粘着剤組成物中の架橋剤の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。このような含有量としては、例えば、本発明の効果をより発現させ得る点で、アクリル系ポリマーの固形分(100重量部)に対して、好ましくは0.05重量部~20重量部であり、より好ましくは0.1重量部~18重量部であり、さらに好ましくは0.5重量部~15重量部であり、特に好ましくは0.5重量部~10重量部である。
As the content of the cross-linking agent in the acrylic pressure-sensitive adhesive composition, any appropriate content can be adopted as long as the effect of the present invention is not impaired. Such a content is, for example, preferably 0.05 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer, from the viewpoint that the effect of the present invention can be exhibited more. It is more preferably 0.1 part by weight to 18 parts by weight, further preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight.
アクリル系粘着剤組成物は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、アクリル系ポリマー以外のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど)、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤(顔料や染料など)、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。
The acrylic pressure-sensitive adhesive composition may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), Anti-aging agent, inorganic filler, organic filler, metal powder, colorant (pigment or dye, etc.), foil, UV absorber, antioxidant, light stabilizer, chain transfer agent, plasticizer, softener, Examples thereof include surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and catalysts.
<1-2-2.ウレタン系粘着剤>
ウレタン系粘着剤としては、本発明の効果を損なわない範囲で、例えば、特開2017-039859号公報などに記載の公知のウレタン系粘着剤など、任意の適切なウレタン系粘着剤を採用し得る。このようなウレタン系粘着剤としては、例えば、ウレタン系粘着剤組成物から形成されるウレタン系粘着剤であって、該ウレタン系粘着剤組成物が、ウレタンプレポリマーおよびポリオールからなる群から選ばれる少なくとも1種と架橋剤とを含むものである。ウレタン系粘着剤は、1種のみであってもよいし、2種以上であってもよい。ウレタン系粘着剤は、本発明の効果を損なわない範囲で、任意の適切な成分を含有し得る。 <1-2-2. Urethane adhesive>
As the urethane-based pressure-sensitive adhesive, any appropriate urethane-based pressure-sensitive adhesive may be adopted, for example, known urethane-based pressure-sensitive adhesives described in JP-A-2017-039859, etc., within a range that does not impair the effects of the present invention. .. As such a urethane-based pressure-sensitive adhesive, for example, a urethane-based pressure-sensitive adhesive formed from a urethane-based pressure-sensitive adhesive composition, wherein the urethane-based pressure-sensitive adhesive composition is selected from the group consisting of a urethane prepolymer and a polyol. It contains at least one kind and a crosslinking agent. The urethane-based pressure-sensitive adhesive may be only one kind or two or more kinds. The urethane-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
ウレタン系粘着剤としては、本発明の効果を損なわない範囲で、例えば、特開2017-039859号公報などに記載の公知のウレタン系粘着剤など、任意の適切なウレタン系粘着剤を採用し得る。このようなウレタン系粘着剤としては、例えば、ウレタン系粘着剤組成物から形成されるウレタン系粘着剤であって、該ウレタン系粘着剤組成物が、ウレタンプレポリマーおよびポリオールからなる群から選ばれる少なくとも1種と架橋剤とを含むものである。ウレタン系粘着剤は、1種のみであってもよいし、2種以上であってもよい。ウレタン系粘着剤は、本発明の効果を損なわない範囲で、任意の適切な成分を含有し得る。 <1-2-2. Urethane adhesive>
As the urethane-based pressure-sensitive adhesive, any appropriate urethane-based pressure-sensitive adhesive may be adopted, for example, known urethane-based pressure-sensitive adhesives described in JP-A-2017-039859, etc., within a range that does not impair the effects of the present invention. .. As such a urethane-based pressure-sensitive adhesive, for example, a urethane-based pressure-sensitive adhesive formed from a urethane-based pressure-sensitive adhesive composition, wherein the urethane-based pressure-sensitive adhesive composition is selected from the group consisting of a urethane prepolymer and a polyol. It contains at least one kind and a crosslinking agent. The urethane-based pressure-sensitive adhesive may be only one kind or two or more kinds. The urethane-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
<1-2-3.ゴム系粘着剤>
ゴム系粘着剤としては、本発明の効果を損なわない範囲で、例えば、特開2015-074771号公報などに記載の公知のゴム系粘着剤など、任意の適切なゴム系粘着剤を採用し得る。これらは、1種のみであってもよいし、2種以上であってもよい。ゴム系粘着剤は、本発明の効果を損なわない範囲で、任意の適切な成分を含有し得る。 <1-2-3. Rubber adhesive>
As the rubber-based pressure-sensitive adhesive, any suitable rubber-based pressure-sensitive adhesive can be adopted, for example, known rubber-based pressure-sensitive adhesives described in JP-A-2005-074771 and the like, within a range that does not impair the effects of the present invention. .. These may be only one kind or two or more kinds. The rubber-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
ゴム系粘着剤としては、本発明の効果を損なわない範囲で、例えば、特開2015-074771号公報などに記載の公知のゴム系粘着剤など、任意の適切なゴム系粘着剤を採用し得る。これらは、1種のみであってもよいし、2種以上であってもよい。ゴム系粘着剤は、本発明の効果を損なわない範囲で、任意の適切な成分を含有し得る。 <1-2-3. Rubber adhesive>
As the rubber-based pressure-sensitive adhesive, any suitable rubber-based pressure-sensitive adhesive can be adopted, for example, known rubber-based pressure-sensitive adhesives described in JP-A-2005-074771 and the like, within a range that does not impair the effects of the present invention. .. These may be only one kind or two or more kinds. The rubber-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
<1-2-4.シリコーン系粘着剤>
シリコーン系粘着剤としては、本発明の効果を損なわない範囲で、例えば、特開2014-047280号公報などに記載の公知のシリコーン系粘着剤など、任意の適切なシリコーン系粘着剤を採用し得る。これらは、1種のみであってもよいし、2種以上であってもよい。シリコーン系粘着剤は、本発明の効果を損なわない範囲で、任意の適切な成分を含有し得る。 <1-2-4. Silicone adhesive>
As the silicone-based pressure-sensitive adhesive, any appropriate silicone-based pressure-sensitive adhesive may be adopted, for example, known silicone-based pressure-sensitive adhesives described in JP-A-2014-047280 and the like, as long as the effects of the present invention are not impaired. .. These may be only one kind or two or more kinds. The silicone-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
シリコーン系粘着剤としては、本発明の効果を損なわない範囲で、例えば、特開2014-047280号公報などに記載の公知のシリコーン系粘着剤など、任意の適切なシリコーン系粘着剤を採用し得る。これらは、1種のみであってもよいし、2種以上であってもよい。シリコーン系粘着剤は、本発明の効果を損なわない範囲で、任意の適切な成分を含有し得る。 <1-2-4. Silicone adhesive>
As the silicone-based pressure-sensitive adhesive, any appropriate silicone-based pressure-sensitive adhesive may be adopted, for example, known silicone-based pressure-sensitive adhesives described in JP-A-2014-047280 and the like, as long as the effects of the present invention are not impaired. .. These may be only one kind or two or more kinds. The silicone-based pressure-sensitive adhesive may contain any appropriate component as long as the effect of the present invention is not impaired.
<1-2-5.導電成分>
粘着剤層(1)は導電成分を含んでいてもよい。代表的には、粘着剤層(1)の材料となる粘着剤組成物(アクリル系粘着剤組成物、ウレタン系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物からなる群から選ばれる少なくとも1種)は、導電成分を含んでいてもよい。 <1-2-5. Conductive component>
The adhesive layer (1) may contain a conductive component. Typically, a pressure-sensitive adhesive composition as a material of the pressure-sensitive adhesive layer (1) (a group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive composition At least one selected from the above may contain a conductive component.
粘着剤層(1)は導電成分を含んでいてもよい。代表的には、粘着剤層(1)の材料となる粘着剤組成物(アクリル系粘着剤組成物、ウレタン系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物からなる群から選ばれる少なくとも1種)は、導電成分を含んでいてもよい。 <1-2-5. Conductive component>
The adhesive layer (1) may contain a conductive component. Typically, a pressure-sensitive adhesive composition as a material of the pressure-sensitive adhesive layer (1) (a group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive composition At least one selected from the above may contain a conductive component.
導電成分としては、本発明の効果を損なわない範囲で、任意の適切な導電成分を採用し得る。このような導電成分としては、好ましくは、イオン性液体、イオン伝導ポリマー、イオン伝導フィラー、電気伝導ポリマーから選ばれる少なくとも1種の化合物である。
As the conductive component, any appropriate conductive component can be adopted as long as the effect of the present invention is not impaired. Such a conductive component is preferably at least one compound selected from an ionic liquid, an ion conductive polymer, an ion conductive filler and an electric conductive polymer.
粘着剤組成物が導電成分を含んでいる場合において、ベースポリマー(例えば、アクリル系ポリマー、ポリオール、ウレタンプレポリマー、ゴム系ポリマー、シリコーン系ポリマー)と導電成分との割合としては、導電成分が、ベースポリマー100重量部に対して、好ましくは0.01重量部~10重量部であり、より好ましくは0.05重量部~9.0重量部であり、さらに好ましくは0.075重量部~8.0重量部であり、特に好ましくは0.1重量部~7.0重量部である。
In the case where the pressure-sensitive adhesive composition contains a conductive component, the ratio of the base polymer (for example, acrylic polymer, polyol, urethane prepolymer, rubber polymer, silicone polymer) to the conductive component is such that the conductive component is With respect to 100 parts by weight of the base polymer, it is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 9.0 parts by weight, and further preferably 0.075 parts by weight to 8 parts by weight. 0.0 parts by weight, particularly preferably 0.1 parts by weight to 7.0 parts by weight.
イオン性液体としては、本発明の効果を損なわない範囲で、任意の適切なイオン性液体を採用し得る。ここで、イオン性液体とは、25℃で液状を呈する溶融塩(イオン性化合物)を意味する。イオン性液体は、1種のみであってもよいし、2種以上であってもよい。
As the ionic liquid, any appropriate ionic liquid can be adopted as long as the effect of the present invention is not impaired. Here, the ionic liquid means a molten salt (ionic compound) which is liquid at 25°C. The ionic liquid may be only one kind or two or more kinds.
このようなイオン性液体としては、好ましくは、フルオロ有機アニオンとオニウムカチオンから構成されるイオン性液体である。
Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation.
イオン性液体を構成し得るオニウムカチオンとしては、本発明の効果を損なわない範囲で、任意の適切なオニウムカチオンを採用し得る。このようなオニウムカチオンとしては、好ましくは、窒素含有オニウムカチオン、硫黄含有オニウムカチオン、リン含有オニウムカチオンから選ばれる少なくとも1種である。
As the onium cation that can form the ionic liquid, any appropriate onium cation can be adopted as long as the effect of the present invention is not impaired. Such an onium cation is preferably at least one selected from nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations.
イオン性液体を構成し得るオニウムカチオンとしては、本発明の効果をより発現させ得る点で、好ましくは、一般式(1)~(5)で表される構造を有するカチオンから選ばれる少なくとも1種である。
The onium cation that can form the ionic liquid is preferably at least one selected from cations having a structure represented by any one of the general formulas (1) to (5) from the viewpoint that the effects of the present invention can be further exhibited. Is.
一般式(1)において、Raは、炭素数4から20の炭化水素基を表し、ヘテロ原子を含んでいてもよく、RbおよびRcは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、ヘテロ原子を含んでいてもよい。ただし、窒素原子が2重結合を含む場合、Rcはない。
In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and Rb and Rc are the same or different and each represents hydrogen or a carbon atom having 1 to 16 carbon atoms. It represents a hydrogen group and may contain a hetero atom. However, when the nitrogen atom contains a double bond, there is no Rc.
一般式(2)において、Rdは、炭素数2から20の炭化水素基を表し、ヘテロ原子を含んでいてもよく、Re、Rf、およびRgは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、ヘテロ原子を含んでいてもよい。
In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and Re, Rf and Rg are the same or different and each represents hydrogen or a carbon number of 1 to It represents 16 hydrocarbon groups and may contain a hetero atom.
一般式(3)において、Rhは、炭素数2から20の炭化水素基を表し、ヘテロ原子を含んでいてもよく、Ri、Rj、およびRkは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、ヘテロ原子を含んでいてもよい。
In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may include a hetero atom, and Ri, Rj, and Rk are the same or different and each represents hydrogen or a carbon number of 1 to It represents 16 hydrocarbon groups and may contain a hetero atom.
一般式(4)において、Zは、窒素原子、硫黄原子、またはリン原子を表し、Rl、Rm、Rn、およびRoは、同一または異なって、炭素数1から20の炭化水素基を表し、ヘテロ原子を含んでいてもよい。ただしZが硫黄原子の場合、Roはない。
In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, Rl, Rm, Rn, and Ro are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms; It may contain atoms. However, when Z is a sulfur atom, there is no Ro.
一般式(5)において、Xは、Li原子、Na原子、またはK原子を表す。
In the general formula (5), X represents a Li atom, a Na atom, or a K atom.
一般式(1)で表されるカチオンとしては、例えば、ピリジニウムカチオン、ピロリジニウムカチオン、ピペリジニウムカチオン、ピロリン骨格を有するカチオン、ピロール骨格を有するカチオンなどが挙げられる。
Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton.
一般式(1)で表されるカチオンの具体例としては、例えば、1-エチルピリジニウムカチオン、1-ブチルピリジニウムカチオン、1-へキシルピリジニウムカチオン、1-エチル-3-メチルピリジニウムカチオン、1-ブチル-3-メチルピリジニウムカチオン、1-へキシル-3-メチルピリジニウムカチオン、1-ブチル-4-メチルピリジニウムカチオン、1-オクチル-4-メチルピリジニウムカチオン等のピリジニウムカチオン;1-エチル-1-メチルピロリジニウムカチオン、1-メチル-1-プロピルピロリジニウムカチオン、1-メチル-1-ブチルピロリジニウムカチオン、1-メチル-1-ペンチルピロリジニウムカチオン、1-メチル-1-へキシルピロリジニウムカチオン、1-メチル-1-ヘプチルピロリジニウムカチオン、1-エチル-1-プロピルピロリジニウムカチオン、1-エチル-1-ブチルピロリジニウムカチオン、1-エチル-1-ペンチルピロリジニウムカチオン、1-エチル-1-へキシルピロリジニウムカチオン、1-エチル-1-へプチルピロリジニウムカチオン等のピロリジニウムカチオン;1-メチル-1-エチルピペリジニウムカチオン、1-メチル-1-プロピルピペリジニウムカチオン、1-メチル-1-ブチルピペリジニウムカチオン、1-メチル-1-ペンチルピペリジニウムカチオン、1-メチル-1-ヘキシルピペリジニウムカチオン、1-メチル-1-へプチルピペリジニウムカチオン、1-エチル-1-プロピルピペリジニウムカチオン、1-エチル-1-ブチルピペリジニウムカチオン、1-エチル-1-ペンチルピペリジニウムカチオン、1-エチル-1-ヘキシルピペリジニウムカチオン、1-エチル-1-へプチルピペリジニウムカチオン、1-プロピル-1-ブチルピペリジニウムカチオン等のピペリジニウムカチオン;などが挙げられ、より好ましくは、1-へキシルピリジニウムカチオン、1-エチル-3-メチルピリジニウムカチオン、1-ブチル-3-メチルピリジニウムカチオン、1-オクチル-4-メチルピリジニウムカチオン、1-メチル-1-プロピルピロリジニウムカチオン、1-メチル-1-プロピルピペリジニウムカチオンである。
Specific examples of the cation represented by the general formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl. Pyridinium cation such as -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrroli Dinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinide Cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation , 1-Ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, etc.; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1 -To propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1- Putylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpi And a piperidinium cation such as 1-ethyl-1-heptylpiperidinium cation and 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexylpyridinium cation , 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propyl It is a piperidinium cation.
一般式(2)で表されるカチオンとしては、例えば、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオンなどが挙げられる。
Examples of the cation represented by the general formula (2) include imidazolium cation, tetrahydropyrimidinium cation, and dihydropyrimidinium cation.
一般式(2)で表されるカチオンの具体例としては、例えば、1,3-ジメチルイミダゾリウムカチオン、1,3-ジエチルイミダゾリウムカチオン、1-エチル-3-メチルイミダゾリウムカチオン、1-ブチル-3-メチルイミダゾリウムカチオン、1-へキシル-3-メチルイミダゾリウムカチオン、1-オクチル-3-メチルイミダゾリウムカチオン、1-デシル-3-メチルイミダゾリウムカチオン、1-ドデシル-3-メチルイミダゾリウムカチオン、1-テトラデシル-3-メチルイミダゾリウムカチオン等のイミダゾリウムカチオンであり、より好ましくは、1-エチル-3-メチルイミダゾリウムカチオン、1-へキシル-3-メチルイミダゾリウムカチオンである。
Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl. -3-Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazole It is an imidazolium cation such as a lithium cation and a 1-tetradecyl-3-methylimidazolium cation, and more preferably a 1-ethyl-3-methylimidazolium cation and a 1-hexyl-3-methylimidazolium cation.
一般式(3)で表されるカチオンとしては、例えば、ピラゾリウムカチオン、ピラゾリニウムカチオンなどが挙げられる。
Examples of the cation represented by the general formula (3) include a pyrazolium cation and a pyrazolinium cation.
一般式(3)で表されるカチオンの具体例としては、例えば、1-メチルピラゾリウムカチオン、3-メチルピラゾリウムカチオン、1-エチル-2-メチルピラゾリニウムカチオン、1-エチル-2,3,5-トリメチルピラゾリウムカチオン、1-プロピル-2,3,5-トリメチルピラゾリウムカチオン、1-ブチル-2,3,5-トリメチルピラゾリウムカチオン等のピラゾリウムカチオン;1-エチル-2,3,5-トリメチルピラゾリニウムカチオン、1-プロピル-2,3,5-トリメチルピラゾリニウムカチオン、1-ブチル-2,3,5-トリメチルピラゾリニウムカチオン等のピラゾリニウムカチオン;などが挙げられる。
Specific examples of the cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl- A pyrazolium cation such as a 2,3,5-trimethylpyrazolium cation, a 1-propyl-2,3,5-trimethylpyrazolium cation, a 1-butyl-2,3,5-trimethylpyrazolium cation; Pyra such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation Zolinium cation; and the like.
一般式(4)で表されるカチオンとしては、例えば、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオンや、上記アルキル基の一部がアルケニル基やアルコキシル基、さらにはエポキシ基に置換されたものなどが挙げられる。
Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the above alkyl group substituted with an alkenyl group, an alkoxyl group, or an epoxy group. Some of them are listed.
一般式(4)で表されるカチオンの具体例としては、例えば、トリエチルメチルアンモニウムカチオン、トリブチルエチルアンモニウムカチオン、トリメチルデシルアンモニウムカチオン、ジエチルメチルスルホニウムカチオン、ジブチルエチルスルホニウムカチオン、ジメチルデシルスルホニウムカチオン、トリエチルメチルホスホニウムカチオン、トリブチルエチルホスホニウムカチオン、トリメチルデシルホスホニウムカチオンなどの非対称のテトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオンや、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムカチオン、グリシジルトリメチルアンモニウムカチオン、ジアリルジメチルアンモニウムカチオン、N,N-ジメチル-N-エチル-N-プロピルアンモニウムカチオン、N,N-ジメチル-N-エチル-N-ブチルアンモニウムカチオン、N,N-ジメチル-N-エチル-N-ペンチルアンモニウムカチオン、N,N-ジメチル-N-エチル-N-ヘキシルアンモニウムカチオン、N,N-ジメチル-N-エチル-N-ヘプチルアンモニウムカチオン、N,N-ジメチル-N-エチル-N-ノニルアンモニウムカチオン、N,N-ジメチル-N,N-ジプロピルアンモニウムカチオン、N,N-ジエチル-N-プロピル-N-ブチルアンモニウムカチオン、N,N-ジメチル-N-プロピル-N-ペンチルアンモニウムカチオン、N,N-ジメチル-N-プロピル-N-ヘキシルアンモニウムカチオン、N,N-ジメチル-N-プロピル-N-ヘプチルアンモニウムカチオン、N,N-ジメチル-N-ブチル-N-ヘキシルアンモニウムカチオン、N,N-ジエチル-N-ブチル-N-ヘプチルアンモニウムカチオン、N,N-ジメチル-N-ペンチル-N-ヘキシルアンモニウムカチオン、N,N-ジメチル-N,N-ジヘキシルアンモニウムカチオン、トリメチルヘプチルアンモニウムカチオン、N,N-ジエチル-N-メチル-N-プロピルアンモニウムカチオン、N,N-ジエチル-N-メチル-N-ペンチルアンモニウムカチオン、N,N-ジエチル-N-メチル-N-ヘプチルアンモニウムカチオン、N,N-ジエチル-N-プロピル-N-ペンチルアンモニウムカチオン、トリエチルプロピルアンモニウムカチオン、トリエチルペンチルアンモニウムカチオン、トリエチルヘプチルアンモニウムカチオン、N,N-ジプロピル-N-メチル-N-エチルアンモニウムカチオン、N,N-ジプロピル-N-メチル-N-ペンチルアンモニウムカチオン、N,N-ジプロピル-N-ブチル-N-ヘキシルアンモニウムカチオン、N,N-ジプロピル-N,N-ジヘキシルアンモニウムカチオン、N,N-ジブチル-N-メチル-N-ペンチルアンモニウムカチオン、N,N-ジブチル-N-メチル-N-ヘキシルアンモニウムカチオン、トリオクチルメチルアンモニウムカチオン、N-メチル-N-エチル-N-プロピル-N-ペンチルアンモニウムカチオンなどが挙げられ、より好ましくは、トリメチルプロピルアンモニウムカチオンである。
Specific examples of the cation represented by the general formula (4) include, for example, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethyl. Asymmetric tetraalkylammonium cations such as phosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, N,N-diethyl-N-methyl-N-(2-methoxyethyl) Ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl ammonium cation, N,N-dimethyl-N-ethyl-N-propyl ammonium cation, N,N-dimethyl-N-ethyl-N-butyl ammonium cation, N,N-dimethyl -N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N -Ethyl-N-nonyl ammonium cation, N,N-dimethyl-N,N-dipropyl ammonium cation, N,N-diethyl-N-propyl-N-butyl ammonium cation, N,N-dimethyl-N-propyl- N-pentyl ammonium cation, N,N-dimethyl-N-propyl-N-hexyl ammonium cation, N,N-dimethyl-N-propyl-N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N- Hexyl ammonium cation, N,N-diethyl-N-butyl-N-heptyl ammonium cation, N,N-dimethyl-N-pentyl-N-hexyl ammonium cation, N,N-dimethyl-N,N-dihexyl ammonium cation, Trimethylheptyl ammonium cation, N,N-diethyl-N-methyl-N-propyl ammonium cation, N,N-diethyl-N-methyl-N-pentyl ammonium cation, N,N-diethyl-N-methyl-N-heptyl Ammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation , Triethylheptyl ammonium cation, N,N-dipropyl-N-methyl-N-ethyl ammonium cation, N,N-dipropyl-N-methyl-N-pentyl ammonium cation, N,N-dipropyl-N-butyl-N- Hexyl ammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl-N-methyl-N-pentyl ammonium cation, N,N-dibutyl-N-methyl-N-hexyl ammonium cation, Examples thereof include trioctylmethylammonium cation and N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and more preferably trimethylpropylammonium cation.
イオン性液体を構成し得るフルオロ有機アニオンとしては、本発明の効果を損なわない範囲で、任意の適切なフルオロ有機アニオンを採用し得る。このようなフルオロ有機アニオンは、完全にフッ素化(パーフルオロ化)されていてもよいし、部分的にフッ素化されていてもよい。
As the fluoroorganic anion that can form the ionic liquid, any appropriate fluoroorganic anion can be adopted as long as the effect of the present invention is not impaired. Such a fluoroorganic anion may be completely fluorinated (perfluorinated) or partially fluorinated.
このようなフルオロ有機アニオンとしては、例えば、パーフルオロアルキルスルホネート、ビス(フルオロスルホニル)イミド、ビス(パーフルオロアルカンスルホニル)イミドであり、より具体的には、例えば、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、ヘプタフルオロプロパンスルホネート、ノナフルオロブタンスルホネート、ビス(フルオロスルホニル)イミド、ビス(トリフルオロメタンスルホニル)イミドである。
Examples of such a fluoroorganic anion include perfluoroalkyl sulfonate, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl)imide, and more specifically, for example, trifluoromethane sulfonate, pentafluoroethane sulfonate. , Heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide.
イオン性液体の具体例としては、上記カチオン成分と上記アニオン成分の組み合わせから適宜選択して用いられ得る。このようなイオン性液体の具体例としては、例えば、1-ヘキシルピリジニウムビス(フルオロスルホニル)イミド、1-エチル-3-メチルピリジニウムトリフルオロメタンスルホネート、1-エチル-3-メチルピリジニウムペンタフルオロエタンスルホネート、1-エチル-3-メチルピリジニウムヘプタフルオロプロパンスルホネート、1-エチル-3-メチルピリジニウムノナフルオロブタンスルホネート、1-ブチル-3-メチルピリジニウムトリフルオロメタンスルホネート、1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミド、1-オクチル-4-メチルピリジニウムビス(フルオロスルホニル)イミド、1-メチル-1-プロピルピロリジニウムビス(トリフルオロメタンスルホニル)イミド、1-メチル-1-プロピルピロリジニウムビス(フルオロスルホニル)イミド、1-メチル-1-プロピルピペリジニウムビス(トリフルオロメタンスルホニル)イミド、1-メチル-1-プロピルピペリジニウムビス(フルオロスルホニル)イミド、1-エチル-3-メチルイミダゾリウムトリフルオロメタンスルホネート、1-エチル-3-メチルイミダゾリウムヘプタフルオロプロパンスルホネート、1-エチル-3-メチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド、1-エチル-3-メチルイミダゾリウムビス(フルオロスルホニル)イミド、1-ヘキシル-3-メチルイミダゾリウムビス(フルオロスルホニル)イミド、トリメチルプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、リチウムビス(トリフルオロメタンスルホニル)イミド、リチウムビス(フルオロスルホニル)イミドである。
As a specific example of the ionic liquid, a combination of the above cation component and the above anion component can be appropriately selected and used. Specific examples of such an ionic liquid include, for example, 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethane sulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethane Sulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(fluoro) Sulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethane Sulfonate, 1-ethyl-3-methylimidazolium heptafluoropropane sulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1 -Hexyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide.
イオン性液体は、市販のものを使用してもよいが、下記のようにして合成することも可能である。イオン性液体の合成方法としては、目的とするイオン性液体が得られれば特に限定されないが、一般的には、文献「イオン性液体-開発の最前線と未来-」((株)シーエムシー出版発行)に記載されているような、ハロゲン化物法、水酸化物法、酸エステル法、錯形成法、および中和法などが用いられる。
As the ionic liquid, a commercially available one may be used, but it is also possible to synthesize it as follows. The method for synthesizing an ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained, but in general, the literature "Ionic liquids-the forefront and future of development-" (CMC Publishing Co., Ltd.) Issue), a halide method, a hydroxide method, an acid ester method, a complex formation method, a neutralization method and the like are used.
下記にハロゲン化物法、水酸化物法、酸エステル法、錯形成法、および中和法について、窒素含有オニウム塩を例にその合成方法について示すが、その他の硫黄含有オニウム塩、リン含有オニウム塩など、その他のイオン性液体についても同様の手法により得ることができる。
The halide method, the hydroxide method, the acid ester method, the complex formation method, and the neutralization method are shown below for the synthesis method using a nitrogen-containing onium salt as an example. Other sulfur-containing onium salts, phosphorus-containing onium salts Other ionic liquids such as the above can be obtained by the same method.
ハロゲン化物法は、反応式(1)~(3)に示すような反応によって行われる方法である。まず3級アミンとハロゲン化アルキルと反応させてハロゲン化物を得る(反応式(1)、ハロゲンとしては塩素、臭素、ヨウ素が用いられる)。
The halide method is a method performed by the reactions shown in the reaction formulas (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction formula (1), chlorine, bromine, or iodine is used as halogen).
得られたハロゲン化物を目的とするイオン性液体のアニオン構造(A-)を有する酸(HA)あるいは塩(MA、Mはアンモニウム、リチウム、ナトリウム、カリウムなど目的とするアニオンと塩を形成するカチオン)と反応させて目的とするイオン性液体(R4NA)が得られる。
The obtained halide is an acid (HA) or salt having the anion structure (A − ) of the desired ionic liquid (MA and M are cations that form a salt with the desired anion such as ammonium, lithium, sodium and potassium). ) And the target ionic liquid (R 4 NA) is obtained.
水酸化物法は、反応式(4)~(8)に示すような反応によって行われる方法である。まずハロゲン化物(R4NX)をイオン交換膜法電解(反応式(4))、OH型イオン交換樹脂法(反応式(5))または酸化銀(Ag2O)との反応(反応式(6))で水酸化物(R4NOH)を得る(ハロゲンとしては塩素、臭素、ヨウ素が用いられる)。
The hydroxide method is a method performed by the reactions shown in the reaction formulas (4) to (8). First, a reaction of a halide (R 4 NX) with an ion exchange membrane method electrolysis (reaction formula (4)), an OH type ion exchange resin method (reaction formula (5)), or silver oxide (Ag 2 O) (reaction formula ( In 6)), a hydroxide (R 4 NOH) is obtained (as halogen, chlorine, bromine or iodine is used).
得られた水酸化物について上記ハロゲン化法と同様に反応式(7)~(8)の反応を用いることにより、目的とするイオン性液体(R4NA)が得られる。
By using the reaction of the reaction formulas (7) to (8) for the obtained hydroxide in the same manner as in the halogenation method, the target ionic liquid (R 4 NA) can be obtained.
酸エステル法は、反応式(9)~(11)に示すような反応によって行われる方法である。まず3級アミン(R3N)を酸エステルと反応させて酸エステル物を得る(反応式(9)、酸エステルとしては、硫酸、亜硫酸、リン酸、亜リン酸、炭酸などの無機酸のエステルやメタンスルホン酸、メチルホスホン酸、ギ酸などの有機酸のエステルなどが用いられる)。
The acid ester method is a method performed by the reactions shown in the reaction formulas (9) to (11). First, a tertiary amine (R 3 N) is reacted with an acid ester to obtain an acid ester product (reaction formula (9). As the acid ester, inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid can be used. Esters and methanesulfonic acid, methylphosphonic acid, and organic acid esters such as formic acid are used).
得られた酸エステル物について上記ハロゲン化法と同様に反応式(10)~(11)の反応を用いることにより、目的とするイオン性液体(R4NA)が得られる。また、酸エステルとしてメチルトリフルオロメタンスルホネート、メチルトリフルオロアセテートなどを用いることにより、直接イオン性液体を得ることもできる。
The target ionic liquid (R 4 NA) is obtained by using the reaction of the reaction formulas (10) to (11) for the obtained acid ester product in the same manner as in the above halogenation method. Alternatively, an ionic liquid can be directly obtained by using methyltrifluoromethanesulfonate, methyltrifluoroacetate, or the like as the acid ester.
中和法は、反応式(12)に示すような反応によって行われる方法である。3級アミンとCF3COOH,CF3SO3H,(CF3SO2)2NH、(CF3SO2)3CH、(C2F5SO2)2NHなどの有機酸とを反応させることにより得ることができる。
The neutralization method is a method performed by the reaction shown in the reaction formula (12). Tertiary amine and CF 3 COOH, CF 3 SO 3 H, is reacted (CF 3 SO 2) 2 NH , (CF 3 SO 2) 3 CH, and organic acids such as (C 2 F 5 SO 2) 2 NH Can be obtained.
上記の反応式(1)~(12)に記載のRは、水素または炭素数1から20の炭化水素基を表し、ヘテロ原子を含んでいてもよい。
R in the above reaction formulas (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms and may contain a hetero atom.
イオン伝導ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切なイオン伝導ポリマーを採用し得る。このようなイオン伝導ポリマーとしては、例えば、4級アンモニウム塩基)を有するモノマーを重合もしくは共重合して得られたイオン導電性重合体;ポリチオフェン、ポリアニリン、ポリピロール、ポリエチレンイミン、アリルアミン系重合体等の導電性ポリマー;などが挙げられる。イオン伝導ポリマーは、1種のみであってもよいし、2種以上であってもよい。
As the ion conductive polymer, any appropriate ion conductive polymer can be adopted as long as the effect of the present invention is not impaired. Examples of such an ion conductive polymer include an ion conductive polymer obtained by polymerizing or copolymerizing a monomer having a quaternary ammonium salt group; polythiophene, polyaniline, polypyrrole, polyethyleneimine, allylamine-based polymer, and the like. Conductive polymer; and the like. The ion conductive polymer may be only one kind or two or more kinds.
イオン伝導フィラーとしては、本発明の効果を損なわない範囲で、任意の適切なイオン伝導フィラーを採用し得る。このようなイオン伝導フィラーとしては、例えば、酸化錫、酸化アンチモン、酸化インジウム、酸化カドミウム、酸化チタン、酸化亜鉛、インジウム、錫、アンチモン、金、銀、銅、アルミニウム、ニッケル、クロム、チタン、鉄、コバルト、ヨウ化銅、ITO(酸化インジウム/酸化錫)、ATO(酸化アンチモン/酸化錫)などが挙げられる。イオン伝導フィラーは、1種のみであってもよいし、2種以上であってもよい。
As the ion conductive filler, any appropriate ion conductive filler can be adopted as long as the effect of the present invention is not impaired. Examples of such an ion conductive filler include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium and iron. , Cobalt, copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide) and the like. The ion conductive filler may be only one kind or two or more kinds.
電気伝導ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な電気伝導ポリマーを採用し得る。このような電気伝導ポリマーとしては、例えば、(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホン酸)などが挙げられる。
As the electrically conductive polymer, any appropriate electrically conductive polymer can be adopted as long as the effect of the present invention is not impaired. Examples of such an electrically conductive polymer include (3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid).
<1-2-6.他の成分>
粘着剤層(1)の材料となる粘着剤組成物(アクリル系粘着剤組成物、ウレタン系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物からなる群から選ばれる少なくとも1種)は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、他のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど)、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤(顔料や染料など)、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 <1-2-6. Other ingredients>
A pressure-sensitive adhesive composition as a material of the pressure-sensitive adhesive layer (1) (at least one selected from the group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, and a silicone pressure-sensitive adhesive composition). The seed) may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents. , Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), foil materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
粘着剤層(1)の材料となる粘着剤組成物(アクリル系粘着剤組成物、ウレタン系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物からなる群から選ばれる少なくとも1種)は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、他のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど)、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤(顔料や染料など)、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 <1-2-6. Other ingredients>
A pressure-sensitive adhesive composition as a material of the pressure-sensitive adhesive layer (1) (at least one selected from the group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, and a silicone pressure-sensitive adhesive composition). The seed) may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents. , Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), foil materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
≪1-3.樹脂フィルム(2)≫
樹脂フィルム(2)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、本発明の効果をより発現させ得る点で、好ましくは25μm~500μmであり、より好ましくは25μm~400μmであり、さらに好ましくは25μm~300μmであり、特に好ましくは25μm~200μmであり、最も好ましくは25μm~150μmである。 <<1-3. Resin film (2)>>
As the thickness of the resin film (2), any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired. Such a thickness is preferably 25 μm to 500 μm, more preferably 25 μm to 400 μm, further preferably 25 μm to 300 μm, and particularly preferably 25 μm to the point that the effect of the present invention can be further exhibited. It is 200 μm, and most preferably 25 μm to 150 μm.
樹脂フィルム(2)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、本発明の効果をより発現させ得る点で、好ましくは25μm~500μmであり、より好ましくは25μm~400μmであり、さらに好ましくは25μm~300μmであり、特に好ましくは25μm~200μmであり、最も好ましくは25μm~150μmである。 <<1-3. Resin film (2)>>
As the thickness of the resin film (2), any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired. Such a thickness is preferably 25 μm to 500 μm, more preferably 25 μm to 400 μm, further preferably 25 μm to 300 μm, and particularly preferably 25 μm to the point that the effect of the present invention can be further exhibited. It is 200 μm, and most preferably 25 μm to 150 μm.
樹脂フィルム(2)は、上述のように、粘着剤層(1)との積層部分が、長手方向と実質的に直交する方向に所定の長さの貫通孔によって複数に区分けされてなる。
As described above, the resin film (2) has a laminated portion with the adhesive layer (1) divided into a plurality of through holes each having a predetermined length in a direction substantially orthogonal to the longitudinal direction.
樹脂フィルム(2)は、樹脂基材フィルム(2a)を含む。
The resin film (2) includes a resin base film (2a).
樹脂基材フィルム(2a)としては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)等のポリエステル系樹脂から構成されるプラスチックフィルム;ポリエチレン(PE)、ポリプロピレン(PP)、ポリメチルペンテン(PMP)、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体(EVA)等のα-オレフィンをモノマー成分とするオレフィン系樹脂から構成されるプラスチックフィルム;ポリ塩化ビニル(PVC)から構成されるプラスチックフィルム;酢酸ビニル系樹脂から構成されるプラスチックフィルム;ポリカーボネート(PC)から構成されるプラスチックフィルム;ポリフェニレンスルフィド(PPS)から構成されるプラスチックフィルム;ポリアミド(ナイロン)、全芳香族ポリアミド(アラミド)等のアミド系樹脂から構成されるプラスチックフィルム;ポリイミド系樹脂から構成されるプラスチックフィルム;ポリエーテルエーテルケトン(PEEK)から構成されるプラスチックフィルム;ポリエチレン(PE)、ポリプロピレン(PP)等のオレフィン系樹脂から構成されるプラスチックフィルム;ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン-フッ化ビニリデン共重合体などのフッ素系樹脂などから構成されるプラスチックフィルム;などが挙げられる。
As the resin substrate film (2a), for example, a plastic film composed of a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyethylene (PE), polypropylene ( PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other plastic films composed of an olefin resin containing α-olefin as a monomer component; polyvinyl chloride Plastic film composed of (PVC); plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), all Plastic film composed of amide resin such as aromatic polyamide (aramid); Plastic film composed of polyimide resin; Plastic film composed of polyetheretherketone (PEEK); Polyethylene (PE), polypropylene (PP) ) And other plastic films composed of olefinic resins; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride And a plastic film composed of a fluororesin such as a copolymer.
樹脂基材フィルム(2a)は、1層のみであってもよいし、2層以上であってもよい。樹脂基材フィルム(2a)は、延伸されたものであってもよい。
The resin base film (2a) may have only one layer or two or more layers. The resin substrate film (2a) may be stretched.
樹脂基材フィルム(2a)は、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理などが挙げられる。
The resin base film (2a) may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric bombardment exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.
樹脂基材フィルム(2a)には、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な添加剤が含まれていてもよい。
The resin substrate film (2a) may contain any appropriate additive depending on the purpose, within a range that does not impair the effects of the present invention.
樹脂フィルム(2)は、導電層(2b)を有していてもよい。導電層(2b)は、粘着剤層(1)と樹脂基材フィルム(2a)の間に配置され得る。
The resin film (2) may have a conductive layer (2b). The conductive layer (2b) may be arranged between the pressure-sensitive adhesive layer (1) and the resin base film (2a).
導電層(2b)は、1層のみであってもよいし、2層以上であってもよい。
The conductive layer (2b) may be only one layer or two or more layers.
導電層(2b)は、任意の適切な基材上に形成することによって設けることができる。このような基材としては、好ましくは、樹脂基材フィルム(2a)である。
The conductive layer (2b) can be provided by forming it on any suitable base material. Such a substrate is preferably a resin substrate film (2a).
導電層(2b)は、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法、スプレー熱分解法、化学メッキ法、電気メッキ法、あるいはこれらの組合せ法などの任意の適切な薄膜形成法により、任意の適切な基材(好ましくは、樹脂基材フィルム(2a))上に導電膜を形成する。これらの薄膜形成法の中でも、導電膜の形成速度や大面積膜の形成性、生産性などの点から、真空蒸着法やスパッタリング法が好ましい。
The conductive layer (2b) is formed by any suitable thin film forming method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, a chemical plating method, an electroplating method, or a combination thereof. The conductive film is formed on any suitable substrate (preferably, the resin substrate film (2a)). Among these thin film forming methods, the vacuum deposition method and the sputtering method are preferable from the viewpoints of the formation speed of the conductive film, the formability of a large-area film, the productivity, and the like.
導電膜を形成するための材料としては、例えば、金、銀、白金、パラジウム、銅、アルミニウム、ニッケル、クロム、チタン、鉄、コバルト、錫、これらの合金等からなる金属系材料;酸化インジウム、酸化スズ、酸化チタン、酸化カドミウム、これらの混合物等からなる金属酸化物系材料;ヨウ化銅等からなる他の金属化合物;などが用いられる。
As the material for forming the conductive film, for example, metal-based materials such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, alloys thereof; indium oxide, A metal oxide-based material composed of tin oxide, titanium oxide, cadmium oxide, a mixture thereof, or the like; another metal compound composed of copper iodide or the like is used.
導電層(2b)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、例えば、金属系材料から形成される場合、好ましくは30Å~600Åであり、金属酸化物系材料から形成される場合、好ましくは80Å~5000Åである。
As the thickness of the conductive layer (2b), any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. Such a thickness is, for example, preferably 30 Å to 600 Å when formed of a metal-based material, and preferably 80 Å to 5000 Å when formed of a metal oxide-based material.
導電層(2b)の表面抵抗値は、好ましくは1.0×1010Ω/□以下であり、より好ましくは1.0×109Ω/□以下であり、さらに好ましくは1.0×108Ω/□以下であり、特に好ましくは1.0×107Ω/□以下である。
The surface resistance value of the conductive layer (2b) is preferably 1.0×10 10 Ω/□ or less, more preferably 1.0×10 9 Ω/□ or less, further preferably 1.0×10 9. It is 8 Ω/□ or less, and particularly preferably 1.0×10 7 Ω/□ or less.
導電膜を任意の適切な基材(好ましくは、樹脂基材フィルム(2a))上に形成する際には、該基材(好ましくは、樹脂基材フィルム(2a))の表面に、コロナ放電処理、紫外線照射処理、プラズマ処理、スパッタエッチング処理、アンダーコート処理等の、任意の適切な前処理を施して、導電膜と該基材(好ましくは、樹脂基材フィルム(2a))の密着性を高めることもできる。
When the conductive film is formed on any suitable substrate (preferably the resin substrate film (2a)), the corona discharge is formed on the surface of the substrate (preferably the resin substrate film (2a)). Adhesion between the conductive film and the substrate (preferably the resin substrate film (2a)) after any suitable pretreatment such as treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, and undercoat treatment. Can also be increased.
樹脂フィルム(2)は、帯電防止層(2c)を有していてもよい。帯電防止層(2c)は、粘着剤層(1)と樹脂基材フィルム(2a)の間、および/または、樹脂基材フィルム(2a)と粘着剤層(2)の間に配置され得る。
The resin film (2) may have an antistatic layer (2c). The antistatic layer (2c) may be arranged between the pressure-sensitive adhesive layer (1) and the resin base film (2a) and/or between the resin base film (2a) and the pressure-sensitive adhesive layer (2).
帯電防止層(2c)は、1層のみであってもよいし、2層以上であってもよい。
The antistatic layer (2c) may be a single layer or two or more layers.
帯電防止層(2c)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは1nm~1000nmであり、より好ましくは5nm~900nmであり、さらに好ましくは7.5nm~800nmであり、特に好ましくは10nm~700nmである。
As the thickness of the antistatic layer (2c), any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
帯電防止層(2c)の表面抵抗値は、好ましくは1.0×1010Ω/□以下であり、より好ましくは8.0×109Ω/□以下であり、さらに好ましくは5.0×109Ω/□以下であり、特に好ましくは1.0×109Ω/□以下である。
The surface resistance value of the antistatic layer (2c) is preferably 1.0×10 10 Ω/□ or less, more preferably 8.0×10 9 Ω/□ or less, further preferably 5.0×. It is 10 9 Ω/□ or less, and particularly preferably 1.0×10 9 Ω/□ or less.
帯電防止層(2c)としては、帯電防止効果を奏することができる層であれば、本発明の効果を損なわない範囲で、任意の適切な帯電防止層を採用し得る。このような帯電防止層としては、好ましくは、導電性ポリマーを含む導電コート液を任意の適切な基材層上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液を樹脂基材フィルム(2a)上にコーティングして形成される帯電防止層である。コーティング後は、必要に応じて乾燥させ、必要に応じて硬化処理(熱処理、紫外線処理など)を行う。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。
As the antistatic layer (2c), any appropriate antistatic layer can be adopted as long as it can exhibit an antistatic effect as long as the effect of the present invention is not impaired. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the resin substrate film (2a). After coating, it is dried if necessary and a curing treatment (heat treatment, ultraviolet treatment, etc.) is performed if necessary. Specific coating methods include a roll coating method, a bar coating method and a gravure coating method.
導電性ポリマーを含む導電コート液としては、本発明の効果を損なわない範囲で、任意の適切な導電コート液を採用し得る。このような導電コート液は、好ましくは、導電性ポリマーとバインダと架橋剤と溶剤を含む。この溶剤は、帯電防止層(2c)を形成する過程で加熱等によって揮発や蒸発等により実質的になくなるので、帯電防止層(2c)は、好ましくは、導電性ポリマーとバインダと架橋剤を含む。
As the conductive coating liquid containing a conductive polymer, any appropriate conductive coating liquid can be adopted as long as the effect of the present invention is not impaired. Such a conductive coating liquid preferably contains a conductive polymer, a binder, a crosslinking agent and a solvent. The solvent is substantially removed by volatilization, evaporation, etc. due to heating in the process of forming the antistatic layer (2c). Therefore, the antistatic layer (2c) preferably contains a conductive polymer, a binder and a crosslinking agent. ..
溶剤としては、例えば、有機溶剤、水、またはこれらの混合溶媒が挙げられる。有機溶剤としては、例えば、酢酸エチル等のエステル類;メチルエチルケトン、アセトン、シクロヘキサノン等のケトン類;テトラヒドロフラン(THF)、ジオキサン等の環状エーテル類;n-ヘキサン、シクロヘキサン等の脂肪族または脂環族炭化水素類;トルエン、キシレン等の芳香族炭化水素類;メタノール、エタノール、n-プロパノール、イソプロパノール、シクロヘキサノール等の脂肪族または脂環族アルコール類;アルキレングリコールモノアルキルエーテル(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル)、ジアルキレングリコールモノアルキルエーテル等のグリコールエーテル類;などが挙げられる。溶剤として、好ましくは、水または水を主成分とする混合溶媒(例えば、水とエタノールとの混合溶媒)である。
Examples of the solvent include organic solvents, water, and mixed solvents thereof. Examples of the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic carbonization such as n-hexane and cyclohexane. Hydrogen; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; alkylene glycol monoalkyl ethers (eg ethylene glycol monomethyl ether, Glycol ethers such as ethylene glycol monoethyl ether) and dialkylene glycol monoalkyl ether; and the like. The solvent is preferably water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
帯電防止層(2c)中の導電性ポリマーの含有割合は、好ましくは3重量%~80重量%であり、より好ましくは5重量%~60重量%である。
The content ratio of the conductive polymer in the antistatic layer (2c) is preferably 3% by weight to 80% by weight, more preferably 5% by weight to 60% by weight.
導電性ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な導電性ポリマーを採用し得る。このような導電性ポリマーとしては、例えば、π共役系導電性ポリマーにポリアニオンがドープされた導電性ポリマーなどが挙げられる。π共役系導電性ポリマーとしては、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレンなどの鎖状導電性ポリマーが挙げられる。ポリアニオンとしては、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリメタクリルカルボン酸などが挙げられる。
As the conductive polymer, any appropriate conductive polymer can be adopted as long as the effect of the present invention is not impaired. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacryl carboxylic acid.
導電性ポリマーは、1種のみであってもよいし、2種以上であってもよい。
The conductive polymer may be only one kind or two or more kinds.
帯電防止層(2c)中のバインダの含有割合は、好ましくは50重量%~95重量%であり、より好ましくは60重量%~90重量%である。
The content ratio of the binder in the antistatic layer (2c) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 90% by weight.
導電コート液に含まれ得るバインダとしては、本発明の効果を損なわない範囲で、任意の適切なバインダを採用し得る。バインダは、1種のみであってもよいし、2種以上であってもよい。このようなバインダとしては、好ましくは、樹脂であり、より好ましくは、ポリエステル樹脂である。バインダに占めるポリエステル樹脂の割合は、好ましくは90重量%~100重量%であり、より好ましくは98重量%~100重量%である。
As the binder that can be contained in the conductive coating liquid, any appropriate binder can be adopted as long as the effect of the present invention is not impaired. The binder may be only one type or two or more types. As such a binder, a resin is preferable, and a polyester resin is more preferable. The proportion of the polyester resin in the binder is preferably 90% by weight to 100% by weight, more preferably 98% by weight to 100% by weight.
ポリエステル樹脂は、ポリエステルを主成分(好ましくは50重量%を超え、より好ましくは75重量%以上であり、さらに好ましくは90重量%以上であり、特に好ましくは実質的に100重量%を占める成分)として含むことが好ましい。
The polyester resin contains polyester as a main component (preferably more than 50% by weight, more preferably 75% by weight or more, further preferably 90% by weight or more, particularly preferably substantially 100% by weight). It is preferable to include as.
ポリエステルとしては、本発明の効果を損なわない範囲で、任意の適切なポリエステルを採用し得る。このようなポリエステルとしては、好ましくは、1分子中に2個以上のカルボキシル基を有する多価カルボン酸(例えば、ジカルボン酸化合物)およびその誘導体(例えば、多価カルボン酸の無水物、エステル化物、ハロゲン化物等)から選択される1種または2種以上の化合物(多価カルボン酸成分)と、1分子中に2個以上の水酸基を有する多価アルコール(例えば、ジオール)から選択される1種または2種以上の化合物(多価アルコール成分)とが縮合した構造を有することが好ましい。
As the polyester, any appropriate polyester can be adopted as long as the effect of the present invention is not impaired. Such a polyester is preferably a polyvalent carboxylic acid having two or more carboxyl groups in one molecule (for example, a dicarboxylic acid compound) and a derivative thereof (for example, an anhydride or an esterified product of the polyvalent carboxylic acid). One or two or more compounds (polyvalent carboxylic acid component) selected from halides and the like, and one selected from a polyhydric alcohol (eg, diol) having two or more hydroxyl groups in one molecule. Alternatively, it preferably has a structure in which two or more compounds (polyhydric alcohol components) are condensed.
多価カルボン酸成分としては、本発明の効果を損なわない範囲で、任意の適切な多価カルボン酸を採用し得る。このような多価カルボン酸成分としては、例えば、シュウ酸、マロン酸、ジフルオロマロン酸、アルキルマロン酸、コハク酸、テトラフルオロコハク酸、アルキルコハク酸、(±)-リンゴ酸、meso-酒石酸、イタコン酸、マレイン酸、メチルマレイン酸、フマル酸、メチルフマル酸、アセチレンジカルボン酸、グルタル酸、ヘキサフルオログルタル酸、メチルグルタル酸、グルタコン酸、アジピン酸、ジチオアジピン酸、メチルアジピン酸、ジメチルアジピン酸、テトラメチルアジピン酸、メチレンアジピン酸、ムコン酸、ガラクタル酸、ピメリン酸、スベリン酸、パーフルオロスベリン酸、3,3,6,6-テトラメチルスベリン酸、アゼライン酸、セバシン酸、パーフルオロセバシン酸、ブラシル酸、ドデシルジカルボン酸、トリデシルジカルボン酸、テトラデシルジカルボン酸などの脂肪族ジカルボン酸類;シクロアルキルジカルボン酸(例えば、1,4-シクロヘキサンジカルボン酸、1,2-シクロヘキサンジカルボン酸)、1,4-(2-ノルボルネン)ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸(ハイミック酸)、アダマンタンジカルボン酸、スピロヘプタンジカルボン酸などの脂環式ジカルボン酸類;フタル酸、イソフタル酸、ジチオイソフタル酸、メチルイソフタル酸、ジメチルイソフタル酸、クロロイソフタル酸、ジクロロイソフタル酸、テレフタル酸、メチルテレフタル酸、ジメチルテレフタル酸、クロロテレフタル酸、ブロモテレフタル酸、ナフタレンジカルボン酸、オキソフルオレンジカルボン酸、アントラセンジカルボン酸、ビフェニルジカルボン酸、ビフェニレンジカルボン酸、ジメチルビフェニレンジカルボン酸、4,4”-p-テレフェニレンジカルボン酸、4,4”-p-クワレルフェニルジカルボン酸、ビベンジルジカルボン酸、アゾベンゼンジカルボン酸、ホモフタル酸、フェニレン二酢酸、フェニレンジプロピオン酸、ナフタレンジカルボン酸、ナフタレンジプロピオン酸、ビフェニル二酢酸、ビフェニルジプロピオン酸、3,3'-[4,4’-(メチレンジ-p-ビフェニレン)]ジプロピオン酸、4,4’-ビベンジル二酢酸、3,3’-[(4,4’-ビベンジル)]ジプロピオン酸、オキシジ-p-フェニレン二酢酸などの芳香族ジカルボン酸類;上記のいずれかの多価カルボン酸の酸無水物;上記のいずれかの多価カルボン酸のエステル(例えば、アルキルエステル。モノエステル、ジエステル等);上記のいずれかの多価カルボン酸に対応する酸ハロゲン化物(例えば、ジカルボン酸クロリド);などが挙げられる。
As the polyvalent carboxylic acid component, any suitable polyvalent carboxylic acid can be adopted as long as the effect of the present invention is not impaired. Examples of such polycarboxylic acid components include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±)-malic acid, meso-tartaric acid, Itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipic acid, Tetramethyl adipic acid, methylene adipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid, perfluorosebacic acid, Aliphatic dicarboxylic acids such as brassic acid, dodecyldicarboxylic acid, tridecyldicarboxylic acid, and tetradecyldicarboxylic acid; cycloalkyldicarboxylic acids (eg, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1,4 Alicyclic dicarboxylic acids such as -(2-norbornene)dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid (hymic acid), adamantanedicarboxylic acid, spiroheptanedicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalic acid, Methyl isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methylterephthalic acid, dimethylterephthalic acid, chloroterephthalic acid, bromoterephthalic acid, naphthalenedicarboxylic acid, oxofluorangecarboxylic acid, anthracenedicarboxylic acid, biphenyldicarboxylic acid Acid, biphenylenedicarboxylic acid, dimethylbiphenylenedicarboxylic acid, 4,4"-p-terephenylenedicarboxylic acid, 4,4"-p-quarrelphenyldicarboxylic acid, bibenzyldicarboxylic acid, azobenzenedicarboxylic acid, homophthalic acid, phenylene di Acetic acid, phenylenedipropionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyldiacetic acid, biphenyldipropionic acid, 3,3′-[4,4′-(methylenedi-p-biphenylene)]dipropionic acid, 4, Aromatic dicarboxylic acids such as 4′-bibenzyldiacetic acid, 3,3′-[(4,4′-bibenzyl)]dipropionic acid, oxydi-p-phenylenediacetic acid; Acid anhydrides; esters of any of the above polycarboxylic acids (eg, For example, alkyl ester. Monoesters, diesters, etc.); acid halides corresponding to any of the above polycarboxylic acids (eg, dicarboxylic acid chloride); and the like.
多価カルボン酸成分としては、好ましくは、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸類およびその酸無水物;アジピン酸、セバシン酸、アゼライン酸、コハク酸、フマル酸、マレイン酸、ハイミック酸、1,4-シクロヘキサンジカルボン酸等の脂肪族ジカルボン酸類およびその酸無水物;これらのジカルボン酸類の低級アルキルエステル(例えば、炭素原子数1~3のモノアルコールとのエステル);などが挙げられる。
As the polycarboxylic acid component, preferably, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Alimic dicarboxylic acids such as hymic acid and 1,4-cyclohexanedicarboxylic acid and their acid anhydrides; lower alkyl esters of these dicarboxylic acids (eg, esters with monoalcohols having 1 to 3 carbon atoms); To be
多価アルコール成分としては、本発明の効果を損なわない範囲で、任意の適切な多価アルコールを採用し得る。このような多価アルコール成分としては、例えば、エチレングリコール、プロピレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチルペンタンジオール、ジエチレングリコール、1,4-シクロヘキサンジメタノール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、キシリレングリコール、水添ビスフェノールA、ビスフェノールA等のジオール類;これらのジオール類のアルキレンオキサイド付加物(例えば、エチレンオキサイド付加物、プロピレンオキサイド付加物等);などが挙げられる。
As the polyhydric alcohol component, any appropriate polyhydric alcohol can be adopted as long as the effect of the present invention is not impaired. Examples of such polyhydric alcohol components include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propane Diols such as diol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, bisphenol A; these diols Alkylene oxide adduct (for example, ethylene oxide adduct, propylene oxide adduct, etc.);
ポリエステル樹脂の分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される標準ポリスチレン換算の重量平均分子量(Mw)として、好ましくは5×103~1.5×105であり、より好ましくは1×104~6×104である。
The molecular weight of the polyester resin is preferably 5×10 3 to 1.5×10 5 , and more preferably 1 as the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). ×10 4 to 6×10 4 .
ポリエステル樹脂のガラス転移温度(Tg)は、好ましくは0℃~120℃であり、より好ましくは10℃~80℃である。
The glass transition temperature (Tg) of the polyester resin is preferably 0°C to 120°C, more preferably 10°C to 80°C.
ポリエステル樹脂としては、例えば、市販の東洋紡社製の商品名「バイロナール」などを用いることができる。
As the polyester resin, for example, commercially available Toyobo Co., Ltd. product name “Bironard” can be used.
導電コート液は、本発明の効果を損なわない範囲で、バインダとして、ポリエステル樹脂以外の樹脂(例えば、アクリル樹脂、アクリルウレタン樹脂、アクリルスチレン樹脂、アクリルシリコーン樹脂、シリコーン樹脂、ポリシラザン樹脂、ポリウレタン樹脂、フッ素樹脂、ポリオレフィン樹脂から選択される少なくとも1種の樹脂)をさらに含有し得る。
The conductive coating liquid, as long as the effect of the present invention is not impaired, as a binder, a resin other than polyester resin (for example, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, silicone resin, polysilazane resin, polyurethane resin, It may further contain at least one resin selected from a fluororesin and a polyolefin resin.
導電コート液に含まれ得る架橋剤としては、本発明の効果を損なわない範囲で、任意の適切な架橋剤を採用し得る。架橋剤は、1種のみであってもよいし、2種以上であってもよい。このような架橋剤としては、好ましくは、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などが挙げられる。なかでも好ましくは、メラミン系架橋剤である。
As the cross-linking agent that can be contained in the conductive coating liquid, any appropriate cross-linking agent can be adopted as long as the effect of the present invention is not impaired. The cross-linking agent may be only one kind or two or more kinds. As such a crosslinking agent, preferably an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent. Agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, amine-based crosslinking agents and the like. Of these, a melamine-based cross-linking agent is preferable.
帯電防止層(2c)中の架橋剤の含有割合は、好ましくは1重量%~30重量%であり、より好ましくは2重量%~20重量%である。
The content ratio of the crosslinking agent in the antistatic layer (2c) is preferably 1% by weight to 30% by weight, more preferably 2% by weight to 20% by weight.
帯電防止層(2c)中には、本発明の効果を損なわない範囲で、任意の適切な他の成分が含まれていてもよい。
The antistatic layer (2c) may contain any appropriate other component as long as the effect of the present invention is not impaired.
≪1-4.粘着剤層(2)≫
粘着剤層(2)は、本発明の効果を損なわない範囲で、任意の適切な粘着剤層を採用し得る。粘着剤層(2)は、1層のみであってもよいし、2層以上であってもよい。 << 1-4. Adhesive layer (2)>>
As the pressure-sensitive adhesive layer (2), any appropriate pressure-sensitive adhesive layer can be adopted as long as the effect of the present invention is not impaired. The pressure-sensitive adhesive layer (2) may be only one layer or may be two or more layers.
粘着剤層(2)は、本発明の効果を損なわない範囲で、任意の適切な粘着剤層を採用し得る。粘着剤層(2)は、1層のみであってもよいし、2層以上であってもよい。 << 1-4. Adhesive layer (2)>>
As the pressure-sensitive adhesive layer (2), any appropriate pressure-sensitive adhesive layer can be adopted as long as the effect of the present invention is not impaired. The pressure-sensitive adhesive layer (2) may be only one layer or may be two or more layers.
粘着剤層(2)の厚みは、本発明の効果をより発現させ得る点で、好ましくは0.5μm~150μmであり、より好ましくは1μm~100μmであり、さらに好ましくは2μm~80μmであり、特に好ましくは3μm~50μmであり、最も好ましくは5μm~30μmである。
The thickness of the pressure-sensitive adhesive layer (2) is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, and further preferably 2 μm to 80 μm, from the viewpoint that the effect of the present invention can be further exhibited. Particularly preferred is 3 μm to 50 μm, and most preferred is 5 μm to 30 μm.
粘着剤層(2)は、任意の適切な方法によって形成し得る。このような方法としては、例えば、粘着剤層(2)を構成する粘着剤を形成する粘着剤組成物を任意の適切な基材(例えば、樹脂フィルム(3))上に塗布し、必要に応じて加熱・乾燥を行い、必要に応じて硬化させて、該基材上において粘着剤層を形成する方法が挙げられる。このような塗布の方法としては、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、エアーナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーター、ロールブラッシュコーターなどの方法が挙げられる。
The adhesive layer (2) can be formed by any appropriate method. As such a method, for example, a pressure-sensitive adhesive composition that forms a pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (2) is applied onto any appropriate base material (for example, the resin film (3)), Examples include a method of forming a pressure-sensitive adhesive layer on the substrate by heating and drying according to need, and curing if necessary. Examples of such a coating method include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater and a roll brush coater. The method of is mentioned.
<1-4-1.アクリル系粘着剤>
粘着剤層(2)は、好ましくは、アクリル系粘着剤から構成される。 <1-4-1. Acrylic adhesive>
The pressure-sensitive adhesive layer (2) is preferably composed of an acrylic pressure-sensitive adhesive.
粘着剤層(2)は、好ましくは、アクリル系粘着剤から構成される。 <1-4-1. Acrylic adhesive>
The pressure-sensitive adhesive layer (2) is preferably composed of an acrylic pressure-sensitive adhesive.
アクリル系粘着剤は、アクリル系粘着剤組成物から形成される。
The acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
アクリル系粘着剤組成物は、本発明の効果をより発現させ得る点で、好ましくは、アクリル系ポリマーと架橋剤を含む。
The acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a crosslinking agent from the viewpoint that the effects of the present invention can be more exhibited.
アクリル系ポリマーは、アクリル系粘着剤の分野においていわゆるベースポリマーと称され得るものである。アクリル系ポリマーは、1種のみであってもよいし、2種以上であってもよい。
The acrylic polymer can be called a so-called base polymer in the field of acrylic pressure-sensitive adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.
アクリル系粘着剤組成物中のアクリル系ポリマーの含有割合は、固形分換算で、好ましくは60重量%~99.9重量%であり、より好ましくは65重量%~99.9重量%であり、さらに好ましくは70重量%~99.9重量%であり、特に好ましくは75重量%~99.9重量%であり、最も好ましくは80重量%~99.9重量%である。
The content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 60% by weight to 99.9% by weight, and more preferably 65% by weight to 99.9% by weight, in terms of solid content. It is more preferably 70% to 99.9% by weight, particularly preferably 75% to 99.9% by weight, and most preferably 80% to 99.9% by weight.
アクリル系ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切なアクリル系ポリマーを採用し得る。
As the acrylic polymer, any suitable acrylic polymer can be adopted as long as the effect of the present invention is not impaired.
アクリル系ポリマーの重量平均分子量は、本発明の効果をより発現させ得る点で、好ましくは30万~250万であり、より好ましくは35万~200万であり、さらに好ましくは40万~180万であり、特に好ましくは50万~150万である。
The weight average molecular weight of the acrylic polymer is preferably 300,000 to 2,500,000, more preferably 350,000 to 2,000,000, and further preferably 400,000 to 1800,000, from the viewpoint that the effects of the present invention can be further exhibited. And particularly preferably 500,000 to 1,500,000.
アクリル系ポリマーとしては、本発明の効果をより発現させ得る点で、好ましくは、(a成分)アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステル、(b成分)OH基を有する(メタ)アクリル酸エステルおよび(メタ)アクリル酸からなる群から選ばれる少なくとも1種、を含む組成物(B)から重合によって形成されるアクリル系ポリマーである。(a成分)、(b成分)は、それぞれ、独立に、1種のみであってもよいし、2種以上であってもよい。
The acrylic polymer is preferably a (meth)acrylic acid alkyl ester in which the alkyl group of the (a component) alkyl ester moiety has 4 to 12 carbon atoms from the viewpoint that the effect of the present invention can be further exhibited, and (b) It is an acrylic polymer formed by polymerization from a composition (B) containing (component) at least one selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid. The (a component) and the (b component) may each independently be only one kind or two or more kinds.
アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステル(a成分)としては、例えば、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシルなどが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸2-エチルヘキシルであり、より好ましくは、アクリル酸n-ブチル、アクリル酸2-エチルヘキシルである。
Examples of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include, for example, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate. S-Butyl acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate And so on. Among these, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable, and n-butyl acrylate and acryl are more preferable, from the viewpoint that the effects of the present invention can be further exhibited. It is 2-ethylhexyl acid.
OH基を有する(メタ)アクリル酸エステルおよび(メタ)アクリル酸からなる群から選ばれる少なくとも1種(b成分)としては、例えば、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシブチルなどのOH基を有する(メタ)アクリル酸エステル、(メタ)アクリル酸などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸であり、より好ましくは、アクリル酸ヒドロキシエチル、アクリル酸である。
Examples of at least one component (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples thereof include (meth)acrylic acid ester having an OH group such as hydroxybutyl (meth)acrylate and (meth)acrylic acid. Among these, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, from the viewpoint that the effects of the present invention can be further exhibited.
組成物(B)は、(a)成分および(b)成分以外の、共重合性モノマーを含んでいてもよい。共重合性モノマーは、1種のみであってもよいし、2種以上であってもよい。このような共重合性モノマーとしては、例えば、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸、これらの酸無水物(例えば、無水マレイン酸、無水イタコン酸などの酸無水物基含有モノマー)などのカルボキシル基含有モノマー(ただし、(メタ)アクリル酸を除く);(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-ヒドロキシエチル(メタ)アクリルアミドなどのアミド基含有モノマー;(メタ)アクリル酸アミノエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチルなどのアミノ基含有モノマー;(メタ)アクリル酸グリシジル、(メタ)アクリル酸メチルグリシジルなどのエポキシ基含有モノマー;アクリロニトリルやメタクリロニトリルなどのシアノ基含有モノマー;N-ビニル-2-ピロリドン、(メタ)アクリロイルモルホリン、N-ビニルピペリドン、N-ビニルピペラジン、N-ビニルピロール、N-ビニルイミダゾール、ビニルピリジン、ビニルピリミジン、ビニルオキサゾールなどの複素環含有ビニル系モノマー;ビニルスルホン酸ナトリウムなどのスルホン酸基含有モノマー;2-ヒドロキシエチルアクリロイルフォスフェートなどのリン酸基含有モノマー;シクロヘキシルマレイミド、イソプロピルマレイミドなどのイミド基含有モノマー;2-メタクリロイルオキシエチルイソシアネートなどのイソシアネート基含有モノマー;シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等の脂環式炭化水素基を有する(メタ)アクリル酸エステル;フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレートなどの芳香族炭化水素基を有する(メタ)アクリル酸エステル;酢酸ビニル、プロピオン酸ビニルなどのビニルエステル;スチレン、ビニルトルエンなどの芳香族ビニル化合物;エチレン、ブタジエン、イソプレン、イソブチレンなどのオレフィン類やジエン類;ビニルアルキルエーテルなどのビニルエーテル類;塩化ビニル;などが挙げられる。
The composition (B) may contain a copolymerizable monomer other than the components (a) and (b). The copolymerizable monomer may be only one type, or may be two or more types. Such copolymerizable monomers include, for example, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). ) And other carboxyl group-containing monomers (excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide , N-butoxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and other amide group-containing monomers; aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, t-butyl (meth)acrylate Amino group-containing monomers such as aminoethyl; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, Heterocycle-containing vinyl monomers such as (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole; sulfonic acids such as sodium vinylsulfonate Group-containing monomer; phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate; imide group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomer such as 2-methacryloyloxyethylisocyanate; cyclopentyl (meth)acrylate, (Meth)acrylic acid ester having an alicyclic hydrocarbon group such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; aromatic such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate and benzyl (meth)acrylate (Meth)acrylic ester having a hydrocarbon group; vinyl ester such as vinyl acetate and vinyl propionate; aromatic vinyl compound such as styrene and vinyltoluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl Vinyl ethers such as alkyl ethers; vinyl chloride; and the like.
共重合性モノマーとしては、多官能性モノマーも採用し得る。多官能性モノマーとは、1分子中に2以上のエチレン性不飽和基を有するモノマーをいう。エチレン性不飽和基としては、本発明の効果を損なわない範囲で、任意の適切なエチレン性不飽和基を採用し得る。このようなエチレン性不飽和基としては、例えば、ビニル基、プロペニル基、イソプロペニル基、ビニルエーテル基(ビニルオキシ基)、アリルエーテル基(アリルオキシ基)などのラジカル重合性官能基が挙げられる。多官能性モノマーとしては、例えば、ヘキサンジオールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、(ポリ)エチレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどが挙げられる。このような多官能性モノマーは、1種のみであってもよいし、2種以上であってもよい。
As the copolymerizable monomer, a polyfunctional monomer can also be adopted. The polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any appropriate ethylenically unsaturated group can be adopted as long as the effects of the present invention are not impaired. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol. Di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl Examples thereof include (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate and urethane acrylate. Only one kind of such a polyfunctional monomer may be used, or two or more kinds thereof may be used.
共重合性モノマーとしては、(メタ)アクリル酸アルコキシアルキルエステルも採用し得る。(メタ)アクリル酸アルコキシアルキルエステルとしては、例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸メトキシトリエチレングリコール、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸3-エトキシプロピル、(メタ)アクリル酸4-メトキシブチル、(メタ)アクリル酸4-エトキシブチルなどが挙げられる。(メタ)アクリル酸アルコキシアルキルエステルは、1種のみであってもよいし、2種以上であってもよい。
As a copolymerizable monomer, (meth)acrylic acid alkoxyalkyl ester can also be adopted. Examples of the (meth)acrylic acid alkoxyalkyl ester include 2-(meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, and (meth)acrylic acid 3-methacrylate. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate. The (meth)acrylic acid alkoxyalkyl ester may be only one kind, or may be two or more kinds.
アルキルエステル部分のアルキル基の炭素数が4~12である(メタ)アクリル酸アルキルエステル(a成分)の含有量は、本発明の効果をより発現させ得る点で、アクリル系ポリマーを構成するモノマー成分全量(100重量%)に対して、好ましくは30重量%以上であり、より好ましくは35重量%~99重量%であり、さらに好ましくは40重量%~98重量%であり、特に好ましくは50重量%~95重量%である。
The content of the (meth)acrylic acid alkyl ester (a component) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer that constitutes the acrylic polymer in that the effects of the present invention can be further exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, further preferably 40% by weight to 98% by weight, particularly preferably 50% by weight based on the total amount of the components (100% by weight). % By weight to 95% by weight.
OH基を有する(メタ)アクリル酸エステルおよび(メタ)アクリル酸からなる群から選ばれる少なくとも1種(b成分)の含有量は、本発明の効果をより発現させ得る点で、アクリル系ポリマーを構成するモノマー成分全量(100重量%)に対して、好ましくは1重量%以上であり、より好ましくは1重量%~30重量%であり、さらに好ましくは2重量%~20重量%であり、特に好ましくは3重量%~10重量%である。
The content of at least one kind (component (b)) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is such that the acrylic polymer is added in that the effect of the present invention can be further exhibited. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, further preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 10% by weight.
組成物(B)は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、重合開始剤、連鎖移動剤、溶剤などが挙げられる。これらの他の成分の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。
The composition (B) may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent. As the content of these other components, any appropriate content can be adopted as long as the effect of the present invention is not impaired.
重合開始剤は、重合反応の種類に応じて、熱重合開始剤や光重合開始剤(光開始剤)などを採用し得る。重合開始剤は、1種のみであってもよいし、2種以上であってもよい。
As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator (photoinitiator) or the like can be adopted depending on the type of the polymerization reaction. The polymerization initiator may be only one type, or may be two or more types.
熱重合開始剤は、好ましくは、アクリル系ポリマーを溶液重合によって得る際に採用され得る。このような熱重合開始剤としては、例えば、アゾ系重合開始剤、過酸化物系重合開始剤(例えば、ジベンゾイルペルオキシド、tert-ブチルペルマレエートなど)、レドックス系重合開始剤などが挙げられる。これらの熱重合開始剤の中でも、特開2002-69411号公報に開示されたアゾ系開始剤が特に好ましい。このようなアゾ系重合開始剤は、重合開始剤の分解物が加熱発生ガス(アウトガス)の発生原因となる部分としてアクリル系ポリマー中に残留しにくい点で好ましい。アゾ系重合開始剤としては、2,2’-アゾビスイソブチロニトリル(以下、AIBNと称する場合がある)、2,2’-アゾビス-2-メチルブチロニトリル(以下、AMBNと称する場合がある)、2,2’-アゾビス(2-メチルプロピオン酸)ジメチル、4,4’-アゾビス-4-シアノバレリアン酸などが挙げられる。
The thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization. Examples of such thermal polymerization initiators include azo-based polymerization initiators, peroxide-based polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox-based polymerization initiators, and the like. .. Among these thermal polymerization initiators, the azo initiators disclosed in JP-A-2002-69411 are particularly preferable. Such an azo-based polymerization initiator is preferable in that the decomposed product of the polymerization initiator is unlikely to remain in the acrylic polymer as a portion causing generation of a heat-generated gas (outgas). Examples of the azo-based polymerization initiator include 2,2′-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN) and 2,2′-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN). , 2,2′-azobis(2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid and the like.
光重合開始剤は、好ましくは、アクリル系ポリマーを活性エネルギー線重合によって得る際に採用され得る。光重合開始剤としては、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α-ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤等などが挙げられる。
The photopolymerization initiator can be preferably used when the acrylic polymer is obtained by active energy ray polymerization. Examples of the photopolymerization initiator include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime photopolymerization initiators. Agents, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like.
ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、アニソールメチルエーテルなどが挙げられる。アセトフェノン系光重合開始剤としては、例えば、2,2-ジエトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、4-フェノキシジクロロアセトフェノン、4-(t-ブチル)ジクロロアセトフェノンなどが挙げられる。α-ケトール系光重合開始剤としては、例えば、2-メチル-2-ヒドロキシプロピオフェノン、1-[4-(2-ヒドロキシエチル)フェニル]-2-メチルプロパン-1-オンなどが挙げられる。芳香族スルホニルクロリド系光重合開始剤としては、例えば、2-ナフタレンスルホニルクロライドなどが挙げられる。光活性オキシム系光重合開始剤としては、例えば、1-フェニル-1,1-プロパンジオン-2-(o-エトキシカルボニル)-オキシムなどが挙げられる。ベンゾイン系光重合開始剤としては、例えば、ベンゾインなどが挙げられる。ベンジル系光重合開始剤としては、例えば、ベンジルなどが挙げられる。ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、3,3'-ジメチル-4-メトキシベンゾフェノン、ポリビニルベンゾフェノン、α-ヒドロキシシクロヘキシルフェニルケトンなどが挙げられる。ケタール系光重合開始剤としては、例えば、ベンジルジメチルケタールなどが挙げられる。チオキサントン系光重合開始剤としては、例えば、チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジイソプロピルチオキサントン、ドデシルチオキサントンなどが挙げられる。
Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. Examples include methyl ether. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-(t-butyl). Examples thereof include dichloroacetophenone. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. .. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalene sulfonyl chloride. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzyl photopolymerization initiator include benzyl and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone, and the like. Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and dodecylthioxanthone.
アクリル系粘着剤組成物は、架橋剤を含んでいてもよい。架橋剤を用いることにより、アクリル系粘着剤の凝集力を向上でき、本発明の効果をより発現させ得る。架橋剤は、1種のみであってもよいし、2種以上であってもよい。
The acrylic pressure-sensitive adhesive composition may contain a crosslinking agent. By using the cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited. The cross-linking agent may be only one kind or two or more kinds.
架橋剤としては、多官能イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、多官能イソシアネート系架橋剤およびエポキシ系架橋剤からなる群から選ばれる少なくとも1種(c成分)である。
As the crosslinking agent, a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt. Examples thereof include a system-based crosslinking agent, a carbodiimide-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, and an amine-based crosslinking agent. Among these, at least one kind (component (c)) selected from the group consisting of a polyfunctional isocyanate cross-linking agent and an epoxy cross-linking agent is preferable from the viewpoint that the effect of the present invention can be further exhibited.
多官能イソシアネート系架橋剤としては、例えば、1,2-エチレンジイソシアネート、1,4-ブチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネートなどの低級脂肪族ポリイソシアネート類;シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネートなどの脂環族ポリイソシアネート類;2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、4,4'-ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート類などが挙げられる。多官能イソシアネート系架橋剤としては、例えば、トリメチロールプロパン/トリレンジイソシアネート付加物(日本ポリウレタン工業株式会社製、商品名「コロネートL」)、トリメチロールプロパン/ヘキサメチレンジイソシアネート付加物(日本ポリウレタン工業株式会社製、商品名「コロネートHL」)、商品名「コロネートHX」(日本ポリウレタン工業株式会社)、トリメチロールプロパン/キシリレンジイソシアネート付加物(三井化学株式会社製、商品名「タケネート110N」)などの市販品も挙げられる。
Examples of the polyfunctional isocyanate cross-linking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Aliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Aromatic polyisocyanates of Examples of the polyfunctional isocyanate cross-linking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”), trimethylolpropane/hexamethylene diisocyanate adduct (Japan Polyurethane Industry Co., Ltd. Company name, product name "Coronate HL"), product name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemicals, Inc., product name "Takenate 110N"), etc. Commercial products are also included.
エポキシ系架橋剤(多官能エポキシ化合物)としては、例えば、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン、ジグリシジルアニリン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、1,6-ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、o-フタル酸ジグリシジルエステル、トリグリシジル-トリス(2-ヒドロキシエチル)イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール-S-ジグリシジルエーテルの他、分子内にエポキシ基を2つ以上有するエポキシ系樹脂などが挙げられる。エポキシ系架橋剤としては、商品名「テトラッドC」(三菱ガス化学株式会社製)などの市販品も挙げられる。
Examples of the epoxy cross-linking agent (polyfunctional epoxy compound) include N,N,N′,N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, and 1,3-bis(N,N-diglycidylamino). Methyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, Glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2- Examples thereof include hydroxyethyl)isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. As the epoxy-based cross-linking agent, commercially available products such as trade name “Tetrad C” (manufactured by Mitsubishi Gas Chemical Co., Inc.) can also be mentioned.
アクリル系粘着剤組成物中の架橋剤の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。このような含有量としては、例えば、本発明の効果をより発現させ得る点で、アクリル系ポリマーの固形分(100重量部)に対して、好ましくは0.05重量部~20重量部であり、より好ましくは0.1重量部~18重量部であり、さらに好ましくは0.5重量部~15重量部であり、特に好ましくは0.5重量部~10重量部である。
As the content of the cross-linking agent in the acrylic pressure-sensitive adhesive composition, any appropriate content can be adopted as long as the effect of the present invention is not impaired. Such a content is, for example, preferably 0.05 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer, from the viewpoint that the effect of the present invention can be exhibited more. It is more preferably 0.1 part by weight to 18 parts by weight, further preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight.
アクリル系粘着剤組成物は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、アクリル系ポリマー以外のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど)、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤(顔料や染料など)、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。
The acrylic pressure-sensitive adhesive composition may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), Anti-aging agent, inorganic filler, organic filler, metal powder, colorant (pigment or dye, etc.), foil, UV absorber, antioxidant, light stabilizer, chain transfer agent, plasticizer, softener, Examples thereof include surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and catalysts.
<1-4-2.導電成分>
粘着剤層(2)は導電成分を含んでいてもよい。導電成分については、<1-2-5.導電成分>の項における説明をそのまま援用し得る。 <1-4-2. Conductive component>
The adhesive layer (2) may contain a conductive component. Regarding the conductive component, <1-2-5. The description in the section of conductive component> can be directly applied.
粘着剤層(2)は導電成分を含んでいてもよい。導電成分については、<1-2-5.導電成分>の項における説明をそのまま援用し得る。 <1-4-2. Conductive component>
The adhesive layer (2) may contain a conductive component. Regarding the conductive component, <1-2-5. The description in the section of conductive component> can be directly applied.
<1-4-3.他の成分>
粘着剤層(2)の材料となる粘着剤組成物(好ましくは、アクリル系粘着剤組成物)は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、他のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど)、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤(顔料や染料など)、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 <1-4-3. Other ingredients>
The pressure-sensitive adhesive composition (preferably an acrylic pressure-sensitive adhesive composition) that is a material of the pressure-sensitive adhesive layer (2) may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents. , Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), foil materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
粘着剤層(2)の材料となる粘着剤組成物(好ましくは、アクリル系粘着剤組成物)は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、他のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど)、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤(顔料や染料など)、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 <1-4-3. Other ingredients>
The pressure-sensitive adhesive composition (preferably an acrylic pressure-sensitive adhesive composition) that is a material of the pressure-sensitive adhesive layer (2) may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents. , Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), foil materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
≪1-5.樹脂フィルム(3)≫
樹脂フィルム(3)の厚みは、本発明の効果をより発現させ得る点で、好ましくは4μm~450μmであり、より好ましくは8μm~350μmであり、さらに好ましくは12μm~250μmであり、特に好ましくは16μm~150μmであり、最も好ましくは20μm~100μmである。 <<1-5. Resin film (3) >>
The thickness of the resin film (3) is preferably from 4 μm to 450 μm, more preferably from 8 μm to 350 μm, further preferably from 12 μm to 250 μm, and particularly preferably from the viewpoint that the effect of the present invention can be further exhibited. It is 16 μm to 150 μm, and most preferably 20 μm to 100 μm.
樹脂フィルム(3)の厚みは、本発明の効果をより発現させ得る点で、好ましくは4μm~450μmであり、より好ましくは8μm~350μmであり、さらに好ましくは12μm~250μmであり、特に好ましくは16μm~150μmであり、最も好ましくは20μm~100μmである。 <<1-5. Resin film (3) >>
The thickness of the resin film (3) is preferably from 4 μm to 450 μm, more preferably from 8 μm to 350 μm, further preferably from 12 μm to 250 μm, and particularly preferably from the viewpoint that the effect of the present invention can be further exhibited. It is 16 μm to 150 μm, and most preferably 20 μm to 100 μm.
樹脂フィルム(3)は、樹脂基材フィルム(3a)を含む。
The resin film (3) includes a resin base film (3a).
樹脂基材フィルム(3a)としては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)等のポリエステル系樹脂から構成されるプラスチックフィルム;ポリエチレン(PE)、ポリプロピレン(PP)、ポリメチルペンテン(PMP)、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体(EVA)等のα-オレフィンをモノマー成分とするオレフィン系樹脂から構成されるプラスチックフィルム;ポリ塩化ビニル(PVC)から構成されるプラスチックフィルム;酢酸ビニル系樹脂から構成されるプラスチックフィルム;ポリカーボネート(PC)から構成されるプラスチックフィルム;ポリフェニレンスルフィド(PPS)から構成されるプラスチックフィルム;ポリアミド(ナイロン)、全芳香族ポリアミド(アラミド)等のアミド系樹脂から構成されるプラスチックフィルム;ポリイミド系樹脂から構成されるプラスチックフィルム;ポリエーテルエーテルケトン(PEEK)から構成されるプラスチックフィルム;ポリエチレン(PE)、ポリプロピレン(PP)等のオレフィン系樹脂から構成されるプラスチックフィルム;ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン-フッ化ビニリデン共重合体などのフッ素系樹脂などから構成されるプラスチックフィルム;などが挙げられる。
Examples of the resin substrate film (3a) include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBT); polyethylene (PE), polypropylene ( PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other plastic films composed of an olefin resin containing α-olefin as a monomer component; polyvinyl chloride Plastic film composed of (PVC); plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), all Plastic film composed of amide resin such as aromatic polyamide (aramid); Plastic film composed of polyimide resin; Plastic film composed of polyetheretherketone (PEEK); Polyethylene (PE), polypropylene (PP) ) And other olefinic resin films; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride And a plastic film composed of a fluororesin such as a copolymer.
樹脂基材フィルム(3a)は、1層のみであってもよいし、2層以上であってもよい。樹脂基材フィルム(3a)は、延伸されたものであってもよい。
The resin base film (3a) may have only one layer or two or more layers. The resin substrate film (3a) may be stretched.
樹脂基材フィルム(3a)は、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理などが挙げられる。
The resin base film (3a) may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric bombardment exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.
樹脂フィルム(3)の粘着剤層(2)を付設しない面に対しては、巻戻しが容易な巻回体の形成などを目的として、例えば、樹脂フィルム(3)に、脂肪酸アミド、ポリエチレンイミン、長鎖アルキル系添加剤等を添加して離型処理を行ったり、シリコーン系、長鎖アルキル系、フッ素系などの任意の適切な剥離剤からなるコート層を設けたりすることができる。
On the surface of the resin film (3) on which the pressure-sensitive adhesive layer (2) is not attached, a fatty acid amide or polyethyleneimine is added to the resin film (3) for the purpose of forming a wound body that can be easily rewound. It is possible to add a long-chain alkyl-based additive or the like for release treatment, or to provide a coating layer made of any suitable release agent such as silicone-based, long-chain alkyl-based or fluorine-based release agent.
樹脂フィルム(3)には、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な添加剤が含まれていてもよい。
The resin film (3) may contain any appropriate additive depending on the purpose, as long as the effects of the present invention are not impaired.
樹脂フィルム(3)は、導電層(3b)を有していてもよい。導電層(3b)は、粘着剤層(2)と樹脂基材フィルム(3a)の間に配置され得る。
The resin film (3) may have a conductive layer (3b). The conductive layer (3b) may be arranged between the pressure-sensitive adhesive layer (2) and the resin base film (3a).
導電層(3b)は、1層のみであってもよいし、2層以上であってもよい。
The conductive layer (3b) may be only one layer or two or more layers.
導電層(3b)は、任意の適切な基材上に形成することによって設けることができる。このような基材としては、好ましくは、樹脂基材フィルム(3a)である。
The conductive layer (3b) can be provided by forming it on any appropriate base material. Such a substrate is preferably a resin substrate film (3a).
導電層(3b)は、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法、スプレー熱分解法、化学メッキ法、電気メッキ法、あるいはこれらの組合せ法などの任意の適切な薄膜形成法により、任意の適切な基材(好ましくは、樹脂基材フィルム(3a))上に導電膜を形成する。これらの薄膜形成法の中でも、導電膜の形成速度や大面積膜の形成性、生産性などの点から、真空蒸着法やスパッタリング法が好ましい。
The conductive layer (3b) is formed by any suitable thin film forming method such as a vacuum deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, a chemical plating method, an electroplating method, or a combination thereof. The conductive film is formed on any suitable base material (preferably, the resin base material film (3a)). Among these thin film forming methods, the vacuum deposition method and the sputtering method are preferable from the viewpoints of the formation speed of the conductive film, the formability of a large-area film, the productivity, and the like.
導電膜を形成するための材料としては、例えば、金、銀、白金、パラジウム、銅、アルミニウム、ニッケル、クロム、チタン、鉄、コバルト、錫、これらの合金等からなる金属系材料;酸化インジウム、酸化スズ、酸化チタン、酸化カドミウム、これらの混合物等からなる金属酸化物系材料;ヨウ化銅等からなる他の金属化合物;などが用いられる。
As the material for forming the conductive film, for example, metal-based materials such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, alloys thereof; indium oxide, A metal oxide-based material composed of tin oxide, titanium oxide, cadmium oxide, a mixture thereof, or the like; another metal compound composed of copper iodide or the like is used.
導電層(3b)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、例えば、金属系材料から形成される場合、好ましくは30Å~600Åであり、金属酸化物系材料から形成される場合、好ましくは80Å~5000Åである。
As the thickness of the conductive layer (3b), any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired. Such a thickness is, for example, preferably 30 Å to 600 Å when formed of a metal-based material, and preferably 80 Å to 5000 Å when formed of a metal oxide-based material.
導電層(3b)の表面抵抗値は、好ましくは1.0×1010Ω/□以下であり、より好ましくは1.0×109Ω/□以下であり、さらに好ましくは1.0×108Ω/□以下であり、特に好ましくは1.0×107Ω/□以下である。
The surface resistance value of the conductive layer (3b) is preferably 1.0×10 10 Ω/□ or less, more preferably 1.0×10 9 Ω/□ or less, and further preferably 1.0×10 9. It is 8 Ω/□ or less, and particularly preferably 1.0×10 7 Ω/□ or less.
導電膜を任意の適切な基材(好ましくは、樹脂基材フィルム(3a))上に形成する際には、該基材(好ましくは、樹脂基材フィルム(3a))の表面に、コロナ放電処理、紫外線照射処理、プラズマ処理、スパッタエッチング処理、アンダーコート処理等の、任意の適切な前処理を施して、導電膜と該基材(好ましくは、樹脂基材フィルム(3a))の密着性を高めることもできる。
When the conductive film is formed on any suitable base material (preferably the resin base material film (3a)), a corona discharge is formed on the surface of the base material (preferably the resin base film (3a)). Adhesion between the conductive film and the substrate (preferably the resin substrate film (3a)) after any suitable pretreatment such as treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, and undercoat treatment. Can also be increased.
樹脂フィルム(3)は、帯電防止層(3c)を有していてもよい。帯電防止層(3c)は、粘着剤層(2)と樹脂基材フィルム(3a)の間、および/または、樹脂基材フィルム(3a)の粘着剤層(2)の反対側に配置され得る。
The resin film (3) may have an antistatic layer (3c). The antistatic layer (3c) may be disposed between the pressure-sensitive adhesive layer (2) and the resin base film (3a) and/or on the opposite side of the resin base film (3a) from the pressure-sensitive adhesive layer (2). ..
帯電防止層(3c)は、1層のみであってもよいし、2層以上であってもよい。
The antistatic layer (3c) may be a single layer or two or more layers.
帯電防止層(3c)の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは1nm~1000nmであり、より好ましくは5nm~900nmであり、さらに好ましくは7.5nm~800nmであり、特に好ましくは10nm~700nmである。
As the thickness of the antistatic layer (3c), any appropriate thickness can be adopted according to the purpose within the range where the effect of the present invention is not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
帯電防止層(3c)の表面抵抗値は、好ましくは1.0×1010Ω/□以下であり、より好ましくは8.0×109Ω/□以下であり、さらに好ましくは5.0×109Ω/□以下であり、特に好ましくは1.0×109Ω/□以下である。
The surface resistance value of the antistatic layer (3c) is preferably 1.0×10 10 Ω/□ or less, more preferably 8.0×10 9 Ω/□ or less, and further preferably 5.0×. It is 10 9 Ω/□ or less, and particularly preferably 1.0×10 9 Ω/□ or less.
帯電防止層(3c)としては、帯電防止効果を奏することができる層であれば、本発明の効果を損なわない範囲で、任意の適切な帯電防止層を採用し得る。このような帯電防止層としては、好ましくは、導電性ポリマーを含む導電コート液を任意の適切な基材層上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液を樹脂基材フィルム(3a)上にコーティングして形成される帯電防止層である。コーティング後は、必要に応じて乾燥させ、必要に応じて硬化処理(熱処理、紫外線処理など)を行う。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。
As the antistatic layer (3c), any suitable antistatic layer can be adopted as long as it is a layer capable of exhibiting an antistatic effect, as long as the effect of the present invention is not impaired. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the resin substrate film (3a). After coating, it is dried if necessary and a curing treatment (heat treatment, ultraviolet treatment, etc.) is performed if necessary. Specific coating methods include a roll coating method, a bar coating method and a gravure coating method.
導電性ポリマーを含む導電コート液としては、本発明の効果を損なわない範囲で、任意の適切な導電コート液を採用し得る。このような導電コート液は、好ましくは、導電性ポリマーとバインダと架橋剤と溶剤を含む。この溶剤は、帯電防止層(3c)を形成する過程で加熱等によって揮発や蒸発等により実質的になくなるので、帯電防止層(3c)は、好ましくは、導電性ポリマーとバインダと架橋剤を含む。
As the conductive coating liquid containing a conductive polymer, any appropriate conductive coating liquid can be adopted as long as the effect of the present invention is not impaired. Such a conductive coating liquid preferably contains a conductive polymer, a binder, a crosslinking agent and a solvent. The solvent is substantially eliminated by volatilization or evaporation by heating or the like in the process of forming the antistatic layer (3c). Therefore, the antistatic layer (3c) preferably contains a conductive polymer, a binder and a crosslinking agent. ..
溶剤としては、例えば、有機溶剤、水、またはこれらの混合溶媒が挙げられる。有機溶剤としては、例えば、酢酸エチル等のエステル類;メチルエチルケトン、アセトン、シクロヘキサノン等のケトン類;テトラヒドロフラン(THF)、ジオキサン等の環状エーテル類;n-ヘキサン、シクロヘキサン等の脂肪族または脂環族炭化水素類;トルエン、キシレン等の芳香族炭化水素類;メタノール、エタノール、n-プロパノール、イソプロパノール、シクロヘキサノール等の脂肪族または脂環族アルコール類;アルキレングリコールモノアルキルエーテル(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル)、ジアルキレングリコールモノアルキルエーテル等のグリコールエーテル類;などが挙げられる。溶剤として、好ましくは、水または水を主成分とする混合溶媒(例えば、水とエタノールとの混合溶媒)である。
Examples of the solvent include organic solvents, water, and mixed solvents thereof. Examples of the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic carbonization such as n-hexane and cyclohexane. Hydrogen; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; alkylene glycol monoalkyl ethers (eg ethylene glycol monomethyl ether, Glycol ethers such as ethylene glycol monoethyl ether) and dialkylene glycol monoalkyl ether; and the like. The solvent is preferably water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
帯電防止層(3c)中の導電性ポリマーの含有割合は、好ましくは3重量%~80重量%であり、より好ましくは5重量%~60重量%である。
The content ratio of the conductive polymer in the antistatic layer (3c) is preferably 3% by weight to 80% by weight, more preferably 5% by weight to 60% by weight.
導電性ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な導電性ポリマーを採用し得る。このような導電性ポリマーとしては、例えば、π共役系導電性ポリマーにポリアニオンがドープされた導電性ポリマーなどが挙げられる。π共役系導電性ポリマーとしては、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレンなどの鎖状導電性ポリマーが挙げられる。ポリアニオンとしては、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリメタクリルカルボン酸などが挙げられる。
As the conductive polymer, any appropriate conductive polymer can be adopted as long as the effect of the present invention is not impaired. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacryl carboxylic acid.
導電性ポリマーは、1種のみであってもよいし、2種以上であってもよい。
The conductive polymer may be only one kind or two or more kinds.
帯電防止層(3c)中のバインダの含有割合は、好ましくは50重量%~95重量%であり、より好ましくは60重量%~90重量%である。
The content ratio of the binder in the antistatic layer (3c) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 90% by weight.
導電コート液に含まれ得るバインダとしては、本発明の効果を損なわない範囲で、任意の適切なバインダを採用し得る。バインダは、1種のみであってもよいし、2種以上であってもよい。このようなバインダとしては、好ましくは、樹脂であり、より好ましくは、ポリエステル樹脂である。バインダに占めるポリエステル樹脂の割合は、好ましくは90重量%~100重量%であり、より好ましくは98重量%~100重量%である。
As the binder that can be contained in the conductive coating liquid, any appropriate binder can be adopted as long as the effect of the present invention is not impaired. The binder may be only one type or two or more types. As such a binder, a resin is preferable, and a polyester resin is more preferable. The proportion of the polyester resin in the binder is preferably 90% by weight to 100% by weight, more preferably 98% by weight to 100% by weight.
ポリエステル樹脂は、ポリエステルを主成分(好ましくは50重量%を超え、より好ましくは75重量%以上であり、さらに好ましくは90重量%以上であり、特に好ましくは実質的に100重量%を占める成分)として含むことが好ましい。
The polyester resin contains polyester as a main component (preferably more than 50% by weight, more preferably 75% by weight or more, further preferably 90% by weight or more, particularly preferably substantially 100% by weight). It is preferable to include as.
ポリエステルとしては、本発明の効果を損なわない範囲で、任意の適切なポリエステルを採用し得る。このようなポリエステルとしては、好ましくは、1分子中に2個以上のカルボキシル基を有する多価カルボン酸(例えば、ジカルボン酸化合物)およびその誘導体(例えば、多価カルボン酸の無水物、エステル化物、ハロゲン化物等)から選択される1種または2種以上の化合物(多価カルボン酸成分)と、1分子中に2個以上の水酸基を有する多価アルコール(例えば、ジオール)から選択される1種または2種以上の化合物(多価アルコール成分)とが縮合した構造を有することが好ましい。
As the polyester, any appropriate polyester can be adopted as long as the effect of the present invention is not impaired. Such a polyester is preferably a polyvalent carboxylic acid having two or more carboxyl groups in one molecule (for example, a dicarboxylic acid compound) and a derivative thereof (for example, an anhydride or an esterified product of the polyvalent carboxylic acid). One or two or more compounds (polyvalent carboxylic acid component) selected from halides and the like, and one selected from a polyhydric alcohol (eg, diol) having two or more hydroxyl groups in one molecule. Alternatively, it preferably has a structure in which two or more compounds (polyhydric alcohol components) are condensed.
多価カルボン酸成分としては、本発明の効果を損なわない範囲で、任意の適切な多価カルボン酸を採用し得る。このような多価カルボン酸成分としては、例えば、シュウ酸、マロン酸、ジフルオロマロン酸、アルキルマロン酸、コハク酸、テトラフルオロコハク酸、アルキルコハク酸、(±)-リンゴ酸、meso-酒石酸、イタコン酸、マレイン酸、メチルマレイン酸、フマル酸、メチルフマル酸、アセチレンジカルボン酸、グルタル酸、ヘキサフルオログルタル酸、メチルグルタル酸、グルタコン酸、アジピン酸、ジチオアジピン酸、メチルアジピン酸、ジメチルアジピン酸、テトラメチルアジピン酸、メチレンアジピン酸、ムコン酸、ガラクタル酸、ピメリン酸、スベリン酸、パーフルオロスベリン酸、3,3,6,6-テトラメチルスベリン酸、アゼライン酸、セバシン酸、パーフルオロセバシン酸、ブラシル酸、ドデシルジカルボン酸、トリデシルジカルボン酸、テトラデシルジカルボン酸などの脂肪族ジカルボン酸類;シクロアルキルジカルボン酸(例えば、1,4-シクロヘキサンジカルボン酸、1,2-シクロヘキサンジカルボン酸)、1,4-(2-ノルボルネン)ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸(ハイミック酸)、アダマンタンジカルボン酸、スピロヘプタンジカルボン酸などの脂環式ジカルボン酸類;フタル酸、イソフタル酸、ジチオイソフタル酸、メチルイソフタル酸、ジメチルイソフタル酸、クロロイソフタル酸、ジクロロイソフタル酸、テレフタル酸、メチルテレフタル酸、ジメチルテレフタル酸、クロロテレフタル酸、ブロモテレフタル酸、ナフタレンジカルボン酸、オキソフルオレンジカルボン酸、アントラセンジカルボン酸、ビフェニルジカルボン酸、ビフェニレンジカルボン酸、ジメチルビフェニレンジカルボン酸、4,4”-p-テレフェニレンジカルボン酸、4,4”-p-クワレルフェニルジカルボン酸、ビベンジルジカルボン酸、アゾベンゼンジカルボン酸、ホモフタル酸、フェニレン二酢酸、フェニレンジプロピオン酸、ナフタレンジカルボン酸、ナフタレンジプロピオン酸、ビフェニル二酢酸、ビフェニルジプロピオン酸、3,3'-[4,4’-(メチレンジ-p-ビフェニレン)]ジプロピオン酸、4,4’-ビベンジル二酢酸、3,3’-[(4,4’-ビベンジル)]ジプロピオン酸、オキシジ-p-フェニレン二酢酸などの芳香族ジカルボン酸類;上記のいずれかの多価カルボン酸の酸無水物;上記のいずれかの多価カルボン酸のエステル(例えば、アルキルエステル。モノエステル、ジエステル等);上記のいずれかの多価カルボン酸に対応する酸ハロゲン化物(例えば、ジカルボン酸クロリド);などが挙げられる。
As the polyvalent carboxylic acid component, any suitable polyvalent carboxylic acid can be adopted as long as the effect of the present invention is not impaired. Examples of such polycarboxylic acid components include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±)-malic acid, meso-tartaric acid, Itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipic acid, Tetramethyl adipic acid, methylene adipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid, perfluorosebacic acid, Aliphatic dicarboxylic acids such as brassic acid, dodecyldicarboxylic acid, tridecyldicarboxylic acid, and tetradecyldicarboxylic acid; cycloalkyldicarboxylic acids (eg, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1,4 Alicyclic dicarboxylic acids such as -(2-norbornene)dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid (hymic acid), adamantanedicarboxylic acid, spiroheptanedicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalic acid, Methyl isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methylterephthalic acid, dimethylterephthalic acid, chloroterephthalic acid, bromoterephthalic acid, naphthalenedicarboxylic acid, oxofluorangecarboxylic acid, anthracenedicarboxylic acid, biphenyldicarboxylic acid Acid, biphenylenedicarboxylic acid, dimethylbiphenylenedicarboxylic acid, 4,4"-p-terephenylenedicarboxylic acid, 4,4"-p-quarrelphenyldicarboxylic acid, bibenzyldicarboxylic acid, azobenzenedicarboxylic acid, homophthalic acid, phenylene di Acetic acid, phenylenedipropionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyldiacetic acid, biphenyldipropionic acid, 3,3′-[4,4′-(methylenedi-p-biphenylene)]dipropionic acid, 4, Aromatic dicarboxylic acids such as 4′-bibenzyldiacetic acid, 3,3′-[(4,4′-bibenzyl)]dipropionic acid, oxydi-p-phenylenediacetic acid; Acid anhydrides; esters of any of the above polycarboxylic acids (eg, For example, alkyl ester. Monoesters, diesters, etc.); acid halides corresponding to any of the above polycarboxylic acids (eg, dicarboxylic acid chloride); and the like.
多価カルボン酸成分としては、好ましくは、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸類およびその酸無水物;アジピン酸、セバシン酸、アゼライン酸、コハク酸、フマル酸、マレイン酸、ハイミック酸、1,4-シクロヘキサンジカルボン酸等の脂肪族ジカルボン酸類およびその酸無水物;これらのジカルボン酸類の低級アルキルエステル(例えば、炭素原子数1~3のモノアルコールとのエステル);などが挙げられる。
As the polycarboxylic acid component, preferably, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Alimic dicarboxylic acids such as hymic acid and 1,4-cyclohexanedicarboxylic acid and their acid anhydrides; lower alkyl esters of these dicarboxylic acids (eg, esters with monoalcohols having 1 to 3 carbon atoms); To be
多価アルコール成分としては、本発明の効果を損なわない範囲で、任意の適切な多価アルコールを採用し得る。このような多価アルコール成分としては、例えば、エチレングリコール、プロピレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチルペンタンジオール、ジエチレングリコール、1,4-シクロヘキサンジメタノール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、キシリレングリコール、水添ビスフェノールA、ビスフェノールA等のジオール類;これらのジオール類のアルキレンオキサイド付加物(例えば、エチレンオキサイド付加物、プロピレンオキサイド付加物等);などが挙げられる。
As the polyhydric alcohol component, any appropriate polyhydric alcohol can be adopted as long as the effect of the present invention is not impaired. Examples of such polyhydric alcohol components include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propane Diols such as diol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, bisphenol A; these diols Alkylene oxide adduct (for example, ethylene oxide adduct, propylene oxide adduct, etc.);
ポリエステル樹脂の分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される標準ポリスチレン換算の重量平均分子量(Mw)として、好ましくは5×103~1.5×105であり、より好ましくは1×104~6×104である。
The molecular weight of the polyester resin is preferably 5×10 3 to 1.5×10 5 , and more preferably 1 as the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). ×10 4 to 6×10 4 .
ポリエステル樹脂のガラス転移温度(Tg)は、好ましくは0℃~120℃であり、より好ましくは10℃~80℃である。
The glass transition temperature (Tg) of the polyester resin is preferably 0°C to 120°C, more preferably 10°C to 80°C.
ポリエステル樹脂としては、例えば、市販の東洋紡社製の商品名「バイロナール」などを用いることができる。
As the polyester resin, for example, commercially available Toyobo Co., Ltd. product name “Bironard” can be used.
導電コート液は、本発明の効果を損なわない範囲で、バインダとして、ポリエステル樹脂以外の樹脂(例えば、アクリル樹脂、アクリルウレタン樹脂、アクリルスチレン樹脂、アクリルシリコーン樹脂、シリコーン樹脂、ポリシラザン樹脂、ポリウレタン樹脂、フッ素樹脂、ポリオレフィン樹脂から選択される少なくとも1種の樹脂)をさらに含有し得る。
The conductive coating liquid, as long as the effect of the present invention is not impaired, as a binder, a resin other than polyester resin (for example, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, silicone resin, polysilazane resin, polyurethane resin, It may further contain at least one resin selected from a fluororesin and a polyolefin resin.
導電コート液に含まれ得る架橋剤としては、本発明の効果を損なわない範囲で、任意の適切な架橋剤を採用し得る。架橋剤は、1種のみであってもよいし、2種以上であってもよい。このような架橋剤としては、好ましくは、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などが挙げられる。なかでも好ましくは、メラミン系架橋剤である。
As the cross-linking agent that can be contained in the conductive coating liquid, any appropriate cross-linking agent can be adopted as long as the effect of the present invention is not impaired. The cross-linking agent may be only one kind or two or more kinds. As such a crosslinking agent, preferably an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent. Agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, amine-based crosslinking agents and the like. Of these, a melamine-based cross-linking agent is preferable.
帯電防止層(3c)中の架橋剤の含有割合は、好ましくは1重量%~30重量%であり、より好ましくは2重量%~20重量%である。
The content ratio of the cross-linking agent in the antistatic layer (3c) is preferably 1% by weight to 30% by weight, more preferably 2% by weight to 20% by weight.
帯電防止層(3c)中には、本発明の効果を損なわない範囲で、任意の適切な他の成分が含まれていてもよい。
The antistatic layer (3c) may contain any appropriate other component as long as the effect of the present invention is not impaired.
≪≪2.積層体の製造方法≫≫
本発明の積層体は、本発明の効果を損なわない範囲で、任意の適切な方法によって製造し得る。 <<<<2. Manufacturing method of laminated body ≫≫
The layered product of the present invention can be manufactured by any appropriate method as long as the effects of the present invention are not impaired.
本発明の積層体は、本発明の効果を損なわない範囲で、任意の適切な方法によって製造し得る。 <<<<2. Manufacturing method of laminated body ≫≫
The layered product of the present invention can be manufactured by any appropriate method as long as the effects of the present invention are not impaired.
本発明の積層体の製造方法の代表例として、本発明の積層体が、樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有して、これらの構成要素からなる積層体である場合について説明する。
As a typical example of the method for producing a laminate of the present invention, the laminate of the present invention comprises a resin film (1), an adhesive layer (1), a resin film (2), an adhesive layer (2) and a resin film (3). ) Are provided in this order, and a case of a laminated body composed of these components will be described.
本発明の積層体の製造方法の一つの実施形態は、樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)をこの順に有して、これらの構成要素からなる積層体(I)と、粘着剤層(2)と樹脂フィルム(3)をこの順に有して、これらの構成要素からなる積層体(II)とを、それぞれ製造し、その後、積層体(I)の樹脂フィルム(2)の面と、積層体(II)の粘着剤層(2)の面とを貼り付ける。
One embodiment of the method for producing a laminate of the present invention has a resin film (1), a pressure-sensitive adhesive layer (1), and a resin film (2) in this order, and a laminate (I ), a pressure-sensitive adhesive layer (2) and a resin film (3) in this order to produce a laminate (II) composed of these components, and then, the resin film of the laminate (I). The surface of (2) and the surface of the pressure-sensitive adhesive layer (2) of the laminate (II) are attached.
積層体(I)は、例えば、粘着剤層(1)を構成する粘着剤を形成する粘着剤組成物(アクリル系粘着剤組成物、ウレタン系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物からなる群から選ばれる少なくとも1種)を樹脂フィルム(2)上に塗布し、必要に応じて加熱・乾燥を行い、必要に応じて硬化させて、該樹脂フィルム(2)上に該粘着剤層(1)を形成し、その後、該粘着剤層(1)の該樹脂フィルム(2)とは反対側の面に樹脂フィルム(1)(離型層(1b)を有しているときはその側)を貼り付ける。その後、樹脂フィルム(2)側からCO2レーザー等によって、カットする箇所の幅が所定の幅となるように、また、カットされない箇所の幅が所定の幅になるように、複数箇所を樹脂フィルム(1)の面までハーフカットし(つまり、樹脂フィルム(1)はカットされない)、ハーフカットした部分を任意の適切な方法によって除去する。
The laminate (I) is, for example, a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition, urethane-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive composition, silicone, which forms a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (1). At least one selected from the group consisting of the adhesive system) is applied on the resin film (2), heated and dried if necessary, and cured as necessary to obtain the resin film (2). The pressure-sensitive adhesive layer (1) is formed thereon, and then the resin film (1) (release layer (1b) is provided on the surface of the pressure-sensitive adhesive layer (1) opposite to the resin film (2). If that is the case, paste that side). After that, a plurality of portions of the resin film are cut from the resin film (2) side with a CO 2 laser or the like so that the width of the portion to be cut has a predetermined width and the width of the portion that is not cut has a predetermined width. Half-cut up to the surface of (1) (that is, the resin film (1) is not cut), and the half-cut portion is removed by any appropriate method.
積層体(II)は、例えば、粘着剤層(2)を構成する粘着剤を形成する粘着剤組成物(好ましくは、アクリル系粘着剤組成物)を樹脂フィルム(3)上に塗布し、必要に応じて加熱・乾燥を行い、必要に応じて硬化させて、該樹脂フィルム(3)上に該粘着剤層(2)を形成する。なお、積層体(I)と積層体(II)を貼り付けるまでの間は、粘着剤層(2)の露出面を保護するために、任意の適切なセパレータ(例えば、樹脂フィルム(1)と同様のフィルム)を貼り付けておいてもよい。
The laminate (II) is required, for example, by applying a pressure-sensitive adhesive composition (preferably an acrylic pressure-sensitive adhesive composition) forming a pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (2) onto the resin film (3). The adhesive layer (2) is formed on the resin film (3) by heating and drying according to the above, and curing as necessary. In addition, in order to protect the exposed surface of the pressure-sensitive adhesive layer (2) until the laminated body (I) and the laminated body (II) are attached, any suitable separator (for example, the resin film (1)) may be used. A similar film) may be attached.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。なお、実施例等における、試験および評価方法は以下のとおりである。なお、「部」と記載されている場合は、特記事項がない限り「重量部」を意味し、「%」と記載されている場合は、特記事項がない限り「重量%」を意味する。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The tests and evaluation methods in Examples and the like are as follows. In addition, when it is described as “part”, it means “part by weight” unless otherwise specified, and when described as “%”, it means “weight %” unless otherwise specified.
<重量平均分子量の測定>
重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)法により測定した。具体的には、GPC測定装置として、商品名「HLC-8120GPC」(東ソー株式会社製)を用いて、下記の条件にて測定し、標準ポリスチレン換算値により算出した。
(分子量測定条件)
・サンプル濃度:0.2重量%(テトラヒドロフラン溶液)
・サンプル注入量:10μL
・カラム:商品名「TSKguardcolumn SuperHZ-H(1本)+TSKgel SuperHZM-H(2本)」(東ソー株式会社製)
・リファレンスカラム:商品名「TSKgel SuperH-RC(1本)」(東ソー株式会社製)
・溶離液:テトラヒドロフラン(THF)
・流量:0.6mL/min
・検出器:示差屈折計(RI)
・カラム温度(測定温度):40℃ <Measurement of weight average molecular weight>
The weight average molecular weight was measured by the gel permeation chromatograph (GPC) method. Specifically, the product name "HLC-8120GPC" (manufactured by Tosoh Corporation) was used as a GPC measuring device, and the measurement was performed under the following conditions, and the standard polystyrene conversion value was calculated.
(Molecular weight measurement conditions)
・Sample concentration: 0.2 wt% (tetrahydrofuran solution)
・Sample injection volume: 10 μL
-Column: Product name "TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)" (manufactured by Tosoh Corporation)
・Reference column: Product name "TSKgel Super H-RC (1)" (manufactured by Tosoh Corporation)
・Eluent: Tetrahydrofuran (THF)
・Flow rate: 0.6 mL/min
・Detector: Differential refractometer (RI)
・Column temperature (measurement temperature): 40°C
重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)法により測定した。具体的には、GPC測定装置として、商品名「HLC-8120GPC」(東ソー株式会社製)を用いて、下記の条件にて測定し、標準ポリスチレン換算値により算出した。
(分子量測定条件)
・サンプル濃度:0.2重量%(テトラヒドロフラン溶液)
・サンプル注入量:10μL
・カラム:商品名「TSKguardcolumn SuperHZ-H(1本)+TSKgel SuperHZM-H(2本)」(東ソー株式会社製)
・リファレンスカラム:商品名「TSKgel SuperH-RC(1本)」(東ソー株式会社製)
・溶離液:テトラヒドロフラン(THF)
・流量:0.6mL/min
・検出器:示差屈折計(RI)
・カラム温度(測定温度):40℃ <Measurement of weight average molecular weight>
The weight average molecular weight was measured by the gel permeation chromatograph (GPC) method. Specifically, the product name "HLC-8120GPC" (manufactured by Tosoh Corporation) was used as a GPC measuring device, and the measurement was performed under the following conditions, and the standard polystyrene conversion value was calculated.
(Molecular weight measurement conditions)
・Sample concentration: 0.2 wt% (tetrahydrofuran solution)
・Sample injection volume: 10 μL
-Column: Product name "TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)" (manufactured by Tosoh Corporation)
・Reference column: Product name "TSKgel Super H-RC (1)" (manufactured by Tosoh Corporation)
・Eluent: Tetrahydrofuran (THF)
・Flow rate: 0.6 mL/min
・Detector: Differential refractometer (RI)
・Column temperature (measurement temperature): 40°C
<剥離角度180度、剥離速度30mm/分で粘着剤層(2)を樹脂フィルム(2)から剥離するときの粘着力の測定>
10cm×10cmの積層体(I)のセパレータを剥離し、温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面を10cm×10cmガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)にハンドローラーにて貼り付け、その後、0.25MPaの圧力にて圧着した。予め除電しておいたセパレータ付表面保護フィルム(キャリアシートと称してもよい)を幅25mm、長さ150mmに切断し、温度23℃、湿度50%RHの雰囲気下で、ガラスに固定した積層体(I)の樹脂フィルム側に、2.0kgローラー1往復により貼り付け、その後、0.25MPaの圧力にて圧着した。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、剥離速度30mm/分で、粘着剤層(2)を樹脂フィルム(2)から剥離し、粘着力を測定した。 <Measurement of adhesive strength when peeling the pressure-sensitive adhesive layer (2) from the resin film (2) at a peeling angle of 180 degrees and a peeling speed of 30 mm/min>
The separator of the laminate (I) having a size of 10 cm×10 cm was peeled off, and the pressure-sensitive adhesive layer surface of the sample for evaluation was subjected to a 10 cm×10 cm glass plate (manufactured by Matsunami Glass Industry Co., Ltd., under an atmosphere of a temperature of 23° C. and a humidity of 50% RH). The product was attached to a micro slide glass S) with a hand roller and then pressure-bonded at a pressure of 0.25 MPa. A laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used at a peeling angle of 180 degrees and a peeling speed of 30 mm/min. The adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
10cm×10cmの積層体(I)のセパレータを剥離し、温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面を10cm×10cmガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)にハンドローラーにて貼り付け、その後、0.25MPaの圧力にて圧着した。予め除電しておいたセパレータ付表面保護フィルム(キャリアシートと称してもよい)を幅25mm、長さ150mmに切断し、温度23℃、湿度50%RHの雰囲気下で、ガラスに固定した積層体(I)の樹脂フィルム側に、2.0kgローラー1往復により貼り付け、その後、0.25MPaの圧力にて圧着した。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、剥離速度30mm/分で、粘着剤層(2)を樹脂フィルム(2)から剥離し、粘着力を測定した。 <Measurement of adhesive strength when peeling the pressure-sensitive adhesive layer (2) from the resin film (2) at a peeling angle of 180 degrees and a peeling speed of 30 mm/min>
The separator of the laminate (I) having a size of 10 cm×10 cm was peeled off, and the pressure-sensitive adhesive layer surface of the sample for evaluation was subjected to a 10 cm×10 cm glass plate (manufactured by Matsunami Glass Industry Co., Ltd., under an atmosphere of a temperature of 23° C. and a humidity of 50% RH). The product was attached to a micro slide glass S) with a hand roller and then pressure-bonded at a pressure of 0.25 MPa. A laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used at a peeling angle of 180 degrees and a peeling speed of 30 mm/min. The adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
<剥離角度180度、剥離速度300mm/分で粘着剤層(2)を樹脂フィルム(2)から剥離するときの粘着力の測定>
10cm×10cmの積層体(I)のセパレータを剥離し、温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面を10cm×10cmガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)にハンドローラーにて貼り付け、その後、0.25MPaの圧力にて圧着した。予め除電しておいたセパレータ付表面保護フィルム(キャリアシートと称してもよい)を幅25mm、長さ150mmに切断し、温度23℃、湿度50%RHの雰囲気下で、ガラスに固定した積層体(I)の樹脂フィルム側に、2.0kgローラー1往復により貼り付け、その後、0.25MPaの圧力にて圧着した。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、剥離速度300mm/分で、粘着剤層(2)を樹脂フィルム(2)から剥離し、粘着力を測定した。 <Measurement of adhesive force when peeling the pressure-sensitive adhesive layer (2) from the resin film (2) at a peeling angle of 180 degrees and a peeling speed of 300 mm/min>
The separator of the laminate (I) having a size of 10 cm×10 cm was peeled off, and the pressure-sensitive adhesive layer surface of the sample for evaluation was subjected to a 10 cm×10 cm glass plate (manufactured by Matsunami Glass Industry Co., Ltd., under an atmosphere of a temperature of 23° C. and a humidity of 50% RH). The product was attached to a micro slide glass S) with a hand roller and then pressure-bonded at a pressure of 0.25 MPa. A laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used at a peeling angle of 180 degrees and a peeling speed of 300 mm/min. The adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
10cm×10cmの積層体(I)のセパレータを剥離し、温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面を10cm×10cmガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)にハンドローラーにて貼り付け、その後、0.25MPaの圧力にて圧着した。予め除電しておいたセパレータ付表面保護フィルム(キャリアシートと称してもよい)を幅25mm、長さ150mmに切断し、温度23℃、湿度50%RHの雰囲気下で、ガラスに固定した積層体(I)の樹脂フィルム側に、2.0kgローラー1往復により貼り付け、その後、0.25MPaの圧力にて圧着した。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、剥離速度300mm/分で、粘着剤層(2)を樹脂フィルム(2)から剥離し、粘着力を測定した。 <Measurement of adhesive force when peeling the pressure-sensitive adhesive layer (2) from the resin film (2) at a peeling angle of 180 degrees and a peeling speed of 300 mm/min>
The separator of the laminate (I) having a size of 10 cm×10 cm was peeled off, and the pressure-sensitive adhesive layer surface of the sample for evaluation was subjected to a 10 cm×10 cm glass plate (manufactured by Matsunami Glass Industry Co., Ltd., under an atmosphere of a temperature of 23° C. and a humidity of 50% RH). The product was attached to a micro slide glass S) with a hand roller and then pressure-bonded at a pressure of 0.25 MPa. A laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used at a peeling angle of 180 degrees and a peeling speed of 300 mm/min. The adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
<剥離角度180度、剥離速度2400mm/分で粘着剤層(2)を樹脂フィルム(2)から剥離するときの粘着力の測定>
10cm×10cmの積層体(I)のセパレータを剥離し、温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面を10cm×10cmガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)にハンドローラーにて貼り付け、その後、0.25MPaの圧力にて圧着した。予め除電しておいたセパレータ付表面保護フィルム(キャリアシートと称してもよい)を幅25mm、長さ150mmに切断し、温度23℃、湿度50%RHの雰囲気下で、ガラスに固定した積層体(I)の樹脂フィルム側に、2.0kgローラー1往復により貼り付け、その後、0.25MPaの圧力にて圧着した。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、剥離速度2400mm/分で、粘着剤層(2)を樹脂フィルム(2)から剥離し、粘着力を測定した。 <Measurement of adhesive force when peeling the pressure-sensitive adhesive layer (2) from the resin film (2) at a peeling angle of 180 degrees and a peeling speed of 2400 mm/min>
The separator of the laminate (I) having a size of 10 cm×10 cm was peeled off, and the pressure-sensitive adhesive layer surface of the sample for evaluation was subjected to a 10 cm×10 cm glass plate (manufactured by Matsunami Glass Industry Co., Ltd., under an atmosphere of a temperature of 23° C. and a humidity of 50% RH). The product was attached to a micro slide glass S) with a hand roller and then pressure-bonded at a pressure of 0.25 MPa. A laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used at a peeling angle of 180 degrees and a peeling speed of 2400 mm/min. The adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
10cm×10cmの積層体(I)のセパレータを剥離し、温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面を10cm×10cmガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)にハンドローラーにて貼り付け、その後、0.25MPaの圧力にて圧着した。予め除電しておいたセパレータ付表面保護フィルム(キャリアシートと称してもよい)を幅25mm、長さ150mmに切断し、温度23℃、湿度50%RHの雰囲気下で、ガラスに固定した積層体(I)の樹脂フィルム側に、2.0kgローラー1往復により貼り付け、その後、0.25MPaの圧力にて圧着した。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、剥離速度2400mm/分で、粘着剤層(2)を樹脂フィルム(2)から剥離し、粘着力を測定した。 <Measurement of adhesive force when peeling the pressure-sensitive adhesive layer (2) from the resin film (2) at a peeling angle of 180 degrees and a peeling speed of 2400 mm/min>
The separator of the laminate (I) having a size of 10 cm×10 cm was peeled off, and the pressure-sensitive adhesive layer surface of the sample for evaluation was subjected to a 10 cm×10 cm glass plate (manufactured by Matsunami Glass Industry Co., Ltd., under an atmosphere of a temperature of 23° C. and a humidity of 50% RH). The product was attached to a micro slide glass S) with a hand roller and then pressure-bonded at a pressure of 0.25 MPa. A laminated body in which a surface protective film with a separator (which may be referred to as a carrier sheet) that has been decharged in advance is cut into a width of 25 mm and a length of 150 mm, and is fixed to glass under an atmosphere of a temperature of 23° C. and a humidity of 50% RH. The resin film of (I) was attached by reciprocating once with a 2.0 kg roller and then pressure-bonded at a pressure of 0.25 MPa. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used at a peeling angle of 180 degrees and a peeling speed of 2400 mm/min. The adhesive layer (2) was peeled off from the resin film (2), and the adhesive strength was measured.
<粘着力(1)の測定>
樹脂フィルム(1)/粘着剤層(1)/樹脂フィルム(2)からなる積層体(I)を幅25mm、長さ150mmに切断して評価用サンプルを作製した。温度23℃、湿度50%RHの雰囲気下において、作製した評価用サンプルから樹脂フィルム(1)を剥離し、ガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)に、2.0kgローラー1往復により貼り付けた。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機を用い、剥離角度180度、剥離速度300mm/分で剥離し、粘着力(1)を測定した。 <Measurement of adhesive strength (1)>
A laminate (I) composed of resin film (1)/adhesive layer (1)/resin film (2) was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample. In an atmosphere of a temperature of 23° C. and a humidity of 50% RH, the resin film (1) was peeled from the produced evaluation sample, and the glass plate (Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) was used. It was attached by reciprocating once with a 0 kg roller. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester was used to perform peeling at a peeling angle of 180° and a peeling speed of 300 mm/min, and the adhesive strength (1) was measured.
樹脂フィルム(1)/粘着剤層(1)/樹脂フィルム(2)からなる積層体(I)を幅25mm、長さ150mmに切断して評価用サンプルを作製した。温度23℃、湿度50%RHの雰囲気下において、作製した評価用サンプルから樹脂フィルム(1)を剥離し、ガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)に、2.0kgローラー1往復により貼り付けた。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機を用い、剥離角度180度、剥離速度300mm/分で剥離し、粘着力(1)を測定した。 <Measurement of adhesive strength (1)>
A laminate (I) composed of resin film (1)/adhesive layer (1)/resin film (2) was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample. In an atmosphere of a temperature of 23° C. and a humidity of 50% RH, the resin film (1) was peeled from the produced evaluation sample, and the glass plate (Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) was used. It was attached by reciprocating once with a 0 kg roller. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester was used to perform peeling at a peeling angle of 180° and a peeling speed of 300 mm/min, and the adhesive strength (1) was measured.
<粘着力(2)の測定>
セパレータ/粘着剤層(2)/樹脂フィルム(3)からなるセパレータ付きの積層体(II)を幅25mm、長さ150mmに切断して評価用サンプルを作製した。別途、<粘着力(1)の測定>の項目で説明した、積層体(I)から樹脂フィルム(1)を剥離した後にガラス板に張り付けた被着体を準備しておき、温度23℃、湿度50%RHの雰囲気下において、上記評価用サンプルからセパレータを剥離し、上記被着体に、2.0kgローラー1往復により貼り付けた。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機を用い、剥離角度180度、剥離速度300mm/分で剥離し、粘着力(2)を測定した。 <Measurement of adhesive strength (2)>
A laminate (II) with a separator composed of separator/adhesive layer (2)/resin film (3) was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample. Separately, an adherend prepared by peeling the resin film (1) from the laminate (I) and adhered to a glass plate as described in the section <Measurement of adhesive strength (1)> is prepared at a temperature of 23° C. In an atmosphere of a humidity of 50% RH, the separator was peeled from the evaluation sample and attached to the adherend by reciprocating a 2.0 kg roller once. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester was used to peel at a peeling angle of 180° and a peeling speed of 300 mm/min, and the adhesive strength (2) was measured.
セパレータ/粘着剤層(2)/樹脂フィルム(3)からなるセパレータ付きの積層体(II)を幅25mm、長さ150mmに切断して評価用サンプルを作製した。別途、<粘着力(1)の測定>の項目で説明した、積層体(I)から樹脂フィルム(1)を剥離した後にガラス板に張り付けた被着体を準備しておき、温度23℃、湿度50%RHの雰囲気下において、上記評価用サンプルからセパレータを剥離し、上記被着体に、2.0kgローラー1往復により貼り付けた。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機を用い、剥離角度180度、剥離速度300mm/分で剥離し、粘着力(2)を測定した。 <Measurement of adhesive strength (2)>
A laminate (II) with a separator composed of separator/adhesive layer (2)/resin film (3) was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample. Separately, an adherend prepared by peeling the resin film (1) from the laminate (I) and adhered to a glass plate as described in the section <Measurement of adhesive strength (1)> is prepared at a temperature of 23° C. In an atmosphere of a humidity of 50% RH, the separator was peeled from the evaluation sample and attached to the adherend by reciprocating a 2.0 kg roller once. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, a universal tensile tester was used to peel at a peeling angle of 180° and a peeling speed of 300 mm/min, and the adhesive strength (2) was measured.
<全光線透過率、ヘイズの測定>
村上色彩技術研究所のHM-150Nを使用し、JIS-K-7361の条件で全光線透過率を、JIS-K-7136の条件でヘイズを測定した。この際、5層積層品は光源側に樹脂フィルム(3)が向くように設置した。 <Measurement of total light transmittance and haze>
Using HM-150N of Murakami Color Research Laboratory, total light transmittance was measured under the conditions of JIS-K-7361 and haze was measured under the conditions of JIS-K-7136. At this time, the 5-layer laminated product was installed so that the resin film (3) faced to the light source side.
村上色彩技術研究所のHM-150Nを使用し、JIS-K-7361の条件で全光線透過率を、JIS-K-7136の条件でヘイズを測定した。この際、5層積層品は光源側に樹脂フィルム(3)が向くように設置した。 <Measurement of total light transmittance and haze>
Using HM-150N of Murakami Color Research Laboratory, total light transmittance was measured under the conditions of JIS-K-7361 and haze was measured under the conditions of JIS-K-7136. At this time, the 5-layer laminated product was installed so that the resin film (3) faced to the light source side.
<浮きの測定>
積層体(I)を、幅50mm、長さ300mmに切断し、樹脂フィルム(2)側からCO2レーザーによって1mm幅で等間隔になるように5か所を、または、3mm幅で等間隔になるように5か所を、または、5mm幅で等間隔になるように5か所を、樹脂フィルム(1)の面までハーフカットし(つまり、樹脂フィルム(1)はカットされない)、ハーフカットした部分を手で除去した。このとき、ハーフカット・除去された箇所の間の距離が50mmとなるようにサンプルを作製した。その後、幅60mm、長さ400mmに切断した積層体(II)の粘着剤層(2)の面を、積層体(I)の樹脂フィルム(2)の面に貼り付け、測定サンプルとした。
測定サンプルを、直径6インチのロールに対して樹脂フィルム(1)が外側になるように巻き付け、区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分が粘着剤層(2)から浮いている最大量をルーペにて測定し、任意の5か所の測定の平均値を浮き量とした。 <Float measurement>
The laminate (I) is cut into a width of 50 mm and a length of 300 mm, and is cut from the resin film (2) side by a CO 2 laser at 5 positions so as to be evenly spaced at 1 mm or at 3 mm equally spaced. Half-cut to the surface of the resin film (1) (that is, the resin film (1) is not cut), and half-cut at 5 positions so that The removed part was removed by hand. At this time, the sample was manufactured so that the distance between the half-cut/removed portions was 50 mm. Then, the surface of the pressure-sensitive adhesive layer (2) of the laminate (II) cut into a width of 60 mm and a length of 400 mm was attached to the surface of the resin film (2) of the laminate (I) to obtain a measurement sample.
The measurement sample was wound around a roll having a diameter of 6 inches so that the resin film (1) was on the outer side, and the laminated portion of the plurality of divided adhesive layers (1) and the resin film (2) formed an adhesive layer ( The maximum amount floating from 2) was measured with a magnifying glass, and the average value of the measurements at any 5 points was taken as the floating amount.
積層体(I)を、幅50mm、長さ300mmに切断し、樹脂フィルム(2)側からCO2レーザーによって1mm幅で等間隔になるように5か所を、または、3mm幅で等間隔になるように5か所を、または、5mm幅で等間隔になるように5か所を、樹脂フィルム(1)の面までハーフカットし(つまり、樹脂フィルム(1)はカットされない)、ハーフカットした部分を手で除去した。このとき、ハーフカット・除去された箇所の間の距離が50mmとなるようにサンプルを作製した。その後、幅60mm、長さ400mmに切断した積層体(II)の粘着剤層(2)の面を、積層体(I)の樹脂フィルム(2)の面に貼り付け、測定サンプルとした。
測定サンプルを、直径6インチのロールに対して樹脂フィルム(1)が外側になるように巻き付け、区分けされた複数の粘着剤層(1)と樹脂フィルム(2)の積層部分が粘着剤層(2)から浮いている最大量をルーペにて測定し、任意の5か所の測定の平均値を浮き量とした。 <Float measurement>
The laminate (I) is cut into a width of 50 mm and a length of 300 mm, and is cut from the resin film (2) side by a CO 2 laser at 5 positions so as to be evenly spaced at 1 mm or at 3 mm equally spaced. Half-cut to the surface of the resin film (1) (that is, the resin film (1) is not cut), and half-cut at 5 positions so that The removed part was removed by hand. At this time, the sample was manufactured so that the distance between the half-cut/removed portions was 50 mm. Then, the surface of the pressure-sensitive adhesive layer (2) of the laminate (II) cut into a width of 60 mm and a length of 400 mm was attached to the surface of the resin film (2) of the laminate (I) to obtain a measurement sample.
The measurement sample was wound around a roll having a diameter of 6 inches so that the resin film (1) was on the outer side, and the laminated portion of the plurality of divided adhesive layers (1) and the resin film (2) formed an adhesive layer ( The maximum amount floating from 2) was measured with a magnifying glass, and the average value of the measurements at any 5 points was taken as the floating amount.
〔製造例1〕粘着剤組成物(1)の製造
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、ブチルアクリレート(日本触媒社製)95部、アクリル酸(東亜合成社製)5部、重合開始剤として2,2’-アゾビスイソブチロニトリル(和光純薬工業社製)0.2部、酢酸エチル156重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を63℃付近に保って10時間重合反応を行い、重量平均分子量70万の(メタ)アクリル系重合体(1)溶液(40重量%)を調製した。(メタ)アクリル系重合体(1)溶液に、(メタ)アクリル系重合体(1)溶液の固形分100重量部に対して、架橋剤としてTETRAD-C(三菱瓦斯化学社製)を固形分換算で6重量部を加えて、全体の固形分が20重量%となるように酢酸エチルで希釈し、ディスパーで攪拌し、アクリル系樹脂を含む粘着剤組成物(1)を得た。 [Production Example 1] Production of pressure-sensitive adhesive composition (1) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, 95 parts of butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) and acrylic acid ( Toa Gosei Co., Ltd.) 5 parts, as a polymerization initiator 2,2'-azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.2 part, ethyl acetate 156 parts by weight were charged, and nitrogen was gently stirred. A gas was introduced and a polymerization reaction was carried out for 10 hours while maintaining the liquid temperature in the flask at around 63° C. to prepare a (meth)acrylic polymer (1) solution (40% by weight) having a weight average molecular weight of 700,000. In the (meth)acrylic polymer (1) solution, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) as a cross-linking agent was added as a solid content to 100 parts by weight of the solid content of the (meth)acrylic polymer (1) solution. 6 parts by weight in terms of conversion was added, diluted with ethyl acetate so that the total solid content was 20% by weight, and stirred with a disper to obtain a pressure-sensitive adhesive composition (1) containing an acrylic resin.
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、ブチルアクリレート(日本触媒社製)95部、アクリル酸(東亜合成社製)5部、重合開始剤として2,2’-アゾビスイソブチロニトリル(和光純薬工業社製)0.2部、酢酸エチル156重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を63℃付近に保って10時間重合反応を行い、重量平均分子量70万の(メタ)アクリル系重合体(1)溶液(40重量%)を調製した。(メタ)アクリル系重合体(1)溶液に、(メタ)アクリル系重合体(1)溶液の固形分100重量部に対して、架橋剤としてTETRAD-C(三菱瓦斯化学社製)を固形分換算で6重量部を加えて、全体の固形分が20重量%となるように酢酸エチルで希釈し、ディスパーで攪拌し、アクリル系樹脂を含む粘着剤組成物(1)を得た。 [Production Example 1] Production of pressure-sensitive adhesive composition (1) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, 95 parts of butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) and acrylic acid ( Toa Gosei Co., Ltd.) 5 parts, as a polymerization initiator 2,2'-azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.2 part, ethyl acetate 156 parts by weight were charged, and nitrogen was gently stirred. A gas was introduced and a polymerization reaction was carried out for 10 hours while maintaining the liquid temperature in the flask at around 63° C. to prepare a (meth)acrylic polymer (1) solution (40% by weight) having a weight average molecular weight of 700,000. In the (meth)acrylic polymer (1) solution, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) as a cross-linking agent was added as a solid content to 100 parts by weight of the solid content of the (meth)acrylic polymer (1) solution. 6 parts by weight in terms of conversion was added, diluted with ethyl acetate so that the total solid content was 20% by weight, and stirred with a disper to obtain a pressure-sensitive adhesive composition (1) containing an acrylic resin.
〔製造例2〕粘着剤組成物(2)の製造
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに2-エチルヘキシルアクリレート(日本触媒社製)100重量部、2-ヒドロキシエチルアクリレート(東亜合成社製)4重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル(和光純薬工業社製)0.2重量部、酢酸エチル156重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を65℃付近に保って8時間重合反応を行い、重量平均分子量55万の(メタ)アクリル系重合体(2)溶液(40重量%)を調製した。(メタ)アクリル系重合体(2)溶液に、(メタ)アクリル系重合体(2)溶液の固形分100重量部に対して、架橋剤としてコロネートHX(東ソー社製)を固形分換算で4重量部、架橋触媒としてエンビライザーOL-1(東京ファインケミカル社製)を固形分換算で0.01重量部を加えて、全体の固形分が25重量%となるように酢酸エチルで希釈し、ディスパーで攪拌し、アクリル系樹脂を含む粘着剤組成物(2)を得た。 [Production Example 2] Production of pressure-sensitive adhesive composition (2) 100 parts by weight of 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser. -Hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.) 4 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 0.2 parts by weight as a polymerization initiator, and ethyl acetate 156 parts by weight were charged. Then, nitrogen gas was introduced with gentle stirring, the temperature of the liquid in the flask was kept at about 65° C., and the polymerization reaction was carried out for 8 hours to give a (meth)acrylic polymer (2) solution (40) having a weight average molecular weight of 550,000. Wt%) was prepared. In the (meth)acrylic polymer (2) solution, Coronate HX (manufactured by Tosoh Corporation) as a cross-linking agent was added as solid content to 4 parts by weight per 100 parts by weight of the solid content of the (meth)acrylic polymer (2) solution. By weight, 0.01 part by weight of Enbilizer OL-1 (manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst in terms of solid content is added, and the mixture is diluted with ethyl acetate so that the total solid content is 25% by weight. The mixture was stirred with to obtain an adhesive composition (2) containing an acrylic resin.
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに2-エチルヘキシルアクリレート(日本触媒社製)100重量部、2-ヒドロキシエチルアクリレート(東亜合成社製)4重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル(和光純薬工業社製)0.2重量部、酢酸エチル156重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を65℃付近に保って8時間重合反応を行い、重量平均分子量55万の(メタ)アクリル系重合体(2)溶液(40重量%)を調製した。(メタ)アクリル系重合体(2)溶液に、(メタ)アクリル系重合体(2)溶液の固形分100重量部に対して、架橋剤としてコロネートHX(東ソー社製)を固形分換算で4重量部、架橋触媒としてエンビライザーOL-1(東京ファインケミカル社製)を固形分換算で0.01重量部を加えて、全体の固形分が25重量%となるように酢酸エチルで希釈し、ディスパーで攪拌し、アクリル系樹脂を含む粘着剤組成物(2)を得た。 [Production Example 2] Production of pressure-sensitive adhesive composition (2) 100 parts by weight of 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser. -Hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.) 4 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 0.2 parts by weight as a polymerization initiator, and ethyl acetate 156 parts by weight were charged. Then, nitrogen gas was introduced with gentle stirring, the temperature of the liquid in the flask was kept at about 65° C., and the polymerization reaction was carried out for 8 hours to give a (meth)acrylic polymer (2) solution (40) having a weight average molecular weight of 550,000. Wt%) was prepared. In the (meth)acrylic polymer (2) solution, Coronate HX (manufactured by Tosoh Corporation) as a cross-linking agent was added as solid content to 4 parts by weight per 100 parts by weight of the solid content of the (meth)acrylic polymer (2) solution. By weight, 0.01 part by weight of Enbilizer OL-1 (manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst in terms of solid content is added, and the mixture is diluted with ethyl acetate so that the total solid content is 25% by weight. The mixture was stirred with to obtain an adhesive composition (2) containing an acrylic resin.
〔製造例3〕粘着剤組成物(3)の製造
架橋触媒としてエンビライザーOL-1の使用量を固形分換算で0.05重量部とする以外は、製造例2と同じ手順によって、アクリル系樹脂を含む粘着剤組成物(3)を得た。 [Production Example 3] Production of pressure-sensitive adhesive composition (3) Acrylic resin was produced in the same procedure as in Production Example 2 except that the amount of the emulizer OL-1 used as a crosslinking catalyst was 0.05 parts by weight in terms of solid content. An adhesive composition (3) containing a resin was obtained.
架橋触媒としてエンビライザーOL-1の使用量を固形分換算で0.05重量部とする以外は、製造例2と同じ手順によって、アクリル系樹脂を含む粘着剤組成物(3)を得た。 [Production Example 3] Production of pressure-sensitive adhesive composition (3) Acrylic resin was produced in the same procedure as in Production Example 2 except that the amount of the emulizer OL-1 used as a crosslinking catalyst was 0.05 parts by weight in terms of solid content. An adhesive composition (3) containing a resin was obtained.
〔製造例4〕粘着剤組成物(4)の製造
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに2-エチルヘキシルアクリレート(日本触媒社製)100重量部、酢酸ビニルモノマー(昭和電工社製)80重量部、アクリル酸(東亞合成社製)5重量部、トルエン45重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、重合開始剤としてナイパーBW(日油社製)0.2重量部、フラスコ内の液温を40℃付近に保って3時間重合反応を行い、重量平均分子量70万の(メタ)アクリル系重合体(4)溶液(35重量%)を調製した。(メタ)アクリル系重合体(4)溶液に、(メタ)アクリル系重合体(4)溶液の固形分100重量部に対して、架橋剤としてTETRAD-C(三菱瓦斯化学社製)を固形分換算で10重量部を加えて、全体の固形分が20重量%となるようにメチルエチルケトンで希釈し、ディスパーで攪拌し、アクリル系樹脂を含む粘着剤組成物(4)を得た。 [Production Example 4] Production of pressure-sensitive adhesive composition (4) 100 parts by weight of 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) and acetic acid were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Charge 80 parts by weight of vinyl monomer (Showa Denko KK), 5 parts by weight of acrylic acid (Toagosei Co., Ltd.), and 45 parts by weight of toluene, introduce nitrogen gas with gentle stirring, and use Niper BW (Japan) as a polymerization initiator. (Manufactured by Yuya Co., Ltd.) 0.2 part by weight, the temperature of the liquid in the flask is kept at about 40° C. to carry out a polymerization reaction for 3 hours, and a (meth)acrylic polymer (4) solution having a weight average molecular weight of 700,000 (35% by weight ) Was prepared. In the (meth)acrylic polymer (4) solution, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) as a cross-linking agent was added as a solid content to 100 parts by weight of the solid content of the (meth)acrylic polymer (4) solution. 10 parts by weight in terms of conversion was added, diluted with methyl ethyl ketone so that the total solid content was 20% by weight, and stirred with a disper to obtain a pressure-sensitive adhesive composition (4) containing an acrylic resin.
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに2-エチルヘキシルアクリレート(日本触媒社製)100重量部、酢酸ビニルモノマー(昭和電工社製)80重量部、アクリル酸(東亞合成社製)5重量部、トルエン45重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、重合開始剤としてナイパーBW(日油社製)0.2重量部、フラスコ内の液温を40℃付近に保って3時間重合反応を行い、重量平均分子量70万の(メタ)アクリル系重合体(4)溶液(35重量%)を調製した。(メタ)アクリル系重合体(4)溶液に、(メタ)アクリル系重合体(4)溶液の固形分100重量部に対して、架橋剤としてTETRAD-C(三菱瓦斯化学社製)を固形分換算で10重量部を加えて、全体の固形分が20重量%となるようにメチルエチルケトンで希釈し、ディスパーで攪拌し、アクリル系樹脂を含む粘着剤組成物(4)を得た。 [Production Example 4] Production of pressure-sensitive adhesive composition (4) 100 parts by weight of 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) and acetic acid were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Charge 80 parts by weight of vinyl monomer (Showa Denko KK), 5 parts by weight of acrylic acid (Toagosei Co., Ltd.), and 45 parts by weight of toluene, introduce nitrogen gas with gentle stirring, and use Niper BW (Japan) as a polymerization initiator. (Manufactured by Yuya Co., Ltd.) 0.2 part by weight, the temperature of the liquid in the flask is kept at about 40° C. to carry out a polymerization reaction for 3 hours, and a (meth)acrylic polymer (4) solution having a weight average molecular weight of 700,000 (35% by weight ) Was prepared. In the (meth)acrylic polymer (4) solution, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) as a cross-linking agent was added as a solid content to 100 parts by weight of the solid content of the (meth)acrylic polymer (4) solution. 10 parts by weight in terms of conversion was added, diluted with methyl ethyl ketone so that the total solid content was 20% by weight, and stirred with a disper to obtain a pressure-sensitive adhesive composition (4) containing an acrylic resin.
〔製造例5〕粘着剤組成物(5)の製造
多官能ポリオールとして、プレミノールS3011(旭硝子株式会社製、Mn=10000)を固形分換算で100重量部、架橋剤としてコロネートHX(日本ポリウレタン工業社製)を固形分換算で18重量部、架橋触媒としてナーセム第2鉄(日本化学産業社製)を固形分換算で0.04重量部、劣化防止剤としてIrganox1010(BASF社製)を固形分換算で0.5重量部を加えて、全体の固形分が35重量%となるように酢酸エチルで希釈し、ディスパーで攪拌し、ウレタン系樹脂を含む粘着剤組成物(5)を得た。 [Production Example 5] Production of pressure-sensitive adhesive composition (5) As a polyfunctional polyol, 100 parts by weight of preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) in terms of solid content, Coronate HX (Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent. 18 parts by weight in terms of solid content, 0.04 parts by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) in terms of solid content as a crosslinking catalyst, and Irganox 1010 (manufactured by BASF Corporation) in terms of solid content as a deterioration inhibitor. 0.5 parts by weight was added, and the mixture was diluted with ethyl acetate so that the total solid content was 35% by weight and stirred with a disper to obtain a pressure-sensitive adhesive composition (5) containing a urethane resin.
多官能ポリオールとして、プレミノールS3011(旭硝子株式会社製、Mn=10000)を固形分換算で100重量部、架橋剤としてコロネートHX(日本ポリウレタン工業社製)を固形分換算で18重量部、架橋触媒としてナーセム第2鉄(日本化学産業社製)を固形分換算で0.04重量部、劣化防止剤としてIrganox1010(BASF社製)を固形分換算で0.5重量部を加えて、全体の固形分が35重量%となるように酢酸エチルで希釈し、ディスパーで攪拌し、ウレタン系樹脂を含む粘着剤組成物(5)を得た。 [Production Example 5] Production of pressure-sensitive adhesive composition (5) As a polyfunctional polyol, 100 parts by weight of preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) in terms of solid content, Coronate HX (Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent. 18 parts by weight in terms of solid content, 0.04 parts by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) in terms of solid content as a crosslinking catalyst, and Irganox 1010 (manufactured by BASF Corporation) in terms of solid content as a deterioration inhibitor. 0.5 parts by weight was added, and the mixture was diluted with ethyl acetate so that the total solid content was 35% by weight and stirred with a disper to obtain a pressure-sensitive adhesive composition (5) containing a urethane resin.
〔製造例6〕粘着剤組成物(6)の製造
架橋剤としてTETRAD-C(三菱瓦斯化学社製)の使用量を固形分換算で0.07重量部とする以外は、製造例1と同じ手順によって、アクリル系樹脂を含む粘着剤組成物(6)を得た。 [Production Example 6] Production of adhesive composition (6) Same as Production Example 1 except that the amount of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) used as a cross-linking agent is 0.07 parts by weight in terms of solid content. By the procedure, an adhesive composition (6) containing an acrylic resin was obtained.
架橋剤としてTETRAD-C(三菱瓦斯化学社製)の使用量を固形分換算で0.07重量部とする以外は、製造例1と同じ手順によって、アクリル系樹脂を含む粘着剤組成物(6)を得た。 [Production Example 6] Production of adhesive composition (6) Same as Production Example 1 except that the amount of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) used as a cross-linking agent is 0.07 parts by weight in terms of solid content. By the procedure, an adhesive composition (6) containing an acrylic resin was obtained.
〔製造例7〕積層体(A)の製造
製造例6で得られた粘着剤組成物(6)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み75μm、東レ社製)にファウンテンロールで乾燥後の厚みが15μmとなるよう塗布し、乾燥温度130℃、乾燥時間2分の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ75μmのポリエステル樹脂「ルミラーS10」(厚み75μm、東レ社製)からなる基材のシリコーン処理面を貼合せて、樹脂フィルム(シリコーン処理面付)/粘着剤層/樹脂フィルムの構成の積層体(A)を得た。 [Production Example 7] Production of Laminate (A) The pressure-sensitive adhesive composition (6) obtained in Production Example 6 was formed on a polyester resin substrate "Lumirror S10" (thickness: 75 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 15 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 2 minutes. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a substrate made of a 75 μm-thick polyester resin “Lumirror S10” (thickness: 75 μm, manufactured by Toray Industries, Inc.) having a silicone treatment on one surface is bonded to the surface of the adhesive layer to form a resin. A laminate (A) having a structure of film (with silicone-treated surface)/adhesive layer/resin film was obtained.
製造例6で得られた粘着剤組成物(6)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み75μm、東レ社製)にファウンテンロールで乾燥後の厚みが15μmとなるよう塗布し、乾燥温度130℃、乾燥時間2分の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ75μmのポリエステル樹脂「ルミラーS10」(厚み75μm、東レ社製)からなる基材のシリコーン処理面を貼合せて、樹脂フィルム(シリコーン処理面付)/粘着剤層/樹脂フィルムの構成の積層体(A)を得た。 [Production Example 7] Production of Laminate (A) The pressure-sensitive adhesive composition (6) obtained in Production Example 6 was formed on a polyester resin substrate "Lumirror S10" (thickness: 75 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 15 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 2 minutes. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a substrate made of a 75 μm-thick polyester resin “Lumirror S10” (thickness: 75 μm, manufactured by Toray Industries, Inc.) having a silicone treatment on one surface is bonded to the surface of the adhesive layer to form a resin. A laminate (A) having a structure of film (with silicone-treated surface)/adhesive layer/resin film was obtained.
〔製造例8〕積層体(B1)の製造
製造例1で得られた粘着剤組成物(1)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが5μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B1)を得た。 [Production Example 8] Production of Laminate (B1) The pressure-sensitive adhesive composition (1) obtained in Production Example 1 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 5 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B1) was obtained.
製造例1で得られた粘着剤組成物(1)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが5μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B1)を得た。 [Production Example 8] Production of Laminate (B1) The pressure-sensitive adhesive composition (1) obtained in Production Example 1 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 5 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B1) was obtained.
〔製造例9〕積層体(B2)の製造
ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)を「ルミラーS10」(厚み50μm、東レ社製)に変更した以外は、製造例8と同様の手順により、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B2)を得た。 [Production Example 9] Production of laminate (B2) Production except that the base material "Lumirror S10" (thickness 38 µm, manufactured by Toray) made of polyester resin was changed to "Lumirror S10" (thickness 50 µm, manufactured by Toray). By the same procedure as in Example 8, a laminate (B2) having a constitution of separator/adhesive layer/resin film was obtained.
ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)を「ルミラーS10」(厚み50μm、東レ社製)に変更した以外は、製造例8と同様の手順により、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B2)を得た。 [Production Example 9] Production of laminate (B2) Production except that the base material "Lumirror S10" (thickness 38 µm, manufactured by Toray) made of polyester resin was changed to "Lumirror S10" (
〔製造例10〕積層体(B3)の製造
ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)を基材「ルミラーS10」(厚み75μm、東レ社製)に変更し、粘着剤層の厚みを15μmに変更した以外は、製造例8と同じ手順により、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B3)を得た。 [Production Example 10] Production of Laminate (B3) The base material "Lumirror S10" (thickness 38 µm, manufactured by Toray) made of polyester resin was changed to the base material "Lumirror S10" (thickness 75 µm, manufactured by Toray) and adhesive A laminate (B3) having a constitution of separator/adhesive layer/resin film was obtained by the same procedure as in Production Example 8 except that the thickness of the agent layer was changed to 15 μm.
ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)を基材「ルミラーS10」(厚み75μm、東レ社製)に変更し、粘着剤層の厚みを15μmに変更した以外は、製造例8と同じ手順により、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B3)を得た。 [Production Example 10] Production of Laminate (B3) The base material "Lumirror S10" (thickness 38 µm, manufactured by Toray) made of polyester resin was changed to the base material "Lumirror S10" (thickness 75 µm, manufactured by Toray) and adhesive A laminate (B3) having a constitution of separator/adhesive layer/resin film was obtained by the same procedure as in Production Example 8 except that the thickness of the agent layer was changed to 15 μm.
〔製造例11〕積層体(B4)の製造
製造例2で得られた粘着剤組成物(2)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが20μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B4)を得た。 [Production Example 11] Production of Laminate (B4) The pressure-sensitive adhesive composition (2) obtained in Production Example 2 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 20 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B4) was obtained.
製造例2で得られた粘着剤組成物(2)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが20μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B4)を得た。 [Production Example 11] Production of Laminate (B4) The pressure-sensitive adhesive composition (2) obtained in Production Example 2 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 20 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B4) was obtained.
〔製造例12〕積層体(B5)の製造
製造例3で得られた粘着剤組成物(3)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが20μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B5)を得た。 [Production Example 12] Production of Laminate (B5) The pressure-sensitive adhesive composition (3) obtained in Production Example 3 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 20 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B5) was obtained.
製造例3で得られた粘着剤組成物(3)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが20μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B5)を得た。 [Production Example 12] Production of Laminate (B5) The pressure-sensitive adhesive composition (3) obtained in Production Example 3 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 20 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B5) was obtained.
〔製造例13〕積層体(B6)の製造
製造例4で得られた粘着剤組成物(4)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが20μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B6)を得た。 [Production Example 13] Production of laminate (B6) The pressure-sensitive adhesive composition (4) obtained in Production Example 4 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 20 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B6) was obtained.
製造例4で得られた粘着剤組成物(4)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが20μmとなるよう塗布し、乾燥温度130℃、乾燥時間30秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B6)を得た。 [Production Example 13] Production of laminate (B6) The pressure-sensitive adhesive composition (4) obtained in Production Example 4 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 20 μm, and was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B6) was obtained.
〔製造例14〕積層体(B7)の製造
製造例5で得られた粘着剤組成物(5)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが12μmとなるよう塗布し、乾燥温度130℃、乾燥時間30sの条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B7)を得た。 [Production Example 14] Production of Laminate (B7) The pressure-sensitive adhesive composition (5) obtained in Production Example 5 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 12 μm, and cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 s. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B7) was obtained.
製造例5で得られた粘着剤組成物(5)を、ポリエステル樹脂からなる基材「ルミラーS10」(厚み38μm、東レ社製)にファウンテンロールで乾燥後の厚みが12μmとなるよう塗布し、乾燥温度130℃、乾燥時間30sの条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ25μmのポリエステル樹脂からなる基材のシリコーン処理面を貼合せて、セパレータ/粘着剤層/樹脂フィルムの構成の積層体(B7)を得た。 [Production Example 14] Production of Laminate (B7) The pressure-sensitive adhesive composition (5) obtained in Production Example 5 was formed on a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) with a fountain roll. It was applied so that the thickness after drying would be 12 μm, and cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 s. In this way, the pressure-sensitive adhesive layer was prepared on the substrate. Then, a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm, one surface of which is treated with silicone, is attached to the surface of the adhesive layer to form a laminate having a constitution of separator/adhesive layer/resin film. (B7) was obtained.
〔実施例1〕
製造例8で得られた積層体(B1)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(1)を得た。結果を表1に示した。 [Example 1]
The separator was peeled off from the laminate (B1) obtained in Production Example 8, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (1). The results are shown in Table 1.
製造例8で得られた積層体(B1)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(1)を得た。結果を表1に示した。 [Example 1]
The separator was peeled off from the laminate (B1) obtained in Production Example 8, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (1). The results are shown in Table 1.
〔実施例2〕
製造例9で得られた積層体(B2)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(2)を得た。結果を表1に示した。 [Example 2]
The separator was peeled off from the laminate (B2) obtained in Production Example 9, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (2). The results are shown in Table 1.
製造例9で得られた積層体(B2)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(2)を得た。結果を表1に示した。 [Example 2]
The separator was peeled off from the laminate (B2) obtained in Production Example 9, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (2). The results are shown in Table 1.
〔実施例3〕
製造例10で得られた積層体(B3)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(3)を得た。結果を表1に示した。 [Example 3]
The separator was peeled off from the laminate (B3) obtained in Production Example 10, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The side was attached to obtain a laminate (3). The results are shown in Table 1.
製造例10で得られた積層体(B3)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(3)を得た。結果を表1に示した。 [Example 3]
The separator was peeled off from the laminate (B3) obtained in Production Example 10, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The side was attached to obtain a laminate (3). The results are shown in Table 1.
〔実施例4〕
製造例11で得られた積層体(B4)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(4)を得た。結果を表1に示した。 [Example 4]
The separator was peeled off from the laminate (B4) obtained in Production Example 11, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (4). The results are shown in Table 1.
製造例11で得られた積層体(B4)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(4)を得た。結果を表1に示した。 [Example 4]
The separator was peeled off from the laminate (B4) obtained in Production Example 11, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (4). The results are shown in Table 1.
〔実施例5〕
製造例12で得られた積層体(B5)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(5)を得た。結果を表1に示した。 [Example 5]
The separator was peeled off from the laminate (B5) obtained in Production Example 12, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (5). The results are shown in Table 1.
製造例12で得られた積層体(B5)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(5)を得た。結果を表1に示した。 [Example 5]
The separator was peeled off from the laminate (B5) obtained in Production Example 12, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (5). The results are shown in Table 1.
〔実施例6〕
製造例13で得られた積層体(B6)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(6)を得た。結果を表1に示した。 [Example 6]
The separator was peeled off from the laminate (B6) obtained in Production Example 13, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (6). The results are shown in Table 1.
製造例13で得られた積層体(B6)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(6)を得た。結果を表1に示した。 [Example 6]
The separator was peeled off from the laminate (B6) obtained in Production Example 13, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (6). The results are shown in Table 1.
〔比較例1〕
製造例14で得られた積層体(B7)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(C1)を得た。結果を表1に示した。 [Comparative Example 1]
The separator was peeled off from the laminate (B7) obtained in Production Example 14, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (C1). The results are shown in Table 1.
製造例14で得られた積層体(B7)からセパレータを剥離し、露出した粘着剤層に、製造例7で得られた積層体(A)の樹脂フィルム(シリコーン処理がされていない樹脂フィルム)側を貼り付け、積層体(C1)を得た。結果を表1に示した。 [Comparative Example 1]
The separator was peeled off from the laminate (B7) obtained in Production Example 14, and the exposed adhesive layer was covered with the resin film of the laminate (A) obtained in Production Example 7 (resin film not treated with silicone). The sides were attached to obtain a laminate (C1). The results are shown in Table 1.
本発明の積層体は、光学部材や電子部材の製造工程などに好適に利用し得る。
The laminated body of the present invention can be suitably used in the manufacturing process of optical members and electronic members.
樹脂フィルム(1) 10
粘着剤層(1) 20
樹脂フィルム(2) 30
粘着剤層(2) 40
樹脂フィルム(3) 50
貫通孔 60
積層体 100 Resin film (1) 10
Adhesive layer (1) 20
Resin film (2) 30
Adhesive layer (2) 40
Resin film (3) 50
Throughhole 60
Laminate 100
粘着剤層(1) 20
樹脂フィルム(2) 30
粘着剤層(2) 40
樹脂フィルム(3) 50
貫通孔 60
積層体 100 Resin film (1) 10
Adhesive layer (1) 20
Resin film (2) 30
Adhesive layer (2) 40
Resin film (3) 50
Through
Claims (2)
- 樹脂フィルム(1)、粘着剤層(1)、樹脂フィルム(2)、粘着剤層(2)、樹脂フィルム(3)をこの順に有する、5層以上の積層体であって、
該粘着剤層(1)と該樹脂フィルム(2)が直接に積層されてなり、
該樹脂フィルム(2)と該粘着剤層(2)が直接に積層されてなり、
該粘着剤層(1)と該樹脂フィルム(2)の積層部分は、長手方向と実質的に直交する方向に、幅0.5mm~10mmの貫通孔によって複数に区分けされてなり、
該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分の長手方向の長さが、1mm~2000mmであり、
直径6インチのロールに対して該樹脂フィルム(1)が外側になるように巻き付けたとき、該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分が該粘着剤層(2)から浮いている最大量が、該貫通孔の幅が5mm、該貫通孔によって区分けされた複数の該粘着剤層(1)と該樹脂フィルム(2)の積層部分の長手方向の長さが50mmのときに、0.2mm以下である、
積層体。 A laminate having five or more layers, which has a resin film (1), a pressure-sensitive adhesive layer (1), a resin film (2), a pressure-sensitive adhesive layer (2), and a resin film (3) in this order,
The pressure-sensitive adhesive layer (1) and the resin film (2) are directly laminated,
The resin film (2) and the adhesive layer (2) are directly laminated,
The laminated portion of the adhesive layer (1) and the resin film (2) is divided into a plurality of through holes having a width of 0.5 mm to 10 mm in a direction substantially orthogonal to the longitudinal direction,
The length in the longitudinal direction of the laminated portion of the plurality of pressure-sensitive adhesive layers (1) and the resin film (2) divided by the through holes is 1 mm to 2000 mm,
When the resin film (1) is wound around a roll having a diameter of 6 inches so that the resin film (1) is on the outer side, a laminated portion of a plurality of the adhesive layers (1) and the resin film (2) divided by the through holes Is the maximum amount of floating from the pressure-sensitive adhesive layer (2), the width of the through-hole is 5 mm, the plurality of pressure-sensitive adhesive layer (1) and the resin film (2) laminated portion divided by the through-hole When the length in the longitudinal direction of is 50 mm, it is 0.2 mm or less,
Laminate. - 前記樹脂フィルム(2)の平面方向側の総面積が、前記粘着剤層(2)の平面方向側の総面積よりも小さい、請求項1に記載の積層体。
The laminate according to claim 1, wherein the total area of the resin film (2) in the plane direction is smaller than the total area of the adhesive layer (2) in the plane direction.
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KR1020217023647A KR20210121042A (en) | 2019-01-29 | 2019-12-03 | laminate |
CN201980090792.7A CN113365810B (en) | 2019-01-29 | 2019-12-03 | Laminate body |
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JP2012126855A (en) * | 2010-12-17 | 2012-07-05 | Toyo Aluminum Ekco Products Kk | Adhesive sheet |
JP2013014012A (en) * | 2011-06-30 | 2013-01-24 | Three M Innovative Properties Co | Window adhesion laminated layer film having through-hole |
JP2014180847A (en) * | 2013-03-21 | 2014-09-29 | Nitto Denko Corp | Thin glass long-length body |
WO2018092904A1 (en) * | 2016-11-21 | 2018-05-24 | 日東電工株式会社 | Adhesive sheet |
WO2019230495A1 (en) * | 2018-05-30 | 2019-12-05 | 日東電工株式会社 | Pressure-sensitive-adhesive sheet for surface protection |
Cited By (1)
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US20220123257A1 (en) * | 2020-10-19 | 2022-04-21 | Samsung Display Co., Ltd. | Protective film and display device including the same |
Also Published As
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CN113365810B (en) | 2023-08-15 |
KR20210121042A (en) | 2021-10-07 |
JP7249160B2 (en) | 2023-03-30 |
JP2020121424A (en) | 2020-08-13 |
TWI826611B (en) | 2023-12-21 |
TW202037486A (en) | 2020-10-16 |
CN113365810A (en) | 2021-09-07 |
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