JP6301032B2 - Release film - Google Patents
Release film Download PDFInfo
- Publication number
- JP6301032B2 JP6301032B2 JP2017558029A JP2017558029A JP6301032B2 JP 6301032 B2 JP6301032 B2 JP 6301032B2 JP 2017558029 A JP2017558029 A JP 2017558029A JP 2017558029 A JP2017558029 A JP 2017558029A JP 6301032 B2 JP6301032 B2 JP 6301032B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- component
- resin
- modified polyolefin
- release film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 229920005989 resin Polymers 0.000 claims description 152
- 239000011347 resin Substances 0.000 claims description 152
- 229920005672 polyolefin resin Polymers 0.000 claims description 111
- -1 acrylic ester Chemical class 0.000 claims description 54
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 42
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 41
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 41
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 10
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 7
- 229920006267 polyester film Polymers 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 92
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- 238000000034 method Methods 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 23
- 238000003756 stirring Methods 0.000 description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000011344 liquid material Substances 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
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- 239000004743 Polypropylene Substances 0.000 description 9
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
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- 229920001296 polysiloxane Polymers 0.000 description 7
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- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
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- 229920001567 vinyl ester resin Polymers 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 1
- UFUAASKHUNQXBP-UHFFFAOYSA-N 2-[2-(4,4-dimethyl-5h-1,3-oxazol-2-yl)ethyl]-4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC(CCC=2OCC(C)(C)N=2)=N1 UFUAASKHUNQXBP-UHFFFAOYSA-N 0.000 description 1
- ZKTPGXSTOJXHIG-UHFFFAOYSA-N 2-cyclohexyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1CCCCC1 ZKTPGXSTOJXHIG-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
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- JHDONXSUZJAJEY-UHFFFAOYSA-N C=CC(C)(C)N=C=N Chemical compound C=CC(C)(C)N=C=N JHDONXSUZJAJEY-UHFFFAOYSA-N 0.000 description 1
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- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
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- 230000001680 brushing effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229960003574 milrinone Drugs 0.000 description 1
- VWUPWEAFIOQCGF-UHFFFAOYSA-N milrinone lactate Chemical compound [H+].CC(O)C([O-])=O.N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C VWUPWEAFIOQCGF-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- AMAWVOFJIULRGK-UHFFFAOYSA-N n'-(2,6-dimethylphenyl)-n-[4-[(2,6-dimethylphenyl)iminomethylideneamino]phenyl]methanediimine Chemical compound CC1=CC=CC(C)=C1N=C=NC1=CC=C(N=C=NC=2C(=CC=CC=2C)C)C=C1 AMAWVOFJIULRGK-UHFFFAOYSA-N 0.000 description 1
- MOQZJHKYQDFURQ-UHFFFAOYSA-N n'-tert-butyl-n-[4-(tert-butyliminomethylideneamino)butyl]methanediimine Chemical compound CC(C)(C)N=C=NCCCCN=C=NC(C)(C)C MOQZJHKYQDFURQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、粘着性、接着性を有するテープやフィルムなどを保護するためのフィルムとして好適な離型フィルムに関する。 The present invention relates to a release film suitable as a film for protecting tapes and films having adhesiveness and adhesiveness.
粘着・接着フィルムやシート（以下、単に粘着シートという）は、化粧板、塗装鋼板、窓ガラス、液晶パネル板、位相差板、導光板などの表面保護用フィルム等として広く用いられ、フレキシブルプリント基板や航空機等の構成部材として用いられている。 Adhesive / adhesive films and sheets (hereinafter simply referred to as adhesive sheets) are widely used as surface protection films such as decorative plates, coated steel plates, window glass, liquid crystal panel plates, retardation plates, light guide plates, etc., flexible printed circuit boards It is used as a component for aircraft and aircraft.
これらの粘着シートは、ブロッキングの防止や粘着・接着面（以下、単に粘着面という）の保護のために、粘着面に離型フィルムが貼り付けられている。一般的に離型フィルムは、製造工程においては軽い振動や衝撃で剥がれず、かつ、剥がす際には、スムーズに剥離できるように、適度な接着強度を有することが望まれている。
たとえば、特許文献１には、ポリエステルフィルムにポリプロピレン系変性ポリオレフィン樹脂を含有する樹脂層を設けてなる離型シートが開示されている。また、特許文献２には、ベースフィルムと接着剤からなる粘着シートに保護シート（離型フィルム）が積層されたカバーレイにおいて、打ち抜き性が良好な保護シート（離型フィルム）として、延伸ポリプロピレンフィルムとポリエチレンテレフタレートフィルムとが貼り合わされ、離型層が延伸ポリプロピレンフィルムであるものが開示されている。In these pressure-sensitive adhesive sheets, a release film is attached to the pressure-sensitive adhesive surface in order to prevent blocking and protect the pressure-sensitive adhesive / bonded surface (hereinafter simply referred to as a pressure-sensitive adhesive surface). In general, a release film is desired not to be peeled off by light vibration or impact in the manufacturing process, and to have an appropriate adhesive strength so that the release film can be smoothly peeled off.
For example, Patent Document 1 discloses a release sheet in which a polyester film is provided with a resin layer containing a polypropylene-based modified polyolefin resin. Patent Document 2 discloses a stretched polypropylene film as a protective sheet (release film) having good punchability in a coverlay in which a protective sheet (release film) is laminated on a pressure-sensitive adhesive sheet made of a base film and an adhesive. And a polyethylene terephthalate film are bonded together, and the release layer is a stretched polypropylene film.
一方、粘着剤成分が反応性（硬化性）樹脂である粘着シートは、離型フィルムを貼り合わせて室温で長期保管すると、粘着シートの粘着力が経時的に昂進し、離型フィルムが粘着シートから剥がれなくなるといった問題がある。
この問題を解決する方法として、たとえば、特許文献３には、シリコーン系離型剤を用いる方法が提案されている。On the other hand, the pressure-sensitive adhesive sheet whose pressure-sensitive adhesive component is a reactive (curable) resin, when the release film is laminated and stored for a long time at room temperature, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet increases over time, and the release film becomes the pressure-sensitive adhesive sheet. There is a problem that it will not peel off.
As a method for solving this problem, for example, Patent Document 3 proposes a method using a silicone-based release agent.
しかしながら、特許文献１の離型シートや、特許文献２のカバーレイを構成する保護シートは、貼り付けた離型シートや保護シートごと穴を開ける打ち抜き加工には適しているが、離型シートや保護シートを貼り付けた状態で粘着シートのみを打ち抜く加工（いわゆるハーフカット）では、離型シートや保護シートが粘着シートから浮いてしまうことがあった。これら離型シートや保護シートに浮きが生じると、部品の型に打ち抜かれた粘着シートが、搬送時に脱落してしまうことがあった。
また、特許文献３のシリコーン系離型剤を用いた離型フィルムは、粘着シートに貼り合わせて室温で長期保管しても、経時的に離型性が低下することがなく経時安定性に優れるが、シリコーン系離型剤の中に含まれる低分子量のシリコーン化合物が、粘着シートの粘着剤表面に移行して、残存することがあった。粘着シートの粘着剤表面に残存するシリコーン化合物は、粘着剤の粘着力の低下を起すだけでなく、印刷インクを弾いたり、電気の導通不良を引き起こす原因となる。このため、特にカバーレイや電磁波シールドフィルムなどの電子部品用の粘着シートに対しては、シリコーン類を一切使用しない「シリコーンフリー」の離型フィルムの開発が求められていた。 However, the release sheet of Patent Document 1 and the protective sheet constituting the cover lay of Patent Document 2 are suitable for punching processing to make a hole together with the attached release sheet or protective sheet, In the process of punching only the adhesive sheet with the protective sheet attached (so-called half cut), the release sheet or the protective sheet may float from the adhesive sheet. When the release sheet or the protective sheet is lifted, the pressure-sensitive adhesive sheet punched into the part mold may fall off during transportation.
In addition, the release film using the silicone-based release agent of Patent Document 3 is excellent in stability over time without degrading the release properties over time even when bonded to an adhesive sheet and stored for a long time at room temperature. However, the low molecular weight silicone compound contained in the silicone release agent may migrate to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet and remain. The silicone compound remaining on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet not only causes a decrease in the pressure-sensitive adhesive strength of the pressure-sensitive adhesive, but also causes the printing ink to repel and causes poor electrical conduction. For this reason, the development of a “silicone-free” release film that does not use any silicone has been demanded particularly for adhesive sheets for electronic parts such as coverlays and electromagnetic wave shielding films.
すなわち、本発明は、これらの問題点に鑑み、粘着シートに離型フィルムを貼り付けた状態で粘着シートのみを打ち抜くハーフカットなどの加工の際に、粘着シートからの浮きを抑制できる適度な接着強度を有し、かつ、粘着シートに貼り付けて室温で長期保管した場合でも保管前と変わらずスムーズに剥離できるという、相反する効果を併せ持つとともに、剥離時に離型剤が粘着シートの粘着剤表面に移行することがない離型フィルムを提供することを目的とする。 That is, in view of these problems, the present invention provides an appropriate adhesive capable of suppressing lifting from the pressure-sensitive adhesive sheet during processing such as half cut in which only the pressure-sensitive adhesive sheet is punched out with the release film attached to the pressure-sensitive adhesive sheet. It has strength and has the conflicting effect that it can be peeled off smoothly as it was before storage even when pasted on the pressure sensitive adhesive sheet and stored at room temperature for a long time. It aims at providing the release film which does not transfer to.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定の組成を有する樹脂層を基材フィルムに形成することによって、上記課題が解決できることを見出し、本発明に到達した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by forming a resin layer having a specific composition on a base film, and have reached the present invention.
すなわち、本発明の要旨は下記（１）〜（９）である。
（１）硬化性樹脂の粘着剤を有する粘着シート用の離型フィルムであって、
離型フィルムは、基材フィルムの少なくとも一方の面に樹脂層を有し、
樹脂層が、酸変性ポリオレフィン樹脂１００質量部、水酸基含有樹脂１０〜１０００質量部、および架橋剤０．３〜５０質量部を含有し、
酸変性ポリオレフィン樹脂が、酸変性成分と、アクリル酸エステル成分と、オレフィン成分とを含有し、
オレフィン成分がプロピレン成分を含有し、１−ブテン成分を含有しないことを特徴とする離型フィルム。
（２）酸変性ポリオレフィン樹脂における、アクリル酸エステル成分の含有量が１０質量％以下であり、かつ、プロピレン成分の含有量が１〜９６質量％であることを特徴とする（１）記載の離型フィルム。
（３）酸変性ポリオレフィン樹脂における、アクリル酸エステル成分とプロピレン成分の含有量の質量比（アクリル酸エステル成分／プロピレン成分）が０．１／９９．９〜２５．０／７５．０であることを特徴とする（１）または（２）記載の離型フィルム。
（４）酸変性ポリオレフィン樹脂のオレフィン成分におけるプロピレン成分の含有量が５０質量％以上であることを特徴とする（１）〜（３）のいずれかに記載の離型フィルム。
（５）酸変性ポリオレフィン樹脂における、アクリル酸エステル成分とプロピレン成分の含有量の合計と酸変性成分の含有量との質量比（（アクリル酸エステル成分＋プロピレン成分）／酸変性成分）が９９／１〜９５／５であることを特徴とする（１）〜（４）のいずれかに記載の離型フィルム。
（６）樹脂層における、アクリル酸エステル成分とプロピレン成分の含有量の合計と架橋剤の含有量との質量比（（アクリル酸エステル成分＋プロピレン成分）／架橋剤）が９９／１〜９０／１０であることを特徴とする（１）〜（５）のいずれかに記載の離型フィルム。
（７）酸変性ポリオレフィン樹脂は、酸変性成分およびアクリル酸エステル成分を含有する樹脂と、酸変性成分およびプロピレン成分を含有する樹脂との混合物であることを特徴とする（１）〜（６）のいずれかに記載の離型フィルム。
（８）基材フィルムがポリエステルフィルムまたはポリアミドフィルムであり、樹脂層の厚みが０．０１〜１μｍであることを特徴とする（１）〜（７）のいずれかに記載の離型フィルム。
（９）電磁波シールドフィルム用途で用いることを特徴とする（１）〜（８）のいずれかに記載の離型フィルム。
That is, the gist of the present invention is the following (1) to ( 9 ).
(1) A release film for a pressure-sensitive adhesive sheet having a curable resin pressure-sensitive adhesive,
Release film, on at least one surface of the substrate film have a resin layer,
The resin layer contains 100 parts by mass of an acid-modified polyolefin resin, 10 to 1000 parts by mass of a hydroxyl group-containing resin, and 0.3 to 50 parts by mass of a crosslinking agent.
The acid-modified polyolefin resin contains an acid-modified component, an acrylate component, and an olefin component,
A release film comprising an olefin component containing a propylene component and no 1-butene component .
(2) The acid-modified polyolefin resin has an acrylic ester component content of 10% by mass or less and a propylene component content of 1 to 96% by mass, according to (1). Mold film.
(3) The mass ratio (acrylic acid ester component / propylene component) of the content of the acrylic acid ester component and the propylene component in the acid-modified polyolefin resin is from 0.1 / 99.9 to 25.0 / 75.0. A release film as described in (1) or (2).
(4) The release film according to any one of (1) to (3), wherein the content of the propylene component in the olefin component of the acid-modified polyolefin resin is 50% by mass or more .
(5 ) In the acid-modified polyolefin resin, the mass ratio of the total content of the acrylic ester component and the propylene component and the content of the acid-modified component ((acrylic ester component + propylene component) / acid-modified component) is 99 / It is 1-95 / 5, The release film in any one of (1)-( 4 ) characterized by the above-mentioned.
( 6 ) The mass ratio of the total content of the acrylic ester component and the propylene component and the content of the crosslinking agent ((acrylic ester component + propylene component) / crosslinking agent) in the resin layer is 99/1 to 90 /. 10. The release film according to any one of (1) to ( 5 ), which is 10.
( 7 ) The acid-modified polyolefin resin is a mixture of a resin containing an acid-modified component and an acrylic ester component, and a resin containing an acid-modified component and a propylene component (1) to ( 6 ), A release film according to any one of the above.
( 8 ) The release film according to any one of (1) to ( 7 ), wherein the base film is a polyester film or a polyamide film, and the thickness of the resin layer is 0.01 to 1 μm .
(9 ) The release film according to any one of (1) to ( 8 ), which is used for electromagnetic shielding film applications.
本発明によれば、ハーフカットなどの打ち抜き加工工程においても浮きが生じない程度の適度な接着強度を有し、また、粘着シートに貼り付けた状態において室温で長期保管した場合でも保管前と同等の優れた離型性を有し、さらに剥離時に離型剤が粘着シートの粘着剤表面に移行することがない離型フィルムを提供することができる。 According to the present invention, it has an appropriate adhesive strength that does not cause floating even in a punching process such as half-cut, and even when stored for a long time at room temperature in a state of being attached to an adhesive sheet, it is equivalent to that before storage In addition, it is possible to provide a release film that has excellent release properties and that does not migrate to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet during peeling.
本発明の離型フィルムは、基材フィルムの少なくとも一方の面に樹脂層を有するものであり、樹脂層は、酸変性ポリオレフィン樹脂、水酸基含有樹脂、および架橋剤を含有することが必要である。 The release film of the present invention has a resin layer on at least one surface of a base film, and the resin layer needs to contain an acid-modified polyolefin resin, a hydroxyl group-containing resin, and a crosslinking agent.
本発明において、樹脂層を構成する酸変性ポリオレフィン樹脂は、酸変性成分、オレフィン成分としてプロピレン成分、およびアクリル酸エステル成分を含有することが必要である。本発明において、酸変性ポリオレフィン樹脂は、単独の樹脂としてこれらの３成分を含有するものでもよく、またこれら３成分の一部を含有する樹脂を２種以上混合して、混合物においてこれら３成分を含有するものでもよい。本発明における酸変性ポリオレフィン樹脂は、前記３成分を後述する質量比で含有させることが好ましいことから、３成分の一部を含有する樹脂を２種以上混合することが好ましい。 In the present invention, the acid-modified polyolefin resin constituting the resin layer needs to contain a propylene component and an acrylate component as the acid-modified component and the olefin component. In the present invention, the acid-modified polyolefin resin may contain these three components as a single resin, or two or more kinds of resins containing a part of these three components are mixed, and these three components are mixed in the mixture. It may be contained. Since the acid-modified polyolefin resin in the present invention preferably contains the three components at a mass ratio described later, it is preferable to mix two or more resins containing a part of the three components.
本発明において、酸変性ポリオレフィン樹脂は、オレフィン成分としてプロピレン成分を含有することが必要である。
酸変性ポリオレフィン樹脂における、プロピレン成分の含有量は、離型性の点から、１〜９６質量％、１〜９２質量％、もしくは１〜９０質量％であることが好ましく、３０〜９６質量％、３０〜９２質量％、もしくは３０〜９０質量％であることがより好ましく、４０〜９６質量、４０〜９２質量％、もしくは４０〜９０質量％であることがさらに好ましく、５０〜９６質量％、５０〜９２質量％、もしくは５０〜９０質量％であることが特に好ましい。
オレフィン成分におけるプロピレン成分の含有量は、得られる樹脂層に適度な剥離強度を付与することができるとともに、剥離力の経時的増加を抑制することができるため、５０質量％以上であることが好ましい。In the present invention, the acid-modified polyolefin resin needs to contain a propylene component as an olefin component.
The content of the propylene component in the acid-modified polyolefin resin is preferably 1 to 96% by mass, 1 to 92% by mass, or 1 to 90% by mass, from 30 to 96% by mass, from the viewpoint of releasability. More preferably, it is 30-92 mass%, or 30-90 mass%, It is more preferable that it is 40-96 mass, 40-92 mass%, or 40-90 mass%, 50-96 mass%, 50 It is especially preferable that it is -92 mass% or 50-90 mass%.
The content of the propylene component in the olefin component is preferably 50% by mass or more because it can impart an appropriate peel strength to the resulting resin layer and suppress an increase in peel strength over time. .
本発明において、酸変性ポリオレフィン樹脂のオレフィン成分は、プロピレン成分以外のオレフィン成分を含んでいてもよく、プロピレン成分以外のオレフィン成分としては、特に限定されないが、エチレン、イソブチレン、２−ブテン、１−ブテン、１−ペンテン、１−ヘキセン等の炭素数２〜６のアルケン等が挙げられ、これらの混合物であってもよい。本発明では、長期保管後の剥離性、打ち抜き性の観点から、酸変性ポリオレフィン樹脂のオレフィン成分は、１−ブテンを含有しない方が好ましい。 In the present invention, the olefin component of the acid-modified polyolefin resin may contain an olefin component other than the propylene component, and the olefin component other than the propylene component is not particularly limited, but ethylene, isobutylene, 2-butene, 1- C2-C6 alkenes, such as butene, 1-pentene, 1-hexene, etc. are mentioned, A mixture thereof may be sufficient. In the present invention, it is preferable that the olefin component of the acid-modified polyolefin resin does not contain 1-butene from the viewpoint of peelability after long-term storage and punchability.
本発明において、酸変性ポリオレフィン樹脂の酸変性成分としては、不飽和カルボン酸成分が挙げられ、具体的には、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸等のほか、不飽和ジカルボン酸のハーフエステル、ハーフアミド等が挙げられる。中でも、後述する樹脂の水性分散化において、樹脂を安定的に分散するために、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましく、アクリル酸、メタクリル酸、無水マレイン酸が特に好ましい。これらの酸変性成分は酸変性ポリオレフィン樹脂中に２種類以上含まれていてもよい。 In the present invention, an acid-modified component of the acid-modified polyolefin resin includes an unsaturated carboxylic acid component, specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid. In addition to acids, crotonic acid, and the like, unsaturated dicarboxylic acid half esters, half amides and the like can be mentioned. Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable in order to stably disperse the resin in the aqueous dispersion of the resin that will be described later. Two or more of these acid-modified components may be contained in the acid-modified polyolefin resin.
酸変性ポリオレフィン樹脂における酸変性成分の割合は、１〜１０質量％であることが好ましく、１．５〜７質量％であることがより好ましく、２〜５質量％であることがさらに好ましい。酸変性成分の割合が１質量％未満の場合は、樹脂層に含まれる酸変性ポリオレフィン樹脂中の極性基の割合が少なくなるため、基材フィルムとの十分な密着性が得られないことがあり、粘着シートを汚染する可能性がある。さらに後述する樹脂の水性分散化において、当該樹脂を安定的に分散するのが困難になる傾向がある。一方、酸変性成分の割合が１０質量％を超える場合は、極性基の割合が多くなるため樹脂層と基材フィルムとの密着性が十分にはなるが、樹脂層と粘着シートとの密着性も同時に高くなるため、粘着シートとの離型性が低下する傾向がある。 The ratio of the acid-modified component in the acid-modified polyolefin resin is preferably 1 to 10% by mass, more preferably 1.5 to 7% by mass, and further preferably 2 to 5% by mass. When the ratio of the acid-modified component is less than 1% by mass, the ratio of the polar group in the acid-modified polyolefin resin contained in the resin layer decreases, so that sufficient adhesion to the base film may not be obtained. There is a possibility of contaminating the adhesive sheet. Furthermore, in the aqueous dispersion of the resin described later, it tends to be difficult to stably disperse the resin. On the other hand, when the proportion of the acid-modified component exceeds 10% by mass, the proportion of the polar group increases, so that the adhesion between the resin layer and the substrate film is sufficient, but the adhesion between the resin layer and the pressure-sensitive adhesive sheet. At the same time, the releasability from the pressure-sensitive adhesive sheet tends to decrease.
酸変性ポリオレフィン樹脂を構成するアクリル酸エステル成分としては、（メタ）アクリル酸と炭素数１〜３０のアルコールとのエステル化物が挙げられ、中でも入手のし易さの点から、（メタ）アクリル酸と炭素数１〜２０のアルコールとのエステル化物が好ましい。そのような化合物の具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル等が挙げられる。これらの混合物を用いてもよい。この中で、基材フィルムとの接着性の点から、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸オクチルがより好ましく、アクリル酸エチル、アクリル酸ブチルがさらに好ましく、アクリル酸エチルが特に好ましい。「（メタ）アクリル酸〜」とは、「アクリル酸〜またはメタクリル酸〜」を意味する。
アクリル酸エステル成分は、酸変性成分と同様、分子内に極性基を有している。そのためアクリル酸エステル成分を酸変性ポリオレフィン樹脂中に含めることによって、粘着シートとの接着性や、基材フィルムとの密着性が高くなる。しかし、アクリル酸エステル成分量が多すぎると、オレフィン由来の樹脂の性質が失われ、粘着シートとの離型性が低下する可能性がある。酸変性ポリオレフィン樹脂における、アクリル酸エステル成分の含有量は、１０質量％以下であることが好ましく、０．１〜１０質量％、０．１〜８質量％であることがより好ましく、０．１〜４質量％、０．３〜１０質量％、もしくは０．３〜８質量％であることがさらに好ましく、０．３〜４質量％であることが特に好ましい。
なお、アクリル酸エステル成分を含有しても、基材フィルムとの密着性以外に樹脂層が有する離型性を損ねることがない。Examples of the acrylic ester component constituting the acid-modified polyolefin resin include esterified products of (meth) acrylic acid and alcohols having 1 to 30 carbon atoms, and (meth) acrylic acid is particularly easy to obtain. And an esterified product of C1-20 alcohol. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, and octyl acrylate are more preferable from the viewpoint of adhesion to the base film, and ethyl acrylate. Further, butyl acrylate is more preferable, and ethyl acrylate is particularly preferable. “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”.
The acrylic ester component has a polar group in the molecule, like the acid-modified component. Therefore, by including the acrylic ester component in the acid-modified polyolefin resin, the adhesion to the pressure-sensitive adhesive sheet and the adhesion to the base film are enhanced. However, if the amount of the acrylate component is too large, the properties of the olefin-derived resin are lost, and the releasability from the pressure-sensitive adhesive sheet may be reduced. The content of the acrylic ester component in the acid-modified polyolefin resin is preferably 10% by mass or less, more preferably 0.1 to 10% by mass, and more preferably 0.1 to 8% by mass. It is more preferable that it is -4 mass%, 0.3-10 mass%, or 0.3-8 mass%, and it is especially preferable that it is 0.3-4 mass%.
In addition, even if it contains an acrylic ester component, the releasability of the resin layer other than the adhesion to the base film is not impaired.
酸変性ポリオレフィン樹脂における、上記アクリル酸エステル成分とプロピレン成分の含有量の質量比（アクリル酸エステル／プロピレン）は、初期剥離性と長期保管後の剥離性を両立する観点から、０．１／９９．９〜２５．０／７５．０であることが好ましく、０．２／９９．８〜１５．０／８５．０であることがより好ましく、０．５／９９．５〜１０．０／９０．０であることがさらに好ましく、０．７／９９．３〜７．０／９３．０であることが特に好ましい。 In the acid-modified polyolefin resin, the mass ratio (acrylic ester / propylene) of the acrylate component and the propylene component is 0.1 / 99 from the viewpoint of achieving both initial peelability and peelability after long-term storage. 9.9 to 25.0 / 75.0, more preferably 0.2 / 99.8 to 15.0 / 85.0, 0.5 / 99.5 to 10.0 / 90.0 is more preferable, and 0.7 / 99.3 to 7.0 / 93.0 is particularly preferable.
上記、酸変性成分と、アクリル酸エステル成分と、プロピレン成分とを含有する酸変性ポリオレフィン樹脂は、アクリル酸エステル成分とプロピレン成分の含有量の合計と、酸変性成分の含有量との質量比（（アクリル酸エステル成分＋プロピレン成分）／酸変性成分）が９９／１〜９５／５であることがより好ましい。 The acid-modified polyolefin resin containing the acid-modified component, the acrylate component, and the propylene component is a mass ratio of the total content of the acrylate component and the propylene component and the content of the acid-modified component ( (Acrylic ester component + propylene component) / acid-modified component) is more preferably 99/1 to 95/5.
また酸変性ポリオレフィン樹脂は、ポリプロピレン系樹脂に前述の酸変性成分としての不飽和カルボン酸成分を導入したものが好ましく、その方法は特に限定されない。例えば、ラジカル発生剤の存在下で、ポリプロピレン系樹脂と不飽和カルボン酸とをプロピレン系樹脂の融点以上に加熱溶融して反応させる方法や、ポリプロピレン系樹脂と不飽和カルボン酸とを有機溶剤に溶解させた後、ラジカル発生剤の存在下で加熱、撹拌して反応させる方法などにより、ポリプロピレン系樹脂に不飽和カルボン酸成分をグラフト共重合する方法が挙げられる。操作が簡便である点から、前者の方法が好ましい。
グラフト共重合に使用するラジカル発生剤としては、例えば、ジ−ｔｅｒｔ−ブチルパーオキシド、ジクミルパーオキシド、ｔｅｒｔ−ブチルヒドロパーオキシド、ｔｅｒｔ−ブチルクミルパーオキシド、ベンゾイルパーオキシド、ジラウリルパーオキシド、クメンハイドロパーオキシド、ｔｅｒｔ−ブチルパーオキシベンゾエート、メチルエチルケトンパーオキシド、ジ−ｔｅｒｔ−ブチルジパーフタレートなどの有機過酸化物類や、アゾビスイソブチロニトリルなどのアゾニトリル類が挙げられる。これらは、反応温度に基づいて適宜選択して使用すればよい。The acid-modified polyolefin resin is preferably a polypropylene resin in which the unsaturated carboxylic acid component as the acid-modifying component described above is introduced, and the method is not particularly limited. For example, a method in which a polypropylene resin and an unsaturated carboxylic acid are heated and melted to a temperature higher than the melting point of the propylene resin in the presence of a radical generator, or a polypropylene resin and an unsaturated carboxylic acid are dissolved in an organic solvent. Examples thereof include a method in which an unsaturated carboxylic acid component is graft copolymerized with a polypropylene resin by a method of reacting by heating and stirring in the presence of a radical generator. The former method is preferable because the operation is simple.
Examples of the radical generator used for graft copolymerization include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, Examples thereof include organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, and di-tert-butyl diperphthalate, and azonitriles such as azobisisobutyronitrile. These may be appropriately selected and used based on the reaction temperature.
酸変性ポリオレフィン樹脂は、上記成分以外に、他の成分を、酸変性ポリオレフィン樹脂全体の１０質量％以下程度、含有してもよい。他の成分としては、１−オクテン；（メタ）アクリル酸アミド類；メチルビニルエーテル、エチルビニルエーテルなどのアルキルビニルエーテル類；ぎ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニルなどのビニルエステル類ならびにビニルエステル類を塩基性化合物などでケン化して得られるビニルアルコール；２−ヒドロキシエチルアクレート；グリシジル（メタ）アクリレート；（メタ）アクリロニトリル；スチレン；置換スチレン；ハロゲン化ビニル類；ハロゲン化ビニル類；ハロゲン化ビリニデン類；一酸化炭素；二酸化硫黄；などが挙げられる。これらの混合物を用いることもできる。 In addition to the above components, the acid-modified polyolefin resin may contain other components in an amount of about 10% by mass or less based on the total acid-modified polyolefin resin. Other components include 1-octene; (meth) acrylic amides; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate Vinyl alcohol obtained by saponifying esters and vinyl esters with basic compounds, etc .; 2-hydroxyethyl acrylate; glycidyl (meth) acrylate; (meth) acrylonitrile; styrene; substituted styrene; halogenated vinyls; And vinylidene halides, carbon monoxide, sulfur dioxide, and the like. Mixtures of these can also be used.
酸変性ポリオレフィン樹脂において、各成分の共重合形態は限定されず、ランダム共重合、ブロック共重合等が挙げられる。なかでも、重合のし易さの点から、ランダム共重合されていることが好ましい。また、本発明の構成成分比率となるように２種以上のポリオレフィン樹脂を混合したものであってもよい。 In the acid-modified polyolefin resin, the copolymerization form of each component is not limited, and examples thereof include random copolymerization and block copolymerization. Of these, random copolymerization is preferred from the viewpoint of ease of polymerization. Moreover, what mixed 2 or more types of polyolefin resin so that it may become the structural component ratio of this invention may be sufficient.
本発明において、樹脂層は、上記酸変性ポリオレフィン樹脂とともに、水酸基含有樹脂を含有することが必要である。樹脂層において、水酸基含有樹脂が、酸変性ポリオレフィン樹脂中に分散することによって、酸変性ポリオレフィン樹脂と架橋剤が有する離型性を向上させると同時に、剥離力の経時的増加を抑制することができ、また、水酸基含有樹脂自体が有する基材フィルムとの密着性を発揮することができる。 In the present invention, the resin layer needs to contain a hydroxyl group-containing resin together with the acid-modified polyolefin resin. In the resin layer, when the hydroxyl group-containing resin is dispersed in the acid-modified polyolefin resin, the release property of the acid-modified polyolefin resin and the crosslinking agent can be improved, and at the same time, the increase in peel strength can be suppressed. Moreover, adhesiveness with the base film which hydroxyl-containing resin itself has can be exhibited.
水酸基含有樹脂の種類は、特に限定されないが、ビニルエステルの（共）重合体を完全または部分ケン化したポリビニルアルコール、ブテンジオール−ビニルアルコール共重合体、エチレン−ビニルアルコール共重合体などのビニルアルコール系樹脂などが挙げられる。
水酸基含有樹脂は、後述のように液状物として使用する場合のために、水溶性を有していることが好ましい。
水酸基含有樹脂としてのポリビニルアルコールの平均重合度は、特に限定されるものではなく、例えば、２００〜５，０００であり、樹脂層を形成するための液状物の安定性向上の観点からは、３００〜２，０００であることが好ましい。The type of the hydroxyl group-containing resin is not particularly limited, but vinyl alcohol such as polyvinyl alcohol, butenediol-vinyl alcohol copolymer, ethylene-vinyl alcohol copolymer obtained by completely or partially saponifying vinyl ester (co) polymer. Based resins and the like.
The hydroxyl group-containing resin preferably has water solubility for use as a liquid as described later.
The average polymerization degree of polyvinyl alcohol as the hydroxyl group-containing resin is not particularly limited, and is, for example, 200 to 5,000. From the viewpoint of improving the stability of the liquid material for forming the resin layer, 300 is used. It is preferably ˜2,000.
樹脂層における、水酸基含有樹脂の含有量は、酸変性ポリオレフィン樹脂１００質量部に対して、１０〜１０００質量部であることが必要であり、２０〜５００質量部であることが好ましく、５０〜３００質量部であることがより好ましい。水酸基含有樹脂の含有量が１０質量部未満では、経時的に離型性に乏しくなる傾向があり、１０００質量部を超えると、樹脂層を形成するための液状物の粘度が高くなり、塗工ムラを生じやすくなるとともに、ゲルが生じることがある。 The content of the hydroxyl group-containing resin in the resin layer is required to be 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, and 50 to 300 parts per 100 parts by mass of the acid-modified polyolefin resin. More preferably, it is part by mass. If the content of the hydroxyl group-containing resin is less than 10 parts by mass, the releasability tends to be poor over time, and if it exceeds 1000 parts by mass, the viscosity of the liquid material for forming the resin layer increases, Unevenness is likely to occur, and gel may be generated.
本発明において水酸基含有樹脂として市販のものを使用することができ、例えば、日本酢ビ・ポバール社製「Ｊ−ポバール」の「ＪＴ−０５」、「ＶＣ−１０」、「ＪＰ−１８」、「ＵＭＲ−１０ＨＨ」；クラレ社製「クラレポバール」の「ＰＶＡ−１０３」、「ＰＶＡ−１０５」などのポリビニルアルコール、日本合成化学社製ソアノール「１６ＤＸ」などのエチレン−ビニルアルコール共重合体、日本合成化学社製ニチゴーＧポリマー「ＯＫＳ−８０４９Ｐ」などのブテンジオール−ビニルアルコール共重合体などが挙げられる。 In the present invention, a commercially available one can be used as the hydroxyl group-containing resin. For example, “J-05”, “VC-10”, “JP-18” of “J-Poval” manufactured by Nippon Vinegar Poval Corporation, “UMR-10HH”; polyvinyl alcohol such as “PVA-103” and “PVA-105” of “Kuraray Poval” manufactured by Kuraray Co., Ltd., ethylene-vinyl alcohol copolymer such as Soarnol “16DX” manufactured by Nippon Synthetic Chemical Co., Ltd., Japan Examples include butenediol-vinyl alcohol copolymers such as Nichigo G polymer “OKS-8049P” manufactured by Synthetic Chemical Co., Ltd.
本発明において、樹脂層は、上記酸変性ポリオレフィン樹脂や水酸基含有樹脂とともに架橋剤を含有することが必要である。架橋剤を含むことにより樹脂層の構成成分が架橋し、樹脂層の凝集力を向上させて粘着シートに移行しにくくさせたり、剥離力の経時的増加を抑制することができ、また耐水性を向上させたりすることができる。 In the present invention, the resin layer needs to contain a crosslinking agent together with the acid-modified polyolefin resin and the hydroxyl group-containing resin. By containing a cross-linking agent, the constituent components of the resin layer are cross-linked, the cohesive force of the resin layer is improved and it is difficult to transfer to the pressure-sensitive adhesive sheet, the increase in peel strength with time can be suppressed, and the water resistance is improved. It can be improved.
樹脂層における、架橋剤の含有量は、酸変性ポリオレフィン樹脂１００質量部に対して、０．３〜５０質量部であることが必要であり、０．５〜３０質量部であることが好ましく、１〜１０質量部であることがより好ましい。架橋剤の含有量が０．３質量部未満であると、樹脂層の凝集力が弱くなり、樹脂層が粘着シートに移行しやすくなり、また、経時的に離型性に乏しくなり、５０質量部を超えると、樹脂層と粘着シートとの間で反応を生じ、離型性に乏しくなることがある。 The content of the crosslinking agent in the resin layer is required to be 0.3 to 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin, and preferably 0.5 to 30 parts by mass, It is more preferable that it is 1-10 mass parts. When the content of the crosslinking agent is less than 0.3 parts by mass, the cohesive force of the resin layer becomes weak, the resin layer easily moves to the pressure-sensitive adhesive sheet, and the releasability becomes poor with time, and 50 mass. When it exceeds the part, a reaction occurs between the resin layer and the pressure-sensitive adhesive sheet, and the releasability may be poor.
樹脂層を構成する酸変性ポリオレフィン樹脂、水酸基含有樹脂、および架橋剤のうち、酸変性ポリオレフィン樹脂を構成するアクリル酸エステル成分とプロピレン成分の含有量の合計と、架橋剤の含有量との質量比（（アクリル酸エステル成分＋プロピレン成分）／酸変性成分）が９９／１〜９５／５であることが、長期保管後の剥離性と接着シートの残留接着性を両立させる観点から好ましい。 Of the acid-modified polyolefin resin, the hydroxyl group-containing resin, and the crosslinking agent constituting the resin layer, the mass ratio of the total content of the acrylic ester component and the propylene component constituting the acid-modified polyolefin resin and the content of the crosslinking agent It is preferable that ((acrylic ester component + propylene component) / acid-modified component) is 99/1 to 95/5 from the viewpoint of achieving both peelability after long-term storage and residual adhesiveness of the adhesive sheet.
架橋剤としては、カルボキシル基と反応する官能基を分子内に複数個有する化合物等を用いることができ、このうちイソシアネート化合物、メラミン化合物、尿素化合物、エポキシ化合物、カルボジイミド化合物、オキサゾリン化合物等が好ましく、特に、カルボジイミド化合物、オキサゾリン化合物が効果的である。これらの架橋剤は組み合わせて使用してもよい。 As the crosslinking agent, a compound having a plurality of functional groups that react with a carboxyl group in the molecule can be used, among which an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, a carbodiimide compound, an oxazoline compound, and the like are preferable. In particular, carbodiimide compounds and oxazoline compounds are effective. These crosslinking agents may be used in combination.
架橋剤として用いるカルボジイミド化合物は、分子中に１つ以上のカルボジイミド基を有しているものであれば特に限定されるものではない。カルボジイミド化合物は、１つのカルボジイミド部分において、酸変性ポリオレフィン樹脂の酸変性部分における２つのカルボキシル基とエステルを形成し、架橋を達成する。
カルボジイミド化合物の具体例として、例えば、ｐ−フェニレン−ビス（２，６−キシリルカルボジイミド）、テトラメチレン−ビス（ｔ−ブチルカルボジイミド）、シクロヘキサン−１，４−ビス（メチレン−ｔ−ブチルカルボジイミド）などのカルボジイミド基を有する化合物や、カルボジイミド基を有する重合体であるポリカルボジイミドが挙げられる。これらの１種または２種以上を用いることができる。これらの中でも、取り扱いやすさから、ポリカルボジイミドが好ましい。
ポリカルボジイミドの市販品としては、日清紡社製のカルボジライトシリーズが挙げられ、具体的には、水溶性タイプの「ＳＶ−０２」、「Ｖ−０２」、「Ｖ−０２−Ｌ２」、「Ｖ−０４」；エマルションタイプの「Ｅ−０１」、「Ｅ−０２」；有機溶液タイプの「Ｖ−０１」、「Ｖ−０３」、「Ｖ−０７」、「Ｖ−０９」；無溶剤タイプの「Ｖ−０５」が挙げられる。The carbodiimide compound used as the crosslinking agent is not particularly limited as long as it has one or more carbodiimide groups in the molecule. The carbodiimide compound forms an ester with two carboxyl groups in the acid-modified part of the acid-modified polyolefin resin in one carbodiimide part to achieve crosslinking.
Specific examples of the carbodiimide compound include, for example, p-phenylene-bis (2,6-xylylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide). Examples thereof include compounds having a carbodiimide group such as polycarbodiimide which is a polymer having a carbodiimide group. These 1 type (s) or 2 or more types can be used. Among these, polycarbodiimide is preferable from the viewpoint of ease of handling.
Examples of commercially available products of polycarbodiimide include carbodilite series manufactured by Nisshinbo Co., Ltd. Specifically, water-soluble types “SV-02”, “V-02”, “V-02-L2”, “ Emulsion type “E-01”, “E-02”; Organic solution type “V-01”, “V-03”, “V-07”, “V-09”; Type "V-05".
架橋剤として用いるオキサゾリン化合物は、分子中にオキサゾリン基を２つ以上有しているものであれば、特に限定されるものではない。オキサゾリン化合物は、２つのオキサゾリン部分のそれぞれにおいて、酸変性ポリオレフィン樹脂の酸変性部分における１つのカルボキシル基とアミドエステルを形成し、架橋を達成する。
オキサゾリン化合物の具体例として、例えば、２，２′−ビス（２−オキサゾリン）、２，２′−エチレン−ビス（４，４′−ジメチル−２−オキサゾリン）、２，２′−ｐ−フェニレン−ビス（２−オキサゾリン）、ビス（２−オキサゾリニルシクロヘキサン）スルフィドなどのオキサゾリン基を有する化合物や、オキサゾリン基含有ポリマーが挙げられる。これらの１種または２種以上を用いることができる。これらの中でも、取り扱いやすさからオキサゾリン基含有ポリマーが好ましい。
オキサゾリン基含有ポリマーの市販品としては、日本触媒社製のエポクロスシリーズが挙げられ、具体的には、水溶性タイプの「ＷＳ−５００」、「ＷＳ−７００」；エマルションタイプの「Ｋ−１０１０Ｅ」、「Ｋ−１０２０Ｅ」、「Ｋ−１０３０Ｅ」、「Ｋ−２０１０Ｅ」、「Ｋ−２０２０Ｅ」、「Ｋ−２０３０Ｅ」などが挙げられる。The oxazoline compound used as the crosslinking agent is not particularly limited as long as it has two or more oxazoline groups in the molecule. The oxazoline compound forms an amide ester with one carboxyl group in the acid-modified portion of the acid-modified polyolefin resin in each of the two oxazoline portions to achieve crosslinking.
Specific examples of the oxazoline compound include, for example, 2,2'-bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene. Examples thereof include compounds having an oxazoline group such as bis (2-oxazoline) and bis (2-oxazolinylcyclohexane) sulfide, and oxazoline group-containing polymers. These 1 type (s) or 2 or more types can be used. Among these, an oxazoline group-containing polymer is preferable because of ease of handling.
Commercially available products of the oxazoline group-containing polymer include EPOCROSS series manufactured by Nippon Shokubai Co., Ltd. Specifically, water-soluble type “WS-500”, “WS-700”; emulsion type “K-1010E” ”,“ K-1020E ”,“ K-1030E ”,“ K-2010E ”,“ K-2020E ”,“ K-2030E ”, and the like.
本発明において、樹脂層は、本発明の効果を損なわない範囲で、滑剤を含有してもよい。滑剤として、例えば、炭酸カルシウム、炭酸マグネシウム、酸化カルシウム、酸化亜鉛、酸化マグネシウム、酸化ケイ素、ケイ酸ソーダ、水酸化アルミニウム、酸化鉄、酸化ジルコニウム、硫酸バリウム、酸化チタン、酸化錫、三酸化アンチモン、カーボンブラック、二硫化モリブデン等の無機粒子や、アクリル系架橋重合体、スチレン系架橋重合体、シリコーン樹脂、フッ素樹脂、ベンゾグアナミン樹脂、フェノール樹脂、ナイロン樹脂、ポリエチレンワックス等の有機粒子、界面活性剤等が挙げられる。 In the present invention, the resin layer may contain a lubricant as long as the effects of the present invention are not impaired. As a lubricant, for example, calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, Inorganic particles such as carbon black and molybdenum disulfide, organic particles such as acrylic cross-linked polymers, styrene cross-linked polymers, silicone resins, fluororesins, benzoguanamine resins, phenol resins, nylon resins, polyethylene wax, surfactants, etc. Is mentioned.
本発明における樹脂層は、酸変性ポリオレフィン樹脂に加えて、特定量の水酸基含有樹脂と架橋剤とを含有するため、例えば、ウレタンやエポキシ系の接着シートなどの反応性を有する粘着シートに貼り付けても、優れた離型性を有し、また、このような接着シートに離型フィルムの樹脂層を貼り付けた状態で、室温で保管しても、経時的に剥離強度が高くなることを抑制することができる。具体的には、本発明の離型フィルムの樹脂層をウレタン系熱硬化接着シート（トーヨーケム社製ＬＩＯＥＬＭ ＴＳＵ００４１ＳＩ−２５ＤＬ）に貼り付けて測定したときの接着シートと樹脂層との間の剥離力（ｇｆ／５０ｍｍ）は、貼り付けた直後の剥離力Ｐ０と、２５℃で３０日間経過した後の剥離力Ｐ１において、式（１）〜（２）を満たすことが好ましい。
Ｐ１／Ｐ０≦１０ （１）
５０≦Ｐ０≦２００ （２）Since the resin layer in the present invention contains a specific amount of a hydroxyl group-containing resin and a crosslinking agent in addition to the acid-modified polyolefin resin, for example, it is affixed to a reactive adhesive sheet such as urethane or an epoxy adhesive sheet. However, it has excellent releasability, and even if it is stored at room temperature with the resin layer of the release film attached to such an adhesive sheet, the peel strength increases with time. Can be suppressed. Specifically, the peel strength between the adhesive sheet and the resin layer when the resin layer of the release film of the present invention is attached to a urethane thermosetting adhesive sheet (LIOELM TSU0041SI-25DL manufactured by Toyochem Corp.) gf / 50 mm) preferably satisfies the formulas (1) to (2) in the peel force P0 immediately after being attached and the peel force P1 after 30 days at 25 ° C.
P1 / P0 ≦ 10 (1)
50 ≦ P0 ≦ 200 (2)
また本発明の離型フィルムは、樹脂層成分が粘着シートへ移行しがたいため、粘着シートとしてのウレタン系熱硬化接着シートは、樹脂層を貼り付けた後においても粘着剤の接着強度の低下が少なく、残留接着率を７０％以上とすることができ、好ましくは８０％以上、より好ましくは８５％以上とすることができる。
粘着シートのウレタン系粘着剤表面が離型フィルムの樹脂層により汚染された場合、粘着シートの再粘着性が低下し、粘着シートとしての性能を損なう。したがって、残留接着率は高い方が好ましい。In addition, since the release layer film of the present invention is difficult for the resin layer component to transfer to the pressure-sensitive adhesive sheet, the urethane thermosetting adhesive sheet as the pressure-sensitive adhesive sheet has a reduced adhesive strength even after the resin layer is attached. The residual adhesion rate can be 70% or more, preferably 80% or more, and more preferably 85% or more.
When the urethane-based adhesive surface of the pressure-sensitive adhesive sheet is contaminated by the resin layer of the release film, the re-adhesiveness of the pressure-sensitive adhesive sheet is lowered and the performance as a pressure-sensitive adhesive sheet is impaired. Therefore, it is preferable that the residual adhesion rate is high.
本発明において樹脂層の厚みは、０．０１〜１μｍであることが好ましく、０．０３〜０．７μｍであることがより好ましく、０．０５〜０．５μｍであることがさらに好ましい。樹脂層の厚みが０．０１μｍ未満であると、十分な離型性が得られず、１μｍを超えると、離型性は飽和して改善しないばかりか、凝集力を低下させ、粘着シートに移行しやすくなる。 In the present invention, the thickness of the resin layer is preferably 0.01 to 1 μm, more preferably 0.03 to 0.7 μm, and further preferably 0.05 to 0.5 μm. If the thickness of the resin layer is less than 0.01 μm, sufficient releasability cannot be obtained, and if it exceeds 1 μm, the releasability will not be saturated and will not be improved, but the cohesive force will be reduced and transferred to an adhesive sheet. It becomes easy to do.
本発明の離型フィルムを構成する基材フィルムとしては、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリ乳酸（ＰＬＡ）などのポリエステルフィルム、ポリプロピレンなどのポリオレフィンフィルム、ポリスチレンフィルム、ポリアミド６、ポリ−ｐ−キシリレンアジパミド（ＭＸＤ６ナイロン）、ポリアミド６６、ポリアミド４６、ポリアミド４Ｔ、ポリアミド６Ｔ、ポリアミド９Ｔなどのポリアミドフィルム、ポリカーボネートフィルム、ポリアクリルニトリルフィルム、ポリイミドフィルム、これらの複層体（例えば、ポリアミド６／ＭＸＤ６ナイロン／ポリアミド６、ポリアミド６／エチレン−ビニルアルコール共重合体／ポリアミド６）や混合体などが用いられ、機械的強度や寸法安定性を有するポリエステルフィルム、ポリアミドフィルムが好ましい。 Examples of the base film constituting the release film of the present invention include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polylactic acid (PLA), and polyolefins such as polypropylene. Film, polystyrene film, polyamide 6, poly-p-xylylene adipamide (MXD6 nylon), polyamide 66, polyamide 46, polyamide 4T, polyamide 6T, polyamide 9T and other polyamide films, polycarbonate film, polyacrylonitrile film, polyimide Films, multilayers of these (eg polyamide 6 / MXD6 nylon / polyamide 6, polyamide 6 / ethylene-vinyl alcohol copolymer / polyamide 6) and mixtures Body like are used, a polyester film having mechanical strength and dimensional stability, the polyamide film is preferable.
基材フィルムは、単層のフィルムでもよいが、高い平滑性を実現しつつハンドリング性をよくするため、２種の層からなる多層フィルムであることが好ましく、また３種以上の層を積層してなる多層フィルムであってもよい。
基材フィルムとして多層フィルムを使用する場合、多層フィルムの外層のうち、樹脂層が設けられない層は、粗面化物質を含有することが好ましく、樹脂層が設けられる層は、粗面化物質を含有しないことが好ましい。粗面化物質としては例えば、二酸化ケイ素、炭酸カルシウム、カオリナイト、二酸化チタン、シリカアルミナ等の無機粒子や、シリコーンやポリメタクリル酸メチル、エチルビニルベンゼン等の有機粒子が挙げられる。樹脂層が設けられる層に粗面化物質を含有させないことにより、樹脂層を設けた層の表面粗さが小さくなる。また、樹脂層との界面および樹脂層表面へ粗面化物質がブリードアウトすることがなく、樹脂層と基材フィルムの密着性低下や、剥離時に粘着剤表面の汚染を防ぐことができる。
多層フィルムは、それぞれの層を構成する樹脂や樹脂組成物を別々に溶融して、複層ダイスを用いて押出し、固化前に積層融着させた後、二軸延伸、熱固定する方法や、２種以上のポリエステルを別々に溶融、押出してそれぞれフィルム化し、未延伸状態でまたは延伸後に、それらを積層融着させる方法などによって製造することができる。プロセスの簡便性から、複層ダイスを用い、固化前に積層融着させることが好ましい。The base film may be a single-layer film, but in order to improve handling properties while realizing high smoothness, it is preferably a multilayer film composed of two types of layers, and three or more types of layers are laminated. It may be a multilayer film.
When a multilayer film is used as the base film, the outer layer of the multilayer film in which the resin layer is not provided preferably contains a roughening substance, and the layer in which the resin layer is provided is a roughening substance. It is preferable not to contain. Examples of the roughening substance include inorganic particles such as silicon dioxide, calcium carbonate, kaolinite, titanium dioxide, and silica alumina, and organic particles such as silicone, polymethyl methacrylate, and ethyl vinylbenzene. By not including a roughening material in the layer provided with the resin layer, the surface roughness of the layer provided with the resin layer is reduced. Further, the roughening substance does not bleed out to the interface with the resin layer and the surface of the resin layer, and it is possible to prevent the adhesion of the resin layer and the base film from being deteriorated and contamination of the pressure-sensitive adhesive surface during peeling.
The multilayer film is a method in which the resin and resin composition constituting each layer are melted separately, extruded using a multilayer die, laminated and fused before solidification, biaxially stretched, heat-fixed, Two or more kinds of polyesters can be separately melted and extruded to form a film, which can be produced by a method of laminating and fusing them in an unstretched state or after stretching. From the simplicity of the process, it is preferable to use a multilayer die and laminate and fuse before solidification.
本発明の離型フィルムは、酸変性ポリオレフィン樹脂と水酸基含有樹脂と架橋剤とを液状媒体中に含有してなる液状物を、基材フィルムに塗布し、液状物の塗布された基材フィルムを乾燥、延伸および熱処理して樹脂層を形成する方法によって、工業的に簡便に製造することができる。 The release film of the present invention is obtained by applying a liquid material containing an acid-modified polyolefin resin, a hydroxyl group-containing resin, and a cross-linking agent in a liquid medium to the base film. It can be easily produced industrially by a method of forming a resin layer by drying, stretching and heat treatment.
本発明において、樹脂層形成用液状物を構成する液状媒体は、水性媒体であることが好ましい。水性媒体とは、水と両親媒性有機溶剤とを含み、水の含有量が２質量％以上である溶媒を意味し、水のみでもよい。
両親媒性有機溶剤とは、２０℃における有機溶剤に対する水の溶解性が５質量％以上である有機溶剤をいう（２０℃における有機溶剤に対する水の溶解性については、例えば「溶剤ハンドブック」（講談社サイエンティフィク、１９９０年第１０版）等の文献に記載されている）。
両親媒性有機溶剤の具体例としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール等のアルコール類、テトラヒドロフラン、１，４−ジオキサン等のエーテル類、アセトン、メチルエチルケトン等のケトン類、酢酸メチル、酢酸−ｎ−プロピル、酢酸イソプロピル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジメチル等のエステル類、エチレングリコール−ｎ−ブチルエーテル等のエチレングリコール誘導体類、そのほか、アンモニアを含む、ジエチルアミン、トリエチルアミン、ジエタノールアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン等の有機アミン化合物、２−ピロリドン、Ｎ−メチル−２−ピロリドンなどのラクタム類等を挙げることができる。In the present invention, the liquid medium constituting the resin layer-forming liquid material is preferably an aqueous medium. The aqueous medium means a solvent containing water and an amphiphilic organic solvent and having a water content of 2% by mass or more, and may be water alone.
The amphiphilic organic solvent means an organic solvent having a water solubility of 5% by mass or more at 20 ° C. (For the solubility of water in an organic solvent at 20 ° C., for example, “Solvent Handbook” (Kodansha) (Scientific, 1990, 10th edition)).
Specific examples of the amphiphilic organic solvent include alcohols such as methanol, ethanol, n-propanol and isopropanol, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, methyl acetate, acetic acid- Esters such as n-propyl, isopropyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, ethylene glycol derivatives such as ethylene glycol-n-butyl ether, and also ammonia, diethylamine, triethylamine, diethanolamine, triethanolamine And organic amine compounds such as N, N-dimethylethanolamine and N, N-diethylethanolamine, and lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone.
樹脂層形成用液状物は、酸変性ポリオレフィン樹脂の液状物に、水酸基含有樹脂や架橋剤を添加することにより、調製することができる。
酸変性ポリオレフィン樹脂の液状物としては、酸変性ポリオレフィン樹脂の水性分散体を用いることができる。酸変性ポリオレフィン樹脂を水性分散化する方法は、特に限定されないが、例えば、国際公開第０２／０５５５９８号に記載された方法が挙げられる。
水性媒体中の酸変性ポリオレフィン樹脂の分散粒子径は、他の成分との混合時の安定性および混合後の保存安定性の点から、数平均粒子径が１μｍ以下であることが好ましく、０．８μｍ以下であることがより好ましい。このような粒径は、国際公開第０２／０５５５９８号に記載の製法により達成可能である。なお、酸変性ポリオレフィン樹脂の数平均粒子径は動的光散乱法によって測定される。
酸変性ポリオレフィン樹脂の水性分散体の固形分濃度は、特に限定されるものではないが、水性分散体の粘性を適度に保つためには、１〜６０質量％が好ましく、５〜３０質量％がより好ましい。The liquid for forming the resin layer can be prepared by adding a hydroxyl group-containing resin or a crosslinking agent to the liquid of the acid-modified polyolefin resin.
As the liquid material of the acid-modified polyolefin resin, an aqueous dispersion of the acid-modified polyolefin resin can be used. The method for aqueous dispersion of the acid-modified polyolefin resin is not particularly limited, and examples thereof include the method described in WO 02/055598.
The dispersed particle size of the acid-modified polyolefin resin in the aqueous medium preferably has a number average particle size of 1 μm or less from the viewpoint of stability when mixed with other components and storage stability after mixing. More preferably, it is 8 μm or less. Such a particle size can be achieved by the production method described in WO 02/055598. The number average particle size of the acid-modified polyolefin resin is measured by a dynamic light scattering method.
The solid content concentration of the aqueous dispersion of the acid-modified polyolefin resin is not particularly limited, but is preferably 1 to 60% by mass, and 5 to 30% by mass in order to keep the viscosity of the aqueous dispersion moderate. More preferred.
酸変性ポリオレフィン樹脂の水性分散体と、水酸基含有樹脂と、架橋剤とを混合して得られる樹脂層形成用液状物の固形分濃度は、積層条件、目的とする厚さや性能等により適宜選択でき、特に限定されるものではない。しかし、液状物の粘性を適度に保ち、かつ、均一な樹脂層を形成させるためには、２〜３０質量％が好ましく、３〜２０質量％がより好ましい。
樹脂層形成用液状物には、その性能が損なわれない範囲で、酸化防止剤、紫外線吸収剤、滑剤、着色剤などを添加することもできる。The solid content concentration of the liquid material for forming a resin layer obtained by mixing an aqueous dispersion of an acid-modified polyolefin resin, a hydroxyl group-containing resin, and a crosslinking agent can be appropriately selected depending on the lamination conditions, the desired thickness and performance, etc. There is no particular limitation. However, in order to keep the viscosity of the liquid material moderate and to form a uniform resin layer, 2 to 30% by mass is preferable, and 3 to 20% by mass is more preferable.
Antioxidants, ultraviolet absorbers, lubricants, colorants, and the like can be added to the resin layer-forming liquid as long as the performance is not impaired.
本発明において、上記樹脂層形成用液状物を基材フィルムに塗布する方法としては、公知の方法、例えば、グラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法等を挙げることができる。 In the present invention, the method for applying the resin layer forming liquid to the base film is a known method such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, Examples thereof include spray coating, dip coating, and brushing.
本発明においては、樹脂層形成用液状物を基材フィルムの製造工程中に塗布する工程と、基材フィルムと共に乾燥、配向延伸および熱固定処理する工程を含むことが好ましい。製造工程中に塗布することにより、基材フィルム表面の配向結晶化の程度が小さい状態で樹脂層を形成することができるため、基材フィルムと樹脂層の密着力が向上する。また、基材フィルムが緊張した状態で、より高温で樹脂層を熱処理できるので、基材フィルムの品位を低下させることなく、離型性や残存接着力を向上させることができる。さらに、オフラインでの塗布に比べると、製造工程を簡略化することができるばかりか、樹脂層の薄膜化によりコスト面でも有利である。なお、逐次二軸延伸法を採用する場合には、一軸方向に延伸された基材フィルムに前記液状物を塗布し、液状物の塗布された基材フィルムを乾燥、その後、基材フィルムを前記方向と直交する方向にさらに延伸し、熱処理することが、簡便さや操業上の理由から好ましい。 In this invention, it is preferable to include the process of apply | coating the liquid substance for resin layer formation in the manufacturing process of a base film, and the process of drying, orientation extending | stretching, and heat setting with a base film. By applying during the manufacturing process, the resin layer can be formed in a state where the degree of orientation crystallization on the surface of the base film is small, so that the adhesion between the base film and the resin layer is improved. In addition, since the resin layer can be heat-treated at a higher temperature while the base film is in tension, the releasability and the remaining adhesive force can be improved without deteriorating the quality of the base film. Furthermore, as compared with the off-line coating, not only the manufacturing process can be simplified, but also the cost can be improved by reducing the thickness of the resin layer. In the case of adopting the sequential biaxial stretching method, the liquid material is applied to the base film stretched in the uniaxial direction, the base film coated with the liquid material is dried, and then the base film is Further stretching and heat treatment in a direction perpendicular to the direction is preferred for convenience and operational reasons.
本発明の効果を損ねない範囲で、本発明における基材フィルムに設けた樹脂層と反対面に、易滑性や帯電防止性を有する機能層を積層してもよく、積層方法としては公知の方法が用いられ、例えば塗剤を塗布する方法等が挙げられる。 As long as the effect of the present invention is not impaired, a functional layer having slipperiness and antistatic property may be laminated on the surface opposite to the resin layer provided on the base film in the present invention. The method is used, for example, the method of apply | coating a coating agent etc. are mentioned.
本発明の離型フィルムは、一部がリサイクルされてフィルムの原料として再利用されてもよい。 A part of the release film of the present invention may be recycled and reused as a raw material for the film.
本発明の離型フィルムは、これに限定するものでないが、粘着シートに対して用いる離型フィルムとして好適であり、特に硬化性樹脂の粘着剤を有する粘着シートの離型フィルムとして好適に用いることができる。好ましい用途としては、カバーレイや電磁波シールドフィルムなどの電子部品用の粘着シートの離型フィルムとして好適に用いることができる。 Although the release film of this invention is not limited to this, it is suitable as a release film used with respect to an adhesive sheet, and should be used suitably especially as a release film of the adhesive sheet which has an adhesive of curable resin. Can do. As a preferred application, it can be suitably used as a release film for pressure-sensitive adhesive sheets for electronic parts such as coverlays and electromagnetic shielding films.
以下、実施例によって本発明を具体的に説明する。なお、本発明はこれらの実施例のみに限定されるものではない。
なお、後述する各種の特性は、以下の方法によって測定または評価した。Hereinafter, the present invention will be described specifically by way of examples. In addition, this invention is not limited only to these Examples.
Various properties described below were measured or evaluated by the following methods.
（１）カルボキシル基を有する酸変性成分の含有量
酸変性ポリオレフィン樹脂の酸価をＪＩＳ Ｋ５４０７に準じて測定し、その値からカルボキシル基を有する酸変性成分の含有量を求めた。(1) Content of acid-modified component having carboxyl group The acid value of the acid-modified polyolefin resin was measured according to JIS K5407, and the content of the acid-modified component having a carboxyl group was determined from the value.
（２）カルボキシル基を有する酸変性成分以外の樹脂の構成
オルトジクロロベンゼン（ｄ4）中で、１２０℃にて１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ分析（バリアン社製、３００ＭＨｚ）を行い求めた。１３Ｃ−ＮＭＲ分析では、定量性を考慮したゲート付きデカップリング法を用いて測定した。(2) Constitution of resin other than acid-modified component having carboxyl group In orthodichlorobenzene (d 4 ), 1 H-NMR and 13 C-NMR analysis (manufactured by Varian, 300 MHz) was performed at 120 ° C. . In 13 C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.
（３）酸変性ポリオレフィン樹脂の重量平均分子量
ＧＰＣ分析（東ソー社製、ＨＬＣ−８０２０、カラムはＴＳＫ−ＧＥＬ）を用いて、試料をテトラヒドロフランに溶解して４０℃で測定し、ポリスチレン標準試料で作成した検量線から重量平均分子量を求めた。テトラヒドロフランに溶解し難い場合はオルトジクロロベンゼンを用いた。(3) Weight average molecular weight of acid-modified polyolefin resin Using GPC analysis (manufactured by Tosoh Corporation, HLC-8020, column is TSK-GEL), the sample was dissolved in tetrahydrofuran, measured at 40 ° C., and prepared as a polystyrene standard sample The weight average molecular weight was determined from the calibration curve. Ortho-dichlorobenzene was used when it was difficult to dissolve in tetrahydrofuran.
（４）酸変性ポリオレフィン樹脂のメルトフローレート（ＭＦＲ）
ＪＩＳ Ｋ７２１０：１９９９記載の方法に準じて、１９０℃、２１６０ｇ荷重で測定した。(4) Melt flow rate (MFR) of acid-modified polyolefin resin
According to the method described in JIS K7210: 1999, the measurement was performed at 190 ° C. under a load of 2160 g.
（５）酸変性ポリオレフィン樹脂の水性分散体の固形分濃度
酸変性ポリオレフィン樹脂の水性分散体を適量秤量し、これを１５０℃で残存物（固形分）の質量が恒量に達するまで加熱し、固形分濃度を求めた。(5) Solid content concentration of aqueous dispersion of acid-modified polyolefin resin An appropriate amount of an aqueous dispersion of acid-modified polyolefin resin is weighed and heated at 150 ° C. until the mass of the residue (solid content) reaches a constant weight. The partial concentration was determined.
（６）酸変性ポリオレフィン樹脂粒子の数平均および重量平均粒子径
日機装社製、マイクロトラック粒度分布計ＵＰＡ１５０（ＭＯＤＥＬ Ｎｏ．９３４０）を用い、数平均粒子径（ｍｎ）および重量平均粒子径（ｍｗ）を求めた。なお、樹脂の屈折率は１．５とした。(6) Number average and weight average particle diameter of acid-modified polyolefin resin particles A number average particle diameter (mn) and a weight average particle diameter (mw) using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) manufactured by Nikkiso Co., Ltd. Asked. The refractive index of the resin was 1.5.
（７）ウレタン系熱硬化性接着シートとの剥離性（初期剥離性）
離型フィルムの樹脂層側に、巾５０ｍｍ、長さ１５０ｍｍのウレタン系熱硬化性接着シート（トーヨーケム社製、ＬＩＯＥＬＭ ＴＳＵ００４１ＳＩ−２５ＤＬ）とポリイミドフィルム（東レ・デュポン社製、Ｋａｐｔｏｎ３００Ｈ）をこの順になるように、ゴムロールを用いて温度８０℃、線圧１．５ｋｇ／３００ｍｍ、速度１ｍ／ｍｉｎで圧着して、試料とした。試料を、金属板／ゴム板／試料／ゴム板／金属板の形で挟み、２ｋＰａ荷重、７０℃の雰囲気で２０時間放置し、その後３０分以上冷却して常温に戻して、剥離強度測定用試料を得た。２５℃の恒温室で、この剥離強度測定用試料のウレタン系熱硬化性接着シートと離型フィルムとを剥離して、下記の基準で初期剥離性を評価した。
○：抵抗なくスムーズに剥離することができる。
△：抵抗があるが、少し力をいれると剥離できる。
×：剥離しようとすると破断するか、または剥離できない。(7) Peelability from urethane-based thermosetting adhesive sheet (initial peelability)
On the resin layer side of the release film, a urethane-based thermosetting adhesive sheet (Toyochem, LIOELM TSU0041SI-25DL) and polyimide film (Toray DuPont, Kapton 300H) having a width of 50 mm and a length of 150 mm are arranged in this order. The sample was pressure-bonded to a sample using a rubber roll at a temperature of 80 ° C., a linear pressure of 1.5 kg / 300 mm, and a speed of 1 m / min. Sample is sandwiched in the form of metal plate / rubber plate / sample / rubber plate / metal plate, left at 2 kPa load and 70 ° C. atmosphere for 20 hours, then cooled to room temperature for 30 minutes or more, for peel strength measurement A sample was obtained. In a thermostatic chamber at 25 ° C., the urethane thermosetting adhesive sheet and the release film of this peel strength measurement sample were peeled, and the initial peelability was evaluated according to the following criteria.
○: Can be peeled smoothly without resistance.
Δ: There is resistance, but it can be peeled off when a little force is applied.
X: When it tries to peel, it fractures | ruptures or cannot peel.
（８）長期保管後のウレタン系熱硬化性接着シートとの剥離性
上記（７）で示した方法で作製した剥離強度測定用試料を２５℃の恒温室で３０日間保管した後、２５℃の恒温室で、この剥離強度測定用試料のウレタン系熱硬化性接着シートと離型フィルムとを剥離し、上記（７）の基準で長期保管後の剥離性を評価した。(8) Peelability from urethane-based thermosetting adhesive sheet after long-term storage After the sample for peel strength measurement produced by the method shown in (7) above is stored in a thermostatic chamber at 25 ° C for 30 days, In a thermostatic chamber, the urethane thermosetting adhesive sheet and the release film of this peel strength measurement sample were peeled off, and the peelability after long-term storage was evaluated according to the above criteria (7).
（９）ウレタン系熱硬化性接着シートの残留接着性
上記（８）長期保管後のウレタン系熱硬化性接着シートとの剥離性の試験により離型フィルム表面から剥離したポリイミドフィルム上のウレタン系熱硬化性接着シートを、二軸延伸ポリエステル樹脂フィルム（ユニチカ社製、エンブレットＰＥＴ−１２、厚さ１２μｍ）のコロナ処理面に貼付し、２ｋＰａ荷重、室温で２０時間放置した。その後、２５℃の恒温室で、ウレタン系熱硬化性接着シートと二軸延伸ポリエステル樹脂フィルムとを剥離して接着性を評価した。
一方、二軸延伸ポリエステル樹脂フィルムのコロナ処理面に、巾５０ｍｍ、長さ１５０ｍｍの未使用のウレタン系熱硬化性接着シートとポリイミドフィルムをこの順になるように貼付し、２ｋＰａ荷重、室温で２０時間放置した。その後、２５℃の恒温室で、ウレタン系熱硬化性接着シートと二軸延伸ポリエステル樹脂フィルムとを剥離して接着性を評価した。
前者の接着性を後者の接着性と比較して、離型フィルム表面から剥離したウレタン系熱硬化性接着シートの残留接着性を評価した。
○：８０％以上
△：７０％以上、８０％未満
×：７０％未満(9) Residual adhesiveness of urethane-based thermosetting adhesive sheet (8) Urethane-based heat on the polyimide film peeled from the surface of the release film by a peelability test with the urethane-based thermosetting adhesive sheet after long-term storage The curable adhesive sheet was affixed to the corona-treated surface of a biaxially stretched polyester resin film (manufactured by Unitika, Emblet PET-12, thickness 12 μm) and allowed to stand at room temperature for 20 hours at a load of 2 kPa. Thereafter, in a thermostatic chamber at 25 ° C., the urethane thermosetting adhesive sheet and the biaxially stretched polyester resin film were peeled off to evaluate the adhesiveness.
On the other hand, an unused urethane-based thermosetting adhesive sheet having a width of 50 mm and a length of 150 mm and a polyimide film are stuck on the corona-treated surface of the biaxially stretched polyester resin film in this order, and the load is 2 kPa at room temperature for 20 hours. I left it alone. Thereafter, in a thermostatic chamber at 25 ° C., the urethane thermosetting adhesive sheet and the biaxially stretched polyester resin film were peeled off to evaluate the adhesiveness.
The former adhesiveness was compared with the latter adhesiveness, and the residual adhesiveness of the urethane-based thermosetting adhesive sheet peeled from the release film surface was evaluated.
○: 80% or more Δ: 70% or more, less than 80% ×: less than 70%
（１０）打ち抜き性（ハーフカット性）
上記（７）で示した方法で作製した剥離強度測定用試料のポリイミドフィルム側からハーフカットを行い、離型フィルムに発生した浮きを、カットした部分からの寸法を測定することにより、打ち抜き性を評価した。浮きの幅が２ｍｍ未満のときを「○」、２ｍｍ以上、４ｍｍ未満のときを「△」、４ｍｍ以上のときを「×」と評価した。(10) Punchability (half cut property)
By performing half-cut from the polyimide film side of the peel strength measurement sample prepared by the method shown in (7) above and measuring the float generated in the release film from the cut part, evaluated. When the float width was less than 2 mm, “◯” was evaluated, and when it was 2 mm or more and less than 4 mm, “Δ” was evaluated, and when it was 4 mm or more, “X” was evaluated.
酸変性ポリオレフィン樹脂「Ｐ−１」〜「Ｐ−６」を以下の方法で製造した。 Acid-modified polyolefin resins “P-1” to “P-6” were produced by the following method.
（１）酸変性ポリオレフィン樹脂「Ｐ−１」
プロピレン−エチレン共重合体（プロピレン／エチレン＝９５．５／２．０質量比）２８０ｇを、４つ口フラスコ中において、窒素雰囲気下で加熱溶融させた。その後、系内温度を１７０℃に保って、撹拌下、不飽和カルボン酸としての無水マレイン酸１０．０ｇとラジカル発生剤としてのジクミルパーオキサイド６．０ｇとをそれぞれ１時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性ポリオレフィン樹脂「Ｐ−１」を得た。得られた樹脂の特性を表１に示す。(1) Acid-modified polyolefin resin “P-1”
280 g of propylene-ethylene copolymer (propylene / ethylene = 95.5 / 2.0 mass ratio) was heated and melted in a four-necked flask under a nitrogen atmosphere. Thereafter, while maintaining the system temperature at 170 ° C., with stirring, 10.0 g of maleic anhydride as an unsaturated carboxylic acid and 6.0 g of dicumyl peroxide as a radical generator were added over 1 hour, respectively. The reaction was carried out for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. The resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polyolefin resin “P-1”. The properties of the obtained resin are shown in Table 1.
（２）酸変性ポリオレフィン樹脂「Ｐ−２」
ポリプロピレン２８０ｇを、４つ口フラスコ中において、窒素雰囲気下で加熱溶融させた。その後、系内温度を１７０℃に保って、撹拌下、不飽和カルボン酸としての無水マレイン酸１２．０ｇとラジカル発生剤としてのジクミルパーオキサイド６．０ｇとをそれぞれ１時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性ポリオレフィン樹脂「Ｐ−２」を得た。得られた樹脂の特性を表１に示す。(2) Acid-modified polyolefin resin “P-2”
280 g of polypropylene was heated and melted in a four-necked flask under a nitrogen atmosphere. Thereafter, while maintaining the system temperature at 170 ° C., 12.0 g of maleic anhydride as an unsaturated carboxylic acid and 6.0 g of dicumyl peroxide as a radical generator were added over 1 hour with stirring. The reaction was carried out for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polyolefin resin “P-2”. The properties of the obtained resin are shown in Table 1.
（３）酸変性ポリオレフィン樹脂「Ｐ−３」
プロピレン−エチレン共重合体（プロピレン／エチレン＝８１．８／１８．２質量％、重量平均分子量８５,０００）２８０ｇを、４つ口フラスコ中において、窒素雰囲気下で加熱溶融させた。その後、系内温度を１８０℃に保って、撹拌下、不飽和カルボン酸としての無水マレイン酸３５．０ｇとラジカル発生剤としてのジ−ｔ−ブチルパーオキサイド６．０ｇとをそれぞれ２時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性ポリオレフィン樹脂「Ｐ−３」を得た。得られた樹脂の特性を表１に示す。(3) Acid-modified polyolefin resin “P-3”
280 g of a propylene-ethylene copolymer (propylene / ethylene = 81.8 / 18.2% by mass, weight average molecular weight 85,000) was heated and melted in a four-necked flask under a nitrogen atmosphere. Thereafter, the system temperature was kept at 180 ° C., and 35.0 g of maleic anhydride as an unsaturated carboxylic acid and 6.0 g of di-t-butyl peroxide as a radical generator were stirred for 2 hours with stirring. Thereafter, the reaction was allowed to proceed for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polyolefin resin “P-3”. The properties of the obtained resin are shown in Table 1.
（４）酸変性ポリオレフィン樹脂「Ｐ−４」
プロピレン−ブテン−エチレン三元共重合体（ヒュルスジャパン社製、ベストプラスト７０８、プロピレン／ブテン／エチレン＝６４．８／２３．９／１１．３質量％）２８０ｇを、４つ口フラスコ中において、窒素雰囲気下で加熱溶融させた。その後、系内温度を１７０℃に保って、撹拌下、不飽和カルボン酸としての無水マレイン酸３２．０ｇとラジカル発生剤としてのジクミルパーオキサイド６．０ｇとをそれぞれ１時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性ポリオレフィン樹脂「Ｐ−４」を得た。得られた樹脂の特性を表１に示す。(4) Acid-modified polyolefin resin “P-4”
280 g of propylene-butene-ethylene terpolymer (manufactured by Huls Japan, Bestplast 708, propylene / butene / ethylene = 64.8 / 23.9 / 11.3 mass%) in a four-necked flask And heated and melted in a nitrogen atmosphere. Thereafter, while maintaining the system temperature at 170 ° C., 32.0 g of maleic anhydride as an unsaturated carboxylic acid and 6.0 g of dicumyl peroxide as a radical generator were added over 1 hour with stirring. The reaction was carried out for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polyolefin resin “P-4”. The properties of the obtained resin are shown in Table 1.
（５）酸変性ポリオレフィン樹脂「Ｐ−５」
プロピレン−ブテン−エチレン三元共重合体（ヒュルスジャパン社製、ベストプラスト７０８、プロピレン／ブテン／エチレン＝６４．８／２３．９／１１．３質量％）１００ｇ、トルエン５００ｇを、撹拌機と冷却管と滴下ロートとを取り付けた４つ口フラスコ中において、窒素雰囲気下で加熱溶融させた。その後、系内温度を１１０℃に保って、撹拌下、ラジカル発生剤としてジクミルパーオキサイド１．０ｇのヘプタン２０ｇ溶液を１時間かけて加えた。その後、不飽和カルボン酸として無水マレイン酸７．０ｇ、アクリル酸ラウリル１０．０ｇ、ジクミルパーオキサイド０．５ｇのヘプタン１０ｇ溶液をそれぞれ１時間かけて滴下し、その後３０分間反応させた。反応終了後、室温まで冷却し、その後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応物を除去した後、減圧乾燥機中で減圧乾燥して酸変性ポリオレフィン樹脂「Ｐ−５」を得た。得られた樹脂の特性を表１に示す。(5) Acid-modified polyolefin resin “P-5”
Propylene-butene-ethylene terpolymer (manufactured by Huls Japan Co., Ltd., Bestplast 708, propylene / butene / ethylene = 64.8 / 23.9 / 11.3% by mass) 100 g, toluene 500 g, In a four-necked flask equipped with a cooling tube and a dropping funnel, it was heated and melted in a nitrogen atmosphere. Then, the system temperature was maintained at 110 ° C., and a solution of 1.0 g of dicumyl peroxide in 20 g of heptane was added as a radical generator over 1 hour with stirring. Thereafter, 7.0 g of maleic anhydride, 10.0 g of lauryl acrylate, and 10 g of heptane containing 0.5 g of dicumyl peroxide were added dropwise as an unsaturated carboxylic acid over 1 hour, followed by reaction for 30 minutes. After completion of the reaction, the reaction mixture was cooled to room temperature, and then the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted substances, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polyolefin resin “P-5”. The properties of the obtained resin are shown in Table 1.
（６）酸変性ポリオレフィン樹脂「Ｐ−６」
プロピレン−ブテン−エチレン三元共重合体（ヒュルスジャパン社製、ベストプラスト４０８、プロピレン／ブテン／エチレン＝１２．３／８２．２／５．５質量％）を用いた以外は酸変性ポリオレフィン樹脂「Ｐ−４」と同様にして、酸変性ポリオレフィン樹脂「Ｐ−６」を得た。得られた樹脂の特性を表１に示す。(6) Acid-modified polyolefin resin “P-6”
Acid-modified polyolefin resin except that propylene-butene-ethylene terpolymer (Hels Japan, Bestplast 408, propylene / butene / ethylene = 12.3 / 82.2 / 5.5% by mass) was used. In the same manner as “P-4”, an acid-modified polyolefin resin “P-6” was obtained. The properties of the obtained resin are shown in Table 1.
上記以外の酸変性ポリオレフィン樹脂は、下記の市販のものを使用し、上記方法で製造したものとあわせて、酸変性ポリオレフィン樹脂の組成、特性を表１に示す。
酸変性ポリオレフィン樹脂「Ｐ−７」：ダウケミカル社製、プリマコール５９８０Ｉ
酸変性ポリオレフィン樹脂「Ｐ−８」：アルケマ社製、ボンダインＬＸ−４１１０
酸変性ポリオレフィン樹脂「Ｐ−９」：アルケマ社製、ボンダインＡＸ−８３９０Table 1 shows the composition and characteristics of the acid-modified polyolefin resin other than the above-mentioned acid-modified polyolefin resins, using the following commercially available products and those manufactured by the above method.
Acid-modified polyolefin resin “P-7”: manufactured by Dow Chemical Company, Primacor 5980I
Acid-modified polyolefin resin “P-8”: Arkema, Bondine LX-4110
Acid-modified polyolefin resin “P-9”: Arkema, Bondine AX-8390
酸変性ポリオレフィン樹脂の水性分散体を以下の方法で製造した。 An aqueous dispersion of acid-modified polyolefin resin was produced by the following method.
（１）酸変性ポリオレフィン樹脂水性分散体「Ｅ−１」
ヒーター付きの密閉できる耐圧１Ｌ容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂「Ｐ−１」、６０．０ｇのエチレングリコール−ｎ−ブチルエーテル、４．５ｇのＮ，Ｎ−ジメチルエタノールアミンおよび１８８．１ｇの蒸留水を上記のガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０℃に保ってさらに６０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した。その後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白色の均一な酸変性ポリオレフィン樹脂水性分散体「Ｅ−１」を得た。なお、フィルター上には残存樹脂は殆どなかった。(1) Acid-modified polyolefin resin aqueous dispersion “E-1”
Using a stirrer equipped with a heat-resistant 1 L glass container with a heater, 60.0 g of acid-modified polyolefin resin “P-1”, 60.0 g of ethylene glycol-n-butyl ether, 4.5 g of N, N-dimethylethanolamine and 188.1 g of distilled water were charged into the glass container. When the stirring blade was rotated at a rotational speed of 300 rpm, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. Then, pressure filtration (air pressure 0.2 MPa) was performed with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform acid-modified polyolefin resin aqueous dispersion “E-1”. There was almost no residual resin on the filter.
（２）酸変性ポリオレフィン樹脂水性分散体「Ｅ−２」
ヒーター付きの密閉できる耐圧１Ｌ容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂「Ｐ−２」、６０．０ｇのエチレングリコール−ｎ−ブチルエーテル、５．０ｇのＮ，Ｎ−ジメチルエタノールアミンおよび１８８．１ｇの蒸留水を上記のガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０℃に保ってさらに６０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した。その後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白色の均一な酸変性ポリオレフィン樹脂水性分散体「Ｅ−２」を得た。なお、フィルター上には残存樹脂は殆どなかった。(2) Acid-modified polyolefin resin aqueous dispersion “E-2”
Using a stirrer equipped with a 1 L glass container that can be sealed with a heater, 60.0 g of acid-modified polyolefin resin “P-2”, 60.0 g of ethylene glycol-n-butyl ether, 5.0 g of N, N-dimethylethanolamine and 188.1 g of distilled water were charged into the glass container. When the stirring blade was rotated at a rotational speed of 300 rpm, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. Then, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform acid-modified polyolefin resin aqueous dispersion “E-2”. There was almost no residual resin on the filter.
（３）酸変性ポリオレフィン樹脂水性分散体「Ｅ−３」
ヒーター付きの密閉できる耐圧１Ｌ容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂「Ｐ−３」、４５．０ｇのエチレングリコール−ｎ−ブチルエーテル、６．９ｇのＮ，Ｎ−ジメチルエタノールアミンおよび１８８．１ｇの蒸留水を上記のガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０℃に保ってさらに６０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した。その後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白黄色の均一な酸変性ポリオレフィン樹脂水性分散体「Ｅ−３」を得た。なお、フィルター上には残存樹脂は殆どなかった。(3) Acid-modified polyolefin resin aqueous dispersion “E-3”
Using a stirrer equipped with a 1 L glass container that can be sealed with a heater, 60.0 g of acid-modified polyolefin resin “P-3”, 45.0 g of ethylene glycol-n-butyl ether, 6.9 g of N, N-dimethylethanolamine and 188.1 g of distilled water were charged into the glass container. When the stirring blade was rotated at a rotational speed of 300 rpm, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. Then, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky-yellow uniform acid-modified polyolefin resin aqueous dispersion “E-3”. There was almost no residual resin on the filter.
（４）酸変性ポリオレフィン樹脂水性分散体「Ｅ−４」、「Ｅ−６」
酸変性ポリオレフィン樹脂として「Ｐ−４」、「Ｐ−６」を用いた以外は「Ｅ−３」と同様にして、水性分散体「Ｅ−４」、「Ｅ−６」を得た。(4) Acid-modified polyolefin resin aqueous dispersions “E-4” and “E-6”
Aqueous dispersions “E-4” and “E-6” were obtained in the same manner as “E-3” except that “P-4” and “P-6” were used as the acid-modified polyolefin resins.
（５）酸変性ポリオレフィン樹脂水性分散体「Ｅ−５」
ヒーター付きの密閉できる耐圧１Ｌ容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂「Ｐ−５」、９０．０ｇのｎ−プロパノール、６．２ｇのトリエチルアミンおよび１４３．８ｇの蒸留水をガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０℃に保ってさらに６０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白黄色の均一な酸変性ポリオレフィン樹脂水性分散体「Ｅ−５」を得た。(5) Acid-modified polyolefin resin aqueous dispersion “E-5”
Using a stirrer equipped with a heat-resistant 1 L glass container with a heater, 60.0 g of acid-modified polyolefin resin “P-5”, 90.0 g of n-propanol, 6.2 g of triethylamine and 143.8 g Of distilled water was charged into a glass container. When the stirring blade was rotated at a rotational speed of 300 rpm, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky-yellow uniform acid-modified polyolefin resin aqueous dispersion “E-5” was obtained.
（６）酸変性ポリオレフィン樹脂水性分散体「Ｅ−７」
ポリオレフィン樹脂としてエチレン−アクリル酸共重合体樹脂（Ｐ−７、ダウケミカル製 プリマコール５９８０Ｉ、アクリル酸２０質量％共重合体）を用いた。ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、６０．０ｇのプリマコール５９８０Ｉ、１６．８ｇのトリエチルアミン、および２２３．２ｇの蒸留水をガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１２０℃に保ってさらに４０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま攪拌しつつ室温（約２５℃）まで冷却した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、微白濁の酸変性ポリオレフィン樹脂水性分散体「Ｅ−７」を得た。(6) Acid-modified polyolefin resin aqueous dispersion “E-7”
As the polyolefin resin, an ethylene-acrylic acid copolymer resin (P-7, Dow Chemical's Primacol 5980I, acrylic acid 20% by mass copolymer) was used. Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g of Primacol 5980I, 16.8 g of triethylamine, and 223.2 g of distilled water were charged into the glass container, and a stirring blade When stirring was performed at a rotation speed of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, confirming that it was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 40 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a slightly cloudy acid-modified polyolefin resin aqueous dispersion “E-7” was obtained.
（７）酸変性ポリオレフィン樹脂水性分散体「Ｅ−８」
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂（Ｐ−８、アルケマ社製、ボンダインＬＸ−４１１０）、７５．０ｇのｎ−プロパノール、２．５ｇのトリエチルアミンおよび１６２．５ｇの蒸留水をガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１２０℃に保ってさらに２０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま攪拌しつつ室温（約２５℃）まで冷却した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白色の均一な酸変性ポリオレフィン樹脂水性分散体「Ｅ−８」を得た。(7) Acid-modified polyolefin resin aqueous dispersion “E-8”
60.0 g of acid-modified polyolefin resin (P-8, Arkema, Bondine LX-4110), 75.0 g of n-propanol using a stirrer equipped with a 1 liter glass container that can be sealed with a heater. When 2.5 g of triethylamine and 162.5 g of distilled water were charged into a glass container and stirred at a stirring blade rotation speed of 300 rpm, no sedimentation of resin particles was observed at the bottom of the container, and the suspension became floating. It was confirmed that Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 20 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform acid-modified polyolefin resin aqueous dispersion “E-8” was obtained.
（８）酸変性ポリオレフィン樹脂水性分散体「Ｅ−９」
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂（Ｐ−９、アルケマ社製、ボンダインＡＸ−８３９０）、１００．０ｇのｎ−プロパノール、２．５ｇのトリエチルアミンおよび１３７．５ｇの蒸留水をガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１２０℃に保ってさらに２０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま攪拌しつつ室温（約２５℃）まで冷却した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白色の均一な酸変性ポリオレフィン樹脂水性分散体「Ｅ−９」を得た。(8) Acid-modified polyolefin resin aqueous dispersion “E-9”
60.0 g of acid-modified polyolefin resin (P-9, Arkema, Bondine AX-8390), 100.0 g of n-propanol using a stirrer equipped with a heater and a pressure-resistant 1 liter glass container with a heater. When 2.5 g of triethylamine and 137.5 g of distilled water were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm, no sedimentation of resin particles was observed at the bottom of the container, and the suspension became floating. It was confirmed that Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 20 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform acid-modified polyolefin resin aqueous dispersion “E-9” was obtained.
製造した酸変性ポリオレフィン樹脂水性分散体の特性を表１に示す。 The properties of the acid-modified polyolefin resin aqueous dispersion produced are shown in Table 1.
水酸基含有樹脂として、下記のものを使用した。
（１）ポリビニルアルコール水溶液（ＯＨ−１）
水酸基含有樹脂としてポリビニルアルコール（日本酢ビ・ポバール社製、ＪＴ−０５、重合度５００、ケン化度９４％）を用いた。８ｇのＪＴ−０５を９２ｇの水中に添加し、室温で３０分撹拌した後、９０℃まで昇温し、さらに３０分撹拌した後、室温まで冷却して８質量％のポリビニルアルコール水溶液（ＯＨ−１）を得た。
（２）ブテンジオール−ビニルアルコール共重合樹脂（ＢＶＯＨ）水溶液
水酸基含有樹脂としてＪＴ−０５の代わりにブテンジオール−ビニルアルコール共重合樹脂（日本合成化学社製、ＯＫＳ−８０４９Ｐ）を用いた以外は上記（ＯＨ−１）と同様にして８質量％ブテンジオール−ビニルアルコール共重合樹脂（ＢＶＯＨ）水溶液（ＯＨ−２）を得た。The following were used as the hydroxyl group-containing resin.
(1) Polyvinyl alcohol aqueous solution (OH-1)
As the hydroxyl group-containing resin, polyvinyl alcohol (manufactured by Nippon Vinegar Poval, JT-05, polymerization degree 500, saponification degree 94%) was used. 8 g of JT-05 was added to 92 g of water, stirred at room temperature for 30 minutes, then heated to 90 ° C., further stirred for 30 minutes, cooled to room temperature, and 8% by weight aqueous polyvinyl alcohol solution (OH— 1) was obtained.
(2) Butenediol-vinyl alcohol copolymer resin (BVOH) aqueous solution The above except that butenediol-vinyl alcohol copolymer resin (manufactured by Nippon Synthetic Chemical Co., Ltd., OKS-8049P) was used instead of JT-05 as the hydroxyl group-containing resin. In the same manner as (OH-1), an 8% by mass butenediol-vinyl alcohol copolymer resin (BVOH) aqueous solution (OH-2) was obtained.
実施例１
酸変性ポリオレフィン樹脂の水性分散体「Ｅ−１」と「Ｅ−８」と、ポリビニルアルコール水溶液「ＯＨ−１」とオキサゾリン化合物の水性溶液（日本触媒社製、エポクロスＷＳ−７００、固形分濃度２５質量％）を各成分の固形分比率が表２に示した値となるように混合して、樹脂層形成用液状物を得た。
ポリエチレンテレフタレート（日本エステル社製、ＵＴ−ＵＢＲ、固有粘度：０．６２、ガラス転移温度：７８℃、融点：２５５℃）をスクリュー径９０ｍｍの押出機に投入して２８０℃で溶融したＡ層形成用の樹脂と、シリカ粒子（日揮触媒社製、ＯＳＣＡＬ（ＥＮ−５００１ＳＩＶ）、粒径１．０μｍ）を含有量が０．０３０質量％になるように添加したポリエチレンテレフタレート（固有粘度：０．６２、ガラス転移温度：７８℃、融点：２５５℃）をスクリュー径６５ｍｍの押出機に投入して２８０℃で溶融したＢ層形成用の樹脂とを、２層フィードブロック内で合流させ、総厚みが３８０μｍ、厚みの比（Ａ層／Ｂ層）が２２／３となるよう調整してＴダイ出口より押出し、急冷固化してＡ層とＢ層とからなる未延伸フィルムを得た。
この未延伸フィルムをロール式縦延伸機で８５℃の条件下、３．５倍に延伸し、その後、樹脂層形成用液状物を２．７ｇ／ｍ２となるように、Ａ層表面に塗布し、５０℃の熱風乾燥炉を２０秒通過させた。
その後、連続的にシート端部をフラット式延伸機のクリップに把持させ、１００℃の条件下、横４．５倍に延伸を施し、その後、横方向の弛緩率を３％として、２００〜２１０℃で２秒間以上熱処理した後で、２３０℃で３秒間の熱処理を施して、厚さ２５μｍの２軸延伸ポリエステルフィルムの一方の面に、厚さ０．０５μｍの樹脂層が設けられた離型フィルムを得た。Example 1
Aqueous dispersions of acid-modified polyolefin resins “E-1” and “E-8”, an aqueous solution of polyvinyl alcohol aqueous solution “OH-1” and an oxazoline compound (Nippon Shokubai Co., Ltd., Epocross WS-700, solid content concentration 25 (Mass%) was mixed so that the solid content ratio of each component would be the value shown in Table 2 to obtain a resin layer forming liquid.
A layer formation in which polyethylene terephthalate (manufactured by Nihon Ester Co., Ltd., UT-UBR, intrinsic viscosity: 0.62, glass transition temperature: 78 ° C., melting point: 255 ° C.) was put into an extruder with a screw diameter of 90 mm and melted at 280 ° C. Resin and silica particles (manufactured by JGC Catalysts, OSCAL (EN-5001SIV), particle size: 1.0 μm) added to a content of 0.030% by mass (inherent viscosity: 0.62) The glass transition temperature: 78 ° C., melting point: 255 ° C.) was introduced into an extruder with a screw diameter of 65 mm and the resin for forming the B layer melted at 280 ° C. was merged in the two-layer feed block, and the total thickness was 380 μm, the thickness ratio (A layer / B layer) was adjusted to 22/3, extruded from the T-die outlet, and rapidly cooled and solidified to obtain an unstretched film composed of the A layer and the B layer. .
This unstretched film is stretched 3.5 times on a roll type longitudinal stretching machine at 85 ° C., and then the resin layer forming liquid is applied to the surface of layer A so as to be 2.7 g / m 2. And passed through a hot air drying oven at 50 ° C. for 20 seconds.
Thereafter, the end of the sheet is continuously gripped by a clip of a flat type stretching machine, stretched 4.5 times laterally under the condition of 100 ° C., and then the lateral relaxation rate is set to 3%. Release after heat treatment at 230 ° C. for 2 seconds or more and then heat treatment at 230 ° C. for 3 seconds to provide a 0.05 μm thick resin layer on one surface of a 25 μm thick biaxially stretched polyester film A film was obtained.
実施例２〜１１、１５〜２０、参考例１〜３、比較例１〜８
樹脂層形成用液状物の組成を変更して、樹脂層の組成が表２〜４の記載になるようした以外は実施例１と同様にして、離型フィルムを得た。
なお、実施例１９においては、基材フィルムを層の厚み比（Ａ層／Ｂ層／Ａ層）が２／６／２である２種３層に変更し、実施例２０においては、基材フィルムを層の厚み比（Ａ層／Ｂ層）が１０／０である単層に変更した。
Examples 2 to 11 , 15 to 20, Reference Examples 1 to 3, Comparative Examples 1 to 8
A release film was obtained in the same manner as in Example 1 except that the composition of the liquid for forming the resin layer was changed and the composition of the resin layer was as described in Tables 2 to 4.
In Example 19, the base film was changed to 2 types / 3 layers having a layer thickness ratio (A layer / B layer / A layer) of 2/6/2. The film was changed to a single layer having a layer thickness ratio (A layer / B layer) of 10/0.
実施例２１
実施例１で調製した樹脂層形成用液状物を、二軸延伸ポリエステルフィルム（ユニチカ社製、エンブレットＰＥＴ−３８、厚さ３８μｍ）のコロナ処理面に、マイヤーバーを用いて塗布した後、１２０℃で３０秒間乾燥させて、厚さ０．５μｍの樹脂層をフィルム上に形成させたのち、５０℃で２日間エージングを行うことで離型フィルムを得た。Example 21
The liquid material for forming a resin layer prepared in Example 1 was applied to the corona-treated surface of a biaxially stretched polyester film (manufactured by Unitika, Emblet PET-38, thickness 38 μm) using a Meyer bar, and then 120 After drying at 30 ° C. for 30 seconds to form a 0.5 μm thick resin layer on the film, aging was performed at 50 ° C. for 2 days to obtain a release film.
実施例２２
実施例１で調製した樹脂層形成用液状物を、ポリアミドフィルム（ユニチカ社製、ＥＸ２５、厚さ２５μｍ）のコロナ処理面に、マイヤーバーを用いて塗布した後、１２０℃で３０秒間乾燥させて、厚さ０．５μｍの樹脂層をフィルム上に形成させたのち、５０℃で２日間エージングを行うことで離型フィルムを得た。Example 22
The liquid material for forming a resin layer prepared in Example 1 was applied to a corona-treated surface of a polyamide film (manufactured by Unitika, EX25, thickness 25 μm) using a Meyer bar, and then dried at 120 ° C. for 30 seconds. After forming a 0.5 μm thick resin layer on the film, a release film was obtained by aging at 50 ° C. for 2 days.
実施例１〜１１、１５〜２２、参考例１〜３、比較例１〜８で得られた離型フィルムの構成、特性を表２〜４に示す。 The structures and properties of the release films obtained in Examples 1 to 11 , 15 to 22, Reference Examples 1 to 3, and Comparative Examples 1 to 8 are shown in Tables 2 to 4.
実施例１〜１１、１５〜２２の離型フィルムは、接着シートに貼り付けて室温で長期保管した場合であっても剥離性に優れていた。また、離型フィルムを剥離した接着シートの残留接着性にも優れており、適度な接着強度を有していたため、打ち抜き性にも優れていた。特に実施例１、３、４、８、１７、１９〜２２においては、酸変性ポリオレフィン樹脂の酸変性成分、プロピレン成分、アクリル酸エステル成分の質量比が好適な範囲であり、水酸基含有樹脂および架橋剤おいても好適な含有量であるため、長期保管後の剥離性や接着シートの残留接着性、打ち抜き性に優れていた。
一方、比較例１の離型フィルムは、樹脂層を構成する酸変性ポリオレフィン樹脂がアクリル酸エステル成分を含有しないため、剥離が軽すぎるため、打ち抜き性評価で浮きが生じた。
比較例２の離型フィルムは、樹脂層を構成する酸変性ポリオレフィン樹脂がプロピレン成分を含有しないため、接着シートに貼り付けて室温で長期保管した場合に剥離できなかった。
比較例３〜５の離型フィルムは、水酸基含有樹脂の含有量がそれぞれ本発明で規定する範囲から外れるため、接着シートに貼り付けて室温で長期保管した場合に剥離できず、離型フィルムを剥離した粘着シートにおいても、残留接着性が低下した。
比較例６〜８の離型フィルムは、架橋剤の含有量が、それぞれ本発明で規定する範囲から外れるため、いずれの離型フィルムも接着シートに貼り付けて室温で長期保管した場合に剥離できず、離型フィルムを剥離した粘着シートにおいても、残留接着性が低下した。比較例６の離型フィルムにおいては打ち抜き性についても劣っていた。
The release films of Examples 1 to 11, 15 to 22 were excellent in releasability even when pasted on an adhesive sheet and stored for a long time at room temperature. Further, the adhesive sheet from which the release film was peeled was also excellent in the residual adhesiveness, and had an appropriate adhesive strength, so that it was excellent in punchability. Particularly in Examples 1, 3, 4, 8, 17, and 19 to 22, the mass ratio of the acid-modified component, propylene component, and acrylate component of the acid-modified polyolefin resin is in a suitable range, and the hydroxyl group-containing resin and the crosslinked resin Since the content of the agent is also suitable, it was excellent in peelability after long-term storage, residual adhesiveness of the adhesive sheet, and punchability.
On the other hand, in the release film of Comparative Example 1, since the acid-modified polyolefin resin constituting the resin layer did not contain an acrylate ester component, peeling was too light, so that floating occurred in the punching evaluation.
Since the acid-modified polyolefin resin constituting the resin layer did not contain a propylene component, the release film of Comparative Example 2 could not be peeled off when attached to an adhesive sheet and stored at room temperature for a long time.
In the release films of Comparative Examples 3 to 5, since the content of the hydroxyl group-containing resin is out of the range specified in the present invention, the release film cannot be peeled off when it is attached to an adhesive sheet and stored at room temperature for a long time. Also in the peeled adhesive sheet, the residual adhesiveness was lowered.
In the release films of Comparative Examples 6 to 8, the content of the cross-linking agent deviates from the range specified in the present invention. Therefore, any release film can be peeled off when attached to an adhesive sheet and stored at room temperature for a long time. In addition, even in the pressure-sensitive adhesive sheet from which the release film was peeled, the residual adhesiveness was lowered. The release film of Comparative Example 6 was inferior in punchability.
Claims (9)
離型フィルムは、基材フィルムの少なくとも一方の面に樹脂層を有し、
樹脂層が、酸変性ポリオレフィン樹脂１００質量部、水酸基含有樹脂１０〜１０００質量部、および架橋剤０．３〜５０質量部を含有し、
酸変性ポリオレフィン樹脂が、酸変性成分と、アクリル酸エステル成分と、オレフィン成分とを含有し、
オレフィン成分がプロピレン成分を含有し、１−ブテン成分を含有しないことを特徴とする離型フィルム。 A release film for a pressure-sensitive adhesive sheet having a curable resin pressure-sensitive adhesive,
Release film, on at least one surface of the substrate film have a resin layer,
The resin layer contains 100 parts by mass of an acid-modified polyolefin resin, 10 to 1000 parts by mass of a hydroxyl group-containing resin, and 0.3 to 50 parts by mass of a crosslinking agent.
The acid-modified polyolefin resin contains an acid-modified component, an acrylate component, and an olefin component,
A release film comprising an olefin component containing a propylene component and no 1-butene component .
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| TW202033350A (en) * | 2018-12-20 | 2020-09-16 | 日商東洋紡股份有限公司 | Release film |
| CN113733698A (en) * | 2021-08-20 | 2021-12-03 | 江苏澳盛复合材料科技有限公司 | Polypropylene release film and method thereof |
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| JP4815745B2 (en) * | 2003-01-30 | 2011-11-16 | 三菱樹脂株式会社 | Release agent solution and release film |
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| JP5989995B2 (en) * | 2011-02-04 | 2016-09-07 | 日東電工株式会社 | Release agent, release material and adhesive tape |
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