WO2018056276A1 - 離型フィルムおよびその製造方法 - Google Patents
離型フィルムおよびその製造方法 Download PDFInfo
- Publication number
- WO2018056276A1 WO2018056276A1 PCT/JP2017/033795 JP2017033795W WO2018056276A1 WO 2018056276 A1 WO2018056276 A1 WO 2018056276A1 JP 2017033795 W JP2017033795 W JP 2017033795W WO 2018056276 A1 WO2018056276 A1 WO 2018056276A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin layer
- acid
- film
- release film
- mass
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 title description 38
- 229920005989 resin Polymers 0.000 claims abstract description 135
- 239000011347 resin Substances 0.000 claims abstract description 135
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 60
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 43
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 35
- 238000007127 saponification reaction Methods 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000011344 liquid material Substances 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 105
- -1 polyethylene terephthalate Polymers 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 26
- 239000007787 solid Substances 0.000 description 16
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000004640 Melamine resin Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000003522 acrylic cement Substances 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate 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
- 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 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 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
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- PBYIFPWEHGSUEY-UHFFFAOYSA-N 2-ethenyl-4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C=C)=N1 PBYIFPWEHGSUEY-UHFFFAOYSA-N 0.000 description 1
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 1
- XYOSFLPUWVWHOA-UHFFFAOYSA-N 2-ethylidenepropane-1,3-diol;urea Chemical compound NC(N)=O.CC=C(CO)CO XYOSFLPUWVWHOA-UHFFFAOYSA-N 0.000 description 1
- LCANECIWPMDASZ-UHFFFAOYSA-N 2-isocyanatoethanol Chemical compound OCCN=C=O LCANECIWPMDASZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- MBLQIMSKMPEILU-UHFFFAOYSA-N 4-methyl-2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C(C)=C)=N1 MBLQIMSKMPEILU-UHFFFAOYSA-N 0.000 description 1
- IRHWINGBSHBXAD-UHFFFAOYSA-N 5-ethyl-2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CCC1CN=C(C(C)=C)O1 IRHWINGBSHBXAD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920006153 PA4T Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 150000001718 carbodiimides Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 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
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000005690 diesters 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
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 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
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 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
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- YVOQADGLLJCMOE-UHFFFAOYSA-N n-[6-(aziridine-1-carbonylamino)hexyl]aziridine-1-carboxamide Chemical compound C1CN1C(=O)NCCCCCCNC(=O)N1CC1 YVOQADGLLJCMOE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 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
- 239000003921 oil Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000002923 oximes 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
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 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
- 229920003987 resole Polymers 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001248 thermal gelation Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 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
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/005—Oriented
- B29K2995/0053—Oriented bi-axially
-
- 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
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a release film and a manufacturing method thereof.
- Release films are widely used in the medical and industrial fields. Specific examples include process materials for manufacturing printed wiring boards, flexible printed wiring boards, multilayer printed wiring boards, etc., and protection for protecting medical tapes, haptic agents, adhesive materials, liquid crystal display components, etc. Materials.
- Patent Document 1 discloses a release film in which an acid-modified polyolefin resin layer having good release properties with respect to various adherends is used as a release layer.
- the release film described in Patent Document 1 cannot be said to have a sufficient surface state when a high degree of flatness is required for the adherend after release.
- unevenness occurs when the resin layer is coated on the base material, and the surface of the resin layer has a height of about several tens nm to several hundreds nm.
- a minute non-planar shape such as a continuous streak shape or a discrete shape is generated, which is transferred to the adherend, which may lead to deterioration of the quality of the adherend.
- the present invention can prevent the occurrence of a minute non-planar shape with a height of several tens to several hundreds of nanometers, and can provide a high-quality release film with better coating film uniformity.
- the present invention intends to provide a release film in which the warping of the film end portion is suppressed even when stored for a long time under a high humidity environment.
- a release film having a resin layer containing a polyvinyl alcohol having a specific saponification rate as a release layer can solve the above problems. And reached the present invention.
- the gist of the present invention is as follows.
- the release film of the present invention is excellent in releasability and can prevent the occurrence of a minute non-planar shape with a height of several tens to several hundreds of nanometers. It is a quality release film, and even when stored for a long time in a high-humidity environment, warping of the film edge is suppressed. Furthermore, peeling electrification that occurs when peeling in a low humidity environment can be suppressed.
- the release film of the present invention is not only excellent in releasability, but also improves the yield and stabilizes the quality when a laminated film in which adherends are laminated is used as a product. It can use suitably as.
- a resin layer is provided on at least one surface of a base film, and the resin layer contains an acid-modified polyolefin resin, polyvinyl alcohol, and a crosslinking agent.
- Examples of the base film constituting the release film of the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly (1,4-cyclohexylenedimethylene terephthalate), poly Polyester film such as lactic acid (PLA), polyolefin film such as polypropylene, polystyrene film, polyamide 6, poly-p-xylylene adipamide (MXD6 nylon), polyamide 66, polyamide 46, polyamide 4T, polyamide 6T, polyamide 9T, etc.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- Poly Polyester film such as lactic acid (PLA), polyolefin film such as polypropylene, polystyrene film, polyamide 6, poly-p-xylylene adip
- Polyamide films polycarbonate films, polyacrylonitrile films, polyimide films, and multilayers thereof (for example, polyamide 6 / MXD6 nylon / polyamide 6, polyamide 6 / ethylene - vinyl alcohol copolymer / polyamide 6) and mixtures and used, a polyester film having mechanical strength and dimensional stability, the polyamide film is preferable.
- the intrinsic viscosity of the resin constituting the base film is preferably 0.55 to 0.80, and more preferably 0.60 to 0.75.
- the intrinsic viscosity is less than the above range, cutting is likely to occur during film formation, and it is difficult to produce stably, and the strength of the obtained film is low.
- the intrinsic viscosity exceeds the above range, in the film production process, shear heat generation becomes large at the time of melt extrusion of the resin, the load on the extruder increases, and the production speed must be sacrificed, The thickness of the film becomes difficult to control, and the productivity of the film decreases.
- thermal decomposition and gelation increase, and surface defects, foreign matters, and surface coarse protrusions increase.
- the intrinsic viscosity is too high, the polymerization time and the polymerization process are long, which increases the cost.
- the polymerization method of the resin constituting the base film is not particularly limited.
- a transesterification method, a direct polymerization method and the like can be mentioned.
- the transesterification catalyst include oxides such as Mg, Mn, Zn, Ca, Li, and Ti, and compounds such as acetates.
- the polycondensation catalyst include oxides such as Sb, Ti, and Ge, and compounds such as acetate. Since the polyester after polymerization contains monomers, oligomers, acetaldehyde as a by-product, and the like, solid-state polymerization may be performed at a temperature of 200 ° C. or higher under reduced pressure or under an inert gas flow.
- additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, and a pinning agent can be added to the base film.
- Antioxidants include hindered phenol compounds, hindered amine compounds, etc.
- thermal stabilizers include phosphorus compounds
- ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, and the like. Can be mentioned.
- polyester film As a specific example, fully dried polyester is supplied to an extruder, fully plasticized, melted at a temperature that exhibits fluidity, passed through a filter selected as necessary, and then passed through a T die to form a sheet. Extrude into. This sheet is brought into close contact with a cooling drum whose temperature is adjusted to be equal to or lower than the glass transition temperature (Tg) of the polyester to obtain an unstretched film.
- Tg glass transition temperature
- the obtained unstretched film is uniaxially oriented by a uniaxial stretching method or biaxially oriented by a biaxial stretching method.
- the biaxial stretching method is not particularly limited, but a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used.
- an unstretched film is stretched at a stretching ratio of about 2 to 6 times in the longitudinal or width direction within a temperature range of 50 ° C. higher than Tg to Tg of the resin.
- an unstretched film is biaxially stretched in the temperature range of 50 ° C. higher than the resin Tg to Tg so that the stretching ratio is about 2 to 4 times in the longitudinal and width directions.
- preliminary longitudinal stretching up to about 1.2 times may be performed on the unstretched film.
- an unstretched film is heated with a heating roll or infrared rays and stretched in the longitudinal direction to obtain a longitudinally stretched film.
- the longitudinal stretching the difference in peripheral speed between two or more rolls is used, and the stretching ratio is preferably 2.5 to 4.0 times within a temperature range of 40 ° C. higher than Tg to Tg of polyester.
- the longitudinally stretched film is successively subjected to the transverse stretching, heat setting, and thermal relaxation treatment in the width direction in order to obtain a biaxially oriented film.
- the transverse stretching starts at a temperature 40 ° C. higher than Tg to Tg of the resin, and the maximum temperature is preferably (100 to 40) ° C. lower than the melting point (Tm) of the resin.
- the transverse stretching ratio is adjusted depending on the required physical properties of the final film, but is preferably 3.5 times or more, more preferably 3.8 times or more, and more preferably 4.0 times or more. .
- the elastic modulus of the film and the dimensional stability can be enhanced.
- a heat setting treatment for several seconds at a temperature (50 to 10) ° C. lower than the Tm of the resin and a relaxation of 1 to 10% in the film width direction simultaneously with the heat setting treatment. After the heat setting treatment, the film is cooled to Tg or less to obtain a biaxially stretched film.
- a single layer film is obtained by the above production method, but the base film constituting the release film may be a multilayer film formed by laminating two or more layers.
- the multilayer film is obtained by separately melting the resin constituting each layer, extruding using a multilayer die, laminating and fusing before solidification, biaxial stretching, heat fixing, Two or more kinds of resins can be melted and extruded separately to form films, respectively, and 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.
- the release film of the present invention has a resin layer provided on at least one surface of the base film, and the resin layer contains an acid-modified polyolefin resin, polyvinyl alcohol, and a crosslinking agent.
- the acid-modified polyolefin resin contained in the resin layer is a resin having an olefin component as a main component and modified with an acid-modified component.
- the olefin component constituting the acid-modified polyolefin resin preferably contains at least one selected from ethylene, propylene, and butene, and more preferably contains propylene from the viewpoint of releasability with the epoxy prepreg.
- the content of propylene in the olefin component is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass or more. More preferably, the content is 99% by mass or more.
- Examples of the acid-modifying component that constitutes the acid-modified polyolefin resin include unsaturated carboxylic acid components. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, In addition to 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.
- the ratio of the acid-modified component in the acid-modified polyolefin resin is preferably 1 to 10% by mass, and more preferably 2 to 9% by mass.
- the acid-modified component is less than 1% by mass, the ratio of polar groups in the acid-modified polyolefin resin contained in the resin layer decreases, and therefore the resin layer tends not to have sufficient adhesion to the base film. In some cases, the adherend released from the resin layer may be contaminated. Furthermore, in the aqueous dispersion of the resin described later, it tends to be difficult to stably disperse the resin.
- acid-modified polyolefin resin may contain the ethylenically unsaturated component which contains an oxygen atom in a side chain.
- the ethylenically unsaturated component containing an oxygen atom in the side chain include esterified products of (meth) acrylic acid and alcohols having 1 to 30 carbon atoms. Among these, (meth) acrylic is easy to obtain. An esterified product of an acid and an alcohol having 1 to 20 carbon atoms is preferable.
- 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.
- methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate.
- “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”.
- the ethylenically unsaturated component containing an oxygen atom in the side chain has a polar group in the molecule, like the acid-modified component.
- the resin layer has high adhesion to the base film.
- the ratio of the ethylenically unsaturated component containing an oxygen atom in the side chain in the acid-modified polyolefin resin is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and 3 to 30% by mass.
- the acid-modified polyolefin resin may be copolymerized with a small amount of other monomers.
- other monomers include dienes, (meth) acrylonitrile, vinyl halides, vinylidene halides, carbon monoxide, sulfur dioxide, and the like.
- Each component constituting the acid-modified polyolefin resin may be copolymerized in the acid-modified polyolefin resin, and the form is not limited.
- Examples of the state of copolymerization include random copolymerization, block copolymerization, and graft copolymerization (graft modification).
- the melting point of the acid-modified polyolefin resin is preferably 80 to 200 ° C, more preferably 90 to 150 ° C.
- fusing point exceeds 200 degreeC, a high temperature process may be needed at the time of resin layer formation to the base film surface.
- the melting point is less than 80 ° C., the release property of the resin layer is lowered.
- the resin layer needs to contain polyvinyl alcohol together with the acid-modified polyolefin resin.
- polyvinyl alcohol is dispersed in the acid-modified polyolefin resin, whereby the releasability by the acid-modified polyolefin resin and the crosslinking agent can be improved.
- the polyvinyl alcohol constituting the resin layer needs to have a saponification rate of 99% or less, and the preferable upper limit is less than 98%, more preferably less than 96%, and still more preferably. Is less than 95%.
- the resin layer With a saponification rate of polyvinyl alcohol of 99% or less, it is possible to prevent the occurrence of a minute non-planar shape with a height of several tens to several hundreds of nanometers generated in the resin layer.
- the saponification rate of polyvinyl alcohol exceeds 99%, the fine non-planar shape generated in the resin layer tends to increase, and this fine non-planar shape is transferred to the adherend and is released from the mold.
- the lower limit of the saponification rate of polyvinyl alcohol is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more. preferable.
- the saponification rate of polyvinyl alcohol is less than 80%, the stability of the liquid material for forming the resin layer is lowered, and the productivity is lowered.
- polyvinyl alcohol having a saponification rate in the above range it is possible to suppress warping of the film edge when stored in a high humidity environment, and when using it as a release film in a low humidity environment, peeling charge is prevented. Can be suppressed.
- the content of the polyvinyl alcohol is required to be 10 to 1000 parts by mass, preferably 100 to 1000 parts by mass, and 210 to 800 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. More preferred is 300 to 600 parts by mass.
- the content of polyvinyl alcohol exceeds 1000 parts by mass, the liquid material for forming the resin layer has a high viscosity, and the above-described minute non-planar shape tends to occur in the coating film. A minute non-planar shape is likely to be generated, and the resin layer is easily transferred to the adherend.
- the content of polyvinyl alcohol is less than 10 parts by mass, the effect of adding to the resin layer is lost.
- the liquid medium constituting the liquid for forming the resin layer is preferably an aqueous medium, and therefore, polyvinyl alcohol is preferably water-soluble for ease of mixing.
- a commercially available polyvinyl alcohol can be used, for example, “JP-15”, “JT-05”, “JL-05E” of “J-Poval” manufactured by Nippon Vinegar Poval. ”,“ JM-33 ”,“ JM-17 ”,“ JF-05 ”,“ JF-10 ”“ Pura-CST ”,“ PVA-624 ”,“ PVA-203 ”of“ Kuraray Poval ”manufactured by Kuraray Co., Ltd. ”,“ PVA-220 ”,“ PVA-405 ”, and the like.
- the resin layer needs to contain a crosslinking agent together with the acid-modified polyolefin resin and polyvinyl alcohol.
- a cross-linking agent By including a cross-linking agent, the constituent components of the resin layer are cross-linked to improve releasability, improve the cohesive strength of the resin layer, make it difficult to migrate to the adherend, or improve water resistance. it can.
- the content of the crosslinking agent needs to be 1 to 20 parts by mass, preferably 2 to 15 parts by mass, and preferably 2 to 10 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. More preferred.
- the content of the crosslinking agent is less than 1 part by mass, the resin layer has a weak cohesive force, is inferior in adhesion to the base film, and tends to easily migrate to the adherend.
- the amount exceeds 20 parts by mass the resin layer reacts with the adherend and becomes poor in releasability, or the liquid material for forming the resin layer is thickened and the stability is lowered. There is.
- a compound having a plurality of functional groups that react with carboxyl groups in the molecule can be used, such as a polyfunctional epoxy compound; a polyfunctional isocyanate compound; a polyfunctional aziridine compound; a carbodiimide group-containing compound; Compounds; phenol resins; and amino resins such as urea compounds, melamine resins, and benzoguanamine resins. You may use 1 type of these, or may use 2 or more types together.
- polyfunctional isocyanate compounds, melamine compounds, urea compounds, polyfunctional epoxy compounds, carbodiimide group-containing compounds, oxazoline group-containing compounds are preferred, carbodiimide group-containing compounds, oxazoline group-containing compounds are more preferred, and oxazoline group-containing compounds are preferred. Further preferred.
- the oxazoline group-containing compound it is possible to obtain a release film having excellent release properties from the adherend and adhesion to the substrate.
- crosslinking agents may be used in combination.
- polyepoxy compound specifically, a polyepoxy compound, a diepoxy compound, or the like can be used.
- the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
- Polyglycidyl ether can be used.
- diepoxy compound examples include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diester.
- Glycidyl ether and polytetramethylene glycol diglycidyl ether can be used.
- polyfunctional isocyanate compound examples include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, tolylene diisocyanate and hexanetriol.
- Adduct adduct of tolylene diisocyanate and trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3 '-Bitrylene-4,4'-diisocyanate,3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, metaphenylene diisocyanate Etc.
- polyol-modified diphenylmethane-4,4'-diisocyanate carbodiimide-modified diphenylmethane-4,4'-diisocyanate
- isophorone diisocyanate 1,5-naphthalene diisocyanate
- Block isocyanate compounds obtained by blocking these isocyanate groups with phenols, alcohols, lactams, oximes and active methylene compounds containing bisulfites and sulfonic acid groups may be used.
- Examples of commercially available polyfunctional isocyanate compounds include “Basonate HW-100” manufactured by BASF.
- polyfunctional aziridine compound for example, N, N′-hexamethylene-1,6-bis- (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate can be used. is there.
- the carbodiimide group-containing compound 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.
- polycarbodiimide which is a polymer having a carbodiimide group
- examples of commercially available products of polycarbodiimide include the Carbodilite series manufactured by Nisshinbo Co., Ltd.
- 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”.
- the oxazoline group-containing compound 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.
- Such a polymer can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
- Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like.
- the addition polymerizable oxazoline group-containing monomer one or a mixture of two or more of these can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
- the other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer, for example, alkyl acrylate, alkyl methacrylate (the alkyl group includes methyl group, ethyl group, n-propyl group, isopropyl group, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamide, me
- 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.
- phenol resin examples include a resol type phenol resin and / or a novolak type prepared from a raw material such as phenol, bisphenol A, pt-butylphenol, octylphenol, alkylphenols such as p-cumylphenol, p-phenylphenol, cresol and the like. Phenolic resins can be used.
- urea resin for example, dimethylol urea, dimethylol ethylene urea, dimethylol propylene urea, tetramethylol acetylene urea, 4-methoxy 5-dimethylpropylene urea dimethylol can be used.
- the melamine resin is a compound having, for example, an imino group, a methylol group, and / or an alkoxymethyl group (for example, a methoxymethyl group or a butoxymethyl group) as a functional group in one molecule.
- an imino group-type methylated melamine resin, a methylol group-type melamine resin, a methylol group-type methylated melamine resin, a complete alkyl-type methylated melamine resin, or the like can be used.
- methylolated melamine resins are most preferred.
- an acidic catalyst such as p-toluenesulfonic acid in order to accelerate the thermosetting of the melamine resin.
- benzoguanamine resin for example, trimethylol benzoguanamine, hexamethylol benzoguanamine, trismethoxymethylbenzoguanamine, hexakismethoxymethylbenzoguanamine and the like can be used.
- the resin layer may contain a lubricant as long as the effects of the present invention are not impaired.
- 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.
- the resin layer constituting the release film of the present invention is excellent in appearance by suppressing the occurrence of a minute non-planar shape having a height of several tens to several hundreds of nm. Specifically, it is observed at the total film width at each point at a total of 10 points including a point 1 m from one edge in the longitudinal direction of the film, a point 1 m from the other edge, and a point equally divided by 9 between the two points.
- the average value of the existence rate of minute non-planar shapes such as continuous streaks or discrete shapes per 1 m of film width can be set to 1.0 piece / m or less.
- Such a minute non-planar shape can be visually confirmed by light interference under a high-intensity light source (300 lumens or more), for example. However, confirmation is difficult under a low-intensity light source such as a fluorescent lamp.
- the peeling force from the adherend when measured by attaching the acrylic adherend as the adhesive material to the resin layer is preferably 3.0 N / cm or less, preferably Can be 2.8 N / cm or less, more preferably 2.6 N / cm or less.
- the peeling force exceeds 3.0 N / cm, it is heavy peeling, and it becomes difficult to use it practically as a release film.
- the release film of the present invention the release property when the epoxy prepreg is attached to the resin layer and measured is excellent.
- the peel force between the resin layer and the epoxy prepreg is required to be 0.2 N / cm or less, and the release film of the present invention has a peel force of 0.2 N / cm or less. And preferably 0.01 to 0.1 N / cm, more preferably 0.01 to 0.05 N / cm. When the peeling force exceeds 0.2 N / cm, it becomes difficult to peel off from the epoxy prepreg, and handling properties are deteriorated.
- the thickness of the resin layer is preferably 0.01 to 1 ⁇ m, more preferably 0.03 to 0.7 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the thickness of the resin layer is less than 0.01 ⁇ m, sufficient releasability cannot be obtained, and if it exceeds 1 ⁇ m, the resin layer tends to move to the adherend and the cost increases, which is not preferable.
- the occurrence of warping after standing for 7 days under conditions of 25 ° C. and 80% can be 2.0 mm or less, preferably 1.0 mm or less, more preferably 0.8 mm. It can be 5 mm or less.
- the warpage exceeds 2.0 mm it becomes difficult to adhere to the adherend when used as a release film, and handling properties are deteriorated.
- 100 parts by mass of an acid-modified polyolefin resin, 1 to 20 parts by mass of a crosslinking agent, and 10 to 1000 parts by mass of polyvinyl alcohol having a saponification rate of 99% or less are liquid.
- examples include a method of applying a liquid material for forming a resin layer contained in a medium to at least one surface of an unstretched or uniaxially stretched film, and then drying, stretching, and heat-treating the film on which the coating film has been formed.
- 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)).
- amphiphilic organic solvent examples 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 other substances including ammonia, diethylamine, triethylamine, diethanolamine, triethanolamine Organic amine compounds such as N, N-dimethylethanolamine and N, N-diethylethanolamine, and lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone.
- alcohols such as methanol, ethanol, n-propanol and isopropan
- the liquid material for forming the resin layer is not limited to this method, but can be prepared, for example, by adding polyvinyl alcohol or a crosslinking agent to the liquid material of the acid-modified polyolefin resin.
- an aqueous dispersion of the acid-modified polyolefin resin can be used as the liquid material of the acid-modified polyolefin resin.
- 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 ⁇ m or less from the viewpoint of stability when mixed with other components and storage stability after mixing. More preferably, it is 8 ⁇ m 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.
- 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, polyvinyl alcohol, and a crosslinking agent can be appropriately selected depending on the lamination conditions, the target thickness and performance, It is not particularly limited. However, in order to keep the viscosity of the liquid material moderate and to form a uniform resin layer, the content is preferably 2 to 30% by mass, and more preferably 3 to 20% by mass. 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.
- the liquid material for forming the resin layer is applied to the polyester film by a known method such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spraying. Coating, dip coating, brushing method, etc. can be mentioned.
- the liquid material for forming the resin layer can suppress the occurrence of the above-mentioned minute non-planar shape in the coating film, so it is particularly effective when performing gravure roll coating. It is.
- the manufacturing method of the release film of this invention includes the process of drying and extending
- in-line method compared to the offline method of applying and drying the resin layer forming liquid on the substrate film. Since the resin layer can be formed in a state where the degree of orientation crystallization is small, the adhesion between the base film and the resin layer is improved.
- the resin layer can be heat-treated at a higher temperature while the film is in tension, the releasability and the residual adhesion rate can be improved without deteriorating the quality of the release film.
- the liquid material is applied to the base film stretched in the uniaxial direction, the film coated with the liquid material is dried, and further stretched in the direction perpendicular to the direction, heat treatment It is preferable for reasons of convenience and operation.
- the release film of the present invention is a protective film for double-sided tapes, adhesive materials, liquid crystal display parts, printed wiring boards, and other protective materials and process materials, sheets such as ion exchange membranes, ceramic green sheets, and heat dissipation sheets.
- a protective film for double-sided tapes adhesive materials, liquid crystal display parts, printed wiring boards, and other protective materials and process materials, sheets such as ion exchange membranes, ceramic green sheets, and heat dissipation sheets.
- sheets such as ion exchange membranes, ceramic green sheets, and heat dissipation sheets.
- it can be suitably used for forming a shaped structure.
- the release films obtained in Examples and Comparative Examples were evaluated by the following two methods.
- the points to be evaluated are a total of 10 points including a point 1 m from the one end edge in the longitudinal direction of the release film, a point 1 m from the other end edge, and a point obtained by dividing the two points into nine equal parts.
- TD width direction
- a straight line is drawn with a black oil-based pen and intersects the straight line. The presence or absence was observed with respect to the full width of the film.
- Fluorescent white light (100 lumens) is applied to the surface of the release layer on the resin layer side at a distance of 30 to 30 cm from the film at an angle of 5 to 45 ° to form continuous streaks and discrete minute non-planar surfaces. The presence or absence of a portion showing light interference corresponding to the presence of the shape was visually confirmed. “None” in which the continuous width and discrete minute non-planar shape having a height of about several tens of nanometers to several hundreds of nanometers cannot be confirmed at any point in the entire film width at the above 10 points. Items that can be confirmed are "Yes".
- an acrylic pressure-sensitive adhesive tape having a width of 50 mm and a length of 150 mm (No. 31B / acrylic pressure-sensitive adhesive manufactured by Nitto Denko Corporation) is a rubber roll.
- a sample was prepared by pressure bonding. A sample is sandwiched in the form of a metal plate / rubber plate / sample / rubber plate / metal plate, left in a 2 kPa load, 70 ° C. atmosphere for 20 hours, then cooled to room temperature for 30 minutes or longer, and a sample for peel strength measurement Got.
- the peel strength between the acrylic adhesive tape and the release film of the peel strength measurement sample was peeled at a peel angle of 180 degrees with a tensile tester (Autograph AGS-100B manufactured by Shimadzu Corporation) in a constant temperature room at 23 ° C. The measurement was performed at a speed of 300 mm / min.
- the peel strength between the acrylic pressure-sensitive adhesive tape and the biaxially stretched polyester resin film was measured with a tensile tester (Autograph AGS-100B manufactured by Shimadzu Corporation) in a thermostatic chamber at 23 ° C.
- the peeling angle was 180 degrees and the peeling speed was 300 mm / min.
- the peel force obtained by this measurement was defined as F1.
- an unused acrylic pressure-sensitive adhesive tape (Nitto Denko No. 31B, 50 mm wide and 150 mm long) on the corona-treated surface of a biaxially stretched polyester resin film (Embret PET-38 manufactured by Unitika, thickness 38 ⁇ m). / Acrylic adhesive) was affixed and left at room temperature for 20 hours under a load of 2 kPa.
- the sample was obtained by cooling to room temperature.
- the peel strength between the cured epoxy prepreg and the release film of the obtained sample was measured with a tensile tester (Autograph AGS-100B manufactured by Shimadzu Corporation) in a thermostatic chamber at 23 ° C.
- the peeling angle was 180 degrees and the peeling speed was 300 mm / min.
- Warpage of release film Immediately after production, the release film after leaving in a high humidity environment of 25 ° C. and 80% RH for 7 days is cut out to 30 mm ⁇ 150 mm and placed on the plate from which the charge has been removed. The height (mm) of lifting from the plate surface at the end portion of the short side portion was measured, and the warpage was evaluated. Practically, those having a warp height of less than 1 mm are required, and it is preferable that the warp height is low in consideration of workability.
- an acid-modified polyolefin resin and an aqueous dispersion thereof were produced by the following method.
- WS-700 Nippon Shokubai Epocross WS-700, aqueous solution of oxazoline group-containing compound, solid content concentration 25% by mass
- V-02-L2 Carbodilite V-02-L2 manufactured by Nisshinbo Co., Ltd., an aqueous solution of a carbodiimide group-containing compound, solid content concentration 25% by mass
- HW-100 Basonto HW-100 manufactured by BASF, aqueous solution of polyfunctional isocyanate compound, solid content concentration of 25% by mass
- Example 1 Preparation of liquid for resin layer formation>
- the acid-modified polyolefin resin aqueous dispersion “A-1”, the polyvinyl alcohol aqueous solution “JP-15”, and the aqueous solution “WS-700” of the oxazoline group-containing compound as a cross-linking agent each had a solid content of 100 mass. Part, 300 parts by mass, and 7 parts by mass, and adjusted with water so that the final solid content concentration becomes 6.0% by mass to obtain a liquid material for forming a resin layer.
- this longitudinally stretched film On one side of this longitudinally stretched film, using a reverse gravure coater, the above liquid material was applied so as to have a coating amount of 5 g / m 2 (WET conversion), and stretched 4.5 times at 120 ° C. in a lateral stretching tenter. Then, after heat-treating at 230 ° C. for 10 seconds, it was cooled and wound up.
- the obtained release film had a thickness of 38 ⁇ m, and the resin layer had a thickness of about 0.08 ⁇ m.
- Examples 2 to 16, 20 and Comparative Examples 1 to 7 A release film was obtained in the same manner as in Example 1 except that a liquid material for forming a resin layer was prepared so as to have the structure shown in Table 1, and this liquid material was used.
- Example 17 In the same manner as in Example 1, the unstretched film was stretched 3.5 times with a roll-type longitudinal stretching machine at 85 ° C. to obtain a stretched film. Without applying the liquid material for forming the resin layer to the stretched film, the end of the film is held by a clip of a flat stretching machine and stretched 4.5 times in width under the condition of 100 ° C. Heat treatment was performed at 230 ° C. for 3 seconds with a direction relaxation rate of 3% to obtain a polyethylene terephthalate film having a thickness of 38 ⁇ m. A liquid material for forming a resin layer having the structure shown in Table 1 was applied to the surface of the obtained polyethylene terephthalate film using a Mayer bar, and then dried at 120 ° C. for 30 seconds. Thereafter, aging was performed at 50 ° C. for 2 days to obtain a release film in which a resin layer having a thickness of 0.3 ⁇ m was provided on one side of a polyester film having a thickness of 38 ⁇ m.
- Example 18 Polybutylene terephthalate containing 0.08% by mass of amorphous silica particles having an average particle size of 2.3 ⁇ m (PBT, polymerization catalyst: antimony trioxide, intrinsic viscosity: 1.08, glass transition temperature: 55 ° C., melting point: 233 ° C. ) was melt-extruded at 270 ° C., and tightly cooled to the casting drum by T-die method-electrostatic pinning method to form an unstretched film having a thickness of 600 ⁇ m. Subsequently, this unstretched film was stretched 3.5 times with a longitudinal stretching roll heated to 60 ° C.
- PBT polymerization catalyst: antimony trioxide, intrinsic viscosity: 1.08, glass transition temperature: 55 ° C., melting point: 233 ° C.
- the above liquid material was applied to a coating amount of 5 g / m 2 (WET conversion), and stretched 4.5 times at 80 ° C. in a transverse stretching tenter. Then, after heat-treating at 210 ° C. for 10 seconds, it was cooled and wound up.
- the obtained release film had a thickness of 38 ⁇ m, and the resin layer had a thickness of about 0.08 ⁇ m.
- Example 19 Nylon 6 (Ny, relative viscosity: 3.03) containing 0.08% by mass of amorphous silica particles having an average particle size of 2.3 ⁇ m is melt extruded at 260 ° C. and cast into a casting drum by the T-die method-electrostatic pinning method. Adhesion and rapid cooling were performed to form an unstretched film having a thickness of 600 ⁇ m. Next, the unstretched film was immersed in water at a temperature of 53 ° C. for 1 minute, and then immersed in water at a temperature of 60 ° C. for 20 seconds.
- the liquid material was applied to one side of an unstretched film that had been subjected to water immersion treatment so as to have an application amount of 10 g / m 2 (WET conversion) and dried.
- the water-absorbed unstretched film was guided to a simultaneous biaxial stretching machine and subjected to simultaneous biaxial stretching at a magnification of 3.3 times in length and 3.0 times in width.
- heat treatment was performed at a temperature of 210 ° C., and a 5% relaxation treatment was performed in the lateral direction to obtain a release film having a thickness of 38 ⁇ m and a resin layer thickness of approximately 0.08 ⁇ m.
- Table 1 shows the results of various evaluations of the release films obtained in Examples and Comparative Examples.
- the resin layers of the release films of Examples 1 to 20 have continuous streak and discrete minute non-planar shapes.
- the number of continuous streaks and discrete minute non-planar shapes having a height of about several tens to several hundreds of nanometers is 1 as well. It was 0.0 pieces / m or less and had higher-quality coating film uniformity. In addition, even when stored in a high humidity environment, the warp of the release film has been reduced to a level that can be used practically. Did not occur. Furthermore, the release property was good for both the acrylic pressure-sensitive adhesive and the epoxy prepreg, and the residual adhesion rate to the acrylic pressure-sensitive adhesive was also good.
- the resin layers of the release films of Examples 2 to 3 and 6 to 8 contain polyvinyl alcohol having a saponification rate in a particularly preferable range in a more preferable range. Neither continuous streaks nor discrete non-planar shapes of about several tens to several hundreds of nanometers were confirmed, and warpage in a high humidity environment was also controlled.
- the release films of Examples 6 to 12 have a higher propylene ratio in the olefin component of the acid-modified polyolefin resin constituting the resin layer than the release films of other examples, so that the release properties for the epoxy prepreg are improved. It was excellent.
- the release films of Comparative Examples 1, 2, and 7 were provided with a resin layer containing polyvinyl alcohol having a saponification rate exceeding 99%. Therefore, in the evaluation method A with a low accuracy using a low-luminance light source, Although generation of continuous streaky and discrete minute non-planar shapes with a height of about several tens to several hundreds of nanometers was not confirmed, in the highly accurate evaluation method B using a high-intensity light source, the height number Many continuous streaky and discrete minute non-planar shapes of about 10 nm to several hundred nm were confirmed. In addition, the warpage of the film was large under a high humidity environment, and peeling electrification occurred under a low humidity environment.
- the release film of Comparative Example 3 since the content of polyvinyl alcohol in the resin layer did not satisfy the range specified in the present invention, the adhesiveness between the base film and the resin layer was low, and the acrylic pressure-sensitive adhesive after peeling The resin layer was transferred and the residual adhesion rate was low.
- the release film of Comparative Example 4 had a polyvinyl alcohol content in the resin layer that exceeded the range defined in the present invention. Therefore, in the highly accurate evaluation method B using a high-intensity light source, the height was several tens of nm. Many continuous non-planar shapes of continuous streaks and discrete shapes of about several hundred nm were confirmed.
- the release film of Comparative Example 5 did not satisfy the range defined by the present invention in the content of the crosslinking agent in the resin layer, the adhesiveness between the base film and the resin layer was low, and during the peel force evaluation, There were cases where peeling did not occur between the adhesive tape and the resin layer, but peeling between the base film and the resin layer. Moreover, the acrylic adhesive after peeling had the resin layer moved, and the residual adhesive rate was low. Further, the release film of Comparative Example 6 was formed because the content of the crosslinking agent in the resin layer exceeded the range specified in the present invention, and the liquid material for forming the resin layer was thickened with time and low in stability. The obtained resin layer was inferior in releasability.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
Description
また、特許文献1に記載された離型フィルムは、海上輸送時や梅雨時期など高湿度環境下で長期間保管した場合、フィルムの端部に反りが発生してしまい、離型フィルムとして使用する際に、反った端部が被着体を保護できないなどの不具合を生じることがあった。
(1)基材フィルムの少なくとも片面に樹脂層が設けられた離型フィルムであって、樹脂層が、酸変性ポリオレフィン樹脂100質量部と、架橋剤1~20質量部と、ケン化率が99%以下であるポリビニルアルコール10~1000質量部とを含むことを特徴とする離型フィルム。
(2)ポリビニルアルコールのケン化率が98%未満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のオレフィン成分が、エチレンおよび/またはプロピレンを含むことを特徴とする(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のオレフィン成分におけるプロピレンの含有量が95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。
(6)アクリル系被着体を樹脂層に貼り付けて測定したときの樹脂層と被着体との間の剥離力が3.0N/cm以下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)基材フィルムを構成する樹脂がポリエステル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)上記(1)~(7)のいずれかに記載の離型フィルムを製造するための方法であって、基材フィルムに、酸変性ポリオレフィン樹脂100質量部と、架橋剤1~20質量部と、ケン化率が99%以下であるポリビニルアルコール10~1000質量部とを含む樹脂層形成用液状物が塗布されたフィルムを乾燥、延伸する工程を含むことを特徴とする離型フィルムの製造方法。
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、樹脂層が設けられたものであり、樹脂層は、酸変性ポリオレフィン樹脂とポリビニルアルコールと架橋剤とを含有する。
重合後のポリエステルは、モノマーやオリゴマー、副生成物のアセトアルデヒド等を含有しているため、減圧もしくは不活性ガス流通下、200℃以上の温度で固相重合してもよい。
まず、十分に乾燥されたポリエステルを、押出機に供給し、十分に可塑化され、流動性を示す温度以上で溶融し、必要に応じて選ばれたフィルターを通過させ、その後Tダイを通じてシート状に押出す。このシートを、ポリエステルのガラス転移温度(Tg)以下に温度調節した冷却ドラム上に密着させて、未延伸フィルムを得る。
得られた未延伸フィルムを一軸延伸法により一軸配向させるか、もしくは二軸延伸法により二軸配向させる。二軸延伸法としては、特に限定はされないが、逐次二軸延伸法や同時二軸延伸法を用いることができる。
同時二軸延伸法では、未延伸フィルムを、樹脂のTg~Tgより50℃高い温度の範囲で、長手および巾方向にそれぞれ2~4倍程度の延伸倍率となるよう二軸延伸する。同時二軸延伸機に導く前に、未延伸フィルムに1.2倍程度までの予備縦延伸を施しておいてもよい。
また、逐次二軸延伸法では、未延伸フィルムを、加熱ロールや赤外線等で加熱し、長手方向に延伸して縦延伸フィルムを得る。縦延伸は2個以上のロールの周速差を利用し、ポリエステルのTg~Tgより40℃高い温度の範囲で、延伸倍率2.5~4.0倍とするのが好ましい。縦延伸フィルムを、続いて連続的に、巾方向に横延伸、熱固定、熱弛緩の処理を順次施して、二軸配向フィルムとする。横延伸は樹脂のTg~Tgより40℃高い温度で開始し、最高温度は樹脂の融点(Tm)より(100~40)℃低い温度であることが好ましい。横延伸の倍率は最終的なフィルムの要求物性に依存し調整されるが、3.5倍以上、さらには3.8倍以上とするのが好ましく、4.0倍以上とするのがより好ましい。長手方向と巾方向に延伸後、さらに、長手方向および/または巾方向に再延伸することにより、フィルムの弾性率を高めたり寸法安定性を高めたりすることもできる。
延伸に続き、樹脂のTmより(50~10)℃低い温度で数秒間の熱固定処理と、熱固定処理と同時にフィルム巾方向に1~10%の弛緩することが好ましい。熱固定処理後、フィルムをTg以下に冷却して二軸延伸フィルムを得る。
多層フィルムは、上記製造方法において、それぞれの層を構成する樹脂を別々に溶融して、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種以上の樹脂を別々に溶融、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。
酸変性ポリオレフィン樹脂を構成するオレフィン成分は、エチレン、プロピレン、ブテンから選ばれる少なくとも1種を含むことが好ましく、エポキシプリプレグとの離型性の観点でプロピレンを含むことがより好ましい。エポキシプリプレグとの離型性をさらに向上させる観点で、オレフィン成分におけるプロピレンの含有量は、50質量%以上であることが好ましく、80質量%以上であることがより好ましく、95質量%以上であることがさらに好ましく、99質量%以上であることが特に好ましい。
側鎖に酸素原子を含むエチレン性不飽和成分としては、(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、ポリエステル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。
側鎖に酸素原子を含むエチレン性不飽和成分は、酸変性成分と同様、分子内に極性基を有している。そのため側鎖に酸素原子を含むエチレン性不飽和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、樹脂層は、基材フィルムとの密着性が高くなる。しかし、側鎖に酸素原子を含むエチレン性不飽和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、樹脂層は、被着体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中における、側鎖に酸素原子を含むエチレン性不飽和成分の割合は、1~40質量%であることが好ましく、2~35質量%であることがより好ましく、3~30質量%であることがさらに好ましく、6~18質量%であること特に好ましい。
なお、側鎖に酸素原子を含むエチレン性不飽和成分を含有する酸変性ポリオレフィン樹脂を用いても、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。
また、本発明において、樹脂層を形成するための液状物の安定性の観点で、ポリビニルアルコールのケン化率の下限は、80%以上が好ましく、85%以上がより好ましく、90%以上がさらに好ましい。ポリビニルアルコールのケン化率が80%未満であると、樹脂層を形成するための液状物の安定性が低下し、生産性が低下する。
上記範囲のケン化率のポリビニルアルコールを用いることで、高湿度環境下で保管した場合のフィルム端部の反りを抑制でき、また、低湿度環境下で離型フィルムとして使用する場合、剥離帯電を抑制することができる。
多官能イソシアネート化合物の市販品としては、例えば、BASF社製「バソナートHW-100」などが挙げられる。
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。
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。
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。
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。
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。
樹脂層形成用液状物が塗布されたフィルムを乾燥、延伸することにより(インライン方式)、基材フィルムに樹脂層形成用液状物を塗布、乾燥するオフライン方式と比較して、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、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、離型フィルムの品位を低下させることなく、離型性や残留接着率を向上させることができる。
逐次二軸延伸法を採用して、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フィルムを乾燥し、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。
ポリビニルアルコールのケン化率は、JIS K-6726に準拠して測定を行った。
B型粘度計(トキメック社製、DVL-BII型デジタル粘度計)を用いて、温度25℃、回転速度60rpmの条件で、溶液粘度(mPa・s)を測定した。塗布開始前の樹脂層形成用液状物の粘度をH0、塗布開始時から5時間経過後の粘度をH1とした。得られた粘度H1、H2より、下記の基準で、樹脂層形成用液状物の安定性の評価を行った。
良:0.9≦H1/H0<1.1
可:0.7≦H1/H0<0.9、1.1≦H1/H0<1.3
不可:H1/H0<0.7、1.3≦H1/H0
実施例、比較例で得られた離型フィルムについて、下記2種の方法で評価した。
いずれの手法においても評価する地点は、離型フィルムの長手方向の片端縁から1mの地点と、他端縁から1mの地点と、前記2地点の間を9等分した地点の合計10地点とし、各地点のフィルムの幅方向(TD)に黒色油性ペンで直線を引き直線上を交差する、高さ数十nm~数百nm程度の連続した筋状および離散状の微小な非平面形状の有無を、フィルム全幅に対して観察した。
(評価方法A)
離型フィルムの樹脂層側表面に対して、蛍光灯の白色光線(100ルーメン)を、フィルムから30cm離して5~45°の角度から当てて、連続した筋状および離散状の微小な非平面形状の存在に対応した光の干渉を示す部分の有無を、目視で確認した。前記10地点のフィルム全幅において、どの地点においても高さ数十nm~数百nm程度の連続した筋状および離散状の微小な非平面形状が全く確認できないものを「なし」、1地点以上において確認できるものを「あり」とした。
(評価方法B)
離型フィルムの樹脂層側表面に対して、高輝度のLED懐中電灯(レッドレンザー社製M7R型、400ルーメン)の光を、フィルムから30cm離して10~45°の角度から当てることにより、フィルム全幅における、高さ数十nm~数百nm程度の連続した筋状および離散状の微小な非平面形状の存在に対応した光の干渉を示す部分の有無を、目視で確認して計数した。そして、フィルム幅1mあたりの、微小非平面形状による欠点数を算出し、10地点の平均値を求めた。
得られた離型フィルムの樹脂層側表面を、JIS K-5600-5-6に準拠し、クロスカット法によって、接着性を確認した。詳しくは、切り込みを入れて100区画の格子パターンをつくった樹脂層表面に粘着テープ(ニチバン社製TF-12)を貼り、勢いよくテープを剥離した。なお、「100/100」が、100区画に全く剥がれがなく、最も良い状態であり、「0/100」が、100区画全てが剥がれ、最も良くない状態を示す。100/100~90/100を合格とし、100/100~95/100、特に100/100~98/100が優れており、100/100が最も優れていることを示す。
得られた離型フィルムの樹脂層側に、巾50mm、長さ150mmのアクリル系粘着テープ(日東電工社製No.31B/アクリル系粘着剤)をゴムロール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。
剥離強度測定用試料の、アクリル系粘着テープと離型フィルムとの剥離力を、23℃の恒温室で引張試験機(島津製作所社製オートグラフAGS-100B)にて、剥離角度180度、剥離速度300mm/分の条件で測定した。
上記(5)アクリル系粘着剤に対する離型性の試験により離型フィルム表面から剥離した巾50mm、長さ150mmのアクリル系粘着テープ(日東電工社製No.31B/アクリル系粘着剤)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、アクリル系粘着テープと二軸延伸ポリエステル樹脂フィルムとの剥離力を、23℃の恒温室で引張試験機(島津製作所社製オートグラフAGS-100B)にて測定した。剥離角度は180度、剥離速度は300mm/分とした。この測定により得られた剥離力をF1とした。
一方、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-38、厚さ38μm)のコロナ処理面に、巾50mm、長さ150mmの未使用のアクリル系粘着テープ(日東電工社製No.31B/アクリル系粘着剤)を貼付し、2kPa荷重、室温で20時間放置した。その後、アクリル系粘着テープと二軸延伸ポリエステル樹脂フィルムとの剥離力を、23℃の恒温室で引張試験機(島津製作所社製オートグラフAGS-100B)にて測定(剥離角度は180度、剥離速度は300mm/分)し、得られた剥離力をF2とした。
得られた剥離力F1、F2より下記式を用いて残留接着率を得た。
残留接着率(%)=(F1/F2)×100
60mm×100mmの大きさのエポキシプリプレグ(住友ベークライト社製EI-6765)の両面を、得られた離型フィルムの樹脂層側で挟み、1.07kPa(8Torr)の真空プレス機中で、30℃から150℃まで15℃/分で昇温し、150℃で22分間保持した後、さらに5℃/分で190℃まで昇温し、5kg/cm2の圧力を10分間かけた後、15kg/cm2の圧力をかけながら、190℃で70分間保持した。その後、室温まで冷却を行うことで、試料を得た。
得られた試料の、硬化後のエポキシプリプレグと離型フィルムとの剥離力を、23℃の恒温室で引張試験機(島津製作所社製オートグラフAGS-100B)にて測定した。剥離角度は180度、剥離速度は300mm/分とした。
作製直後から、25℃、80%RHの高湿環境下に7日間放置した後の離型フィルムを、30mm×150mmに切り出し、帯電が除去された板の上に乗せ、短辺部の端部の板面からの持ち上がりの高さ(mm)を測定し、反りの評価を行った。実用的には、反りの高さが1mm未満のものが求められており、加工性を考慮し反りの高さは低い方が好ましい。
25℃、10%RHの低湿環境下で、離型フィルムを10枚重ねあわせ、暗室で一番上のフィルムを勢いよく取り除いた際の静電気の発生について、下記の基準で評価を行った。
なし:静電気光や静電気音の発生は確認されなかった。
あり:静電気光や静電気音の発生を確認した。
プロピレン-ブテン-エチレン三元共重合体(プロピレン/ブテン/エチレン=68.0/16.0/16.0(質量比))280gを、4つ口フラスコ中、窒素雰囲気下で加熱溶融させた後、系内温度を170℃に保って攪拌下、不飽和カルボン酸として無水マレイン酸32.0gとラジカル発生剤としてジクミルパーオキサイド6.0g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、得られた反応生成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A-1を得た。
上記酸変性ポリオレフィン樹脂A-1の製造において、プロピレン-ブテン-エチレン三元共重合体(プロピレン/ブテン/エチレン=68.0/16.0/16.0(質量比))を、プロピレン-エチレン共重合体(プロピレン/エチレン=99/1(質量比))に変更する以外は、同様にして、酸変性ポリオレフィン樹脂A-2を得た。
また、エチレン-アクリル酸エチル共重合体(エチレン/アクリル酸エチル=93/7(質量比))に変更する以外は、同様にして、酸変性ポリオレフィン樹脂A-3を得た。
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、上記方法で製造した60.0gの酸変性ポリオレフィン樹脂A-1と、45.0gのエチレングリコール-n-ブチルエーテル(沸点171℃)と、6.9gのN,N-ジメチルエタノールアミン(沸点134℃、樹脂中の無水マレイン酸単位のカルボキシル基に対して1.0倍当量)と、188.1gの蒸留水とを、上記の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。そうしたところ、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。さらに、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)することで、均一な酸変性ポリオレフィン樹脂A-1の水性分散体(固形分濃度25質量%)を得た。なお、フィルター上には残存樹脂はほとんどなかった。
用いる酸変性ポリオレフィン樹脂をA-2、A-3に変更する以外は、前述した方法と同様の方法で、酸変性ポリオレフィン樹脂A-2、A-3の水性分散体(固形分濃度25質量%)を得た。
・JL-05E:日本酢ビ・ポバール社製JL-05E、ケン化率82.0%。重合度500、固形分濃度8質量%
・JP-15:日本酢ビ・ポバール社製JP-15、ケン化率88.0%、重合度1,500、固形分濃度8質量%
・JT-05:日本酢ビ・ポバール社製JT-05、ケン化率94.5%、重合度500、固形分濃度8質量%
・JM-17:日本酢ビ・ポバール社製JM-17、ケン化率95.0%、重合度1700、固形分濃度8質量%
・JF-05:日本酢ビ・ポバール社製JF-05、ケン化率98.5%、重合度500、固形分濃度8質量%
・JF-10:日本酢ビ・ポバール社製JF-10、ケン化率98.5%、重合度1,000、固形分濃度8質量%
・VC-10:日本酢ビ・ポバール社製VC-10、ケン化率99.4%、重合度1,000、固形分濃度8質量%
・WS-700:日本触媒社製エポクロスWS-700、オキサゾリン基含有化合物の水性溶液、固形分濃度25質量%
・V-02-L2:日清紡社製カルボジライトV-02-L2、カルボジイミド基含有化合物の水性溶液、固形分濃度25質量%
・HW-100:BASF社製バソナートHW-100、多官能イソシアネート化合物の水性溶液、固形分濃度25質量%
<樹脂層形成用液状物の調製>
酸変性ポリオレフィン樹脂水性分散体「A-1」と、ポリビニルアルコール水溶液「JP-15」と、架橋剤としてのオキサゾリン基含有化合物の水性溶液「WS-700」とを、それぞれ固形分が、100質量部と、300質量部と、7質量部とになるように混合し、最終固形分濃度が6.0質量%になるように水で調整して、樹脂層形成用液状物を得た。
<離型フィルムの製造>
平均粒径2.3μmの無定形シリカ粒子を0.08質量%含有するポリエチレンテレフタレート(PET、重合触媒:三酸化アンチモン、固有粘度:0.62、ガラス転移温度:78℃、融点:255℃)を280℃で溶融押出し、Tダイ法-静電ピニング方式でキャスティングドラムに密着急冷し、厚さ600μmの未延伸フィルムを成形した。続いてこの未延伸フィルムを90℃に加熱した縦延伸ロールで3.5倍に延伸した。
この縦延伸したフィルムの片面に、リバースグラビアコーターを用いて、上記液状物を5g/m2(WET換算)の塗布量になるように塗布し、横延伸テンターにおいて120℃で4.5倍延伸後、230℃で10秒間熱処理したのち、冷却し巻き取った。得られた離型フィルムの厚さは38μmであり、樹脂層の厚さはおよそ0.08μmであった。
表1に記載した構成になるように樹脂層形成用液状物を調製し、この液状物を用いた以外は、実施例1と同様にして離型フィルムを得た。
実施例1と同様にして、未延伸フィルムをロール式縦延伸機で85℃の条件下、3.5倍に延伸して延伸フィルムを得た。この延伸フィルムに樹脂層形成用液状物を塗布することなく、フィルムの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、230℃で3秒間の熱処理を施して、厚さ38μmのポリエチレンテレフタレートフィルムを得た。
得られたポリエチレンテレフタレートフィルムの表面に、表1の構成の樹脂層形成用液状物を、マイヤーバーを用いて塗布した後、120℃で30秒間乾燥させた。その後、50℃で2日間エージングを行うことで、厚さ38μmのポリエステルフィルムの片面に厚さ0.3μmの樹脂層が設けられた離型フィルムを得た。
平均粒径2.3μmの無定形シリカ粒子を0.08質量%含有するポリブチレンテレフタレート(PBT、重合触媒:三酸化アンチモン、固有粘度:1.08、ガラス転移温度:55℃、融点:233℃)を270℃で溶融押出し、Tダイ法-静電ピニング方式でキャスティングドラムに密着急冷し、厚さ600μmの未延伸フィルムを成形した。続いてこの未延伸フィルムを60℃に加熱した縦延伸ロールで3.5倍に延伸した。
この縦延伸したフィルムの片面に、リバースグラビアコーターを用いて、上記液状物を5g/m2(WET換算)の塗布量になるように塗布し、横延伸テンターにおいて80℃で4.5倍延伸後、210℃で10秒間熱処理したのち、冷却し巻き取った。得られた離型フィルムの厚さは38μmであり、樹脂層の厚さはおよそ0.08μmであった。
平均粒径2.3μmの無定形シリカ粒子を0.08質量%含有するナイロン6(Ny、相対粘度:3.03)を260℃で溶融押出し、Tダイ法-静電ピニング方式でキャスティングドラムに密着急冷し、厚さ600μmの未延伸フィルムを成形した。
次に、未延伸フィルムを温度53℃の水中に1分間浸漬し、その後、温度60℃の水中に20秒浸漬した。次に、浸水処理を施した未延伸フィルムの片面に、リバースグラビアコーターを用いて、上記液状物を10g/m2(WET換算)の塗布量になるように塗布し、乾燥した。次に、吸水された未延伸フィルムを同時二軸延伸機に導き、縦3.3倍、横3.0倍の倍率で同時二軸延伸を施した。続いて、温度210℃で熱処理し、横方向に5%の弛緩処理を行い、厚み38μm、樹脂層の厚さがおよそ0.08μmの離型フィルムを得た。
なかでも、実施例2~3、6~8の離型フィルムの樹脂層は、ケン化率が特に好ましい範囲のポリビニルアルコールをより好ましい範囲で含有しているものであり、評価方法Bにおいて高さ数十nm~数百nm程度の連続した筋状および離散状の微小な非平面形状は全く確認されず、高湿度環境下における反りも制御されているものであった。
また、実施例6~12の離型フィルムは、他の実施例の離型フィルムに比べて樹脂層を構成する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比率が高いため、エポキシプリプレグに対する離型性に優れるものであった。
比較例3の離型フィルムは、樹脂層におけるポリビニルアルコールの含有量が本発明で規定する範囲を満たしていなかったため、基材フィルムと樹脂層との密着性が低く、剥離後のアクリル系粘着剤は、樹脂層が移行しており、残留接着率が低かった。また、比較例4の離型フィルムは、樹脂層におけるポリビニルアルコールの含有量が本発明で規定する範囲を超えていたため、高輝度光源を用いた精度の高い評価方法Bにおいては高さ数十nm~数百nm程度の連続した筋状および離散状の微小な非平面形状が多く確認された。
比較例5の離型フィルムは、樹脂層における架橋剤の含有量が本発明で規定する範囲を満たしていなかったため、基材フィルムと樹脂層との密着性が低く、剥離力評価の際に、粘着テープと樹脂層との間で剥離せず、基材フィルムと樹脂層との間で剥離する場合があった。また、剥離後のアクリル系粘着剤は、樹脂層が移行しており、残留接着率が低かった。また、比較例6の離型フィルムは、樹脂層における架橋剤の含有量が本発明で規定する範囲を超えていたため、樹脂層形成用液状物は経時的に増粘し安定性が低く、形成された樹脂層は離型性で劣っていた。
Claims (8)
- 基材フィルムの少なくとも片面に樹脂層が設けられた離型フィルムであって、樹脂層が、酸変性ポリオレフィン樹脂100質量部と、架橋剤1~20質量部と、ケン化率が99%以下であるポリビニルアルコール10~1000質量部とを含むことを特徴とする離型フィルム。
- ポリビニルアルコールのケン化率が98%未満であることを特徴とする請求項1記載の離型フィルム。
- 酸変性ポリオレフィン樹脂のオレフィン成分が、エチレンおよび/またはプロピレンを含むことを特徴とする請求項1または2記載の離型フィルム。
- 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の含有量が50質量%以上であることを特徴とする請求項1~3のいずれかに記載の離型フィルム。
- 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の含有量が95質量%以上であることを特徴とする請求項1~3のいずれかに記載の離型フィルム。
- アクリル系被着体を樹脂層に貼り付けて測定したときの樹脂層と被着体との間の剥離力が3.0N/cm以下であることを特徴とする請求項1~5のいずれかに記載の離型フィルム。
- 基材フィルムを構成する樹脂がポリエステルであることを特徴とする請求項1~6のいずれかに記載の離型フィルム。
- 請求項1~7のいずれかに記載の離型フィルムを製造するための方法であって、基材フィルムに、酸変性ポリオレフィン樹脂100質量部と、架橋剤1~20質量部と、ケン化率が99%以下であるポリビニルアルコール10~1000質量部とを含む樹脂層形成用液状物が塗布されたフィルムを乾燥、延伸する工程を含むことを特徴とする離型フィルムの製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17853046.5A EP3517296B1 (en) | 2016-09-20 | 2017-09-20 | Release film and method for manufacturing same |
CN201780057530.1A CN109715402B (zh) | 2016-09-20 | 2017-09-20 | 脱模膜及其制造方法 |
US16/333,711 US11040515B2 (en) | 2016-09-20 | 2017-09-20 | Release film and method for manufacturing same |
KR1020197009673A KR102470784B1 (ko) | 2016-09-20 | 2017-09-20 | 이형 필름 및 그 제조 방법 |
JP2018504810A JPWO2018056276A1 (ja) | 2016-09-20 | 2017-09-20 | 離型フィルムおよびその製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-182501 | 2016-09-20 | ||
JP2016182501 | 2016-09-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018056276A1 true WO2018056276A1 (ja) | 2018-03-29 |
Family
ID=61689984
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/033795 WO2018056276A1 (ja) | 2016-09-20 | 2017-09-20 | 離型フィルムおよびその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11040515B2 (ja) |
EP (1) | EP3517296B1 (ja) |
JP (3) | JPWO2018056276A1 (ja) |
KR (1) | KR102470784B1 (ja) |
CN (1) | CN109715402B (ja) |
TW (1) | TWI724240B (ja) |
WO (1) | WO2018056276A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020055307A (ja) * | 2018-09-27 | 2020-04-09 | ユニチカ株式会社 | 離型フィルム |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114262579B (zh) * | 2021-12-30 | 2023-11-24 | 江苏睿捷新材料科技有限公司 | 金属复合膜及其应用 |
CN116021798B (zh) * | 2023-01-28 | 2023-10-20 | 哈尔滨远驰航空装备有限公司 | 一种进气道用复合材料零吸胶成型方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08176372A (ja) * | 1994-12-21 | 1996-07-09 | Sekisui Chem Co Ltd | 水分散系離型剤組成物 |
JPH0977890A (ja) * | 1995-09-08 | 1997-03-25 | Sekisui Chem Co Ltd | 樹脂ペレットの表面処理方法 |
JP2001105547A (ja) * | 1999-10-06 | 2001-04-17 | Unitika Ltd | ガスバリア性フィルム |
WO2002055598A1 (fr) | 2001-01-15 | 2002-07-18 | Unitika Ltd. | Dispersion de resine polyolefinique aqueuse |
WO2014109340A1 (ja) | 2013-01-11 | 2014-07-17 | ユニチカ株式会社 | 離型フィルムおよびその製造方法 |
WO2014109341A1 (ja) * | 2013-01-11 | 2014-07-17 | ユニチカ株式会社 | 離型フィルムおよびその製造方法 |
JP2015189014A (ja) * | 2014-03-27 | 2015-11-02 | ユニチカ株式会社 | 離型フィルム |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07286127A (ja) * | 1994-04-19 | 1995-10-31 | Seiko Instr Inc | 被記録媒体のコーティング材料及び記録装置 |
JPH0929756A (ja) * | 1995-07-17 | 1997-02-04 | Sekisui Chem Co Ltd | 水分散系離型剤組成物及び離型シート |
KR101454712B1 (ko) * | 2007-08-22 | 2014-10-27 | 유니띠까 가부시키가이샤 | 이형용 시트 |
JP5160469B2 (ja) * | 2009-02-20 | 2013-03-13 | ユニチカ株式会社 | 凸版印刷用感光性樹脂構成体 |
US20130183522A1 (en) * | 2010-07-29 | 2013-07-18 | Hisamitsu Pharmaceutical Co., Inc. | Support film for tape and tape |
US9085123B2 (en) * | 2012-02-29 | 2015-07-21 | E I Du Pont De Nemours And Company | Ionomer-poly(vinylalcohol) coatings |
JP6030341B2 (ja) * | 2012-05-18 | 2016-11-24 | ユニチカ株式会社 | コーティング組成物、塗膜及び積層体 |
JP5523512B2 (ja) * | 2012-06-21 | 2014-06-18 | ユニチカ株式会社 | 包装材料用接着剤および包装材料 |
JP2015139925A (ja) * | 2014-01-28 | 2015-08-03 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
-
2017
- 2017-09-20 US US16/333,711 patent/US11040515B2/en active Active
- 2017-09-20 KR KR1020197009673A patent/KR102470784B1/ko active IP Right Grant
- 2017-09-20 JP JP2018504810A patent/JPWO2018056276A1/ja active Pending
- 2017-09-20 WO PCT/JP2017/033795 patent/WO2018056276A1/ja active Application Filing
- 2017-09-20 EP EP17853046.5A patent/EP3517296B1/en active Active
- 2017-09-20 CN CN201780057530.1A patent/CN109715402B/zh active Active
- 2017-09-20 TW TW106132241A patent/TWI724240B/zh active
-
2018
- 2018-08-16 JP JP2018153023A patent/JP7106112B2/ja active Active
-
2022
- 2022-07-06 JP JP2022108723A patent/JP2022132338A/ja active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08176372A (ja) * | 1994-12-21 | 1996-07-09 | Sekisui Chem Co Ltd | 水分散系離型剤組成物 |
JPH0977890A (ja) * | 1995-09-08 | 1997-03-25 | Sekisui Chem Co Ltd | 樹脂ペレットの表面処理方法 |
JP2001105547A (ja) * | 1999-10-06 | 2001-04-17 | Unitika Ltd | ガスバリア性フィルム |
WO2002055598A1 (fr) | 2001-01-15 | 2002-07-18 | Unitika Ltd. | Dispersion de resine polyolefinique aqueuse |
WO2014109340A1 (ja) | 2013-01-11 | 2014-07-17 | ユニチカ株式会社 | 離型フィルムおよびその製造方法 |
WO2014109341A1 (ja) * | 2013-01-11 | 2014-07-17 | ユニチカ株式会社 | 離型フィルムおよびその製造方法 |
JP2015189014A (ja) * | 2014-03-27 | 2015-11-02 | ユニチカ株式会社 | 離型フィルム |
Non-Patent Citations (1)
Title |
---|
"Solvent Handbook", 1990, KODANSHA SCIENTIFIC LTD. |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020055307A (ja) * | 2018-09-27 | 2020-04-09 | ユニチカ株式会社 | 離型フィルム |
Also Published As
Publication number | Publication date |
---|---|
EP3517296B1 (en) | 2020-04-22 |
TWI724240B (zh) | 2021-04-11 |
EP3517296A1 (en) | 2019-07-31 |
JP2022132338A (ja) | 2022-09-08 |
CN109715402B (zh) | 2021-09-17 |
EP3517296A4 (en) | 2019-09-25 |
KR102470784B1 (ko) | 2022-11-25 |
US20190224945A1 (en) | 2019-07-25 |
US11040515B2 (en) | 2021-06-22 |
KR20190055117A (ko) | 2019-05-22 |
TW201821276A (zh) | 2018-06-16 |
JPWO2018056276A1 (ja) | 2018-09-20 |
JP7106112B2 (ja) | 2022-07-26 |
CN109715402A (zh) | 2019-05-03 |
JP2018202872A (ja) | 2018-12-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5818958B2 (ja) | 離型フィルムおよびその製造方法 | |
JP2022132338A (ja) | 離型フィルムおよびその製造方法 | |
JP5697808B2 (ja) | 離型フィルムおよびその製造方法 | |
JP5774857B2 (ja) | 易滑性ポリエステルフィルムおよびその製造方法 | |
WO2006001151A1 (ja) | 両面離型フィルム | |
TWI715717B (zh) | 離型膜 | |
JP2018161797A (ja) | 離型フィルム | |
JP2020055307A (ja) | 離型フィルム | |
JP2014226922A (ja) | 積層フィルム | |
JP2022057020A (ja) | 離型フィルム | |
JP7493740B2 (ja) | 離型フィルムおよびその製造方法 | |
JP2021055081A (ja) | 水性分散体および離型フィルム | |
JP2021133645A (ja) | 積層フィルムおよびその製造方法 | |
JP2021138129A (ja) | 積層フィルムおよびその製造方法 | |
JP2020147723A (ja) | 離型フィルムおよびその製造方法 | |
JP2021133646A (ja) | 積層フィルムおよびその製造方法 | |
JP2022155604A (ja) | 積層フィルムおよびその製造方法 | |
JP2022077786A (ja) | 水性分散体、塗膜、積層フィルムおよびそれらの製造方法 | |
JP2014226923A (ja) | 積層フィルム | |
JP2014156070A (ja) | 基材レス両面粘着シート | |
JP5637921B2 (ja) | 積層ポリエステルフィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2018504810 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17853046 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197009673 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2017853046 Country of ref document: EP Effective date: 20190423 |