JP5317385B2 - Film - Google Patents
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- Publication number
- JP5317385B2 JP5317385B2 JP2005151569A JP2005151569A JP5317385B2 JP 5317385 B2 JP5317385 B2 JP 5317385B2 JP 2005151569 A JP2005151569 A JP 2005151569A JP 2005151569 A JP2005151569 A JP 2005151569A JP 5317385 B2 JP5317385 B2 JP 5317385B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- monomer
- weight
- styrene
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 229920005989 resin Polymers 0.000 claims abstract description 170
- 239000011347 resin Substances 0.000 claims abstract description 170
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 150000001993 dienes Chemical class 0.000 claims abstract description 28
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000000806 elastomer Substances 0.000 claims abstract description 13
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 9
- 229920001897 terpolymer Polymers 0.000 claims abstract description 7
- 238000007666 vacuum forming Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 85
- 239000000203 mixture Substances 0.000 claims description 23
- 229920001400 block copolymer Polymers 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920005604 random copolymer Polymers 0.000 claims description 14
- 239000002216 antistatic agent Substances 0.000 claims description 11
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- 239000002952 polymeric resin Substances 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 10
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- -1 polypropylene Polymers 0.000 description 31
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 13
- 239000002356 single layer Substances 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 150000004665 fatty acids Chemical class 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- VEOIIOUWYNGYDA-UHFFFAOYSA-N 2-[2-(6-aminopurin-9-yl)ethoxy]ethylphosphonic acid Chemical compound NC1=NC=NC2=C1N=CN2CCOCCP(O)(O)=O VEOIIOUWYNGYDA-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 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
- 239000002981 blocking agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012860 organic pigment Substances 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
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 description 1
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- HBKBEZURJSNABK-MWJPAGEPSA-N 2,3-dihydroxypropyl (1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(=O)OCC(O)CO HBKBEZURJSNABK-MWJPAGEPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- OHDSHGBRKMRPHC-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-dimethylethanamine Chemical compound CN(C)CCC1=CC=C(C=C)C=C1 OHDSHGBRKMRPHC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 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
- 239000004164 Wax ester Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005907 alkyl ester 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KKPMZLPPEXRJOM-UHFFFAOYSA-N butane-1,3-diol;hexanedioic acid Chemical compound CC(O)CCO.OC(=O)CCCCC(O)=O KKPMZLPPEXRJOM-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
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- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、ポリ塩化ビニル（ＰＶＣ）に代替し得るスチレン系フイルムに関する。 The present invention relates to a styrenic film that can replace polyvinyl chloride (PVC).
近年、環境問題への関心の高まりから、種々の分野において脱ハロゲン化が技術課題となっている。特にポリ塩化ビニル 系樹脂については、高濃度の可塑剤による汚染や、燃焼時のダイオキシン発生の懸念があり、このため、ポリプロピレン系材料等のポリオレフィン系材料を代替品として用いることが検討されている（例えば、特許文献１）。しかしながら、ポリ塩化ビニル 系樹脂の持つ、優れた透明性、真空成形性等とを同時に満足するポリオレフィン系材料の開発は難しく、そのような材料の出現が望まれてきた。
本発明は、ポリ塩化ビニル（ＰＶＣ）に代替し得る、優れた透明性と真空成形性等とを同時に満足し得るフイルム材料を提供することを目的とする。 An object of the present invention is to provide a film material that can be replaced with polyvinyl chloride (PVC) and can simultaneously satisfy excellent transparency and vacuum formability.
本発明者は、上記の課題を解決するために鋭意研究を行った結果、スチレン系エラストマー樹脂８０〜２０重量％、及び（メタ）アクリル酸アルキルエステル系単量体とスチレン系単量体との２元共重合樹脂２０〜８０重量％からなるブレンド樹脂を含むフイルムが、ポリ塩化ビニル（ＰＶＣ）に匹敵する、優れた透明性、真空成形性等を有することを見出した。かかる知見に基づき、さらに研究を重ねて本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that 80 to 20% by weight of a styrene elastomer resin and a (meth) acrylic acid alkyl ester monomer and a styrene monomer. It has been found that a film containing a blend resin comprising 20 to 80% by weight of a binary copolymer resin has excellent transparency, vacuum moldability and the like comparable to polyvinyl chloride (PVC). Based on this knowledge, further studies have been made and the present invention has been completed.
即ち、本発明は下記のフイルムを提供する。 That is, the present invention provides the following film.
項１．（ｉ）スチレン系エラストマー樹脂８０〜２０重量％、並びに（ii）（メタ）アクリル酸アルキルエステル系単量体とジエン系単量体とスチレン系単量体との３元共重合樹脂、及び（メタ）アクリル酸アルキルエステル系単量体とスチレン系単量体との２元共重合樹脂からなる群より選ばれる少なくとも１種の樹脂２０〜８０重量％からなるブレンド樹脂を含む層を有するフイルム。 Item 1. (I) 80 to 20% by weight of a styrene elastomer resin, and (ii) a terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer, and ( A film having a layer containing a blend resin composed of 20 to 80% by weight of at least one resin selected from the group consisting of binary copolymer resins of (meth) acrylic acid alkyl ester monomers and styrene monomers.
項２．前記スチレン系エラストマー樹脂が、スチレン系単量体とジエン系単量体とのランダム共重合樹脂の水添樹脂、及び／又は、スチレン系単量体とジエン系単量体とのブロック共重合樹脂の水添樹脂である項１に記戴のフイルム。
項３．さらにフイルム全重量に対して０．０５〜３０重量％の帯電防止剤を含有する項２に記載のフイルム。
Item 3. Item 3. The film according to
項４．前記帯電防止剤が、ポリエーテルエステルアミド又は親水性ポリオレフィンである項５に記載のフイルム。 Item 4. Item 6. The film according to Item 5, wherein the antistatic agent is polyetheresteramide or hydrophilic polyolefin.
項５．さらにフイルムの最外層上に粘着剤層を有する項１〜４のいずれかに記載のフイルム。 Item 5. Item 5. The film according to any one of Items 1 to 4, further comprising an adhesive layer on the outermost layer of the film.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のフイルムは、（ｉ）スチレン系エラストマー樹脂（以下、ＳＥ樹脂と呼ぶ）８０〜２０重量％、並びに（ii）（メタ）アクリル酸アルキルエステル系単量体とジエン系単量体とスチレン系単量体との３元共重合樹脂（以下、ＭＢＳ３元樹脂と呼ぶ）、及び（メタ）アクリル酸アルキルエステル系単量体とスチレン系単量体との２元共重合樹脂（以下、ＭＳ２元樹脂と呼ぶ）からなる群より選ばれる少なくとも１種の樹脂２０〜８０重量％からなるブレンド樹脂を含むフイルムである。つまり、本発明のフイルムは、上記のブレンド樹脂フイルムを含む単層或いは２層以上のフイルムである。 The film of the present invention comprises (i) styrene elastomer resin (hereinafter referred to as SE resin) 80 to 20% by weight, and (ii) (meth) acrylic acid alkyl ester monomer, diene monomer and styrene. Ternary copolymer resin (hereinafter referred to as MBS ternary resin) and binary copolymer resin (hereinafter referred to as MS2) of (meth) acrylic acid alkyl ester monomer and styrene monomer. A film containing a blend resin consisting of 20 to 80% by weight of at least one resin selected from the group consisting of: That is, the film of the present invention is a single layer film or a film having two or more layers containing the above blend resin film.
なお、（メタ）アクリル酸アルキルエステル系単量体とは、メタアクリル酸アルキルエステル系単量体又はアクリル酸アルキルエステル系単量体を意味する。 The (meth) acrylic acid alkyl ester monomer means a methacrylic acid alkyl ester monomer or an acrylic acid alkyl ester monomer.
本発明のフイルムは、ＰＶＣのように燃焼処理時に有害物質の発生がなく、しかもＰＶＣが有する、優れた透明性、真空成形性等を備えたフイルムである。 The film of the present invention is a film that does not generate harmful substances during combustion treatment like PVC and has excellent transparency, vacuum formability, etc. possessed by PVC.
本発明のフイルムの透明性（ヘイズ値；ＪＩＳ−Ｚ−８７４１）は、５〜４０％程度、好ましくは１０〜３０％程度である。また、１００℃に予備加熱した後に真空成形した場合に、厚みが均一に成形できしかも成形不足や破れなどが発生しない。 The transparency (haze value; JIS-Z-8741) of the film of the present invention is about 5 to 40%, preferably about 10 to 30%. Further, when vacuum forming is performed after preheating to 100 ° C., the thickness can be uniformly formed, and insufficient molding or tearing does not occur.
本発明のフイルムの一態様として、（ｉ）ＳＥ樹脂８０〜２０重量％、並びに（ii）ＭＢＳ３元樹脂及びＭＳ２元樹脂からなる群より選ばれる少なくとも１種の樹脂２０〜８０重量％からなるブレンド樹脂を含む層（Ａ）の単層フイルムが挙げられる。 As one aspect of the film of the present invention, (i) a blend comprising 80 to 20% by weight of SE resin and (ii) 20 to 80% by weight of at least one resin selected from the group consisting of MBS ternary resin and MS binary resin A monolayer film of the layer (A) containing a resin can be mentioned.
ＳＥ樹脂
本発明のフイルムで使用するＳＥ樹脂は、フイルムに必要な柔軟性（弾性）を付与する機能を有している。ＳＥ樹脂は、スチレン系単量体とジエン系単量体からなる共重合体、或いはその水素添加物である。ＳＥ樹脂は、弾性を有する軟質の熱可塑性樹脂（熱可塑性エラストマー）であり、それ自身フイルム成形も可能である。
SE resin The SE resin used in the film of the present invention has a function of imparting necessary flexibility (elasticity) to the film. The SE resin is a copolymer composed of a styrene monomer and a diene monomer, or a hydrogenated product thereof. The SE resin is a soft thermoplastic resin (thermoplastic elastomer) having elasticity, and can be film-formed by itself.
ＳＥ樹脂を構成するスチレン系単量体としては、例えば、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ジビニルベンゼン、１，１−ジフェニルエチレン、Ｎ，Ｎ−ジメチル−ｐ−アミノエチルスチレン、Ｎ，Ｎ−ジエチル−ｐ−アミノエチルスチレン等があげられ、これらは一種のみならず二種以上を使用してもよい。特にスチレンが好適である。 Examples of the styrene monomer constituting the SE resin include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N , N-diethyl-p-aminoethylstyrene, and the like. These may be used alone or in combination of two or more. Styrene is particularly preferred.
また、ＳＥ樹脂を構成するジエン系単量体は、１対の共役二重結合を有するジオレフィンであり、例えば１，３−ブタジエン、２−メチル−１，３−ブタジエン（イソプレン）、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエンなどであるが、特に一般的なものとしては１，３−ブタジエン、イソプレンが挙げられる。これらは一種のみならず二種以上を使用してもよい。特にブタジエンが好適である。
ＳＥ樹脂におけるスチレン系単量体単位の含有量は、通常８〜７５重量％、好ましくは１０〜７０重量％であり、また、ジエン系単量体単位の含有量は、通常２５〜９２重量％、好ましくは３０〜９０重量％である。スチレン系単量体単位の含有量は、紫外分光光度計又は核磁気共鳴装置（ＮＭＲ）を用いて、ジエン系単量体単位の含有量は、核磁気共鳴装置（ＮＭＲ）を用いて測定することができる。
The diene monomer constituting the SE resin is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2, 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like, with 1,3-butadiene and isoprene being particularly common Is mentioned. These may be used alone or in combination of two or more. In particular, butadiene is preferred.
The content of the styrene monomer unit in the SE resin is usually 8 to 75% by weight, preferably 10 to 70% by weight, and the content of the diene monomer unit is usually 25 to 92% by weight. It is preferably 30 to 90% by weight. The content of styrene monomer units is measured using an ultraviolet spectrophotometer or a nuclear magnetic resonance apparatus (NMR), and the content of diene monomer units is measured using a nuclear magnetic resonance apparatus (NMR). be able to.
ＳＥ樹脂の硬度（ＪＩＳ Ｋ６２５３ デュロメータータイプＡ）は４０〜９０程度、好ましくは、５０〜８０程度である。その比重（ＡＳＴＭ Ｄ２９７）は０．８５〜１．０程度であり、ＭＦＲ（ＡＳＴＭ Ｄ１２３８：２３０℃、２１．２Ｎ）は３〜６ｇ／１０ｍｉｎ程度であり、ガラス転移温度（Ｔｇ）は、示差走査熱量測定法（ＤＳＣ法）により測定した値で−５０〜３０℃程度、好ましくは、−４０〜２０℃程度である。 The SE resin has a hardness (JIS K6253 durometer type A) of about 40 to 90, preferably about 50 to 80. Its specific gravity (ASTM D297) is about 0.85 to 1.0, MFR (ASTM D1238: 230 ° C., 21.2 N) is about 3 to 6 g / 10 min, and glass transition temperature (Tg) is differential scanning. The value measured by the calorimetric method (DSC method) is about -50 to 30 ° C, preferably about -40 to 20 ° C.
ＳＥ樹脂の重量平均分子量（Ｍｗ）は、例えば、１０万〜５０万程度、好ましくは１５万〜３０万程度であればよい。重量平均分子量は、市販の標準ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定できる。 The SE resin has a weight average molecular weight (Mw) of, for example, about 100,000 to 500,000, preferably about 150,000 to 300,000. The weight average molecular weight can be measured using commercially available standard gel permeation chromatography (GPC).
本発明で使用するＳＥ樹脂は、スチレン系単量体とジエン系単量体からなる共重合物を用いても良いが、ジエン系単量体由来の２重結合が残っているので、公知の方法により水素添加（例えば、ニッケル触媒等）して飽和にしておくのが良い。これにより、耐熱性、耐薬品性、耐久性等に優れたより安定な樹脂になるからである。そのＳＥ樹脂の水添率は、共重合体中の共役ジエン化合物に基づく二重結合の８５％以上、好ましくは９０％以上、より好ましくは９５％以上である。この水添率は、核磁気共鳴装置（ＮＭＲ）を用いて測定できる。 The SE resin used in the present invention may be a copolymer comprising a styrene monomer and a diene monomer, but since a double bond derived from a diene monomer remains, it is known. It is good to saturate by hydrogenation (for example, nickel catalyst etc.) by the method. This is because it becomes a more stable resin excellent in heat resistance, chemical resistance, durability and the like. The hydrogenation rate of the SE resin is 85% or more, preferably 90% or more, more preferably 95% or more of the double bond based on the conjugated diene compound in the copolymer. This hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).
本発明で使用するＳＥ樹脂としては、スチレン系単量体とジエン系単量体からなるランダム共重合体の水素添加物（以下、「水添ランダム共重合体」とも呼ぶ）、スチレン系単量体とジエン系単量体からなるブロック共重合体の水素添加物（以下、「水添ブロック共重合体」とも呼ぶ）、或いはそれらをブレンドしたもの等が挙げられる。 Examples of the SE resin used in the present invention include a hydrogenated random copolymer composed of a styrene monomer and a diene monomer (hereinafter also referred to as “hydrogenated random copolymer”), a styrene monomer And a hydrogenated product of a block copolymer composed of a monomer and a diene monomer (hereinafter also referred to as “hydrogenated block copolymer”), or a blend thereof.
水添ランダム共重合体の具体例としては、式：−ＣＨ（Ｃ６Ｈ５）ＣＨ２−で示されるスチレン系単量体単位と、式：−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−で示されるエチレン単位と、式：−ＣＨ（Ｃ２Ｈ５）ＣＨ２−で示されるブチレン単位とがランダムに結合している水添ランダム共重合体が挙げられる。 Specific examples of the hydrogenated random copolymer include a styrene monomer unit represented by the formula: —CH (C 6 H 5 ) CH 2 — and a formula: —CH 2 CH 2 CH 2 CH 2 —. And a hydrogenated random copolymer in which an ethylene unit and a butylene unit represented by the formula: —CH (C 2 H 5 ) CH 2 — are randomly bonded.
上記の水添ランダム共重合体において、スチレン系単量体単位の含有量は６０〜７５重量％程度、好ましくは６５〜７０重量％程度である。また、ガラス転移温度（Ｔｇ）は０〜３０℃程度、好ましくは１０〜２０℃程度である。また、重量平均分子量は１０万〜５０万程度、好ましくは１５万〜３０万程度である。 In the hydrogenated random copolymer, the content of the styrene monomer unit is about 60 to 75% by weight, preferably about 65 to 70% by weight. The glass transition temperature (Tg) is about 0 to 30 ° C, preferably about 10 to 20 ° C. The weight average molecular weight is about 100,000 to 500,000, preferably about 150,000 to 300,000.
式（Ｉ）で表されこの様な特性を有する水添ランダム共重合体は、例えば、特開２００４−５９７４１号公報に記載の方法により、或いはこれに準じて製造することができる。 The hydrogenated random copolymer represented by the formula (I) and having such characteristics can be produced, for example, by the method described in JP-A No. 2004-59741 or in accordance therewith.
一方、水添ブロック共重合体としては、該共重合体の一端又は両末端にスチレン系単量体由来のブロックセグメントを有しさらにジエン系単量体由来のブロックセグメントを有するもの、或いはこれらをブレンドしたもの等が挙げられる。 On the other hand, as a hydrogenated block copolymer, one having a block segment derived from a styrene monomer at one end or both ends of the copolymer and further having a block segment derived from a diene monomer, or these Blended ones are listed.
水添ブロック共重合体としては、例えば、該共重合体の一端に、式：−ＣＨ（Ｃ６Ｈ５）ＣＨ２−で示されるスチレン系単量体由来のブロックセグメントを有し、その中程に、式：−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−で示されるエチレン単位、及び／又は、式：−ＣＨ（Ｃ２Ｈ５）ＣＨ２−で示されるブチレン単位を含むブロックセグメントを有し、該共重合体の他端に、式：−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−で示されるエチレン単位を含むセグメントを有する水添ブロック共重合体が挙げられる。 The hydrogenated block copolymer has, for example, a block segment derived from a styrenic monomer represented by the formula: —CH (C 6 H 5 ) CH 2 — at one end of the copolymer, The block segment includes an ethylene unit represented by the formula: —CH 2 CH 2 CH 2 CH 2 — and / or a butylene unit represented by the formula: —CH (C 2 H 5 ) CH 2 —. And a hydrogenated block copolymer having a segment containing an ethylene unit represented by the formula: —CH 2 CH 2 CH 2 CH 2 — at the other end of the copolymer.
上記の水添ブロック共重合体において、スチレン系単量体単位の含有量は８〜５０重量％程度、好ましくは１０〜４０重量％程度である。また、ガラス転移温度（Ｔｇ）は−５０〜０℃程度、好ましくは−４０〜−１０℃程度である。また、重量平均分子量は１０万〜５０万程度、好ましくは１５万〜３０万程度である。上記の様な特性を有する水添ブロック共重合体の具体例としては、ＳＥＢＣが例示される。 In the hydrogenated block copolymer, the content of the styrenic monomer unit is about 8 to 50% by weight, preferably about 10 to 40% by weight. The glass transition temperature (Tg) is about −50 to 0 ° C., preferably about −40 to −10 ° C. The weight average molecular weight is about 100,000 to 500,000, preferably about 150,000 to 300,000. SEBC is exemplified as a specific example of the hydrogenated block copolymer having the above-described characteristics.
或いは、水添ブロック共重合体として、例えば、該共重合体の両末端に、式：−ＣＨ（Ｃ６Ｈ５）ＣＨ２−で示されるスチレン系単量体由来のブロックセグメントを有し、その中程に、式：−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−で示されるエチレン単位、及び／又は、式：−ＣＨ（Ｃ２Ｈ５）ＣＨ２−で示されるブチレン単位を含むブロックセグメントを有する水添ブロック共重合体が挙げられる。 Alternatively, as a hydrogenated block copolymer, for example, at both ends of the copolymer, it has a block segment derived from a styrenic monomer represented by the formula: —CH (C 6 H 5 ) CH 2 —, In the middle, a block segment containing an ethylene unit represented by the formula: —CH 2 CH 2 CH 2 CH 2 — and / or a butylene unit represented by the formula: —CH (C 2 H 5 ) CH 2 — Examples thereof include a hydrogenated block copolymer.
上記の水添ブロック共重合体において、スチレン系単量体単位の含有量は８〜５０重量％程度、好ましくは１０〜４０重量％程度である。また、ガラス転移温度（Ｔｇ）は−５０〜０℃程度、好ましくは−４０〜−１０℃程度である。また、重量平均分子量は１０万〜５０万程度、好ましくは１５万〜３０万程度である。上記の様な特性を有する水添ブロック共重合体の具体例としては、ＳＥＢＳが例示される。 In the hydrogenated block copolymer, the content of the styrenic monomer unit is about 8 to 50% by weight, preferably about 10 to 40% by weight. The glass transition temperature (Tg) is about −50 to 0 ° C., preferably about −40 to −10 ° C. The weight average molecular weight is about 100,000 to 500,000, preferably about 150,000 to 300,000. SEBS is exemplified as a specific example of the hydrogenated block copolymer having the above characteristics.
ＳＥ樹脂のうち、水添ランダム共重合体は、水添ブロック共重合体ほど柔軟性は高くないが、フイルム同士のブロッキングの程度は、水添ランダム共重合体の方が水添ブロック共重合体より強くなる傾向がある。そのため、適度な柔軟性と耐ブロッキング性を併せ持つフイルムとするためには、水添ランダム共重合体と水添ブロック共重合体をブレンドした、ブレンドＳＥ樹脂が好適である。 Among SE resins, the hydrogenated random copolymer is not as flexible as the hydrogenated block copolymer, but the degree of blocking between films is that the hydrogenated random copolymer is more hydrogenated block copolymer. There is a tendency to become stronger. Therefore, in order to obtain a film having both moderate flexibility and blocking resistance, a blend SE resin obtained by blending a hydrogenated random copolymer and a hydrogenated block copolymer is preferable.
このブレンドＳＥ樹脂における水添ランダム共重合体と水添ブロック共重合体の重量比は、例えば、水添ランダム共重合体が５５〜８０重量％程度、水添ブロック共重合体が４５〜２０重量％程度が好適である。 The weight ratio of the hydrogenated random copolymer to the hydrogenated block copolymer in the blended SE resin is, for example, about 55 to 80% by weight for the hydrogenated random copolymer and 45 to 20% by weight for the hydrogenated block copolymer. % Is preferred.
ＭＳ２元樹脂又はＭＢＳ３元樹脂
本発明のフイルムで使用するＭＳ２元樹脂又はＭＢＳ３元樹脂は、該フィルムのブロッキングを抑制すると共に、適正な腰の硬さを与える役割を果たしている。
MS binary resin or MBS ternary resin The MS binary resin or MBS ternary resin used in the film of the present invention plays a role of preventing blocking of the film and imparting appropriate waist hardness.
まず、ＭＳ２元樹脂は、アクリル酸アルキルエステル系単量体とスチレン系単量体との共重合体である。具体的には、（メタ）アクリル酸アルキルエステル（ＭＡＡ）系単量体単位３５〜７０重量％と、スチレン系単量体単位６５〜３０重量％とからなる共重合体である。ここで、ＭＡＡ系単量体単位のアルキルエステルのアルキルは、一般に炭素数１〜５のアルキル（特に、メチル、エチル等）であり、炭素数が大きくなる程該硬度は低下する傾向にある。ＭＡＡ系単量体単位の具体例としては、例えば、アクリル酸メチル、アクリル酸エチル、メタアクリル酸メチル、メタアクリル酸エチル等が挙げられる。なお、スチレン系単量体は、上記のＳＥ樹脂の原料として記載されたものを用いることができる。 First, the MS binary resin is a copolymer of an acrylic acid alkyl ester monomer and a styrene monomer. Specifically, it is a copolymer composed of 35 to 70% by weight of (meth) acrylic acid alkyl ester (MAA) monomer units and 65 to 30% by weight of styrene monomer units. Here, the alkyl of the alkyl ester of the MAA monomer unit is generally an alkyl having 1 to 5 carbon atoms (particularly methyl, ethyl, etc.), and the hardness tends to decrease as the carbon number increases. Specific examples of the MAA monomer unit include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and the like. In addition, what was described as a raw material of said SE resin can be used for a styrene-type monomer.
ＭＳ２元樹脂は硬質樹脂であり、その硬度（ＪＩＳＫ６２５３ デュロメーター タイプＤ）は、６０〜１００程度、好ましくは、８０〜９０である。その比重（ＡＳＴＭ Ｄ２９７）は１．１０〜１．１３程度であり、ＭＦＲ（ＡＳＴＭ Ｄ１２３８：２３０℃、２１．２Ｎ）は０．８〜４．０ｇ／１０ｍｉｎ程度であり、ガラス転移温度（Ｔｇ）は、示差走査熱量測定法（ＤＳＣ法）により測定した値で８５〜１１０℃程度、好ましくは、９０〜１０５℃程度である。また、ＭＳ２元樹脂の重量平均分子量（Ｍｗ）は１０万〜４０万程度、好ましくは１０万〜２０万程度である。測定は、ＧＰＣ法による。 MS binary resin is a hard resin, and its hardness (JISK6253 durometer type D) is about 60 to 100, preferably 80 to 90. Its specific gravity (ASTM D297) is about 1.10 to 1.13, MFR (ASTM D1238: 230 ° C., 21.2 N) is about 0.8 to 4.0 g / 10 min, and glass transition temperature (Tg) Is a value measured by a differential scanning calorimetry (DSC method) of about 85 to 110 ° C, preferably about 90 to 105 ° C. The weight average molecular weight (Mw) of the MS binary resin is about 100,000 to 400,000, preferably about 100,000 to 200,000. The measurement is based on the GPC method.
ＭＢＳ３元樹脂は、上記したように（メタ）アクリル酸アルキルエステル系単量体とジエン系単量体（特に、ブタジエン）とスチレン系単量体との共重合体である。ＭＢＳ３元樹脂は、具体的には、（メタ）アクリル酸アルキルエステル（ＭＡＡ）系単量体単位３０〜６２重量％と、ジエン系単量体単位３〜３５重量％と、スチレン系単量体単位３５〜６７重量％とからなる共重合体である。ここで、ＭＡＡ系単量体はＭＳ２元樹脂で挙げたものが用いられる。なお、ジエン系単量体及びスチレン系単量体は、上記のＳＥ樹脂の原料として記載されたものを用いることができる。 The MBS ternary resin is a copolymer of a (meth) acrylic acid alkyl ester monomer, a diene monomer (particularly butadiene), and a styrene monomer as described above. Specifically, the MBS ternary resin comprises (meth) acrylic acid alkyl ester (MAA) monomer units of 30 to 62% by weight, diene monomer units of 3 to 35% by weight, and styrene monomers. It is a copolymer composed of 35 to 67% by weight of units. Here, as the MAA monomer, those mentioned for the MS binary resin are used. In addition, what was described as a raw material of said SE resin can be used for a diene monomer and a styrene monomer.
ＭＢＳ３元樹脂は硬質樹脂であり、その硬度（ＪＩＳ Ｋ６２５３ デュロメーター タイプＤ）は、２０〜５０程度、好ましくは、３０〜４０である。その比重（ＡＳＴＭ Ｄ２９７）は１．０９〜１．１１程度であり、ＭＦＲ（ＡＳＴＭ Ｄ１２３８：２３０℃、２１．２Ｎ）は２．０〜６．０ｇ／１０ｍｉｎ程度であり、ガラス転移温度（Ｔｇ）は、示差走査熱量測定法（ＤＳＣ法）により測定した値で８０〜９５℃程度、好ましくは、８５〜９０℃程度である。また、ＭＢＳ３元樹脂の重量平均分子量（Ｍｗ）は、１０万〜４０万程度、好ましくは１０万〜２０万程度である。測定は、ＧＰＣ法による。 The MBS ternary resin is a hard resin, and its hardness (JIS K6253 durometer type D) is about 20 to 50, preferably 30 to 40. Its specific gravity (ASTM D297) is about 1.09 to 1.11, MFR (ASTM D1238: 230 ° C., 21.2 N) is about 2.0 to 6.0 g / 10 min, and glass transition temperature (Tg) Is a value measured by a differential scanning calorimetry (DSC method) of about 80 to 95 ° C, preferably about 85 to 90 ° C. The weight average molecular weight (Mw) of the MBS ternary resin is about 100,000 to 400,000, preferably about 100,000 to 200,000. The measurement is based on the GPC method.
本発明のフイルムは、上記軟質系のＳＥ樹脂と硬質系のＭＳ２元樹脂及び／又はＭＢＳ３元樹脂とが所定割合でブレンドされた樹脂であることを特徴とし、そのブレンド割合は、ＳＥ樹脂を８０〜２０重量％、好ましくは６０〜４５重量％、ＭＳ２元樹脂及び／又はＭＢＳ３元樹脂を２０〜８０重量％、好ましくは４５〜５５重量％である。これにより、ＰＶＣに匹敵する、優れた透明性、真空成形性等が発揮される。 The film of the present invention is a resin in which the soft SE resin and the hard MS binary resin and / or MBS ternary resin are blended at a predetermined ratio, and the blend ratio is 80% of the SE resin. -20 wt%, preferably 60-45 wt%, MS binary resin and / or MBS ternary resin 20-80 wt%, preferably 45-55 wt%. Thereby, excellent transparency comparable to PVC, vacuum formability, etc. are exhibited.
ＳＥ樹脂が８０重量％を超え、ＭＳ２元樹脂及び／又はＭＢＳ３元樹脂が２０重量％未満になると、特に適正な腰の硬さが低下したり、真空成形性に劣る傾向にある。逆にＳＥ樹脂が２０重量％を未満で、ＭＳ２元樹脂及び／又はＭＢＳ３元樹脂が８０重量％を超えると、腰の硬さが強すぎる傾向にある。 When the SE resin exceeds 80% by weight and the MS binary resin and / or MBS ternary resin is less than 20% by weight, particularly suitable waist hardness tends to be lowered or the vacuum formability tends to be poor. Conversely, when the SE resin is less than 20% by weight and the MS binary resin and / or MBS ternary resin exceeds 80% by weight, the waist hardness tends to be too strong.
また、ＳＥ樹脂とＭＳ２元樹脂及び／又はＭＢＳ３元樹脂とは、いずれも非晶質であるため、結晶質であるポリプロピレン（ＰＰ）樹脂やポリエチレン（ＰＥ）樹脂に比べて、成形（特に、真空成形）し易いという特徴を有している。 In addition, since SE resin and MS binary resin and / or MBS ternary resin are all amorphous, they are molded (particularly vacuum) compared to crystalline polypropylene (PP) resin and polyethylene (PE) resin. It has the feature that it is easy to form).
特に、本発明のフイルムを、ブリスターパック等の剛性が必要とされる用途に用いる場合には、硬質樹脂であるＭＳ２元樹脂及び／又はＭＢＳ３元樹脂を６０重量％以上、特に６５〜８０重量％用いるのが好適であり、また、保護フイルム、床材等の柔軟性が必要とされる用途に用いる場合には、軟質樹脂であるＳＥ樹脂を５０重量％以上、特に６０〜８０重量％用いるのが好適である。 In particular, when the film of the present invention is used for an application requiring rigidity such as a blister pack, the hard resin MS binary resin and / or MBS ternary resin is 60 wt% or more, particularly 65 to 80 wt%. It is preferable to use it, and when it is used for applications that require flexibility such as protective film and flooring, the SE resin, which is a soft resin, is used in an amount of 50% by weight or more, particularly 60 to 80% by weight. Is preferred.
本発明のフイルムの全厚は、その用途に応じて適宜選択することができるが、ロ−ル状に巻くことができる程度であれば良く、例えば、約０．０３〜３ｍｍ、好ましくは約０．０４〜２ｍｍが例示できる。 The total thickness of the film of the present invention can be appropriately selected according to the use, but it is sufficient that the film can be wound in a roll shape, for example, about 0.03 to 3 mm, preferably about 0. 0.04 to 2 mm can be exemplified.
次に、本発明の単層フイルムの製造方法を説明する。ＳＥ樹脂８０〜２０重量％及びＭＳ２元樹脂及び／又はＭＢＳ３元樹脂２０〜８０重量％をドライブレンド又は溶融混練して均一に混合分散する。次に、得られた混合物をスクリュー式押出機に供給し、２００〜２２５℃で単層Ｔダイからフイルム状に押出し、これを５０〜７０℃の冷却ロ−ルに通しながら冷却して、実質的に無延伸、或いは縦方向及び又は横方向に延伸して引き取る。 Next, the manufacturing method of the single layer film of this invention is demonstrated. 80 to 20% by weight of SE resin and 20 to 80% by weight of MS binary resin and / or MBS ternary resin 20 to 80% by weight are uniformly blended and dispersed by dry blending or melt kneading. Next, the obtained mixture was supplied to a screw type extruder, extruded from a single-layer T die at 200 to 225 ° C., and cooled while passing through a cooling roll at 50 to 70 ° C. Thus, the film is not stretched, or stretched in the longitudinal direction and / or the transverse direction.
多層フイルム
本発明のフイルムは、上記したような層（Ａ）を有する単層フイルムだけでなく、他の層と積層されてなる多層フイルムとしても良い。
Multilayer Film The film of the present invention is not limited to a single layer film having the layer (A) as described above, but may be a multilayer film laminated with other layers.
例えば、本発明の多層フイルムの態様として、前記層（Ａ）と、（iii）ＳＥ樹脂１００〜８０重量％、並びに（iv）ＭＢＳ３元樹脂及びＭＳ２元樹脂からなる群より選ばれる少なくとも１種の樹脂０〜２０重量％からなるブレンド樹脂を含む層（Ｂ）とが積層されてなるフイルム、特に２層フイルムが挙げられる。 For example, as an aspect of the multilayer film of the present invention, the layer (A), (iii) 100-80% by weight of SE resin, and (iv) at least one selected from the group consisting of MBS ternary resin and MS binary resin Examples include a film formed by laminating a layer (B) containing a blend resin composed of 0 to 20% by weight of a resin, particularly a two-layer film.
層（Ｂ）のブレンド樹脂は、ＳＥ樹脂を８０重量％以上、好ましくは９０重量％以上含有し、また、ＭＳ２元樹脂及び／又はＭＢＳ３元樹脂を２０重量％以下、好ましくは１０重量％以下含有する。層（Ｂ）は、層（Ａ）に比べ軟質系のＳＥ樹脂の含有量が高いため、層（Ａ）に積層してフイルムに柔軟性（弾性）、透明性を付与するものである。 The blend resin of the layer (B) contains SE resin at 80% by weight or more, preferably 90% by weight or more, and MS binary resin and / or MBS ternary resin at 20% by weight or less, preferably 10% by weight or less. To do. Since the layer (B) has a higher content of soft SE resin than the layer (A), the layer (B) is laminated on the layer (A) to impart flexibility (elasticity) and transparency to the film.
本発明の２層（Ａ）／（Ｂ）からなるフイルムの全厚は、前記単層の場合と同じ理由から、０．０３〜３ｍｍ程度、好ましくは０．０４〜２ｍｍ程度が例示できる。この中で各層（Ａ）の厚さはそれぞれ０．００１〜１．５ｍｍ程度、好ましくは０．００３〜１ｍｍ程度であり、層（Ｂ）は０．０２７〜２ｍｍ程度、好ましくは０．０２９〜１．５ｍｍ程度である。 The total thickness of the film comprising the two layers (A) / (B) of the present invention is about 0.03 to 3 mm, preferably about 0.04 to 2 mm, for the same reason as in the case of the single layer. Among them, the thickness of each layer (A) is about 0.001 to 1.5 mm, preferably about 0.003 to 1 mm, and the layer (B) is about 0.027 to 2 mm, preferably 0.029 to It is about 1.5 mm.
或いは、本発明の多層フイルムの他の態様として、前記層（Ａ）と前記層（Ｂ）とが、（Ａ）／（Ｂ）／（Ａ）の順で積層されてなる３層フイルムが挙げられる。 Alternatively, as another aspect of the multilayer film of the present invention, there is a three-layer film in which the layer (A) and the layer (B) are laminated in the order of (A) / (B) / (A). It is done.
本発明の３層（Ａ）／（Ｂ）／（Ａ）からなるフイルムの全厚は、前記単層の場合と同じ理由から、０．０３〜３ｍｍ程度、好ましくは０．０４〜２ｍｍ程度が例示できる。この中で各層（Ａ）の厚さはそれぞれ０．００１〜１ｍｍ程度、好ましくは約０．００２〜０．８ｍｍ程度であり、層（Ｂ）は０．０２６〜１．４ｍｍ程度、好ましくは約０．０２８〜１ｍｍ程度である。 The total thickness of the three layers (A) / (B) / (A) of the present invention is about 0.03 to 3 mm, preferably about 0.04 to 2 mm for the same reason as in the case of the single layer. It can be illustrated. Of these, the thickness of each layer (A) is about 0.001 to 1 mm, preferably about 0.002 to 0.8 mm, and the layer (B) is about 0.026 to 1.4 mm, preferably about It is about 0.028 to 1 mm.
或いは、本発明の多層フイルムの他の態様として、前記した多層フイルムは、さらに耐ブロッキング性を向上させるために、その用途に応じて、最外層の片面或いは両面に耐ブロッキング層（Ｃ）を設けても良い。耐ブロッキング層としては、ポリエチレン系樹脂層、ポリプロピレン系樹脂層、ポリエステル系樹脂層などが例示される。 Alternatively, as another aspect of the multilayer film of the present invention, in order to further improve the blocking resistance, the multilayer film described above is provided with a blocking resistant layer (C) on one or both sides of the outermost layer depending on the application. May be. Examples of the anti-blocking layer include a polyethylene resin layer, a polypropylene resin layer, and a polyester resin layer.
この多層フイルムの形態としては、例えば、（Ａ）／（Ｃ）、（Ａ）／（Ｂ）／（Ｃ）、（Ａ）／（Ｂ）／（Ａ）／（Ｃ）、（Ｃ）／（Ａ）／（Ｂ）／（Ａ）／（Ｃ）等が例示される。 As the form of this multilayer film, for example, (A) / (C), (A) / (B) / (C), (A) / (B) / (A) / (C), (C) / (A) / (B) / (A) / (C) etc. are illustrated.
次に、本発明の多層フイルムの製造方法を説明する。この場合は共押出成形法が好ましく採用される。 Next, the manufacturing method of the multilayer film of this invention is demonstrated. In this case, a coextrusion method is preferably employed.
具体的には、各層を構成する樹脂組成物を溶融してＴダイからフイルム状に同時押出しを行い、これを５０〜７０℃の冷却ロ−ルに通しながら冷却して、実質的に無延伸、或いは縦方向及び又は横方向に延伸して引き取ることにより、多層フイルムが製造される。 Specifically, the resin composition constituting each layer is melted and co-extruded from a T die into a film, and cooled while passing through a cooling roll at 50 to 70 ° C., so that it is substantially unstretched. Alternatively, a multilayer film is produced by drawing in the longitudinal and / or transverse direction.
添加剤
また、前記した単層乃至多層のフイルムは、その用途に応じて、フイルムの透明性に悪影響を与えない範囲で、上記した層（Ａ）、層（Ｂ）及び層（Ｃ）のいずれか、或いは全ての層に、例えば、帯電防止剤、滑剤、アンチブロッキング剤、着色剤、酸化防止剤、耐候剤等の添加剤を含んでいても良い。
Additives The above-mentioned single-layer to multi-layer films may be any of the above-described layers (A), (B), and (C) within a range that does not adversely affect the transparency of the film. Alternatively, all layers may contain additives such as antistatic agents, lubricants, antiblocking agents, colorants, antioxidants, weathering agents, and the like.
前記した単層乃至多層のフイルムは、基本的には電気絶縁性である。そのため、例えば、保護フイルム、文具、包装材料等の用途に用いる場合は、低湿度下での作業や取り扱い方により発生するフイルムからの静電気を抑制する必要がある。 The above described single layer or multilayer film is basically electrically insulating. Therefore, for example, when it is used for applications such as protective film, stationery, and packaging material, it is necessary to suppress static electricity from the film generated by work or handling under low humidity.
この静電気の発生を抑制するために、本発明フイルムには、帯電防止剤を含んでいても良い。上記した層（Ａ）、層（Ｂ）及び層（Ｃ）のいずれか、或いは全ての層に帯電防止剤を含んでいても良い。帯電防止剤を含む場合、各層におけるその含有量は、各層の重量に対して０．０５〜４０重量％程度、好ましくは０．１〜３０重量％程度であればよい。 In order to suppress the generation of static electricity, the film of the present invention may contain an antistatic agent. Any or all of the above-described layer (A), layer (B), and layer (C) may contain an antistatic agent. When an antistatic agent is included, the content in each layer may be about 0.05 to 40% by weight, preferably about 0.1 to 30% by weight, based on the weight of each layer.
帯電防止剤としては、アニオン系，カチオン系、ノニオン系等の公知の界面活性剤を選択できるが、とりわけ持続性，耐久性の点から、ポリエーテルエステルアミド樹脂（以下、ＰＥＥＡ樹脂と呼ぶ。）、親水性ポリオレフィン樹脂（以下、親水性ＰＯ樹脂と呼ぶ。）等のノニオン系界面活性剤が好適である。 As the antistatic agent, known surfactants such as anionic, cationic, and nonionic surfactants can be selected. In particular, polyether ester amide resin (hereinafter referred to as PEEA resin) from the viewpoint of durability and durability. Nonionic surfactants such as hydrophilic polyolefin resins (hereinafter referred to as hydrophilic PO resins) are suitable.
前記ＰＥＥＡ樹脂は、親水性付与の主たるユニット成分であるポリエーテルエステルと、ポリアミドユニットとから構成されるポリマであり、市販されているか或いは公知の方法で容易に製造することができる。ＰＥＥＡ樹脂として、例えば、三洋化成工業（株）のペレスタットＮＣ６３２１等が例示される。また、特開昭６４−４５４２９号公報、特開平６−２８７５４７号公報等にその製法が記載されており、これによれば、例えば、主鎖中にエーテル基を有するポリジオ−ル成分にジカルボン酸成分を反応させて末端エステルに変え、これにアミノカルボン酸又はラクタムを反応させて製造できる。ＰＥＥＡ樹脂は、前記いずれの層の樹脂とも相溶性が良く、ブリードアウトするような現象は一切ない。 The PEEA resin is a polymer composed of a polyether ester which is a main unit component for imparting hydrophilicity and a polyamide unit, and is commercially available or can be easily produced by a known method. Examples of the PEEA resin include Pelestat NC6321 from Sanyo Chemical Industries, Ltd. In addition, the production method is described in JP-A-64-45429, JP-A-6-287547, etc. According to this, for example, a polydiol component having an ether group in the main chain is added to a dicarboxylic acid. It can be produced by reacting the components into a terminal ester and reacting this with an aminocarboxylic acid or lactam. The PEEA resin has good compatibility with any of the above-mentioned layers of resin, and there is no phenomenon of bleeding out.
親水性ＰＯ樹脂としては、例えば、親水性ポリエチレン（以下、親水性ＰＥ樹脂と呼ぶ。）又は親水性ポリプロピレン（以下、親水性ＰＰ樹脂と呼ぶ。）が例示される。 Examples of the hydrophilic PO resin include hydrophilic polyethylene (hereinafter referred to as hydrophilic PE resin) or hydrophilic polypropylene (hereinafter referred to as hydrophilic PP resin).
親水性ＰＥ樹脂又は親水性ＰＰ樹脂は、基本的にはポリエチレン鎖又はポリプロピレン鎖とポリオキシアルキレン鎖とがブロック結合したものであり、高い除電作用が発揮され静電気の蓄積をなくす。この結合は、エステル基、アミド基、エーテル基、ウレタン基等によって行われている。前記各層の樹脂との相溶性の点から、この結合はエステル基又はエーテル基であるのが好ましい。 The hydrophilic PE resin or the hydrophilic PP resin is basically a block in which a polyethylene chain or a polypropylene chain and a polyoxyalkylene chain are bonded to each other, exhibiting a high static elimination action and eliminating the accumulation of static electricity. This bonding is performed by an ester group, an amide group, an ether group, a urethane group or the like. From the viewpoint of compatibility with the resin of each layer, this bond is preferably an ester group or an ether group.
親水性ＰＰ樹脂として、例えば、三洋化成工業（株）社のペレスタット３００等が例示される。 Examples of the hydrophilic PP resin include Pelestat 300 manufactured by Sanyo Chemical Industries, Ltd.
親水性ＰＯ樹脂又は親水性ＰＥ樹脂におけるポリエチレン鎖又はポリプロピレン鎖の分子量は、例えば１２００〜６０００程度である。この分子量範囲であると、ポリオキシアルキレン鎖にポリエチレン又はポリプロピレンをブロック結合させる前段階の、ポリエチレン又はポリプロピレンの酸変性化が容易であるためである。 The molecular weight of the polyethylene chain or the polypropylene chain in the hydrophilic PO resin or the hydrophilic PE resin is, for example, about 1200 to 6000. This is because, within this molecular weight range, it is easy to acid-modify polyethylene or polypropylene at the stage before block bonding polyethylene or polypropylene to the polyoxyalkylene chain.
また、親水性ＰＯ樹脂又は親水性ＰＥ樹脂におけるポリオキシアルキレン鎖の分子量は、耐熱性及び酸変性後のポリエチレン又はポリプロピレンとの反応性の点から、１０００〜１５０００程度であるのが良い。なお、上記した分子量は、ＧＰＣを用いて測定した値である。 The molecular weight of the polyoxyalkylene chain in the hydrophilic PO resin or hydrophilic PE resin is preferably about 1000 to 15000 from the viewpoint of heat resistance and reactivity with polyethylene or polypropylene after acid modification. The molecular weight described above is a value measured using GPC.
親水性ＰＥ樹脂又は親水性ＰＰ樹脂は、例えば、前記した分子量を有するポリエチレン又はポリプロピレンを酸変性し、これにポリアルキレングリコールを反応させて製造することができる。より詳細については、例えば、特開２００１−２７８９８５号公報、特開２００３−４８９９０号公報に記載されている。 The hydrophilic PE resin or the hydrophilic PP resin can be produced by, for example, acid-modifying polyethylene or polypropylene having the above-described molecular weight and reacting this with polyalkylene glycol. More details are described in, for example, Japanese Patent Application Laid-Open Nos. 2001-278985 and 2003-48990.
ＰＥＥＡ樹脂又は親水性ＰＯ樹脂は、上記したいずれかの層、或いは全ての層に含まれていても良く、各層におけるその含有量は、各層の重量に対して５〜４０重量％程度、好ましくは１０〜３０重量％程度である。かかる範囲であれば、本発明のフイルムの特性を損なうことなく有効に半導電性が付与されるため、発生する静電気をすばやく徐電することができる。例えば、上記した範囲で本発明のフイルムに帯電防止剤を含有させた場合、表面抵抗率は、１０７〜１０１２Ω／□程度となる。 The PEEA resin or the hydrophilic PO resin may be contained in any one of the above-mentioned layers or all the layers, and the content of each layer is about 5 to 40% by weight, preferably about the weight of each layer. About 10 to 30% by weight. Within such a range, semi-conductivity is effectively imparted without impairing the properties of the film of the present invention, so that generated static electricity can be gradually reduced. For example, when an antistatic agent is contained in the film of the present invention within the above-described range, the surface resistivity is about 10 7 to 10 12 Ω / □.
また、前記した単層乃至多層フイルムを、例えば、包装材料、文具，雑貨等の用途に用いる場合は、適度な滑性やアンチブロッキング性を有する必要がある。その場合、フイルムの最外層には、滑剤やアンチブロッキング剤を含有させても良い。 In addition, when the above-described single layer or multilayer film is used for, for example, packaging materials, stationery, miscellaneous goods, etc., it is necessary to have appropriate slipperiness and antiblocking property. In that case, a lubricant or an antiblocking agent may be contained in the outermost layer of the film.
かかる滑剤や、アンチブロッキング剤をフイルムの最外層の樹脂に含有させることにより、シーラント面にパウダーを散布することなく、シーラント押出工程、スリット工程、製袋工程、または内容物充填工程等において、シーラント面とフイルム面とのブロッキングを防止し、充填機械のロールやガイド、フォーマーと積層体のシーラント面とのスリップ性を向上させることができる。 By including such a lubricant or an anti-blocking agent in the outermost resin layer of the film, the sealant can be used in the sealant extrusion process, slit process, bag making process, contents filling process, etc. without spraying the powder onto the sealant surface. Blocking between the surface and the film surface can be prevented, and the slip property between the roll and guide of the filling machine, the former and the sealant surface of the laminate can be improved.
滑剤としては、例えば、流動パラフィン、白色ワセリン、石油系ワックス、マイクロクリスタリンワックス、モンタンワックス、ポリエチレンワックス、炭素数が８〜２２の高級脂肪酸；、高級脂肪酸アルミニウム、高級脂肪酸カルシウム、高級脂肪酸マグネシウム、高級脂肪酸亜鉛、高級脂肪酸リチウムなどの高級脂肪酸の金属塩；炭素数が８〜１８の直鎖脂肪族１価アルコールや；グリセリン、ソルビトール、プロピレングリコール、ペンタエリスリトール、トリエチレングリコールなどの脂肪族アルコール；炭素数が４〜２２の高級脂肪酸と炭素数が８〜１８の直鎖脂肪族１価アルコールとのエステル；アセチルクエン酸トリブチル、アジピン酸ジー２エチルーヘキシル、アゼライン酸−ｎ−ヘキシル、エタンジオールモンタン酸エステル、ポリ（１，３ブタンジオールアジピン酸）エステル、アセチルリシノール酸メチル、ポリ（１，３ーブチレングリコール、１，４ーブチレングリコール、アジピン酸オクチルアルコール）エステル、糠ろうなどのアルコールと脂肪酸とのエステル；水添食用油脂、ひまし油、スパームアセチワックス、アセチル化モノグリセライドなどのグリセライド；炭素数が１６〜１８の例えばエチレンビスオレイルアマイドに代表されるエチレンビス脂肪酸アマイド、炭素数が８〜２２の高級脂肪酸アマイド、ステアリルエルカアマイド、エルカ酸アマイド、オレイルパルミトアマイドなどの高級脂肪酸アマイド；メチルヒドロジエンポリシロキサン、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ポリオキシアルキレン・ジメチルポリシロキサンなどのシリコーン油；ロジンやマレイン酸変性ロジンのグリセリンエステル；フッ素樹脂 エラストマー等が挙げられる。中でも、脂肪酸のアミド誘導体を主成分とする滑剤は、透明性が高く、良好な成形性を有するため好ましい。 Examples of the lubricant include liquid paraffin, white petrolatum, petroleum wax, microcrystalline wax, montan wax, polyethylene wax, higher fatty acid having 8 to 22 carbon atoms; higher fatty acid aluminum, higher fatty acid calcium, higher fatty acid magnesium, higher Metal salts of higher fatty acids such as fatty acid zinc and higher fatty acid lithium; linear aliphatic monohydric alcohols having 8 to 18 carbon atoms; aliphatic alcohols such as glycerin, sorbitol, propylene glycol, pentaerythritol, triethylene glycol; carbon Esters of higher fatty acids having 4 to 22 carbon atoms and linear aliphatic monohydric alcohols having 8 to 18 carbon atoms; tributyl acetyl citrate, di-2-ethylhexyl adipate, azelaic acid-n-hexyl, ethanediol montan Acid S Alcohols and fatty acids such as poly (1,3-butanediol adipic acid) ester, methyl acetylricinoleate, poly (1,3-butylene glycol, 1,4-butylene glycol, octyl alcohol adipate) ester, and wax Esters of hydrogenated edible oils, castor oil, spalm acetyl wax, glycerides such as acetylated monoglycerides; ethylene bis-fatty acid amides having 16 to 18 carbon atoms, such as ethylene bisoleyl amide, and higher grades having 8 to 22 carbon atoms Higher fatty acid amides such as fatty acid amide, stearyl erucamide, erucic acid amide, oleyl palmitoamide; methyl hydrodiene polysiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, polyoxyalkylene dimethyl Silicone oils, such as polysiloxane; glycerol ester of rosin and the maleic acid-modified rosin; fluororesin elastomers, and the like. Among these, a lubricant mainly composed of an amide derivative of a fatty acid is preferable because it has high transparency and good moldability.
本発明のフイルムの最外層における滑剤の含有量としては、最外層の重量に対して、０．０１〜１重量％程度であればよい。 The content of the lubricant in the outermost layer of the film of the present invention may be about 0.01 to 1% by weight with respect to the weight of the outermost layer.
また、アンチブロッキング剤としては、無機化合物の微粒子、有機化合物の微粒子などを使用できるが、フイルムの透明性を損なわずに、良好な成形性を有するものが好ましい。 As the anti-blocking agent, fine particles of inorganic compounds, fine particles of organic compounds, and the like can be used, but those having good moldability without impairing the transparency of the film are preferable.
無機化合物の微粒子としては、例えば、酸化アルミニウム、酸化マグネシウム、シリカ、酸化カルシウム、酸化チタン、酸化鉄、酸化亜鉛などの酸化物；水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウムなどの水酸化物；炭酸マグネシウム、炭酸カルシウム、炭酸亜鉛、炭酸リチウムなどの炭酸塩；硫酸カルシウム、硫酸亜鉛、硫酸バリウムなどの硫酸塩；ケイ酸マグネシウム、ケイ酸アルミニウム、ケイ酸カルシウム、アルミノケイ酸塩、ケイ酸アルミニウムなどのケイ酸塩；カオリン、タルク、けいそう土などの無機化合物などが挙げられる。中でも、シリカ微粒子では、透明性を損なわずに、また、ブロッキングを防止できるため好ましい。 Examples of the fine particles of the inorganic compound include oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, iron oxide, and zinc oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; Carbonates such as magnesium carbonate, calcium carbonate, zinc carbonate, lithium carbonate; sulfates such as calcium sulfate, zinc sulfate, barium sulfate; magnesium silicate, aluminum silicate, calcium silicate, aluminosilicate, aluminum silicate, etc. Silicates: inorganic compounds such as kaolin, talc and diatomaceous earth. Among these, silica fine particles are preferable because they can prevent blocking without impairing transparency.
また、有機化合物の微粒子としては、例えば、高密度ポリエチレン、分子量が３０００００以上の超高分子ポリエチレン、ポリプロピレン、ポリカーボネート、ポリアマイド、ポリエステル、メラミン樹脂、ジアリルフタレート樹脂、アクリル系樹脂などの微粉末を単独あるいは上記の無機系の微粒子と混合して使用できる。 Examples of the organic compound fine particles include high-density polyethylene, ultra-high molecular polyethylene having a molecular weight of 300,000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic resin, and the like alone or It can be used by mixing with the above inorganic fine particles.
本発明のフイルムの最外層におけるアンチブロッキング剤の含有量は、最外層の重量に対して、０．０１〜１重量％程度であればよい。 The content of the antiblocking agent in the outermost layer of the film of the present invention may be about 0.01 to 1% by weight with respect to the weight of the outermost layer.
着色剤としては、一般的な有機及び無機顔料が挙げられ、通常の成形温度である１５０〜２５０℃程度で耐熱性を有するものであれば適宜選択可能であり、例えば、（ポリ）アゾ系、フタロシアニン系、スレン系、染料レーキ系、キナクリドン系、ジオキサジン系などの各種有機顔料、酸化チタンなどの酸化物系、クロム酸モリブデン酸系、硫化物・セレン化物系、フェロシアン化物系、炭酸カルシウム、カーボンブラックなどの各種無機顔料が挙げられる。本発明のフイルムの各層における着色剤の含有量は、各層の重量に対して、１〜３０重量％程度であればよい。 Examples of the colorant include general organic and inorganic pigments, which can be appropriately selected as long as they have heat resistance at about 150 to 250 ° C. which is a normal molding temperature. Various organic pigments such as phthalocyanine, selenium, dye lake, quinacridone, dioxazine, oxides such as titanium oxide, molybdate chromate, sulfide / selenide, ferrocyanide, calcium carbonate, Examples include various inorganic pigments such as carbon black. The content of the colorant in each layer of the film of the present invention may be about 1 to 30% by weight with respect to the weight of each layer.
また、フイルムが少なくとも内層、中間層及び外層を有する多層構造からなる場合は、着色剤を中間層に配合するのが、フイルムの成形加工時に着色剤が成形機内面に堆積し難くフイルムの外観が損なわれることがなく、またフイルムの色相が安定するので好ましい。 In addition, when the film has a multilayer structure having at least an inner layer, an intermediate layer, and an outer layer, the colorant is blended in the intermediate layer, so that the colorant hardly accumulates on the inner surface of the molding machine during the film forming process, and the appearance of the film is improved. It is preferable because it is not damaged and the hue of the film is stabilized.
酸化防止剤としては、例えば、フェノール系、サルファイド系、リン系、イソシアヌレート系酸化防止剤等が挙げられる。中でも、フェノール系酸化防止剤が酸化防止効果に優れるので好ましく、更にフェノール系とリン系酸化防止剤を併用すると熱安定性が良好となるので特に好ましい。本発明のフイルムの各層における酸化防止剤の含有量は、各層の重量に対して、０．０１〜１重量％程度であればよい。 Examples of the antioxidant include phenol-based, sulfide-based, phosphorus-based, and isocyanurate-based antioxidants. Among these, a phenolic antioxidant is preferable because it has an excellent antioxidant effect, and a combination of phenolic and phosphorus antioxidants is particularly preferable because thermal stability is improved. The content of the antioxidant in each layer of the film of the present invention may be about 0.01 to 1% by weight with respect to the weight of each layer.
耐候剤としては、紫外線吸収剤、光安定剤、消光剤などが知られており、これらの中でもヒンダードアミン系光安定剤が好適である。ヒンダードアミン系耐候剤としては、分子量が２５０以上のものが好ましく、４−位に置換基を有する２，２，６，６−テトラアルキルピペリジン誘導体であり、その４−位の置換基としては、例えばカルボン酸残基、アルコキシ基、アルキルアミノ基等が挙げられる。またＮ−位にはアルキル基が置換していても良い。 As weathering agents, ultraviolet absorbers, light stabilizers, quenchers and the like are known, and among these, hindered amine light stabilizers are preferred. The hindered amine weathering agent preferably has a molecular weight of 250 or more, and is a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position. Examples of the substituent at the 4-position include A carboxylic acid residue, an alkoxy group, an alkylamino group, etc. are mentioned. Further, an alkyl group may be substituted at the N-position.
また、前記した単層又は多層のフイルムは、その用途に応じて、最外層の片面又は両面（特に、層（Ａ）面）上に公知の粘着剤をコートして粘着剤層（Ｄ）を形成してもよく、さらに該粘着剤層（Ｄ）上に離型層（Ｅ）を形成しても良い。これら粘着剤層（Ｄ）及び離型層（Ｅ）の形成方法は、公知の方法を用いることができる。 In addition, the above-described single layer or multilayer film is coated with a known pressure-sensitive adhesive on one or both surfaces (particularly, the layer (A) surface) of the outermost layer, depending on the application, and the pressure-sensitive adhesive layer (D) is formed. It may be formed, and a release layer (E) may be formed on the pressure-sensitive adhesive layer (D). A known method can be used as a method for forming the pressure-sensitive adhesive layer (D) and the release layer (E).
粘着剤層（Ｄ）で用いられる粘着剤成分としては、公知のものを用いることができる。 A well-known thing can be used as an adhesive component used by an adhesive layer (D).
具体的には、粘着剤としては、例えば、アクリル系粘着剤、ポリエステル系粘着剤、ウレタン系粘着剤が挙げられる。その中でも、アクリル系粘着剤が好ましい。 Specifically, examples of the pressure sensitive adhesive include acrylic pressure sensitive adhesive, polyester pressure sensitive adhesive, and urethane pressure sensitive adhesive. Among these, an acrylic adhesive is preferable.
例えば、粘着剤 がアクリル系粘着剤である場合、かかる粘着剤は、粘着性を与える主モノマー成分、接着性や凝集力を与えるコモノマー成分、架橋点や接着性改良のための官能基含有モノマー成分を主とする重合体または共重合体から構成することができる。 For example, when the pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive, such a pressure-sensitive adhesive includes a main monomer component that provides tackiness, a comonomer component that provides adhesiveness and cohesive force, and a functional group-containing monomer component for improving crosslinking points and adhesion. It can comprise from the polymer or copolymer which has as a main.
主モノマー成分としては、例えば、アクリル酸エチル、アクリル酸ブチル、アクリル酸アミル、アクリル酸２−エチルヘキシル、アクリル酸オクチル、アクリル酸シクロヘキシル、アクリル酸ベンジル、アクリル酸メトキシエチル等のアクリル酸アルキルエステルや、メタクリル酸ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル等のメタクリル酸アルキルエステル等が挙げられる。 As the main monomer component, for example, acrylic acid alkyl esters such as ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, methoxyethyl acrylate, Examples include methacrylic acid alkyl esters such as butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.
コモノマー成分としては、例えば、アクリル酸メチル、メタクリル酸メチル、メタクリル酸エチル、酢酸ビニル、スチレン、アクリロニトリル等が挙げられる。 Examples of the comonomer component include methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, styrene, acrylonitrile, and the like.
官能基含有モノマー成分としては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸等のカルボキシル基含有モノマーや、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、Ｎ−メチロールアクリルアミド等のヒドロキシル基含有モノマー、アクリルアミド、メタクリルアミド、グリシジルメタクリレート等が挙げられる。 Examples of the functional group-containing monomer component include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. And hydroxyl group-containing monomers such as N-methylolacrylamide, acrylamide, methacrylamide, glycidyl methacrylate and the like.
これらの各成分を含むことにより、粘着剤組成物の粘着力、凝集力が向上する。また、このようなアクリル系樹脂は、通常、分子中に不飽和結合を有しないため、光や酸素に対する安定性の向上を図ることができる。さらに、モノマーの種類や分子量を適宜選択することにより、用途に応じた品質、特性を備える粘着剤組成物を得ることができる。 By including these components, the adhesive force and cohesive force of the pressure-sensitive adhesive composition are improved. In addition, since such an acrylic resin usually does not have an unsaturated bond in the molecule, stability to light and oxygen can be improved. Furthermore, a pressure-sensitive adhesive composition having quality and characteristics according to the application can be obtained by appropriately selecting the type and molecular weight of the monomer.
このような粘着剤組成物には、架橋処理を施す架橋型および架橋処理を施さない非架橋型のいずれのものを用いてもよいが、架橋型のものがより好ましい。架橋型のものを用いると、凝集力のより優れた粘着剤層を形成することができる。架橋型粘着剤組成物に用いる架橋剤としては、エポキシ系化合物、イソシアナート化合物、金属キレート化合物、金属アルコキシド、金属塩、アミン化合物、ヒドラジン化合物、アルデヒド系化合物等が挙げられる。 As such a pressure-sensitive adhesive composition, any of a crosslinked type that undergoes crosslinking treatment and a non-crosslinked type that does not undergo crosslinking treatment may be used, but a crosslinked type is more preferred. When a cross-linked type is used, a pressure-sensitive adhesive layer having better cohesive force can be formed. Examples of the crosslinking agent used in the crosslinking adhesive composition include an epoxy compound, an isocyanate compound, a metal chelate compound, a metal alkoxide, a metal salt, an amine compound, a hydrazine compound, and an aldehyde compound.
本発明に用いられる粘着剤組成物中には、必要に応じて、帯電防止剤や、可塑剤、粘着付与剤、安定剤等の各種添加剤が含まれていてもよい。 The pressure-sensitive adhesive composition used in the present invention may contain various additives such as an antistatic agent, a plasticizer, a tackifier, and a stabilizer, as necessary.
また、離型剤層（Ｅ）に用いられる離型剤としては、例えば、ポリエチレン樹脂等のポリオレフィン、オレフィン系熱可塑性エラストマー等の熱可塑性エラストマー、テトラフルオロエチレン等のフッ素樹脂、これらの混合物などが挙げられる。 Examples of the release agent used for the release agent layer (E) include polyolefins such as polyethylene resins, thermoplastic elastomers such as olefinic thermoplastic elastomers, fluororesins such as tetrafluoroethylene, and mixtures thereof. Can be mentioned.
本発明は、（ｉ）ＳＥ樹脂８０〜２０重量％、並びに（ii）ＭＢＳ３元樹脂及びＭＳ２元樹脂からなる群より選ばれる少なくとも１種の樹脂２０〜８０重量％からなるブレンド樹脂を含む層を有するスチレン系フイルムである。 The present invention comprises (i) a SE resin 80 to 20% by weight, and (ii) a layer containing a blend resin consisting of 20 to 80% by weight of at least one resin selected from the group consisting of MBS ternary resin and MS binary resin. It is a styrenic film.
このフイルムは、塩化ビニル樹脂を代替するのに最適であり、ポリ塩化ビニル（ＰＶＣ）に匹敵する、優れた透明性、真空成形性等を有している。 This film is optimal for replacing vinyl chloride resin, and has excellent transparency, vacuum moldability and the like comparable to polyvinyl chloride (PVC).
そのため、本発明のフイルムは、ブリスターパック等の包装材料、保護フイルム等の粘着テープ、床材等の建築材料、自動車内外層、文具、雑貨、自動車用フロアマット、壁紙、建材用遮音シート、防音材、制振材、カーペット裏打ち材、防水シート、容器、電気及び電子機器部品、絶縁電線、ハウジングなどの家電部品、中空容器、各種工業材料等広い分野で使用することができる。 Therefore, the film of the present invention comprises a packaging material such as a blister pack, an adhesive tape such as a protective film, a building material such as a flooring material, an inner and outer layer of an automobile, stationery, miscellaneous goods, an automobile floor mat, wallpaper, a sound insulation sheet for a building material, a soundproof It can be used in a wide range of fields such as materials, vibration-damping materials, carpet backing materials, waterproof sheets, containers, electrical and electronic equipment parts, insulated electric wires, household electrical appliance parts such as housings, hollow containers, and various industrial materials.
以下に、本発明を、実施例及び比較例を用いてより詳細に説明するが、本発明はこの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to these Examples.
参考例１（単層フイルム）
ＳＥ樹脂（スチレン／ブタジエン・ランダムエラストマ−の水添樹脂）（旭化成ケミカルズ株式会社製、品種ＳＳ９０００、硬度JIS K6253 デュロメータータイプＡ：８０、Ｔｇ：２０℃、重量平均分子量：１８万）５０重量％と、ＭＳ２元樹脂（ＭＭＡ／スチレン）（電気化学工業株式会社製、品種ＴＸ６００Ｓ、硬度JIS K6253 デュロメータータイプＤ：８２、Ｔｇ：９９℃、重量平均分子量：１４万）５０重量％とをドライブレンドし、これをバレル温度１８０〜２２０℃のスクリュ−式押出機に供給して、２２０℃の単層Ｔダイから押出し、６０℃冷却ロ−ルを通しながら冷却固化して、無延伸状態で巻き取った。
Reference Example 1 (single layer film)
SE resin (hydrogenated resin of styrene / butadiene random elastomer) (produced by Asahi Kasei Chemicals Corporation, variety SS9000, hardness JIS K6253 durometer type A: 80, Tg: 20 ° C., weight average molecular weight: 180,000) 50% by weight , MS binary resin (MMA / styrene) (manufactured by Denki Kagaku Kogyo Co., Ltd., variety TX600S, hardness JIS K6253 durometer type D: 82, Tg: 99 ° C., weight average molecular weight: 140,000) 50% by weight, This was supplied to a screw type extruder having a barrel temperature of 180 to 220 ° C., extruded from a single layer T die at 220 ° C., cooled and solidified through a 60 ° C. cooling roll, and wound in an unstretched state. .
得られたフイルムの厚さは１００μｍで、この一部をカットして測定用サンプルとし、透明性、真空成形性を評価し表１にまとめた。 The thickness of the obtained film was 100 μm. A part of this film was cut to obtain a measurement sample, and the transparency and vacuum formability were evaluated and summarized in Table 1.
実施例２（３層フイルム）
参考例１と同じＳＥ樹脂５０重量％とＭＳ２元樹脂５０重量％とをドライブレンドした樹脂を層（Ａ）用樹脂とした。また、参考例１と同じＳＥ樹脂１００重量％（単独）を層（Ｂ）用樹脂とした。
Example 2 (Three-layer film)
A resin obtained by dry blending 50 wt% SE resin and 50 wt% MS binary resin as in Reference Example 1 was used as the resin for the layer (A). Further, 100% by weight (single) of the same SE resin as in Reference Example 1 was used as the resin for the layer (B).
上記の各樹脂を使って、３層共押出し成形した。つまり、層（Ａ）用樹脂は２台のスクリュ−式押出機に、層（Ｂ）用樹脂は１台のスクリュ−式押出機に各々供給して、３層Ｔダイから（Ａ）／（Ｂ）／（Ａ）となるように共押出しを行い、冷却して無延伸で引き取った。尚、この時の該押出機のバレル温度、Ｔダイ温度、冷却ロ−ル温度は参考例１と同じであった。 Three-layer coextrusion molding was performed using each of the above resins. That is, the resin for layer (A) is supplied to two screw extruders, and the resin for layer (B) is supplied to one screw extruder, respectively, and the (A) / ( B) / (A) was co-extruded, cooled and taken off without stretching. At this time, the barrel temperature, T die temperature, and cooling roll temperature of the extruder were the same as in Reference Example 1.
得られた３層フイルムの全厚は１００μｍ、両外面の各層（Ａ）はそれぞれ１０μｍ、中間の層（Ｂ）は８０μｍであった。 The total thickness of the obtained three-layer film was 100 μm, each outer layer (A) was 10 μm, and the middle layer (B) was 80 μm.
比較例１
参考例１で使用したＳＥ樹脂９０重量％と同ＭＳ２元樹脂１０重量％とのドライブレンド樹脂について、参考例１と同じ条件でフイルムを得た。得られたフイルムの厚さは１００μｍであった。
Comparative Example 1
A film was obtained under the same conditions as in Reference Example 1 for the dry blend resin of 90% by weight of SE resin and 10% by weight of MS binary resin used in Reference Example 1. The thickness of the obtained film was 100 μm.
比較例２
参考例１で使用したＳＥ樹脂１０重量％と同ＭＳ２元樹脂９０重量％とのドライブレンド樹脂について、参考例１と同じ条件でフイルムを得た。得られたフイルムの厚さは１００μｍであった。
Comparative Example 2
A film was obtained under the same conditions as in Reference Example 1 for the dry blend resin of 10% by weight of SE resin and 90% by weight of MS binary resin used in Reference Example 1. The thickness of the obtained film was 100 μm.
比較例３
結晶性ポリプロピレン（三井石油化学工業株式会社製 Ｆ１０２Ｗ 密度＝０．９１、引張弾性率１６００ＭＰａ）について、参考例１と同じ条件でフイルムを得た。得られたフイルムの厚さは１００μｍであった。
Comparative Example 3
A film was obtained under the same conditions as in Reference Example 1 for crystalline polypropylene (F102W density = 0.91, tensile elastic modulus 1600 MPa, manufactured by Mitsui Petrochemical Co., Ltd.). The thickness of the obtained film was 100 μm.
試験例１
参考例１、実施例２、比較例１〜３の各フイルムの一部をカットして測定用サンプルとし、透明性及び真空成形性を評価した。その結果を表１にまとめた。
Test example 1
A part of each film of Reference Example 1 , Example 2, and Comparative Examples 1 to 3 was cut to obtain a measurement sample, and transparency and vacuum formability were evaluated. The results are summarized in Table 1.
以下の評価基準により評価した。 Evaluation was performed according to the following evaluation criteria.
参考例、実施例及び比較例で得られたフイルムの、透明性及び真空成形性の評価は、次の様にして行った。
＜透明性（Ｈａｚｅ，％）＞
ＪＩＳ−Ｚ−８７４１により測定した。２０％以下を「○」とし、２０％を越える場合を「×」とした。
＜真空成形性＞
山崎機械株式会社製真空成形機（ＴＶＦ−Ｙ−１）を使用した。直径１０７ｍｍ，深さ１２ｍｍ，Ｒ＝１ｍｍの型を用い、１００℃予備加熱後のフイルムを真空成形した（図１を参照）。厚みが均一のまま正常に成型できたものを「○」とし、成型不足、破れ又は厚み不均一となったものを「×」とした。
Evaluation of transparency and vacuum formability of the films obtained in Reference Examples, Examples and Comparative Examples was performed as follows.
<Transparency (Haze,%)>
It measured according to JIS-Z-8741. The case where 20% or less is “◯” and the case where it exceeds 20% is “×”.
<Vacuum formability>
A vacuum forming machine (TVF-Y-1) manufactured by Yamazaki Kikai Co., Ltd. was used. Using a mold having a diameter of 107 mm, a depth of 12 mm, and R = 1 mm, the film after preheating at 100 ° C. was vacuum formed (see FIG. 1). Those that could be molded normally with a uniform thickness were rated as “◯”, and those that were insufficiently molded, torn, or non-uniform in thickness were rated as “x”.
表１で示すように、参考例１及び実施例２のフイルムは、高い透明性、良好な真空成形性を有していることが分かった。 As shown in Table 1, the films of Reference Example 1 and Example 2 were found to have high transparency and good vacuum formability.
Claims (5)
（ｉ）スチレン系エラストマー樹脂８０〜２０重量％、並びに（ｉｉ）（メタ）アクリル酸アルキルエステル系単量体とジエン系単量体とスチレン系単量体との３元共重合樹脂、及び（メタ）アクリル酸アルキルエステル系単量体とスチレン系単量体との２元共重合樹脂からなる群より選ばれる少なくとも１種の樹脂２０〜８０重量％からなるブレンド樹脂を含む層（Ａ）と、
（ｉｉｉ）スチレン系エラストマー樹脂１００〜８０重量％、並びに（ｉｖ）（メタ）アクリル酸アルキルエステル系単量体とジエン系単量体とスチレン系単量体との３元共重合樹脂、及び（メタ）アクリル酸アルキルエステル系単量体とスチレン系単量体との２元共重合樹脂からなる群より選ばれる少なくとも１種の樹脂０〜２０重量％からなるブレンド樹脂を含む層（Ｂ）とが
（Ａ）／（Ｂ）／（Ａ）の順で積層されてなり、
前記スチレン系エラストマー樹脂が、スチレン系単量体とジエン系単量体とのランダム共重合樹脂の水添樹脂、及び／又は、スチレン系単量体とジエン系単量体とのブロック共重合樹脂の水添樹脂であり、前記３元共重合樹脂が、（メタ）アクリル酸アルキルエステル系単量体単位３０〜６２重量％と、ジエン系単量体単位３〜３５重量％と、スチレン系単量体単位３５〜６７重量％とからなる共重合体であり、
無延伸で引き取ることにより製造されるものであり、真空成形用である、
フイルム。 A multilayer film comprising at least (i) 80 to 20% by weight of a styrene elastomer resin, and (ii) a (meth) acrylic acid alkyl ester monomer, a diene monomer, and a styrene monomer; Blend resin comprising at least one resin selected from the group consisting of an original copolymer resin and a binary copolymer resin of a (meth) acrylic acid alkyl ester monomer and a styrene monomer. A layer (A) containing
(Iii) 100 to 80% by weight of a styrene elastomer resin, and (iv) a terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer, and ( A layer (B) containing a blend resin consisting of 0 to 20% by weight of at least one resin selected from the group consisting of binary copolymer resins of (meth) acrylic acid alkyl ester monomers and styrene monomers; Are stacked in the order of (A) / (B) / (A),
The styrene elastomer resin is a hydrogenated resin of a random copolymer resin of a styrene monomer and a diene monomer, and / or a block copolymer resin of a styrene monomer and a diene monomer. der hydrogenated resin is, the terpolymer resin, (meth) and 30 to 62 wt% alkyl acrylate monomer units, and 3 to 35 wt% diene monomer unit, styrenic A copolymer consisting of 35 to 67% by weight of monomer units,
And those prepared by taking up in unstretched, Ru der vacuum forming,
Film.
前記各層を構成する樹脂組成物を溶融して、（Ａ）／（Ｂ）／（Ａ）の順で積層される様にフイルム状に共押出しを行い、無延伸で引き取ることにより、成形することを特徴とする製造方法。 At least (i) a styrene elastomer resin of 80 to 20% by weight, and (ii) a terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer, and Layer (A) containing a blend resin comprising 20 to 80% by weight of at least one resin selected from the group consisting of binary copolymer resins of (meth) acrylic acid alkyl ester monomers and styrene monomers And (iii) 100-80% by weight of a styrene elastomer resin, and (iv) a terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer, And 0 to 20% by weight of at least one resin selected from the group consisting of binary copolymer resins of (meth) acrylic acid alkyl ester monomers and styrene monomers The resin-containing layer (B) is laminated in the order of (A) / (B) / (A), and the styrene elastomer resin is a random copolymer of a styrene monomer and a diene monomer. hydrogenated resin of polymer resin, and / or, Ri hydrogenated resins der block copolymer of a styrene monomer and a diene monomer, the terpolymer resin, (meth) acrylic acid alkyl A copolymer comprising 30 to 62% by weight of ester monomer units, 3 to 35% by weight of diene monomer units, and 35 to 67% by weight of styrene monomer units. Oh Ru a method of manufacturing a multi-layer film,
To melt the resin composition constituting each layer performs a coextrusion City filmy as laminated in this order (A) / (B) / (A), by taking up without stretching, molding The manufacturing method characterized by the above-mentioned.
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