JP3931994B2 - Vinylidene chloride copolymer-containing resin composition, film thereof, extrusion process thereof, and production method of the film - Google Patents
Vinylidene chloride copolymer-containing resin composition, film thereof, extrusion process thereof, and production method of the film Download PDFInfo
- Publication number
- JP3931994B2 JP3931994B2 JP53235596A JP53235596A JP3931994B2 JP 3931994 B2 JP3931994 B2 JP 3931994B2 JP 53235596 A JP53235596 A JP 53235596A JP 53235596 A JP53235596 A JP 53235596A JP 3931994 B2 JP3931994 B2 JP 3931994B2
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- Prior art keywords
- vinylidene chloride
- copolymer
- chloride copolymer
- mass
- resin composition
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- 229920001577 copolymer Polymers 0.000 title claims description 191
- 239000011342 resin composition Substances 0.000 title claims description 48
- 238000001125 extrusion Methods 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 30
- 230000008569 process Effects 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 7
- 229920005989 resin Polymers 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 65
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 14
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- 239000000654 additive Substances 0.000 description 15
- 238000004806 packaging method and process Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 101000969770 Homo sapiens Myelin protein zero-like protein 2 Proteins 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 102100021272 Myelin protein zero-like protein 2 Human genes 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000005670 ethenylalkyl group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- 241000251468 Actinopterygii Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- AZUZXOSWBOBCJY-UHFFFAOYSA-N Polyethylene, oxidized Polymers OC(=O)CCC(=O)C(C)C(O)CCCCC=O AZUZXOSWBOBCJY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- 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
- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
技術の分野
本発明は、塩化ビニリデン共重合体含有樹脂組成物、その押出加工方法、それから形成されるフィルム、更には前記フィルムの製造方法に関する。さらに詳しくは、混合塩化ビニリデン樹脂（Ａ）と特定の共重合体（Ｂ）とからなる塩化ビニリデン共重合体含有樹脂組成物、混合塩化ビニリデン樹脂（Ａ）または塩化ビニリデン共重合体（Ａ’）と特定の共重合体（Ｂ）とからなる塩化ビニリデン共重合体含有樹脂組成物の押出加工方法、それから形成される押出加工性、更には包装機械適性、耐寒性、ガスバリヤー性に優れたフィルムに関する。
背景技術
一般に、塩化ビニリデン系共重合体は水蒸気や酸素などの気体の遮蔽性に優れた特性を持つので、押出加工され食品包装用フィルムなどに使用されている。しかし、通常の塩化ビニリデン系共重合体それ自体は熱安定性が悪く、熱分解しやすいので押出加工が不安定となり、その特性を生かした均質な包装用フィルムを得難い。そのため従来より以下のような種々の改良が提案されている。
特公昭４０−１６１４１号公報には塩化ビニリデン重合体とエチレンとビニルアルカノエート類との共重合体などの弾性物質またはゴム状体２〜２０重量％を含む成形用組成物が記載されている。特開昭５５−１０８４４２号公報にはポリ塩化ビニリデン共重合体６０〜９５重量％と、酢酸ビニル含有量５〜１８重量％でかつ溶融流れ約０．１〜１．０ｄｇ／分のエチレンと酢酸ビニルとの共重合体約５〜約４０重量％とからなるフィルムが記載されている。特開昭６２−７２７３６号公報には塩化ビニリデンインターポリマーとオレフィンポリマーと相溶化性ポリマーとからなる溶融加工の可能なブレンドが記載されている。
特開平１−１３１２６８号公報には塩化ビニリデンコポリマー約７０〜約９７重量％とアクリル酸またはメタクリル酸が約１５〜約３重量％が重合されているオレフィンコポリマー約３０〜約３重量％と酢酸ビニル約３０〜約３重量％が重合されているオレフィンコポリマー約０〜約１５重量％とを含むブレンドポリマーからなるインフレートフィルムが記載されている。特公表３−５０３２９０号公報には塩化ビニリデンインターポリマーと約０．０１〜約０．５重量％の酸化ポリエチレン、酸化ポリプロピレンもしくはそれらの混合物、約０．０１〜約２重量％のエチレン−ビニルアセテートコポリマー、約０．００５〜約１重量％のパラフィンワックスおよび約０．１〜約３重量％のエポキシ化油もしくは樹脂からなる群から選ばれた押出助剤を含む添加剤の組み合わせにより押し出し適性を改良する方法が提案されている。特開平３−３５０４３号公報には低重量平均分子量の塩化ビニリデンコポリマーと加工助剤約０．０１〜６重量％の組成物が提案されている。米国特許第４，７９８，７５１号には共重合体の組成の異なる塩化ビニリデン系共重合体の混合物が提案されている。
特開昭６１−１２０７１９号公報には塩化ビニリデン−メチルアクリレート系共重合体のメチルアクリレート成分の含量と共重合体の重量平均分子量（７万〜２５万）と分子量２万以下の共重合体含有率とを規定した塩化ビニリデン−メチルアクリレート系共重合体を用いることを特徴とした溶融押し出し法を用いた成形加工方法の改良が提案されている。
しかし、以上のように塩化ビニリデン共重合体の押出加工性を改良するために種々樹脂や添加剤を混合すると、包装機械適性、耐寒性、ガスバリヤー性等のフィルムに要求される他のフィルム特性を低下させることが多く、これら諸特性を具備した塩化ビニリデン系樹脂が要望されている。
塩化ビニリデン共重合体樹脂の押出加工性の改良手段として、樹脂の発熱を抑制する方法が採用される。それには、例えば樹脂の重合度を小さくしたり、添加剤を多く使用することが考えられる。樹脂の重合度を小さくするとＰＶＤＣ（塩化ビニリデン共重合体の略称）自体が脆化し、耐寒性が低下する。また、添加剤を多く使用すればガスバリヤー性が低下する。
また塩化ビニリデン共重合体樹脂の押出加工性は包装機械適性と密接に関係する。押出加工性が劣る樹脂では押し出しモーター負荷の変動が大きくなり、押し出し量に斑が発生し、流れ方向のフィルムの厚み斑を生じる。このようなフィルムを包装機械にかけると、フィルムが薄すぎる部分ではシールするとき溶融し過ぎてピンホール破袋となり、フィルムが厚すぎる部分ではシールされないトラブルが発生する。また押出時にダイ流出口より分解物が流出し、フィルム中に分散したこれら分解物が高周波溶着可能な包装機械のシール電極の導通を誘発し、スパークによりフィルムを微小破壊しピンホールとなる。またダイ流出口に付着する分解物により部分的に押出量が変化し、フィルムの巾方向の部分的な厚み斑が生じ、シール部が溶着しなくなったり、フィルムが均等に走行しなくなってシールができない等の要因となる。
本発明は、上記のような問題点を改善し押出加工性に優れ、包装機械適性、耐寒性、ガスバリヤー性に関してバランスのとれたフィルムを与える塩化ビニリデン共重合体含有樹脂組成物、塩化ビニリデン共重合体含有樹脂組成物を用いた押出加工方法、それから得られるフィルム、さらにそのフィルムの製造方法を提供することにある。
発明の開示
本発明者らは、還元粘度の異なる特定の塩化ビニリデン共重合体を特定割合で混合した混合塩化ビニリデン樹脂（Ａ）と特定の共重合体（Ｂ）とからなる塩化ビニリデン共重合体含有樹脂組成物が押出加工性に優れ、それから形成されたフィルムが包装機械適性、耐寒性、ガスバリヤー性に関してバランスの優れたものであること、また塩化ビニリデン共重合体含有樹脂組成物からフィルムを形成する際に真空ホッパーを使用することにより、上記の特性を一層向上させることが可能であることを見い出して本発明に至った。
すなわち本発明は、少なくとも２種の塩化ビニリデン共重合体からなる混合塩化ビニリデン樹脂（Ａ）１００質量部とエチレンと酢酸ビニル共重合体（Ｂ1）、エチレンとアクリル酸、メタクリル酸またはそれらのアルキルエステルとの共重合体（Ｂ2）およびＭＢＳ樹脂（Ｂ3）から選ばれる少なくとも１種の共重合体（Ｂ）０．１〜２０質量部とからなる塩化ビニリデン共重合体含有樹脂組成物であって、
混合塩化ビニリデン樹脂（Ａ）が還元粘度０．０４８以上の塩化ビニリデン共重合体（Ａ 1 ）５０質量％以上と還元粘度０．０４８未満の塩化ビニリデン共重合体（Ａ 2 ）５０質量％未満とからなる（但し、両者の合計は１００質量％）ことを特徴とする塩化ビニリデン共重合体含有樹脂組成物およびそれから形成されるフィルムを提供するものである。
本発明は、少なくとも２種の塩化ビニリデン共重合体からなる混合塩化ビニリデン樹脂（Ａ）１００質量部と、エチレンと酢酸ビニル共重合体（Ｂ1）、エチレンとアクリル酸、メタクリル酸またはそれらのアルキルエステルとの共重合体（Ｂ2）およびＭＢＳ樹脂（Ｂ3）から選ばれる少なくとも１種の共重合体（Ｂ）０．１〜２０質量部とからなる塩化ビニリデン共重合体含有樹脂組成物を真空ホッパーを経由して押出機へ供給する押出加工方法であって、
混合塩化ビニリデン樹脂（Ａ）が還元粘度０．０４８以上の塩化ビニリデン共重合体（Ａ 1 ）５０質量％以上と還元粘度０．０４８未満の塩化ビニリデン共重合体（Ａ 2 ）５０質量％未満とからなる（但し、両者の合計は１００質量％）ものである押出加工方法を提供するものである。
発明を実施するための最良の形態
以下、本発明の第一について詳述する。
本発明で使用する塩化ビニリデン共重合体（Ａ1）および塩化ビニリデン共重合体（Ａ2）は、塩化ビニリデンと塩化ビニリデンに共重合可能な少なくとも１種のモノエチレン系不飽和単量体との共重合体である。共重合体のモノエチレン系不飽和単量体の含量は約４０〜約２質量％、押出加工性とガスバリヤー性とのバランスから好ましくは約３５〜約４質量％である。モノエチレン系不飽和単量体としては塩化ビニル、酢酸ビニル、プロピオン酸ビニル、アルキルアクリレート、アルキルメタクリレート、アクリル酸、メタクリル酸、イタコン酸、アクリルニトリル、メタクリロニトリル、アクリルアミド、ビニルアルキルエーテル、ビニルアルキルケトン、アクロレイン、アリルエステルおよびエーテル、ブタジエン、クロロプレンを挙げることができる。塩化ビニリデン共重合体（Ａ1）および（Ａ2）はこれらモノエチレン系不飽和単量体を二種以上共重合させた三元以上の共重合体であってもよい。前記モノエチレン系不飽和単量体の中では、好ましくは塩化ビニル、アルキル基の炭素数１〜８個を有するアルキルアクリレートおよびアルキルメタクリレート、例えばメチルアクリレート、エチルアクリレート、メチルメタクリレートが挙げられ、塩化ビニルであることが押出加工性とガスバリヤー性のバランスを取りやすいので、さらに好ましい。
塩化ビニリデン共重合体（Ａ1）と塩化ビニリデン共重合体（Ａ2）とを押出機内部で均一溶融しやすくして、成形フィルムの品質上好ましくない樹脂の分解、未溶融などにより生成するフィッシュアイの発生を低減させるため、（Ａ1）と（Ａ2）とは同種の共重合成分であることが好ましい。例えば塩化ビニリデン共重合体（Ａ1）が塩化ビニリデンと塩化ビニルとの共重合体であれば、塩化ビニリデン共重合体（Ａ2）も塩化ビニリデンと塩化ビニルとの共重合体であることが好ましい。さらに好ましくは、塩化ビニリデン共重合体（Ａ1）と塩化ビニリデン共重合体（Ａ2）はそれぞれ塩化ビニリデンと塩化ビニルとの二元共重合体であることが樹脂の均一な溶融のために好ましい。また、塩化ビニリデン共重合体（Ａ1）の塩化ビニリデンの組成割合が塩化ビニリデン共重合体（Ａ2）の塩化ビニリデンの組成割合より大きいことは押出加工性、フィルムの耐寒性の点で好ましい。
前記塩化ビニリデン共重合体（Ａ1）は還元粘度が０．０４８以上であることがよく、０．０４８〜０．０８０の範囲のものが好んで用いられる。レトルト食品などの包装体用フィルムには塩化ビニリデン共重合体（Ａ1）の還元粘度が０．０５２〜０．０８０、さらに好ましくは０．０５５〜０．０７５の範囲であることが包装機械適性、耐寒性、延伸加工性の点から望ましい。
塩化ビニリデン共重合体（Ａ2）は好ましくは還元粘度が０．０４８未満であり、更に好ましくは０．０２５〜０．０４８未満、特には０．０３５〜０．０４５未満であることがフィルムの耐寒性、塩化ビニリデン共重合体含有樹脂組成物の押出加工性の点から好ましい。塩化ビニリデン共重合体（Ａ2）は押出機内での発熱を抑えてダイ流出口での樹脂の付着分解の低減、押出機のモーター負荷の変動減少などの押出加工性の改善に寄与するが、耐寒性とのバランスから塩化ビニリデン共重合体（Ａ2）の混合割合は塩化ビニリデン共重合体の合計１００質量％に対して好ましくは５０質量％未満、更に好ましくは３〜２５質量％、最も好ましくは５〜２５質量％の範囲である。
共重合体（Ｂ）はエチレンと酢酸ビニル共重合体（Ｂ1）、エチレンとアクリル酸、メタクリル酸またはそれらのアルキルエステル（特に、炭素数１〜４個を持つアルキルエステル）との共重合体（Ｂ2）およびＭＢＳ樹脂（Ｂ3）から選ばれる少なくとも１種である。
前記共重合体（Ｂ1）および（Ｂ2）としては、エチレン含量６５〜８５質量％、より好ましくは７５〜８０質量％の範囲にあるものである。成形フィルムの透明性を維持するために、これらのエチレン含量が８５質量％以下であることが好ましく、押出機モーター負荷の安定性および成形フィルムのガスバリヤー性の点からエチレン含量６５質量％以上が好ましい。共重合体（Ｂ）が混合物の場合には、混合塩化ビニリデン樹脂（Ａ）との相溶性を上げる目的で、エチレン含量６５質量％未満の共重合体（Ｂ1）または（Ｂ2）を少量添加することができる。
ＭＢＳ樹脂は特公昭４６−１９５５０号公報に記載されているブタジエン単独重合体またはブタジエンを主とし、これとスチレン、メタクリル酸エステル、アクリルニトリル、塩化ビニリデンの何れか単独またはそれらの任意の混合物との共重合体であり、ゴム成分５０〜８０重量部を含むラテックスにメチルメタクリレート、スチレン、塩化ビニリデンの単独またはそれらの任意の混合物５０乃至２０重量部をこれと共重合可能な架橋剤０．０１〜５重量部の存在下に後重合して得たゴムプラスチック成分を含む呉羽化学工業（株）製ＢＴＡ−ＩＶ ＳＳ等が挙げられる。
塩化ビニリデン共重合体（Ａ1）と塩化ビニリデン共重合体（Ａ2）との混合塩化ビニリデン樹脂（Ａ）に、共重合体（Ｂ）を添加混合すると、得られるフィルムの耐寒性が改善される。両者の混合割合は混合塩化ビニリデン樹脂（Ａ）１００質量部に対して共重合体（Ｂ）０．１〜２０質量部の範囲であり、好ましくは０．５〜５質量部、さらに好ましくは０．７〜１．５質量部の範囲である。共重合体（Ｂ）の混合割合が２０質量部より多いと押出機のモーター負荷が変動し不安定になり、さらにダイ流出口の付着分解物が多くなるなどの押し出し加工性が低下する。逆に混合量が０．１質量部より少ないと分解物の流出が増え、また得られるフィルムの耐寒性の維持が難しくなる。
塩化ビニリデン共重合体（Ａ1）の混合割合は塩化ビニリデン共重合体の合計１００質量％に対して好ましくは５０質量％以上、更に好ましくは７５〜９７質量％、最も好ましくは７５〜９５質量％の範囲であり、残りは塩化ビニリデン共重合体（Ａ2）である。共重合体（Ｂ）の混合割合は塩化ビニリデン共重合体（Ａ2）より少ない方が好ましい。塩化ビニリデン共重合体（Ａ1）に共重合体（Ｂ）を適量混合しても押出機のモーター負荷が変動することがあるが、塩化ビニリデン共重合体（Ａ2）を含む混合塩化ビニリデン共重合体（Ａ）により改善することができる。特に顔料が配合されるフィルムの場合、塩化ビニリデン共重合体（Ａ2）／共重合体（Ｂ）の混合比が１．５〜１０であると摩擦による擦れからフィルム表面の色落ち現象を抑えることができる。
共重合体（Ｂ）のＡＳＴＭ Ｄ−１２３８改によるメルトインデックス（ＭＩ）は押出加工性、ガスバリヤー性の点から約３以上が好ましい。通常、５〜４０ｇ/分、好ましくは１０〜３０ｇ/分のものである。ＭＩ３０ｇ/分の重量平均分子量は約１１万程度である。
本発明の塩化ビニリデン共重合体含有樹脂組成物には公知の可塑剤、熱安定剤、加工助剤、光安定剤、顔料、滑剤、抗酸化剤、フィラー、界面活性剤などの添加剤を配合することができる。具体的にはジオクチルフタレート、アセチルトリブチルサイトレート、ジブチルセバケート、ジオクチルセバケートおよびジイソブチルアジペート、エポキシ化大豆油、エポキシ化アマニ油などのエポキシ化油および樹脂、アルキルエステルのアミド誘導体、水酸化マグネシウム、ピロリン酸四ナトリウム、酸化マグネシウムおよびカルシウムヒドロキシホスフェート、酸化ポリエチレン、パラフィンワックス、ポリエチレンワックス、モンタンエステルワックスなどのワックス類等の可塑剤、熱安定剤、加工助剤、滑剤として作用のあるもの、更には酸化ケイ素、炭酸カルシウム等のフィラー、および、ソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステル類等の界面活性剤など、各種添加剤が挙げられる。酸化チタン系顔料はソーセージなどの食品内容物の紫外線による変色防止に効果があるが、ダイ流出口の付着分解を増加させる。しかし、この付着分解は真空ホッパーを使用して押出すと効果的に低減されるので、０．１０〜１０質量部迄の多量に添加することが可能になった。
前記添加剤の内、可塑剤と安定剤は混合塩化ビニリデン樹脂（Ａ）１００質量部に対して、約１〜約１０質量部、好ましくは２〜６質量部の範囲で添加する。これらの添加剤は、その一部を塩化ビニリデン共重合体（Ａ1）または（Ａ2）の重合中に加えてもよい。添加剤は押出時には塩化ビニリデン共重合体に吸着または吸収され、押出加工性に寄与するが、フィルム成形後は共重合体（Ｂ）に移行しフィルムのガスバリヤー性を向上させるので押出加工性とのバランスがとれたフィルムが得られる。可塑剤や熱安定剤以外の添加剤は必要に応じて使用するのが好ましい。
塩化ビニリデン共重合体（Ａ1）、塩化ビニリデン共重合体（Ａ2）、共重合体（Ｂ）および添加剤の混合方法は特に制限されるものではなく、従来の方法が適用できる。例えば、２本ロール機による混練、羽根ブレンダーやリボンブレンダー等のブレンダーによる混合、ヘンシェル高速ミキサーによる混合などにより、また６０℃を超える加熱混合方式または６０℃以下の低温混合方式の何れでも適用できる。
また、塩化ビニリデン共重合体（Ａ1）、塩化ビニリデン共重合体（Ａ2）および必要に応じて添加される上述の添加剤を予め混合しておき、この混合塩化ビニリデン樹脂（Ａ）に共重合体（Ｂ）を混合してもよい。その際には、混合樹脂温度が約６０℃以下、好ましくは５０℃から室温の温度範囲で混合することが、得られる塩化ビニリデン共重合体含有樹脂組成物の均質性の点から好ましい。
混合装置としてはヘンシェル高速ミキサー、羽根ブレンダー、リボンブレンダー等の公知の乾燥混合装置が挙げられる。また、塩化ビニリデン共重合体含有樹脂組成物を押し出す直前に押出機の機上ホッパー装置内でスクリューフィーダーなどを使用してこれらの原料を混合する方法もあるが、６０℃以下の温度で混合することによりダイ流出口で樹脂の付着による分解物の発生、樹脂の着色や分解物流出などを低減できる。また６０℃以下の温度で混合する方法とエチレン含量が少ない共重合体（Ｂ）を含むこと、あるいは前記ワックス類を添加することなどの組み合わせで混合樹脂の粉体のブロッキングを防ぎ、押出加工時の粉体のスクリュへの食い込み斑を防止し、モーター負荷の変動、押し出し量の変動を更に小さく改善できる。混合により得られた塩化ビニリデン共重合体含有樹脂組成物は粉体のまま、あるいはペレットの形状で押出加工され、フィルムの成形に使用される。
塩化ビニリデン共重合体含有樹脂組成物の均質化のため必要に応じて添加する上述の可塑剤、熱安定剤、加工助剤、光安定剤、顔料、滑剤、抗酸化剤、フィラー、界面活性剤等から選ばれる添加剤は、共重合体（Ｂ）を加える以前に予め塩化ビニリデン共重合体（Ａ1）と塩化ビニリデン共重合体（Ａ2）との混合塩化ビニリデン樹脂（Ａ）に添加混合しておくことが好ましい。これにより、共重合体（Ｂ）に添加剤が局在的に吸収あるいは吸着されるのを抑え、ダイ流出口の付着分を減少させることができる。塩化ビニリデン共重合体の回収粉砕物（リサイクル樹脂）を混合塩化ビニリデン樹脂（Ａ）に混合してリサイクルすることができる。この時の粉砕品の混合割合は混合塩化ビニリデン樹脂（Ａ）に対して１〜５０質量％、好ましくは１〜３０質量％程度である。
本発明の前記塩化ビニリデン共重合体含有樹脂組成物は、溶融押出して延伸あるいは未延伸フィルム、シートなどに成形される。成形方法としては当業者に公知のような、例えばサーキュラーダイによるインフレーション押出成形法などが適用できる。延伸、特に好ましくは二軸延伸により配向して得られるフィルムは熱収縮性を有し、またはレトルト可能な耐熱性フィルムとして好適に用いられる。延伸倍率としては縦方向に２．０〜４．５倍、横方向に３．０〜５．０倍が好ましい。フィルム厚さはシングルフィルムとして５〜３０μｍ、好ましくは１０〜２５μｍである。用途によりダブルフィルムとしても使用される。通常、熱収縮率は縦、横ともに約３０〜約６０％（１２０℃グリセリン浴，３分）である。食品包装用としての主な使用方法は、インフレーション後、２枚に重ねてダブルフィルムとしてフィルム両端の耳の部分をスリットし、包装機械で円筒状にしながらシールし、内容物を充填し、両端をグリップした包装体を得るのに使われる。またレトルト条件は１２０℃（加圧０．２４５ＭＰａ）２０分である。また、本発明のフィルムを同種の樹脂または塩化ビニリデン共重合体と共押出加工が可能な他の樹脂や樹脂組成物からなるフィルムと積層しても差し支えない。
本発明の第二は塩化ビニリデン共重合体（Ａ’）を含む樹脂組成物の押出加工方法に関するものである。塩化ビニリデン共重合体（Ａ’）を含む樹脂組成物を押出加工するに際し、該樹脂組成物を真空ホッパーを経由して押出機へ供給することが特徴であり、これにより押出加工性が向上する。すなわち、真空ホッパーを使用することによりダイ流出口での樹脂の付着分解、樹脂の着色および分解物の流出などの低減、インフレーション成形時のバブルの破裂の減少などに効果がある。真空ホッパーの真空度は、水銀柱−５００ｍｍ以下、好ましくは−６００から−７５５ｍｍの範囲である。このような条件に設定された真空ホッパーを経由して該樹脂組成物を押出機へ供給することにより、押出加工性を向上できる。塩化ビニリデン共重合体（Ａ’）は特に限定はしないが、好ましくは還元粘度０．０４８以上の塩化ビニリデン共重合体（Ａ1）５０質量％以上と還元粘度０．０４８未満の塩化ビニリデン共重合体（Ａ2）５０質量％未満との混合塩化ビニリデン樹脂（Ａ）（但し、両者の合計は１００質量％）または還元粘度が０．０４５以上である塩化ビニリデン共重合体（Ａ3）から選ばれることが望ましい。還元粘度が０．０４５以上である塩化ビニリデン共重合体（Ａ3）は還元粘度０．０４５から０．０８０の範囲のものが好んで用いられる。また、好ましくは塩化ビニリデン共重合体（Ａ’）１００質量部に対して、少なくとも1種の共重合体（Ｂ）を０．１〜２０質量部を加えるとよい。なお、真空ホッパーを使用するのでダイ流出口の付着分解が低減され、酸化チタン系顔料の使用は効果的である。
本発明の第三は、塩化ビニリデン共重合体（Ａ”）を含む樹脂組成物を調製する工程と本発明の第二である前記塩化ビニリデン共重合体（Ａ’）を含む樹脂組成物の押出加工方法とからなるフィルムの製造方法を提供するものである。
すなわち、還元粘度が０．０４５以上である塩化ビニリデン共重合体（Ａ3）または還元粘度０．０４８以上の塩化ビニリデン共重合体（Ａ1）５０質量％以上と還元粘度０．０４８未満の塩化ビニリデン共重合体（Ａ2）５０質量％未満との混合塩化ビニリデン樹脂（Ａ4）（Ａ1とＡ2の合計は１００質量％）から選ばれた塩化ビニリデン共重合体（Ａ”）１００質量部と、エチレンと酢酸ビニル共重合体（Ｂ1）、エチレンとアクリル酸、メタクリル酸またはそれらのアルキルエステルとの共重合体（Ｂ2）およびＭＢＳ樹脂（Ｂ3）から選ばれる少なくとも1種の共重合体（Ｂ）０．１〜２０質量部を加えるに際し、これら原料樹脂の温度を６０℃以下、好ましくは５０℃から室温の範囲で混合する工程と、得られた塩化ビニリデン共重合体含有樹脂組成物を真空ホッパーを経由して押出機へ供給する工程とからなるフィルムの製造方法である。真空ホッパーの下部に連結された溶融押出機を経て公知の方法で延伸され、または延伸されずにフィルム、シートなどに成形される。真空ホッパーの真空度は、本発明の第二の押出加工方法の発明で説明した通りである。フィルムの成形方法は前記のような公知の方法が適用できる。例えばサーキュラーダイによるインフレーション押出成形法などが適用できる。延伸配向して得られるフィルム、特に二軸延伸フィルムは良好な熱収縮性を有し、またはレトルト可能な耐熱性フィルムとして好適に用いられる。本発明の二軸延伸フィルムの熱収縮率は、試験片で測定して縦、横ともに約３０〜約６０％（１２０℃グリセリン浴，３分）である。レトルト条件は１２０℃（加圧０．２４５ＭＰａ）２０分である。フィルム厚さはシングルで５〜３０μｍ、好ましくは１０〜２５μｍである。また、本発明により得られるフィルムを同種の樹脂または他の樹脂からなるフィルムと積層しても差し支えない。本発明の第一にかかる塩化ビニリデン共重合体含有樹脂組成物は比較的均質であり、このことが押出加工性や延伸性を安定維持させる。このように本発明の第三にかかるフィルムの製造方法によれば、溶融押出機への塩化ビニリデン共重合体含有樹脂組成物の供給が安定に行われるので、押出機のモーターの負荷の変動、押出量の変動が小さく抑えられる。これによりダイ流出口での樹脂の付着分解、樹脂の着色および分解物の流出などの低減、インフレーション成形時のバブルの破裂の減少などの押出性がさらに改善される。また、これらの塩化ビニリデン共重合体含有樹脂組成物をガスバリヤ層に配置して、共押出法、ラミネート法により多層フィルム、シートにすることができる。
実施例
以下、実施例により本発明を具体的に説明するが、本発明はこれにより限定されるものではない。
（測定方法）
還元粘度：塩化ビニリデン共重合体の１ｇを５０ｃｃのテトラヒドロフランに加え、４０℃で溶解し、濾過後メタノールによりポリマーを析出させ洗浄乾燥する。この乾燥ポリマー８０ｍｇを精秤し、３０℃のシクロヘキサノン２０ｃｃを加え、７０℃で６０分間加熱溶解させ、室温で冷却後濾紙で濾過し、溶液粘度測定試料とする。シクロヘキサノン溶液５ｃｃをウベローデ粘度計に入れ、３０℃の恒温槽に５分間放置後、通常の操作法で流下秒数を測定し、次式により還元粘度を求めた。
還元粘度＝（１／４）×｛（Ｔ2／Ｔ1）−１｝
Ｔ1：３０℃のシクロヘキサノンの流下秒数
Ｔ2：３０℃のシクロヘキサノン試料溶液の流下秒数
酸素ガス透過性：酸素ガス透過度測定装置（Ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌ社製Ｏｘ−ｔｒａｎ２／２０）を用いて３０℃、１００％相対湿度で測定した。単位はｃｍ３／ｍ２／ｄａｙ／ａｔｍであり、ダブルフィルムで測定した。
耐寒性試験：フィルム脆化温度試験機（呉羽−野上式）を用いて試験した。測定温度に２３秒間保持した幅３０ｍｍ、長さ約５００ｍｍにカットしたダブルフィルムの一方の端を内部に伝熱媒体を流し測定温度に調製した上下２個のフィルム保持板の間に挟む。下側フィルム保持板にはフィルム保持板の下側から先端部Ｒ＝１．５ｍｍ、３ｍｍφの突き上げピンの先端が貫通する穴が設けられており、上側保持板には下側フィルム保持板を貫通した突き上げピンの先端部を受ける凹状の受け孔が設けられている。フィルムの下側面から突き上げピンを衝撃力４．４ｋｇ・ｍ／ｓｅｃ、突き上げスピード０．９２ｍ／ｓｅｃでフィルム面に向けて突き上げ、フィルムの破壊の有無を調べる。フィルムに穴が開いていたら破壊と判定する。突き上げは２３秒間に１回動作するとフィルムの新しい面が供給される。突き上げ回数は各測定温度で５回ずつ行う。測定温度で全試料が破壊しない（破壊率０％）温度から２℃間隔で温度を変えて測定し、全ての試料が破壊する（破壊率１００％）温度まで測定し、次式によりフィルムの５０％破壊温度（Ｔｂ）を求める。
Ｔｂ＝Ｔ100＋Ｂ｛（Ａ／１００）−０．５｝
Ｔ100：試験品が１００％破壊する温度（℃）
Ｂ：測定温度間隔（２℃）
Ａ：総破壊数／総測定数（％）
色落ち試験：染色摩擦堅ろう度試験機（東洋精機製作所）を使用し試験を行った。３５Ｎの荷重でラード付きガーゼをダブルフィルムの片方の表面に押し付け、３０ｃｍ／ｍｉｎの速度と１００回の往復摩擦運動を行い色差計（ミノルタ製ＣＲ−２００）によりガーゼに着色した度合いを無地のガーゼと比較測定し、色差△Ｅで表した。
分解物流出：フィルム中の長さ約１ｍｍ以上の大きさの分解物を目視観察で検出した。「少」は原反１５００ｍ当たり１０個未満を表し、「やや目立つ」は原反１５００ｍ当たり１０〜１５個未満を表し、「目立つ」は原反１５００ｍ当たり１５個以上を表す。
包装機械適性：フィルム供給部、高周波シール部、自動充填部、結紮部が一体化された自動充填結紮装置（呉羽型ＫＡＰ５００型、呉羽化学工業（株）社製）に折幅が４０ｍｍになるようにスリットしたダブルフィルムを掛け、高周波シールによりセンターシールした円筒状フィルムに充填物として水を充填し、両端を金属ワイヤでクリップした包装体を得た。そのときのシール部の状態、シール電極のスパーク発生状況を観察した。「安定」は包装機械を３０ｍ／分のシール速度で運転中、運転時間５０分間にシールに起因するトラブルおよびスパークの発生が認められないこと、「やや不安定」は、フィルムが部分的に薄く、シール線が溶融しすぎている個所が５０分間に１〜２回の頻度で発生したこと、「ややスパーク」はスパークが５０分間に１〜２回の頻度で発生したことを示し、「スパーク」はスパークが５０分間に３回以上の発生を示す。
着色：「目立」とはフィルムの黄色味が強く、分解臭がする。「少」とはフィルム着色が目立たない。「やや目立」とは「目立」と「少」の間の着色程度を表す。
（実施例１）
還元粘度０．０６１の塩化ビニリデン（ＶＤ）−塩化ビニル（ＶＣ）共重合体（懸濁重合による塩化ビニリデン／塩化ビニル質量比：ＶＤ／ＶＣ＝８０／２０）｛以下ＰＶＤＣ１と呼ぶ｝８５質量％、還元粘度０．０４０の塩化ビニリデン−塩化ビニル共重合体（懸濁重合による塩化ビニリデン／塩化ビニル質量比：ＶＤ／ＶＣ＝７５／２５）｛以下ＰＶＤＣ５と呼ぶ｝１５質量％の混合物に添加剤としてエポキシ化アマニ油、セバシン酸ジブチルを合計で塩化ビニリデン共重合体の合計量１００質量部に対して５．５質量部、抗酸化剤、滑剤、赤色顔料を合計３質量部加え、混合し冷却した後、ＭＩ（メルトインデックス）＝１５、酢酸ビニル含量２５％のエチレンと酢酸ビニル共重合体（ＥＶＡ１と呼ぶ）を塩化ビニリデン共重合体の合計量１００質量部に対して１．５質量部を加えて３０℃の温度で混合し、コンパウンド（塩化ビニリデン共重合体含有樹脂組成物）を作製した。ついで直径９０ｍｍの押出機で、真空ホッパーの真空圧約−６８０ｍｍ水銀柱にして環状に押し出した後、常法によって１０℃の冷却槽で急冷し、２０℃の温水浴槽を通過させ、２組の回転表面速度の異なるピンチロール間で空気を圧入して膨張させ、長手方向に２．８倍、幅方向に３．７倍に延伸配向させた。得られたフィルムの厚みはシングルで２０μｍであった。
（実施例２）
真空ホッパーを使用しないことを除いて実施例１と同様に行った。
（実施例３）
ＰＶＤＣ１を８０質量％、ＰＶＤＣ５を２０質量％、ＭＩ＝１５、酢酸ビニル含量２８％のエチレンと酢酸ビニル共重合体（ＥＶＡ２と呼ぶ）３質量部（塩化ビニリデン−塩化ビニル共重合体の合計量１００質量部に対して）と変更したことを除いて実施例１と同様に行った。
（実施例４）
実施例１のＥＶＡ１に代えてＢＴＡ−ＩＶＳＳ（呉羽化学工業（株）製ＭＢＳ樹脂）１．５質量部を使用したことを除いて実施例１と同様に行った。
（比較例５）
還元粘度０．０５７の塩化ビニリデン−塩化ビニル共重合体（懸濁重合による塩化ビニリデン／塩化ビニル質量比：ＶＤ／ＶＣ＝７８／２２）｛以下ＰＶＤＣ２と呼ぶ｝１００質量部に対し、ＥＶＡ２を３質量部使用したことを除いて、実施例１と同様に行った。
（比較例６）
還元粘度０．０４７の塩化ビニリデン−塩化ビニル共重合体（懸濁重合による塩化ビニリデン／塩化ビニル質量比：ＶＤ／ＶＣ＝８０／２０）｛以下ＰＶＤＣ３と呼ぶ｝１００質量部に対し、ＥＶＡ２を３質量部使用したことを除いて、実施例１と同様に行った。
（比較例７）
ＰＶＤＣ１を１００重量部に対して、ＥＶＡ２を１．５重量部使用したことを除いて実施例１と同様に行った。
（比較例１）
真空ホッパーを使用しないことを除いて実施例５と同様に行った。
（比較例２）
真空ホッパーを使用せずＥＶＡ２の３質量部を７０℃で加熱混合することを除いて実施例５と同様に行った。
（比較例３）
還元粘度０．０４４の塩化ビニリデン−塩化ビニル共重合体（懸濁重合による塩化ビニリデン／塩化ビニル質量比：ＶＤ／ＶＣ＝８０／２０）｛以下ＰＶＤＣ４と呼ぶ｝１００質量部、ＭＩ＝３の酢酸ビニル含量１０％のエチレンと酢酸ビニル共重合体（ＥＶＡ３と呼ぶ）を２５質量部使用し、真空ホッパーを使用しないことを除いて、実施例１と同様に行った。延伸成形が難しく、包装機械適性や耐寒性の試験をするに充分なサンプルが得られなかった。
（比較例４）
ＰＶＤＣ３を８５質量％、ＰＶＤＣ５を１５質量％、添加剤としてエポキシ化アマニ油、セバシン酸ジブチルを合計で５．５質量部、抗酸化剤、滑剤、赤色顔料の合計３質量部を混合しコンパウンドを作製し、直ちにこのコンパウンドを常圧のホッパーへ移し、押出機へ供給したことを除き実施例１と同様に処理した。実施例および比較例の試験結果を表−１および表−２に示した。
なお、以下の方法で測定した熱収縮率は縦横共に４０〜５０％であり、実施例および比較例との差は認められなかった。熱収縮率は、各実施例および比較例で得たダブルフィルムを縦方向、横方向共に１０ｃｍの長さに切り取り、この試験片を１２０℃、グリセリン浴に３分保持後取り出し、縦横の長さを測定し、もとの長さに対する変化率を％で示した。
また、水充填した包装体をレトルト缶内で加熱殺菌した時の破袋は１〜２本／１０００本であった。この値は比較例および参考例と比して差が認められないものであった。
本発明により、押出加工性（例えば押出量の変動の低減、ダイ流出口での樹脂の分解物付着性の減少、インフレーション成形時のバブル破壊の減少）に優れ、包装機械適性（自動充填結紮装置にかけた際にフィルムの厚み斑によるシール不良、フィルム中の分解物のスパークによる破袋等が起こり難くシール工程が安定して操業できる）、耐寒性、ガスバリヤー性に関してバランスのとれたフィルムを与える塩化ビニリデン共重合体含有樹脂組成物が得られる。また、塩化ビニリデン共重合体含有樹脂組成物を真空ホッパーを経由して押出機へ供給する押出方法および前記塩化ビニリデン共重合体含有樹脂組成物を調製する工程とその押出加工方法とからなるフィルムの製造方法により、押出加工性の改良効果をより一層向上させることができる。Technology field
The present invention relates to a vinylidene chloride copolymer-containing resin composition, an extrusion method thereof, a film formed therefrom, and a method for producing the film. More specifically, a vinylidene chloride copolymer-containing resin composition comprising a mixed vinylidene chloride resin (A) and a specific copolymer (B), a mixed vinylidene chloride resin (A) or a vinylidene chloride copolymer (A ′). And a specific copolymer (B) and a method of extruding a resin composition containing a vinylidene chloride copolymer, an extrudability formed therefrom, and a film excellent in packaging machine suitability, cold resistance and gas barrier properties About.
Background art
Generally, a vinylidene chloride copolymer has an excellent property of shielding gas such as water vapor and oxygen, and thus is extruded and used for food packaging films. However, ordinary vinylidene chloride copolymers themselves have poor thermal stability and are easily decomposed by heat, so that the extrusion process becomes unstable, and it is difficult to obtain a uniform packaging film taking advantage of the characteristics. For this reason, the following various improvements have been proposed.
Japanese Examined Patent Publication No. 40-16141 discloses a molding composition containing 2 to 20% by weight of an elastic material such as a vinylidene chloride polymer and a copolymer of ethylene and vinyl alkanoates or a rubber-like material. JP-A-55-108442 discloses ethylene and acetic acid having a polyvinylidene chloride copolymer of 60 to 95% by weight, a vinyl acetate content of 5 to 18% by weight and a melt flow of about 0.1 to 1.0 dg / min. Films comprising about 5 to about 40% by weight of a copolymer with vinyl are described. JP-A-62-72736 describes a melt-processable blend comprising a vinylidene chloride interpolymer, an olefin polymer and a compatibilizing polymer.
JP-A-1-131268 discloses about 30 to about 3% by weight of an olefin copolymer obtained by polymerizing about 70 to about 97% by weight of a vinylidene chloride copolymer and about 15 to about 3% by weight of acrylic acid or methacrylic acid, and vinyl acetate. An blown film comprising a blend polymer comprising from about 0 to about 15% by weight of an olefin copolymer polymerized from about 30 to about 3% by weight is described. Japanese Patent Publication No. 3-503290 discloses a vinylidene chloride interpolymer and about 0.01 to about 0.5% by weight of oxidized polyethylene, oxidized polypropylene or a mixture thereof, and about 0.01 to about 2% by weight of ethylene-vinyl acetate. Extrudability is achieved by a combination of additives comprising an extrusion aid selected from the group consisting of a copolymer, about 0.005 to about 1% by weight paraffin wax and about 0.1 to about 3% by weight epoxidized oil or resin. Improvement methods have been proposed. JP-A-3-35043 proposes a composition having a low weight average molecular weight vinylidene chloride copolymer and a processing aid of about 0.01 to 6% by weight. US Pat. No. 4,798,751 proposes a mixture of vinylidene chloride copolymers having different copolymer compositions.
Japanese Patent Application Laid-Open No. 61-120719 discloses a content of a methyl acrylate component of a vinylidene chloride-methyl acrylate copolymer, a weight average molecular weight of the copolymer (70,000 to 250,000), and a copolymer having a molecular weight of 20,000 or less. An improvement of a molding method using a melt extrusion method characterized by using a vinylidene chloride-methyl acrylate copolymer having a specified rate is proposed.
However, when various resins and additives are mixed in order to improve the extrusion processability of vinylidene chloride copolymer as described above, other film properties required for films such as packaging machine suitability, cold resistance, and gas barrier properties. There is a demand for vinylidene chloride resins having these characteristics.
As a means for improving the extrusion processability of the vinylidene chloride copolymer resin, a method of suppressing the heat generation of the resin is employed. For this purpose, for example, it is conceivable to reduce the degree of polymerization of the resin or to use many additives. If the degree of polymerization of the resin is reduced, PVDC (abbreviation for vinylidene chloride copolymer) itself becomes brittle and cold resistance decreases. Moreover, if many additives are used, gas barrier property will fall.
The extrusion processability of vinylidene chloride copolymer resin is closely related to the suitability of packaging machinery. In the case of a resin having poor extrusion processability, the fluctuation of the extrusion motor load becomes large, and unevenness occurs in the extrusion amount, resulting in unevenness in the thickness of the film in the flow direction. When such a film is applied to a packaging machine, when the film is too thin, it melts too much when sealed, resulting in pinhole breaking, and the film is not sealed when the film is too thick. In addition, decomposition products flow out from the die outlet at the time of extrusion, and these decomposition products dispersed in the film induce conduction of a seal electrode of a packaging machine capable of high-frequency welding, and the film is microdestructed by sparks to form pinholes. In addition, the amount of extrusion partially changes due to the decomposition product adhering to the die outlet, resulting in partial thickness unevenness in the width direction of the film, the seal part does not weld, and the film does not run evenly and the seal It becomes a factor of being unable to do so.
The present invention provides a vinylidene chloride copolymer-containing resin composition, a vinylidene chloride copolymer, which improves the above-mentioned problems, has excellent extrudability, and provides a film that is well-balanced in terms of packaging machine suitability, cold resistance, and gas barrier properties. An object of the present invention is to provide an extrusion method using a polymer-containing resin composition, a film obtained therefrom, and a method for producing the film.
Disclosure of the invention
The inventors of the present invention provide a vinylidene chloride copolymer-containing resin composition comprising a mixed vinylidene chloride resin (A) and a specific copolymer (B) in which specific vinylidene chloride copolymers having different reduced viscosities are mixed at a specific ratio. When the film is formed from a resin composition containing a vinylidene chloride copolymer, the product is excellent in extrudability, and the film formed therefrom has a good balance in terms of suitability for packaging machinery, cold resistance and gas barrier properties. It was found that the above characteristics can be further improved by using a vacuum hopper, and the present invention has been achieved.
That is, the present invention relates to 100 parts by mass of a mixed vinylidene chloride resin (A) composed of at least two kinds of vinylidene chloride copolymers, an ethylene and vinyl acetate copolymer (B1), Copolymers of ethylene and acrylic acid, methacrylic acid or their alkyl esters (B2) And MBS resin (BThree) At least one copolymer (B) selected from 0.1 to 20 parts by massA vinylidene chloride copolymer-containing resin composition,
The mixed vinylidene chloride resin (A) is a vinylidene chloride copolymer (A 1 ) Vinylidene chloride copolymer (A) having 50% by mass or more and a reduced viscosity of less than 0.048 2 ) Less than 50% by mass (however, the total of both is 100% by mass)A vinylidene chloride copolymer-containing resin composition and a film formed therefrom are provided.
The present invention100 parts by mass of a mixed vinylidene chloride resin (A) composed of at least two types of vinylidene chloride copolymers;Ethylene and vinyl acetate copolymer (B1), Copolymers of ethylene and acrylic acid, methacrylic acid or their alkyl esters (B2) And MBS resin (BThree) At least one copolymer selected from (B)0.1 to 20 parts by massA vinylidene chloride copolymer-containing resin composition consisting of the above is supplied to an extruder via a vacuum hopperAn extrusion process,
The mixed vinylidene chloride resin (A) is a vinylidene chloride copolymer (A 1 ) Vinylidene chloride copolymer (A) having 50% by mass or more and a reduced viscosity of less than 0.048 2 ) Less than 50% by mass (however, the total of both is 100% by mass)An extrusion method is provided.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the first of the present invention will be described in detail.
Vinylidene chloride copolymer (A1) And vinylidene chloride copolymer (A2) Is a copolymer of vinylidene chloride and at least one monoethylenically unsaturated monomer copolymerizable with vinylidene chloride. The content of the monoethylenically unsaturated monomer in the copolymer is about 40 to about 2% by mass, and preferably about 35 to about 4% by mass from the balance between extrusion processability and gas barrier property. Monoethylenically unsaturated monomers include vinyl chloride, vinyl acetate, vinyl propionate, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile, acrylamide, vinyl alkyl ether, vinyl alkyl Mention may be made of ketones, acrolein, allyl esters and ethers, butadiene, chloroprene. Vinylidene chloride copolymer (A1) And (A2) May be a ternary or higher copolymer obtained by copolymerizing two or more of these monoethylenically unsaturated monomers. Among the monoethylenically unsaturated monomers, preferably vinyl chloride, alkyl acrylates and alkyl methacrylates having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, and methyl methacrylate are exemplified. It is more preferable that it is easy to balance the extrusion processability and gas barrier property.
Vinylidene chloride copolymer (A1) And vinylidene chloride copolymer (A2) Is easily melted inside the extruder to reduce the generation of fish eyes generated by decomposition, unmelting, etc. of the resin, which is undesirable in terms of the quality of the formed film.1) And (A2) Is preferably a copolymer component of the same kind. For example, vinylidene chloride copolymer (A1) Is a copolymer of vinylidene chloride and vinyl chloride, a vinylidene chloride copolymer (A2) Is also preferably a copolymer of vinylidene chloride and vinyl chloride. More preferably, the vinylidene chloride copolymer (A1) And vinylidene chloride copolymer (A2) Are each preferably a binary copolymer of vinylidene chloride and vinyl chloride for uniform melting of the resin. In addition, vinylidene chloride copolymer (A1) Is a vinylidene chloride copolymer (A2It is preferable that it is larger than the composition ratio of vinylidene chloride in terms of extrudability and cold resistance of the film.
The vinylidene chloride copolymer (A1) Preferably has a reduced viscosity of 0.048 or more, and a range of 0.048 to 0.080 is preferably used. For films for packaging such as retort foods, vinylidene chloride copolymer (A1) Is preferably in the range of 0.052 to 0.080, more preferably in the range of 0.055 to 0.075 from the viewpoints of packaging machine suitability, cold resistance, and stretch processability.
Vinylidene chloride copolymer (A2) Preferably has a reduced viscosity of less than 0.048, more preferably less than 0.025 to 0.048, and particularly preferably less than 0.035 to 0.045, and the cold resistance of the film, vinylidene chloride copolymer It is preferable from the point of the extrudability of the containing resin composition. Vinylidene chloride copolymer (A2) Suppresses heat generation in the extruder and contributes to improvements in extrusion processability, such as reducing resin adhesion and decomposition at the die outlet and reducing fluctuations in the motor load of the extruder, but vinylidene chloride from the balance with cold resistance Copolymer (A2) Is preferably less than 50% by weight, more preferably 3 to 25% by weight, and most preferably 5 to 25% by weight with respect to the total 100% by weight of the vinylidene chloride copolymer.
The copolymer (B) is an ethylene and vinyl acetate copolymer (B1), Copolymers of ethylene and acrylic acid, methacrylic acid or their alkyl esters (particularly alkyl esters having 1 to 4 carbon atoms) (B2) And MBS resin (BThree) At least one selected from.
The copolymer (B1) And (B2) Is an ethylene content in the range of 65 to 85% by mass, more preferably in the range of 75 to 80% by mass. In order to maintain the transparency of the molded film, the ethylene content is preferably 85% by mass or less, and the ethylene content is 65% by mass or more from the viewpoint of the stability of the extruder motor load and the gas barrier property of the molded film. preferable. When the copolymer (B) is a mixture, the copolymer (B) having an ethylene content of less than 65% by mass is intended to increase the compatibility with the mixed vinylidene chloride resin (A).1) Or (B2) Can be added in small amounts.
The MBS resin is mainly composed of a butadiene homopolymer or butadiene described in JP-B-46-19550, and any one of styrene, methacrylic acid ester, acrylonitrile and vinylidene chloride, or any mixture thereof. A cross-linking agent that is a copolymer and can copolymerize 50 to 20 parts by weight of methyl methacrylate, styrene, or vinylidene chloride alone or any mixture thereof in a latex containing 50 to 80 parts by weight of a rubber component. Examples include BTA-IV SS manufactured by Kureha Chemical Industry Co., Ltd., which contains a rubber plastic component obtained by post-polymerization in the presence of 5 parts by weight.
Vinylidene chloride copolymer (A1) And vinylidene chloride copolymer (A2When the copolymer (B) is added to and mixed with the vinylidene chloride resin (A), the cold resistance of the resulting film is improved. The mixing ratio of both is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 0 to 100 parts by mass of the mixed vinylidene chloride resin (A). .7 to 1.5 parts by mass. When the mixing ratio of the copolymer (B) is more than 20 parts by mass, the motor load of the extruder fluctuates and becomes unstable, and the extrusion processability such as an increased amount of decomposed substances attached to the die outlet exits. On the other hand, when the mixing amount is less than 0.1 parts by mass, the outflow of decomposed products increases, and it becomes difficult to maintain the cold resistance of the resulting film.
Vinylidene chloride copolymer (A1) Is preferably 50% by mass or more, more preferably 75 to 97% by mass, and most preferably 75 to 95% by mass with respect to the total 100% by mass of the vinylidene chloride copolymer, and the remainder is chloride. Vinylidene copolymer (A2). The mixing ratio of the copolymer (B) is vinylidene chloride copolymer (A2Less) is preferred. Vinylidene chloride copolymer (A1) May be mixed with an appropriate amount of copolymer (B), but the motor load of the extruder may fluctuate, but the vinylidene chloride copolymer (A2) Containing a mixed vinylidene chloride copolymer (A). Particularly in the case of a film containing a pigment, a vinylidene chloride copolymer (A2) / Copolymer (B) mixing ratio of 1.5 to 10 can suppress the color fading phenomenon on the film surface from rubbing due to friction.
The melt index (MI) of the copolymer (B) according to ASTM D-1238 is preferably about 3 or more from the viewpoint of extrusion processability and gas barrier property. Usually, it is 5 to 40 g / min, preferably 10 to 30 g / min. The weight average molecular weight of MI 30 g / min is about 110,000.
Additives such as known plasticizers, heat stabilizers, processing aids, light stabilizers, pigments, lubricants, antioxidants, fillers, surfactants and the like are blended in the vinylidene chloride copolymer-containing resin composition of the present invention. can do. Specifically, dioctyl phthalate, acetyl tributyl citrate, dibutyl sebacate, dioctyl sebacate and diisobutyl adipate, epoxidized oil and resin such as epoxidized soybean oil, epoxidized linseed oil, amide derivative of alkyl ester, magnesium hydroxide, Plasticizers such as tetrasodium pyrophosphate, magnesium oxide and calcium hydroxyphosphate, polyethylene oxide, paraffin wax, polyethylene wax, montan ester wax and the like plasticizers, heat stabilizers, processing aids, those acting as lubricants, and Examples of the additives include fillers such as silicon oxide and calcium carbonate, and surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters. Titanium oxide pigments are effective in preventing discoloration of food contents such as sausages due to ultraviolet rays, but increase adhesion and decomposition at the die outlet. However, since this adhesion decomposition is effectively reduced when extrusion is performed using a vacuum hopper, a large amount of up to 0.10 to 10 parts by mass can be added.
Among the additives, the plasticizer and the stabilizer are added in the range of about 1 to about 10 parts by weight, preferably 2 to 6 parts by weight, with respect to 100 parts by weight of the mixed vinylidene chloride resin (A). A part of these additives is a vinylidene chloride copolymer (A1) Or (A2) May be added during the polymerization. The additive is adsorbed or absorbed by the vinylidene chloride copolymer during extrusion and contributes to the extrusion processability. However, after film formation, it shifts to the copolymer (B) and improves the gas barrier property of the film. A balanced film can be obtained. Additives other than plasticizers and heat stabilizers are preferably used as necessary.
Vinylidene chloride copolymer (A1), Vinylidene chloride copolymer (A2), The mixing method of the copolymer (B) and the additive is not particularly limited, and a conventional method can be applied. For example, kneading with a two-roll machine, mixing with a blender such as a blade blender or a ribbon blender, mixing with a Henschel high-speed mixer, and the like can be applied to either a heating mixing method exceeding 60 ° C. or a low temperature mixing method not exceeding 60 ° C.
In addition, vinylidene chloride copolymer (A1), Vinylidene chloride copolymer (A2) And the above-mentioned additive added as necessary may be mixed in advance, and the copolymer (B) may be mixed with the mixed vinylidene chloride resin (A). In that case, it is preferable from the point of the homogeneity of the obtained vinylidene chloride copolymer containing resin composition that mixed resin temperature is about 60 degrees C or less, Preferably it mixes in the temperature range of 50 degreeC to room temperature.
Examples of the mixing device include known dry mixing devices such as a Henschel high-speed mixer, a blade blender, and a ribbon blender. In addition, there is a method of mixing these raw materials using a screw feeder or the like in an on-board hopper device of an extruder immediately before extruding the vinylidene chloride copolymer-containing resin composition, but mixing at a temperature of 60 ° C. or less. As a result, generation of decomposition products due to adhesion of resin at the die outlet, coloring of resin, outflow of decomposition products, and the like can be reduced. In addition, a combination of a method of mixing at a temperature of 60 ° C. or less and a copolymer (B) having a low ethylene content, or the addition of the waxes described above prevents blocking of the mixed resin powder, during extrusion processing. This prevents the powder from getting into the screw and can improve the fluctuation of the motor load and the amount of extrusion. The vinylidene chloride copolymer-containing resin composition obtained by mixing is extruded as a powder or in the form of pellets and used for film formation.
The above-mentioned plasticizer, heat stabilizer, processing aid, light stabilizer, pigment, lubricant, antioxidant, filler, surfactant added as necessary for homogenization of the vinylidene chloride copolymer-containing resin composition The additive selected from, for example, a vinylidene chloride copolymer (A) in advance before adding the copolymer (B).1) And vinylidene chloride copolymer (A2It is preferable to add to and mix with the vinylidene chloride resin (A). Thereby, it can suppress that an additive is locally absorbed or adsorb | sucked to a copolymer (B), and can reduce the adhesion part of die | dye exit. The recovered pulverized product (recycle resin) of the vinylidene chloride copolymer can be mixed with the mixed vinylidene chloride resin (A) and recycled. The mixing ratio of the pulverized product at this time is about 1 to 50% by mass, preferably about 1 to 30% by mass with respect to the mixed vinylidene chloride resin (A).
The vinylidene chloride copolymer-containing resin composition of the present invention is melt extruded and formed into a stretched or unstretched film, sheet or the like. As a molding method, for example, an inflation extrusion molding method using a circular die as known to those skilled in the art can be applied. A film obtained by orientation by stretching, particularly preferably biaxial stretching, is suitably used as a heat-resistant film having heat shrinkability or retortability. The stretching ratio is preferably 2.0 to 4.5 times in the longitudinal direction and 3.0 to 5.0 times in the transverse direction. Film thickness is 5-30 micrometers as a single film, Preferably it is 10-25 micrometers. It is also used as a double film depending on the application. Usually, the heat shrinkage is about 30 to about 60% (120 ° C. glycerin bath, 3 minutes) both vertically and horizontally. The main method of use for food packaging is to inflate two sheets after inflation, slit the ears at both ends of the film as a double film, seal it in a cylindrical shape with a packaging machine, fill the contents, Used to obtain a gripped package. The retort condition is 120 ° C. (pressure 0.245 MPa) for 20 minutes. Further, the film of the present invention may be laminated with a film made of another resin or resin composition that can be coextruded with the same kind of resin or vinylidene chloride copolymer.
The second of the present invention relates to a method for extruding a resin composition containing a vinylidene chloride copolymer (A '). When extruding the resin composition containing the vinylidene chloride copolymer (A ′), the resin composition is supplied to an extruder via a vacuum hopper, thereby improving the extrudability. . That is, the use of a vacuum hopper is effective in reducing the adhesion and decomposition of the resin at the die outlet, the coloring of the resin and the outflow of the decomposition product, and the reduction of bubble bursting during inflation molding. The degree of vacuum of the vacuum hopper is −500 mm or less, preferably −600 to −755 mm of mercury. Extrudability can be improved by supplying the resin composition to an extruder via a vacuum hopper set to such conditions. The vinylidene chloride copolymer (A ') is not particularly limited, but is preferably a vinylidene chloride copolymer (A') having a reduced viscosity of 0.048 or more.1) Vinylidene chloride copolymer (A) having 50% by mass or more and a reduced viscosity of less than 0.0482) Mixed vinylidene chloride resin (A) with less than 50% by mass (provided that the total of both is 100% by mass) or a vinylidene chloride copolymer having a reduced viscosity of 0.045 or more (AThree) Is preferred. Vinylidene chloride copolymer having a reduced viscosity of 0.045 or more (AThree) Preferably has a reduced viscosity in the range of 0.045 to 0.080. Preferably, 0.1 to 20 parts by mass of at least one copolymer (B) is added to 100 parts by mass of the vinylidene chloride copolymer (A ′). Since the vacuum hopper is used, the adhesion decomposition at the die outlet is reduced, and the use of the titanium oxide pigment is effective.
The third aspect of the present invention is a process for preparing a resin composition containing a vinylidene chloride copolymer (A ″) and an extrusion of the resin composition containing the vinylidene chloride copolymer (A ′) which is the second aspect of the present invention. The manufacturing method of the film which consists of a processing method is provided.
That is, a vinylidene chloride copolymer having a reduced viscosity of 0.045 or more (AThree) Or a vinylidene chloride copolymer having a reduced viscosity of 0.048 or more (A1) Vinylidene chloride copolymer (A) having 50% by mass or more and a reduced viscosity of less than 0.0482) Mixed vinylidene chloride resin (A) with less than 50% by massFour(A1And A2Of vinylidene chloride copolymer (A ″) selected from 100% by mass), ethylene and vinyl acetate copolymer (B1), Copolymers of ethylene and acrylic acid, methacrylic acid or their alkyl esters (B2) And MBS resin (BThreeAnd at least one copolymer (B) selected from 0.1 to 20 parts by mass, the step of mixing these raw material resins at a temperature of 60 ° C. or lower, preferably 50 ° C. to room temperature, and And a step of supplying the obtained vinylidene chloride copolymer-containing resin composition to an extruder via a vacuum hopper. The film is stretched by a known method through a melt extruder connected to the lower part of the vacuum hopper, or formed into a film, a sheet or the like without being stretched. The degree of vacuum of the vacuum hopper is as described in the invention of the second extrusion method of the present invention. A known method as described above can be applied to the film forming method. For example, an inflation extrusion molding method using a circular die can be applied. A film obtained by stretching and orientation, particularly a biaxially stretched film, has good heat shrinkability or is suitably used as a heat-resistant film that can be retorted. The thermal contraction rate of the biaxially stretched film of the present invention is about 30 to about 60% (120 ° C. glycerin bath, 3 minutes) in both length and width as measured with a test piece. The retort condition is 120 ° C. (pressure 0.245 MPa) for 20 minutes. The film thickness is single and is 5 to 30 μm, preferably 10 to 25 μm. Further, the film obtained by the present invention may be laminated with a film made of the same kind of resin or another resin. The vinylidene chloride copolymer-containing resin composition according to the first aspect of the present invention is relatively homogeneous, and this stably maintains extrusion processability and stretchability. Thus, according to the method for producing a film according to the third aspect of the present invention, since the supply of the vinylidene chloride copolymer-containing resin composition to the melt extruder is stably performed, fluctuations in the load on the motor of the extruder, The fluctuation of the extrusion amount can be kept small. This further improves extrudability such as resin adhesion and decomposition at the die outlet, reduction of resin coloring and outflow of decomposed products, and reduction of bubble bursting during inflation molding. Moreover, these vinylidene chloride copolymer containing resin compositions can be arrange | positioned in a gas barrier layer, and can be made into a multilayer film and a sheet | seat by the coextrusion method and the lamination method.
Example
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Measuring method)
Reduced viscosity: 1 g of vinylidene chloride copolymer is added to 50 cc of tetrahydrofuran, dissolved at 40 ° C., filtered, precipitated with methanol, washed and dried. 80 mg of this dried polymer is precisely weighed, 20 cc of cyclohexanone at 30 ° C. is added, dissolved by heating at 70 ° C. for 60 minutes, cooled at room temperature, filtered through filter paper, and used as a solution viscosity measurement sample. 5 cc of a cyclohexanone solution was put in an Ubbelohde viscometer, left in a thermostatic bath at 30 ° C. for 5 minutes, then the number of seconds flowing down was measured by a normal operation method, and the reduced viscosity was determined by the following formula.
Reduced viscosity = (1/4) × {(T2/ T1-1]
T1: Flow time of cyclohexanone flowing down at 30 ° C
T2: Number of seconds that the cyclohexanone sample solution flows at 30 ° C.
Oxygen gas permeability: Measured at 30 ° C. and 100% relative humidity using an oxygen gas permeability measuring device (Ox-tran 2/20 manufactured by Modern Control). The unit was cm3 / m2 / day / atm, and the measurement was performed with a double film.
Cold resistance test: Tested using a film embrittlement temperature tester (Kureha-Nogami formula). One end of a double film cut to a width of 30 mm and a length of about 500 mm held at the measurement temperature for 23 seconds is sandwiched between two upper and lower film holding plates adjusted to the measurement temperature by flowing a heat transfer medium therein. The lower film holding plate is provided with a hole through which the tip of the tip R = 1.5 mm, 3 mmφ push-up pin passes from the lower side of the film holding plate, and the lower film holding plate passes through the upper film holding plate. A concave receiving hole is provided for receiving the tip of the raised pin. The push-up pin is pushed up from the lower surface of the film toward the film surface with an impact force of 4.4 kg · m / sec and a push-up speed of 0.92 m / sec, and the film is checked for breakage. If there is a hole in the film, it is determined to be broken. When the push-up operates once every 23 seconds, a new side of the film is supplied. The number of push-ups is 5 times at each measurement temperature. Measured by changing the temperature at intervals of 2 ° C from the temperature at which all samples do not break at the measurement temperature (breakage rate 0%), and measures until the temperature at which all samples break (breakage rate 100%). Determine the% fracture temperature (Tb).
Tb = T100+ B {(A / 100) -0.5}
T100: Temperature at which the test product breaks 100% (° C)
B: Measurement temperature interval (2 ° C)
A: Total number of fractures / total number of measurements (%)
Color fading test: A test was performed using a dyeing friction fastness tester (Toyo Seiki Seisakusho). A gauze with lard was pressed against one surface of a double film with a load of 35 N, and the speed of 30 cm / min and 100 reciprocating frictional movements were performed. And measured by a color difference ΔE.
Decomposition product outflow: Decomposition product having a length of about 1 mm or more in the film was detected by visual observation. “Small” represents less than 10 per 1500 m of fabric, “Slightly conspicuous” represents less than 10 to 15 per 1500 m of raw material, and “Conspicuous” represents 15 or more per 1500 m of fabric.
Packing machine suitability: Folding width of 40mm in automatic filling and ligating apparatus (Kureha type KAP500, Kureha Chemical Co., Ltd.) with integrated film supply unit, high frequency sealing unit, automatic filling unit and ligating unit A double-walled slit film was hung on, a cylindrical film center-sealed by high-frequency sealing was filled with water as a filling material, and a package was obtained in which both ends were clipped with metal wires. The state of the seal part at that time and the spark generation state of the seal electrode were observed. “Stable” means that trouble and sparks due to sealing are not observed during the operation time of 50 minutes when the packaging machine is operated at a sealing speed of 30 m / min. “Slightly unstable” means that the film is partially thin , The part where the seal line was melted too much occurred once or twice in 50 minutes, “Slightly spark” indicates that the spark occurred once or twice in 50 minutes, "" Indicates the occurrence of sparks 3 times or more in 50 minutes.
Coloring: “Conspicuous” means that the film has a strong yellowish color and has a decomposition odor. “Low” means that the film coloring is not noticeable. “Slightly conspicuous” represents the degree of coloring between “conspicuous” and “low”.
Example 1
Vinylidene chloride (VD) -vinyl chloride (VC) copolymer having a reduced viscosity of 0.061 (vinylidene chloride / vinyl chloride mass ratio by suspension polymerization: VD / VC = 80/20) {hereinafter referred to as PVDC1} 85% by mass , Reduced viscosity 0.040 vinylidene chloride-vinyl chloride copolymer (vinylidene chloride / vinyl chloride mass ratio by suspension polymerization: VD / VC = 75/25) {hereinafter referred to as PVDC5} As the total amount of epoxidized linseed oil and dibutyl sebacate in a total amount of 100 parts by mass of vinylidene chloride copolymer, 5.5 parts by mass, antioxidant, lubricant, red pigment in total 3 parts by mass were added, mixed and cooled After that, an ethylene and vinyl acetate copolymer (referred to as EVA1) having a MI (melt index) of 15 and a vinyl acetate content of 25% was combined with the vinylidene chloride copolymer. 1.5 parts by weight were mixed at a temperature of addition 30 ° C. relative to the amount 100 parts by mass, to prepare a compound (vinylidene copolymer-containing resin composition chloride). Next, with a 90 mm diameter extruder, the vacuum pressure of the vacuum hopper was about −680 mm and extruded in a circular shape, and then rapidly cooled in a 10 ° C. cooling bath by a conventional method, passed through a 20 ° C. hot water bath, and two sets of rotating surfaces Air was injected between pinch rolls having different speeds to expand them, and the film was stretched and oriented 2.8 times in the longitudinal direction and 3.7 times in the width direction. The obtained film had a single thickness of 20 μm.
(Example 2)
The same operation as in Example 1 was performed except that a vacuum hopper was not used.
(Example 3)
80% by mass of PVDC1, 20% by mass of PVDC5, MI = 15, 3 parts by mass of ethylene and vinyl acetate copolymer (referred to as EVA2) having a vinyl acetate content of 28% (total amount of vinylidene chloride-vinyl chloride copolymer of 100) Example 1
(Example 4)
It replaced with EVA1 of Example 1, and carried out similarly to Example 1 except having used 1.5 mass parts of BTA-IVSS (Kureha Chemical Industry Co., Ltd. MBS resin).
(Comparative Example 5)
Vinylidene chloride-vinyl chloride copolymer having a reduced viscosity of 0.057 (vinylidene chloride / vinyl chloride mass ratio by suspension polymerization: VD / VC = 78/22) {hereinafter referred to as PVDC2} It carried out like Example 1 except having used the mass part.
(Comparative Example 6)
Vinylidene chloride-vinyl chloride copolymer having a reduced viscosity of 0.047 (vinylidene chloride / vinyl chloride mass ratio by suspension polymerization: VD / VC = 80/20) {hereinafter referred to as PVDC3} It carried out like Example 1 except having used the mass part.
(Comparative Example 7)
The same procedure as in Example 1 was performed except that 1.5 parts by weight of EVA2 was used with respect to 100 parts by weight of PVDC1.
(Comparative Example 1)
The same operation as in Example 5 was performed except that a vacuum hopper was not used.
(Comparative Example 2)
The same operation as in Example 5 was performed except that 3 parts by mass of EVA2 was heated and mixed at 70 ° C. without using a vacuum hopper.
(Comparative Example 3)
Vinylidene chloride-vinyl chloride copolymer having a reduced viscosity of 0.044 (vinylidene chloride / vinyl chloride mass ratio by suspension polymerization: VD / VC = 80/20) {hereinafter referred to as PVDC4} 100 parts by mass, acetic acid with MI = 3 The same procedure as in Example 1 was carried out except that 25 parts by mass of ethylene and vinyl acetate copolymer (referred to as EVA3) having a vinyl content of 10% were used and no vacuum hopper was used. Stretch molding was difficult, and sufficient samples could not be obtained for testing packaging machine suitability and cold resistance.
(Comparative Example 4)
Mix 85 parts by weight of PVDC3, 15 parts by weight of PVDC5, 5.5 parts by weight of epoxidized linseed oil and dibutyl sebacate as additives, 3 parts by weight of antioxidant, lubricant and red pigment. The compound was prepared and immediately transferred to a normal pressure hopper and processed in the same manner as in Example 1 except that the compound was supplied to an extruder. The test results of Examples and Comparative Examples are shown in Table-1 and Table-2.
In addition, the heat shrinkage rate measured by the following method was 40 to 50% in both length and width, and a difference from the examples and comparative examples was not recognized. The heat shrinkage ratio was obtained by cutting the double film obtained in each Example and Comparative Example to a length of 10 cm in both the vertical and horizontal directions, and taking out this test piece after holding it in a glycerin bath at 120 ° C. for 3 minutes. Was measured and the rate of change relative to the original length was expressed in%.
Further, the number of broken bags when the water-filled package was heat sterilized in the retort can was 1 to 2/1000. This value was not different from the comparative example and the reference example.
According to the present invention, it has excellent extrudability (for example, reduction in variation in extrusion amount, reduction in adhesion of resin decomposition products at the die outlet, reduction in bubble breakage during inflation molding), and suitability for packaging machinery (automatic filling and ligating apparatus The film has a poor seal due to uneven thickness of the film, and it is difficult to break the bag due to sparks of the decomposed material in the film, so that the sealing process can be operated stably), giving a balanced film with respect to cold resistance and gas barrier properties A vinylidene chloride copolymer-containing resin composition is obtained. Further, an extrusion method for supplying a vinylidene chloride copolymer-containing resin composition to an extruder via a vacuum hopper, and a step of preparing the vinylidene chloride copolymer-containing resin composition and an extrusion processing method thereof By the production method, the effect of improving the extrudability can be further improved.
Claims (19)
混合塩化ビニリデン樹脂（Ａ）が還元粘度０．０４８以上の塩化ビニリデン共重合体（Ａ 1 ）５０質量％以上と還元粘度０．０４８未満の塩化ビニリデン共重合体（Ａ 2 ）５０質量％未満とからなる（但し、両者の合計は１００質量％）ことを特徴とする塩化ビニリデン共重合体含有樹脂組成物。Copolymer of 100 parts by mass of a mixed vinylidene chloride resin (A) composed of at least two kinds of vinylidene chloride copolymers, ethylene and vinyl acetate copolymer (B 1 ), ethylene and acrylic acid, methacrylic acid or alkyl esters thereof. A vinylidene chloride copolymer-containing resin composition comprising 0.1 to 20 parts by mass of at least one copolymer (B) selected from a polymer (B 2 ) and an MBS resin (B 3 ) ,
The mixed vinylidene chloride resin (A) is 50% by mass or more of a vinylidene chloride copolymer (A 1 ) having a reduced viscosity of 0.048 or more and less than 50% by mass of a vinylidene chloride copolymer (A 2 ) having a reduced viscosity of less than 0.048. (However, the total of both is 100 mass%) The vinylidene chloride copolymer containing resin composition characterized by the above-mentioned .
混合塩化ビニリデン樹脂（Ａ）が還元粘度０．０４８以上の塩化ビニリデン共重合体（Ａ 1 ）５０質量％以上と還元粘度０．０４８未満の塩化ビニリデン共重合体（Ａ 2 ）５０質量％未満とからなる（但し、両者の合計は１００質量％）ものである押出加工方法。 Copolymer of 100 parts by mass of a mixed vinylidene chloride resin (A) composed of at least two kinds of vinylidene chloride copolymers, ethylene and vinyl acetate copolymer (B 1 ), ethylene and acrylic acid, methacrylic acid or alkyl esters thereof. A vinylidene chloride copolymer-containing resin composition comprising 0.1 to 20 parts by mass of at least one copolymer (B) selected from a polymer (B 2 ) and an MBS resin (B 3 ) is passed through a vacuum hopper. An extrusion process method for supplying to an extruder ,
The mixed vinylidene chloride resin (A) is 50% by mass or more of a vinylidene chloride copolymer (A 1 ) having a reduced viscosity of 0.048 or more and less than 50% by mass of a vinylidene chloride copolymer (A 2 ) having a reduced viscosity of less than 0.048. (However, the total of both is 100 mass%) .
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12702995 | 1995-04-27 | ||
| JP12703095 | 1995-04-27 | ||
| PCT/JP1996/001118 WO1996034050A1 (en) | 1995-04-27 | 1996-04-25 | Vinylidene chloride copolymer resin composition, film produced therefrom, extrusion process for the composition, and process for producing the film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP3931994B2 true JP3931994B2 (en) | 2007-06-20 |
Family
ID=26463073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53235596A Expired - Fee Related JP3931994B2 (en) | 1995-04-27 | 1996-04-25 | Vinylidene chloride copolymer-containing resin composition, film thereof, extrusion process thereof, and production method of the film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3931994B2 (en) |
| KR (1) | KR100427629B1 (en) |
| CN (4) | CN100410317C (en) |
| WO (1) | WO1996034050A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2818485A1 (en) * | 2012-02-23 | 2014-12-31 | Asahi Kasei Chemicals Corporation | Vinylidene chloride copolymer latex and film for blister pack |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3999880B2 (en) * | 1997-06-20 | 2007-10-31 | 株式会社クレハ | Vinylidene chloride copolymer resin composition, film thereof, extrusion method thereof |
| JP4861223B2 (en) * | 2001-05-09 | 2012-01-25 | 株式会社クレハ | Polyvinylidene chloride resin composition Coloring resin composition |
| KR100591221B1 (en) * | 2001-07-13 | 2006-06-19 | 아사히 가세이 가부시키가이샤 | Vinylidene Chloride Copolymer Particles and Compositions Comprising the Same, and Films and Sheets Obtained from them |
| FR2905378B1 (en) * | 2006-09-05 | 2009-04-17 | Solvay | COMPOSITION OF AT LEAST ONE VINYLIDENE CHLORIDE POLYMER. |
| JP2008063418A (en) * | 2006-09-06 | 2008-03-21 | Asahi Kasei Chemicals Corp | Composition for coloring vinylidene chloride resin and its manufacturing method |
| CN102443231B (en) * | 2011-11-07 | 2014-07-02 | 中国科学院宁波材料技术与工程研究所 | Manufacturing method of PVDC film with crystal point eliminated and barrier property improved |
| JP6999384B2 (en) * | 2017-11-30 | 2022-01-18 | 株式会社クレハ | Vinylidene chloride-based resin film, packed packaging using it, and its manufacturing method |
| JP6577068B2 (en) * | 2018-01-30 | 2019-09-18 | ダイセルバリューコーティング株式会社 | Gas barrier film and method for producing the same |
| CN114044995A (en) * | 2021-12-01 | 2022-02-15 | 郑州新生印务有限公司 | PVDC high-barrier substrate film and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1139513A (en) * | 1979-01-03 | 1983-01-18 | Theodore Churma | Polyvinylidene chloride and ethylene vinyl acetate film and method for making the same |
| JPS55108492A (en) * | 1979-02-14 | 1980-08-20 | Yasutake Kamiezu | Liquid fuel |
| JP2528399B2 (en) * | 1991-07-26 | 1996-08-28 | 呉羽化学工業株式会社 | Resin film or sheet with excellent heat sealability |
| CN1042440C (en) * | 1993-03-05 | 1999-03-10 | 旭化成工业株式会社 | Vinylidene chloride copolymer resin composition and monolayer film |
-
1996
- 1996-04-25 JP JP53235596A patent/JP3931994B2/en not_active Expired - Fee Related
- 1996-04-25 WO PCT/JP1996/001118 patent/WO1996034050A1/en active IP Right Grant
- 1996-04-25 KR KR1019970707494A patent/KR100427629B1/en not_active IP Right Cessation
- 1996-04-25 CN CNB021079137A patent/CN100410317C/en not_active Expired - Lifetime
- 1996-04-25 CN CN96193539A patent/CN1126789C/en not_active Expired - Lifetime
-
2002
- 2002-03-22 CN CNB021079145A patent/CN1172783C/en not_active Expired - Lifetime
- 2002-03-22 CN CNB021079153A patent/CN1172784C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2818485A1 (en) * | 2012-02-23 | 2014-12-31 | Asahi Kasei Chemicals Corporation | Vinylidene chloride copolymer latex and film for blister pack |
| EP2818485A4 (en) * | 2012-02-23 | 2015-01-21 | Asahi Kasei Chemicals Corp | Vinylidene chloride copolymer latex and film for blister pack |
| US9884931B2 (en) | 2012-02-23 | 2018-02-06 | Asahi Kasei Chemicals Corporation | Vinylidene chloride copolymer latex and film for blister pack |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996034050A1 (en) | 1996-10-31 |
| CN1375518A (en) | 2002-10-23 |
| CN1172784C (en) | 2004-10-27 |
| CN1375388A (en) | 2002-10-23 |
| KR100427629B1 (en) | 2004-07-19 |
| CN1172783C (en) | 2004-10-27 |
| CN1375389A (en) | 2002-10-23 |
| CN100410317C (en) | 2008-08-13 |
| CN1126789C (en) | 2003-11-05 |
| CN1183111A (en) | 1998-05-27 |
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