CN102321320A - Vinylidene chloride copolymer resin composition and film thereof and extrusion processing method - Google Patents
Vinylidene chloride copolymer resin composition and film thereof and extrusion processing method Download PDFInfo
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- CN102321320A CN102321320A CN2011101886603A CN201110188660A CN102321320A CN 102321320 A CN102321320 A CN 102321320A CN 2011101886603 A CN2011101886603 A CN 2011101886603A CN 201110188660 A CN201110188660 A CN 201110188660A CN 102321320 A CN102321320 A CN 102321320A
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- Prior art keywords
- vinylidene chloride
- chloride copolymer
- film
- copolymer
- vinylidene
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- 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 title claims abstract description 27
- 239000011342 resin composition Substances 0.000 title abstract description 6
- 238000001125 extrusion Methods 0.000 title abstract description 5
- 229920006026 co-polymeric resin Polymers 0.000 title abstract 2
- 238000003672 processing method Methods 0.000 title abstract 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 101
- 238000009835 boiling Methods 0.000 abstract description 23
- 230000004888 barrier function Effects 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 41
- 239000011347 resin Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 30
- 239000000654 additive Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 19
- 230000000996 additive effect Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 12
- -1 compound vinylidene chloride Chemical class 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000005033 polyvinylidene chloride Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000010557 suspension polymerization reaction Methods 0.000 description 7
- 239000004902 Softening Agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000013580 sausages Nutrition 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 229920006163 vinyl copolymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-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
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-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
- 239000005977 Ethylene Substances 0.000 description 1
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 description 1
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013475 authorization Methods 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
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000029087 digestion 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating 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
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 235000009566 rice 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
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
A vinylidene chloride copolymer resin composition having excellent extrusion processability when in film formation and capable of manufacturing a film having excellent gas barrier property, tightness and boiling resistance is provided. The resin composition is composed of (by weight) more than 50% of vinylidene chloride copolymer(I) and less than 50% of vinylidene chloride copolymer(II), the reduced viscosity of the vinylidene chloride copolymer(I) is between 0.048 and 0.075, the reduced viscosity of the vinylidene chloride copolymer(II) is between 0.048 and 0.060, and the reduced viscosity of the vinylidene chloride copolymer(I) is greater than the reduced viscosity of the vinylidene chloride copolymer(II). The invention also relates to a film made of the resin composition and an extrusion processing method characterized by using an extruder with a vacuum hopper to extrude the resin composition.
Description
The application be the application number submitted on June 19th, 1998 be 98114995.2, name is called the dividing an application of Chinese invention patent application of " vinylidene copolymer compsns and film thereof and extruding process thereof ".
The present invention relates to contain resin combination and the extruding process thereof thereof of vinylidene chloride copolymer and the film that forms thus.More particularly, the present invention relates to contain resin combination and the extruding process thereof thereof of at least two kinds of vinylidene chloride copolymers with different reducing viscosities and the film that forms thus.Said resin combination has the excellent processing characteristics of extruding when processing film, the film that makes thus has excellent stopping property, boiling resistance and gas barrier property.
Generally speaking, therefore the vinylidene chloride based copolymer, is used as used for packing foods film etc. owing to have the characteristic of gases such as excellent obstruct water vapour and oxygen.Yet, the poor heat stability of common vinylidene chloride based copolymer self, be prone to thermolysis, therefore, extrude and add the instability in man-hour, be difficult to obtain bringing into play the film for packaging of its characteristic.For this reason, up to now, existing various modification methods propose.
Yet; The method of extruding processibility as the improvement vinylidene chloride copolymer; Simple method of mixing such as resin and additive was tended to reduce to other characteristics such as the desired stopping property of film, boiling resistance and gas barrier properties in the past; Therefore, press for a kind of vinylidene chloride resin that has these characteristics evenly.
As the improved means of the resin extruded processibility of vinylidene chloride copolymer, the method that suppresses heating during extrusion resin obtains adopting.For this reason, for example can consider to reduce the polymerization degree of resin or use additive in a large number.Yet, if reduce the polymerization degree of resin, PVDC (abbreviation of vinylidene chloride copolymer) self embrittlement, stopping property and boiling resistance descend.On the other hand, if increase the polymerization degree of resin, use additive in a large number, then gas barrier property descends.
In addition; Have the technology of the vinylidene chloride based copolymer of different molecular weight as use, disclosed in the open communique of Japanese Patent nineteen ninety-five No. 179703 by molecular weight at the vinylidene chloride acrylic copolymer resin compsn A 50,000 or more, below 300,000 and molecular weight more than 0.5 ten thousand but be not more than the compound vinylidene chloride acrylic copolymer resin compsn that any the vinylidene copolymer compsns B in 0.8 times or 80,000 (reducing viscosity is about 0.044) of vinylidene chloride acrylic copolymer resin compsn A forms and reach the unitary film of processing by this compound vinylidene chloride acrylic copolymer resin compsn.And report that said resin combination has excellent shaping processability, said film has excellent gas barrier property etc.In open communique WO96-34050 number of international monopoly; Disclosed a kind of resin combination of being made up of mixing PVDC and other multipolymers (accounting for 0.1-20 quality %) that contains PVDC, said mixing PVDC is made up of at the PVDC below 0.048 at PVDC more than 0.048 and reducing viscosity reducing viscosity.Yet, aspect the stopping property of film and boiling resistance, also need further to improve.
The objective of the invention is to the above-mentioned film that a kind of vinylidene chloride copolymer compsn that can produce the film with excellent stopping property, boiling resistance and gas barrier property and extruding process thereof thereof is provided and obtains thus.
The present inventor finds; The vinylidene chloride copolymer that will have different reducing viscosities mix by specified proportion and vinylidene copolymer compsns have the excellent processibility of extruding, the film that forms thus has excellent stopping property, boiling resistance and gas barrier property.The present inventor also finds, when forming film by this vinylidene copolymer compsns, uses the forcing machine of band vacuum charging bucket, can further improve above-mentioned characteristic.The present invention ties up to and accomplishes on the basis of above-mentioned discovery.
Promptly; First aspect of the present invention is; A kind of vinylidene copolymer compsns with following characteristic is provided: by forming more than vinylidene chloride copolymer (I) the 50 quality % and below vinylidene chloride copolymer (II) the 50 quality %; The reducing viscosity of vinylidene chloride copolymer (I) is between greater than 0.048 to 0.075; The reducing viscosity of vinylidene chloride copolymer (II) is between 0.048 to 0.060, and the reducing viscosity of vinylidene chloride copolymer (I) big than vinylidene chloride copolymer (II).
Second aspect of the present invention be, provides that to be extruded by the forcing machine of band vacuum charging bucket with above-mentioned vinylidene copolymer compsns be the extruding process thereof of characteristic.
The 3rd aspect of the present invention is the film that the vinylidene copolymer compsns that providing is provided by first aspect of the present invention is processed.
Specify first aspect of the present invention below.
Be easy to get the calmly angle of the multipolymer that can extrude processing of vinylidene chloride copolymer (I) that uses in the present invention and vinylidene chloride copolymer (II) is set out, preferably obtain by suspension polymerization, vinylidene chloride and can be with the multipolymer of at least a ethylenically unsaturated monomers of vinylidene chloride copolymerization.In the multipolymer, the content of ethylenically unsaturated monomers is about 40-2 quality %, and the balance of extruding processibility and gas barrier property when forming film by the gained resin combination preferably is about 35-4 quality %.The example of ethylenically unsaturated monomers has dienes unsaturated monomers such as monoene class unsaturated monomer, divinyl, chloroprene such as vinylchlorid, vinyl-acetic ester, propionate, alkyl acrylate, alkyl methacrylate, vinylformic acid, methylacrylic acid, methylene-succinic acid or its alkyl ester, vinyl cyanide, methacrylonitrile, acrylic amide, vinyl alkyl ethers, vinyl alkyl ketone, propenal, allyl ester and ether, vinylbenzene.Vinylidene chloride copolymer (I) and (II) can be, but preferred copolymer with the multipolymer more than the ternary that copolymerization forms more than two kinds of these ethylenically unsaturated monomers.In the above-mentioned ethylenically unsaturated monomers; The carbonatoms of preferred vinylchlorid, alkyl is 1-8 alkyl acrylate and an alkyl methacrylate; For example methyl acrylate, ethyl propenoate and TEB 3K, vinylchlorid is preferred especially owing to be prone to obtain the balance extruded between processibility and the gas barrier property.
The reducing viscosity scope of above-mentioned vinylidene chloride copolymer (I) is preferably between greater than 0.048 to 0.065 between greater than 0.048 to 0.075, is more preferably between greater than 0.055 to 0.065.If the reducing viscosity of vinylidene chloride copolymer (I) greater than 0.075, then is prone to produce resin resolvent etc., extrude the processibility variation.At this moment, extrude processibility, additives such as aqueous softening agent of the heavy addition of having to and stablizer for improvement.The aqueous additive of heavy addition can make the gas barrier property of gained film descend, and bleeding of additive also can make film become easy and adhere to.The amount of aqueous additive in resin combination of the present invention should be at most 7 mass parts.And if the reducing viscosity of vinylidene chloride copolymer (I) less than 0.048, though it is good then to extrude processibility, the decline of stretch process property is difficult to obtain the stable film of thickness.Fusion flexibility decrease when in the digestion process of making packed sausage, carrying out the high frequency sealing causes that when filling the bag breaks, the stopping property variation.In addition, when cooking disinfection, the tensile strength of hermetic unit (thermotolerance) descends, and can cause also that sometimes problems such as bag breaks take place hermetic unit.
The reducing viscosity scope of vinylidene chloride copolymer (II) is between greater than 0.048 to 0.060; From the angle of extruding processibility of stopping property, boiling resistance and the vinylidene copolymer compsns of film, be preferably in greater than 0.048 to less than between 0.055.Vinylidene chloride copolymer (II) suppresses the resin heating when extruding, reduce the resin resolvent at the outlet of extruder place adheres to die head, reduces forcing machine motor load fluctuation etc. and extrude the improvement of processibility and have contribution; But less than 0.048, then stopping property, boiling resistance descend as if reducing viscosity.When the reducing viscosity of vinylidene chloride copolymer (II) is in above-mentioned 0.048 to 0.060 scope; For making stopping property and boiling resistance satisfactory to both parties; The mixture ratio of vinylidene chloride copolymer (II) is preferably below the 50 quality % that account for the vinylidene chloride copolymer total amount; Be more preferably and account for 3-25 quality %, preferably account for 5-25 quality %.
As stated, with vinylidene chloride copolymer (I) and (II) resin combination of the present invention that mixes of these two kinds of higher and approaching vinylidene chloride copolymers of reducing viscosity innerly be prone to fusion equably at forcing machine, can reduce generation the disadvantageous not melts of formed film quality etc.
In addition, preferably the ratio of vinylidene chloride component is bigger than the ratio of the middle vinylidene chloride component of vinylidene chloride copolymer (II) in the vinylidene chloride copolymer (I), and this is favourable to stopping property, boiling resistance.
Have again; For making vinylidene chloride copolymer (I) and (II) be prone to fusion equably and reduce by to the disadvantageous resin resolvent of formed film quality, the not flake generation that generates such as melts in that forcing machine is inner, the vinylidene chloride copolymer (I) and (II) copolymer composition of same kind preferably.Consider vinylidene chloride copolymer (I) and (II) preferably be respectively the copolymer of vinylidene chloride and vinylchlorid from the even fused angle of resin.
Vinylidene chloride copolymer (I) and (II) also can form by the mixture of vinylidene chloride copolymer more than two kinds respectively.At this moment; The reducing viscosity of each multipolymer that constitutes vinylidene chloride copolymer (I) is between greater than 0.048 to 0.075; Likewise, the reducing viscosity of each multipolymer of formation vinylidene chloride copolymer (II) must be than the little of each multipolymer that constitutes vinylidene chloride copolymer (I) and between 0.048 to 0.060.The reducing viscosity of its reason and above-mentioned vinylidene chloride copolymer (II) is if identical when departing from above-mentioned scope.
Except that vinylidene chloride copolymer, the example that can be added on other polymkeric substance in the resin combination of the present invention has the vinyl copolymer and the MBS resin of multipolymer, ethene and the vinylformic acid of ethene and vinyl-acetic ester, methylacrylic acid or their alkyl ester (especially carbonatoms is the alkyl ester of 1-4).Wherein, the ethylene content of preferred vinyl copolymer is 55-80 quality %, the MI (melt index) that recorded by JIS K-6730 is 5-40g/10 minute multipolymer.Add these multipolymers, can reduce sealing bag and when boiling, break, but its addition preferably accounts for below the 2.5 quality % of vinylidene chloride copolymer total amount.If surpass 2.5 quality %, hermetic unit is prone to produce to be peeled off.
Above-mentioned MBS resin is record in the Japanese Patent authorization communique 1971 No. 19550, with dienite or with the divinyl be base, in itself and vinylbenzene, methacrylic ester, vinyl cyanide, the vinylidene chloride any individually or the multipolymer of their mixture arbitrarily; Its example comprises the BTA-IV SS that Kureha Kagaku Kogyo K.K. produces etc.; BTA-IV SS is through in the latex that contains 50-80 parts by weight of rubber composition, adding any or their mixture arbitrarily in TEB 3K, vinylbenzene, the vinylidene chloride, can obtain with polymerization in the presence of the linking agent of these monomer copolymerizations at the 0.01-5 weight part.
In vinylidene copolymer compsns of the present invention, can mix additives such as known softening agent, thermo-stabilizer, processing aid, photostabilizer, pigment, lubricant, inhibitor, filler, tensio-active agent.Specifically; The example of aqueous softening agent has DOP, tributyl acetylcitrate, diacetyl direactive glyceride, Uniflex DBS, dioctyl sebacate and diisobutyl adipate etc.; The example of aqueous stablizer has epoxidized oils such as epoxidised soybean oil, epoxidised linseed oil and resin etc.; In addition; Also can enumerate the compound with softening agent, thermo-stabilizer, processing aid, lubricant of the wax class such as amide derivatives, Marinco H, TSPP, Natural manganese dioxide and calcium phosphate powder, polyethylene oxide, paraffin, polyethylene wax, montanin wax of alkyl ester; Also can enumerate various additives, like tensio-active agents such as fillers such as silicon oxide, lime carbonate and sorbitan fatty acid esters class, polyoxyethylene sorbitan fatty acid esters class etc.Though titanium oxide based pigment has the effect that the ultraviolet ray of preventing makes food contents variable colors such as sausage, be prone to cause that the resin resolvent adheres at the forcing machine spout.Yet, if extrude, can reduce this resin resolvent effectively with the forcing machine of band loading hopper, therefore, the addition of titanium oxide based pigment can be as big as the 0.10-10 mass parts.
In above-mentioned additive, the addition of aqueous softening agent and stablizer accounts for about 1-10 quality % of vinylidene chloride copolymer total amount, accounts for 4-7 quality % preferably.The part of these additives also can be added in vinylidene chloride copolymer (I) or polymerization process (II).Additive by vinylidene chloride copolymer absorption or absorption, produces contribution to extruding processibility when extruding.Additive beyond aqueous softening agent and the thermo-stabilizer can use as required.
Blending means to vinylidene chloride copolymer (I), (II) and additive does not have special qualification, can use method in the past.For example, available turbine mixer or Henschel mixer mix, and perhaps employing surpasses 60 ℃ heating hybrid mode or the low-temperature mixed mode below 60 ℃.
The vinylidene copolymer compsns that obtains through mixing can be directly with powder or extrude processing granulating plate shape, be used for the shaping of film.
Can the recovery crushed material (regenerating resin) of vinylidene chloride copolymer be mixed with powder, the grain sheet of vinylidene chloride copolymer, recycle.The crushed material of this moment vinylidene chloride copolymer (I) and (II) in the total amount the shared ratio of sneaking into be 1-50 quality %, be about 1-30 quality % preferably.When extruding after regenerating resin sneaked into, if extrude with the forcing machine of band loading hopper, can suppress coloring resin and take place with decomposing, therefore, extruding process thereof of the present invention is useful.
Vinylidene copolymer compsns of the present invention is through melt extruding, and is configured as drawn or unstretched film, sheet etc.Manufacturing process is well known to a person skilled in the art, the method for for example useful annular die head blow molding etc.Because the film of crossing through the orientation that obtains of stretching (especially Biaxially stretched) has heat-shrinkable, therefore, but be suitable as the thermotolerance film of shrinkable films or boiling.Biaxially stretchedly be preferably 2.0-4.5 than in the vertical doubly, be preferably 3.0-5.0 in the horizontal doubly.The thickness of film (unitary film) is the 5-30 micron, is preferably the 10-25 micron.According to purposes, also can be used as duplicature and use.Usually, percent thermal shrinkage is in length and breadth to all being about 30-60% (120 ℃ of glycerol baths, 3 minutes).During as food product pack, main method of use is: after film is blow molded into tubular membrane, with its flattening; Make to be overlapped into duplicature substantially, the surplus limit part of film both sides is cut the shape form flat film; Process round shape with wrapping machine then and seal; Then the filling content is clamped two ends, obtains packing material thus.In addition, the condition of cooking disinfection has various, generally to the sausage sterilization time, though look the diameter of packing material and different, roughly carries out 10-20 minute at 120 ℃.Also has the film lamination that also can the resin of film of the present invention and same kind or other resins that can process with the vinylidene chloride copolymer coextrusion or resin combination be processed.
Second aspect of the present invention relates to the extruding process thereof of vinylidene copolymer compsns.That is, the method is characterized in that, add man-hour in that vinylidene copolymer compsns is extruded, this resin combination is to extrude with the forcing machine of band vacuum charging bucket, can improve thus and extrude processibility.That is,, can reduce the outflow of coloring resin and resolvent etc. through extruding with the forcing machine of band vacuum charging bucket, and the breaking etc. of film body can reduce blow molding the time.The vacuum tightness of vacuum charging bucket is preferably in-600mm is between-the 755mm below mercury column-500mm.Forcing machine with setting vacuum charging bucket with this understanding is housed is extruded this resin combination, can improve and extrude processibility.
As stated, if use titanium oxide based pigment, the adhesion of resin resolvent on the die head in exit can increase, but in the present invention, owing to used vacuum hopper, therefore, the adhesion of resin resolvent has reduced.Thus, when using titanium oxide based pigment, extruding process thereof of the present invention is useful.
The film that the vinylidene copolymer compsns that the 3rd aspect of the present invention relates to be provided by first aspect of the present invention is processed is preferably the film of processing with the extruding process thereof of above-mentioned second aspect of the present invention.About this film, of the present invention aspect first in related explanation, can above-mentioned vinylidene copolymer compsns be configured in the gas barrier layer, process multilayer film, sheet with coetrusion or laminating.
Below in conjunction with embodiment the present invention is specified, but the present invention does not receive the restriction of these embodiment.
Measuring method
Reducing viscosity: vinylidene chloride copolymer 1g is joined in the 50ml THF,, after the filtration, polymkeric substance is separated out, washing, drying with methyl alcohol 40 ℃ of dissolvings.Accurately take by weighing this exsiccant polymkeric substance 80mg, add 30 ℃ pimelinketone 20ml as solvent, 70 ℃ of heating for dissolving 60 minutes, be cooled to room temperature after, use filter paper filtering, the sample solution that filtrating is used as the mensuration soltion viscosity.Sample solution 5ml is joined in the Ubbelohde viscometer, in 30 ℃ thermostatic bath, places after 5 minutes, measure with common methodology and flow down required number in second, obtain reducing viscosity by following formula:
Reducing viscosity=(1/4) * ((T
2/ T
1)-1)
T
1: 30 ℃ pimelinketone (solvent) flows down required number in second
T
2: 30 ℃ sample solution flows down required number in second
Oxygen permeability: under 30 ℃, the condition of 100% relative humidity, measure with oxygen permeability determinator (Modern Control Company products, Ox-tran 2/20).Unit is centimetre
3/ rice
2Day normal atmosphere is measured with duplicature (total thickness is 40 microns).
Extrude processibility: using light projector irradiation total thickness is that 40 microns, width are 1250 millimeters moving film (duplicature); With receiver the shade of light is made a video recording; After the signal processing, size in the film of 1500 meters length is checked for the foreign matter of 0.5mm * 0.5mm with the optical profile type defect detecting device (Futec Company products) that detects foreign matter.Measure the result with below zero: 30, △: 31-100 is individual, *: represent more than 101.
Sealing is broken (stopping property a kind of) during boiling: will be cut into and widely supply with automatic filling apparatus for ligating (the Wu Yu KAP500 type that part, high frequency hermetic unit, automatic pack portion, ligation partly are integrated for the duplicature of 70mm places film; Kureha Kagaku Kogyo K.K.'s product) on; Carry out central authorities' sealing with the high frequency Sealing Method, obtain cylindrical membrane.Filling is clamped two ends as filling meat (sausage ingredient) 50g of charges with metal wire in the gained cylindrical membrane, obtains packaged product.
100 of packaged products are arranged on the dish, put in boiler's formula jar (RCS-60/10 TG, day slope make Co., Ltd. of institute product), 133 ℃ of boilings of sterilization temperature 15 minutes.Then, put into water coolant and cool off, obtain the packaged product that boiling was handled.
Check each packaged product, the statistics hermetic unit has disruptive number (root).Evaluation result is with zero: break the number below 5, △: break the number for the 6-10 root, *: break the number representing more than 11.
T shape sealing stripping strength (stopping property a kind of): will handle 15 minutes 120 ℃ of boilings with the same packaged product that is used to seal bursting test, and after the cooling, obtain the packaged product that boiling was handled.At random choose the packaged product that 1 boiling was handled, choose 10 places, pinch sealed edge, peel off, the intensity of inspection hermetic unit with finger along the whole hermetic unit of packaged product length direction.Evaluation result is with zero: do not shell, *: partly peel off easily and represent.
Embodiment 1
Vinylidene chloride (VD)-vinylchlorid (VC) multipolymer at reducing viscosity 0.056 (is made by suspension polymerization; VD/VC mass ratio=88/12) vinylidene chloride-vinyl chloride copolymer of (to call PVDC1 in the following text) 87 quality %, reducing viscosity 0.052 (is made by suspension polymerization; VD/VC mass ratio=82/18) add in mixture 100 mass parts of (to call PVDC2 in the following text) 13 quality % be altogether 6 mass parts as the epoxidised linseed oil of additive and Uniflex DBS, be the additive that comprises inhibitor, lubricant and red pigment of 1.7 mass parts altogether; Mix, make mixture (vinylidene copolymer compsns).Then, use the forcing machine (vacuum pressure is adjusted to-the 680mm mercury column) of the diameter 90mm of band vacuum charging bucket that mixture is melt extruded circlewise, with well-established law extrudate is cooled off in 10 ℃ cooling tank then; Make its warm water bath that passes through 20 ℃, between the different nip rolls of 2 groups of surface of revolution speed, be pressed into air, make extrudate swelling; Then; Orientation stretching stretches 2.8 times it on length, on width, stretch 3.7 times.The gained film is an individual layer, and thickness is 20 microns.
The sealing during through degree, boiling of foreign matter number in the inspection gained film, oxygen break degree, sealing T stripping strength.The result sees table 1.
Embodiment 2
Except that the Zerol that has added as other additives, all the other are identical with embodiment 1.Powder drops to the forcing machine from the vacuum charging bucket swimmingly, the steady load of forcing machine.
Embodiment 3
Added with the same additive of embodiment 1 after; Mix, cool off; And then add MI (melt index)=15, vinyl acetate content is the vinyl-vinyl acetate copolymer (claiming EVA-1) (mass ratio of EVA-1 and vinylidene chloride copolymer total amount is 1: 100) of 25 quality %; 30 ℃ of mixing, make mixture (vinylidene copolymer compsns).Likewise this mixture is extruded with embodiment 1, obtained the film of embodiment 3.
Embodiment 4-5
Except that vinylidene chloride (VD)-vinylchlorid (VC) multipolymer of the raw material that uses as reducing viscosity 0.063 (made by suspension polymerization; VD/VC mass ratio=88/12) vinylidene chloride-vinyl chloride copolymer of (to call PVDC3 in the following text) 80 quality %, reducing viscosity 0.050 (is made by suspension polymerization; VD/VC mass ratio=88/12) outside the mixture of (to call PVDC6 in the following text) 20 quality %; Make the film of embodiment 4 by the method for embodiment 1, make the film of embodiment 5 by the method for embodiment 3.
Comparative example 1
Except that the usage quantity of only using PVDC3 as resin Composition, additive is 9 mass parts, make the film of comparative example 1 by the method for embodiment 1.The result shows shown in the table 1, and the foreign matter number increases in the film, and in addition, resistance oxygen property has also descended.
Comparative example 2
Removing has used the vinylidene chloride-vinyl chloride copolymer of reducing viscosity 0.058 (to be made by suspension polymerization; VD/VC mass ratio=88/12) vinylidene chloride-vinyl chloride copolymer of (to call PVDC5 in the following text) 96 quality % and reducing viscosity 0.040 (is made by suspension polymerization; VD/VC mass ratio=83/17) total mass ratio of the usage quantity of (to call PVDC4 in the following text) 4 quality %, additive and vinylidene chloride copolymer is outside 6.8: 100, makes the film of comparative example 2 by the method for embodiment 1.The result shows shown in the table 1, occurs sealing during boiling and breaks and hinder the decline of oxygen property.
Comparative example 3
Except that the PVDC4 of PVDC3 that uses 85 quality % and 15 quality % and to have used the mass ratio as the total amount of the EVA-1 of other multipolymers and additive, EVA-1 and additive and vinylidene chloride copolymer be 3: 5.5: 100, make the film of comparative example 3 by the method for embodiment 1.The result shows shown in the table 1, and the foreign matter number increases in the film, and in addition, sealing T stripping strength has also descended.
Embodiment 6 and 7
Added with the same additive of embodiment 1 after; Cooling; (mass ratio of EVA-2 and vinylidene chloride copolymer total amount is 1.5 (embodiment 6) and 2.5 (embodiment 7): 100) to sneak into MI (melt index)=30, vinyl acetate content more respectively and be the vinyl-vinyl acetate copolymer (claiming EVA-2) of 33 quality %; 30 ℃ of mixing, make mixture (vinylidene copolymer compsns).Likewise this mixture is extruded with embodiment 1, obtained the film of embodiment 6 and 7.
Table 1
*1: zero expression " use " loading hopper
*2: the oxygen perviousness before the boiling
*3: the interpolation mass parts in PVDC multipolymer total amount 100 mass parts
According to the present invention, can obtain to make the vinylidene copolymer compsns of the film of extruding excellent in workability and gas barrier property, stopping property and boiling resistance acquisition optimum balance.In addition, adopt the extrusion method of extruding above-mentioned vinylidene copolymer compsns with the forcing machine of band vacuum charging bucket, can further improve these characteristics.
Claims (4)
1. vinylidene copolymer compsns; It is characterized in that; Form by vinylidene chloride copolymer (I) 75-97 quality % and vinylidene chloride copolymer (II) 3-25 quality %; The reducing viscosity of vinylidene chloride copolymer (I) is 0.055-0.065, the reducing viscosity of vinylidene chloride copolymer (II) be 0.048-less than 0.060, and the reducing viscosity of vinylidene chloride copolymer (I) big than vinylidene chloride copolymer (II).
2. vinylidene copolymer compsns as claimed in claim 1, its characteristic are that also the ratio of vinylidene chloride component is bigger than the ratio of the middle vinylidene chloride component of vinylidene chloride copolymer (II) in the vinylidene chloride copolymer (I).
3. vinylidene copolymer compsns as claimed in claim 1, its characteristic are that also the amount of vinylidene chloride copolymer (I) is 75-95 quality %, and the amount of vinylidene chloride copolymer (II) is 5-25 quality %.
4. film is characterized in that, is processed by each described vinylidene copolymer compsns among the claim 1-3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18077097 | 1997-06-20 | ||
| JP180770/97 | 1997-06-20 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98114995 Division CN1205348A (en) | 1997-06-20 | 1998-06-19 | Vinylidene copolymer compsns., its film and extruding process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102321320A true CN102321320A (en) | 2012-01-18 |
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ID=45449166
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101886603A Pending CN102321320A (en) | 1997-06-20 | 1998-06-19 | Vinylidene chloride copolymer resin composition and film thereof and extrusion processing method |
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|---|---|---|---|---|
| CN110248998A (en) * | 2017-05-16 | 2019-09-17 | 株式会社吴羽 | Vinylidene chloride resin film and Permalon composition |
-
1998
- 1998-06-16 KR KR1019980022505A patent/KR19990007022A/en not_active Application Discontinuation
- 1998-06-19 CN CN2011101886603A patent/CN102321320A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110248998A (en) * | 2017-05-16 | 2019-09-17 | 株式会社吴羽 | Vinylidene chloride resin film and Permalon composition |
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