CN1249154C - Composition of vinylidene chloride copolymer particles - Google Patents
Composition of vinylidene chloride copolymer particles Download PDFInfo
- Publication number
- CN1249154C CN1249154C CNB028083601A CN02808360A CN1249154C CN 1249154 C CN1249154 C CN 1249154C CN B028083601 A CNB028083601 A CN B028083601A CN 02808360 A CN02808360 A CN 02808360A CN 1249154 C CN1249154 C CN 1249154C
- Authority
- CN
- China
- Prior art keywords
- vinylidene chloride
- weight
- chloride copolymer
- particle
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 title claims abstract description 134
- 229920001577 copolymer Polymers 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 150000002148 esters Chemical class 0.000 claims abstract description 32
- -1 2-EHA Chemical compound 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 36
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 28
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 28
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 230000005484 gravity Effects 0.000 claims description 15
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 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 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 81
- 238000006116 polymerization reaction Methods 0.000 description 49
- 239000003795 chemical substances by application Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 239000000725 suspension Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 238000005502 peroxidation Methods 0.000 description 19
- 230000008859 change Effects 0.000 description 18
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 238000010557 suspension polymerization reaction Methods 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 13
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000004902 Softening Agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000000944 linseed oil Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical class ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical group CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 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
- 235000021388 linseed oil Nutrition 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- MOOYVEVEDVVKGD-UHFFFAOYSA-N oxaldehydic acid;hydrate Chemical compound O.OC(=O)C=O MOOYVEVEDVVKGD-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical group CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- WSTQBYXHFIDCEQ-UHFFFAOYSA-N C(OC(C)(C)C)(OC(C)(C)C)=O.C(C(=O)O)(=O)O Chemical compound C(OC(C)(C)C)(OC(C)(C)C)=O.C(C(=O)O)(=O)O WSTQBYXHFIDCEQ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-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
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 239000012861 aquazol Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IAWYWVVBKGWUEP-UHFFFAOYSA-N benzyl phenylmethoxycarbonyloxy carbonate Chemical compound C=1C=CC=CC=1COC(=O)OOC(=O)OCC1=CC=CC=C1 IAWYWVVBKGWUEP-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 235000019820 disodium diphosphate Nutrition 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- 229940038485 disodium pyrophosphate Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229920002521 macromolecule 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
- 235000012254 magnesium hydroxide Nutrition 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
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 1
- WCJQKTUPBIICNI-UHFFFAOYSA-N octoxycarbonyloxyperoxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOOOC(=O)OCCCCCCCC WCJQKTUPBIICNI-UHFFFAOYSA-N 0.000 description 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- IOTAYCLTDJEUCF-UHFFFAOYSA-N pentyl 2,2-dimethylpropanoate Chemical compound CCCCCOC(=O)C(C)(C)C IOTAYCLTDJEUCF-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 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
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- VXHFNALHLRWIIU-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)C VXHFNALHLRWIIU-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 150000003712 vitamin E derivatives Chemical class 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
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
- C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- 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
-
- 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
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A composition of vinylidene chloride copolymer particles which, when extruded into a film or sheet, is capable of being stably extruded evenly and which has improved thermal stability. The vinylidene chloride copolymer particles are characterized by having a weight-average particle diameter of 200 to 500 [micro]m and having a content of particles having a particle diameter smaller than 150 [micro]m of 3 wt.% or lower. The vinylidene chloride copolymer composition is characterized by being obtained by compounding the copolymer particles with an ethylene/vinyl acetate copolymer and an ester of an [alpha],ss-unsaturated carboxylic acid.
Description
Technical field
The film, the thin slice that the present invention relates to the vinylidene chloride copolymer particle composition and adopt said composition to make.
Background technology
Vinylidene chloride copolymer has excellent characteristic aspect the gas barrier property of water vapour or oxygen etc. and oil-proofness, therefore be specially adapted to food packing film.The manufacture method that is used for the vinylidene chloride copolymer of food packing film has suspension polymerization and emulsion polymerization, and owing to there is not the problem of residual emulsifying agent etc. in suspension polymerization, therefore adopts suspension polymerization.Suspension polymerization is a kind of such method: form the blending dispersion oil droplet of vinylidene chloride and polymerisable vinyl monomer by mechanical stirring in containing the water of dispersion agent, after this add polymerization starter and carry out polymerization.
When making food packing film, adopt the vinylidene chloride copolymer that makes in the suspension polymerization mode, and adopt common melt-shaping method to make its stretching, or do not make its stretching, be processed into the single or multiple lift film.
The general vinylidene chloride copolymer that makes in the suspension polymerization mode is the particle shape, and this is known in the public clear 55-18242 communique of spy, special public clear 57-9575 communique etc., but only can obtain size distribution, copolymer particle composition that Bulk Specific Gravity is wide.In addition, the mode that discloses in USP3706722 by combined body polymerization and suspension polymerization makes vinylchlorid and vinylidene resin polymerization, obtains the method for vinylidene analog copolymer particle composition.But in the method can not with stable resin extrude, be difficult to obtain to have the film of homogeneous film thickness.That is, the shape and size of vinylidene chloride copolymer change to make the changing of volume production that is filled into the multipolymer in the cylinder in the mould, influence the output of forcing machine.The pressure of pressure head changes thus, and the result makes the membrane thickness unevenness of extruding.When the film of employing membrane thickness unevenness makes film package, when carrying out the high frequency sealing, because the sealing intensity inequality makes productivity descend easily.For addressing this problem, need in forcing machine, stably provide a certain amount of copolymer particle composition.But the technology that does not still exist concrete effort to work out so far to this problem.
On the other hand, vinylidene chloride copolymer is thermolysis easily in extrusion process, and the carbide that thermolysis produces flows out sometimes, makes gained film generation xanthochromia sometimes.For thermostability is improved, following scheme was proposed in the past.
Improve the method for extruding the thermostability that adds man-hour and improving the cold property of gained film by the multipolymer (being designated hereinafter simply as EVA) that in vinylidene chloride copolymer, cooperates ethene and vinyl acetate ester, being disclosed in the spy opens clear 55-108442 communique (the about 5～about 18 weight % of vinyl acetate ester content cooperates about 5～about 40 weight %'s, melt flow rate (MFR) is the EVA of about 0.1～about 1.0dg/ branch), special public table 3-503290 communique (cooperates about 0.01～about 2 weight %'s, the vinyl acetate ester content is about 28% EVA), special public clear 40-16141 communique (cooperates 2～20 weight %'s, the vinyl acetate ester content is 3～20% EVA), Te Kaiping 1-131268 communique (cooperating the vinyl acetate ester content is the EVA of about 3～about 30 weight %), public again table special permission WO96/34050 be (cooperation 1.5～3 weight parts, the EVA that contains ethene 65～85 weight %) in.But in these methods, can not obtain enough thermostabilitys.
On the other hand, extrude the method for processibility as other improvement, be disclosed in the spy and open clear 53-16753 communique (cooperation contains specific softening temperature, the cinnamic styrenic polymer of melt viscosity or vinylbenzene-methyl methacrylate analog copolymer), specially permit No. 2947931 communique (in vinylidene chloride-methyl acrylate copolymer, adding the methyl methacrylate-butyl acrylate-styrene copolymer of 0.5 weight part at least), No. 3078663 communique of special permission communique (cooperates butyl acrylate, butyl methacrylate and methyl methacrylate derived polymers), Te Kaiping 6-234902 communique (cooperation is no more than the acrylate copolymer of about 4 weight %), Te Kaiping 8-208926 communique (cooperating acrylate/styrol copolymer), Te Kaiping 7-268162 communique (cooperates by the vinylbenzene composition, the styrene copolymer resin that butyl acrylate composition and methyl methacrylate composition constitute) method in.
But,, the characteristic of the food product pack filling machine adaptability that can be obtained by vinylidene chloride copolymer, gas barrier property etc. is descended even by cooperating various multipolymers and additive to satisfy thermostability according to these methods.On the other hand, if the molecular weight of vinylidene chloride copolymer reduces, the physical strength of film will descend.In addition, continuously implementing to extrude to add man-hour, the inner thermal degradation that produces of forcing machine is attached on screw rod and the mould, and the film of gained is exerted an influence, and therefore needs breaks in production, cleans screw rod and mould.Make thus to extrude and produce the time shortening that consumes, productivity descends.
The purpose of this invention is to provide a kind of vinylidene chloride copolymer, it is extruded excellent in stability, and finally can produce the film of film uniformity excellence, and the present invention also provides a kind of thermostability, extrudes the vinylidene resin composition of excellent in stability.
Disclosure of an invention
Inventor of the present invention is when addressing the above problem, if find to adopt and have the specified particle diameter that obtains by suspension polymerization, the particles contained amount vinylidene chloride copolymer composition below certain is a certain amount of, perhaps adopt vinylidene chloride copolymer particle composition, can address this problem preferably with specific Bulk Specific Gravity.In addition, by cooperation ethylene-vinyl acetate ester copolymer in this specified particle composition with by the multipolymer of from α, β esters of unsaturated carboxylic acids monomer, selecting that monomer constitutes more than 2 kinds, form composition, find can further improve and stablize extrudabilityly, finish the present invention thus.
Promptly, the application's main invention is a kind of vinylidene chloride copolymer particle composition, it is characterized by weight average particle diameter in 200～500 mu m ranges, and the particle ratio of particle diameter less than 150 μ m is below the 3 weight %, and a kind of vinylidene chloride copolymer composition, wherein contain the above-mentioned vinylidene chloride copolymer particle compositions of 100 weight parts (A), 0.05～2.95 parts by weight of ethylene-vinyl acetate ester copolymer (B1) and 0.05～2.95 weight part are by from α, the multipolymer (B2) that the monomer more than 2 kinds selected in the β esters of unsaturated carboxylic acids monomer constitutes, and cooperation weight (B1) and cooperation weight sum (B2) are below 3 weight parts.
The optimised form that carries out an invention
Vinylidene chloride copolymer of the present invention is by vinylidene and can obtains with the vinyl monomer copolymerization of this monomer generation copolymerization.
As can with the vinyl monomer of vinylidene generation copolymerization, can enumerate for example vinyl esters of vinylchlorid, vinyl acetate ester, propionate etc.; α, the β unsaturated carboxylate type of methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, Hydroxyethyl acrylate, Propylene glycol monoacrylate, phenyl acrylate, cyclohexyl acrylate, glycidyl acrylate and methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic acid 2-ethylhexyl, hydroxyethyl methylacrylate, Rocryl 410, phenyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate etc.; The olefines of ethene and propylene etc.; The vinyl ethers of methylvinylether, ethyl vinyl ether, lauryl vinyl ether and IVE etc.; Also have methylene-succinic acid, toxilic acid, maleic anhydride, vinyl cyanide, methacrylonitrile, vinylbenzene, vinyl toluene, alpha-methyl styrene, chlorostyrene, chloro vinyl toluene etc. in addition.These polymerisable vinyl monomers can use separately, also can be used in combination of two or more.
Wherein preferred vinylchlorid, methyl acrylate, methyl methacrylate, 2-EHA, vinyl cyanide and vinylbenzene.
The weight average particle diameter of vinylidene chloride copolymer particle composition of the present invention is 200～500 μ m.Be preferably 230～400 μ m, more preferably 250～350 μ m.Extrude load constant by making this particle diameter in this scope, can making, thereby can stably extrude processing.As a result, can obtain uniform thickness.The コ one Le one マ Le チ セ イ ザ one particle assay device TA-II type that size distribution can adopt day machine society of section to make is measured.
In addition, must make the part by weight of the particle of less than 150 μ m is below the 3 weight %.More than 3 weight % when above, it is non-constant to extrude the fusion tension force that adds the needs in man-hour when particles contained, makes the thickness inequality, and more preferably the following particle of 150 μ m is below the 2.5 weight %.
In addition, from can stably supply with the viewpoint of vinylidene chloride copolymer particle composition with constant basis, preferably making Bulk Specific Gravity is 0.80g/cm
3～1.0g/cm
3Be preferably 0.90g/cm
3～0.98g/cm
3Bulk Specific Gravity can be measured according to JIS K-6722.
The optimum condition of particle composition is that weight average particle diameter is that the part by weight of the fine particle of 230～400 μ m, less than 150 μ m is below the 1.5 weight %, and Bulk Specific Gravity is 0.90g/cm
3～0.98g/cm
3
In addition, the weight average molecular weight range of vinylidene chloride copolymer particle composition is 60,000～200,000 preferably, is preferably 70,000～150,000.Further preferably 80,000～130,000.If in above-mentioned scope, be suitable from thermostability, packaging-filling machine adaptability and gas barrier property aspect.Cooperate with arbitrary proportion by the vinylidene chloride copolymer particle composition more than 2 kinds that weight-average molecular weight is different, the weight-average molecular weight of composition also can in above-mentioned scope.Weight-average molecular weight is to adopt the polystyrene conversion weight-average molecular weight of gel permeation chromatography to measure.
The method that obtains vinylidene chloride copolymer particle composition of the present invention is as follows.
At first, make above-mentioned vinylidene and can with the monomer polymerization of its generation copolymerization.The polymerization starter that uses during polymerization can exemplify out as di-isopropyl peroxydicarbonate, dioctyl peroxy dicarbonate, peroxy dicarbonate two lauryls, peroxy dicarbonate two myristins, peroxy dicarbonate two cetyl, the peroxy dicarbonate di tert butyl carbonate, peroxy dicarbonate two (ethoxyethyl group) ester, peroxy dicarbonate two (methoxyl group sec.-propyl) ester, peroxy dicarbonate two (3-methoxyl group butyl) ester, peroxy dicarbonate two (3-methoxyl group-3-methyl butyl) ester, peroxy dicarbonate two (butoxyethyl group) ester, peroxy dicarbonate two (2-isopropoxy ethyl) ester, peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate two (2-isopropoxy ethyl) ester, dibenzyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, the peroxocarbonate class initiator of peroxy dicarbonate di-t-butyl cyclohexyl etc.; New peroxide tert-butyl caprate, the own ester of peroxidation neodecanoic acid uncle, peroxidation neodecanoic acid pentyl ester, peroxidation neodecanoic acid uncle monooctyl ester, peroxidation neodecanoic acid α-sec.-propyl phenyl ester, peroxidation neodecanoic acid 1-cyclohexyl-1-methyl ethyl ester, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation trimethylacetic acid pentyl ester, peroxidation trimethylacetic acid uncle monooctyl ester, the own ester of peroxidation trimethylacetic acid uncle, peroxidation trimethylacetic acid α-sec.-propyl phenyl ester, cross the own ester of oxalic acid (パ one ヘ キ シ Le オ キ サ レ one ト), peroxidation oxalic acid di tert butyl carbonate, acetyl cyclohexyl-sulfonyl peroxide, 1,1,3, the peresters class initiator of 3-tetramethyl butyl peroxidation phenoxyethanoic acid ester etc.; Lauroyl peroxide, peroxidation diisobutyl, peroxidation 2-ethyl hexanoyl, peroxidation 3,5, the peroxidation diacyl class initiator of 5-trimethyl acetyl etc.; The peroxidation Glyoxylic acid hydrate two tertiary alkyl ester class initiators of tertbutyl peroxide, di-t-butyl peroxide, benzoyl peroxide, di-isopropyl peroxydicarbonate, peroxidation tert-butyl isobutyrate, the own ester of peroxidation Glyoxylic acid hydrate uncle etc.; 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 4,4-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-amidine propane) hydrochloride, 2, the azo-initiator of 2 '-azo two (N, N '-dimethylene isobutyl amidine) hydrochloride etc.; The water-soluble peroxide of Potassium Persulphate, ammonium persulphate etc., or to wherein having added amine, the initiator of reductive agents such as sodium bisulfite etc.For making the polymerization rate homogenization, also can be used in combination different polymerization starter of 10 hour transformation period more than 2 kinds.These polymerization starters can directly use, and also it can be made aqueous emulsion, aqeous suspension use.
For the mixed solution of vinylidene and vinyl monomer, the usage quantity of initiator is preferably 100～7000ppm, 500～5000ppm more preferably, further 1000～3000ppm preferably.
Make the vinylidene chloride copolymer polymerization obtain particle composition then
According to the present invention, for obtaining to have the vinylidene chloride copolymer particle composition of specified range Bulk Specific Gravity, preferred suspension polymerization.
As suspension dispersive agent, can enumerate various random copolymerss, graft copolymer and the segmented copolymer of the homopolymer, maleic anhydride vinyl acetate copolymer etc. of Polyvinylpyrolidone (PVP), polyacrylic acid, polyvinyl alcohol, polymethyl vinyl ether, polyacrylamide, polymine, poly-(2-ethyl-2-oxazoline) etc., big synthetic macromolecules such as monomer; The water-soluble cellulose derivative of methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, carboxymethyl cellulose etc.; The natural high molecular substance of starch, gelatin etc. etc.In addition, can in above-mentioned dispersion stabilizer, add auxiliary stabilizer as required.As this auxiliary stabilizer, can enumerate anion surfactant, cats product, nonionogenic tenside, amphoterics and long-chain alcohol etc.Wherein special preferable methyl Mierocrystalline cellulose, hydroxypropylcellulose, hydroxyl propoxy-methylcellulose gum.From the viewpoint of gained particle diameter, the aqueous solution of 0.2 weight % of these stablizers is more than the preferred 5mN/m of the surface tension under 20 ℃, from carrying out the polymeric angle, preferably below the 60mN/m.
From the viewpoint of suspension polymerization stability, the addition of suspension dispersive agent is preferably more than the 30ppm with respect to vinylidene, is preferably below the 8000ppm from the viewpoint of gained particle diameter.100～5000ppm more preferably, further preferred 200～3000ppm.By making it in above-mentioned scope, can produce very effectively and have suspension stability, weight average particle diameter is 200～500 μ m, and the resin combination that reduced of the atomic quantity of particle diameter less than 150 μ m.Suspension dispersive agent can all add once, also can gradation add, to interpolation time of these suspension dispersive agents without limits.
In addition, owing in the polymerization machine and in the corrosion speed of the device of subsequent handling, accelerate, think that the pH value that makes the vinylidene chloride copolymer slurries does not descend to such an extent that adjust the pH value at polymerization initial stage or polymerization too much midway, also can add necessary minimal alkaline matter.
The suspension polymerization of vinylidene is vinylidene, water and the suspension dispersive agent of packing in the polymerization machine and being almost the predetermined amount total amount, and after stirring formation vinylidene drop it is begun.
For polyreaction is carried out well, preferably in reactor, form the atmosphere of nitrogen, argon gas etc.Polymerization temperature, polymerization time can suit to determine according to the kind of kind, amount and the chain-transfer agent of the kind of vinylidene chloride and polymerisable vinyl monomer, amount, polymerization starter, amount etc., but preferably at about 30 ℃ to 90 ℃, make its polymerization 10 hours～100 hours, more preferably 20 hours～60 hours, further preferred 25 hours～50 hours.
In vinylidene chloride copolymer of the present invention, can add the additive that lubricant, gelation improving agent, pH regulator agent, chain-transfer agent, antistatic agent, linking agent, defoamer, stablizer, weighting agent, antioxidant, dirt adhere to inhibitor etc. aptly.These materials can or add after the polymerization in polymerization initial stage, polymerization way.
The stirrer of the polymerizer that suspension polymerization is used is not particularly limited, and also can use dividing plate (バ Star Off Le) as required.In stirrer, can enumerate impeller vane, fan turbine blade, Off ア ウ De ラ one blade and the Block Le one マ one ジ Application blade etc. that when the polyvinyl chloride-base monomer polymerization, use usually, wherein, preferred Off ア ウ De ラ one blade of control size droplet diameter easily that uses.As dividing plate, can enumerate finger type, round tube type, D type and annular etc.
For obtaining the vinylidene chloride copolymer particle of special weight average grain diameter of the present invention, need to adopt suspension agent that surface tension is descended and also keep the balance of stirrer stirring velocity preferably, make the polymer particle sedimentation of generation simultaneously, it is not sticked on reactor and the agitating vane, finish polymerization thus.For this reason, particularly importantly control mechanical agitation condition, by selecting stirring velocity and stirring revolution, make its polymerization when polymer particle is swum specifically.
Usually, be floating state for making polymer particle, stirring velocity is to make high-speed that polymer particle fully swims, but in this case, polymer particle is bearing the shearing force of agitating vane, and the particle diameter of polymkeric substance is diminished.In addition, when the polymkeric substance particle diameter being become reduce stirring velocity greatly, polymkeric substance begins sedimentation, and polymkeric substance also condenses, adheres to, and may all stick in the reactor.Therefore, in order stably to implement polymerization, need avoid adopting low speed rotation in the past, select high speed rotating as much as possible.The result makes polymer particle below 200 μ m.
In the present invention, preventing that this polymkeric substance from the stirring velocity of suspension polymerization taking place to have found stably to implement near the settled boundary, obtains to stablize the polymer particle particle size range of extrudability excellence thus.
For example, under the situation that adopts Off ア ウ De ラ one blade, be 0.7m/s when above with the stirring velocity of following formula (1) expression, can stably implement suspension polymerization, so preferably; When 5.5m/s was following, the particle diameter of resulting polymers is in suitable scope, and was therefore preferred.Actual conditions need change according to the size of the scale of stirring.
Stirring velocity (m/s)=n π d/60 (1)
(n: the revolution of agitating vane (rpm), π: pi, d: the agitating vane exhibition is long)
For example, when agitating vane exhibition length is 400mm φ, under 60～200rpm, be preferably about 1.3～4.2m/s, when the agitating vane diameter is 2000mm φ, under 20～50rpm, be preferably about 2.0～5.3rpm.
For make vinylidene resin particle composition of the present invention to extrude processibility more stable, preferably in the above-mentioned vinylidene resin particle compositions of 100 weight parts (A), further comprise the ethylene-vinyl acetate copolymer (B1) of specified quantitative and by the vinylidene resin particle composition of the multipolymer of from α, β esters of unsaturated carboxylic acids monomer, selecting that monomer constitutes more than 2 kinds (B2).
The ethylene content that is used for ethylene-vinyl acetate copolymer of the present invention (B1) is 60～90 weight %, more preferably in the scope of 70～90 weight %.In order to keep the transparency of formed film, preferably this ethylene content is below the 90 weight %, and from the stability of forcing machine motor load and the gas barrier property of formed film, optimal ethylene content is more than the 60 weight %.
The cooperation ratio of multipolymer (B1) is preferably with respect to 100 weight part vinylidene resin particle compositions (A), in the scope of 0.05～2.95 weight part, is preferably 0.1～2.5 weight part, more preferably in the scope of 0.2～2.0 weight part.When the cooperation ratio of multipolymer (B1) when 2.95 weight parts are following, can improve thermostability and keep gas barrier property.And when the cooperation ratio of multipolymer (B1) when 0.05 weight part is above, have the effusive effect of abundant inhibition resolvent, and thermostability improves also.
The melting index (MI) of multipolymer (B1) from extrude processibility, the gas barrier property aspect is preferably 3～180g/ branch.Be preferably 5～160g/ branch.And weight-average molecular weight is preferably in 30,000～150,000 scope.
Be used for multipolymer of the present invention (B2) multipolymer that the monomer more than 2 kinds selected from α, β esters of unsaturated carboxylic acids monomer constitutes of serving as reasons.As α, β esters of unsaturated carboxylic acids monomer, the alkyl acrylate that preferably has the alkyl of 1～8 carbon atom for example can be enumerated butyl acrylate, propyl acrylate, ethyl propenoate, methyl acrylate, 2-EHA, Hydroxyethyl acrylate, Propylene glycol monoacrylate, phenyl acrylate, cyclohexyl acrylate.Wherein, from extruding the balance of processibility and gas barrier property, more preferably butyl acrylate, ethyl propenoate and methyl acrylate.
In addition as alkyl methacrylate monomer, the alkyl methacrylate that preferably has the alkyl of 1～8 carbon atom for example can be enumerated methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid 2-ethylhexyl, hydroxyethyl methylacrylate, Rocryl 410, phenyl methacrylate, cyclohexyl methacrylate.Wherein, from extruding the balance of processibility and gas barrier property, more preferably methyl methacrylate, Jia Jibingxisuanyizhi and butyl methacrylate.
The multipolymer that α, the monomeric multipolymer of β esters of unsaturated carboxylic acids (B2) can adopt any polymerization process by letex polymerization, suspension polymerization, solution polymerization and mass polymerization etc. to make.Wherein preferred emulsion polymerization.Has the crystal seed polymerization in the emulsion polymerisation process, graft polymerization and multi-stage polymeric etc., but the multipolymer that more preferably obtains by multi-stage polymeric.
The polymerization process of implementing in multi-stage polymeric is after forming core phase (コ ア phase) polymkeric substance, this core mutually in enforcement graft polymerization and polymerization step by step, and form the shell phase successively.
Wherein from making the viewpoint of film, preferably adopting alkyl acrylate so mutually as core, is monomer below 0 ℃ as the second-order transition temperature of polymkeric substance.
Core can be enumerated the product that is obtained by alkyl acrylate monomer or monomer mixture polymerization mutually.Preferably adopt for example butyl acrylate, propyl acrylate, ethyl propenoate, 2-EHA etc.Preferred especially butyl acrylate.
Above-mentioned shell adopts the monomer or the monomer mixture of alkyl methacrylate and alkyl acrylate mutually.Preferably adopt for example methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, butyl acrylate and methyl acrylate etc.Special preferable methyl methyl acrylate.
Core can make up with arbitrary proportion in the scope of 10～90 weight %:90～10 weight % with shell mass ratio mutually mutually, and carries out polymerization, preferred 30～70 weight %:70～30 weight %, more preferably 50～70 weight %:30～50 weight %.
Compare example in above-mentioned scope as shell, can make that multipolymer is uniformly dispersed in the film, and keep the characteristic of shell.
In addition, shell mutually in the ratio of preferable methyl alkyl acrylate be more than the 60 weight %, more preferably more than the 80 weight %.If alkyl methacrylate in above-mentioned scope, then has intermiscibility with vinylidene chloride copolymer, and multipolymer is uniformly dispersed.
The weight-average molecular weight of multipolymer (B2) is preferably 10,000～500,000, and more preferably 30,000～300,000, further preferred 50,000～250,000.
If in above-mentioned scope, be preferred from meltbility, thermostability, the viewpoint uniformly dispersed and sealing intensity of vinylidene chloride copolymer composition.
From extruding the viewpoint of processibility, the cooperation ratio of multipolymer (B2) with respect to 100 weight part vinylidene chloride copolymer compositions (A) preferably in the scope of 0.05～2.95 weight part, preferably at 0.1～2.5 weight part, more preferably in the scope of 0.2～2.0 weight part.The cooperation ratio of multipolymer (B2) is 2.95 weight parts when following, and good thermal stability also keeps gas barrier property simultaneously.And use level is 0.05 weight part when above, can fully suppress resolvent outflow etc., and improve thermostability.
In addition, the summation of the cooperation ratio of the cooperation ratio of above-mentioned multipolymer (B1) and multipolymer (B2) is that 3 weight parts are better when following.Preferably in the scope of 0.2～2.5 weight part, more preferably in the scope of 0.5～2.0 weight part.Use level is 3 weight parts when following, and the balance of thermostability and gas barrier property is good especially.In addition, use level is 0.1 weight part when above, and it is good especially to suppress the effusive effect of resolvent, and thermostability is also high.
The additive that in the vinylidene chloride copolymer particle composition that obtains by the present invention, can further comprise known softening agent, thermo-stabilizer, processing aid, photostabilizer, pigment, lubricant, antioxidant, filler, tensio-active agent etc.
For example, can enumerate adjacent dioctyl phthalate dioctyl ester, tributyl acetylcitrate, Uniflex DBS, the softening agent of dioctyl sebacate and diisobutyl adipate etc., or the polyester softening agent that forms by saturated aliphatic dicarboxylic acids and polyvalent alcohol, epoxidised soybean oil, epoxy linseed oil, the epoxidation octyl stearate, the epoxies stablizer that contains the resin etc. of epoxy group(ing), the amide derivatives of alkyl ester etc., polyoxyethylene, paraffin, polyethylene wax, the wax class of montanic acid ester type waxes etc., the fatty acid ester of monoglyceride etc., the lubricant of the list of lipid acid or diamide etc.: sorbitan fatty(acid)ester, polyglycerol fatty acid ester, the softening agent of the nonionic class tensio-active agent of polyoxyethylene sorbitan fatty acid ester etc. etc. etc.
The cooperation ratio of above-mentioned additive is preferably about 0.01～about 10 weight parts, more preferably 0.05～6 weight part with respect to 100 weight part vinylidene chloride copolymer particle compositions.
In addition, can enumerate the vitamin-E class, citric acid and its esters, magnesium hydroxide, trisodium phosphate, Disodium pyrophosphate, tetrasodium pyrophosphate, magnesium oxide and calcium phosphate powder, second two tetraacethyls and its esters, butylated hydroxy anisole, [3-(3 for tetramethylolmethane four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], 2,2 '-methylene radical-two-(4-methyl-6-tert butyl-phenol), octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, ethylene (oxygen ethene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic ester], the 2-tertiary butyl-6-(uncle 3--2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) ethyl]-4, the phenol antioxidant of 6-di-tert-pentyl-phenyl acrylate etc., thio-2 acid; The thio-2 acid alkyl ester of Tyox B, thio-2 acid two (tetradecyl) ester, distearylthiodi-propionate etc.; The phosphorous acid class antioxidant of the thioether class antioxidant of the Pentaerythritols propane thioic acid alkyl ester of tetramethylolmethane four (3-lauryl-thiopropionate) etc., tricresyl phosphite (nonyl benzene) ester, tricresyl phosphite (list and/or dinonyl benzene) ester, phosphorous acid 4,4 '-isopropylidene biphenol alkyl ester, distearyl pentaerythrityl diphosphite etc.The used antioxidant of the present invention can also use in two or more mixing.
From improving the viewpoint of thermostability, the cooperation ratio of above-mentioned thermo-stabilizer is preferably 0.0005～0.4 weight part separately with respect to 100 weight part vinylidene chloride copolymer particle compositions, more preferably 0.001～0.1 weight part.
Can add the various additives etc. of the filler etc. of silicon oxide, lime carbonate etc. in addition.
Normally before vinylidene resin processing, mix (B1) and additive (B2) with pulverulence, but also can when finishing, the vinylidene polymerization add with the slurries shape, perhaps be added in advance in the polymerization vinylidene before, after this carry out polymerization and also can.
Additive attached to absorbing on the vinylidene chloride copolymer or by vinylidene chloride copolymer, is given thermostability thus when extruding.Preferably use softening agent and thermo-stabilizer additive in addition as required.The blending means of these additives has no particular limits, applicable existing method.For example adopt 2 roller rolling mills to mix, adopt the agitator of propeller agitator and ribbon agitator etc. to mix, adopt that Henschel (ヘ Application シ エ Le) super mixer mixes etc., or employing is surpassing heating blended method under 60 ℃ the temperature, or adopt in the low-temperature mixed method below 60 ℃ etc., these methods all can be used.
In addition, be pre-mixed vinylidene chloride copolymer particle composition (A) and the above-mentioned additive that adds as required after, mixed copolymer (B1) and multipolymer (B2) successively.At this moment, about below 80 ℃ in the temperature of hybrid resin, preferably mix in the temperature range from 50 ℃ to room temperature, this is preferred from the uniformity viewpoint of the resin combination that comprises the gained vinylidene chloride copolymer.
In addition, when under the temperature below 60 ℃, mixing and adopt under the situation of the little multipolymer (B1) of ethylene content, blend compositions powder agglomeration in the time of can preventing to make up the step of adding above-mentioned wax class etc., prevent to extrude to add to produce to press to the powder sense of rotation man-hour and fall into spot, and the change that further reduces engine loading and extrusion capacity.
In addition, during as the raw material supplying forcing machine, the funnel on the preferred continuous measurement slave is invested the composition of device inside, and adopts the weight feed feeder at the composition that will (B2) be made of vinylidene chloride copolymer composition and additive (B1).Can exemplify out feeding screw, annular feeder (サ one Network Le Off イ one ダ one), electromagnetic feeder, weight-type feeder, positive displacement feeder etc. as this feeder.Wherein, preferably adopt the weight-type feeder to implement the blended method.Because this method can suppress the variation of engine loading and the variation of extrusion capacity man-hour extruding to add, can be to forcing machine feed and can stably extruding consistently, therefore preferred.In addition, the effect that inhibition resin resolvent adheres to the mould spout also is improved, and can reduce coloring resin and reduce decomposition effluent etc.
Above-mentioned vinylidene chloride copolymer particle composition of the present invention can stretch by after melt extruding, or not stretch forming is film, thin slice etc.As manufacturing process, but application examples is as adopting the inflation extrusion molding method of circular die.By carrying out the film that orientation obtains and have heat-shrinkable, also can be used as under 120 ℃ (pressurization 0.245MPa) following 20 minutes condition, i.e. heat-resistant film also applicatory under distillation (レ ト Le ト) condition by biaxial stretch-formed.Draw ratio vertically is being 2.0～4.5 times preferably, laterally is 3.0～5.0 times.Thickness is preferably 5～30 μ m, more preferably 10～25 μ m in monofilm (シ Application グ Le Off イ Le system).Also can be used as two films (ダ Block Le Off イ Le system) according to purposes uses.Packing the physical strength that to give full play to its film when filling, after packing is filled, can give full play to its gas barrier property at the film that obtains under this condition, therefore be specially adapted to the Food preservation purposes.
In addition, can also adopt these vinylidene chloride copolymer compositions further are layered in coextrusion method on the gas barrier layer, and form multilayer film, sheet by laminating method.
Extruding processing vinylidene chloride copolymer particle composition or when wherein having added the composition of processing aid, stablizing extrudability and thermostability by providing said composition to improve to forcing machine via vacuum pump.The vacuum tightness of vacuum pump is preferably-6.66 * 10
-2Below the MPa, more preferably-7.99 * 10
-2MPa is to-10.1 * 10
-2In the scope of MPa.By providing said composition to forcing machine, can stably keep and extrude processibility and stretchiness via the vacuum pump that is set under this condition.Adopt known method to stretch by the machine that melt extrudes that is connected the vacuum pump bottom, or do not stretch formation film, thin slice etc.
Can stably provide said composition by above-mentioned extruding process thereof, therefore can suppress the variation of the load of forcing machine engine, the variation of extrusion capacity, make it less to melt extruding machine.Have thus and suppress coloring resin, suppress the effusive effect of resin resolvent and suppress the effect etc. that resolvent adheres to mould spout place, and improve thermostability.In addition, when inflation is shaped, can further improves and reduce bubble and break.
Embodiment
Followingly the present invention is specifically described, but the present invention is not subjected to the qualification of these embodiment according to embodiment.
In present embodiment and comparative example, adopt following compound and device.
Suspension dispersive agent
(M1) methylcellulose gum
(2% viscosity in aqueous solution 4000mPas)
(M2) Vltra tears
(2% viscosity in aqueous solution 4000mPas)
(M3) Vltra tears
(2% viscosity in aqueous solution 400mPas)
Agitating vane
(S1) Off ア ウ De ラ one blade
Ethylene-vinyl acetate copolymer (B1)
(B1-1): vinyl acetate content=30 weight %, melting index=6
(B1-2): vinyl acetate content=25 weight %, melting index=15
(B1-3): vinyl acetate content=20 weight %, melting index=160
(B1-4): vinyl acetate content=10 weight %, melting index=75
α, β unsaturated carboxylate type multipolymer (B2)
(B2-1): BA/BMA/MMA=14/16/70 weight %
Weight-average molecular weight (Mw) 220000
(B2-2): BA/MMA/MA=40/55/5 weight %
Weight-average molecular weight (Mw) 300000
(B2-3): BA/MMA=50/50 weight %
Weight-average molecular weight (Mw) 50000
* following monomer is represented in above-mentioned abbreviation.
BA: butyl acrylate
BMA: butyl methacrylate
MMA: methyl methacrylate
MA: methyl acrylate
Characteristic measurement method of the present invention and evaluation method below have been described.
1) size distribution of vinylidene chloride copolymer particle composition
The particle ratio of weight average particle diameter and less than 150 μ m is measured by the particle size distribution method that adopts コ one Le one マ Le チ セ イ ザ one particle assay device TA-II type (day machine society of section makes).
Level value of weight average particle diameter (water Quasi value) and evaluation thereof
In the scope of 200～500 μ m: ◎
Less than 200 μ m: *
The level value of the vinylidene chloride copolymer particle ratio of less than 150 μ m is estimated
In the scope below 0～1.5 weight %: ◎
In the scope of 1.5 weight %～3 weight %: zero
Surpass 3 weight %: *
2) Bulk Specific Gravity
With JIS K-6722 is that benchmark is measured.
(パ ウ ダ one テ ス one PT-R type (manufacturing of powder determinator ホ ソ カ ワ ミ Network ロ Application society))
Value according to Bulk Specific Gravity is carried out to judge.
0.9～1.0g/cm
3：◎
0.8～0.9g/cm
3：○
Not enough 0.8g/cm
3: *
3) weight-average molecular weight
The weight-average molecular weight of polymer particle composition adopts gel permeation chromatography (GPC), measures in the following manner.
The determinator: East ソ gel permeation chromatograph HLC-8020 of society
Post: 7.8mm * 30cm * 2 TSK gel SuperHM-H (East ソ society)
Elutriant: THF, flow velocity: 1mL/min, temperature: 40 ℃, detection: RI
4) extrude stability: the rate of change of the feed speed of vinylidene chloride copolymer particle composition
Use about 50kg vinylidene chloride copolymer particle composition, the feed rate of feeding screw is set at 100kg/ hour, measure the feed rate (n=5) of the certain hour of 10～20 minutes scopes, try to achieve its simple average value and standard deviation.
Try to achieve the rate of change of feed speed according to following formula (2), as the judgment standard of flowability.
At this, adopt Off ァ イ ト ロ Application SK-S (manufacturing of ホ ソ カ ワ ミ Network ロ Application society) as feeding screw.
The rate of change of feed speed (%)=(standard deviation/simple average value) * 100 (2)
In addition, according to this rate of change, judge mobile in the following manner.
0%～5%: ◎ (not having processability problems)
Surpass 5%: * (poor in processability, the phenomenon of generation feed inequality)
5) film uniformity
On about 300m length of the film of producing, measure average film thickness and standard deviation, try to achieve the rate of change of film thickness according to following formula (3), as the determinating reference of extruding processibility.
The rate of change of film thickness (σ) (%)=(standard deviation/average film thickness) * 100 (3)
0%～2%: ◎ (do not exist and extrude processability problems)
Surpass 2%: * (extrude poor in processability, the phenomenon of thickness inequality takes place)
6) outflow of resolvent
Adopt the range estimation mode to detect to the resolvent more than the about 1mm of length contained in the film.
Represent 10 of every 1500m less thaies: ◎
Represent 15 of every 1500m 10～less thaies: zero
Represent that every 1500m is more than 15: *
7) packaging-filling machine adaptability
On automatic filling apparatus for ligating (ADP of Asahi Chemical Industry food product pack filling machine) with membrane supplying unit, high frequency sealing unit, automatic filler cells, ligation unit integral, hang up so that two films that folding width is the mode of 40mm to cut into, in the cylindrical thin-film of (the セ Application one シ one Le レ) that seal by the high frequency center seal, fill water as weighting material, adopt metal wire to clamp its two ends, obtain wrapping body.Observe the state of sealing this moment, enclosed electrode produces the situation of spark.
The sealing speed of dividing with 30m/ turns round, confirm not take place the fault and the spark that are caused by sealing in 60 minutes runtime: ◎
The part of film is thin, the excessive fused of potted line position frequency with 1～2 time in 60 minutes produces: zero
The fault and the spark that are caused by sealing produced with the frequency more than 1～2 time in 60 minutes: *
8) film xanthochromia degree
The xanthochromia of range estimation film.
The xanthochromia of film is not obvious: ◎
The expression * and ◎ between coloring degree: zero
The xanthochromia degree of film is strong: *
9) oxygen perviousness:
Adopt oxygen permeability determinator (Ox-trans 2/20 that Modem Control society makes),, measure under the condition of 100% relative humidity at 30 ℃.Lifting the position is cm
3/ m
2/ sky/atm adopts two films to measure.
Below 25: ◎
25～30：○
More than 30: *
10)＜comprehensive evaluation 〉
: each assessment item all satisfies.
Zero: each assessment item all satisfies, but comprises a part zero.
*: characteristic is poor.
[embodiment 1]
In the reactor (internal capacity is 300 liters) that has Off ァ ウ De ラ one blade (deployment diameter is 400mm), finger-type dividing plate, thermometer and nitrogen ingress pipe, add deionized water and suspension dispersive agent (M1), lysed suspension is adjusted into 100 weight parts (concentration of suspension dispersive agent is 500ppm).
Add 80 weight part vinylidene chlorides, 20 weight part vinylchlorid, 0.15 weight part initiator di-isopropyl peroxydicarbonate, 2 parts of epoxy linseed oils then, after this stirring velocity is set at 1.4m/s, under nitrogen atmosphere, be heated to 45 ℃, the beginning polymerization.Continue reaction after about 10 hours, be warming up to 55 ℃ in about 1 hour, making stirring velocity is 1.2 times (1.68m/s) of initial stage speed, and proceeds polymerization 15 hours.After reaction was finished, the weight average particle diameter of isolating vinylidene chloride copolymer particle composition was 260 μ m, and the mass ratio of the particle of particle diameter less than 150 μ m is 2.2 weight %.In addition, Bulk Specific Gravity is 0.90g/cm
3
This copolymer particle composition dissolves in tetrahydrofuran (THF), is adopted gel gas chromatography determination polystyrene conversion molecular weight, and weight-average molecular weight is 120000.(vinylidene chloride copolymer particle composition (A-1))
Table 1 shows the evaluation result of the characteristic of vinylidene chloride copolymer particle composition.
[comparative example 1]
Except the concentration that makes suspension dispersive agent is that 300ppm, stirring velocity are the 4.5m/s, adopts and implement polymerization with embodiment 1 the same mode.Weight-average molecular weight is 123000.(vinylidene chloride copolymer particle composition (A-6))
The results are shown in table 3.
[embodiment 2]
Except the concentration that makes suspension dispersive agent is that 300ppm, stirring velocity are the 1.2m/s, adopts and implement polymerization with embodiment 1 the same mode.
Weight-average molecular weight is 116000.(vinylidene chloride copolymer particle composition (A-2)).
The results are shown in table 1.
[comparative example 2]
Except the concentration that makes suspension dispersive agent is that 1000ppm, stirring velocity are the 0.6m/s, adopts and implement polymerization with embodiment 1 the same mode.
Weight-average molecular weight is 120000.(vinylidene chloride copolymer particle composition (A-7))
The results are shown in table 3.
[embodiment 3]
Except the concentration that makes suspension dispersive agent is that 300ppm, stirring velocity are the 1.0m/s, adopts and implement polymerization with embodiment 1 the same mode.Weight-average molecular weight is 115000.(vinylidene chloride copolymer particle composition (A-3))
The results are shown in table 1.
[embodiment 4]
Except using suspension dispersive agent (M2), making its concentration is that 500ppm, stirring velocity are beyond the 1.2m/s, adopts and implements polymerization with embodiment 1 the same mode.Weight-average molecular weight is 118000.(vinylidene chloride copolymer particle composition (A-4))
The results are shown in table 1.
[comparative example 3]
Except using suspension dispersive agent (M2), making its concentration is that 1000ppm, stirring velocity are beyond the 0.6m/s, adopts and implements polymerization with embodiment 1 the same mode.Weight-average molecular weight is 121000.(vinylidene chloride copolymer particle composition (A-8))
The results are shown in table 3.
[embodiment 5]
Except using suspension dispersive agent (M3), making its concentration is that 1000ppm, stirring velocity are beyond the 1.0m/s, adopts and implements polymerization with embodiment 1 the same mode.Weight-average molecular weight is 121000.(vinylidene chloride copolymer particle composition (A-5))
The results are shown in table 1.
[embodiment 6]
Add antioxidant, lubricant, the red pigment of 3 weight part Uniflex DBSs in the vinylidene chloride copolymer particle composition (A-1) that in 100 weight part embodiment 1, obtains, obtained the vinylidene chloride copolymer particle composition as additive, total 1 weight part.
Feed intake in diameter is the forcing machine of 40mm then, the vacuum pressure that makes vacuum pump is approximately-9.06 * 10
-2After MPa extruded with ring-type, cooling fast made it pass through 20 ℃ warm water bath then in 10 ℃ cooling tank.After this, being pressed into air between the film in being clipped in the different pinch roll of 2 groups of surface of revolution speed and making its expansion, is that 2.8 times, width are 3.7 times and implement stretch orientations with length direction.Gained film length 100m, monofilm thickness are 20 μ m.Measure the thickness and the thickness rate of change (σ) of the film of producing, the results are shown in table 2.
[embodiment 7]
Except the vinylidene chloride copolymer particle composition (A-2) that adopts embodiment 2 to make, making vacuum tightness is-7.99 * 10
-2Beyond the MPa, adopt and make film with embodiment 6 the same modes.The results are shown in table 2.
[embodiment 8]
Except the vinylidene chloride copolymer particle composition (A-3) that adopts embodiment 3 to make, making vacuum tightness is-7.99 * 10
-2Beyond the MPa, adopt and make film with embodiment 6 the same modes.The results are shown in table 2.
[embodiment 9]
Except the vinylidene chloride copolymer particle composition (A-4) that adopts embodiment 4 to make, making vacuum tightness is-7.99 * 10
-2Beyond the MPa, adopt and make film with embodiment 6 the same modes.The results are shown in table 2.
[embodiment 10]
Except the vinylidene chloride copolymer particle composition (A-5) that adopts embodiment 5 to make, making vacuum tightness is-6.66 * 10
-2Beyond the MPa, adopt and make film with embodiment 6 the same modes.The results are shown in table 2.
[embodiment 11]
Except not using vacuum pump, adopt and make film with embodiment 6 the same modes.
The results are shown in table 2.
[comparative example 4]
The vinylidene chloride copolymer particle composition (A-6) that adopts comparative example 1 to make adopts and makes film with embodiment 6 the same modes.The results are shown in table 4.
[comparative example 5]
The vinylidene chloride copolymer particle composition (A-7) that adopts comparative example 2 to make adopts and makes film with embodiment 6 the same modes.The results are shown in table 4.
[comparative example 6]
Except the vinylidene chloride copolymer particle composition (A-8) that adopts comparative example 3 to make, making vacuum tightness is-7.99 * 10
-2Beyond the MPa, adopt and make film with embodiment 6 the same modes.The results are shown in table 4.
[comparative example 7]
Except not using vacuum pump, adopt and make film with embodiment 4 the same modes.
The results are shown in table 4.
[embodiment 12]
The vinylidene chloride copolymer particle composition (A-1) that makes with respect to 100 weight part embodiment 1, after cooperating 0.3 parts by weight of ethylene-vinyl acetate copolymer (B1-1), 0.3 weight part α, β unsaturated carboxylic acid ester copolymer (B2-1), add the epoxy linseed oil add up to 3.5 weight parts and Uniflex DBS as additive, and further antioxidant, lubricant and the red pigment that adds up to 1.5 weight parts of adding, under 50 ℃ temperature, mix, obtain the vinylidene chloride copolymer particle composition.
Adopting diameter then is the forcing machine of 40mm, makes the vacuum pressure of vacuum pump be about-9.06 * 10
-2After MPa extruded with ring-type, cooling fast made it pass through 20 ℃ warm water bath then in 10 ℃ cooling tank.After this, being pressed into air between the film in being clipped in the different pinch roll of 2 groups of surface of revolution speed and making its expansion, is that 2.8 times, width are 3.7 times and implement stretch orientations with length direction.Gained film length 100m, monofilm thickness are 20 μ m.Measure the thickness rate of change (σ) of the film of producing, the results are shown in table 5.
[embodiment 13]
Except adding 0.5 parts by weight of ethylene-vinyl acetate copolymer (B1-2), 0.5 weight part α, β unsaturated carboxylic acid ester copolymer (B2-2) adopt and make film with embodiment 12 the same modes in addition.The results are shown in table 5.
[embodiment 14]
Except adding 1.0 parts by weight of ethylene-vinyl acetate copolymer (B1-1), 0.3 weight part α, β unsaturated carboxylic acid ester copolymer (B2-2) make the vacuum pressure of vacuum pump be about-7.99 * 10
-2Beyond the MPa, adopt and make film with embodiment 12 the same modes.The results are shown in table 5.
[embodiment 15]
Except adding 1.5 parts by weight of ethylene-vinyl acetate copolymer (B1-3), 0.1 weight part α, β unsaturated carboxylic acid ester copolymer (B2-1) adopt and make film with embodiment 12 the same modes in addition.
The results are shown in table 5.
[embodiment 16]
Except adding 1.0 parts by weight of ethylene-vinyl acetate copolymer (B1-3), 0.5 weight part α, β unsaturated carboxylic acid ester copolymer (B2-2) adopt and make film with embodiment 12 the same modes in addition.The results are shown in table 5.
[embodiment 17]
In the reactor (internal capacity is 300 liters) that has Off ァ ウ De ラ one blade (deployment diameter is 400mm), finger-type dividing plate, thermometer and nitrogen ingress pipe, add deionized water and suspension dispersive agent (M1), lysed suspension is adjusted into 100 weight parts (concentration of suspension dispersive agent is 500ppm).
Add 80 weight part vinylidene chlorides, 20 weight part vinylchlorid, 0.15 weight part initiator di-isopropyl peroxydicarbonate, 2 parts of epoxy linseed oils then, after this stirring velocity is set at 1.4m/s, under nitrogen atmosphere, be heated to 45 ℃, the beginning polymerization.Continue reaction after about 10 hours, be warming up to 60 ℃ in about 1 hour, making stirring velocity is 1.2 times (1.68m/s) of initial stage speed, and proceeds polymerization 15 hours.After reaction was finished, the weight average particle diameter of isolating vinylidene chloride copolymer particle was 260 μ m, and the mass ratio of the particle of particle diameter less than 150 μ m is 2.3 weight %.In addition, Bulk Specific Gravity is 0.91g/cm
3
This copolymer particle is dissolved in the tetrahydrofuran (THF), adopts gel gas chromatography determination polystyrene conversion molecular weight, weight-average molecular weight is 100000.(vinylidene chloride copolymer particle composition (A-9))
Except using this vinylidene chloride copolymer particle composition (A-9) is 100 weight parts, ethylene-vinyl acetate copolymer (B1-4) is 0.2 weight part, α, β unsaturated carboxylic acid ester copolymer (B2-3) are beyond 0.5 weight part, adopt and make film with embodiment 12 the same modes.The results are shown in table 6.
[embodiment 18]
Except adding 1.5 parts by weight of ethylene-vinyl acetate copolymer (B1-1), 0.05 weight part α, β unsaturated carboxylic acid ester copolymer (B2-3) adopt and make film with embodiment 17 the same modes in addition.The results are shown in table 6.
[embodiment 19]
Except not using vacuum pump, adopt with embodiment 18 the same methods and make film.The results are shown in table 6.
[embodiment 20]
In the reactor (internal capacity is 300 liters) that has Off ァ ウ De ラ one blade (deployment diameter is 400mm), finger-type dividing plate, thermometer and nitrogen ingress pipe, add deionized water and suspension dispersive agent (M1), lysed suspension is adjusted into 100 weight parts (concentration of suspension dispersive agent is 500ppm).
Add 90 weight part vinylidene chlorides, 10 weight part vinylchlorid, 0.15 weight part initiator di-isopropyl peroxydicarbonate, 2 parts of epoxy linseed oils then, after this stirring velocity is set at 1.4m/s, under nitrogen atmosphere, be heated to 45 ℃, the beginning polymerization.Continue reaction after about 10 hours, be warming up to 55 ℃ in about 1 hour, making stirring velocity is 1.2 times (1.68m/s) of initial stage speed, and continues polymerization 10 hours.After reaction was finished, the weight average particle diameter of isolating vinylidene chloride copolymer particle was 260 μ m, and the mass ratio of the particle of particle diameter less than 150 μ m is 2.0 weight %.In addition, Bulk Specific Gravity is 0.92g/cm
3
This copolymer particle is dissolved in the tetrahydrofuran (THF), adopts gel gas chromatography determination polystyrene conversion molecular weight, weight-average molecular weight is 90000.(vinylidene chloride copolymer particle composition (A-10))
Except in 10 weight part gained vinylidene chloride copolymer particle compositions (A-10), adding 90 weight part vinylidene chloride copolymer particle compositions (A-1), 0.3 parts by weight of ethylene-vinyl acetate copolymer (B1-1), 0.3 weight part α, β unsaturated carboxylic acid ester copolymer (B2-1) are in addition, adopt and make film with embodiment 12 the same modes.The results are shown in table 6.
[comparative example 8]
Except adding ethylene-vinyl acetate copolymer (B1-1) 3.3 weight parts, do not add α, β esters of unsaturated carboxylic acids (B2) in addition, adopt and make film with embodiment 12 the same modes.The results are shown in table 7.
[comparative example 9]
Except adding α, β esters of unsaturated carboxylic acids (B2-1) 3.3 weight parts, do not add ethylene-vinyl acetate copolymer (B1) in addition, adopt and make film with embodiment 12 the same modes.The results are shown in table 7.
[comparative example 10]
Except cooperating 1.5 parts by weight of ethylene-vinyl acetate copolymer (B1-4), 2.0 weight part α, β esters of unsaturated carboxylic acids (B2-1), adopt and make film with embodiment 12 the same modes.The results are shown in table 7.
Table 1 embodiment
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| The suspension dispersive agent kind | (M1) | (M1) | (M1) | (M2) | (M3) |
| Suspended dispersed agent concentration (ppm) | 500 | 300 | 300 | 500 | 1000 |
| Stirring velocity (m/s) | 1.4 | 1.2 | 1.0 | 1.2 | 1.0 |
| Weight average particle diameter (μ m) | 260 | 300 | 350 | 250 | 270 |
| (judgement) | ◎ | ◎ | ◎ | ◎ | ◎ |
| The part by weight (%) of less than 150 μ m | 2.2 | 1.4 | 0.4 | 2.0 | 2.3 |
| (judgement) | ○ | ◎ | ◎ | ○ | ○ |
| Bulk Specific Gravity (g/cm 3) | 0.9 | 0.93 | 0.95 | 0.89 | 0.92 |
| (judgement) | ◎ | ◎ | ◎ | ○ | ◎ |
| The identification sign of type of polymer | (A-1) | (A-2) | (A-3) | (A-4) | (A-5) |
Table 2 embodiment (system film result)
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | |
| The type of polymer of using | (A-1) | (A-2) | (A-3) | (A-4) | (A-5) | (A-1) |
| The rate of change of feed speed (%) (judgement) | 3.1 ◎ | 2.2 ◎ | 1.8 ◎ | 2.4 ◎ | 2.5 ◎ | 3.1 ◎ |
| Vacuum tightness (MPa) | -9.06×10 -2 | -7.99×10 -2 | -7.99×10 -2 | -7.99×10 -2 | -6.66×10 -2 | 0 |
| Film thickness (μ m) | 20 | 20 | 20 | 20 | 20 | 20 |
| The rate of change (σ) | 1.9 | 1.8 | 1.2 | 1.7 | 1.6 | 2.0 |
| (judgement) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Comprehensive evaluation | ○ | ◎ | ◎ | ○ | ○ | ○ |
Table 3 comparative example
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| The suspension dispersive agent kind | (M1) | (M1) | (M2) |
| Suspended dispersed agent concentration (ppm) | 300 | 1000 | 1000 |
| Stirring velocity (m/s) | 4.5 | 0.6 | 0.6 |
| Weight average particle diameter (μ m) | 160 | 330 | 290 |
| (judgement) | × | ◎ | ◎ |
| The part by weight (%) of less than 150 μ m | 40.7 | 1.8 | 2.9 |
| (judgement) | × | ○ | ○ |
| Bulk Specific Gravity (g/cm 3) | 0.71 | 0.78 | 0.79 |
| (judgement) | × | × | × |
| The identification sign of type of polymer | (A-6) | (A-7) | (A-8) |
Table 4 comparative example (system film result)
| Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| The type of polymer of using | (A-6) | (A-7) | (A-8) | (A-6) |
| The rate of change of feed speed (%) (judgement) | 12.1 × | 7.4 × | 8.1 × | 12.1 × |
| Vacuum tightness (MPa) | -9.06×10 -2 | -9.06×10 -2 | -7.99×10 -2 | 0 |
| Film thickness (μ m) | 20 | 20 | 20 | 20 |
| The rate of change (σ) | 4.5 | 2.4 | 2.7 | 4.6 |
| (judgement) | × | × | × | × |
| Comprehensive evaluation | × | × | × | × |
Table 5 embodiment 12～16
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | |
| The kind of vinylidene chloride copolymer particle and ratio (weight part) | (A-1)100 | (A-1)100 | (A-1)100 | (A-1)100 | (A-1)100 |
| Kind of ethylene-vinyl acetate copolymer (B1) and ratio (weight part) | (B1-1)0.3 | (B1-2)0.5 | (B1-1)1.0 | (B1-3)1.5 | (B1-3)1.0 |
| α, β unsaturated carboxylate type multipolymer (B2) and ratio (weight part) | (B2-1)0.3 | (B2-2)0.5 | (B2-2)0.3 | (B2-1)0.1 | (B2-2)0.5 |
| Vacuum tightness (MPa) | -9.06×10 -2 | -9.06×10 -2 | -7.99×10 -2 | -9.06×10 -2 | -9.06×10 -2 |
| Film thickness (μ m) | 20 | 20 | 20 | 20 | 20 |
| The rate of change (σ) | 1.7 | 1.5 | 1.9 | 1.3 | 1.2 |
| (judgement) | ◎ | ◎ | ◎ | ◎ | ◎ |
| Resolvent flows out | ◎ | ◎ | ◎ | ◎ | ◎ |
| Food product pack filling machine adaptability | ◎ | ◎ | ◎ | ○ | ○ |
| The xanthochromia degree of film | ◎ | ○ | ◎ | ◎ | ◎ |
| The oxygen perviousness | ◎ | ◎ | ◎ | ○ | ○ |
| Comprehensive evaluation | ◎ | ○ | ◎ | ○ | ○ |
Table 6 embodiment 17～20
| Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | |
| The kind of vinylidene chloride copolymer particle and ratio (weight part) | (A-9)100 | (A-9)100 | (A-9)100 | (A-1)90 (A-10)10 |
| Kind of ethylene-vinyl acetate copolymer (B1) and ratio (weight part) | (B1-4)0.2 | (B1-1)1.5 | (B1-1)1.5 | (B1-1)0.3 |
| α, β unsaturated carboxylate type multipolymer (B2) and ratio (weight part) | (B2-3)0.5 | (B2-3)0.05 | (B2-3)0.05 | (B2-1)0.3 |
| Vacuum tightness (MPa) | -9.06×10 -2 | -9.06×10 -2 | 0 | -9.06×10 -2 |
| Film thickness (μ m) | 20 | 20 | 20 | 20 |
| The rate of change (σ) | 1.5 | 1.2 | 1.6 | 1.8 |
| (judgement) | ◎ | ◎ | ◎ | ◎ |
| Resolvent flows out | ◎ | ◎ | ◎ | ◎ |
| Food product pack filling machine adaptability | ◎ | ○ | ○ | ◎ |
| The xanthochromia degree of film | ◎ | ◎ | ◎ | ◎ |
| The oxygen perviousness | ◎ | ○ | ○ | ◎ |
| Comprehensive evaluation | ◎ | ○ | ○ | ◎ |
Table 7 comparative example 8～10
| Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| The kind of vinylidene chloride copolymer particle and ratio (weight part) | (A-1)100 | (A-1)100 | (A-1)100 |
| Kind of ethylene-vinyl acetate copolymer (B1) and ratio (weight part) | (B1-1)3.3 | (B1-4)1.5 | |
| α, β unsaturated carboxylate type multipolymer (B2) and ratio (weight part) | (B2-1)3.3 | (B2-1)2.0 | |
| Vacuum tightness (MPa) | -9.06×10 -2 | -9.06×10 -2 | -9.06×10 -2 |
| Film thickness (μ m) | 20 | 20 | 20 |
| The rate of change (σ) | 1.8 | 2.0 | 1.3 |
| (judgement) | ◎ | ◎ | ◎ |
| Resolvent flows out | ○ | ◎ | ◎ |
| Food product pack filling machine adaptability | × | × | × |
| The xanthochromia degree of film | ◎ | ○ | ◎ |
| The oxygen perviousness | × | × | × |
| Comprehensive evaluation | × | × | × |
Although the detailed or specific form of implementation of above reference describes the present invention, be to make various changes and correction without departing from the spirit and scope of the present invention for those skilled in the art apparently.
The Japanese patent application that the application submitted to based on July 13 calendar year 2001 (special hope 2001-214424) is incorporated herein its content, as reference.
＜industrial applicability 〉
Composition of vinylidene chloride copolymer particles of the present invention can stably be extruded when melt-shaping is film, thin slice, therefore can obtain film and the thin slice of film thickness uniformity excellence. And, by cooperation ethylene-vinyl acetate copolymer in this copolymer particle composition with by the copolymer that monomer consists of more than 2 kinds of from α, β esters of unsaturated carboxylic acids monomer, choosing, formed composition can suppress the outflow of resin analyte when melt-shaping thus, inhibition is decomposed effluent and adhered to mould flow export place, and can obtain packaging-filling machine adaptability, the film of gas barrier property excellence, thin slice. In addition, by via vavuum pump above-mentioned composition being extruded processing, can further improve and extrude processability.
Claims (10)
1. a vinylidene chloride copolymer particle is characterized in that, the scope of weight average particle diameter is 200～500 μ m, and the particle ratio of particle diameter less than 150 μ m is below the 3 weight %.
2. vinylidene chloride copolymer particle as claimed in claim 1 is characterized in that, the Bulk Specific Gravity of vinylidene chloride copolymer particle is 0.80g/cm
3～1.0g/cm
3
3. vinylidene chloride copolymer particle as claimed in claim 1 or 2 is characterized in that, vinylidene chloride copolymer is to be obtained by vinylidene chloride and the monomer copolymerization more than a kind selected from polymerisable vinyl monomer.
4. vinylidene chloride copolymer particle as claimed in claim 1 or 2, wherein, a kind or more the monomer of polymerisable vinyl monomer for from vinylchlorid, methyl acrylate, methyl methacrylate, 2-EHA, vinyl cyanide, vinylbenzene, selecting.
5. film or the thin slice that constitutes by claim 1 or 2 described vinylidene chloride copolymer particles.
6. vinylidene chloride copolymer composition, it is characterized in that, said composition by 100 weight part weight average particle diameter in 200～500 mu m ranges, and the particle ratio of particle diameter less than 150 μ m is the following vinylidene chloride copolymer particle (A) of 3 weight %, is made of the multipolymer of selecting from α, β esters of unsaturated carboxylic acids monomer that monomer constitutes more than 2 kinds (B2) with 0.05～2.95 parts by weight of ethylene-vinyl acetate copolymer (B1) and 0.05～2.95 weight part, and fit quality (B1) is below 3 weight parts with (B2) fit quality sum.
7. vinylidene chloride copolymer composition as claimed in claim 6, wherein the Bulk Specific Gravity of vinylidene chloride copolymer particle (A) is 0.80g/cm
3～1.0g/cm
3
8. as claim 6 or 7 described vinylidene chloride copolymer compositions, wherein, the vinyl acetate components in proportions (Wa) in the ethylene-vinyl acetate copolymer (B1) is 10～40 weight %.
9. as claim 6,7 and 8 each described copolymer compositions, wherein, α, a kind or more the monomer of β esters of unsaturated carboxylic acids monomer for from butyl acrylate, methyl acrylate, 2-EHA, butyl methacrylate, methyl methacrylate, selecting.
10. film or the thin slice that constitutes by claim 8 and 9 each described vinylidene chloride copolymer compositions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP214424/2001 | 2001-07-13 | ||
| JP2001214424 | 2001-07-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1529736A CN1529736A (en) | 2004-09-15 |
| CN1249154C true CN1249154C (en) | 2006-04-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028083601A Expired - Lifetime CN1249154C (en) | 2001-07-13 | 2002-07-11 | Composition of vinylidene chloride copolymer particles |
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| Country | Link |
|---|---|
| JP (1) | JP4322667B2 (en) |
| KR (1) | KR100591221B1 (en) |
| CN (1) | CN1249154C (en) |
| WO (1) | WO2003006548A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224583B (en) * | 2012-01-30 | 2015-05-06 | 旭化成化学株式会社 | Vinylidene chloride copolymer, its composition, and its membrane or sheet material |
| CN103224676B (en) * | 2012-01-30 | 2016-04-13 | 旭化成化学株式会社 | Vinylidene chloride copolymer composition, its manufacture method and film thereof or sheet material |
| CN103224581B (en) * | 2012-01-30 | 2016-03-02 | 旭化成化学株式会社 | Vinylidene chloride analog copolymer, its composition and film thereof or sheet material |
| CN103224580B (en) * | 2012-01-30 | 2016-03-30 | 旭化成化学株式会社 | Vinylidene chloride analog copolymer, its composition and film thereof or sheet material |
| CN103224582B (en) * | 2012-01-30 | 2016-03-02 | 旭化成化学株式会社 | Vinylidene chloride analog copolymer and film thereof or sheet material |
| JP2018177890A (en) * | 2017-04-06 | 2018-11-15 | 旭化成株式会社 | Vinylidene chloride-based copolymer resin composition |
| 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5991169A (en) * | 1982-11-18 | 1984-05-25 | Asahi Chem Ind Co Ltd | High-frequency adhesive comprising crystalline vinylidene halide copolymer |
| JPH0665691B2 (en) * | 1986-05-30 | 1994-08-24 | 旭化成工業株式会社 | Vinylidene Chloride Copolymer Particles and Their Manufacturing Method |
| US5236649A (en) * | 1988-12-23 | 1993-08-17 | The Dow Chemical | Extrudable thermoplastic particulates |
| CN1126789C (en) * | 1995-04-27 | 2003-11-05 | 吴羽化学工业株式会社 | Vinylidene chloride copolymer resin composition, film produced therfrom, extrusion process for the composition, and process for producing the film |
| JP3505870B2 (en) * | 1995-08-28 | 2004-03-15 | Ｊｓｒ株式会社 | Spherical polymer particles |
| JP4394208B2 (en) * | 1999-08-23 | 2010-01-06 | 株式会社クレハ | Polyvinylidene chloride resin powder and activated carbon |
| JP2002256029A (en) * | 2001-02-27 | 2002-09-11 | Asahi Kasei Corp | Vinylidene chloride-based copolymer particle and extrusion method |
-
2002
- 2002-07-11 KR KR1020047000286A patent/KR100591221B1/en active IP Right Grant
- 2002-07-11 CN CNB028083601A patent/CN1249154C/en not_active Expired - Lifetime
- 2002-07-11 JP JP2003512309A patent/JP4322667B2/en not_active Expired - Lifetime
- 2002-07-11 WO PCT/JP2002/007063 patent/WO2003006548A1/en active Application Filing
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|---|---|
| WO2003006548A1 (en) | 2003-01-23 |
| CN1529736A (en) | 2004-09-15 |
| JPWO2003006548A1 (en) | 2004-11-04 |
| JP4322667B2 (en) | 2009-09-02 |
| KR20040020965A (en) | 2004-03-09 |
| KR100591221B1 (en) | 2006-06-19 |
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