JPH03179048A - Vinylidene chloride resin composition - Google Patents
Vinylidene chloride resin compositionInfo
- Publication number
- JPH03179048A JPH03179048A JP31655589A JP31655589A JPH03179048A JP H03179048 A JPH03179048 A JP H03179048A JP 31655589 A JP31655589 A JP 31655589A JP 31655589 A JP31655589 A JP 31655589A JP H03179048 A JPH03179048 A JP H03179048A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- vinylidene chloride
- weight
- parts
- resin composition
- 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.)
- Pending
Links
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000011342 resin composition Substances 0.000 title claims description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 42
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 17
- 238000000465 moulding Methods 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 abstract description 12
- 230000004888 barrier function Effects 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000375 suspending agent Substances 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 239000012986 chain transfer agent Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000003017 thermal stabilizer Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 31
- 238000012360 testing method Methods 0.000 description 17
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- 235000013305 food Nutrition 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920006280 packaging film Polymers 0.000 description 4
- 239000012785 packaging film Substances 0.000 description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- 229930003427 Vitamin E Natural products 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 parachlorobenzoyl peroxide Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 235000019165 vitamin E Nutrition 0.000 description 3
- 229940046009 vitamin E Drugs 0.000 description 3
- 239000011709 vitamin E Substances 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003490 Thiodipropionic acid Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 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 2
- 238000005185 salting out Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000019303 thiodipropionic acid Nutrition 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 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
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000276699 Seriola Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010926 purge Methods 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、可塑剤を配合せずに底形しうる、樹脂組成物
、それからのベレットなどの子11威形体、ならびに該
組成物を食品包装用フィルム、シート及び容器として使
用することに関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a resin composition that can be molded into a bottom shape without adding a plasticizer, a molded body such as a pellet made from the resin composition, and a food product using the composition. It relates to use as packaging films, sheets and containers.
(従来の技術)
塩化ビニリデン系樹脂は、酸素遮断性、防湿性、透明性
、耐薬品性、耐油性、密着性、熱収縮性等に優れており
、食品衛生性も高いために、通常のインフレーシラン法
で成膜したフィルム及び通常のブロー法で底形した容器
は食品包装用として広く使用されている。(Conventional technology) Vinylidene chloride resin has excellent oxygen barrier properties, moisture resistance, transparency, chemical resistance, oil resistance, adhesion, heat shrinkage, etc., and has high food hygiene properties, so it is Films formed by the inflation silane method and containers shaped by the conventional blow method are widely used for food packaging.
従来、この分野に使用されている塩化ビニリデン系樹脂
としては、塩化ビニリデン−塩化ビニル共重合体が市販
されているが、この重合体は押出加工成形時の熱安定性
が悪く、そのため熱安定剤であるエポキシ化合物と可塑
剤であるジブチルセバケー) (DBS) 、アセチル
トリブチルシトレー) (ATBC)等の室温で液状物
、及び抗酸化剤や熱安定助剤等を配合して底形されてい
た。Conventionally, vinylidene chloride-vinyl chloride copolymer is commercially available as a vinylidene chloride-based resin used in this field, but this polymer has poor thermal stability during extrusion processing, so heat stabilizers are required. The base was made by blending an epoxy compound, a plasticizer such as dibutyl sebakey (DBS), acetyl tributyl citrate (ATBC), etc., which are liquid at room temperature, and an antioxidant, a heat stabilizing agent, etc.
しかし、現今、従来から使用していた可塑剤の配合量を
食品衛生性の観点から極力少なくする方向に環境がなり
つつある。その理由は、フィルム・容器で包装した食品
へ可塑剤の一部が移行するからである。However, at present, the environment is moving toward reducing the amount of plasticizers that have traditionally been used as much as possible from the viewpoint of food hygiene. The reason for this is that some of the plasticizer migrates to the food packaged in film or containers.
可塑剤を使用しない塩化ビニリデン系樹脂組成物に関す
る技術としては、例えば特公昭38−26569号公報
が提案されている。この公報には、塩化ビニリデンモノ
マーユニットを70〜90重量%未満を含み、アルコー
ルまたはフェノールのアクリル酸エステル(ただし該エ
ステル中のアルコール残基は炭素数4〜1日の長鎖脂肪
族アルキル、脂環族アルキルもしくはアルキルアリル基
を含み、また該エステル中のフェノール残基は炭素数6
〜18のベンゼン、アルキルベンゼン、クロロベンゼン
を含む)モノマーユニットを5〜30重量%よりなる共
重合体に可塑剤を使用せずに、少量の安定剤を配合して
なる樹脂&[l酸物を成形加工することが開示されてい
る。As a technique related to a vinylidene chloride resin composition that does not use a plasticizer, for example, Japanese Patent Publication No. 38-26569 has been proposed. This publication contains 70 to less than 90% by weight of vinylidene chloride monomer units, and acrylic acid esters of alcohols or phenols (however, the alcohol residues in the esters are long-chain aliphatic alkyls, fatty acids, etc. having 4 to 1 carbon atoms, Contains a cyclic alkyl or alkylaryl group, and the phenol residue in the ester has 6 carbon atoms.
A resin and [l acid product] formed by blending a small amount of stabilizer without using a plasticizer with a copolymer consisting of 5 to 30% by weight of monomer units (including ~18 benzene, alkylbenzene, and chlorobenzene) Processing is disclosed.
この公報記載の技術の特徴は、塩化ビニリデンの使用量
を90重量%未満にして押出加工時の熱安定性を良<シ
、アルコールまたはフェノールのアクリル酸エステルを
共重合することで内部可塑化し、結晶化速度を速くして
成形加工性を向上させたものである。共重合体中の塩化
ビニリデンモノマーユニットが多くなれば結晶化速度が
速くなることは公知であるが、特公昭3B−26569
号公報記載の樹脂組成物では、塩化ビニリデンモノマー
ユニットが90重量%未満であるので酸素遮断性が悪く
、また結晶化速度が十分でないためインフレーション加
工時にバブルがマシン方向に膨張せずトランスバース方
向に膨張して、甚だ成形が困難であり、プロー成形によ
る容器製造時にも金型を十分に時間をかけ冷却して結晶
化を進めないと、容器の原形が壊れて変形してしまい成
形サイクルも悪いという欠点があった。The characteristics of the technology described in this publication are that the amount of vinylidene chloride used is less than 90% by weight to improve thermal stability during extrusion processing, internal plasticization is achieved by copolymerizing acrylic acid ester of alcohol or phenol, The crystallization rate is increased to improve moldability. It is known that the crystallization rate increases as the number of vinylidene chloride monomer units in the copolymer increases, but Japanese Patent Publication No. 3B-26569
In the resin composition described in the publication, the vinylidene chloride monomer unit is less than 90% by weight, so the oxygen barrier property is poor, and the crystallization rate is not sufficient, so the bubbles do not expand in the machine direction during inflation processing and do not expand in the transverse direction. It expands and is extremely difficult to mold, and if the mold is not cooled down enough to promote crystallization when manufacturing containers by blow molding, the original shape of the container will be destroyed and deformed, resulting in poor molding cycles. There was a drawback.
(発明が解決しようとする課題)
本発明は、可塑剤を使用しないでも成形時の熱安定性が
優れ、インフレーション法威膜、プロー成形、造粒成形
化、特に溶融押出ペレット化を可能とする高い結晶化度
を有し、しかも得られた成形品の酸素遮断性の優れた樹
脂&IItc物を得ることにある。(Problems to be Solved by the Invention) The present invention has excellent thermal stability during molding even without the use of plasticizers, and enables inflation method film formation, blow molding, granulation molding, and especially melt extrusion pelletization. The object of the present invention is to obtain a resin & IItc material having a high degree of crystallinity and having an excellent oxygen barrier property of the resulting molded product.
(課題を解決するための手段)
一般的に、アクリル酸エステルはエステル中のアルコー
ル残基の炭素数が多くなると内部可塑化能は劣ってしま
う、このことはホモポリマーのガラス転移温度から推定
できる。(Means for solving the problem) In general, the internal plasticizing ability of acrylic esters decreases as the number of carbon atoms in the alcohol residue in the ester increases, and this can be estimated from the glass transition temperature of the homopolymer. .
本発明者は、アクリル酸エステルのホモポリマーの中で
最もガラス転移温度の低いアクリル酸2−エチルヘキシ
ルエステル(アルコール残基の炭素数が8)について塩
化ビニリデンとの共重合を試み、鋭意検討した結果、加
工時に十分な内部可塑化能及び結晶化速度をもち、さら
に熱安定性に優れた塩化ビニリデン系樹脂組成物となる
ことを見出し、本発明に達したものである。The present inventor attempted to copolymerize acrylic acid 2-ethylhexyl ester (the number of carbon atoms in the alcohol residue is 8) with vinylidene chloride, which has the lowest glass transition temperature among acrylic acid ester homopolymers, and as a result of intensive study. The present invention was achieved by discovering that a vinylidene chloride resin composition can be obtained which has sufficient internal plasticizing ability and crystallization rate during processing and has excellent thermal stability.
すなわち、本発明は;
塩化ビニリデンモノマーユニットが90〜93重量%、
アクリル酸2−エチルヘキシルエステルモノマーユニッ
トが7〜10重量%からなる共重合体を含む樹脂組成物
に特徴を有する。That is, the present invention includes: 90 to 93% by weight of vinylidene chloride monomer units;
It is characterized by a resin composition containing a copolymer containing 7 to 10% by weight of acrylic acid 2-ethylhexyl ester monomer unit.
さらに、本発明では、該樹脂組成物に熱安定剤としてエ
ポキシ化合物を配合することを好適な態様とする。Furthermore, in the present invention, it is a preferred embodiment that an epoxy compound is blended into the resin composition as a heat stabilizer.
さらに、具体的に本発明を説明する。Furthermore, the present invention will be specifically explained.
本発明の樹脂組成物を構成する共重合体は、−般に油溶
性の開始剤と懸濁剤を用いる懸濁重合法あるいは水溶性
の開始剤と乳化剤を用いる乳化重合法で製造できるが、
それに限定されず、塩化ビニリデン系樹脂の製造するの
に使用される任意の重合法が適用できる。しかし、重合
後に塩析工程が不用な懸濁重合法で得る方が好ましい。The copolymer constituting the resin composition of the present invention can generally be produced by a suspension polymerization method using an oil-soluble initiator and a suspending agent or an emulsion polymerization method using a water-soluble initiator and an emulsifier.
Without being limited thereto, any polymerization method used to produce vinylidene chloride resins can be applied. However, it is preferable to use a suspension polymerization method that does not require a salting-out step after polymerization.
懸濁重合法としては、懸濁剤を溶かした水の中に七ツマ
−を添加する直接懸濁法あるいは特開昭62−2802
07号公報に記載のようにモノマーに懸濁剤を溶かした
水を添加してモノマー相が連続相/水が不連続相である
分散状態を経由して、七ツマ−が不連続/水が連続相で
ある分散体にする懸濁法のいずれでも良い。Suspension polymerization methods include the direct suspension method in which nanatsumer is added to water in which a suspending agent is dissolved, or the method disclosed in Japanese Patent Application Laid-Open No. 62-2802.
As described in Publication No. 07, water in which a suspending agent is dissolved is added to the monomer to create a dispersed state in which the monomer phase is a continuous phase and water is a discontinuous phase, and the monomer is discontinuous/water is a discontinuous phase. Any suspension method in which a dispersion is formed as a continuous phase may be used.
本発明の共重合体を製造するのに使用される油溶性の開
始剤としては、ベンゼン溶液中0゜2mol/j!の濃
度で半限期が、10時間になる温度、いわゆる分解温度
が80℃以下の有機過酸化物、例えば、ジアシルパーオ
キサイド系のインブチルパーオキサイド、2.4−ジク
ロロベンゾイルパーオキサイド、オルソメチルベンゾイ
ルバーオキサイド、ビス−3,5,5−)リメチルヘキ
サノールパーオキサイド、アセチルパーオキサイド、ベ
ンゾイルパーオキサイド、パラクロロベンゾイルパーオ
キサイド、アルキルパーエステル系のアセチルシクロヘ
キサンスルフォニルパーオキサイド、2,4.4−トリ
メチルペンチルパーオキシフェノキシアセテート、t−
ブチルパーオキシネオデカノエート、L−ブチルパーオ
キシピバレート、t−ブチルパーオキシ−2−エチルヘ
キサノエート、t−ブチルパーオキシイソブチレート、
パーカーボネート系のジー3−メトオキシブチルパーオ
キシジカーボネート、ジー2−エチルヘキシルパーオキ
シジカーボネート、ビス(1−tブチルシクロヘキシル
)パーオキシジカーボネート、ジイソプロピルパーオキ
シジカーボネート、ジ5ec−ブチルパーオキシジカー
ボネート、t−プチルパーオキシイソブロビルカーボネ
ートや、アゾビス化合物、例えばアゾビスイソブチロニ
トリル、アゾビスジメチルバレロニトリル等から1種以
上を選択できる。使用量は本発明において重要でなく、
目的とする分子量の共重合体となる量を使用すれば良い
。The oil-soluble initiator used to produce the copolymer of the present invention is 0.2 mol/j! in a benzene solution. Organic peroxides whose half-life is 10 hours at a concentration of 80°C or less, the so-called decomposition temperature, such as diacyl peroxide-based imbutyl peroxide, 2,4-dichlorobenzoyl peroxide, orthomethylbenzoyl peroxide, bis-3,5,5-)limethylhexanol peroxide, acetyl peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, alkyl perester acetylcyclohexane sulfonyl peroxide, 2,4,4-trimethyl Pentyl peroxyphenoxy acetate, t-
Butylperoxyneodecanoate, L-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate,
Percarbonate-based di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(1-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-5ec-butylperoxydicarbonate One or more types can be selected from carbonate, t-butylperoxyisobrobyl carbonate, and azobis compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile. The amount used is not critical to the invention;
It is sufficient to use an amount that will result in a copolymer having the desired molecular weight.
本発明の共重合体を製造するのに使用される懸濁剤とし
ては2%水溶液の25℃における粘度が1(1〜30,
0OOcpsのセルロース誘導体、例えば、メチルセル
ロース、エチルセルロース、セルロースアセテート、セ
ルロースアセテートブチレート、カルボキシメチルセル
ロース、ヒドロキシメチルセルロース、ヒドロキシエチ
ルセルロース、ヒドロキシプロピルセルロース、ヒドロ
キシプロピルメチルセルロース、エチルヒドロキシエチ
ルセルロースや、ポリビニルアルコール及びポリ酢酸ビ
ニルの部分ケン化物等から1種以上を選択できる。使用
量としてはモノマー100重量部当たり0.03重量部
以上が好ましい、 この量未満であると懸濁安定性が悪
くなり重合中に粒子同志が癒着して塊状物となることが
ある。The suspending agent used to produce the copolymer of the present invention has a viscosity of 1 (1 to 30,
0OOcps of cellulose derivatives, such as methylcellulose, ethylcellulose, cellulose acetate, cellulose acetate butyrate, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, and partial saccharides of polyvinyl alcohol and polyvinyl acetate. One or more types can be selected from compounds, etc. The amount used is preferably 0.03 parts by weight or more per 100 parts by weight of the monomer. If the amount is less than this amount, suspension stability may deteriorate and particles may adhere to each other during polymerization to form lumps.
また、本発明の共重合体を製造するのに、必要に応じて
連鎖移動剤、例えばトリクロロエチレン、ドデシルメル
カプタン、オクチルメルカプタンなどを重合時に添加混
合しても良い。Furthermore, in order to produce the copolymer of the present invention, a chain transfer agent such as trichlorethylene, dodecyl mercaptan, octyl mercaptan, etc. may be added and mixed during polymerization, if necessary.
本発明の共重合体を製造するのに、重合温度は、特に制
限されないが、一般に0〜100℃、好ましくは55〜
80°Cが適当である。In producing the copolymer of the present invention, the polymerization temperature is not particularly limited, but is generally 0 to 100°C, preferably 55 to 100°C.
80°C is suitable.
上記重合が終了後、必要に応じて濾過、水洗、乾燥する
が、乳濁状物では硫酸アルミ、芒硝などにより塩析して
から、通常の後処理を行い、粉末状、粒状の樹脂を得る
ことができる。After the above polymerization is completed, filtration, washing with water, and drying are performed as necessary, but in the case of emulsions, salting out with aluminum sulfate, Glauber's salt, etc. is performed, and then the usual post-treatment is performed to obtain powdered or granular resin. be able to.
また、このようにして得られた共重合体樹脂は、そのま
ま次の成形工程に付しても良いが、予め後記説明の熱安
定剤、さらに光安定剤、着色剤などを、重合中或いは重
合後に必要に応じて添加しても良い。The copolymer resin thus obtained may be subjected to the next molding process as it is, but a heat stabilizer as described later, a light stabilizer, a coloring agent, etc. may be added in advance during the polymerization or during the polymerization. It may be added later if necessary.
本発明の樹脂&Ii戒物酸物成する共重合体は、本質的
に塩化ビニリデンモノマーユニットが90〜93重量%
、アクリルf112−エチルへキシルエステルモノマー
7〜10重量%を構成することが必須である。The copolymer composed of the resin & II compound acid of the present invention essentially contains 90 to 93% by weight of vinylidene chloride monomer units.
, 7 to 10% by weight of acrylic f112-ethylhexyl ester monomer.
この要件を満たす範囲で他のビニルモノマー例えば塩化
ビニル、アクリルニトリル、メタクリルニトリル、酢酸
ビニルなどの1種以上を、例えば10重量%以下の範囲
の少量で共重合させても支障がない。As long as this requirement is met, there is no problem in copolymerizing one or more other vinyl monomers such as vinyl chloride, acrylonitrile, methacrylnitrile, vinyl acetate, etc. in a small amount, for example, 10% by weight or less.
本発明に使用する共重合体中の塩化ビニリデンモノマー
ユニットが90重量%未満であると、成形加工に必要な
結晶化速度が十分にならず、また93重量%を超えると
成形加工時の熱安定性が悪くなり好ましくない。If the vinylidene chloride monomer unit in the copolymer used in the present invention is less than 90% by weight, the crystallization rate required for molding will not be sufficient, and if it exceeds 93% by weight, thermal stability during molding will be insufficient. It is undesirable because it makes your sex worse.
また、本発明に樹脂組成物に用いる共重合体の分子量は
特に制限されないが、通常の底形グレードの塩化ビニリ
デン系樹脂の分子量の範囲、例えば約70.000〜約
150,000程度の広範囲のものを使用できる。The molecular weight of the copolymer used in the resin composition of the present invention is not particularly limited, but may be within the range of the molecular weight of ordinary bottom grade vinylidene chloride resins, for example from about 70,000 to about 150,000. can use things.
本発明の樹脂組成物を構成する樹脂成分としては、上記
特定の共重合体単独でも、あるいは該共重合体を主成分
とし、その機能を損なわない範囲で他の塩化ビニリデン
系樹脂の少量を含ませても良い。As the resin component constituting the resin composition of the present invention, the above-mentioned specific copolymer may be used alone, or the copolymer may be the main component, and a small amount of other vinylidene chloride resin may be included as long as the function is not impaired. You can let me.
本発明の樹脂組成物に好適に添加できるエポキシ化合物
とは、例えばエポキシ化植物油系のエボキシ化大豆油、
エポキシ化亜麻仁油、エポキシ化ヒ、シ油、エポキシ樹
脂系のビスフェノールAジグリシジルエーテル、エポキ
シ化ポリブタジェン、エポキシ化モノエステル系のエポ
キシ化ステアリン酸オクチル等から1種以上を選択でき
る。Epoxy compounds that can be suitably added to the resin composition of the present invention include, for example, epoxidized vegetable oil-based epoxidized soybean oil,
One or more types can be selected from epoxidized linseed oil, epoxidized amberjack oil, epoxy resin-based bisphenol A diglycidyl ether, epoxidized polybutadiene, epoxidized monoester-based epoxidized octyl stearate, and the like.
その配合量としては共重合体100重量部当たり1〜2
.5重量部が好ましい、1重量部未満であると十分な熱
安定性とならず、2.5重量部を超えると塩化ビニリデ
ン系樹脂組成物の特徴である酸素遮断性が損なわれる。The blending amount is 1 to 2 per 100 parts by weight of the copolymer.
.. The amount is preferably 5 parts by weight, and if it is less than 1 part by weight, sufficient thermal stability will not be achieved, and if it exceeds 2.5 parts by weight, the oxygen barrier property, which is a characteristic of vinylidene chloride resin compositions, will be impaired.
その他、さらに熱安定性を良くするために塩化ビニリデ
ン系樹脂に従来から使用されている抗酸化剤やチオジプ
ロピオン酸アルキルエステル系、金属酸化物系の熱安定
化助剤を配合しても良い。In addition, to further improve thermal stability, antioxidants, thiodipropionic acid alkyl esters, and metal oxide-based thermal stabilization aids that are conventionally used in vinylidene chloride resins may be added. .
抗酸化剤の例としては、ビタミンE、BHT。Examples of antioxidants are vitamin E, BHT.
BHA等であるが、好ましくは食品安定性の高いビタミ
ンEが良い。BHA, etc., but preferably vitamin E, which has high food stability.
熱安定化助剤としては、例えばリン酸塩系ではピロリン
酸ソーダ、トリポリリン酸ソーダが;EDTA塩系では
EDTA・2Naが;チオジプロピオン酸アルキルエス
テル系ではチオジプロピオン酸ジラウリル、チオジプロ
ピオン酸ジステアリルが:金属酸化物系では酸化マグネ
シウム(MgO)が好ましい。Examples of thermal stabilizing aids include sodium pyrophosphate and sodium tripolyphosphate for phosphate salts; EDTA.2Na for EDTA salts; dilauryl thiodipropionate and thiodipropionic acid for alkyl thiodipropionate esters. Distearyl: Among metal oxide systems, magnesium oxide (MgO) is preferred.
また、本発明の樹脂組成物には、本発明の特定の共重合
体の特性を損なわない範囲で種々の添加剤、例えば光安
定剤、着色剤、滑剤などを配合しても良い。Furthermore, the resin composition of the present invention may contain various additives, such as light stabilizers, colorants, lubricants, etc., within a range that does not impair the properties of the specific copolymer of the present invention.
本発明の樹脂組成物は、共重合して得られたままの共重
合体粉末、または粒状体の形態で成形に供してもよいが
、予めペレタイザーなどの造粒機により予備成形された
ペレットなどの予備成形体とすることが好ましい、この
ような予備成形体にすることにより、従来の粉末状のよ
うに溶融成形、例えば押出成形時のホッパー中で団結化
することがなく、成形加工性が極めて良好である。The resin composition of the present invention may be subjected to molding in the form of copolymer powder as obtained by copolymerization or in the form of granules, but it may also be used as pellets preformed with a granulator such as a pelletizer. It is preferable to form a preformed body of 1. By making such a preformed body, it does not aggregate in the hopper during melt molding, for example, extrusion molding, unlike conventional powder forms, and has good moldability. Very good.
さらに、本発明の樹脂組成物は、それ自体公知の成形手
段、例えば射出成形、押出成形、押出ブロー、インフレ
ーション法などにより、フィルム、シートなどの成膜に
及び各種成形品、とくに食品包装用フィルム、シート及
び容器などに成形できる。Furthermore, the resin composition of the present invention can be used to form various molded products such as films and sheets by molding methods known per se, such as injection molding, extrusion molding, extrusion blowing, and inflation methods, and various molded products, especially food packaging films. , can be formed into sheets, containers, etc.
以上のとおり、本発明の樹脂組成物は、可塑剤無配合で
も容易に成形可能で、しかも成形加工時の熱安定性が優
れかつ結晶化速度が速いので、とくに食品包装用フィル
ム、シート及び容器を連続工程で製造でき、かつ酸素遮
断性にも優れているので、食品包装用フィルム、シート
及び容器などの成形材料として極めて有用である。As described above, the resin composition of the present invention can be easily molded without adding a plasticizer, has excellent thermal stability during molding, and has a fast crystallization rate, so it is particularly suitable for food packaging films, sheets, and containers. Since it can be produced in a continuous process and has excellent oxygen barrier properties, it is extremely useful as a molding material for food packaging films, sheets, containers, etc.
次に、本発明を実施例と比較例で詳細に説明するが、こ
れらは本発明の範囲を朝駆するものでない。Next, the present invention will be explained in detail using Examples and Comparative Examples, but these do not limit the scope of the present invention.
例中の熱安定性、結晶化速度、インフレーション法によ
る成膜テスト、ブロー法による容器成形テスト、ペレッ
ト化テスト及び酸素遮断性及び分子量は以下の方法で行
った。Thermal stability, crystallization rate, film formation test by inflation method, container molding test by blow method, pelletization test, oxygen barrier property, and molecular weight in the examples were conducted using the following methods.
(i)熱安定性:
塩化ビニリデン系樹脂組成物を、ブラベンダー社製プラ
ストグラフを用いて、170″C,50rpmで混練り
しながら、溶融した樹脂組成物を2゜5分毎にサンプリ
ングして経時変色を観察し、変色の程度により押出加工
時の熱安定性の評価とした。なお、評価結果は以下の記
号で表した。(i) Thermal stability: While kneading the vinylidene chloride resin composition at 170"C and 50 rpm using a Brabender Plastograph, the molten resin composition was sampled every 2.5 minutes. The discoloration over time was observed, and the thermal stability during extrusion processing was evaluated based on the degree of discoloration.The evaluation results were expressed by the following symbols.
O;優(実用上成形加工に全く問題のないレベル)
O;良(実用上成形加工に問題のないレベル)Δ;可(
実用上底形加工に若干問題のあるレベル)
×;不可(実用上成形加工できないレベル)(ii)結
晶化速度:
共重合体logをテトラヒドロフラン100gに溶解し
て200μのテフロンシートにコーティングし、100
°Cで1分間乾燥させ、さらに220°Cで30秒間熱
処理した後に、直ちに4°Cの冷水中に浸す0次に、冷
水から取り出して、直ちにテフロンシートより共重合体
膜を剥ぎ取り、1゜200 CI−’〜800 cta
−’のIRスペクトルをとる。O: Excellent (level without any problem in practical molding process) O: Good (level without problem in practical molding process) Δ: Fair (
(Level that causes some problems in practical bottom shape processing)
After drying at °C for 1 minute and heat treatment at 220 °C for 30 seconds, immediately immerse in cold water at 4 °C.Next, remove from cold water and immediately peel off the copolymer film from the Teflon sheet.゜200 CI-'~800 cta
-' IR spectrum is taken.
この時に1.046C11−’の吸収がないことを確認
する。その後は共重合体膜を20°Cの雰囲気中に放置
し、時間毎(任意)にIRスペクトルをとる。At this time, it is confirmed that there is no absorption of 1.046C11-'. Thereafter, the copolymer film is left in an atmosphere at 20° C., and an IR spectrum is taken every time (arbitrarily).
相対結晶化度(%)の計算は1.100cm−’と85
0CI−’をターゲントとして線を結び、この線からの
1,070cm−’と1,046cm−’の吸光度比を
計算しくA)、別途95°Cで30分間熱処理した共重
合体膜のIRスペクトルを同様にして吸光度比を計算し
くB)、(A/B)x 10oとして求めた。Calculation of relative crystallinity (%) is 1.100 cm-' and 85
Connect a line using 0CI-' as a target and calculate the absorbance ratio at 1,070 cm-' and 1,046 cm-' from this line. A) IR spectrum of a copolymer film separately heat-treated at 95°C for 30 minutes. In the same manner, the absorbance ratio was calculated as B), (A/B) x 10o.
(iii )インフレーション法による成膜テスト:第
1図に示された押出ml(40m+φ、L/D =21
)で樹脂Allll金物80−185’Cに溶融し、サ
ーキュラ−ダイ3(27msφ、スリット1. 1閣)
から12kg/Hrで押出された管状体樹脂組成物(以
下、パリソンと言う)11に粘着防止剤としてミネラル
オイルを注入して、7°Cの冷却バス4と60″Cの余
熱バス5に通した後、パリソン温度52℃で圧さく空気
を入れてインフレーションバブル(未延伸フィルム)6
を作り、生成した管状延伸フィルム7を巻取った。この
とき連続して巻取ることができる時間で成膜性を評価し
た。(iii) Film formation test by inflation method: Extruded ml (40 m + φ, L/D = 21
) to melt resin Allll hardware 80-185'C, circular die 3 (27msφ, slit 1.1mm)
Mineral oil was injected as an anti-blocking agent into the tubular resin composition (hereinafter referred to as parison) 11 which was extruded at 12 kg/hr from 12 kg/hr, and the mixture was passed through a cooling bath 4 at 7°C and a preheating bath 5 at 60″C. After that, the parison temperature is 52℃ and air is introduced to create an inflation bubble (unstretched film) 6.
The resulting tubular stretched film 7 was wound up. At this time, film formability was evaluated based on the time required for continuous winding.
(iv)ブロー法による容器成形テスト:インフレーシ
ョン法による底膜テストに用いた押出機とサーキュラ−
ダイを用い、樹脂組成物を180〜185°Cに溶融し
、押出されたパリソンを50〜60°Cに保った金型9
(第2図に示す)に挟み、圧さく空気を吹き込んで成形
し、5秒後に金型から取り出して20’C雰囲気中に1
0分間放置し、容器の変形を調べた。(iv) Container molding test using blow method: Extruder and circular used for bottom membrane test using inflation method
A mold 9 in which the resin composition was melted at 180 to 185°C and the extruded parison was kept at 50 to 60°C using a die.
(shown in Figure 2), molded by blowing compressed air, and removed from the mold after 5 seconds and placed in a 20'C atmosphere for 1 hour.
The container was left to stand for 0 minutes and the deformation of the container was examined.
(v)ペレット化テスト:
インフレーション法による底膜テストに用いた、第1図
に示される押出機と、ペレットダイ3(15Wφ)を用
い、樹脂組成物を180−185°Cに溶融し、12k
g/Hrで押出された円柱状体樹脂&lI威物酸物下ス
トランドと言う)を7°Cの冷却バスを通した後、12
〜14°Cの冷却バスを通し、ペレタイザーにてカッテ
ィングを行った。このときのカッティング直前のストラ
ンド温度は45°Cであった。(v) Pelletization test: The resin composition was melted at 180-185°C using the extruder shown in Fig. 1 and pellet die 3 (15Wφ) used for the bottom film test by the inflation method, and
After passing through a cooling bath at 7°C, the cylindrical resin extruded at
It was passed through a cooling bath at ~14°C and cut with a pelletizer. At this time, the strand temperature immediately before cutting was 45°C.
(vi)酸素遮断性:
樹脂&l威酸物押出成膜して、厚み25μのフィルムを
得、このフィルムの酸素透過1をAsTM−D3985
に!#拠して測定し、1μ厚みの値に換算した(単位:
CC・μm/nf・24Hr・atm−at20’c、
、100%RH)。(vi) Oxygen barrier property: A film with a thickness of 25 μm was obtained by extrusion of resin and strong acid, and the oxygen permeability 1 of this film was determined by AsTM-D3985.
To! It was measured based on # and converted into a value of 1μ thickness (unit:
CC・μm/nf・24Hr・atm-at20'c,
, 100%RH).
(vi)分子量:
分子量は、ポリスチレンを標準としたゲルパーミェーシ
ョンクロマトグラフィー法で測定した。(vi) Molecular weight: The molecular weight was measured by gel permeation chromatography using polystyrene as a standard.
(実施例1)
内部がグラスライニングされた攪拌機付き反応機に、ヒ
ドロキシプロピルメチルセルロース0゜2部を溶解した
脱イオン水120部を投入し、系内を30°Cにて窒素
置換後、塩化ビニリデン単量体(以下VDCと略す)9
2.5重量部、アクリル酸2−エチルヘキシルエステル
(以下2已HAと略す)7.5重量部、(−ブチルパー
オキシ2−エチルヘキサノエート0.9重量部の混合物
を投入し、反応機内を75°Cに昇温しで重合を開始す
る。10時間後に反応機内を30°Cに降温してスラリ
ーを取り出す、得られたスラリーを遠心式の脱水機にて
水を分離し、ついで80’Cの熱風乾燥機にて24時間
乾燥してグラニュー状のVDC/2EHA共重合体99
重量部を得た。(Example 1) 120 parts of deionized water in which 0.2 parts of hydroxypropyl methylcellulose was dissolved was put into a reactor equipped with a stirrer and the interior was glass lined, and after purging the system with nitrogen at 30°C, vinylidene chloride was added. Monomer (hereinafter abbreviated as VDC) 9
A mixture of 2.5 parts by weight of acrylic acid 2-ethylhexyl ester (hereinafter abbreviated as 2HA), and 0.9 parts by weight of (-butylperoxy 2-ethylhexanoate) was introduced into the reactor. Polymerization is started by raising the temperature to 75°C. After 10 hours, the temperature inside the reactor is lowered to 30°C and the slurry is taken out. The resulting slurry is separated from water using a centrifugal dehydrator, and then VDC/2EHA copolymer 99 in granule form after drying for 24 hours in a hot air dryer
Parts by weight were obtained.
この共重合体の分子量は、ポリスチレンを標準としたゲ
ルパーミニ−シランクロマトグラフィー法で87,90
0であった。The molecular weight of this copolymer was determined to be 87.90 by gel permini-silane chromatography using polystyrene as a standard.
It was 0.
次に得られた共重合体100重量部に対し、ビスフェノ
ールAジグリシジルエーテルを2,0重量部、ビタミン
Eを0.01重量部、EDTA・2Naを0.02重量
部、MgOを0.4重量部配合して熱安定性の評価を実
施した。Next, to 100 parts by weight of the obtained copolymer, 2.0 parts by weight of bisphenol A diglycidyl ether, 0.01 parts by weight of vitamin E, 0.02 parts by weight of EDTA/2Na, and 0.4 parts by weight of MgO. Thermal stability was evaluated by blending parts by weight.
実施例2
実施例1で得た共重合体の結晶化速度を測定し、さらに
共重合体100重量部に対し、ビスフェノールAジグリ
シジルエーテルを2.0重量部、ビタよンEを0.01
重量部、EDTA・2Naを0.02重量部を配合して
熱安定性の評価、インフレーション法による押出成膜テ
ストと酸素透過量の測定、ブロー法による容器成形テス
ト及びペレット化テストを実施した。Example 2 The crystallization rate of the copolymer obtained in Example 1 was measured, and 2.0 parts by weight of bisphenol A diglycidyl ether and 0.01 part of Vitayon E were added to 100 parts by weight of the copolymer.
parts by weight, and 0.02 parts by weight of EDTA/2Na were blended, and evaluation of thermal stability, extrusion film formation test by inflation method and measurement of oxygen permeation amount, container molding test and pelletization test by blow method were carried out.
実施例3
VDCを90重量部、2EHAを10重量部とする他は
、実施例1と同様にして共重合体9つ重量部を得た。Example 3 Nine parts by weight of a copolymer were obtained in the same manner as in Example 1, except that 90 parts by weight of VDC and 10 parts by weight of 2EHA were used.
得られた共重合体の分子量は、87,100であった0
次に実施例2と同様な評価を実施した。The molecular weight of the obtained copolymer was 87,100.
Next, the same evaluation as in Example 2 was performed.
比較例1
VDCを95重量部、2EHAを5重量部、を−ブチル
パーオキシ2−エチルヘキサノエートを0.775重量
部とする他は、実施例1と同様にして共重合体99重量
部を得た。Comparative Example 1 99 parts by weight of the copolymer was prepared in the same manner as in Example 1, except that 95 parts by weight of VDC, 5 parts by weight of 2EHA, and 0.775 parts by weight of -butylperoxy 2-ethylhexanoate were used. I got it.
得られた共重合体の分子量は86,100であった0次
に実施例1と同様に安定剤を添加して熱安定性を評価し
た。The resulting copolymer had a molecular weight of 86,100.Next, a stabilizer was added in the same manner as in Example 1 to evaluate thermal stability.
比較例2
VDCを87.5重量部、2EHAを12.5重量部と
する他は、実施例1と同様にして共重合体99重量部を
得た。Comparative Example 2 99 parts by weight of a copolymer was obtained in the same manner as in Example 1, except that VDC was changed to 87.5 parts by weight and 2EHA was changed to 12.5 parts by weight.
得られた共重合体の分子量は93.000であった0次
に実施例2と同様な評価を実施した。The obtained copolymer had a molecular weight of 93.000. Next, the same evaluation as in Example 2 was carried out.
比較例3
VDCを80重量部、2EHAを20重量部とする他は
、実施例1と同様にして重合体を得ようとしたが、遠心
脱水中に共重合体粒子同志が癒着してグラニュー状とな
らなかった。Comparative Example 3 An attempt was made to obtain a polymer in the same manner as in Example 1 except that 80 parts by weight of VDC and 20 parts by weight of 2EHA were used, but the copolymer particles adhered to each other during centrifugal dehydration, resulting in a granular shape. It didn't happen.
比較例4
VDCを81.5重量部、塩化ビニル(以下VCと略す
)を18.5重量部、ジイソプロピルパーオキシジカー
ボネートを0.2重量部、反応機内を45°Cにして4
0時間後に降温する他は、実施例1と同様にして共重合
体90重量部を得た。Comparative Example 4 81.5 parts by weight of VDC, 18.5 parts by weight of vinyl chloride (hereinafter abbreviated as VC), 0.2 parts by weight of diisopropyl peroxydicarbonate, and the temperature inside the reactor was set to 45°C.
90 parts by weight of a copolymer was obtained in the same manner as in Example 1, except that the temperature was lowered after 0 hours.
得られた共重合体の分子量は92,500であった0次
に実施例2と同様な安定剤を配合して熱安定性の評価と
インフレーション法による成膜テストを実施した。The obtained copolymer had a molecular weight of 92,500.Next, a stabilizer similar to that in Example 2 was blended, and thermal stability evaluation and a film formation test by an inflation method were conducted.
比較例5
比較例4の共重合体に実施例2と同様な安定剤と、さら
に可塑剤であるATBCを5重量部配合して、熱安定性
の評価、結晶化速度測定、インフレーション法による成
膜テストと酸素透過量の測定、ブロー法による容器成形
テストおよびペレット化テストを実施した。Comparative Example 5 The same stabilizer as in Example 2 and 5 parts by weight of ATBC as a plasticizer were added to the copolymer of Comparative Example 4, and evaluation of thermal stability, crystallization rate measurement, and formation by the inflation method were carried out. Membrane tests, oxygen permeation measurements, container molding tests using the blow method, and pelletizing tests were conducted.
以上の評価結果を表−1に示す。The above evaluation results are shown in Table-1.
表−1のごとく共重合体中のVDCモノマーユニットが
本発明の93重量%を超えると、熱安定性が悪くインフ
レーション法による成膜において樹脂の分解物(カーボ
ン)が発生し、バブル破裂のため10分以上の連続成膜
は不可能であった。As shown in Table 1, when the VDC monomer unit in the copolymer exceeds 93% by weight of the present invention, thermal stability is poor and resin decomposition products (carbon) are generated during film formation by the inflation method, resulting in bubble rupture. Continuous film formation for 10 minutes or more was impossible.
また、共重合体中のVDC七ツマ−ユニットの量が本発
明の90重量%に満たないと、結晶化速度が遅く、イン
フレーション法による成膜においてトランスバース方向
に膨張してバブルが破裂し、連続成膜が不可能であり、
ブロー法による成形品容器の変形も10分以内に起こり
、押出ペレット化ではストランドが固くならず切断でき
なかった。Furthermore, if the amount of VDC heptad units in the copolymer is less than 90% by weight of the present invention, the crystallization rate will be slow, and bubbles will burst in the transverse direction during film formation by the inflation method. Continuous film formation is not possible,
Deformation of the molded container by blowing also occurred within 10 minutes, and in extrusion pelletization the strands did not become hard and could not be cut.
以上のとうり、本発明の樹脂組成物は、主要構成樹脂と
して特定のVDCモノマー含置装共重合体を用いたので
、結晶化速度が例えば500秒以下、好ましくは150
秒以下と速いにもかかられす、酸素遮断性、熱安定性に
優れた成形品に成形できるので、高速連続成形に適する
。As described above, since the resin composition of the present invention uses a specific VDC monomer-containing copolymer as the main constituent resin, the crystallization rate is, for example, 500 seconds or less, preferably 150 seconds or less.
It is suitable for high-speed continuous molding because it can be molded into molded products with excellent oxygen barrier properties and thermal stability in less than a second.
(発明の効果)
本発明の樹脂組成物は、可塑剤無配合で加工時の熱安定
性に優れ、結晶化速度が速いので、連続して■ベレット
化、■インフレーション法による成膜フィルム化、■キ
ャスト法によるシート化、■ブロー法による容器化が容
易となったばかりでなく、酸素遮断性も一層向上した。(Effects of the Invention) The resin composition of the present invention does not contain a plasticizer, has excellent thermal stability during processing, and has a fast crystallization rate. Not only has it become easier to make sheets using the casting method and containers using the blowing method, but the oxygen barrier properties have also been further improved.
第1図は、本発明の樹脂組成物のインフレーション法に
よる成膜テストに用いるフローの概略を示す模式図であ
る。
第2図は、本発明の樹脂&[l酸物のブロー法による容
器底形テストに用いる金型の概略を示す模式1ニスクリ
ユ一押出機
2:ホ・ンパー
3:ダイ
4:冷却バス
5:余熱バス
6:未延伸フィルム
:延伸フィルム
:巻取
:ボトル用金型
:アキュームヘッド
:パリソンFIG. 1 is a schematic diagram showing an outline of the flow used in a film formation test using the inflation method of the resin composition of the present invention. Fig. 2 is a schematic diagram showing the outline of the mold used for the container bottom shape test by the blowing method of the resin and acid of the present invention. Preheat bath 6: Unstretched film: Stretched film: Winding: Bottle mold: Accumulation head: Parison
Claims (1)
、アクリル酸2−エチルヘキシルエステルモノマーユニ
ットが7〜10重量%からなる共重合体を含む塩化ビニ
リデン系樹脂組成物。90-93% by weight vinylidene chloride monomer unit
, a vinylidene chloride resin composition comprising a copolymer containing 7 to 10% by weight of acrylic acid 2-ethylhexyl ester monomer unit.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31655589A JPH03179048A (en) | 1989-12-07 | 1989-12-07 | Vinylidene chloride resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31655589A JPH03179048A (en) | 1989-12-07 | 1989-12-07 | Vinylidene chloride resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03179048A true JPH03179048A (en) | 1991-08-05 |
Family
ID=18078404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31655589A Pending JPH03179048A (en) | 1989-12-07 | 1989-12-07 | Vinylidene chloride resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03179048A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0773254A1 (en) | 1995-11-10 | 1997-05-14 | Kureha Kagaku Kogyo Kabushiki Kaisha | Vinylidene chloride resin composition and process for production thereof |
-
1989
- 1989-12-07 JP JP31655589A patent/JPH03179048A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0773254A1 (en) | 1995-11-10 | 1997-05-14 | Kureha Kagaku Kogyo Kabushiki Kaisha | Vinylidene chloride resin composition and process for production thereof |
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