JPWO2016174978A1 - Vinylidene chloride resin stretched film - Google Patents
Vinylidene chloride resin stretched film Download PDFInfo
- Publication number
- JPWO2016174978A1 JPWO2016174978A1 JP2017515445A JP2017515445A JPWO2016174978A1 JP WO2016174978 A1 JPWO2016174978 A1 JP WO2016174978A1 JP 2017515445 A JP2017515445 A JP 2017515445A JP 2017515445 A JP2017515445 A JP 2017515445A JP WO2016174978 A1 JPWO2016174978 A1 JP WO2016174978A1
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene chloride
- film
- chloride resin
- resin film
- spherical
- 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.)
- Granted
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 67
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 239000012798 spherical particle Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000012360 testing method Methods 0.000 description 21
- 238000004806 packaging method and process Methods 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000000654 additive Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 6
- 239000012748 slip agent Substances 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- YJFCFSVVFTZXBL-UHFFFAOYSA-N o-[3-henicosanethioyloxy-2,2-bis(henicosanethioyloxymethyl)propyl] henicosanethioate Chemical compound CCCCCCCCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCCCCCCCC YJFCFSVVFTZXBL-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000013580 sausages Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- TUTWLYPCGCUWQI-UHFFFAOYSA-N decanamide Chemical compound CCCCCCCCCC(N)=O TUTWLYPCGCUWQI-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000012674 dispersion polymerization 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
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- OOCSVLHOTKHEFZ-UHFFFAOYSA-N icosanamide Chemical compound CCCCCCCCCCCCCCCCCCCC(N)=O OOCSVLHOTKHEFZ-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- QJXZDBOIVBLYSJ-UHFFFAOYSA-N o-[3-heptadecanethioyloxy-2,2-bis(heptadecanethioyloxymethyl)propyl] heptadecanethioate Chemical compound CCCCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCCCC QJXZDBOIVBLYSJ-UHFFFAOYSA-N 0.000 description 1
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical compound CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IPWFJLQDVFKJDU-UHFFFAOYSA-N pentanamide Chemical compound CCCCC(N)=O IPWFJLQDVFKJDU-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本発明に係る塩化ビニリデン系樹脂フィルムは、平均粒子径が4μmより大きく、15μm以下である球状粒子を含む。The vinylidene chloride resin film according to the present invention includes spherical particles having an average particle size larger than 4 μm and 15 μm or less.
Description
本発明は塩化ビニリデン系樹脂フィルムに関する。 The present invention relates to a vinylidene chloride resin film.
一般に、塩化ビニリデン系樹脂組成物は、酸素ガス遮断性および水蒸気遮断性に優れているため、ソーセージなどの食品を包装するフィルムなどに使用されている。 In general, vinylidene chloride resin compositions are excellent in oxygen gas barrier properties and water vapor barrier properties, and are therefore used in films for packaging foods such as sausages.
食品を包装するフィルムにおいては、低温で包装、運搬または保管されるため、耐寒性に優れたものが求められている。また、当該フィルムを包装機械で加工する際に必要な性質である包装機械適性が求められている。しかし、塩化ビニリデン系樹脂自体は耐寒性および包装機械適性に優れた樹脂ではない。耐寒性が不十分であると、例えば、フィルムの脆化、破れおよびピンホール発生などがおこる。また、包装機械適性のうち、例えば、滑り性が不十分であると、フィルムの走行性が悪くなったり、製袋時のシール性に乱れが生じたりするなど、作業性悪化につながる問題が生じる。 Films for packaging foods are required to have excellent cold resistance because they are packaged, transported or stored at low temperatures. Moreover, the packaging machine aptitude which is a property required when processing the film with a packaging machine is required. However, vinylidene chloride resin itself is not a resin excellent in cold resistance and suitability for packaging machinery. If the cold resistance is insufficient, for example, the film becomes brittle, torn and pinholes occur. In addition, among the suitability of packaging machines, for example, if the slipperiness is insufficient, there are problems that lead to deterioration in workability, such as poor film runnability and disorder in the sealing performance during bag making. .
特許文献1には、少なくとも2種の塩化ビニリデン共重合体からなる混合塩化ビニリデン樹脂と、エチレンおよび酢酸ビニルの共重合体とを含む塩化ビニリデン共重合体含有樹脂組成物が開示されている。当該組成物から形成されたフィルムは、耐寒性および包装機械適性等に優れることが記載されている。 Patent Document 1 discloses a vinylidene chloride copolymer-containing resin composition containing a mixed vinylidene chloride resin composed of at least two types of vinylidene chloride copolymers and a copolymer of ethylene and vinyl acetate. It is described that a film formed from the composition is excellent in cold resistance and suitability for packaging machinery.
ところで、特許文献2〜5において、球状シリカ等の球状粒子を含む樹脂からなるフィルムは、球状シリカ等の球状粒子を含まない樹脂からなるフィルムに比べて、特定の性質に優れていることが記載されている。 By the way, in patent documents 2-5, it is described that the film which consists of resin containing spherical particles, such as spherical silica, is excellent in the specific property compared with the film which consists of resin which does not contain spherical particles, such as spherical silica. Has been.
特許文献2には、防曇剤含有球状シリカを含む高分子組成物からなる高分子フィルムが開示されており、この高分子フィルムは透明性および防曇性に優れることが記載されている。 Patent Document 2 discloses a polymer film comprising a polymer composition containing an antifogging agent-containing spherical silica, and describes that this polymer film is excellent in transparency and antifogging properties.
特許文献3には、球状シリカを含むポリプロピレン系樹脂組成物からなるポリプロピレンフィルムが開示されており、このポリプロピレンフィルムは耐ブロッキング性(吸湿時の流動性)および耐傷付き性等に優れることが記載されている。 Patent Document 3 discloses a polypropylene film made of a polypropylene resin composition containing spherical silica, and it is described that this polypropylene film is excellent in blocking resistance (fluidity during moisture absorption) and scratch resistance. ing.
特許文献4には、球状シリカを含むポリオレフィン系樹脂組成物からなる包装用フィルムが開示されており、この包装用フィルムは耐ブロッキング性、滑り性および透明性に優れることが記載されている。 Patent Document 4 discloses a packaging film made of a polyolefin resin composition containing spherical silica, and describes that this packaging film is excellent in blocking resistance, slipperiness and transparency.
特許文献5には、平均粒径が0.2〜4μmである球状シリカを含む熱可塑性重合体からなる熱可塑性重合体フィルムが開示されており、この熱可塑性重合体フィルムは製膜性、ハンドリング性および滑り性等に優れることが記載されている。 Patent Document 5 discloses a thermoplastic polymer film made of a thermoplastic polymer containing spherical silica having an average particle diameter of 0.2 to 4 μm, and this thermoplastic polymer film has a film forming property and handling. It is described that it has excellent properties and slipperiness.
しかしながら、特許文献1に記載のフィルムのように、塩化ビニリデン共重合体にエチレンと酢酸ビニルとの共重合体(EVA)を添加した場合でも、その耐寒性は必ずしも十分ではなく、耐寒性のさらなる向上が求められている。 However, even when a copolymer of ethylene and vinyl acetate (EVA) is added to a vinylidene chloride copolymer as in the film described in Patent Document 1, the cold resistance is not always sufficient, and the cold resistance is further increased. There is a need for improvement.
また、特許文献2〜4では、塩化ビニリデン系樹脂の耐寒性を向上させることについては記載されていない。同様に、特許文献5においても、熱可塑性重合体フィルムの耐寒性を向上させることについては記載されていない。 Patent Documents 2 to 4 do not describe improving the cold resistance of vinylidene chloride-based resins. Similarly, Patent Document 5 does not describe improving the cold resistance of a thermoplastic polymer film.
本発明は、上記課題に鑑みなされたものであり、その目的は、耐寒性および包装機械適性に優れる塩化ビニリデン系樹脂フィルムを提供することにある。 This invention is made | formed in view of the said subject, The objective is to provide the vinylidene chloride type-resin film excellent in cold resistance and packaging machine aptitude.
上記の課題を解決するために、本発明者が鋭意検討した結果、以下の本発明に達した。 In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, have reached the following present invention.
本発明に係る塩化ビニリデン系樹脂フィルムは、平均粒子径が4μmより大きく、15μm以下である球状粒子を含むことを特徴とする。 The vinylidene chloride-based resin film according to the present invention is characterized by containing spherical particles having an average particle diameter of greater than 4 μm and 15 μm or less.
本発明に係る塩化ビニリデン系樹脂フィルムは、耐寒性および包装機械適性に優れるという効果を奏する。 The vinylidene chloride resin film according to the present invention has the effect of being excellent in cold resistance and suitability for packaging machinery.
以下、本発明に係る塩化ビニリデン系樹脂フィルムの一実施形態について説明する。 Hereinafter, an embodiment of a vinylidene chloride resin film according to the present invention will be described.
<塩化ビニリデン系樹脂フィルム>
本実施形態に係る塩化ビニリデン系樹脂フィルムは、平均粒子径が4μmより大きく、15μm以下である球状粒子を含んでいるものである。これにより、耐寒性および包装機械適性に優れる塩化ビニリデン系樹脂フィルムとなる。<Vinylidene chloride resin film>
The vinylidene chloride-based resin film according to the present embodiment includes spherical particles having an average particle size larger than 4 μm and 15 μm or less. Thereby, it becomes a vinylidene chloride resin film excellent in cold resistance and packaging machine suitability.
〔球状粒子〕
塩化ビニリデン系樹脂フィルムに添加される球状粒子は平均粒子径が4μmより大きく、15μm以下であればよい。ここで、平均粒子径は、公知のレーザ回折式粒子径分布測定装置を用いて測定すればよく、例えば、島津製作所製レーザ回折式粒子径分布測定装置SALD−2000Jを用いて測定することが挙げられる。[Spherical particles]
The spherical particles added to the vinylidene chloride-based resin film may have an average particle size larger than 4 μm and 15 μm or less. Here, the average particle size may be measured using a known laser diffraction particle size distribution measuring device, for example, using a Shimadzu laser diffraction particle size distribution measuring device SALD-2000J. It is done.
球状粒子の平均粒子径の下限値としては、4μmより大きければよく、4.5μm以上であることが好ましい。また、上限値としては、15μm以下であればよく、10μm以下であることが好ましく、7μm以下であることがより好ましい。球状粒子の平均粒子径が4μm以下だと、塩化ビニリデン系樹脂フィルムは耐寒性に優れるものの、十分な包装機械適性が得られなくなる。また、球状粒子の平均粒子径が15μmよりも大きいと、包装機械適性に優れるものの、十分な耐寒性が得られなくなる。したがって、上述の範囲内にあることにより、耐寒性および包装機械適性の両方に優れている塩化ビニリデン系樹脂フィルムを得ることができる。 The lower limit of the average particle diameter of the spherical particles may be larger than 4 μm, and is preferably 4.5 μm or more. The upper limit value may be 15 μm or less, preferably 10 μm or less, and more preferably 7 μm or less. If the average particle diameter of the spherical particles is 4 μm or less, the vinylidene chloride resin film is excellent in cold resistance, but sufficient packaging machine suitability cannot be obtained. On the other hand, when the average particle diameter of the spherical particles is larger than 15 μm, sufficient cold resistance cannot be obtained although the packaging machine suitability is excellent. Therefore, by being in the above-mentioned range, it is possible to obtain a vinylidene chloride resin film that is excellent in both cold resistance and suitability for packaging machinery.
一般的な球状シリカの製造方法としては、シリカゾルをスプレードライヤーで造粒乾燥する方法および界面活性剤を含む非極性有機溶媒中で珪酸ソーダを乳化させた後ゲル化させる方法等が挙げられ、界面活性剤を含む非極性有機溶媒中で珪酸ソーダを乳化させた後ゲル化させる方法であることが好ましい。 Examples of the general method for producing spherical silica include a method of granulating and drying silica sol with a spray dryer, a method of emulsifying sodium silicate in a nonpolar organic solvent containing a surfactant, and a method of gelling, and the like. A method in which sodium silicate is emulsified in a nonpolar organic solvent containing an activator and then gelled is preferred.
球状粒子の含有量は、塩化ビニリデン系樹脂フィルムを形成している塩化ビニリデン系樹脂100重量部に対して、0.04〜0.4重量部の範囲であることが好ましく、0.05〜0.2重量部の範囲であることがより好ましい。上述の好ましい範囲内にあることにより、より耐寒性および包装機械適性に優れる塩化ビニリデン系樹脂フィルムを得ることができ、フィルムが白化せず透明なフィルムを得ることができる。 The content of the spherical particles is preferably in the range of 0.04 to 0.4 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin forming the vinylidene chloride resin film. More preferably, it is in the range of 2 parts by weight. By being in the above-mentioned preferable range, it is possible to obtain a vinylidene chloride resin film that is more excellent in cold resistance and suitability for packaging machines, and a transparent film can be obtained without whitening of the film.
球状粒子としては、例えば、球状シリカ、球状炭酸カルシウム、球状アルミナ、球状チタニア、球状ジルコニア等の球状無機粒子およびポリマービーズ等が挙げられ、球状シリカ、球状炭酸カルシウムまたはポリマービーズであることが好ましく、球状シリカであることがより好ましい。球状シリカを添加することにより、より耐寒性および包装機械適性に優れる塩化ビニリデン系樹脂フィルムを得ることができる。なお、ポリマービーズの具体例としては、例えば、ポリブチルメタクリレートのポリマービーズ、ポリメチルメタクリレートのポリマービーズ、シリコーンのポリマービーズ、およびメチルメタクリレート/スチレンのコポリマーのポリマービーズ等が挙げられる。 Examples of the spherical particles include spherical inorganic particles such as spherical silica, spherical calcium carbonate, spherical alumina, spherical titania, and spherical zirconia, and polymer beads, and are preferably spherical silica, spherical calcium carbonate, or polymer beads. Spherical silica is more preferable. By adding spherical silica, it is possible to obtain a vinylidene chloride resin film that is more excellent in cold resistance and packaging machine suitability. Specific examples of the polymer beads include polybutyl methacrylate polymer beads, polymethyl methacrylate polymer beads, silicone polymer beads, and methyl methacrylate / styrene copolymer polymer beads.
〔塩化ビニリデン系樹脂〕
塩化ビニリデン系樹脂フィルムを形成している塩化ビニリデン系樹脂は、塩化ビニリデン共重合体を主成分として含有する。塩化ビニリデン共重合体は、塩化ビニリデン60〜98重量%および塩化ビニリデンと共重合可能な単量体の少なくとも一種2〜40重量%から形成される共重合体である。塩化ビニリデン共重合体は、塩化ビニリデンモノマー(単量体)と塩化ビニリデンと共重合可能な単量体とを、懸濁重合または乳化重合して製造されるものである。塩化ビニリデンと共重合可能な単量体(以下、共単量体)としては、例えば塩化ビニル、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸2−エチルヘキシル、アクリル酸ラウリルおよびアクリル酸ステアリル等のアクリル酸アルキルエステル(アルキル基の炭素数1〜18);メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸2−エチルヘキシル、メタクリル酸ラウリルおよびタクリル酸ステアリル等のメタクリル酸アルキルエステル(アルキル基の炭素数1〜18);アクリロニトリルおよびメタクリロニトリル等のシアン化ビニル;スチレン等の芳香族ビニル;酢酸ビニル等の炭素数1〜18の脂肪族カルボン酸のビニルエステル;炭素数1〜18のアルキルビニルエーテル;アクリル酸、メタクリル酸、マレイン酸、フマル酸およびイタコン酸等のビニル重合性不飽和カルボン酸;マレイン酸、フマル酸およびイタコン酸等のビニル重合性不飽和カルボン酸のアルキルエステル(部分エステルを含み、アルキル基の炭素数1〜18);その他、ジエン系単量体、官能基含有単量体ならびに多官能性単量体等を挙げられる。これらの共単量体は、単独でまたは2種以上を組み合わせて用いることができる。共単量体の中でも、塩化ビニル、アクリル酸メチルまたはアクリル酸ブチルが好ましく、塩化ビニルがより好ましい。したがって、より好ましい塩化ビニリデン共重合体は、塩化ビニリデン−塩化ビニル共重合体である。塩化ビニリデン共重合体における塩化ビニリデンの含有比率は、70重量%以上が好ましく、80重量%以上がより好ましい。塩化ビニリデンの含有比率の上限は特にないが、包装機械適性の一つである押出加工性等の観点から、98重量%が好適であり、95重量%がより好適である。[Vinylidene chloride resin]
The vinylidene chloride resin forming the vinylidene chloride resin film contains a vinylidene chloride copolymer as a main component. The vinylidene chloride copolymer is a copolymer formed from 60 to 98% by weight of vinylidene chloride and 2 to 40% by weight of at least one monomer copolymerizable with vinylidene chloride. The vinylidene chloride copolymer is produced by suspension polymerization or emulsion polymerization of a vinylidene chloride monomer (monomer) and a monomer copolymerizable with vinylidene chloride. Examples of the monomer copolymerizable with vinylidene chloride (hereinafter, comonomer) include, for example, vinyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate. Acrylic acid alkyl esters (alkyl group having 1 to 18 carbon atoms); methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl tacrylate, etc. 1-18); vinyl cyanide such as acrylonitrile and methacrylonitrile; aromatic vinyl such as styrene; vinyl ester of aliphatic carboxylic acid having 1 to 18 carbon atoms such as vinyl acetate; alkyl vinyl ether having 1 to 18 carbon atoms; Acrylic acid, methacrylic acid Vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid (including partial esters, carbon number of alkyl group 1 -18); other examples include diene monomers, functional group-containing monomers, and polyfunctional monomers. These comonomer can be used individually or in combination of 2 or more types. Among the comonomer, vinyl chloride, methyl acrylate or butyl acrylate is preferable, and vinyl chloride is more preferable. Therefore, a more preferred vinylidene chloride copolymer is a vinylidene chloride-vinyl chloride copolymer. The content ratio of vinylidene chloride in the vinylidene chloride copolymer is preferably 70% by weight or more, and more preferably 80% by weight or more. There is no particular upper limit on the content ratio of vinylidene chloride, but 98% by weight is preferable and 95% by weight is more preferable from the viewpoint of extrusion processability, which is one of the suitability for packaging machines.
塩化ビニリデン系樹脂の還元粘度は、0.035〜0.070の範囲であることが好ましく、0.040〜0.065の範囲であることがより好ましい。還元粘度を0.035以上とすることにより、フィルムの成形品への押出加工性に優れたものとなる。また、還元粘度を0.70以下とすることにより、着色を抑えるとともに、溶融成形が容易となる。 The reduced viscosity of the vinylidene chloride-based resin is preferably in the range of 0.035 to 0.070, and more preferably in the range of 0.040 to 0.065. By setting the reduced viscosity to 0.035 or more, the film has excellent extrudability into a molded product. Further, when the reduced viscosity is 0.70 or less, coloring is suppressed and melt molding becomes easy.
[添加剤]
塩化ビニリデン系樹脂は、さらに種々の添加剤を含んでもいてもよい。添加剤としては、例えば、可塑剤、スリップ剤およびアンチブロッキング剤(AB剤)等が挙げられる。[Additive]
The vinylidene chloride resin may further contain various additives. Examples of the additive include a plasticizer, a slip agent, and an antiblocking agent (AB agent).
(可塑剤)
可塑剤としては、例えば、アセチルクエン酸トリブチル、エポキシ化大豆油、ジオクチルフタレート、ジブチルセバケート、ジオクチルセバケート、アセチル化モノグリセライド、アセチル化ジグリセライドおよびアセチル化トリグリセライド等が挙げられる。(Plasticizer)
Examples of the plasticizer include tributyl acetyl citrate, epoxidized soybean oil, dioctyl phthalate, dibutyl sebacate, dioctyl sebacate, acetylated monoglyceride, acetylated diglyceride, and acetylated triglyceride.
(スリップ剤)
スリップ剤としては、例えば、飽和脂肪酸アミド、不飽和脂肪酸アミド、置換アミドおよびチオエーテル系化合物等が挙げられる。(Slip agent)
Examples of the slip agent include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, and thioether compounds.
飽和脂肪酸アミドとしては、例えば、ブチルアミド、吉草酸アミド、カプロン酸アミド、カプリル酸アミド、カプリン酸アミド、ラウリン酸アミド、ミリスチン酸アミド、パルミチン酸アミド、ステアリン酸アミド、アラキジン酸アミドおよびベヘニン酸アミド等が挙げられる。不飽和脂肪酸アミドとしては、オレイン酸アミドおよびエルカ酸アミド等が挙げられる。置換アミドとしては、例えば、N−オレイルパルチミン酸アミド、N−ステアリルステアリン酸アミド、N−ステアリルオレイン酸アミド、N−オレイルステアリン酸アミドおよびN−ステアリルエルカ酸アミド等が挙げられる。チオエーテル系化合物としては、例えば、ジラウリルチオジプロピオネート、ジトリデシルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオジプロピオネート、ペンタエリスリトールテトラキス(3−ラウリルチオプロピオネート)、ペンタエリスリトールテトラキス(3−ドデシルチオプロピオネート)、ペンタエリスリトールテトラキス(3−オクタデシルチオプロピオネート)、ペンタエリスリトールテトラキス(3−ミリスチルチオプロピオネート)およびペンタエリスリトールテトラキス(3−ステアリルチオプロピオネート)等が挙げられる。 Examples of saturated fatty acid amides include butyramide, valeric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, and behenic acid amide. Is mentioned. Examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Examples of the substituted amide include N-oleyl palmitate, N-stearyl stearate, N-stearyl oleate, N-oleyl stearate, N-stearyl erucamide, and the like. Examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), penta Erythritol tetrakis (3-dodecylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate) and pentaerythritol tetrakis (3-stearylthiopropionate) Etc.
(AB剤)
AB剤としては、本実施形態に係る塩化ビニリデン系樹脂フィルムに含まれる球状粒子が該当するため、さらなるAB剤を添加する必要は必ずしもない。しかしながら、さらなるAB剤を含ませる態様を排除するものではなく、球状粒子以外の粒子をAB剤として塩化ビニリデン系樹脂フィルムにさらに含ませてもよい。含ませ得る粒子としては、不定形シリカ、不定形炭酸カルシウムおよびタルク等が挙げられる。球状粒子以外の粒子をAB剤として含ませる場合、本実施形態に係る塩化ビニリデン系樹脂フィルムの奏する効果が損なわれないように、球状粒子の含有量に対して、50重量部以下であることが好ましく、30重量部以下であることがより好ましい。(AB agent)
As AB agent, since the spherical particle contained in the vinylidene chloride resin film which concerns on this embodiment corresponds, it is not necessarily required to add further AB agent. However, this does not exclude an aspect in which a further AB agent is included, and particles other than spherical particles may be further included in the vinylidene chloride resin film as an AB agent. Examples of the particles that can be included include amorphous silica, amorphous calcium carbonate, and talc. When particles other than the spherical particles are included as the AB agent, the content of the spherical particles may be 50 parts by weight or less so that the effect of the vinylidene chloride resin film according to the present embodiment is not impaired. Preferably, it is 30 parts by weight or less.
添加剤の含有量としては、添加剤が可塑剤等の液体添加剤である場合には、塩化ビニリデン系樹脂100重量部に対して0.5〜10重量部の範囲であることが好ましく、1.0〜7.0重量部の範囲であることがより好ましい。可塑剤の添加量が上記範囲内であることにより、より耐寒性および包装機械適性に優れる塩化ビニリデン系樹脂フィルムを最終的に得ることができる。また、添加剤がスリップ剤等の紛体添加剤である場合には、塩化ビニリデン系樹脂100重量部に対して0.05〜10重量部の範囲であることが好ましく、0.1〜6.0重量部の範囲であることがより好ましい。 The content of the additive is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin when the additive is a liquid additive such as a plasticizer. More preferably, it is in the range of 0.0 to 7.0 parts by weight. When the addition amount of the plasticizer is within the above range, a vinylidene chloride resin film having better cold resistance and packaging machine suitability can be finally obtained. Further, when the additive is a powder additive such as a slip agent, the amount is preferably in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of vinylidene chloride resin, and 0.1 to 6.0. More preferably, it is in the range of parts by weight.
〔塩化ビニリデン系樹脂フィルムの製造方法〕
塩化ビニリデン系樹脂フィルムは、溶融押出法、溶液流延法およびカレンダー法等の成形方法によって製造でき、中でも溶融押出法によって製造することが好ましい。溶融押出法としては、Tダイ法およびインフレーション法等があり、中でもインフレーション法が好ましい。インフレーション法は設備そのものが簡易であり、小さな金型から幅の広いフィルムを製造できる。以下、インフレーションを用いた場合の塩化ビニリデン系樹脂フィルムの製造方法の具体例について説明するが、本実施形態はこれに限定されるものではない。[Method for producing vinylidene chloride-based resin film]
The vinylidene chloride-based resin film can be produced by a molding method such as a melt extrusion method, a solution casting method, and a calender method, and among them, it is preferably produced by a melt extrusion method. Examples of the melt extrusion method include a T-die method and an inflation method, and the inflation method is preferable. The inflation method is simple in equipment and can produce a wide film from a small mold. Hereinafter, although the specific example of the manufacturing method of the vinylidene chloride resin film at the time of using inflation is demonstrated, this embodiment is not limited to this.
[工程1]
塩化ビニリデンおよび塩化ビニリデンと共重合可能な単量体を重合して得られた塩化ビニリデン系樹脂に対して、上述の球状粒子、可塑剤およびスリップ剤を混合機等により混合する。このようにして塩化ビニリデン共重合体含有樹脂組成物を作製する。[Step 1]
The above-mentioned spherical particles, plasticizer and slip agent are mixed with a mixer or the like to vinylidene chloride resin obtained by polymerizing vinylidene chloride and a monomer copolymerizable with vinylidene chloride. In this way, a vinylidene chloride copolymer-containing resin composition is prepared.
塩化ビニリデン系樹脂の重合法としては、不均一系重合法である懸濁重合法および乳化重合法が好ましく、懸濁重合法がより好ましい。 As a polymerization method of vinylidene chloride resin, suspension polymerization method and emulsion polymerization method which are heterogeneous polymerization methods are preferable, and suspension polymerization method is more preferable.
球状粒子を混合する割合としては、混合させる塩化ビニリデン系樹脂100重量部に対して、0.04〜0.4重量部の範囲であることが好ましく、0.05〜0.2重量部の範囲であることがより好ましい。上述の好ましい範囲内にあることにより、より耐寒性および包装機械適性に優れる塩化ビニリデン系樹脂フィルムを最終的に得ることができる。 The mixing ratio of the spherical particles is preferably in the range of 0.04 to 0.4 parts by weight and in the range of 0.05 to 0.2 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin to be mixed. It is more preferable that By being in the above-mentioned preferable range, a vinylidene chloride-based resin film that is more excellent in cold resistance and packaging machine suitability can be finally obtained.
混合する装置としては、例えば、ヘンシェルミキサー、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、V型混合機、リボン型混合機、双腕型ニーダー、流動式混合機、気流型混合機、回転円盤型混合機、ロールミキサー、転動式混合機およびレディゲミキサー等が挙げられ、ヘンシェルミキサーまたはリボン型混合器であることが好ましい。 Examples of the mixing apparatus include a Henschel mixer, a cylindrical mixer, a screw mixer, a screw extruder, a turbulator, a nauter mixer, a V mixer, a ribbon mixer, a double arm kneader, Examples thereof include a fluid mixer, an airflow mixer, a rotating disk mixer, a roll mixer, a rolling mixer, and a Redige mixer, and a Henschel mixer or a ribbon mixer is preferable.
[工程2]
調製した混合物を溶融押出し、インフレーション法により、フィルムを得る。フィルムは、シングルフィルムまたは用途によってはダブルフィルムとして用いられる。フィルムの厚さとしては、5μm〜90μmの範囲であることが好ましく、15μm〜70μmの範囲であることがより好ましく、20μm〜50μmの範囲であることがさらに好ましい。[Step 2]
The prepared mixture is melt-extruded and a film is obtained by an inflation method. The film is used as a single film or a double film depending on the application. The thickness of the film is preferably in the range of 5 μm to 90 μm, more preferably in the range of 15 μm to 70 μm, and still more preferably in the range of 20 μm to 50 μm.
本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.
〔まとめ〕 [Summary]
本発明に係る塩化ビニリデン系樹脂フィルムは、平均粒子径が4μmより大きく、15μm以下である球状粒子を含むことを特徴とする。 The vinylidene chloride-based resin film according to the present invention is characterized by containing spherical particles having an average particle diameter of greater than 4 μm and 15 μm or less.
また、本発明に係る塩化ビニリデン系樹脂フィルムにおいて、上記塩化ビニリデン系樹脂フィルムを形成している塩化ビニリデン系樹脂100重量部に対して、上記球状粒子を0.04〜0.4重量部含むことが好ましい。 The vinylidene chloride resin film according to the present invention includes 0.04 to 0.4 parts by weight of the spherical particles with respect to 100 parts by weight of the vinylidene chloride resin forming the vinylidene chloride resin film. Is preferred.
また、本発明に係る塩化ビニリデン系樹脂フィルムにおいて、上記球状粒子は球状シリカ、球状炭酸カルシウムまたはポリマービーズであることが好ましい。 In the vinylidene chloride resin film according to the present invention, the spherical particles are preferably spherical silica, spherical calcium carbonate, or polymer beads.
また、本発明に係る塩化ビニリデン系樹脂フィルムにおいて、上記球状粒子は球状シリカであることが好ましい。 In the vinylidene chloride resin film according to the present invention, the spherical particles are preferably spherical silica.
<塩化ビニリデン系樹脂フィルムの製造例>
〔工程1〕
塩化ビニリデンおよび塩化ビニルの共重合体を重量比81:19で懸濁重合法によって重合させ、還元粘度0.062の塩化ビニリデン系樹脂を得た。この塩化ビニリデン系樹脂に、液体添加剤(可塑剤)、粉末添加剤(スリップ剤)およびAB剤を加え、ヘンシェルミキサーにより混合した。これにより、コンパウンド(塩化ビニリデン共重合体含有樹脂組成物)を調製した。なお、液体添加剤として、アセチルクエン酸トリブチル、エポキシ化大豆油およびジブチルセバケートを合計で6.5重量部添加した。なお、これらの液体添加剤は重合時にも加えることができる。また、粉末添加剤として、ステアリン酸アミドおよびジステアリルチオジプロピネートを合計で0.1重量部添加した。また、AB剤の種類および塩化ビニリデン系樹脂100重量部に対する添加量は表1に示す。<Production example of vinylidene chloride resin film>
[Step 1]
A copolymer of vinylidene chloride and vinyl chloride was polymerized by a suspension polymerization method at a weight ratio of 81:19 to obtain a vinylidene chloride resin having a reduced viscosity of 0.062. To this vinylidene chloride resin, a liquid additive (plasticizer), a powder additive (slip agent) and an AB agent were added and mixed with a Henschel mixer. Thus, a compound (vinylidene chloride copolymer-containing resin composition) was prepared. As liquid additives, 6.5 parts by weight of tributyl acetyl citrate, epoxidized soybean oil and dibutyl sebacate were added. These liquid additives can also be added during polymerization. As a powder additive, stearamide and distearyl thiodipropinate were added in a total of 0.1 parts by weight. Table 1 shows the type of AB agent and the amount added to 100 parts by weight of vinylidene chloride resin.
〔工程2〕
工程1で調製したコンパウンドを、口径40mmの溶融押出機を用いて、180℃で混練、溶融し、環状に溶融押出した。常法によって溶融押出した環状体を7℃の冷却槽で急冷した。急冷した環状体を25℃の温水浴槽を通して温度を上昇させた。その後、2組の回転表面速度の異なるピンチロール間で空気を圧入して環状体を膨張させて二軸延伸を行い、巻き取り側のピンチロールにより折り畳んでフィルムを得た。結果を表1に示す。[Step 2]
The compound prepared in Step 1 was kneaded and melted at 180 ° C. using a melt extruder having a diameter of 40 mm, and melt-extruded in an annular shape. The annular body melt-extruded by a conventional method was rapidly cooled in a cooling bath at 7 ° C. The rapidly cooled annular body was heated through a hot water bath at 25 ° C. Thereafter, air was pressed between the two sets of pinch rolls having different rotational surface speeds to expand the annular body and biaxially stretched, and folded with a pinch roll on the winding side to obtain a film. The results are shown in Table 1.
なお、表1のMDおよびTDは、それぞれ長さ方向および幅方向の延伸倍率を示している。 In addition, MD and TD of Table 1 have shown the draw ratio of the length direction and the width direction, respectively.
<耐寒性試験>
フィルム脆化温度試験機を用いて、上述の実施例1〜4および比較例1〜9の塩化ビニリデン系樹脂フィルムの耐寒性を試験した。試験サンプルとしては、塩化ビニリデン系樹脂フィルムを、幅約30mm、長さ約500mmにカットしたシングルフィルム(以下、試験フィルム)を用いた。フィルム脆化温度試験機は、試験フィルムを挟むための上側フィルム保持板および下側フィルム保持板を備えている。<Cold resistance test>
The cold resistance of the vinylidene chloride resin films of Examples 1 to 4 and Comparative Examples 1 to 9 described above was tested using a film embrittlement temperature tester. As a test sample, a single film (hereinafter referred to as a test film) obtained by cutting a vinylidene chloride resin film into a width of about 30 mm and a length of about 500 mm was used. The film embrittlement temperature tester includes an upper film holding plate and a lower film holding plate for sandwiching the test film.
下側フィルム保持板には、突き上げピンの先端を貫通させるための貫通孔が設けられている。突き上げピンは、直径が3mmで、先端部の曲率半径が1.5mmである。上側フィルム保持板には下側フィルム保持板を貫通した突き上げピンの先端部を受ける凹状の受け孔が設けられている。受け孔の直径は7mmである。試験時には、上側フィルム保持板および下側フィルム保持板の内部に伝熱媒体を流し、各フィルム保持板の温度を予め測定温度に調整している。突き上げピンはスプリングによって動かされ、スプリングのばね定数は、0.71g/cmである。 The lower film holding plate is provided with a through-hole for penetrating the tip of the push-up pin. The push-up pin has a diameter of 3 mm and a curvature radius of the tip portion is 1.5 mm. The upper film holding plate is provided with a concave receiving hole for receiving the tip of the push-up pin that penetrates the lower film holding plate. The diameter of the receiving hole is 7 mm. During the test, a heat transfer medium is passed through the upper film holding plate and the lower film holding plate, and the temperature of each film holding plate is adjusted to the measurement temperature in advance. The push pin is moved by a spring, and the spring constant of the spring is 0.71 g / cm.
試験フィルムを、上側フィルム保持板および下側フィルム保持板の間に挟み、23秒間保持することで測定温度に調整した。 The test film was adjusted between the upper film holding plate and the lower film holding plate and held at the measurement temperature by holding for 23 seconds.
試験フィルムの下面側から、突き上げピンを衝撃力4.41kg・m/秒、打ち抜きスピード0.92m/秒、フィルム面への到達時間0.06秒で試験フィルムに向けて突き上げ、試験フィルムの破壊の有無を調べた。試験フィルムに穴が開いていたら破壊と判定した。突き上げを行った後、毎回新しい試験フィルムを、上側フィルム保持板および下側フィルム保持板の間に挟み、23秒間保持して測定温度に調整した後、新しい試験フィルムに対して突き上げを行った。突き上げ試験は各測定温度で20回ずつ行った。 From the lower surface side of the test film, the push-up pin was pushed toward the test film with an impact force of 4.41 kg · m / sec, a punching speed of 0.92 m / sec, and an arrival time of 0.06 sec. The presence or absence of was investigated. If the test film had a hole, it was determined to be broken. After pushing up, a new test film was sandwiched between the upper film holding plate and the lower film holding plate, held for 23 seconds and adjusted to the measurement temperature, and then pushed up against the new test film. The push-up test was performed 20 times at each measurement temperature.
実施例1〜4および比較例1〜9それぞれにおいて、20回の突き上げ試験において1回も試験フィルムが破壊しない(破壊率0%)最低温度から試験を開始し、2℃間隔で温度を下げながら各温度における破壊の頻度を測定し、20回の突き上げ試験において全ての試験フィルムが破壊する(破壊率100%)温度まで測定した。破壊率100%となる温度および式1により、試験フィルムの50%破壊温度(Tb)(以下、脆化温度)を求めた。また、この脆化温度の結果および表2の基準により、耐寒性の評価をした結果を表3に示す。
Tb=T100+B{(A/100)−0.5} ・・・(式1)
T100:試験フィルムが100%破壊する温度(℃)
B:測定温度間隔(2℃)
A:総破壊数/総測定数(%)In each of Examples 1 to 4 and Comparative Examples 1 to 9, the test film was not broken even once in 20 push-up tests (breakage rate 0%), and the test was started from the lowest temperature while the temperature was lowered at 2 ° C. intervals. The frequency of fracture at each temperature was measured, and the temperature was measured up to a temperature at which all test films were broken (breakage rate 100%) in 20 push-up tests. The 50% fracture temperature (Tb) (hereinafter referred to as the embrittlement temperature) of the test film was determined from the temperature at which the fracture rate was 100% and Equation 1. Table 3 shows the results of the evaluation of cold resistance based on the results of the embrittlement temperature and the criteria shown in Table 2.
Tb = T 100 + B {( A / 100) -0.5} ··· ( Equation 1)
T 100 : temperature at which the test film breaks 100% (° C.)
B: Measurement temperature interval (2 ° C)
A: Total number of fractures / total number of measurements (%)
<滑り性試験>
実施例1〜4および比較例1〜9の試験フィルムの静摩擦係数を、JISK7125(プラスチック−フィルムおよびシート−摩擦係数試験方法)に準拠する方法で測定した。静摩擦係数の測定結果を表5に示す。また、この静摩擦係数の測定結果および表4の基準により、包装機械適性の一つである滑り性の評価をした結果を表5に示す。<Slidability test>
The static friction coefficients of the test films of Examples 1 to 4 and Comparative Examples 1 to 9 were measured by a method based on JISK7125 (plastic-film and sheet-friction coefficient test method). Table 5 shows the measurement results of the coefficient of static friction. Table 5 shows the results of evaluation of slipperiness, which is one of the suitability for packaging machines, based on the measurement result of the static friction coefficient and the criteria in Table 4.
なお、表5の比較例9の静摩擦係数の「−」は、測定可能な範囲を超えるほど大きいものであることを意味する。 In addition, "-" of the static friction coefficient of the comparative example 9 of Table 5 means that it is so large that it exceeds a measurable range.
本発明は、ソーセージなどの食品を包装するフィルムに利用することができる。 The present invention can be used for a film for packaging foods such as sausages.
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JPH09291250A (en) * | 1996-04-25 | 1997-11-11 | C I Kasei Co Ltd | Anti-blocking coating agent and flexible magnet sheet having anti-blocking property |
JP2001343526A (en) * | 2000-06-01 | 2001-12-14 | Konica Corp | Optical film excellent in durability |
JP2008504380A (en) * | 2004-06-26 | 2008-02-14 | クレックナー ペンタプラスト ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Polyvinylidene chloride coating, coating production method and use thereof |
JP2012051203A (en) * | 2010-08-31 | 2012-03-15 | Dainippon Printing Co Ltd | Moisture-proof decorative sheet, and moisture-proof decorative material |
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Also Published As
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WO2016174978A1 (en) | 2016-11-03 |
CN107531923B (en) | 2020-10-30 |
JP6534736B2 (en) | 2019-06-26 |
CN107531923A (en) | 2018-01-02 |
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