CN112795116B - Preservative film - Google Patents
Preservative film Download PDFInfo
- Publication number
- CN112795116B CN112795116B CN202011177516.5A CN202011177516A CN112795116B CN 112795116 B CN112795116 B CN 112795116B CN 202011177516 A CN202011177516 A CN 202011177516A CN 112795116 B CN112795116 B CN 112795116B
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- CN
- China
- Prior art keywords
- preservative film
- vinylidene chloride
- film
- temperature
- content
- 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.)
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- 239000003755 preservative agent Substances 0.000 title claims abstract description 141
- 230000002335 preservative effect Effects 0.000 title claims abstract description 141
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- 238000005259 measurement Methods 0.000 claims description 26
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 21
- 239000008158 vegetable oil Substances 0.000 claims description 21
- -1 acrylic ester Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 33
- 239000000428 dust Substances 0.000 abstract description 20
- 238000005520 cutting process Methods 0.000 abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 29
- 239000000194 fatty acid Substances 0.000 description 29
- 229930195729 fatty acid Natural products 0.000 description 29
- 238000000034 method Methods 0.000 description 24
- 230000000977 initiatory effect Effects 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000003860 storage Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 235000013305 food Nutrition 0.000 description 8
- 230000008707 rearrangement Effects 0.000 description 8
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000004665 fatty acids Chemical group 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000002040 relaxant effect Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 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 5
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 5
- 239000005639 Lauric acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012491 analyte Substances 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001595 flow curve Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
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- 239000002667 nucleating agent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NBMAHNZMRSQCPG-UHFFFAOYSA-N 2,3-diacetyloxypropyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(OC(C)=O)COC(C)=O NBMAHNZMRSQCPG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- UWLPCYBIJSLGQO-UHFFFAOYSA-N dodecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCC(O)=O UWLPCYBIJSLGQO-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- XHALKWMTKWHQLO-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 XHALKWMTKWHQLO-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-M 8-methylnonanoate Chemical compound CC(C)CCCCCCC([O-])=O OAOABCKPVCUNKO-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-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
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
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- 235000021360 Myristic acid Nutrition 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
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- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-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
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000020995 raw meat Nutrition 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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)
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preservative film, and aims to provide a preservative film which is not easy to adhere to dust and the like, is prevented from cracking and faults and is excellent in cutting performance. A preservative film comprising a vinylidene chloride resin and an acetylated fatty glyceride, wherein the content of the acetylated fatty glyceride is 3.1 to 8.6% by weight relative to the total amount of the preservative film, and the proportion of a highly mobile component measured by pulse NMR is 11.5% or less.
Description
Technical Field
The invention relates to a preservative film.
Background
The preservative film made of vinylidene chloride resin is excellent in oxygen barrier property, water vapor barrier property (moisture resistance) and transparency, and can be heated by a microwave oven, and therefore, has been widely used for packaging of fresh fish, raw meat, processed meat, fresh vegetables, and staple foods for the purpose of oxygen resistance, moisture resistance, and the like.
Vinylidene chloride copolymers obtained by copolymerizing vinylidene chloride and another monomer copolymerizable with vinylidene chloride, such as vinyl chloride, are generally used as vinylidene chloride-based resins for forming a preservative film from the viewpoints of film extrusion processability, crystallinity, transparency, softening temperature, and the like.
A preservative film made of a vinylidene chloride resin is generally produced by melt-extruding a vinylidene chloride resin, followed by stretching, and is wound around a paper core and stored in a package (paper box).
In addition, when the shearing force of the extruder is large during melt extrusion, the vinylidene chloride resin is decomposed and carbonized, and the carbide becomes an impurity. When stretching is performed next, for example, when inflation film formation is performed, perforation may occur starting from the impurity, and productivity may be lowered (for example, see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-125561
Disclosure of Invention
Problems to be solved by the invention
As described above, vinylidene chloride resins are used as food packaging materials such as freshness retaining films because they are excellent in transparency, water resistance, gas barrier properties, and the like. In recent years, there has been a demand for materials for packaging foods which have improved properties such as moldability and heat stability as well as improved properties, and further, which have high functionality.
One of such high-functionalization is to prevent adhesion of dust to food packaging materials. For example, when dust adheres to a preservative film in which food is packaged, the aesthetic properties of the food and the like are not preferable.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a preservative film which is less likely to adhere to dust or the like, is suppressed in cracking failure, and is excellent in cuttability.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by adjusting the content of acetylated fatty acid glycerides and the ratio of highly mobile components measured by pulse NMR, and the present invention has been completed.
Namely, the present invention is as follows.
[1]
A preservative film, wherein,
comprises a vinylidene chloride resin and an acetylated fatty glyceride,
the content of the acetylated fatty glyceride is 3.1 to 8.6 weight percent relative to the total amount of the preservative film,
the proportion of the highly mobile component measured by pulse NMR is 11.5% or less.
[2]
The preservative film according to [1], wherein the tearing strength in the TD direction is 4.0-8.0 cN.
[3]
The preservative film according to [1] or [2], wherein the tensile elastic modulus in the MD direction is 250 to 600MPa.
[4]
The cling film of any one of [1] to [3], wherein the low-temperature crystallization onset temperature measured by a temperature-modulated differential scanning calorimeter is 40 to 60 ℃.
[5]
The preservative film according to any one of [1] to [4], wherein the vinylidene chloride resin contains 72 to 93mol% of vinylidene chloride repeating units.
[6]
The preservative film according to any one of [1] to [5], wherein,
Comprises an epoxidized vegetable oil which is used to produce a mixture of vegetable oils,
the content of the epoxidized vegetable oil is 0.5 to 3% by weight relative to the total amount of the preservative film.
[7]
The preservative film according to any one of [1] to [6], wherein the thickness is 6 to 18. Mu.m.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a preservative film which is less likely to adhere to dust or the like, is suppressed in cracking failure, and is excellent in cuttability can be provided.
Drawings
Fig. 1 is a schematic view of an apparatus used in the film forming process of the present invention.
FIG. 2 shows an example of the application form of the film of the present invention.
Description of symbols
1 … extruder, 2 … die head, 3 … die head, 4 … soak section, 5 … soak solution (stripping agent for blow molding), 6 … cold water tank, 7 … 1 st pinch roll, 8 … th parison, 9 … 2 nd pinch roll, 10 … bubble, 11 … 3 rd pinch roll, 12 … double film, 13 … take-up roll, 14 … packaging box, 15 … film serrated edge, 16 … coil, 17 … preservative film
Detailed Description
The following describes embodiments of the present invention (hereinafter referred to as "the present embodiment"), but the present invention is not limited thereto, and various modifications may be made without departing from the gist thereof.
In the present embodiment, the term "TD direction" refers to the width direction of the resin in the film-forming line, and refers to the direction perpendicular to the direction in which the preservative film is drawn from the roll after the preservative film is formed. The "MD direction" refers to the flow direction of the resin in the film-forming line, and refers to the direction in which the preservative film is drawn from the roll when the preservative film is formed.
[ preservative film ]
The preservative film of the present embodiment contains a vinylidene chloride resin and an acetylated fatty acid glyceride, wherein the content of the acetylated fatty acid glyceride is 3.1 to 8.6% by weight relative to the total amount of the preservative film, and the proportion of the highly mobile component measured by pulse NMR is 11.5% or less.
In this embodiment, the content of the acetylated fatty acid glyceride is 3.1 to 8.6 wt%, whereby the effects of suppressing the adhesion of dust and the like, suppressing cracking failure, and improving the cutting performance are exhibited.
The reason why dust and the like are not easily attached by adjusting the content of the above-mentioned acetylated fatty acid glyceride is not clear, and the following is considered. Compared with other additives, the acetylated fatty acid glyceride has a part having high affinity with water, such as an acetyl group and a glycerin moiety, and a part having high affinity with vinylidene chloride resin, such as a fatty acid moiety, in the molecule. Therefore, when the acetylated fatty acid glyceride bleeds out to the surface of the preservative film, the fatty acid moiety interacts with the vinylidene chloride resin, and it is considered that the structure is such that the acetyl group and the glycerin moiety protrude to the surface. It is considered that the structure having the polar portions arranged on the surface of the vinylidene chloride resin can produce an antistatic effect and prevent adhesion of dust.
Further, by setting the proportion of the high-mobility component measured by pulse NMR to 11.5% or less, even if acetylated fatty acid glyceride is added, the high functionality can be achieved without significantly reducing the tear strength and tensile elastic modulus of the vinylidene chloride resin wrap film. The reason is assumed, and is not limited to this. The present embodiment will be described in detail below.
(vinylidene chloride resin)
The vinylidene chloride resin is not particularly limited as long as it contains a vinylidene chloride repeating unit, and examples thereof include vinylidene chloride copolymers containing a monomer repeating unit polymerizable with a vinylidene chloride repeating unit.
The monomer copolymerizable with the vinylidene chloride monomer is not particularly limited, and examples thereof include vinyl chloride; acrylic esters such as methyl acrylate and butyl acrylate; methacrylate esters such as methyl methacrylate and butyl methacrylate; acrylic acid, methacrylic acid; acrylonitrile; vinyl acetate, and the like. These monomers may be used alone or in combination of two or more. Of these, vinyl chloride is more preferable.
The content of the vinylidene chloride repeating unit is preferably 72 to 93mol%, more preferably 81 to 93mol%, and still more preferably 86 to 93mol% based on the total amount of the vinylidene chloride resin. When the vinylidene chloride repeating unit content is 72mol% or more, the vinylidene chloride resin tends to have a low glass transition temperature and the preservative film tends to be soft. Thus, even when used in a low-temperature environment such as winter, cracking of the preservative film can be reduced. On the other hand, when the vinylidene chloride repeating unit content is 93mol% or less, a significant increase in crystallinity is suppressed, and deterioration in molding processability during film stretching tends to be suppressed.
The vinylidene chloride repeating unit content can be measured, for example, using a high-resolution proton nuclear magnetic resonance measuring apparatus (400 MHz or more), but is not particularly limited. More specifically, 0.5g of a preservative film was dissolved in 10ml of THF (tetrahydrofuran), about 30ml of methanol was added to precipitate a resin component, and then the precipitate was separated by centrifugation, and vacuum drying was performed to obtain a sample for measuring a vinylidene chloride resin. The resulting measurement sample was then dissolved in deuterated tetrahydrofuran at 5% by weight, and the solution was subjected to H-NMR measurement at a measurement atmosphere temperature of about 27 ℃. Vinylidene chloride repeating units were calculated using the unique chemical shifts in the resulting spectra based on tetramethylsilane. For example, in the copolymer of vinylidene chloride and vinyl chloride, the calculation is performed by using peaks of 3.50 to 4.20ppm, 2.80 to 3.50ppm, and 2.00 to 2.80 ppm.
The vinylidene chloride copolymer preferably has a weight average molecular weight (Mw) of 80,000 ～ 200,000, more preferably 90,000 ～ 180,000, and even more preferably 100,000 ～ 170,000. When the weight average molecular weight (Mw) is within the above range, the mechanical strength of the preservative film tends to be further improved. The vinylidene chloride resin having a weight average molecular weight in the above range can be obtained by controlling the ratio of vinylidene chloride monomer to vinyl chloride monomer, the amount of the polymerization initiator, or the polymerization temperature, for example. In the present embodiment, the weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC method) using a standard polystyrene calibration curve.
The vinylidene chloride resin content is preferably 77 to 97 wt%, more preferably 83 to 94 wt%, based on the total amount of the preservative film. When the content of the vinylidene chloride resin is within the above range, the shearing force of melt extrusion is reduced by the plasticizing effect of the additive or the like, and thus the generation of impurities tends to be further suppressed. In addition, when the content of the vinylidene chloride resin is within the above range, the film is prevented from being easily elongated, and the film cutting property tends to be further improved. The method of measuring the content of each component by the preservative film varies depending on the analyte. For example, the content of the vinylidene chloride resin can be obtained by vacuum drying the re-precipitated filtrate of the preservative film and measuring the weight of the re-precipitated filtrate.
[ acetylated fatty acid glycerides ]
The acetylated fatty acid glyceride is not particularly limited, and examples thereof include acetylated caprylic acid glyceride, acetylated capric acid glyceride, acetylated lauric acid glyceride, acetylated myristic acid glyceride, acetylated palm kernel oil glyceride, acetylated coconut oil glyceride, acetylated castor oil glyceride, and acetylated hydrogenated castor oil glyceride.
The acetylated fatty acid glyceride may be any of an acetylated monoglyceride of a fatty acid, an acetylated diglyceride of a fatty acid, and an acetylated triglyceride of a fatty acid. For example, the acetylated glycerin laurate includes an acetylated monoglyceride of lauric acid, an acetylated diglyceride of lauric acid (DALG: diacetyl lauroyl glycerol), and an acetylated triglyceride of lauric acid. Among them, acetylated glycerin laurate is preferable, and acetylated diglycerin of lauric acid is more preferable. By using such acetylated fatty acid glycerides, dust tends to be less likely to adhere. In addition, cracking failure is suppressed, and the cuttability is also further improved.
The content of the acetylated fatty acid glyceride is preferably 3.1 to 8.6% by weight, more preferably 3.5 to 8% by weight, and still more preferably 4 to 7% by weight, relative to the total amount of the preservative film. When the content of the acetylated fatty acid glyceride is within the above range, dust tends to be less likely to adhere, and molding processability tends to be further improved. In addition, cracking failure is suppressed, and the cuttability is also further improved. The method of measuring the content of each component by the preservative film varies depending on the analyte. The content of acetylated fatty glyceride may be obtained by extracting the additive from the preservative film with an organic solvent such as acetone at a temperature 5 to 10 ℃ lower than the boiling point of the extraction solvent, and performing gas chromatographic analysis.
(other additives)
The preservative film of the present embodiment may contain epoxidized vegetable oil, citrate, dibasic acid ester, and the like.
(epoxidized vegetable oil)
The preservative film of the present embodiment may contain epoxidized vegetable oil. The epoxidized vegetable oil can function as a stabilizer for extrusion processing of vinylidene chloride-based resins. The epoxidized vegetable oil is not particularly limited, and generally, there is an epoxidized vegetable oil produced by epoxidizing an edible oil or fat. Specifically, examples of the epoxidized vegetable oil include Epoxidized Soybean Oil (ESO) and epoxidized linseed oil. Among these, epoxidized soybean oil is preferred. By using such an epoxidized vegetable oil, the change in color tone of the preservative film tends to be further suppressed, and the film drawability from the package tends to be further improved.
The content of the epoxidized vegetable oil in the present embodiment is preferably 0.5 to 3% by weight, more preferably 1 to 2.5% by weight, and still more preferably 1 to 2% by weight, relative to the total amount of the preservative film. When the content of the epoxidized vegetable oil is 0.5 wt% or more, the quality change of the preservative film tends to be further suppressed. In addition, when the content of the epoxidized vegetable oil is 3 wt% or less, the change in color tone of the preservative film tends to be further suppressed, and the tackiness due to bleeding tends to be suppressed. The method of measuring the content of each component by the preservative film varies depending on the analyte. For example, the re-precipitation filtrate of the preservative film can be subjected to NMR analysis to obtain the content of the epoxidized vegetable oil.
Specifically, 50mg of the sample was weighed and dissolved in a deuterated solvent (solvent: deuterated THF, internal standard: dimethyl terephthalate, capacity: 0.7 ml), and 400MHz proton NMR (cumulative number: 512) measurement was performed, and the quantitative value was calculated by the absolute calibration curve method using the ratio of the integrated value of 2.23 to 2.33ppm to the integrated value of 8.05 to 8.11ppm as the integrated value, whereby the epoxidized vegetable oil content was obtained.
Integration ratio=integration value (2.23 to 2.33 ppm)/integration value (8.05 to 8.11 ppm)
(citrate ester)
The citrate is not particularly limited, and examples thereof include triethyl citrate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate (ATBC), acetyl tri-n-2-ethylhexyl citrate, and the like.
Of these, acetyl tributyl citrate is preferred. By using such a citrate, plasticization and molding processability of the vinylidene chloride resin tend to be further improved. In addition, cracking failure is suppressed, and the cuttability is also further improved.
The content of the citrate is preferably 0.1 to 2.5% by weight, more preferably 0.3 to 1.5% by weight, and still more preferably 0.5 to 1.2% by weight, relative to the total amount of the preservative film. When the content of the citrate is within the above range, the molding processability tends to be further improved. In addition, cracking failure is suppressed, and the cuttability is also further improved. The method of measuring the content of each component by the preservative film varies depending on the analyte. The content of citrate can be obtained by extracting the additive from the preservative film using an organic solvent such as acetone at a temperature 5 to 10 ℃ lower than the boiling point of the extraction solvent, and performing gas chromatography analysis.
(dibasic acid ester)
The dibasic acid ester is not particularly limited, and examples thereof include adipic acid esters such as dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, and dioctyl adipate; azelaic acid esters such as di-2-ethylhexyl azelate and octyl azelate; sebacates such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate; dimethyl phthalate, diethyl phthalate, dioctyl phthalate, and the like.
Of these, aliphatic dibasic acid esters are preferable, and dibutyl sebacate is more preferable. The use of such a dibasic acid ester tends to plasticize the vinylidene chloride resin and further improve the molding processability. In addition, cracking failure is suppressed, and the cuttability is also further improved.
(others)
The preservative film of the present embodiment may contain additives other than the above. Examples of such additives include, but are not particularly limited to, plasticizers other than those described above, stabilizers other than those described above, weather resistance improvers, colorants such as dyes and pigments, antifogging agents, antibacterial agents, lubricants, nucleating agents, oligomers such as polyesters, polymers such as MBS (methyl methacrylate-butadiene-styrene copolymer), and the like.
The plasticizer other than acetylated fatty acid glycerides, citric acid esters, and dibasic acid esters is not particularly limited, and specific examples thereof include glycerin, glycerides, waxes, liquid paraffin, and phosphoric acid esters. One kind of plasticizer may be used alone, or two or more kinds may be used in combination.
The stabilizer other than the epoxidized vegetable oil is not particularly limited, and specific examples thereof include antioxidants such as 2, 5-t-butylhydroquinone, 2, 6-di-t-butyl-p-cresol, 4 '-thiobis (6-t-butylphenol), 2' -methylene-bis (4-methyl-6-t-butylphenol), octadecyl-3- (3 ',5' -di-t-butyl-4 '-hydroxyphenyl) propionate and 4,4' -thiobis (6-t-butylphenol); heat stabilizers such as laurate, myristate, palmitate, stearate, isostearate, oleate, ricinoleate, 2-ethyl-hexanoate, isodecanoate, neodecanoate, and calcium benzoate. The stabilizer may be used alone or in combination of two or more.
The weather resistance improver is not particularly limited, and specific examples thereof include ethylene-2-cyano-3, 3' -diphenylacrylate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, and 2,2' -dihydroxy-4-methoxybenzophenone. The weather resistance improver may be used alone or in combination of two or more.
The colorant such as a dye or a pigment is not particularly limited, and specifically includes carbon black, phthalocyanine, quinacridone, indoline, azo-based pigment, iron oxide red, and the like. The colorant may be used alone or in combination of two or more.
The antifogging agent is not particularly limited, and specifically includes glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene fatty acid alcohol ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like. The antifogging agent may be used alone or in combination of two or more.
The antibacterial agent is not particularly limited, and specific examples thereof include silver-based inorganic antibacterial agents and the like. The antibacterial agent may be used alone or in combination of two or more.
The lubricant is not particularly limited, and specific examples thereof include fatty acid hydrocarbon-based lubricants such as ethylene bis-stearamide, butyl stearate, polyethylene wax, paraffin wax, carnauba wax, myristyl myristate, stearyl stearate, and the like, higher fatty acid lubricants, fatty amide-based lubricants, fatty acid ester lubricants, and the like. The lubricant may be used alone or in combination of two or more.
The nucleating agent is not particularly limited, and specific examples thereof include metal phosphate salts and the like. The nucleating agent may be used alone or in combination of two or more.
The content of the other additives is preferably 5% by weight or less, more preferably 3% by weight or less, further preferably 1% by weight or less, particularly preferably 0.1% by weight or less, relative to the total amount of the preservative film. The lower limit of the content of the other additives is not particularly limited, but is 0 wt% or more with respect to the total amount of the preservative film.
(thickness of preservative film)
The thickness of the preservative film of the present embodiment is preferably 6 to 18. Mu.m, more preferably 9 to 12. Mu.m. When the thickness of the preservative film is within the above range, the failure of film rupture is suppressed, the cutting performance is further improved, and the adhesion is also further improved.
More specifically, when the thickness is 6 μm or more, the tensile strength in the TD direction and MD direction of the preservative film tends to be further improved, and film breakage during use tends to be further suppressed. In addition, when the thickness is 6 μm or more, the tear strength tends to be remarkably reduced. Therefore, the breakage of the preservative film from the end cut by the saw blade attached to the package can be further suppressed when the preservative film is drawn from the roll and when the preservative film is unwound and returned to the end of the film in the package.
On the other hand, when the thickness is 18 μm or less, the force required for cutting the preservative film by the serrated edge attached to the package can be reduced, and the cutting performance tends to be further improved. In addition, the thickness of the preservative film is 18 μm or less, so that the preservative film easily conforms to the shape of the container, and the adhesion to the container tends to be further improved.
(tear Strength)
The tear strength in the TD direction of the preservative film of the present embodiment is preferably 4.0 to 8.0cN, more preferably 5.0 to 7.5cN. By setting the tearing strength in the TD to 4.0cN or more, it is possible to reduce the tendency of cracking particularly when the preservative film is drawn out from the roll, and also to suppress unexpected cracking failure when the preservative film is used. On the other hand, when the film is cut in the TD direction by the serrated edge attached to the package case, the film tends to be easily split by setting the tearing strength in the TD direction to 8.0cN or less, and the cutting property tends to be improved.
The tearing strength in the TD direction of the preservative film of the present embodiment can be adjusted by the composition of the vinylidene chloride resin, the composition of the additive, the stretching ratio of the film, the stretching speed, the thickness of the film, and the like. The stretching ratio in the TD direction is reduced, or the preservative film is thickened, so that the tearing strength in the TD direction tends to be improved; by increasing the stretch ratio in the TD direction or thinning the preservative film, the tear strength in the TD direction tends to be reduced. The tear strength was measured by the method described in examples.
(tensile elastic modulus)
The tensile elastic modulus in the MD direction of the preservative film of the present embodiment is preferably 250 to 600MPa, more preferably 350 to 500MPa, and even more preferably 350 to 470MPa. By setting the tensile elastic modulus in the MD direction to 250MPa or more, when a force is applied to cut the film with the saw blade, the elongation of the film in the MD direction can be suppressed, and the saw blade can easily bite into the film, thereby improving the cutting property. On the other hand, when the tensile elastic modulus in the MD direction is 600MPa or less, the film is soft, and the film can be cut neatly along the shape of the saw blade, and a large number of cracks on the cut end face can be suppressed. As a result, the occurrence of a failure in which the film breaks from the cut end surface can be suppressed when the film is drawn out from the wound body and when the film is unwound and returned to the film end portion in the package.
The tensile elastic modulus in the MD direction of the preservative film of the present embodiment can be adjusted by the composition of the vinylidene chloride resin, the composition of the additive, the stretching ratio and stretching speed of the film, and the like. The stretching ratio is not particularly limited, and for example, by increasing the stretching ratio or decreasing the amount of the additive, the stretching elastic modulus in the MD direction tends to be increased; by decreasing the stretch ratio, or increasing the amount of the additive, the tensile elastic modulus in the MD direction tends to decrease. The tensile elastic modulus was measured by the method described in examples.
(Low temperature crystallization initiation temperature)
In the preservative film according to the present embodiment, physical deterioration of the preservative film occurs due to thermal history experienced during distribution or storage, and a cracking failure occurs due to the physical deterioration, and the cracking failure can be estimated from the low-temperature crystallization initiation temperature. The low-temperature crystallization initiation temperature is an index indicating the thermal stability of crystallites formed and grown by exposure to high temperatures during distribution/warehouse storage after production of the preservative film, and the degree of rearrangement of molecular chains, that is, the ease of occurrence of cracking failure of the preservative film due to physical deterioration, can be evaluated by the low-temperature crystallization initiation temperature.
From the above-described points, the preservative film of the present embodiment preferably has a low-temperature crystallization onset temperature of 40 to 60 ℃, more preferably 40 to 55 ℃, and even more preferably 40 to 50 ℃ as measured by a temperature-modulated differential scanning calorimeter (hereinafter also referred to as "temperature-modulated DSC"). When the low-temperature crystallization initiation temperature is within the above range, cracking failure tends to be suppressed while maintaining the cutting property of the preservative film. Details are described below.
The low-temperature crystallization initial temperature of the existing preservative film is more than 60 ℃. In contrast, the preservative film of the present embodiment has a low-temperature crystallization initiation temperature of 60 ℃ or lower and is set to a lower temperature. By setting the low-temperature crystallization initiation temperature within the above range, rearrangement of the molecular chains is suppressed, and cracking failure of the preservative film is further suppressed.
More specifically, the preservative film according to the present embodiment has a difference in behavior when heated from the conventional preservative film due to a difference in low-temperature crystallization initiation temperature. For example, in the conventional cling film, when exposed to an atmosphere of 20 ℃ or higher for a long period of time during distribution and storage, the molecular chains of the vinylidene chloride resin are thought to rearrange, leading to formation and growth of crystallites. It is assumed that such rearrangement of the molecular chains is caused by insufficient relaxation of the orientation of the molecular chains of the produced preservative film or the stress of the film. It is believed that the more exposed the preservative film to high temperature, the more easily the rearrangement of molecular chains is caused, and thus the film is physically deteriorated, and cracking failure is easily induced.
In contrast, in the preservative film of the present embodiment, the low-temperature crystallization initiation temperature is 60 ℃ or lower by sufficiently relaxing the orientation of the molecular chains of the vinylidene chloride resin or the stress of the film at the time of production. Thus, in the preservative film of the present embodiment, even when the preservative film is exposed to 20 ℃ or higher for a long period of time during distribution and warehouse preservation, rearrangement of molecular chains is not easily caused, degradation of the film is suppressed, and further cracking failure is suppressed. As a result, the problem of suppressing the back of the cracking failure while maintaining the cutting performance can be simultaneously achieved.
On the other hand, according to the study of the present inventors, in the case where the preservative film is stored at-30 ℃ (glass transition temperature or lower) after production, the low-temperature crystallization initiation temperature is 40 ℃. That is, the preservative film is considered to have a low-temperature crystallization initiation temperature of 40 ℃ in the case where it is not heated at all after manufacture. It is considered that the lower limit of the temperature range of the low-temperature crystallization initiation temperature is set to 40 ℃.
The method of adjusting the low-temperature crystallization initiation temperature to the above range is not particularly limited, and examples thereof include a method of sufficiently relaxing the orientation of the molecular chains of the vinylidene chloride resin or the stress of the film. More specifically, a method of storing the preservative film at a low temperature for a predetermined period of time is exemplified. Further, the degree of orientation crystallization may be appropriately set by adjusting the product of the stretching magnification in the MD direction and the stretching magnification in the TD direction (MD stretching magnification×td stretching magnification), or adjusting the temperature during stretching to adjust the stress applied during stretching.
Here, the "low-temperature crystallization initiation temperature" refers to an extrapolated initiation temperature of an exothermic peak caused by low-temperature crystallization in a temperature-heat flow curve of an irreversible component obtained by temperature-modulated DSC measurement (a temperature at an intersection point of a line extending a base line on a low-temperature side toward a high-temperature side in temperature-rise measurement and a tangential line drawn at a point where a slope of a curve on the low-temperature side of a crystallization peak reaches a maximum).
An example of a method for measuring the low-temperature crystallization initiation temperature will be described. The temperature-heat flow curve of the irreversible component was obtained by a step-and-scan measurement mode using a Differential Scanning Calorimeter (DSC) (power-compensated double-heater DSC 8500) manufactured by Perkin Elmer. The step-and-scan measurement conditions at this time were set to 0 to 180℃for the measurement temperature, 10℃per minute for the temperature rise rate, 4℃for the temperature rise step width, and 1 minute for the isothermal time. The extrapolated onset temperature of the exothermic peak in the resulting temperature-heat flow curve due to low-temperature crystallization was taken as the low-temperature crystallization onset temperature.
In the temperature rise measurement of DSC, crystallization and crystallization melting occur in competition. Therefore, in the conventional DSC measurement method, the formation and growth of crystallites offset the heat flow due to melting, and it is difficult to study the thermal behavior of crystallites, and it is difficult to distinguish the conventional preservative film from the preservative film of the present embodiment. On the other hand, in the case of step-and-scan measurement by temperature-modulated DSC, heat flow of irreversible components such as crystallization and reversible components such as crystal melting and glass transition can be separated, and the thermal behavior of crystallites can be evaluated. Therefore, the step-and-scan measurement using temperature-modulated DSC is used for the measurement of the low-temperature crystallization onset temperature in the present embodiment.
(pulse NMR)
In the preservative film of the present embodiment, the high-mobility component ratio measured by pulse NMR is 11.5% or less, preferably 11% or less, more preferably 10% or less, and still more preferably 9.7% or less. The lower limit of the proportion of the highly mobile component is preferably 4% or more, more preferably 6% or more, and still more preferably 8% or more. When the ratio of the high-mobility component is within the above range, even when the acetylated fatty acid glyceride is used in a large amount, the tearing strength and the tensile elastic modulus tend to be further suppressed from being greatly lowered.
Unlike the high-resolution NMR commonly used in the structural determination of organic compounds, the pulse NMR is an analytical method capable of measuring the relaxation times of 1H nuclei associated with molecular mobility in a system and determining the presence ratios of the moving components in the system with high quantitativity.
In this embodiment, cs in the preservative film is determined: mole fraction of low mobility component, cm: mole fraction of intermediate components and Cl: at a high molar fraction of the mobile component, a spin-spin relaxation time T2 of 1H is used.
Specifically, it is preferable to perform the application (fitting) by using the least square method so that the Free Induction Decay (FID) signal obtained in the measurement of the spin-spin relaxation time T2 of 1H is approximately applied to the following equation.
[ 1]
Here the number of the elements is the number,
C s : mole fraction of low mobility component
C m : mole fraction of intermediate component
C l : mole fraction of highly mobile component
T s : relaxation time of low-mobility component
T m : relaxation time of intermediate component
T l : relaxation time of highly motile component
W a : weber (Weibull) coefficient (fixed at 1.0).
As specific conditions for the pulse NMR measurement, the conditions described below in examples can be used.
[ method for producing preservative film ]
The method for producing the preservative film according to the present embodiment is not particularly limited, and examples thereof include a method having the steps of: a step of melt-extruding a composition containing a vinylidene chloride resin and an acetylated fatty acid glyceride to form a film; and stretching the obtained film in the MD and TD directions. The following is a detailed description.
(mixing step)
Fig. 1 is a schematic diagram showing an example of a production process of a preservative film. First, a vinylidene chloride resin, an acetylated fatty acid glyceride, and optionally an epoxidized vegetable oil, etc. are mixed by a mixer to obtain a composition. In this case, various additives may be mixed as needed. The mixer is not particularly limited, and for example, a ribbon mixer, a henschel mixer, or the like can be used. The resulting composition is preferably cured for about 1 to 30 hours and then used in the next step.
(melt extrusion Process)
Next, the obtained composition is melted by the extruder 1, and an annular film is extruded from the die opening 3 of the die 2 to form a dipping portion 4 (also referred to as a deposition portion).
(Cooling step)
The soaking liquid 5 is injected into the inside of the soaking part 4, and the outside of the soaking part 4 is brought into contact with cold water in the cold water tank 6. Thus, the immersing portion 4 is cooled from both the inner side and the outer side, and the film constituting the immersing portion 4 is solidified. The solidified immersed portion 4 is folded by the 1 st pinch roller 7 and formed into a parison 8.
(stretching step)
Then, air is injected into the parison 8, and the parison 8 is opened to form a tubular film. At this time, the soaking liquid 5 applied to the portion corresponding to the inner surface of the soaking part 4 exhibits an effect as an opening agent for the parison 8. Then, the parison 8 is reheated with warm water in the opened state to a temperature suitable for stretching. Warm water adhering to the outside of the parison 8 is squeezed out by the 2 nd pinch roll 9.
Air is injected into the inside of the parison 8 heated to a suitable temperature as described above, and the foam 10 is formed. This air expands the parison from the inside, thereby stretching the film to obtain a stretched film. Stretching of the film in the TD direction is mainly performed by the amount of air, and stretching of the film in the MD direction is mainly performed by applying tension in the flow direction of the film using the 2 nd pinch roll 9, the 3 rd pinch roll 11, and the like.
The process from the 1 st pinch roll 7 to the 3 rd pinch roll 11 is referred to as a stretching process. If the stretching speed is low, the stretchability of the parison 8 is improved, and therefore, in the conventional method for producing a cling film, the stretching speed in the MD direction is adjusted to 0.08 times/s or less and the stretching speed in the TD direction is adjusted to 3.0 times/s or less. In contrast, in the method for producing a preservative film according to the present embodiment, in which the low-temperature crystallization initiation temperature is controlled to 40 to 60 ℃, it is preferable that the stretching ratios in the MD direction and the TD direction and the stretching speeds in the MD direction and the TD direction be adjusted to predetermined ranges.
Specifically, the stretching ratios in the MD direction and the TD direction in the stretching step of the present embodiment are each independently preferably 4 to 6 times, more preferably 4.5 to 5.5 times. Here, the stretch ratio in the MD direction is a stretch ratio at which the parison 8 is stretched in the MD direction, and can be calculated, for example, from a ratio of the rotational speed of the 3 rd pinch roll 11 to the rotational speed of the 1 st pinch roll 7 in fig. 1. The stretch ratio in the TD direction is a stretch ratio at which the parison 8 is stretched in the TD direction, and can be calculated from, for example, the ratio of the web length of the double-layer film 12 to the web length of the parison 8 in fig. 1. The stretching ratio in the MD direction can be adjusted by, for example, the rotation speed ratio of the 1 st pinch roller 7 to the 3 rd pinch roller 11, and the stretching ratio in the TD direction can be adjusted by, for example, the stretching temperature of the parison 8 and the size of the bubble 10.
The stretching speed in the MD direction in the stretching step of the present embodiment is preferably 0.09 to 0.12 times/s. The average stretching speed in the MD direction is a stretching ratio in the MD direction with respect to the time taken for the parison to pass between the 1 st pinch roll 7 and the 3 rd pinch roll 11, and is calculated, for example, by the rotational speed of the 1 st pinch roll 7, the rotational speed of the 3 rd pinch roll 11, and the time taken for the parison 8 to pass between the 1 st pinch roll 7 and the 3 rd pinch roll 11 in fig. 1. The stretching speed in the MD direction can be adjusted by, for example, the rotational speed of the 1 st pinch roll 7 or the 3 rd pinch roll 11, or the distance between the 1 st pinch roll 7 and the 3 rd pinch roll 11.
The stretching speed in the TD direction in the stretching step of the present embodiment is preferably 3.1 to 4.0 times/s. The average stretching speed in the TD direction is a stretching ratio in the TD direction with respect to the time required for the parison 8 to expand to the bubble 10, and can be calculated from the time required for stretching in the TD direction and the stretching ratio in the TD direction calculated from the stretching length measured by using the still images of the parison 8 and the bubble 10 and the rotation speed of the 3 rd pinch roller 11 in fig. 1, for example. The stretching speed in the TD direction can be adjusted by, for example, the rotation speed of the 3 rd pinch roller 11.
The stretching temperature is not particularly limited, but is preferably 30 to 45 ℃.
After the stretching step, the stretched film is folded by the 3 rd pinch roll 11 to form a double-layered film 12. The double-layer film 12 is wound up by a winding roller 13.
(relaxation step)
The method for producing a preservative film according to the present embodiment preferably includes a relaxing step of relaxing the preservative film immediately after stretching. A relatively common relaxation method in the production of a preservative film is a method of relaxing a film by heat such as an infrared heater after stretching. However, in the present embodiment, the following method is preferably used instead of the relaxation step: the stretched film is relaxed by making the rotation speed of the take-up roller 13 slower than that of the 3 rd pinch roller 11. This is because, in the present embodiment, when the conventional relaxation method using heat is adopted, the formation and growth of crystallites that cause film cracking may be caused by the action of heat, and the low-temperature crystallization initiation temperature may be set to be higher than 60 ℃.
The relaxation ratio in the relaxation step using the 3 rd pinch roller 11 and the take-up roller 13 is preferably 7 to 15%, more preferably 9 to 13%. When the relaxation ratio is 15% or less, the occurrence of wrinkles due to the relaxation of the film between the 3 rd pinch roll 11 and the take-up roll 13 can be further suppressed. In addition, by setting the relaxation ratio to 7% or more, the preservative film can be sufficiently relaxed, and even when exposed to a high temperature, the molecular chain rearrangement can be suppressed, and the low-temperature crystallization initiation temperature can be set to 60 ℃ or less. In addition, this can reduce the tendency of cracking failure. The "relaxation ratio" here refers to the ratio of the contraction of the double-layer film 12 between the 3 rd pinch roll 11 and the take-up roll 13, and can be calculated, for example, in the case of fig. 1, by using the ratio of the rotation speed of the take-up roll 13 with respect to the 3 rd pinch roll 11.
The atmosphere temperature in the relaxation step using the 3 rd pinch roll 11 and the winding roll 13 is preferably 25 to 32 ℃. When the atmosphere temperature is within the above range, the formation and growth of crystallites tend to be suppressed.
(cutting step)
The preservative film wound in the above manner is cut, wound while being peeled off so as to be a single preservative film, and temporarily stored in a large roll for 1 to 3 days. Finally, the large roll is rewound onto the paper core and is filled into the packaging box, so that the preservative film winding body contained in the packaging box is obtained.
(preservation step)
In the method for producing a preservative film according to the present embodiment, the preservative film is cut and then stored in a large roll. The storage temperature is preferably 19℃or less, more preferably 5 to 19℃and still more preferably 5 to 15 ℃. The storage time is preferably 20 to 50 hours, more preferably 24 to 40 hours.
The formation and growth of crystallites that induce an increase in film cracking failure can be suppressed by the temperature of the atmosphere at the time of storage. In general, the place where the large roll is stored is adjacent to the production process of the preservative film, or temperature adjustment and control are not performed, and therefore, the place is often at a relatively high temperature.
In contrast, in the method for producing a preservative film according to the present embodiment, the atmosphere temperature at the time of storing the cut large rolls is set to 19 ℃ or lower, whereby physical degradation of the film due to rearrangement of the molecular chains can be suppressed. This tends to prevent the preservative film from being easily broken at the end portion cut by the saw blade attached to the package when the preservative film is drawn from the wound body or when the preservative film is unwound and returned to the film end portion in the package.
In addition, when the atmosphere temperature at the time of storing the cut large rolls is 5 ℃ or higher, the preservative film is sufficiently relaxed, and the rearrangement of the molecular chains tends not to occur when the cut large rolls are exposed to 20 ℃ or higher at the time of subsequent distribution and storage.
Therefore, it is preferable to store the cut large rolls under the above storage conditions, whereby a film can be obtained in which formation and growth of crystallites are suppressed and molecular chain orientations of amorphous portions are relaxed. By relaxing the orientation of the molecular chains during large-volume storage in this manner, crystallites are less likely to form and grow even when exposed to high temperatures during film distribution and storage, and cracking failure can be suppressed.
After the cut large roll is stored, the cut large roll may be rewound on a paper core or the like and stored as a roll 16 in the package 1 having the film saw blade 15 shown in fig. 2, but the present invention is not limited thereto. As illustrated in fig. 2, the preservative film 17 is drawn out for use at the time of use.
Examples (example)
The present invention will be described in more detail by using examples and comparative examples, but the present invention is not limited to the examples.
[ content of vinylidene chloride repeating units ]
The proportion of vinylidene chloride repeating units of the preservative film was measured using a high resolution proton nuclear magnetic resonance measuring apparatus. The reprecipitated filtrate of the preservative film was dried in vacuo, dissolved in deuterated tetrahydrofuran at 5% by weight, and the resulting solution was subjected to H-NMR measurement at a measurement atmosphere temperature of about 27 ℃. For example, regarding the copolymer of vinylidene chloride and vinyl chloride, the content of vinylidene chloride repeating units is calculated from peaks of 3.50 to 4.20ppm, 2.80 to 3.50ppm, and 2.00 to 2.80ppm based on tetramethylsilane. In the case of other copolymers, the content of the repeating unit may be calculated using the peak of each monomer.
[ film thickness ]
The thickness was measured in an atmosphere of 50% RH at 23℃by a dial gauge (manufactured by Teclock Co.).
[ tear Strength ]
In the measurement of the tear strength of the cling film, the tear strength was measured in an atmosphere of 50% RH at 23℃using a light-load tear tester type D (Toyo Seisakusho). The tear strength of the preservative film was measured using only 1 preservative film. In this case, the measurement range is suitably selected so as to reach 20 to 80% of full scale. The sample length in the tearing direction was 63.5mm and the sample width was 50.0mm. In the measurement, the pendulum was lifted and stopped, and then the test piece was carefully mounted on the jig, and the jig was firmly fastened so that the position of the cut mark was the center of the film width. A knife mounted in the apparatus is then used to scribe a cut into the film. At this time, the position of the knife edge was adjusted so that the cut length of the film reached 12.7 mm.+ -. 0.5 mm. After the cut mark was made, the pendulum was carefully released, and the force required to tear the test piece was read. The test was performed by excluding the test in which the tear line was 10mm or more from the extension line of the cut mark, and instead, performing the test by the additional test piece. However, in this case, the case where tearing occurs along the line of the embossed pattern is not limited thereto. In addition, regarding the measurement result, the value of the second digit after the decimal point is rounded.
[ tensile elastic modulus ]
The tensile elastic modulus of the preservative film was measured using an Autograph AG-IS (manufactured by Shimadzu corporation) and evaluated in an atmosphere of 50% RH at 23 ℃. The tensile elastic modulus was measured at 50 times by dividing the load at 2% elongation by the cross-sectional area of the measured sample at a stretching speed of 5 mm/min, a distance between chucks of 100mm and a film width of 10 mm. In the measurement, the test piece was attached to the jig so that the MD direction of the test piece matches the axis of the tester. In order to prevent the test piece from sliding and prevent the clamping part from shifting during the test, the test piece is fastened equally and firmly by a clamp. In addition, the test piece is prevented from being broken and rolled due to the pressure between the clamps. In addition, the measurement result takes 2 significant digits and the 3 rd digit is rounded.
[ Low temperature crystallization initiation temperature ]
In the measurement, a Differential Scanning Calorimeter (DSC) (power-compensated double-heating furnace DSC 8500) manufactured by Perkin Elmer was used, and a step-and-scan measurement mode (sample weight: 6mg, sample pan material: aluminum, measurement temperature: 0 to 180 ℃, heating rate: 10 ℃ C./min, heating step width: 4 ℃ C., isothermal time: 1 min) was used. The empty aluminum sample pan was also measured under the same temperature conditions and was used as a blank. The temperature at which the heat release due to low-temperature crystallization starts in the irreversible component of the temperature-heat flow curve is taken as the low-temperature crystallization start temperature.
[ pulse NMR ]
1g of the cut-out substantially square preservative film was folded into a cylindrical shape and filled into an NMR tube having a diameter of 10 mm. The spin-spin relaxation time T2 was determined using pulse NMR by the following conditions.
[ Condition ]
The device comprises: m inispec M Q20 manufactured by Bruker Bi o spin Co
Nuclide: 1H
And (3) measuring: t2
Assay: solid echo method
Measuring temperature: 40 ℃ (after 5 minutes from reaching the set temperature)
Cumulative number of times: 256 times
Repetition time: 1.0 second
Sample amount: about 1g
The resulting Free Induction Decay (FID) curve was separated into 3 components using the following formula, and the respective component ratios and relaxation times were determined. The component represented by the combined function of the gaussian function and the sinc function of the first term of the following formula is taken as a low-mobility component, the component represented by the lorentz function of the second term of the following formula is taken as an intermediate component, and the component represented by the lorentz function of the third term of the following formula is taken as a high-mobility component.
[ 2]
C s : mole fraction of low mobility component
C m : mole fraction of intermediate component
C l : mole fraction of highly mobile component
T s : relaxation time of low-mobility component
T m : relaxation time of intermediate component
T l : relaxation time of highly motile component
W a : weber factor (fixed 1.0)
[ evaluation of dust adhesion ]
Regarding the dust adhesion of the preservative film, 100 persons who routinely used the food packaging preservative film were selected as an evaluator, and evaluated by sensory evaluation of the evaluator. The evaluators were assigned 10 points and the preservative film was used for 1 week, and the case where dust was attached was designated 0 point and the case where dust was not attached was designated 10 points, so that the average score of 100 evaluators was calculated. This average score was used for evaluation.
[ evaluation criterion for dust adhesion ]
And (3) the following materials: 7 minutes or more: no dust is attached, and no problem is caused in practical use
And (2) the following steps: 5 minutes or more and less than 7 minutes full: dust is not easy to adhere to
Delta: 3 minutes or more and less than 5 minutes: slightly dust adheres to but can be used barely
X: less than 3 minutes: dust is attached to the bag and cannot be used
[ incidence of cracking failure ]
The evaluation was carried out at 23℃in an atmosphere having a relative humidity of 50% RH. As an evaluator, 100 persons who routinely used a preservative film for food packaging were selected, and the evaluator performed a series of operations of extracting the film 1m from a roll of 22cm wide film housed in a package, and then cutting the film with a film saw blade made of tin plating attached to the package 20 times each, and evaluated the frequency at which the film was not smoothly extracted because of occurrence of cracking when the film was extracted from the roll and when the film end was wound back into the package.
The effect of inhibiting cracking failure of the film was evaluated on the following 5 grades.
(evaluation criterion for occurrence of cracking failure)
And (3) the following materials: less than 3%: almost no cracking failure and excellent usability.
O: 3% or more and less than 6%: less cracking faults and excellent usability.
● : more than 6% and less than 9%: less cracking faults and good usability.
Delta: more than 9% and less than 15%: the cracking faults are slightly more, and the usability is poor.
X: 15% or more: the cracking faults are very numerous and the usability is very poor.
[ cleavage Property of film ]
The evaluation was carried out at 23℃in an atmosphere having a relative humidity of 50% RH. As an evaluator, 100 persons who routinely used a preservative film for food packaging were selected, and the evaluator took out 50cm films from a roll of 22cm wide film housed in a package, and then cut the films with a film saw blade made of tin-plated iron sheet attached to the package, and evaluated the ease of cutting at 3 per 1 person, and the total score of 100 persons was evaluated. The score of each evaluator was very good in the cutting property, and was very poor in the cutting property, and was not good in the cutting property, respectively. Based on 100 total scores, the cuttability was evaluated on the following 4 grades.
Evaluation mark
And (3) the following materials: the total division is more than 250: can be cut very easily and smoothly
O: the total division is 200 or more and less than 250: can be easily and smoothly cut
Delta: the total division is 150 or more and less than 200: can cut the film relatively easily
X: the total score is less than 150: the cutting needs to be forced, and the cutting property is poor
Example 1
93.5 wt% of a vinylidene chloride resin having a weight average molecular weight of 90,000 (vinylidene chloride repeating unit: 85 wt% and vinyl chloride repeating unit: 15 wt%), 5.4 wt% of DALG (diacetylated monoglyceride, PL-004, lithospermum Co., ltd.), and 1.1 wt% of epoxidized soybean oil (Newcizer 510R, japanese fat & oil Co., ltd.) were mixed together in total at 10kg for 5 minutes by means of a Henschel mixer. And mixing and curing for more than 24 hours to obtain the composition.
The obtained composition was fed to a melt extruder and melted, and was melt-extruded from an annular die attached to the tip of the extruder to form a dipping portion. At this time, the heating condition of the extruder was adjusted so that the temperature of the molten resin at the outlet of the slit of the annular die was 170℃and the extruder was extruded in the form of an annular shape at an extrusion rate of 10 kg/hr.
After cooling in the soaking liquid and the cold water tank, the parison is opened to form bubbles, and inflation stretching is performed. At this time, the film was stretched at an average stretching speed of 0.12 times/s to 4.4 times in the MD direction and at an average stretching speed of 3.7 times/s to 5.5 times in the TD direction, thereby forming a tubular film (bubble).
After the obtained cylindrical film was folded flat with being sandwiched, the film was relaxed by 12% in the MD direction by controlling the speed ratio of the pinch roller to the winding roller, and 2 overlapped films each having a width of 280mm were wound at a winding speed of 18 m/min. The film was cut into a width of 220mm, and the film was rewound on a paper core having an outer diameter of 92mm while being peeled off into 1 sheet. After that, the film was stored at 17℃and wound on a paper core having an outer diameter of 36mm and a length of 230mm for 20m, thereby obtaining a wound body of the preservative film.
The physical properties of the obtained preservative film were measured by the above-mentioned measurement method, and as a result, the low-temperature crystallization initiation temperature was 55 ℃, the thickness was 11 μm, the tear strength in the TD direction was 5.8cN, and the tensile elastic modulus in the MD direction was 520MPa. Dust adhesion, crack failure suppression effect, and cuttability were evaluated by the above methods. The results are shown in Table 1.
Examples 2 to 6 and comparative examples 1 to 5
A wound body of the preservative films of examples 2 to 6 and comparative examples 1 to 5 was obtained in the same manner as in example 1, except that the conditions shown in table 1 were changed. Each evaluation was performed using the wound body of the obtained preservative film.
DALG: diacetyl lauroyl glycerol
ATBC: acetyl tributyl citrate
DBS: dibutyl sebacate
ESO: epoxidized soybean oil
Industrial applicability
The preservative film of the present invention has industrial applicability as a preservative film for food packaging applications, culinary applications and the like.
Claims (6)
1. A preservative film, wherein,
comprises a vinylidene chloride resin and an acetylated fatty glyceride,
the content of the vinylidene chloride resin is 77 to 95.8 weight percent relative to the total amount of the preservative film, the content of the acetylated fatty glyceride is 3.1 to 8.6 weight percent relative to the total amount of the preservative film,
the vinylidene chloride resin is a vinylidene chloride copolymer comprising vinylidene chloride repeating units and monomer repeating units capable of polymerizing with the vinylidene chloride repeating units, the monomer capable of copolymerizing with the vinylidene chloride monomer is at least one selected from the group consisting of vinyl chloride, acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, acrylonitrile and vinyl acetate, the content of the vinylidene chloride repeating units is 72mol% to 93mol% relative to the total amount of the vinylidene chloride resin, the weight average molecular weight Mw of the vinylidene chloride copolymer is 80,000 ～ 200,000,
the proportion of the highly mobile component measured by pulse NMR at a measurement temperature of 40 ℃ is 11.5% or less.
2. The preservative film according to claim 1, wherein the tearing strength in the TD direction is 4.0 cN-8.0 cN.
3. The preservative film according to claim 1 or 2, wherein the tensile elastic modulus in the MD direction is 250MPa to 600MPa.
4. The preservative film according to claim 1 or 2, wherein the low-temperature crystallization onset temperature measured by a temperature-modulated differential scanning calorimeter is 40 ℃ to 60 ℃.
5. The preservative film according to claim 1 or 2, wherein,
comprises an epoxidized vegetable oil which is used to produce a mixture of vegetable oils,
the content of the epoxidized vegetable oil is 0.5 wt% to 3 wt% relative to the total amount of the preservative film.
6. The preservative film according to claim 1 or 2, wherein the thickness is 6 μm to 18 μm.
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