JPH0267328A - Raw material for food packaging - Google Patents
Raw material for food packagingInfo
- Publication number
- JPH0267328A JPH0267328A JP21509688A JP21509688A JPH0267328A JP H0267328 A JPH0267328 A JP H0267328A JP 21509688 A JP21509688 A JP 21509688A JP 21509688 A JP21509688 A JP 21509688A JP H0267328 A JPH0267328 A JP H0267328A
- Authority
- JP
- Japan
- Prior art keywords
- film
- raw material
- food packaging
- stretching
- poly
- 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
- 235000013305 food Nutrition 0.000 title claims abstract description 11
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 title abstract 5
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 235000013311 vegetables Nutrition 0.000 claims abstract description 7
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000005003 food packaging material Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 abstract description 12
- 230000035699 permeability Effects 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- -1 poly(alkyl styrene Chemical compound 0.000 description 44
- 239000005060 rubber Substances 0.000 description 17
- 229920001971 elastomer Polymers 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000005022 packaging material Substances 0.000 description 8
- 239000012778 molding material Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 150000003440 styrenes Polymers 0.000 description 3
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 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 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- ZAHBNGOLTBLVHO-UHFFFAOYSA-N 1,1-bis(2,6-dibutyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCC)C1=C(C(=CC(=C1)C)CCCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1CCCC)C)CCCC ZAHBNGOLTBLVHO-UHFFFAOYSA-N 0.000 description 1
- WHZTUVMPSVWQNZ-UHFFFAOYSA-N 1-butan-2-ylsulfanyldodecane Chemical compound CCCCCCCCCCCCSC(C)CC WHZTUVMPSVWQNZ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WAOPGHCXGUXHKF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 WAOPGHCXGUXHKF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JOWXNCPELQZFHF-UHFFFAOYSA-N 2-[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoyloxy]ethyl 3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoate Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(CC(=O)OCCOC(=O)CC(C)(C=2C=C(C(O)=CC=2)C(C)(C)C)C=2C=C(C(O)=CC=2)C(C)(C)C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 JOWXNCPELQZFHF-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- JJBOJSJSDIRUGY-UHFFFAOYSA-N 2-tert-butyl-4-[2-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-dodecylsulfanylbutan-2-yl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)(CCSCCCCCCCCCCCC)C1=CC(C(C)(C)C)=C(O)C=C1C JJBOJSJSDIRUGY-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
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QGDJATPTZYWUBA-UHFFFAOYSA-N OP(O)OP(O)O.C(CCC)C1=C(C=CC(=C1)CCCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)CCCC)CCCC Chemical compound OP(O)OP(O)O.C(CCC)C1=C(C=CC(=C1)CCCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)CCCC)CCCC QGDJATPTZYWUBA-UHFFFAOYSA-N 0.000 description 1
- GFLIYGDOQWRMTI-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCC GFLIYGDOQWRMTI-UHFFFAOYSA-N 0.000 description 1
- NTQJRZWGBUJHKP-UHFFFAOYSA-N OP(O)OP(O)O.C1(CCCCC1)C(O)(C(CO)(CO)CO)C1CCCCC1 Chemical compound OP(O)OP(O)O.C1(CCCCC1)C(O)(C(CO)(CO)CO)C1CCCCC1 NTQJRZWGBUJHKP-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- MJPRWNNXQTWWLY-UHFFFAOYSA-N dioctadecyl 2,2-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CC(C(=O)OCCCCCCCCCCCCCCCCCC)(C(=O)OCCCCCCCCCCCCCCCCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 MJPRWNNXQTWWLY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000002667 nucleating agent Substances 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
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920003197 poly( p-chlorostyrene) Polymers 0.000 description 1
- 229920001620 poly(3-methyl styrene) Polymers 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Packages (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、食品包装用素材に関し、詳しくは透明でガス
透過性にすぐれた食品包装用素材に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a food packaging material, and more particularly to a food packaging material that is transparent and has excellent gas permeability.
〔従来の技術及び発明が解決しようとする課題〕最近、
食品衛生の観点から包装材料にプラスチックフィルムが
用いられる場合が増加している。[Problems to be solved by conventional techniques and inventions] Recently,
From the viewpoint of food hygiene, plastic films are increasingly being used as packaging materials.
特に、従来、包装に注意を払われていなかった野菜や果
実についても、プラスチックフィルムで包装されて市場
に出回るようになってきている。この野菜等の包装用フ
ィルムにおいては、野菜等の呼吸の観点から、従来包装
材料に要求されているガス遮蔽性とは逆に、酸素、二酸
化炭素等のガスに対する透過性の良いフィルムが好まし
い。In particular, vegetables and fruits that have traditionally not been carefully packaged are now being sold on the market wrapped in plastic film. In this film for packaging vegetables, etc., from the viewpoint of the breathing of vegetables, etc., it is preferable to use a film that has good permeability to gases such as oxygen and carbon dioxide, contrary to the gas shielding properties conventionally required of packaging materials.
従来、この分野においては、アタクチックポリスチレン
のフィルムが用いられているが、さらにガス透過性が良
好で、透明なフィルムが望まれている。Conventionally, films of atactic polystyrene have been used in this field, but a transparent film with even better gas permeability is desired.
そこで、本発明者らは、透明性を有するとともに、ガス
透過性に優れたプラスチック包装材料を開発すべく、鋭
意研究を重ねた。Therefore, the present inventors conducted extensive research in order to develop a plastic packaging material that is transparent and has excellent gas permeability.
（課題を解決するための手段）
その結果、既に本発明者らのグループが開発した主とし
てシンジオタクチック構造を有するスチレン系重合体（
特開昭６２−１０４８１８号公報）を延伸処理したもの
が、上記の要求特性を満足する素材になることを見出し
た。本発明はかかる知見に基いて完成したものである。(Means for solving the problem) As a result, the styrenic polymer mainly having a syndiotactic structure (
It has been found that a stretched material (Japanese Unexamined Patent Publication No. 104818/1983) can be used to produce a material that satisfies the above-mentioned required properties. The present invention was completed based on this knowledge.
すなわち本発明は、主としてシンジオタクチック構造を
有するスチレン系重合体を延伸処理してなる食品包装用
素材を提供するものである。That is, the present invention provides a food packaging material obtained by stretching a styrene polymer mainly having a syndiotactic structure.
本発明において、食品包装用素材として用いるスチレン
系重合体は、主としてシンジオタクチック構造を有する
ものであるが、ここで主としてシンジオタクチック構造
とは、立体化学構造が主としてシンジオタクチック構造
、即ち炭素−炭素結合から形成される主鎖に対して側鎖
であるフェニル基や置換フェニル基が交互に反対方向に
位置する立体構造を有するものであり、そのタフティシ
ティ−は同位体炭素による核磁気共鳴法（１３Ｃ−ＮＭ
Ｒ法）により定量される。１３ｃｍＮＭＲ法により測定
されるタフティシティ−は、連続する複数個の構成単位
の存在割合、例えば２個の場合はダイアツド、３個の場
合はトリアット、５個の場合はペンタッドによって示す
ことができるが、本発明に言う主としてシンジオタクチ
ック構造を有するスチレン系重合体とは、通常はダイア
ツドで７５％以上、好ましくは８５％以上、若しくはペ
ンタッド（ラセミペンタッド）で３０％以上、好ましく
は５０％以上のシンジオタクテイシテイ−を有するポリ
スチレン、ポリ（アルキルスチレン）。In the present invention, the styrenic polymer used as a material for food packaging mainly has a syndiotactic structure. Here, the term "mainly syndiotactic structure" means that the stereochemical structure is mainly syndiotactic, that is, carbon -It has a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains, are located alternately in opposite directions with respect to the main chain formed from carbon bonds, and its toughness is determined by nuclear magnetism due to isotopic carbon. Resonance method (13C-NM
R method). Toughness measured by the 13 cm NMR method can be expressed by the proportion of consecutive constituent units, for example, diats in the case of two units, triats in the case of three units, and pentads in the case of five units. In the present invention, the styrenic polymer mainly having a syndiotactic structure is usually 75% or more in diad, preferably 85% or more, or 30% or more in pentad (racemic pentad), preferably 50% or more. Polystyrene, poly(alkyl styrene) with syndiotacticity of.
ポリ（ハロゲン化スチレン）、ポリ（アルコキシスチレ
ン）、ポリ（ビニル安息香酸エステル）およびこれらの
混合物、あるいはこれらを主成分とする共重合体を指称
する。シンジオタクテイシテイ−の低いスチレン系重合
体では、延伸処理しても充分な延伸効果が期待できない
。なお、ここでポリ（アルキルスチレン）としては、ポ
リ（メチルスチレン）、ポリ（エチルスチレン）、ポリ
（イソプロピルスチレン）、ポリ（ターシャリ−・ブチ
ルスチレン）などがあり、ポリ（ハロゲン化スチレン）
としては、ポリ（クロロスチレン）、ポリ（ブロモスチ
レン）、ポリ（フルオロスチレン）などがある。また、
ポリ（アルコキシスチレン）としては、ポリ（メトキシ
スチレン）、ポリ（エトキシスチレン）などがある。こ
れらのうち特に好ましいスチレン系重合体としては、ポ
リスチレン、ポリ（ｐ−メチルスチレン）、ポリ （ｍ
−メチルスチレン）、ポリ（Ｐ−ターシャリ−ブチルス
チレン）、ポリ（ｐ−クロロスチレン）、ポリ（ｍ−ク
ロロスチレン）、ポリ（ｐ−フルオロスチレン）、更に
はスチレンとｐ−メチルスチレンとの共重合体をあげる
ことができる。Refers to poly(halogenated styrene), poly(alkoxystyrene), poly(vinyl benzoate), mixtures thereof, or copolymers having these as main components. A styrenic polymer with low syndiotacticity cannot be expected to have a sufficient stretching effect even if it is stretched. Note that poly(alkylstyrene) here includes poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), etc. Poly(halogenated styrene)
Examples include poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene). Also,
Examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene). Among these, particularly preferred styrenic polymers include polystyrene, poly(p-methylstyrene), poly(m
-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and even combinations of styrene and p-methylstyrene. Polymers can be mentioned.
また、本発明に用いるスチレン系重合体は、分子量につ
いは特に制限はないが、重量平均分子量が１０．０００
以上のものが好ましく、とりわけ５０．０００以上のも
のが最適である。ここで重量平均分子量が１０，０００
未満のものでは、延伸が充分にできない。さらに、分子
量分布についてはその広狭は制約がなく、様々なものを
充当することが可能である。なお、この主としてシンジ
オタクチック構造を有するスチレン系重合体は、融点が
１６０〜３１０″Ｃであって、従来のアククチツク構造
のスチレン系重合体に比べて耐熱性が格段に優れている
。Furthermore, the styrenic polymer used in the present invention is not particularly limited in molecular weight, but has a weight average molecular weight of 10.000.
A value of 50,000 or more is preferred, and a value of 50,000 or more is particularly optimal. Here, the weight average molecular weight is 10,000
If it is less than that, sufficient stretching cannot be achieved. Furthermore, there are no restrictions on the width or narrowness of the molecular weight distribution, and various types can be used. The styrenic polymer mainly having a syndiotactic structure has a melting point of 160 to 310''C, and has much better heat resistance than conventional styrenic polymers having an active structure.
このような主としてシンジオタクチック構造を有するス
チレン系重合体は、例えば不活性炭化水素溶媒中または
溶媒の不存在下に、チタン化合物、及び水とトリアルキ
ルアルミニウムの縮合生成物を触媒として、スチレン系
単量体（上記スチレン系重合体に対応する単量体）を重
合することにより製造することができる（特開昭６２−
１８７７０８号公報）。Such styrenic polymers having a mainly syndiotactic structure can be produced by using a titanium compound and a condensation product of water and trialkylaluminum as catalysts, for example, in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrene polymers) (Japanese Patent Application Laid-Open No. 1983-1999).
187708).
本発明においては、上記のように主としてシンジオタク
チック構造を有するスチレン系重合体を用いるが、成形
性、延伸性、その他目的とする性質に応じて、熱可塑性
樹脂、ゴム、無機充填剤。In the present invention, as mentioned above, a styrene polymer having a syndiotactic structure is mainly used, but thermoplastic resins, rubbers, and inorganic fillers may be used depending on moldability, stretchability, and other desired properties.
酸化防止剤、核剤、可塑剤、相溶化剤１着色剤。Antioxidant, nucleating agent, plasticizer, compatibilizer 1 coloring agent.
帯電防止剤などを添加することができる。Antistatic agents and the like can be added.
熱可塑性樹脂としては、例えばアタクチック構造のポリ
スチレン、アイソタクチック構造のポリスチレン、ＡＳ
樹脂、ＡＢＳ樹脂などのスチレン系重合体をはじめ、ポ
リエチレンテレフタレートなどのポリエステル、ポリカ
ーボネート、ポリフェニレンオキサイド、ポリスルホン
、ポリエーテルスルホニノなどのポリエーテル、ポリア
ミド、ポリフェニレンスルフィド（ｐｐｓ）、ポリオキ
シメチレンなどの縮合系重合体、ポリアクリル酸。Examples of thermoplastic resins include atactic polystyrene, isotactic polystyrene, and AS.
In addition to styrenic polymers such as resins and ABS resins, polyesters such as polyethylene terephthalate, polyethers such as polycarbonate, polyphenylene oxide, polysulfone, and polyethersulfonino, condensation systems such as polyamide, polyphenylene sulfide (pps), and polyoxymethylene. Polymer, polyacrylic acid.
ポリアクリル酸エステル、ポリメチルメタクリレートな
どのアクリル系重合体、ポリエチレン、ポリプロピレン
、ポリブテン、ポリ４−メチルペンテン−１，エチレン
−プロピレン共重合体などのポリオレフィン、あるいは
ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ弗化ビニリ
デンなどの含ハロゲンビニル化合物重合体などが挙げら
れる。Acrylic polymers such as polyacrylic acid ester and polymethyl methacrylate, polyolefins such as polyethylene, polypropylene, polybutene, poly4-methylpentene-1, and ethylene-propylene copolymers, or polyvinyl chloride, polyvinylidene chloride, and polyfluoride. Examples include halogen-containing vinyl compound polymers such as vinylidene chloride.
またゴムとしては、様々なものが使用可能であるが、最
も好適なものはスチレン系化合物をその一成分として含
むゴム状共重合体で、例えば、スチレン−ブタジェンブ
ロック共重合体のブタジェン部分を一部あるいは完全に
水素化したゴム（ＳＥＢＳ）、スチレン−ブタジェン共
重合体ゴム（ＳＢＲ）、アクリル酸メチル−ブタジェン
−スチレン共重合体ゴム、アクリロニトリル−ブタジェ
ン−スチレン共重合体ゴム（ＡＢＳゴム）、アクリロニ
トリル−アルキルアクリレート−ブタジェン−スチレン
共重合体ゴム（ＡＡＢＳ）、メタクリル酸メチル−アル
キルアクリレート−スチレン共重合体ゴム（ＭＡＳ）、
メタクリル酸メチル−アルキルアクリレート−ブタジェ
ン−スチレン共重合体ゴム（ＭＡＢＳ）などが挙げられ
る。これらのスチレン系化合物をその一成分として含む
ゴム状共重合体は、スチレン単位を有するため、主とし
てシンジオタクチック構造を有するスチレン系重合体に
対する分散性が良好であり、その結果、物性の改善効果
が著しい。Various rubbers can be used, but the most suitable rubber is a rubbery copolymer containing a styrene compound as one of its components.For example, the butadiene moiety of a styrene-butadiene block copolymer is partially or fully hydrogenated rubber (SEBS), styrene-butadiene copolymer rubber (SBR), methyl acrylate-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber (ABS rubber), Acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber (AABS), methyl methacrylate-alkyl acrylate-styrene copolymer rubber (MAS),
Examples include methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber (MABS). Rubber-like copolymers containing these styrene compounds as one component have styrene units, so they have good dispersibility in styrene polymers that mainly have a syndiotactic structure, and as a result, they have the effect of improving physical properties. is remarkable.
さらに用いることのできるゴムの他の例としては、天然
ゴム、ポリブタジェン、ポリイソプレン。Other examples of rubbers that can also be used include natural rubber, polybutadiene, and polyisoprene.
ポリイソブチレン、ネオブレン、エチレン−プロピレン
共重合体ゴム、ポリスルフィドゴム、チオコールゴム、
アクリルゴム、ウレタンゴム、シリコーンゴム、エピク
ロルヒドリンゴム、ポリエーテル・エステルゴム、ポリ
エステル・エステルゴムなどが挙げられる。Polyisobutylene, neorene, ethylene-propylene copolymer rubber, polysulfide rubber, thiocol rubber,
Examples include acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, polyether/ester rubber, and polyester/ester rubber.
さらに無機充填剤としては、繊維状のものであると、粒
状、粉状のものであるとを問わない。繊維状無機充填材
としてはガラス繊維、炭素繊維。Furthermore, the inorganic filler may be fibrous, granular, or powdery. Glass fiber and carbon fiber are used as fibrous inorganic fillers.
アルミナ繊維等が挙げられる。一方、粒状、粉状無機充
填材としてはタルク、カーボンブラック。Examples include alumina fiber. On the other hand, talc and carbon black are used as granular and powdery inorganic fillers.
グラファイト、二酸化チタン、シリカ、マイカ。Graphite, titanium dioxide, silica, mica.
・炭酸カルシウム、硫酸カルシウム、炭酸バリウム。- Calcium carbonate, calcium sulfate, barium carbonate.
−床酸マグネシウム、硫酸マグネシウム、硫酸バリウム
、オキシサルフェート、酸化スズ、アルミナ。- Magnesium bed acid, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina.
カオリン、炭化ケイ素、金属粉末等が挙げられる。Examples include kaolin, silicon carbide, metal powder, and the like.
また酸化防止剤としては様々なものがあるが、特にトリ
ス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト５
トリス（モノおよびジ−ノニルフェニル）ホスファイ
ト等のモノホスファイトやジホスファイト等のリン系酸
化防止剤およびフェノール系酸化防止剤が好ましい、ジ
ホスファイトとしては、
一般式
〔式中、Ｒ１，Ｒｆｆｉはそれぞれ炭素数１〜２ｏのア
ルキル基、炭素数３〜２ｏのシクロアルキル基あるいは
炭素数６〜２ｏのアリール基を示す、〕で表わされるリ
ン系化合物を用いることが好ましい。There are various antioxidants, especially tris(2,4-di-t-butylphenyl) phosphite 5.
Preferred are phosphorus antioxidants and phenolic antioxidants such as monophosphites and diphosphites such as tris(mono- and di-nonylphenyl)phosphites. It is preferable to use a phosphorus compound represented by ], which represents an alkyl group having 1 to 2 o carbon atoms, a cycloalkyl group having 3 to 2 o carbon atoms, or an aryl group having 6 to 2 o carbon atoms.
上記−数式で表わされるリン系化合物の具体例としては
、ジステアリルペンタエリスリトールジホスファイト：
ジオクチルペンタエリスリトールジホスファイト；ジフ
ェニルペンタエリスリトールジホスファイト；ビス（２
，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトール
ジホスファイト；ビス（２，６−ジーＬ−ブチル−４−
メチルフェニル）ペンタエリスリトールジホスファイト
；ジシクロへキシルペンタエリスリトールジホスファイ
トなどが挙げられる。Specific examples of phosphorus compounds represented by the above formula include distearyl pentaerythritol diphosphite:
Dioctylpentaerythritol diphosphite; diphenylpentaerythritol diphosphite; bis(2
,4-di-t-butylphenyl)pentaerythritol diphosphite; bis(2,6-di-L-butyl-4-
Methylphenyl) pentaerythritol diphosphite; dicyclohexyl pentaerythritol diphosphite, and the like.
また、フェノール系酸化防止剤としては既知のものを使
用することができ、その具体例としては、２．６−ジー
ｔ−ブチル−４−メチルフェノール；２．６−ジフェニ
ル−４−メトキシフェノール；２．２゛−メチレンビス
（６−ｔ−ブチル−４−メチルフェノール）：２．２’
−メチレンビス−（６−ｔ−ブチル−４−メチルフェノ
ール）；２゜２”−メチレンビス〔４−メチル−６−（
α−メチルシクロヘキシル）フェノール）；１，１−ビ
ス（５−ｔ−ブチル−４−ヒドロキシ−２−メチルフェ
ニル）ブタン；２．２’−メチレンビス（４−メチル−
６−シクロヘキジルフエノール）；２．２°−メチレン
ビス−（４−メチル−６−ツニルフエノール）；１，１
．３−トリス−（５−ｔ−ブチル−４−ヒドロキシ−２
−メチルフェニル）ブタン；２，２−ビス−（５−ｔ−
ブチル−４−ヒドロキシ−２−メチルフェニル） −４
−ｎ−ドデシルメルカプトブタン；エチレングリコール
−ビス〔３，３−ビス（３−ｔ−ブチル−４−ヒドロキ
シフェニル）ブチレート〕；１・−１−ビス（３，５−
ジメチル−２−ヒドロキシフェニル）＝３−（ｎ−ドデ
シルチオ）−ブタンｉ４，４’−チオビス（６−も−ブ
チル−３−メチルフェノール）；１，３．５−）リス（
３，５−ジーも一ブチルー４−ヒドロキシベンジル）−
２，４，６−ドリメチルベンゼン；２．２−ビス（３，
５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）マロン
酸ジオクタデシルエステル；ｎ−オクタデシル−３−（
４−ヒドロキシ−３，５−ジ−ｔ−ブチルフェニル）プ
ロピオネート；テトラキス〔メチレン（３，５−ジ−ｔ
−ブチル−４−ヒドロキシハイドロシンナメート）〕メ
タンなどが挙げられる。In addition, known phenolic antioxidants can be used, and specific examples thereof include 2.6-di-t-butyl-4-methylphenol; 2.6-diphenyl-4-methoxyphenol; 2.2'-methylenebis(6-t-butyl-4-methylphenol): 2.2'
-methylenebis-(6-t-butyl-4-methylphenol); 2゜2''-methylenebis[4-methyl-6-(
1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane; 2,2'-methylenebis(4-methyl-
6-cyclohexylphenol); 2.2°-methylenebis-(4-methyl-6-tunylphenol); 1,1
．． 3-tris-(5-t-butyl-4-hydroxy-2
-methylphenyl)butane; 2,2-bis-(5-t-
butyl-4-hydroxy-2-methylphenyl) -4
-n-dodecylmercaptobutane; ethylene glycol-bis[3,3-bis(3-t-butyl-4-hydroxyphenyl)butyrate]; 1-1-bis(3,5-
dimethyl-2-hydroxyphenyl) = 3-(n-dodecylthio)-butane i4,4'-thiobis(6-mo-butyl-3-methylphenol); 1,3.5-)lis(
3,5-di-butyl-4-hydroxybenzyl)-
2,4,6-drimethylbenzene; 2,2-bis(3,
5-di-t-butyl-4-hydroxybenzyl) malonic acid dioctadecyl ester; n-octadecyl-3-(
4-hydroxy-3,5-di-t-butylphenyl)propionate; tetrakis[methylene(3,5-di-t-butylphenyl)propionate;
-butyl-4-hydroxyhydrocinnamate)] methane, and the like.
上記の酸化防止剤は、前記の主としてシンジオタクチッ
ク構造を有するスチレン系重合体１００重量部に対し、
０．０００１〜２重量部、好ましくは０．００１〜１重
量部の割合で配合される。The above antioxidant is based on 100 parts by weight of the styrenic polymer mainly having a syndiotactic structure.
It is blended in a proportion of 0.0001 to 2 parts by weight, preferably 0.001 to 1 part by weight.
ここで酸化防止剤の配合割合が０．０００１重量部未満
であると分子量低下が著しく、一方、２重量部を超える
と機械的強度に影響があるため、いずれも好ましくない
。If the blending ratio of the antioxidant is less than 0.0001 part by weight, the molecular weight will be significantly lowered, while if it exceeds 2 parts by weight, the mechanical strength will be affected, so both are not preferred.
本発明の食品包装用素材の形状は、用途に応じて適宜選
定すればよいが、一般にはフィルム状あるいはシート状
である。ここでフィルム状の食品包装用素材を成形する
には、通常は次の如き操作を行う。即ち、まず上述のス
チレン系重合体あるいはこれに他の成分を適量配合した
ものを成形材料として、これを通常はまず押出成形やカ
レンダー成形、あるいはブロー成形、ブロー延伸成形の
場合にはさらに射出成形等により成形して、延伸用原反
シート（フィルムまたは予備成形体）とする。この成形
にあっては、上記成形材料の加熱溶融したものを各種成
形機にて所定形状に成形するのが一般的であるが、成形
材料を加熱溶融させずに、軟化した状態で成形してもよ
い。ここで成形材料の溶融温度は通常は２６０〜３５０
°Ｃ１好ましくは２８０〜３３０℃である。温度が高す
ぎると成形材料が分解するなどの問題が生じ好ましくな
い。また、ここで成形する原反シートの厚さは任意に選
定すればよいが、一般には５ｍｍ以下、好ましくは３
ｎ＋＋＋＋〜２０ａｍの範囲で適宜室めればよい。厚さ
が５１１Ｉ１１を超えるものでは、内部の結晶化が進み
シートが白濁する場合がある。原反シート（フィルム）
の結晶化度は、３０％以下、好ましくは２０％以下、さ
らに好ましくは１０％以下である。The shape of the food packaging material of the present invention may be appropriately selected depending on the intended use, but it is generally in the form of a film or a sheet. In order to form a film-like food packaging material, the following operations are usually performed. That is, first, the above-mentioned styrenic polymer or a mixture of appropriate amounts of other components is used as a molding material, and this is usually first subjected to extrusion molding, calendar molding, or blow molding, and in the case of blow stretch molding, further injection molding. etc. to form a raw sheet for stretching (film or preform). In this molding, it is common to heat and melt the above-mentioned molding material and mold it into a predetermined shape using various molding machines, but the molding material is molded in a softened state without being heated and melted. Good too. Here, the melting temperature of the molding material is usually 260 to 350.
°C1 Preferably it is 280-330 °C. If the temperature is too high, problems such as decomposition of the molding material occur, which is not preferable. Further, the thickness of the original fabric sheet to be formed here may be arbitrarily selected, but is generally 5 mm or less, preferably 3 mm or less.
The room may be set appropriately within the range of n+++++ to 20 am. If the thickness exceeds 511I11, internal crystallization may progress and the sheet may become cloudy. Raw sheet (film)
The crystallinity of is 30% or less, preferably 20% or less, more preferably 10% or less.
なお、なるべく結晶化度の低い原反シートを製造したい
場合、特に肉厚の厚いシートを成形する際には、加熱溶
融した上記の成形材料を成形時に急冷することが効果的
である。ここで、急冷にあたっては、冷媒温度を１００
″Ｃ以下、好ましくは８０℃以下、さらに好ましくは５
０″Ｃ以下に設定する。冷媒温度が高すぎると緩慢冷却
となり、−部活晶化が起こり白濁する。Note that when it is desired to produce a raw sheet with as low a degree of crystallinity as possible, especially when molding a thick sheet, it is effective to rapidly cool the above-mentioned molding material that has been heated and melted during molding. Here, for rapid cooling, the refrigerant temperature is set to 100
″C or less, preferably 80°C or less, more preferably 5
Set to 0''C or less. If the refrigerant temperature is too high, cooling will be slow, and crystallization will occur in the negative region, resulting in cloudiness.
この原反シートを延伸処理するあたっては、−般には材
料のガラス転移温度〜融点以下の温度で一軸あるいは二
軸に延伸する。ここで延伸温度は低温結晶化温度以下が
好ましく、それ以上の温度では透明なフィルムが得られ
にくい。また、延伸倍率については、−軸延伸の場合は
、延伸方向に２倍以上、好ましくは３倍以上、さらに好
ましくは３〜１０倍の延伸倍率で延伸すべきである。ま
た二輪延伸の場合は、それぞれの延伸方向（二軸方向）
に１．５倍以上、好ましくは２倍以上の延伸倍率で延伸
すべきである。延伸倍率が小さすぎると、得られるフィ
ルムの物性は充分に改善されないものとなる。なお、上
記二軸延伸の場合は、縦方向及び横方向に同時に延伸し
てもよいが、任意の順序で逐次延伸してもよい。When this raw sheet is stretched, it is generally stretched uniaxially or biaxially at a temperature between the glass transition temperature and the melting point of the material. Here, the stretching temperature is preferably below the low-temperature crystallization temperature; if the stretching temperature is higher than that, it is difficult to obtain a transparent film. Regarding the stretching ratio, in the case of -axis stretching, it should be stretched in the stretching direction at a stretching ratio of 2 times or more, preferably 3 times or more, and more preferably 3 to 10 times. In addition, in the case of two-wheel stretching, each stretching direction (biaxial direction)
It should be stretched at a stretching ratio of 1.5 times or more, preferably 2 times or more. If the stretching ratio is too small, the physical properties of the resulting film will not be sufficiently improved. In addition, in the case of the above-mentioned biaxial stretching, the stretching may be carried out simultaneously in the longitudinal direction and the transverse direction, but the stretching may be carried out sequentially in any order.
また本発明では、特に二輪延伸を行う場合には、上述の
成形材料を、原反シートまたは予備成形体とすることな
く、直接インフレーション成形あるいは延伸プロー成形
することによっても二輪延伸成形体（二軸延伸フィルム
など）とすることができる。このインフレーション成形
あるいは延伸プロー成形による場合には、融解時の樹脂
温度を融点よりも２０℃以上高くすることが、メルトワ
ラクチャ−。肌荒れ等を防ぐ上で有効であるが、あまり
高すぎると熱分解が起るため、１８０〜３３０°Ｃの範
囲に設定することが好ましい。さらに、延伸温度は融点
以下１０″Ｃであればよい、延伸ブロー成形に際しては
、延伸前のプリフォームはホットパリソン、コールドパ
リソンのいずれでもよい。In addition, in the present invention, especially when carrying out two-wheel stretching, the above-mentioned molding material may be directly inflation molded or stretch blow-molded without using it as a raw sheet or a preform. stretched film, etc.). In the case of this inflation molding or stretch blow molding, it is necessary to raise the resin temperature at the time of melting by at least 20°C higher than the melting point. Although it is effective in preventing skin roughness, if the temperature is too high, thermal decomposition will occur, so it is preferable to set the temperature in the range of 180 to 330°C. Further, the stretching temperature may be 10"C below the melting point. In stretch blow molding, the preform before stretching may be either a hot parison or a cold parison.
また、このインフレーション成形あるいは延伸ブロー成
形にあたって、ブローアツプ比を小さくすれば、−軸延
伸も可能である。Further, in this inflation molding or stretch blow molding, -axis stretching is also possible if the blow-up ratio is made small.
このようにして得られたフィルムは、厚みが５〜１００
μｍ１好ましくは１０〜５０μｍであって、ガス透過性
に優れ、透明で光沢があり、清潔感があり、酸素、二酸
化炭素等ガスの透過・拡散を必要とする食品（例えば、
野菜や果実など）の包装素材として特に有効である。The film thus obtained has a thickness of 5 to 100
μm1 Preferably 10 to 50 μm, has excellent gas permeability, is transparent, glossy, and has a clean feeling, and is suitable for foods that require permeation and diffusion of gases such as oxygen and carbon dioxide (e.g.
It is particularly effective as a packaging material for vegetables, fruits, etc.
本発明により延伸処理後、さらに熱固定を行うこともで
きる。この熱固定は、ガラス転移温度以上、融点以下の
温度範囲でフィルム等の素材を緊張状態にして熱処理す
ればよい。この熱固定により、フィルｌ、等の包装素材
の耐熱性１寸法安定性。According to the present invention, heat setting can be further performed after the stretching treatment. This heat fixing may be carried out by subjecting the material such as a film to a tensioned state at a temperature range of not less than the glass transition temperature and not more than the melting point. This heat fixation improves the heat resistance and dimensional stability of packaging materials such as fill.
耐薬品性、ガス透過性が一層向上する。Chemical resistance and gas permeability are further improved.
次に、本発明を実施例及び比較例によりさらに詳しく説
明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
参考例１（シンジオタクチック構造を有するポリスチレ
ンの製造）
反応容器に、溶媒としてトルエン２２と触媒成分として
シクロペンタジェニルチタニウムトリクロリド１ミリモ
ル及びメチルアルミノキサンをアルミニウム原子として
０．８モル加え、２０°Ｃにおいてこれにスチレン３．
６１を加え、１時間重合反応を行なった。Reference Example 1 (Production of polystyrene having a syndiotactic structure) To a reaction vessel, 22 toluene as a solvent, 1 mmol of cyclopentadienyl titanium trichloride as a catalyst component, and 0.8 mol of methylaluminoxane as an aluminum atom were added, and the mixture was heated at 20° Styrene 3.
61 was added, and the polymerization reaction was carried out for 1 hour.
反応終了後、生成物を塩酸−メタノール混合液で洗浄し
、触媒成分を分解除去した０次いで乾燥し、スチレン系
重合体（ポリスチレン）３３０ｇを得た。次に、この重
合体をメチルエチルケトンを溶媒としてソックスレー抽
出し、抽出残分９５重量％を得た。このものの重量平均
分子量は２９０．０００、数平均分子量は１５Ｂ、ＯＯ
Ｏであり、融点は２７０ ”Ｃであった。また、この重
合体は、”Ｃ−ＮＭＲによる分析（溶媒：１，２−ジク
ロロベンゼン）から、シンジオタクチック構造に基因す
る１ ４５．３５ｐｐｍに吸収が認められ、そのピーク
面積から算出したラセミペンタッドでのシンジオタクテ
イシテイ−は９６％であった。After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixture to decompose and remove the catalyst component, and then dried to obtain 330 g of a styrene polymer (polystyrene). Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. The weight average molecular weight of this product is 290.000, the number average molecular weight is 15B, OO
The melting point of this polymer was 270"C. Also, this polymer had a concentration of 145.35 ppm due to its syndiotactic structure, according to C-NMR analysis (solvent: 1,2-dichlorobenzene). Absorption was observed, and the syndiotacticity for racemic pentad calculated from the peak area was 96%.
実施例１
上記参考例１で得られたポリスチレンに、酸化防止剤と
して、ビス（２，４−ジーし一ブチルフェニル）ペンタ
エリスリトールジホスファイト及びテトラキス〔メチレ
ン（３，５−ジ−ｔ−ブチル−４−ヒドロキシハイドロ
シンナメート）〕メタンをおのおの０．１重量部ずつ混
合し、直径４゜ｌの二軸押出機にて押出して、ペレット
化した。Example 1 The polystyrene obtained in Reference Example 1 was added with bis(2,4-di-butylphenyl)pentaerythritol diphosphite and tetrakis[methylene(3,5-di-t-butyl)] as antioxidants. -4-Hydroxyhydrocinnamate)] Methane was mixed in an amount of 0.1 part by weight, and the mixture was extruded into pellets using a twin-screw extruder having a diameter of 4.0 L.
”得られたペレットを、直径４０ｍｍの一軸押出機の先
端にＴダイを取り付けた装置に供給し、シリンダー温度
３００°Ｃ，Ｔダイ温度３１０°Ｃ１吐出量４．２ ｋ
ｇ／時の条件で押出し、肉厚４００μｍのシートを得た
。このとき、シートの冷却用ロールは表面温度３０″Ｃ
であった。``The obtained pellets were supplied to a single screw extruder with a diameter of 40 mm with a T-die attached to the tip, and the cylinder temperature was 300°C, the T-die temperature was 310°C, and the output amount was 4.2 k.
It was extruded under conditions of g/hour to obtain a sheet with a wall thickness of 400 μm. At this time, the sheet cooling roll has a surface temperature of 30''C.
Met.
このようにして得られた延伸用原反シートは、透明で密
度１．０４ ｇ／ｒｒｆ、ガラス転移温度１００℃、結
晶化度２％であった。The raw sheet for stretching thus obtained was transparent, had a density of 1.04 g/rrf, a glass transition temperature of 100° C., and a degree of crystallinity of 2%.
次いでこのシートを、延伸温度１２０″Ｃで縦横に３倍
ずつ同時延伸を行った。得られた延伸フィルムを格子状
の固定具に固定し、２５０°Ｃで３０秒間熱処理した。Next, this sheet was simultaneously stretched 3 times in length and width at a stretching temperature of 120''C.The obtained stretched film was fixed to a grid-shaped fixture and heat treated at 250°C for 30 seconds.
この時のフィルムの厚さは４５μｍであった。このフィ
ルムの酸素透過係数、ヘイズ、引張強度を測定し、結果
を第１表に示す。The thickness of the film at this time was 45 μm. The oxygen permeability coefficient, haze, and tensile strength of this film were measured, and the results are shown in Table 1.
実施例２
縦横に３．５倍ずつ同時に延伸し、熱処理を行わなかっ
たこと以外は、実施例１と同様にしてフィルムを得た。Example 2 A film was obtained in the same manner as in Example 1, except that the film was stretched 3.5 times in the length and width directions at the same time and no heat treatment was performed.
得られたフィルムの厚さは３３μｍであった。このフィ
ルムの物性の測定結果を第１表に示す。The thickness of the obtained film was 33 μm. Table 1 shows the measurement results of the physical properties of this film.
実施例３
縦横に３．５倍ずつ同時に延伸したこと以外は、実施例
１と同様にしてフィルムを得た。得られたフィルムの厚
さは３３μｍであった。このフィルムの物性の測定結果
を第１表に示す。Example 3 A film was obtained in the same manner as in Example 1, except that the film was stretched 3.5 times in the length and width at the same time. The thickness of the obtained film was 33 μm. Table 1 shows the measurement results of the physical properties of this film.
実施例４
縦横に４倍ずつ同時に延伸したこと以外は、実施例１と
同様にしてフィルムを得た。得られたフィルムの厚さは
２５μｍであった。このフィルムの物性の測定結果を第
１表に示す。Example 4 A film was obtained in the same manner as in Example 1, except that the film was stretched 4 times in length and width at the same time. The thickness of the obtained film was 25 μm. Table 1 shows the measurement results of the physical properties of this film.
比較例１
アタクチックポリスチレン（商品名：出光スチロールＵ
Ｓ３００、重量平均分子量３７０，０００゜メルトイン
デックス２ｇ／１０分、密度１．０５ｇ／ｃｔｌ、出光
石油化学■製）を用いて、実施例１と同様にして２２０
℃でシート成形を行った。このシートを１２０℃で縦横
に４倍ずつ同時延伸し、厚さ２５μｍのフィルムを得た
。このフィルムの物性の測定結果を第１表に示す。Comparative Example 1 Atactic polystyrene (Product name: Idemitsu Styrene U
220 in the same manner as in Example 1 using S300, weight average molecular weight 370,000° melt index 2 g/10 min, density 1.05 g/ctl, manufactured by Idemitsu Petrochemical.
Sheet molding was performed at ℃. This sheet was simultaneously stretched 4 times in length and width at 120° C. to obtain a film with a thickness of 25 μm. Table 1 shows the measurement results of the physical properties of this film.
以上の如く、本発明によれば透明で、光沢があり、ガス
透過性、耐熱性などの各種の物性に優れたスチレン系重
合体フィルム等の包装用素材が得られる。As described above, according to the present invention, packaging materials such as styrenic polymer films that are transparent, glossy, and excellent in various physical properties such as gas permeability and heat resistance can be obtained.
したがって、本発明の包装用素材は、酸素や二酸化炭素
等のガスの透過・拡散を必要とする野菜。Therefore, the packaging material of the present invention is suitable for vegetables that require permeation and diffusion of gases such as oxygen and carbon dioxide.
果実などの食品の包装材料として非常に有用である。It is very useful as a packaging material for foods such as fruits.
特許出願人 出光興産株式会社 代理人 弁理士 大 谷 保 手続補正書（自発） 平成元年１１月１６日Patent applicant: Idemitsu Kosan Co., Ltd. Agent Patent Attorney Tamotsu Otani Procedural amendment (voluntary) November 16, 1989
Claims (3)
ン系重合体を延伸処理してなる食品包装用素材。(1) A material for food packaging made by stretching a styrene polymer mainly having a syndiotactic structure.
載の食品包装用素材。(2) The food packaging material according to claim 1, wherein the material is in the form of a film.
項１記載の食品包装用素材。(3) The food packaging material according to claim 1, wherein the food to be packaged is a vegetable or a fruit.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63215096A JP2790636B2 (en) | 1988-08-31 | 1988-08-31 | Stretched film for food packaging |
| US07/651,043 US5145950A (en) | 1988-08-31 | 1991-02-04 | Method of storing food or plant materials by wrapping with a stretched syndiotactic polystyrene film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63215096A JP2790636B2 (en) | 1988-08-31 | 1988-08-31 | Stretched film for food packaging |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0267328A true JPH0267328A (en) | 1990-03-07 |
| JP2790636B2 JP2790636B2 (en) | 1998-08-27 |
Family
ID=16666689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63215096A Expired - Fee Related JP2790636B2 (en) | 1988-08-31 | 1988-08-31 | Stretched film for food packaging |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2790636B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02279731A (en) * | 1989-04-21 | 1990-11-15 | Asahi Chem Ind Co Ltd | Transparent syndiotactic polystyrene film |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| JPH0732468A (en) * | 1993-07-16 | 1995-02-03 | Toyobo Co Ltd | Thermal shrinkable polystyrene film |
| EP0742246A4 (en) * | 1994-12-02 | 1999-01-13 | Idemitsu Petrochemical Co | Stretched polystyrene film and process for the preparation of strechted polystyrene film |
| EP0748833A4 (en) * | 1994-12-02 | 1999-01-13 | Idemitsu Petrochemical Co | Stretched polystyrene film, process for producing the same, and photographic process and ohp films |
| JP2015021017A (en) * | 2013-07-16 | 2015-02-02 | 倉敷紡績株式会社 | Polystyrene-based film and method for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6377905A (en) * | 1986-09-22 | 1988-04-08 | Idemitsu Kosan Co Ltd | Styrene polymer molding |
| JPH01110122A (en) * | 1987-10-23 | 1989-04-26 | Asahi Chem Ind Co Ltd | Production of syndiotactic polystyrenic film |
-
1988
- 1988-08-31 JP JP63215096A patent/JP2790636B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6377905A (en) * | 1986-09-22 | 1988-04-08 | Idemitsu Kosan Co Ltd | Styrene polymer molding |
| JPH01110122A (en) * | 1987-10-23 | 1989-04-26 | Asahi Chem Ind Co Ltd | Production of syndiotactic polystyrenic film |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02279731A (en) * | 1989-04-21 | 1990-11-15 | Asahi Chem Ind Co Ltd | Transparent syndiotactic polystyrene film |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| JPH0732468A (en) * | 1993-07-16 | 1995-02-03 | Toyobo Co Ltd | Thermal shrinkable polystyrene film |
| EP0742246A4 (en) * | 1994-12-02 | 1999-01-13 | Idemitsu Petrochemical Co | Stretched polystyrene film and process for the preparation of strechted polystyrene film |
| EP0748833A4 (en) * | 1994-12-02 | 1999-01-13 | Idemitsu Petrochemical Co | Stretched polystyrene film, process for producing the same, and photographic process and ohp films |
| JP2015021017A (en) * | 2013-07-16 | 2015-02-02 | 倉敷紡績株式会社 | Polystyrene-based film and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2790636B2 (en) | 1998-08-27 |
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