JP2006248555A - Container and its manufacturing method - Google Patents
Container and its manufacturing method Download PDFInfo
- Publication number
- JP2006248555A JP2006248555A JP2005065941A JP2005065941A JP2006248555A JP 2006248555 A JP2006248555 A JP 2006248555A JP 2005065941 A JP2005065941 A JP 2005065941A JP 2005065941 A JP2005065941 A JP 2005065941A JP 2006248555 A JP2006248555 A JP 2006248555A
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- acid compound
- polyvalent metal
- unsaturated carboxylic
- metal salt
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- -1 unsaturated carbonic acid compound Chemical class 0.000 claims abstract description 112
- 150000003839 salts Chemical class 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 238000002835 absorbance Methods 0.000 claims abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 22
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 239000011241 protective layer Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 31
- 230000004888 barrier function Effects 0.000 abstract description 26
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005586 carbonic acid group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 31
- 150000002736 metal compounds Chemical class 0.000 description 28
- 239000000126 substance Substances 0.000 description 15
- 229920005992 thermoplastic resin Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005865 ionizing radiation Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000014171 carbonated beverage Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 235000014214 soft drink Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 244000003363 Allium ursinum Species 0.000 description 1
- 235000005336 Allium ursinum Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、透明性を有し、酸素、水蒸気等のガスバリア性、特に高湿度下でのガスバリア性に優れた容器及びその製造方法に関する。 The present invention relates to a container having transparency and excellent gas barrier properties such as oxygen and water vapor, particularly gas barrier properties under high humidity, and a method for producing the same.
熱可塑性樹脂製容器は軽量であることから、調味料、油、飲料、化粧品、洗剤等の容器として幅広く使用されている。中でもポリエチレンテレフタレートなどのポリエステル樹脂は機械的強度、耐熱性、透明性およびガスバリア性に優れているので、特にジュース、清涼飲料、炭酸飲料などの飲料充填用容器の素材として広く用いられている。
一方、熱可塑性樹脂製容器は金属缶、ガラス瓶に比べ酸素等のガスを通し易いので、酸素による変質や香気の低下を嫌う内容物あるいは炭酸ガスを含むビール等の容器には、未だ金属缶やガラス瓶が主に使用されている。
熱可塑性樹脂製容器のガスバリア性を改良する方法として、例えば熱可塑性樹脂製容器の容器壁を多層構造とし、その内の少なくとも一層としてポリグリコール酸等のガスバリア性樹脂を用いる方法(例えば、特許文献1)、ポリカルボン酸系重合体、多価金属化合物、揮発性塩基及び水を含む混合組成物から形成されたガスバリア性樹脂層を用いる方法(例えば、特許文献2)、あるいはポリエチレンテレフタレートに芳香族ポリエステル、ポリオレフィン及び遷移金属触媒からなる酸素吸収剤をブレンドする方法(例えば、特許文献3)などが提案されている。
しかしながら、かかるガスバリア性樹脂は未だ酸素あるいは炭酸ガスの透過を防ぐには不十分であり、金属缶あるいはガラス瓶並のガスバリア性に優れる容器が求められている。
Thermoplastic resin containers are lightweight, and are therefore widely used as containers for seasonings, oils, beverages, cosmetics, detergents, and the like. Among these, polyester resins such as polyethylene terephthalate are widely used as materials for containers for filling beverages such as juices, soft drinks and carbonated drinks because they are excellent in mechanical strength, heat resistance, transparency and gas barrier properties.
On the other hand, a container made of thermoplastic resin is easier to pass gas such as oxygen than metal cans and glass bottles. Therefore, containers such as contents that dislike alteration due to oxygen and deterioration of aroma or beer containing carbon dioxide gas are still Glass bottles are mainly used.
As a method for improving the gas barrier property of a thermoplastic resin container, for example, the container wall of a thermoplastic resin container has a multilayer structure, and at least one of them includes a gas barrier resin such as polyglycolic acid (for example, patent document) 1), a method using a gas barrier resin layer formed from a mixed composition containing a polycarboxylic acid polymer, a polyvalent metal compound, a volatile base and water (for example, Patent Document 2), or an aromatic polyethylene terephthalate A method of blending an oxygen absorbent composed of polyester, polyolefin and a transition metal catalyst (for example, Patent Document 3) has been proposed.
However, such a gas barrier resin is still insufficient to prevent permeation of oxygen or carbon dioxide gas, and a container having excellent gas barrier properties similar to a metal can or a glass bottle is required.
そこで本発明は、透明性を有し、酸素、炭酸ガス、水蒸気等のガスバリア性、特に高湿度下でのガスバリア性に優れた容器を得ることを目的とした。 Accordingly, an object of the present invention is to obtain a container having transparency and excellent gas barrier properties such as oxygen, carbon dioxide gas, and water vapor, particularly gas barrier properties under high humidity.
本発明は、基材層の少なくとも片面に、赤外線吸収スペクトルにおける1700cm−1付近のカルボン酸基のνC=Oに基づく吸光度A0と1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度Aとの比(A0/A)が0.25未満である不飽和カルボン酸化合物多価金属塩の重合体(A)層が形成されてなることを特徴とする容器を提供するものである。 In the present invention, an absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 and an absorbance A based on νC═O of a carboxylate ion near 1520 cm −1 in an infrared absorption spectrum are provided on at least one surface of a base material layer. And a polymer (A) layer of an unsaturated carboxylic acid compound polyvalent metal salt having a ratio (A 0 / A) of less than 0.25 is provided.
本発明は、基材層の少なくとも片面に、重合度が20未満の不飽和カルボン酸化合物多価金属塩の溶液を塗工した後、不飽和カルボン酸化合物多価金属塩を重合し、不飽和カルボン酸化合物多価金属塩の重合体(A)層を形成することを特徴と容器の製造方法を提供するものである。 In the present invention, an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 is applied to at least one surface of the base material layer, and then the unsaturated carboxylic acid compound polyvalent metal salt is polymerized to be unsaturated. It is characterized by forming a polymer (A) layer of a carboxylic acid compound polyvalent metal salt and a method for producing a container.
本発明の不飽和カルボン酸化合物多価金属塩の重合体層が形成された容器は高湿度下でのガスバリア性に優れている。
本発明の製造方法は、重合度が20未満の不飽和カルボン酸化合物を用いることにより、容器の表面あるいは内面に塗工することが容易であり、しかも、中和度が高い、即ち、ガスバリア性に優れる不飽和カルボン酸多価金属化合物の重合体からなる膜を容易に製造し得る。
The container in which the polymer layer of the unsaturated carboxylic acid compound polyvalent metal salt of the present invention is formed has excellent gas barrier properties under high humidity.
The production method of the present invention can be easily applied to the surface or inner surface of a container by using an unsaturated carboxylic acid compound having a degree of polymerization of less than 20, and has a high degree of neutralization, that is, gas barrier properties. A film made of a polymer of an unsaturated carboxylic acid polyvalent metal compound having excellent resistance can be easily produced.
不飽和カルボン酸化合物
本発明に係わる不飽和カルボン酸化合物多価金属塩を形成する不飽和カルボン酸化合物は、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸等のα、β―エチレン性不飽和基を有するカルボン酸化合物であり、重合度が20未満、好ましくは単量体若しくは重合度10以下の重合体である。重合度が20を越える重合体(高分子化合物)を用いた場合は、後述の多価金属化合物との塩が完全には形成されない虞があり、その結果、当該金属塩を重合して得られる層は高湿度下でのガスバリア性が劣る虞がある。これら不飽和カルボン酸化合物は、一種でも二種以上の混合物であってもよい。
これら不飽和カルボン酸化合物の中でも単量体が多価金属化合物で完全に中和された塩が形成し易く、当該塩を重合して得られる重合体層を基材層の少なくとも片面に積層してなるガスバリア性積層体は高湿度下でのガスバリア性に特に優れるので好ましい。
Unsaturated carboxylic acid compound The unsaturated carboxylic acid compound forming the unsaturated carboxylic acid compound polyvalent metal salt according to the present invention is an α, β-ethylenically unsaturated compound such as acrylic acid, methacrylic acid, maleic acid or itaconic acid. It is a carboxylic acid compound having a group, and is a polymer having a polymerization degree of less than 20, preferably a monomer or a polymerization degree of 10 or less. When a polymer (polymer compound) having a degree of polymerization exceeding 20 is used, a salt with a polyvalent metal compound described later may not be completely formed. As a result, it is obtained by polymerizing the metal salt. The layer may have poor gas barrier properties under high humidity. These unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds.
Among these unsaturated carboxylic acid compounds, it is easy to form a salt in which the monomer is completely neutralized with a polyvalent metal compound, and a polymer layer obtained by polymerizing the salt is laminated on at least one side of the base material layer. The gas barrier laminate thus obtained is preferable because it is particularly excellent in gas barrier properties under high humidity.
多価金属化合物
本発明に係わる不飽和カルボン酸化合物多価金属塩を形成する成分である多価金属化合物は、周期表の2A〜7A族、1B〜3B族及び8族に属する金属及び金属化合物であり、具体的には、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)、バリウム(Ba)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、亜鉛(Zn)、アルミニウム(Al)等の二価以上の金属、これら金属の酸化物、水酸化物、ハロゲン化物、炭酸塩、リン酸塩、亜リン酸塩、次亜リン酸塩、硫酸塩若しくは亜硫酸塩等である。これら金属化合物の中でも、二価の金属化合物が好ましく、特には酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化亜鉛、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化亜鉛等が好ましい。これら二価の金属化合物を用いた場合は、前記不飽和カルボン酸化合物との塩を重合して得られる膜の高湿度下でのガスバリア性が特に優れている。これら多価金属化合物は、少なくとも一種が使用され、一種のみの使用であっても、二種以上を併用してもよい。これら多価金属化合物の中でもMg、Ca、Zn、BaおよびAl、特にZnが好ましい。
Polyvalent metal compound The polyvalent metal compound which is a component forming the unsaturated carboxylic acid compound polyvalent metal salt according to the present invention is a metal or metal compound belonging to groups 2A to 7A, 1B to 3B and 8 of the periodic table. Specifically, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Zn), bivalent or higher metals such as aluminum (Al), oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites of these metals Such as salt. Among these metal compounds, divalent metal compounds are preferable, and magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and the like are particularly preferable. When these divalent metal compounds are used, the gas barrier property under high humidity of the film obtained by polymerizing the salt with the unsaturated carboxylic acid compound is particularly excellent. At least one kind of these polyvalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination. Among these polyvalent metal compounds, Mg, Ca, Zn, Ba and Al, and particularly Zn are preferable.
不飽和カルボン酸化合物多価金属塩
本発明の重合体(A)層である不飽和カルボン酸化合物多価金属塩の重合体(A)を構成する成分である不飽和カルボン酸化合物多価金属塩は、前記重合度が20未満の不飽和カルボン酸化合物と前記多価金属化合物との塩である。これら不飽和カルボン酸化合物多価金属塩は一種でも二種以上の混合物であってもよい。かかる不飽和カルボン酸化合物多価金属塩の中でも、特に(メタ)アクリル酸亜鉛が得られる重合体層の耐熱水性に優れるので好ましい。
Unsaturated carboxylic acid compound polyvalent metal salt Unsaturated carboxylic acid compound polyvalent metal salt which is a component constituting polymer (A) of unsaturated carboxylic acid compound polyvalent metal salt which is the polymer (A) layer of the present invention Is a salt of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 and the polyvalent metal compound. These unsaturated carboxylic acid compound polyvalent metal salts may be one kind or a mixture of two or more kinds. Among such unsaturated carboxylic acid compound polyvalent metal salts, the polymer layer from which zinc (meth) acrylate is obtained is particularly excellent in the hot water resistance, which is preferable.
不飽和カルボン酸化合物多価金属塩の重合体(A)層
本発明に係わる不飽和カルボン酸化合物多価金属塩の重合体(A)層は、赤外線吸収スペクトルにおける1700cm−1付近のカルボン酸基のνC=Oに基づく吸光度A0と1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度Aとの比(A0/A)が0.25未満、より好ましくは0.20未満の範囲にある。
本発明に係わる不飽和カルボン酸化合物多価金属塩の重合体(A)層は、不飽和カルボン酸化合物多価金属塩のカルボン酸基と多価金属とがそれぞれイオン架橋してなるカルボキシレートイオンと遊離のカルボン酸基が存在し、夫々、赤外線スペクトルで、遊離のカルボン酸基のνC=Oに基づく吸収が1700cm−1付近にあり、カルボキシレートイオンのνC=Oに基づく吸収が1520cm−1付近にある。
本発明に係る重合体(A)層において、(A0/A)が0.25未満であるということは、遊離のカルボン酸基が存在しないか、少ないことを示しており、0.25を越える層は、遊離のカルボン酸基の含有量が多く、高湿度下での耐ガスバリア性が改良されない虞があるので、(A0/A)が0.25未満であることが好ましい。
Polymer (A) layer of unsaturated carboxylic acid compound polyvalent metal salt The polymer (A) layer of unsaturated carboxylic acid compound polyvalent metal salt according to the present invention comprises a carboxylic acid group near 1700 cm −1 in the infrared absorption spectrum. The ratio (A 0 / A) of the absorbance A 0 based on νC═O to the absorbance A based on νC═O of carboxylate ions near 1520 cm −1 is less than 0.25, more preferably less than 0.20 It is in.
The polymer (A) layer of the unsaturated carboxylic acid compound polyvalent metal salt according to the present invention is a carboxylate ion formed by ionic crosslinking of the carboxylic acid group of the unsaturated carboxylic acid compound polyvalent metal salt and the polyvalent metal. In the infrared spectrum, the absorption of free carboxylic acid groups based on νC═O is around 1700 cm −1 , and the absorption of carboxylate ions based on νC═O is 1520 cm −1, respectively. In the vicinity.
In the polymer (A) layer according to the present invention, (A 0 / A) being less than 0.25 indicates that there are no or few free carboxylic acid groups. The layer exceeding the content has a large content of free carboxylic acid groups, and the gas barrier resistance under high humidity may not be improved. Therefore, (A 0 / A) is preferably less than 0.25.
本発明における1700cm−1付近のカルボン酸基のνC=Oに基づく吸光度A0と赤外線吸収スペクトルにおける1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度Aとの比(A0/A)は、容器から1cm×3cmの測定用サンプルを切り出し、その表面(重合体(A)層)の赤外線吸収スペクトルを赤外線全反射測定(ATR法)に得、以下の手順で、先ず、吸光度A0及び吸光度Aを求めた。
1700cm−1付近のカルボン酸基のνC=Oに基づく吸光度A0:赤外線吸収スペクトルの1660cm−1と1760cm−1の吸光度とを直線(N)で結び、1660〜1760cm−1間の最大吸光度(1700cm−1付近)から垂直に直線(O)を下ろし、当該直線(O)と直線(N)との交点と最大吸光度との吸光度の距離(長さ)を吸光度A0とした。
1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度A:赤外線吸収スペクトルの1480cm−1と1630cm−1の吸光度とを直線(L)で結び、1480〜1630cm−1間の最大吸光度(1520cm−1付近)から垂直に直線(M)を下ろし、当該直線(M)と直線(L)との交点と最大吸光度との吸光度の距離(長さ)を吸光度Aとした。尚、最大吸光度(1520cm−1付近)は、対イオンの金属種によりピーク位置が変化することがあり、例えば、カルシウムでは1520cm−1付近、亜鉛では1520cm−1付近、マグネシウムでは1540cm−1付近である。
次いで、上記方法で求めた吸光度A0及び吸光度Aから比(A0/A)を求めた。
なお、本発明のおける赤外線スペクトルの測定(赤外線全反射測定:ATR法)は、日本分光社製FT−IR350装置を用い、KRS−5(Thallium Bromide−Iodide)結晶を装着して、入射角45度、室温、分解能4cm−1、積算回数150回の条件で行った。
本発明に係わる重合体(A)層の厚さは種々用途により決め得るが、通常は、0.01〜100μm、好ましくは0.05〜50μm、より好ましくは0.1〜10μmの範囲にある。
Ratio of absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in the present invention to absorbance A based on νC═O of a carboxylate ion near 1520 cm −1 in an infrared absorption spectrum (A 0 / A) Cut out a measurement sample of 1 cm × 3 cm from the container, and obtained the infrared absorption spectrum of the surface (polymer (A) layer) by infrared total reflection measurement (ATR method). First, the absorbance A 0 was obtained by the following procedure. And absorbance A were determined.
1700cm absorbance based νC = O -1 vicinity of the carboxylic acid groups A 0: a absorbance of the infrared absorption spectrum of 1660 cm -1 and 1760 cm -1 connected by a straight line (N), 1660~1760cm maximum absorbance between -1 ( The straight line (O) was dropped vertically from around 1700 cm −1, and the absorbance distance (length) between the intersection of the straight line (O) and the straight line (N) and the maximum absorbance was defined as absorbance A 0 .
1520 cm -1 vicinity of carboxylate ion of νC = O based upon the absorbance A: connected by a straight line (L) and the absorbance of the infrared absorption spectrum of 1480 cm -1 and 1630 cm -1, the maximum absorbance between 1480~1630cm -1 (1520cm The straight line (M) was dropped vertically from the vicinity of −1 ), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance A. The peak position of maximum absorbance (near 1520 cm −1 ) may vary depending on the metal species of the counter ion. For example, calcium is near 1520 cm −1 , zinc is near 1520 cm −1 , and magnesium is near 1540 cm −1 . is there.
Next, the ratio (A 0 / A) was determined from the absorbance A 0 and the absorbance A determined by the above method.
In addition, the measurement of the infrared spectrum (infrared total reflection measurement: ATR method) in the present invention uses an FT-IR350 apparatus manufactured by JASCO Corporation, and a KRS-5 (Thallium Bromide-Iodide) crystal is attached, and the incident angle is 45. Degree, room temperature, resolution of 4 cm −1 , and accumulation of 150 times.
The thickness of the polymer (A) layer according to the present invention can be determined depending on various uses, but is usually in the range of 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm. .
本発明に係わる重合体(A)層には、本発明の目的を損なわない範囲で、ポリビニルアルコール、エチレン・ビニルアルコール共重合体、ポリビニルピロリドン、ポリビニルエチルエーテル、ポリアクリルアミド、ポリエチレンイミン、澱粉、アラビアガム、メチルセルロース等の水溶性重合体、アクリル酸エステル重合体、エチレン・アクリル酸共重合体、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、ポリエステル、ポリウレタン等の高分子量の化合物等、滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤が含まれていてもよいし、後述の基材との濡れ性、密着性等を改良するために、各種界面活性剤等が含まれていてもよい。 In the polymer (A) layer according to the present invention, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine, starch, Water-soluble polymers such as gum and methylcellulose, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, high molecular weight compounds such as polyester and polyurethane, lubricants, slips Various additives such as additives, anti-blocking agents, antistatic agents, anti-fogging agents, pigments, dyes, inorganic or organic fillers may be included, and wettability and adhesion to the substrate described below In order to improve the above, various surfactants and the like may be included.
基材層
本発明の容器を形成する基材層は、熱硬化性樹脂あるいは熱可塑性樹脂からなる中空体、カップ等の形状を有するものである。
熱硬化性樹脂としては、種々公知の熱硬化性樹脂、例えば、エポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、ユリア・メラミン樹脂、ポリウレタン樹脂、シリコーン樹脂、アミノ樹脂、ポリイミド等を例示することができる。
熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン(ポリエチレン、ポリプロピレン、ポリ4−メチル・1−ペンテン、ポリブテン等)、ポリエステル(ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等)、ポリアミド(ナイロン−6、ナイロン−66、ポリメタキシレンアジパミド等)、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエステル、ポリアミド等、延伸性、透明性が良好な熱可塑性樹脂が好ましく、とくにポリエチレンテレフタレート及びポリエチレンナフタレート等のポリエステルがバリア性、耐熱性等に優れているので好ましい。
基材層が熱可塑性樹脂であれば、無延伸の基材層でも、延伸された基材層でもよいが、延伸された基材層が、耐熱性、剛性、透明性及びガスバリア性に優れているのでより好ましい。
かかる中空体、カップ状の形状を有する基材は、種々公知の成形方法、例えば、熱硬化性樹脂であれば、鋳型に流し込む方法、トランスファー成形、圧縮成型、射出成形等によりカップ状の基材を得る方法等を採り得る。熱可塑性樹脂であれば、中空成形(吹き込み成形)、射出成形、回転成形あるいは予め射出成形して容器成形用プリフォームを得た後吹き込み成形する、所謂二軸延伸吹き込み(ブロー)成形する方法等を採り得る。
また、これら基材層は、ガスバリア性膜との接着性を改良するために、その表面を、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理、プライマーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。
Base material layer The base material layer forming the container of the present invention has a shape such as a hollow body or cup made of a thermosetting resin or a thermoplastic resin.
Examples of the thermosetting resin include various known thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, amino resins, and polyimides. .
As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Of these, polypropylene, polyester, polyamide and the like are preferable thermoplastic resins having good stretchability and transparency, and polyesters such as polyethylene terephthalate and polyethylene naphthalate are particularly preferable because of excellent barrier properties and heat resistance.
If the base material layer is a thermoplastic resin, it may be an unstretched base material layer or a stretched base material layer, but the stretched base material layer has excellent heat resistance, rigidity, transparency and gas barrier properties. This is more preferable.
Such a hollow body or base material having a cup-like shape can be obtained by various known molding methods, for example, a method of pouring into a mold if it is a thermosetting resin, transfer molding, compression molding, injection molding, etc. The method etc. which obtain can be taken. In the case of a thermoplastic resin, a so-called biaxial stretch blow (blow) molding method in which hollow molding (blow molding), injection molding, rotational molding, or injection molding is performed in advance to obtain a preform for container molding, and then blow molding is performed. Can be taken.
In addition, in order to improve the adhesion with the gas barrier film, these base material layers have surface activity such as corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, flame treatment, etc. It is also possible to carry out the conversion process.
容器
本発明の容器は、基材層の少なくとも片面に前記赤外線吸収スペクトルにおける1700cm−1付近のカルボン酸基のνC=Oに基づく吸光度A0と1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度Aとの比(A0/A)が0.25未満である不飽和カルボン酸化合物多価金属塩の重合体(A)層が形成されてなる。重合体(A)層は容器の内面に形成さていても、外面に形成されていてもよい。
本発明の容器の厚さは用途に応じて種々決定され得るが、通常は、基材層の厚さが5〜500μm、好ましくは5〜100μm、より好ましくは9〜30μm、不飽和カルボン酸化合物多金属塩の共重合体層の厚さが0.01〜100μm、好ましくは0.05〜50μm、より好ましくは0.1〜10μm、ガスバリア性積層体の全体の厚さが20〜750μm、より好ましくは25〜430μmの範囲にある。
本発明の容器は、重合体(A)層上に保護層が積層されていてもよい。
かかる保護層としては、重合体(A)層を保護し得る層であればとくに限定はされず、種々公知の保護層、例えば、ポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、ユリア・メラミン樹脂、ポリウレタン樹脂、シリコーン樹脂、アミノ樹脂、ポリイミド等の熱硬化性樹脂、ポリオレフィン(ポリエチレン、ポリプロピレン、ポリ4−メチル・1−ペンテン、ポリブテン等)、ポリエステル(ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等)、ポリアミド(ナイロン−6、ナイロン−66、ポリメタキシレンアジパミド等)、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等の熱可塑性樹脂等が挙げられる。
Container vessels present invention, νC = O at least one surface to the absorbance based on νC = O of the carboxylic acid groups in the vicinity of 1700 cm -1 in the infrared absorption spectrum A 0 and around 1520 cm -1 of the carboxylate ion of the base layer A polymer (A) layer of an unsaturated carboxylic acid compound polyvalent metal salt having a ratio (A 0 / A) to absorbance A based on less than 0.25 is formed. The polymer (A) layer may be formed on the inner surface or the outer surface of the container.
Although the thickness of the container of the present invention can be variously determined depending on the application, the thickness of the base layer is usually 5 to 500 μm, preferably 5 to 100 μm, more preferably 9 to 30 μm, and an unsaturated carboxylic acid compound. The thickness of the copolymer layer of the multimetal salt is 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and the total thickness of the gas barrier laminate is 20 to 750 μm. Preferably it exists in the range of 25-430 micrometers.
In the container of the present invention, a protective layer may be laminated on the polymer (A) layer.
Such a protective layer is not particularly limited as long as it can protect the polymer (A) layer, and various known protective layers such as a poxy resin, an unsaturated polyester resin, a phenol resin, a urea melamine resin, Thermosetting resins such as polyurethane resin, silicone resin, amino resin, polyimide, polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.) , Polyamide (nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene , And ionomer or thermoplastic resins such as these mixtures, it is.
容器の製造方法
本発明の容器の製造方法は、前記中空体、カップ等の形状を有する基材層の少なくとも片面に、重合度が20未満の不飽和カルボン酸化合物多価金属塩の溶液を塗工した後、不飽和カルボン酸化合物多価金属塩を重合し、不飽和カルボン酸化合物多価金属塩の重合体(A)層を形成させることを特徴とする。
重合度が20未満の不飽和カルボン酸化合物多価金属塩の溶液を作成する方法としては、予め前記不飽和カルボン酸化合物と前記多価金属化合物とを反応させて、不飽和カルボン酸化合物の多価金属塩とした後、溶液としてもよいし、直接溶媒に前記不飽和カルボン酸化合物と前記多価金属化合物を溶かして多価金属塩の溶液としてもよい。
本発明の容器の製造方法として、直接溶媒に前記不飽和カルボン酸化合物と前記多価金属化合物を溶かす場合、即ち、前記不飽和カルボン酸化合物と前記多価金属化合物とを含む溶液を用いる場合は、前記不飽和カルボン酸化合物に対して、0.3化学当量比を越える量の前記多価金属化合物を添加することが好ましい。多価金属化合物の添加量が0.3化学当量比以下の混合溶液を用いた場合は、遊離のカルボン酸基の含有量が多い重合体層となり、結果として、ガスバリア性が低い容器となる虞がある。また、多価金属化合物の添加量の上限はとくに限定はされないが、多価金属化合物の添加量が1化学当量比を越えると未反応の多価金属化合物が多くなるので、通常、5化学当量比以下、好ましくは2化学当量比以下で十分である。
なお、本発明における化学当量比は、不飽和カルボン酸化合物に対する多価金属化合物の化学当量比を示し、以下の式により算出される値である。
化学当量比=(多価金属化合物のモル数)×(多価金属化合物の価数)/不飽和カルボン酸化合物に含まれるカルボキシル基のモル数
例えば、多価金属化合物として水酸化カルシウム(分子量74g/モル)を37g、不飽和カルボン酸化合物としてアクリル酸単量体(分子量72g/モル)72gを混合した場合の化学当量比は1となる。
また、不飽和カルボン酸化合物と多価金属化合物との混合溶液を用いる場合は、通常、不飽和カルボン酸化合物と多価金属化合物とを溶媒に溶かしている間に、不飽和カルボン酸化合物の多価金属塩が形成されるが、多価金属塩の形成を確実にするために、1分以上混合しておくことが好ましい。
不飽和カルボン酸化合物多価金属塩の溶液に用いる溶媒は、水、メチルアルコール、エチルアルコール、イソプロピルアルコール等の低級アルコール若しくはアセトン、メチルエチルケトン等の有機溶媒あるいはそれらの混合溶媒が挙げられるが、水が最も好ましい。
基材層の表面に不飽和カルボン酸化合物多価金属塩の溶液を塗工する方法としては、種々公知の方法、例えば、刷毛等により塗布する方法、当該溶液に基材層を浸漬する方法、当該溶液を基材層表面に噴霧する方法等を採り得る。
不飽和カルボン酸化合物多価金属塩の溶液の塗工量は、通常、溶液中(固形分)の量で0.05〜10g/m2、好ましくは0.1〜5g/m2となるよう塗工すればよい。
Method for Manufacturing Container The method for manufacturing a container according to the present invention is to apply a solution of an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 to at least one surface of a substrate layer having a shape such as a hollow body or a cup. After the processing, the unsaturated carboxylic acid compound polyvalent metal salt is polymerized to form a polymer (A) layer of the unsaturated carboxylic acid compound polyvalent metal salt.
As a method of preparing a solution of an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20, the unsaturated carboxylic acid compound and the polyvalent metal compound are reacted in advance to obtain a large number of unsaturated carboxylic acid compounds. After forming the valent metal salt, the solution may be used, or the solution of the unsaturated carboxylic acid compound and the polyvalent metal compound may be directly dissolved in a solvent to form a solution of the polyvalent metal salt.
As a method for producing the container of the present invention, when the unsaturated carboxylic acid compound and the polyvalent metal compound are directly dissolved in a solvent, that is, when a solution containing the unsaturated carboxylic acid compound and the polyvalent metal compound is used. The polyvalent metal compound is preferably added in an amount exceeding 0.3 chemical equivalent ratio with respect to the unsaturated carboxylic acid compound. When a mixed solution having a polyvalent metal compound addition amount of 0.3 chemical equivalent ratio or less is used, a polymer layer having a high content of free carboxylic acid groups may be formed, resulting in a container having a low gas barrier property. There is. In addition, the upper limit of the amount of polyvalent metal compound added is not particularly limited, but when the amount of polyvalent metal compound added exceeds 1 chemical equivalent ratio, unreacted polyvalent metal compound increases. The ratio is preferably less than the ratio, preferably less than the 2 chemical equivalent ratio.
In addition, the chemical equivalent ratio in this invention shows the chemical equivalent ratio of the polyvalent metal compound with respect to an unsaturated carboxylic acid compound, and is a value calculated by the following formula | equation.
Chemical equivalent ratio = (number of moles of polyvalent metal compound) × (valence of polyvalent metal compound) / number of moles of carboxyl group contained in unsaturated carboxylic acid compound For example, calcium hydroxide (molecular weight 74 g) as the polyvalent metal compound The chemical equivalent ratio is 1 when 37 g of acrylic acid monomer (molecular weight 72 g / mol) is mixed as an unsaturated carboxylic acid compound.
In addition, when a mixed solution of an unsaturated carboxylic acid compound and a polyvalent metal compound is used, the unsaturated carboxylic acid compound is usually added while the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved in a solvent. Although a valent metal salt is formed, it is preferable to mix for 1 minute or more in order to ensure the formation of the polyvalent metal salt.
Examples of the solvent used for the solution of the unsaturated carboxylic acid compound polyvalent metal salt include water, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, organic solvents such as acetone and methyl ethyl ketone, and mixed solvents thereof. Most preferred.
As a method of applying a solution of an unsaturated carboxylic acid compound polyvalent metal salt to the surface of the base material layer, various known methods, for example, a method of applying with a brush, a method of immersing the base material layer in the solution, A method of spraying the solution on the surface of the base material layer can be employed.
The coating amount of the solution of the unsaturated carboxylic acid compound polyvalent metal salt is usually, 0.05 to 10 g / m 2 in an amount of solution (solids), and preferably no greater 0.1-5 g / m 2 Just apply.
不飽和カルボン酸化合物多価金属塩を溶解させる際には、本発明の目的を損なわない範囲で、(メタ)アクリル酸メチル、(メタ)アクリル酸エチルなどのその他の不飽和カルボン酸(ジ)エステル化合物、酢酸ビニルなどのビニルエステル化合物等の単量体あるいは低分子量の化合物、ポリビニルアルコール、エチレン・ビニルアルコール共重合体、ポリビニルピロリドン、ポリビニルエチルエーテル、ポリアクリルアミド、ポリエチレンイミン、澱粉、アラビアガム、メチルセルロース等の水溶性重合体、アクリル酸エステル重合体、エチレン・アクリル酸共重合体、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、ポリエステル、ポリウレタン等の高分子量の化合物等を添加してもよい。
また、不飽和カルボン酸化合物多価金属塩を溶解させる際には、本発明の目的を損なわない範囲で、滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤を添加しておいてもよいし、基材層との濡れ性を改良するために、各種界面活性剤等を添加しておいてもよい。
When the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, other unsaturated carboxylic acids (di) such as methyl (meth) acrylate and ethyl (meth) acrylate, as long as the object of the present invention is not impaired. Monomers such as ester compounds, vinyl ester compounds such as vinyl acetate or low molecular weight compounds, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine, starch, gum arabic, Water-soluble polymers such as methyl cellulose, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, high molecular weight compounds such as polyester and polyurethane may be added. .
When the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, the lubricant, slip agent, anti-blocking agent, antistatic agent, antifogging agent, pigment, dye, Various additives such as inorganic or organic fillers may be added, and various surfactants may be added to improve wettability with the base material layer.
基材層の少なくとも片面に形成した(塗工した)不飽和カルボン酸化合物多価金属塩の溶液(塗工層)を重合させるには、種々公知の方法、具体的には例えば、電離性放射線の照射また加熱等による方法が挙げられる。
電離性放射線を使用する場合は、波長領域が0.0001〜800nmの範囲のエネルギー線であれば特に限定されないが、かかるエネルギー線としては、α線、β線、γ線、X線、可視光線、紫外線、電子線等が上げられる。これらの電離性放射線の中でも、波長領域が400〜800nmの範囲の可視光線、50〜400nmの範囲の紫外線および0.01〜0.002nmの範囲の電子線が、取り扱いが容易で、装置も普及しているので好ましい。
電離性放射線として可視光線および紫外線を用いる場合は、不飽和カルボン酸化合物多価金属塩の溶液に光重合開始剤を添加することが必要となる。光重合開始剤としては、公知のものを使用することができ、例えば、2−ヒドロキシ−2メチル−1−フェニル−プロパン−1−オン(チバ・スペシャリティ・ケミカルズ社製 商品名;ダロキュアー 1173)、1−ヒドロキシーシクロヘキシルーフェニルケトン(チバ・スペシャリティ・ケミカルズ社製 商品名;イルガキュアー 184)、ビス(2,4,6−トリメチルベンゾイル)−フェニルフォスフィンオキサイド(チバ・スペシャリティ・ケミカルズ社製 商品名;イルガキュアー819)、1−[4−(2−ヒドロキシエトキシ)−フェニル]−2−ヒドロキシ−2−メチル−1−プロパン−1−オン(チバ・スペシャリティ・ケミカルズ社製 商品名;イルガキュアー 2959)、α―ヒドロキシケトン、アシルホスフィンオキサイド、4−メチルベンゾフェノン及び2,4,6−トリメチルベンゾフェノンの混合物(ランベルティ・ケミカル・スペシャルティ社製 商品名;エサキュアー KT046)、エサキュアー KT55(ランベルティー・ケミカル・スペシャルティ)、2,4,6−トリメチルベンゾイルジフェニルフォスフィンオキサイド(ラムソン・ファイア・ケミカル社製 商品名;スピードキュアTPO)の商品名で製造・販売されているラジカル重合開始剤を挙げることができる。さらに、重合度または重合速度を向上させるため重合促進剤を添加することができ、例えば、N、N-ジメチルアミノ-エチル-(メタ)アクリレート、N-(メタ)アクリロイル-モルフォリン等が挙げられる。
In order to polymerize the solution (coating layer) of the unsaturated carboxylic acid compound polyvalent metal salt formed (coated) on at least one surface of the base material layer, various known methods, specifically, for example, ionizing radiation The method by irradiation or heating.
When ionizing radiation is used, it is not particularly limited as long as the wavelength region is an energy ray in the range of 0.0001 to 800 nm. Examples of such energy rays include α rays, β rays, γ rays, X rays, and visible rays. , Ultraviolet rays, electron beams and the like. Among these ionizing radiations, visible light in the wavelength range of 400 to 800 nm, ultraviolet light in the range of 50 to 400 nm, and electron beam in the range of 0.01 to 0.002 nm are easy to handle and the devices are widespread. Therefore, it is preferable.
When visible light and ultraviolet light are used as the ionizing radiation, it is necessary to add a photopolymerization initiator to the solution of the unsaturated carboxylic acid compound polyvalent metal salt. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals), 1-Hydroxy-cyclohexyl ruphenyl ketone (Ciba Specialty Chemicals product name; Irgacure 184), Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals product name) Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) ), Α-hydroxyketone, acylphosphine oxy A mixture of id, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name; Essaure KT046 manufactured by Lamberti Chemical Specialty), Esacure KT55 (Lamberti Chemical Specialty), 2,4,6- A radical polymerization initiator manufactured and sold under the trade name of trimethylbenzoyldiphenylphosphine oxide (trade name; Speed Cure TPO manufactured by Ramson Fire Chemical Co., Ltd.) can be mentioned. Furthermore, a polymerization accelerator can be added to improve the polymerization degree or polymerization rate, and examples thereof include N, N-dimethylamino-ethyl- (meth) acrylate and N- (meth) acryloyl-morpholine. .
不飽和カルボン酸化合物多価金属塩を重合させる際は、溶液が水等の溶媒を含んだ状態で重合させてもよいし、一部乾燥させた後に重合させてもよいが、溶液を塗工後直ぐに重合させた場合は、金属塩が重合する際に溶媒の蒸発が多いためか、得られる重合体層が白化する場合がある。一方、溶媒(水分)が少なくなるとともに、不飽和カルボン酸化合物多価金属塩が結晶として析出する場合があり、かかる状態で重合を行うと得られる重合体層の形成が不十分になり、重合体層が白化を起こしたりしてガスバリア性が安定しない虞がある。したがって、塗工した不飽和カルボン酸化合物多価金属塩を重合させる際には、適度な水分を含んだ状態で重合することが好ましい。 When the unsaturated carboxylic acid compound polyvalent metal salt is polymerized, the solution may be polymerized in a state containing a solvent such as water, or may be polymerized after partially drying, but the solution may be applied. When polymerized immediately afterwards, the resulting polymer layer may be whitened because of the large evaporation of the solvent when the metal salt is polymerized. On the other hand, the solvent (moisture) decreases, and the unsaturated carboxylic acid compound polyvalent metal salt may precipitate as crystals. When polymerization is performed in such a state, formation of the resulting polymer layer becomes insufficient, resulting in heavy polymerization. There is a possibility that the gas barrier property may not be stable due to whitening of the combined layer. Therefore, when the coated unsaturated carboxylic acid compound polyvalent metal salt is polymerized, it is preferably polymerized in a state containing appropriate moisture.
本発明の容器の製造方法は、前記方法に加え、容器形成用プリフォームからなる基材層の表面に重合度が20未満の不飽和カルボン酸化合物多価金属塩の溶液を塗工し、不飽和カルボン酸化合物多価金属塩を予備重合し、次いで、容器形成用プリフォームを吹き込み成形して容器とした後、予備重合した不飽和カルボン酸化合物多価金属塩を重合し、不飽和カルボン酸化合物多価金属塩の重合体(A)層を形成させる方法も採り得る。
予備重合を行う場合は、重合率が高くなり過ぎると容器形成用プリフォームを吹き込み成形する際に、不飽和カルボン酸化合物多価金属塩の重合体層に亀裂が入る場合があるので、通常、予備重合の重合率(重合率の求め方は下記に示す)を1〜70%、好ましくは3〜60%、より好ましくは5〜50%の範囲にすることが好ましい。
In addition to the above method, the method for producing a container of the present invention comprises applying a solution of an unsaturated carboxylic acid compound polyvalent metal salt having a polymerization degree of less than 20 to the surface of a base material layer comprising a container forming preform. Saturated carboxylic acid compound polyvalent metal salt is prepolymerized, and then a container forming preform is blown to form a container, and then prepolymerized unsaturated carboxylic acid compound polyvalent metal salt is polymerized to obtain unsaturated carboxylic acid A method of forming a polymer (A) layer of a compound polyvalent metal salt can also be employed.
When performing prepolymerization, when the polymerization rate becomes too high, when the preform for container formation is blown and molded, the polymer layer of unsaturated carboxylic acid compound polyvalent metal salt may crack, usually, The prepolymerization rate (how to obtain the polymerization rate is shown below) is 1 to 70%, preferably 3 to 60%, more preferably 5 to 50%.
重合体(A)層上に、保護層を形成させる場合は、種々公知の方法、例えば、熱硬化性樹脂からなる保護層を形成させる場合は、モノマーあるいはプレポリマーを重合体(A)層上に塗工した後、硬化させる方法、熱可塑性樹脂からなる保護層を形成させる場合は、熱可塑性樹脂の溶液あるいはエマルションを塗工した後、乾燥させる方法等を採り得る。 When a protective layer is formed on the polymer (A) layer, various known methods, for example, when a protective layer made of a thermosetting resin is formed, a monomer or a prepolymer is added on the polymer (A) layer. In the case of forming a protective layer made of a thermoplastic resin after coating, a method of drying after coating a solution or emulsion of a thermoplastic resin can be employed.
次に、本発明を実施例によりさらに具体的に説明するが、本発明はこれら実施例により何等限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
実施例及び比較例における物性値等は、以下の評価方法により求める。
<評価方法>
(1)酸素透過度[ml/(m2・day・MPa)]:容器を、モコン社製 OX−TRAN2/21 MLを用いて、JIS K 7126に準じ、温度20℃、湿度90%R.H.の条件で測定する。
(2)吸光度比(A0/A):上記記載の方法で測定する。
(3)重合率:〔1−(A1/A)UV後/(A1/A)モノマー〕×100
*(A1/A)UV後:紫外線照射(重合後)後の(A1/A)
*(A1/A)モノマー:モノマー(重合前)の(A1/A)
(A1/A)については下記に記載のとおり規定した。
830cm−1付近のビニル基に結合する水素のδC−Hに基づく吸光度A1と赤外線吸収スペクトルにおける1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度Aとの比(A1/A)は、容器から1cm×3cmの測定用サンプルを切り出し、その表面(重合体(A)層)の赤外線吸収スペクトルを赤外線全反射測定(ATR法)により得、以下の手順で、先ず、吸光度A1及び吸光度Aを求める。
830cm−1付近のビニル基に結合する水素のδC−Hに基づく吸光度A1:赤外線吸収スペクトルの800cm−1と850cm−1の吸光度とを直線(P)で結び、800〜850cm−1間の最大吸光度(830cm−1付近)から垂直に直線(Q)を下ろし、当該直線(Q)と直線(P)との交点と最大吸光度との吸光度の距離(長さ)を吸光度A1とする。
1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度A:赤外線吸収スペクトルの1480cm−1と1630cm−1の吸光度とを直線(L)で結び、1480〜1630cm−1間の最大吸光度(1520cm−1付近)から垂直に直線(M)を下ろし、当該直線(M)と直線(L)との交点と最大吸光度との吸光度の距離(長さ)を吸光度Aとした。尚、最大吸光度(1520cm−1付近)は、対イオンの金属種によりピーク位置が変化することがあり、例えば、カルシウムでは1520cm−1付近、亜鉛では1520cm−1付近、マグネシウムでは1540cm−1付近である。
次いで、上記方法で求めた吸光度A1及び吸光度Aから比(A1/A)を求める。また重合率は上記計算式のように、モノマーの吸光度比(A1/A)モノマーとUV照射(重合後)後の(A1/A)UV後を測定し求める。
なお、本発明のおける赤外線スペクトルの測定(赤外線全反射測定:ATR法)は、日本分光社製FT−IR350装置を用い、KRS−5(Thallium Bromide−Iodide)結晶を装着して、入射角45度、室温、分解能4cm−1、積算回数150回の条件で行う。
The physical property values and the like in Examples and Comparative Examples are obtained by the following evaluation methods.
<Evaluation method>
(1) Oxygen permeability [ml / (m 2 · day · MPa)]: Using a OX-TRAN 2/21 ML manufactured by Mocon Co., Ltd., according to JIS K 7126, temperature 20 ° C., humidity 90% R.P. H. Measure under the following conditions.
(2) Absorbance ratio (A 0 / A): Measured by the method described above.
(3) Polymerization rate: [1- (A 1 / A) after UV / (A 1 / A) monomer ] × 100
* (A 1 / A) after UV: ultraviolet irradiation (after polymerization) after (A 1 / A)
* (A 1 / A) monomer: monomer (before polymerization) of (A 1 / A)
(A 1 / A) was defined as described below.
Ratio of absorbance A 1 based on δC—H of hydrogen bonded to a vinyl group near 830 cm −1 to absorbance A based on νC═O of carboxylate ions near 1520 cm −1 in the infrared absorption spectrum (A 1 / A) Cut out a measurement sample of 1 cm × 3 cm from the container, and obtained an infrared absorption spectrum of the surface (polymer (A) layer) by infrared total reflection measurement (ATR method). First, the absorbance A 1 was obtained by the following procedure. And the absorbance A is determined.
830cm absorbance based .delta.C-H of hydrogen binding to vinyl groups in the vicinity of -1 A 1: bear and the absorbance of the infrared absorption spectrum of 800 cm -1 and 850 cm -1 in a straight line (P), between 800~850Cm -1 A straight line (Q) is dropped vertically from the maximum absorbance (near 830 cm −1 ), and the distance (length) of absorbance between the intersection of the straight line (Q) and the straight line (P) and the maximum absorbance is defined as absorbance A 1 .
1520 cm -1 vicinity of carboxylate ion of νC = O based upon the absorbance A: connected by a straight line (L) and the absorbance of the infrared absorption spectrum of 1480 cm -1 and 1630 cm -1, the maximum absorbance between 1480~1630cm -1 (1520cm The straight line (M) was dropped vertically from the vicinity of −1 ), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance A. The peak position of maximum absorbance (near 1520 cm −1 ) may vary depending on the metal species of the counter ion. For example, calcium is near 1520 cm −1 , zinc is near 1520 cm −1 , and magnesium is near 1540 cm −1 . is there.
Next, the ratio (A 1 / A) is determined from the absorbance A 1 and the absorbance A determined by the above method. Further, the polymerization rate is determined by measuring the monomer absorbance ratio (A 1 / A) monomer and the UV irradiation (after polymerization) (A 1 / A) after UV .
In addition, the measurement of the infrared spectrum (infrared total reflection measurement: ATR method) in the present invention uses an FT-IR350 apparatus manufactured by JASCO Corporation, and a KRS-5 (Thallium Bromide-Iodide) crystal is attached, and the incident angle is 45. Degree, room temperature, resolution of 4 cm −1 , and 150 times of integration.
<溶液(X)の作製>
アクリル酸亜鉛(アクリル酸のZn塩)水溶液〔浅田化学社製、濃度:15重量%(アクリル酸成分:10重量%、Zn成分:5重量%)〕と、メチルアルコールで25重量%に希釈した光重合開始剤〔1−[4−(2−ヒドロキシエトキシ)−フェニル]−2−ヒドロキシ−2−メチル−1−プロパン−1−オン(チバ・スペシャリティ・ケミカルズ社製 商品名;イルガキュアー 2959)〕及び界面活性剤(花王社製 商品名;エマルゲン120)をモル分率でそれぞれ98.5%、1.2%、0.3%となるように混合し、不飽和カルボン酸化合物Zn塩溶液(X)を作製する。
<Preparation of solution (X)>
Aqueous solution of zinc acrylate (Zn salt of acrylic acid) [Asada Chemical Co., Ltd., concentration: 15 wt% (acrylic acid component: 10 wt%, Zn component: 5 wt%)] and methyl alcohol diluted to 25 wt% Photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) ] And a surfactant (trade name; Emulgen 120 manufactured by Kao Corporation) are mixed so that the molar fractions are 98.5%, 1.2%, and 0.3%, respectively, and the unsaturated carboxylic acid compound Zn salt solution is mixed. (X) is prepared.
実施例1
市販のポリエチレンテレフタレート製容器(PETボトル)(500ml 耐圧タイプ)に、不飽和カルボン酸化合物Zn塩溶液(X)を浸漬法にて塗工した。次いで、オーブン中で60℃、1分の条件で乾燥後、紫外線照射装置を用い照射光量200mJ/cm2になるように容器全体に照射し、重合体層が表面に形成された容器を得た。重合体層の厚さ3μmであり、赤外線吸収スペクトルにおける1700cm−1付近のカルボン酸基のνC=Oに基づく吸光度A0と1520cm−1付近のカルボキシレートイオンのνC=Oに基づく吸光度Aとの比(A0/A)が0.1であり、二重結合部分の重合率は95%であった。また、容器から90mm×90mmの大きさでサンプルを切り出しその酸素透過度を測定すると、0.1ml/m2・day・MPa以下であった。
Example 1
An unsaturated carboxylic acid compound Zn salt solution (X) was applied to a commercially available polyethylene terephthalate container (PET bottle) (500 ml pressure-resistant type) by a dipping method. Next, after drying in an oven at 60 ° C. for 1 minute, the entire container was irradiated with an ultraviolet irradiation device so that the irradiation light amount was 200 mJ / cm 2 , thereby obtaining a container having a polymer layer formed on the surface. . Is the thickness 3μm of the polymer layer, the carboxylic acid groups in the vicinity of 1700 cm -1 in the infrared absorption spectrum NyuC = absorbance based on O A 0 and around 1520 cm -1 carboxyalkyl of carboxylate ions NyuC = the absorbance A, based on the O The ratio (A 0 / A) was 0.1, and the polymerization rate of the double bond portion was 95%. Further, when a sample was cut out from the container with a size of 90 mm × 90 mm and its oxygen permeability was measured, it was 0.1 ml / m 2 · day · MPa or less.
実施例2
ポリエチレンテレフタレートからなる容器形成用プリフォームの表面に不飽和カルボン酸化合物Zn塩溶液(X)を浸漬法にて塗工する。次いで、プリフォーム全体をオーブン中で60℃、1分の条件で乾燥後、紫外線照射装置を用い照射光量5mJ/cm2になるようにプリフォーム全体に照射しプレ重合させる。このとき塗工した重合体層の重合率は35%である。次いで、容器形成用プリフォームを二軸延伸吹き込み成形して容器とした後、その容器にさらに紫外線を照射光量200mJ/cm2になるよう照射し、重合率を90%として、重合体層が形成された容器を得る。容器の重合体層の厚さ1μmであり、吸光度比(A0/A)が0.1である。また、容器から90mm×90mmの大きさでサンプルを切り出しその酸素透過度を測定すると、1.1ml/m2・day・MPaである。
Example 2
An unsaturated carboxylic acid compound Zn salt solution (X) is applied to the surface of a container-forming preform made of polyethylene terephthalate by a dipping method. Next, after drying the entire preform in an oven at 60 ° C. for 1 minute, the entire preform is irradiated with an ultraviolet irradiation device so that the irradiation light quantity is 5 mJ / cm 2 and prepolymerized. The polymerization rate of the polymer layer applied at this time is 35%. Next, the container forming preform was formed by biaxial stretching and blow molding to form a container, and then the container was further irradiated with ultraviolet rays so that the irradiation light quantity was 200 mJ / cm 2 , and the polymerization rate was 90% to form a polymer layer. To obtain a sealed container. The container has a polymer layer thickness of 1 μm and an absorbance ratio (A 0 / A) of 0.1. Further, when a sample was cut out of the container with a size of 90 mm × 90 mm and the oxygen permeability thereof was measured, it was 1.1 ml / m 2 · day · MPa.
参考例1
PETボトル(500ml 耐圧タイプ)から90mm×90mmの大きさでサンプルを切り出しその酸素透過度を測定すると、53ml/m2・day・MPaであった。
Reference example 1
When a sample was cut out from a PET bottle (500 ml pressure-resistant type) with a size of 90 mm × 90 mm and its oxygen permeability was measured, it was 53 ml / m 2 · day · MPa.
本発明の不飽和カルボン酸化合物多価金属塩の重合体層が形成された容器は高湿度下でのガスバリア性に優れており、かかる特徴を活かして、ジュース、清涼飲料水を始め、種々の液体用容器と使用されるばかりでなく、特に、炭酸ガスを含むビール、発泡酒、炭酸飲料等の容器として好適に使用し得る。 The container in which the polymer layer of the unsaturated carboxylic acid compound polyvalent metal salt of the present invention is formed is excellent in gas barrier properties under high humidity. By utilizing such characteristics, various kinds of juice such as juices and soft drinks are used. In addition to being used as a liquid container, it can be suitably used as a container for beer, sparkling liquor, carbonated drink, etc. containing carbon dioxide gas.
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