TWI793259B - 酒用鋁製容器 - Google Patents
酒用鋁製容器 Download PDFInfo
- Publication number
- TWI793259B TWI793259B TW108103985A TW108103985A TWI793259B TW I793259 B TWI793259 B TW I793259B TW 108103985 A TW108103985 A TW 108103985A TW 108103985 A TW108103985 A TW 108103985A TW I793259 B TWI793259 B TW I793259B
- Authority
- TW
- Taiwan
- Prior art keywords
- aluminum
- wine
- polyester resin
- coating
- container
- Prior art date
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 111
- 235000014101 wine Nutrition 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 74
- 239000011248 coating agent Substances 0.000 claims abstract description 72
- 229920001225 polyester resin Polymers 0.000 claims abstract description 64
- 239000004645 polyester resin Substances 0.000 claims abstract description 64
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims description 17
- 238000005452 bending Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 4
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000007765 extrusion coating Methods 0.000 claims description 2
- 238000010409 ironing Methods 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 17
- 239000000796 flavoring agent Substances 0.000 abstract description 17
- 235000019634 flavors Nutrition 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- FQORROGUIFBEFC-UHFFFAOYSA-N OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O Chemical compound OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O FQORROGUIFBEFC-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 235000015040 sparkling wine Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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- B65D7/00—Containers having bodies formed by interconnecting or uniting two or more rigid, or substantially rigid, components made wholly or mainly of metal
- B65D7/02—Containers having bodies formed by interconnecting or uniting two or more rigid, or substantially rigid, components made wholly or mainly of metal characterised by shape
- B65D7/04—Containers having bodies formed by interconnecting or uniting two or more rigid, or substantially rigid, components made wholly or mainly of metal characterised by shape of curved cross-section, e.g. cans of circular or elliptical cross-section
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- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
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- B65D1/14—Cans, casks, barrels, or drums characterised by shape
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- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
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- B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
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- C—CHEMISTRY; METALLURGY
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- C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
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Abstract
本發明係關於一種酒用鋁製容器,由鋁製罐體及覆蓋該罐體之開口部的鋁製罐蓋構成,在該鋁製罐體之內側面,於罐體之罐身部形成有厚度4μm以上之聚酯樹脂被覆,在該鋁製罐蓋之內側面,形成有厚度6μm以上之由聚酯/酚醛系塗料構成的塗膜,藉此,即使在不使用用以捕捉亞硫酸之特別的捕捉劑而將含有亞硫酸鹽之酒予以填充、密封的情況下,仍可有效地防止容器之腐蝕的產生、酒之風味的減損。
Description
本發明係關於酒用鋁製容器,更詳細係關於一種酒用鋁製容器,即使在填充、密封含有亞硫酸鹽作為抗氧化劑的酒的情況,仍可有效地抑制容器的腐蝕或酒之風味的減損。
酒係容易氧化,且容易因為氧化而使風味減損,故通常填充、密封至氧氣無法穿透的玻璃瓶中來保存、流通。另一方面,因為玻璃瓶重量重且不耐衝擊,故期望將酒填充、密封至輕量且耐衝擊強的容器中。
金屬製容器係與玻璃瓶同樣地阻氣性優良,且具有遮光性,故也有人提案將酒填充、密封至金屬製容器中。然而,一般而言酒中含有作為抗氧化劑的亞硫酸鹽,而該亞硫酸對於金屬的腐蝕性高,故有著會對於金屬產生腐蝕,且與金屬反應所產生的硫化氫會導致酒之風味減損的問題。
為了解決如此之金屬製容器的問題,下述專利文獻1中提出一種酒罐裝用金屬罐,於罐內側形成有添加了作為與亞硫酸反應之酸捕捉劑之碳酸鈣的樹脂層。此外,下述專利文獻2中,提出含有聚酯樹脂、酚醛樹脂及氧化鋅之罐身及罐蓋用的塗料樹脂組成物,並記載藉由氧化鋅來捕捉亞硫酸系化合物,可發揮耐腐蝕性及內容物保持性。專利文獻3中記載,藉由將酒中之亞硫酸濃度減低至50ppm以下,而不會產生金屬罐之腐蝕或風味變差的酒罐裝。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開2006-62688號公報
[專利文獻2] 日本特開2012-31223號公報
[專利文獻3] 日本特開平2-76565號公報
[發明所欲解決之課題]
上述專利文獻1係將穿透樹脂層之亞硫酸藉由樹脂層之黏接劑層中含有之碳酸鈣來捕捉者,故就生產性或經濟性之觀點無法令人滿意。
此外,在使用上述專利文獻2記載之塗料組成物時,需要於金屬罐之成形後形成塗膜,就生產性之觀點尚無法令人滿意,且因為與上述專利文獻1同樣地需要用以捕捉亞硫酸的捕捉劑,故就經濟性之觀點亦無法令人滿意。
在使用上述專利文獻3記載之酒罐裝時,有著無法填充游離亞硫酸濃度為50ppm以上之酒的問題。
因此本發明之目的係提供一種酒用鋁製容器,即使在不使用用以捕捉亞硫酸之特別的捕捉劑而將含有亞硫酸鹽之酒予以填充、密封的情況下,仍可有效地防止容器之腐蝕的產生、酒之風味的減損。
本發明之另一目的係提供品質不會降低,輕量且處理性優良的容器盛裝酒。
[解決課題之手段]
根據本發明,提供一種酒用鋁製容器,係由鋁製罐體、及覆蓋該罐體之開口部的鋁製罐蓋構成的酒用鋁製容器,其特徵在於:在該鋁製罐體之內側面,於罐體之罐身部形成有厚度4μm以上之聚酯樹脂被覆,在該鋁製罐蓋之內側面,形成有厚度6μm以上之由聚酯/酚醛系塗料構成的塗膜。
本發明之酒用鋁製容器中,適宜為:
1.於該罐身部之該聚酯樹脂被覆的厚度落在4~30μm之範圍內,
2.該罐蓋之塗膜之厚度落在6~20μm之範圍內,
3.該聚酯樹脂被覆係由對苯二甲酸乙二酯系聚酯樹脂構成,
4.該聚酯/酚醛系塗料係由聚酯樹脂作為主劑,可溶酚醛樹脂(resol)型酚醛樹脂作為硬化劑之塗料組成物形成而成,
5.該罐體係將聚酯樹脂被覆鋁板藉由抽拉加工、彎曲拉伸加工及/或引縮加工(ironing)成形而成,
6.該罐蓋係留置拉環(stay-on-tab)式之易開罐罐蓋。
根據本發明,還提供一種容器盛裝酒,係將酒填充、密封至上述酒用鋁製容器而成。
本發明之容器盛裝酒係適合填充、密封含有亞硫酸鹽的酒。
[發明之效果]
本發明之酒用鋁製容器中,藉由組合具有特定厚度之由聚酯樹脂薄膜構成之內側面被覆的鋁製罐體、及具有特定之厚度的聚酯/酚醛系內側面塗膜的鋁製罐蓋,即使填充、密封含有亞硫酸鹽之酒,會抑制亞硫酸穿透鋁製罐體之樹脂被覆及鋁製罐蓋的塗膜,故可持續長時間有效地防止鋁之腐蝕及風味的降低。
而且可提供不需要對於上述內側面被覆摻合用以捕捉亞硫酸的捕捉劑,且藉由抽拉引縮加工等嚴峻之加工亦不會產生聚酯樹脂被覆之密接不良,生產性、經濟性亦優良,為輕量且沒有破損之虞,處理性優良的酒用鋁製容器。
此外,聚酯樹脂被覆鋁製罐體因為有機成分幾乎不會從被覆溶出,耐溶出性優良,故與抑制亞硫酸與金屬反應所致之硫化氫的產生相輔相成,不會損害酒的風味。
本發明之酒用鋁製容器之上述效果從後述實施例之結果可明瞭。亦即,即使使用本發明中使用之聚酯樹脂被覆鋁製罐體,在將該罐體與具有環氧/丙烯酸系塗膜之鋁製罐蓋組合使用時,即使塗膜厚度落在上述範圍內,罐蓋仍會產生腐蝕(比較例1及2),在聚酯樹脂被覆之厚度比上述範圍更薄時,雖然罐體不產生腐蝕,但酒的風味降低(比較例3)。此外,在罐體及罐蓋皆形成有環氧/丙烯酸系塗膜時,酒之風味係大幅降低,且在罐體及罐蓋兩者產生腐蝕(比較例4)。即使使用本發明中使用之具有環氧/酚醛系塗膜的鋁製罐蓋,在將該罐蓋與具有環氧/丙烯酸製塗膜之鋁製罐體組合使用時,酒的風味大幅降低,且於罐體產生腐蝕(比較例5)。相對於此,將本發明中使用之聚酯樹脂被覆鋁製罐體與具有環氧/酚醛系塗膜之鋁製罐蓋組合使用時,在官能評價(酒之風味)、以及罐體及罐蓋兩者的耐腐蝕性皆獲得令人滿意之結果(實施例1)。
(酒用鋁製容器)
本發明之酒用鋁製容器係由鋁製罐體、及覆蓋該罐體之開口部的鋁製罐蓋構成,其特徵在於:在該鋁製罐體之內側面,於罐體之罐身部形成有厚度4μm以上,宜為4~30μm之範圍的聚酯樹脂被覆,在該鋁製罐蓋之內側面,形成有厚度6μm以上,宜為6~20μm之範圍的由聚酯/酚醛系塗料構成的塗膜。
在鋁製罐體之內側面樹脂被覆之厚度比上述範圍薄時,無法抑制亞硫酸穿透樹脂被覆,風味會降低。另一方面,在鋁製罐體之內側面樹脂被覆之厚度比上述範圍厚時,不僅就經濟性差,且有在成形時產生樹脂被覆之密接不良之虞。
同樣地,在鋁製罐蓋之內側面塗膜之厚度比上述範圍薄時,會損害耐腐蝕性,另一方面,在鋁製罐蓋之內側面塗膜之厚度比上述範圍厚時,不僅就經濟性差,且有因為產生塗料垂軟、塗膜形成之時的起泡而導致無法形成正常之塗膜,結果無法形成能抑制亞硫酸穿透之塗膜之虞。
[鋁製罐體]
本發明之酒用鋁製容器所使用之鋁製罐體只要是罐體之罐身部具有厚度為4μm以上,適宜為4~30μm之範圍的聚酯樹脂被覆即可,其形狀或成形方法並沒有特別之限定,尤其為將聚酯樹脂被覆鋁金屬板以使聚酯樹脂被覆成為內側面之方式予以成形而得的無縫罐較理想。
本發明中規定之聚酯樹脂被覆之厚度,係罐體中樹脂被覆最薄部分的厚度,就藉由抽拉加工、引縮加工等成形而得之無縫罐而言,係指聚酯樹脂被覆金屬板被製為最薄壁之罐體罐身部的聚酯樹脂被覆之厚度,該部分的聚酯樹脂被覆也因嚴峻之成形加工而製為最薄壁。
為了成形本發明之鋁製罐體而使用之聚酯樹脂被覆鋁板係至少於鋁板之成為罐內側面的面被覆後述之聚酯樹脂而成者。
就鋁板而言,可使用由純鋁或鋁合金構成之鋁板(本說明書中,包括鋁合金板在內統稱為「鋁板」)。
鋁板為了改善與樹脂被覆之密接性及耐腐蝕性,宜實施以往公知的表面處理,其雖沒有限定,宜為經實施磷酸鉻酸鹽處理、含鋯之有機無機系表面處理等表面處理的鋁板。
使用之鋁板的厚度期望為0.15~0.40mm,尤其期望為0.20~0.30mm。
就構成實施於鋁板之聚酯樹脂被覆的聚酯樹脂而言,宜為芳香族羧酸成分之80莫耳%以上,尤其為90莫耳%以上係由對苯二甲酸成分構成,醇成分之80莫耳%以上,尤其為90莫耳%以上係由乙二醇構成之對苯二甲酸乙二酯系之聚酯樹脂(以下有時簡稱為「PET樹脂」)。該聚酯樹脂可為均聚對苯二甲酸乙二酯,也可為共聚合聚酯,或也可為此等之2種以上之摻混樹脂。
就對苯二甲酸成分以外之羧酸成分而言,可列舉間苯二甲酸、萘二羧酸、對β-氧基乙氧基苯甲酸、聯苯基-4,4’-二羧酸、二苯氧基乙烷-4,4’-二羧酸、5-鈉磺基間苯二甲酸、六氫對苯二甲酸、己二酸、癸二酸、偏苯三酸、均苯四酸、1,2,3-苯三甲酸、1,1,2,2-乙烷四羧酸、1,1,2-乙烷三羧酸、1,3,5-戊烷三羧酸、1,2,3,4-環戊烷四羧酸、聯苯基-3,4,3’,4’-四羧酸、二聚酸等,尤其適宜含有間苯二甲酸、二聚酸。
另一方面,就乙二醇以外之醇成分而言,可列舉丙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、二乙二醇、三乙二醇、環己烷二甲醇、雙酚A環氧乙烷加成物、甘油、三羥甲基丙烷、新戊四醇、二新戊四醇、山梨醇酐(Sorbitan)等醇成分。
聚酯樹脂應具有薄膜形成範圍的分子量,使用苯酚/四氯乙烷混合溶劑作為溶劑所測定之固有黏度(IV)為0.55dL/g以上,尤其為0.6~1.0dL/g之範圍,就對於腐蝕成分之阻隔性或機械性質之觀點係良好。
聚酯樹脂被覆係不僅限於單層,亦可為多層,並沒有限定,也可成為下述之二層構成:表層係間苯二甲酸含量為5莫耳%以下之均聚PET或共聚合PET、下層係由間苯二甲酸含量為5~15莫耳%、二聚酸含量為1~6莫耳%之共重合PET構成,表層與下層之厚度比落在2:8~8:2之範圍內。
此外,在利用抽拉加工、彎曲拉伸加工及/或引縮加工予以成形時,考量將成形後之罐體罐身部之內側面的聚酯樹脂被覆的厚度設定在上述範圍內的觀點,針對聚酯樹脂被覆鋁板之狀態宜為聚酯樹脂被覆之厚度落在8~30μm的範圍內較理想。聚酯樹脂被覆為多層的情況,總厚度宜在上述厚度範圍內。
此外,對於鋁板之聚酯樹脂的被覆可藉由以往公知的疊層方法來進行,適宜藉由澆鑄薄膜(多層澆鑄薄膜)的層合、或擠製塗布(共擠製塗布)而可不使用黏接劑進行被覆,當然,並沒有限制黏接劑的使用,亦可使用用於與鋁板之黏接之以往公知的黏接用底漆。
又,聚酯樹脂被覆鋁板之外側,並沒有限制而可形成有以往之公知的罐用塗料或聚酯樹脂被覆。
本發明中,可將上述聚酯樹脂被覆鋁板,藉由使用抽拉加工與再抽拉加工、抽拉加工與彎曲拉伸加工、抽拉加工與彎曲拉伸加工與引縮加工、或抽拉與引縮加工等以往公知之方法來進行製造,尤其是宜從抽拉加工、彎曲拉伸加工及/或引縮加工成形而成。罐體之薄壁化宜為:與底部相比,罐身藉由彎曲拉伸加工及/或引縮加工使其薄壁化成為聚酯樹脂被覆鋁板之原料板厚度的20~95%,尤其宜成為30~85%之厚度。
成形而得之罐體可藉由以往公知之方法,實施修邊(trimming)加工、熱處理、頸縮(neck-in)加工、摺緣(flanging)加工,因應需求對於罐體外側面實施印刷,可製成後述之罐蓋捲封用之無縫罐。
[鋁製罐蓋]
本發明之鋁用鋁製容器中使用之鋁製罐蓋,只要是具有6μm以上,適宜為6~20μm之範圍之厚度的聚酯/酚醛系內側面塗膜,其形狀或成形方法便沒有特別之限定。
為了成形鋁製罐蓋所使用之具有聚酯/酚醛系塗膜的塗層鋁板,係對於上述鋁製罐體之成形中使用的鋁板,塗布含有聚酯樹脂作為主劑、酚醛樹脂作為硬化劑的塗料組成物而成者。
本發明中,就上述可形成聚酯/酚醛系塗膜之塗料組成物而言,只要是含有聚酯樹脂作為主劑、酚醛樹脂作為硬化劑的塗料組成物便沒有特別之限定。
例如,並不限定於下述內容,可適當地使用在日本特開2003-321646號公報中記載之一種水性塗料組成物,含有具10~30mgKOH/g之酸價及3000~10000之數目平均分子量之含羧基芳香族聚酯樹脂及從間甲酚衍生而得之酚醛樹脂,或在日本特開2013-249376號公報中記載之一種塗料組成物,含有酸價為2~50mgKOH/g、玻璃轉移溫度(Tg)為35~100℃之聚酯樹脂(A)、與酸價為0~50mgKOH/g、玻璃轉移溫度(Tg)為-20~25℃之聚酯樹脂(B)混合而得之混合聚酯樹脂、及相對於該混合聚酯樹脂之樹脂固體成分每100重量份,為1~30重量份之可溶酚醛樹脂(resol)型酚醛樹脂、及相對於全部樹脂固體成分100重量份為1~30重量份之量的硬化觸媒等。
本發明中,如同前述,將該塗料組成物以塗膜厚成為6μm以上,尤其為6~20μm之方式塗布於鋁板。使用之鋁板係可使用與鋁製罐體所使用之同樣的鋁板。
就塗料組成物之對於鋁板的塗層方法而言,沒有特別之限制,可藉由以往公知的塗層方法,例如噴塗、輥塗布器塗層、浸漬塗層等任意方法進行塗層。此外,就塗膜之烘烤條件而言,一般而言宜為於100~300℃進行5秒鐘~30分鐘,適宜為於150~270℃進行15秒鐘~15分鐘。
本發明之鋁製罐蓋除了使用上述罐蓋材料的點之外,可藉由其本身公知的成形法進行成形。亦即,將塗層鋁板沖壓成為預定之形狀及大小,然後可藉由加壓模成形為蓋的形狀。本發明中使用之鋁製蓋並沒有限定,可為留置拉環(SOT)式之易開罐蓋、全開式之易開罐蓋等,尤其適宜為SOT蓋。
(容器盛裝酒)
本發明之容器盛裝酒係將酒填充、密封至由上述鋁製罐體及鋁製罐蓋構成之容器中而得者,如同前述,即使為含有亞硫酸鹽作為抗氧化劑的酒,亦不會產生容器內部的腐蝕,且酒的風味即使經歷長時間也不會減損。
酒係沒有限制而可儲存紅酒、白酒、粉紅酒等以往公知的酒,亦可填充游離亞硫酸濃度為50ppm以上的酒。此外,亦可應用於氣泡酒。
[實施例]
(罐體之製作)
就鋁板而言,使用磷酸鉻酸鹽表面處理鋁板(板厚0.28mm)。
藉由將該表面處理鋁板加熱至250℃,以層合輥於其兩面熱壓接聚酯樹脂薄膜後,迅速地進行水冷,而製得聚酯樹脂被覆鋁板。此外,就罐內側之聚酯樹脂薄膜而言,使用表1所示之厚度的間苯二甲酸含量為10莫耳%的共聚合PET樹脂薄膜,於罐外側,使用10μm厚之間苯二甲酸含量為12莫耳%的共聚合PET樹脂薄膜。
於獲得之聚酯樹脂被覆鋁板的兩面經靜電塗布石蠟後,沖壓成為直徑156mm之圓形,製作成為淺抽拉杯。然後,將該淺抽拉杯進行再抽拉-引縮加工及拱凸(Doming)成形,進行開口端緣部之修邊加工,實施在201℃75秒鐘,接著在210℃80秒鐘的熱處理,將開口端進行頸縮加工、摺緣加工,製作罐體211徑且罐頸部206徑之容量500ml的聚酯樹脂被覆鋁製無縫罐。
此外,無縫罐係罐體直徑:66mm,罐體高度:168mm,相對於原板厚之罐側壁部的平均板厚減少率:60%。
此外,作為比較品,將上述表面處理鋁板不被覆聚酯樹脂薄膜,與上述同樣的方式製作無縫罐後,於罐內側面形成表1所示之厚度的環氧/丙烯酸系塗膜,製作具有內面塗膜之鋁製無縫罐。
(罐蓋之製作)
將聚酯/酚醛系塗料或環氧/丙烯酸系塗料,以在成為內側面的面上使乾燥塗膜成為表1所記載之厚度的方式予以卷材塗布至板厚0.26mm之JIS A5182H19鋁合金卷,然後於烘箱以鋁板之峰值溫度為260℃且全加熱時間為28秒鐘之方式烘烤塗膜,獲得塗層鋁卷。此外,於鋁板之外側,形成與內側種類不同之乾燥膜厚為4μm的環氧/丙烯酸系塗料。
此外,就聚酯/酚醛系塗料而言,使用日本特開2013-249376號公報之實施例8中記載之塗料,亦即使用下述之塗料組成物:以90:10之重量比含有玻璃轉移溫度50℃、酸價15mgKOH/g、數目平均分子量17000之聚酯(A)及玻璃轉移溫度7℃、酸價1mgKOH/g、數目平均分子量18000之聚酯(B),且相對於聚酯100重量份,摻合作為交聯劑之衍生自間甲酚的可溶酚醛樹脂(resol)型酚醛樹脂10重量份、作為硬化觸媒之胺封端(amine blocking)之十二烷基苯磺酸1.0重量份而成之塗料組成物。此外,就於成為內側面之面所使用的環氧/丙烯酸系塗料而言,係使用國際公開第2010/013655號之實施例1中記載的塗料。
使用上述塗層鋁卷,藉由殼(開罐用拉環裝設用蓋)成形機,成形為強化環狀溝之半徑部之從中央板算起的深度為2.5mm,且半徑部之曲率半徑為0.50mm之206徑殼。對於其進行鉚釘加工、從蓋外面側進行切口加工(切口殘留厚度95μm)、及開罐用拉環的裝設,製作SOT蓋。
(實驗例1)
將白酒(pH3.4、遊離亞硫酸濃度80ppm、總亞硫酸濃度225ppm)各別填充至表1表示之實施例1及比較例4的容器中並密封。將該容器盛裝酒以23℃之恆溫條件下保存6個月後,觀察罐內側面,結果實施例1之容器很明顯地抑制了腐蝕。
經過6個月後之罐內側面的圖像((A)為罐頸部,(B)為罐身筆直部)表示於圖1(實施例1)及圖2(比較例4)。
(實驗例2)
將白酒(pH3.2、遊離亞硫酸濃度30ppm、總亞硫酸濃度105ppm)填充至實施例1製作的無縫罐,使用下述表2所示之內側面塗膜不同之3種的鋁製罐蓋加以密封。將該容器盛裝酒於23℃或37℃之恆溫條件下保存3個月後,觀察罐蓋內側面,結果聚酯/酚醛塗膜形式的蓋係很明顯地抑制腐蝕。最小膜厚為5μm時,在37℃恆溫條件下經過3個月後產生腐蝕,最小膜厚為8μm時,在23℃及37℃之恆溫條件下經過3個月後之腐蝕產生率皆為0。
(實驗例3)
單離實施例1、比較例2、比較例4之無縫罐之罐身的內側面樹脂皮膜,使用如圖3所示之球型玻璃製管柱層析管(AS ONE Corporation,OF-30),比較亞硫酸穿透量的大小。
介隔氟橡膠製之墊料2將內側面樹脂被膜3以管柱1(A)及管柱1(B)夾持並固定後,對於管柱1(A)填充純水,對於管柱1(B)填充添加有亞硫酸鈉的檸檬酸溶液(製備為pH3.1,總亞硫酸量500ppm),以聚矽氧橡膠製之管塞4密封。
於23℃之恆溫條件下保存1週後,測定管柱1(A)所填充之純水中的亞硫酸量。
亞硫酸量測定係使用離子層析儀(Thermo Fisher Scientific Inc.,ICS-2100)。結果表示於圖4。
針對3種內側面樹脂皮膜進行評價,相對於具有環氧/丙烯酸系塗膜之比較例4之無縫罐,具有最小膜厚為4μm以上之聚酯薄膜的實施例1、比較例2係將亞硫酸之穿透抑制為少量。
(實驗例4)
將白酒(pH3.2,遊離亞硫酸濃度30ppm,總亞硫酸濃度105ppm)填充、密封至表1所示之實施例1、比較例1~5的容器後,於23℃之恆溫條件下經歷3個月後,實施酒之官能評價。
於罐身使用聚酯薄膜,該膜越厚則越能抑制酒之風味的降低。官能評價及耐腐蝕性評價之結果合併表示於表1。
(實驗例5)
將蒸餾水填充至表1所示之實施例1及比較例4之容器,經90℃30分鐘之殺菌處理後,藉由滴定法測定內容液之過錳酸鉀消耗量。過錳酸鉀消耗量係使水中之有機物或還原性物質(被氧化性物質)氧化所必需的過錳酸鉀量,係容易被氧化(反應性高)成分之溶解量的指標。
就實施例1之容器而言過錳酸鉀消耗量為0.1~0.2ppm,反觀比較例4之容器則為0.4~0.5ppm。相對於比較例4之具有環氧/丙烯酸系塗膜的無縫罐,實施例1之具有聚酯樹脂被覆之無縫罐因為有損害酒之風味之虞的易被氧化(反應性高)之有機成分的溶出量少,據認為對於風味性優良。
1(A)、1(B)‧‧‧管柱
2‧‧‧墊料
3‧‧‧內側面樹脂皮膜
4‧‧‧管塞
5‧‧‧管柱層析管
[圖1] 將酒密封填充至實施例1之無縫罐中並在23℃之恆溫條件下經過6個月後之罐頸部(A)及罐身筆直部(B)之內側面的圖像。
[圖2] 將酒密封填充至比較例4之無縫罐中並在23℃之恆溫條件下經過6個月後之罐頸部(A)及罐身筆直部(B)之內側面的圖像。
[圖3] 展示實驗例3中使用之裝置的圖。
[圖4] 展示實驗例3所測定之亞硫酸穿透量的圖。
Claims (7)
- 一種酒用鋁製容器,由鋁製罐體、及覆蓋該罐體之開口部的鋁製罐蓋構成,其特徵在於:在該鋁製罐體之內側面,於罐體之罐身部形成有最小厚度4~6μm之聚酯樹脂被覆,且該聚酯樹脂被覆中並未摻合用以捕捉亞硫酸之捕捉劑;在該鋁製罐蓋之內側面,形成有厚度6μm以上之由聚酯/酚醛系塗料構成的塗膜,且該鋁製罐蓋係留置拉環(stay-on-tab)式之易開罐罐蓋;該鋁製罐體係藉由下列步驟(i)及(ii)來製作而成:(i)將聚酯樹脂藉由澆鑄薄膜的層合或擠製塗布,不使用黏接劑而被覆於鋁板,獲得聚酯樹脂被覆鋁板;(ii)將該聚酯樹脂被覆鋁板成形為該鋁製罐體。
- 如申請專利範圍第1項之酒用鋁製容器,其中,該罐蓋之塗膜的厚度落在6~20μm之範圍內。
- 如申請專利範圍第1或2項之酒用鋁製容器,其中,該聚酯樹脂被覆係由對苯二甲酸乙二酯系聚酯樹脂構成。
- 如申請專利範圍第1或2項之酒用鋁製容器,其中,該聚酯/酚醛系塗料係由聚酯樹脂作為主劑,可溶酚醛樹脂(resol)型酚醛樹脂作為硬化劑之塗料組成物形成而成。
- 如申請專利範圍第1或2項之酒用鋁製容器,其中,該罐體係將聚酯樹脂被覆鋁板藉由抽拉加工、彎曲拉伸加工及/或引縮加工(ironing)成形而成之無縫罐。
- 一種容器盛裝酒,係將酒填充且密封至如申請專利範圍第1至5項中任一項之酒用鋁製容器而成。
- 如申請專利範圍第6項之容器盛裝酒,其中,該酒含有亞硫酸鹽。
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2019
- 2019-01-28 BR BR112020015645-0A patent/BR112020015645A2/pt active Search and Examination
- 2019-01-28 EP EP19748121.1A patent/EP3747790A4/en active Pending
- 2019-01-28 US US16/966,640 patent/US20210031981A1/en not_active Abandoned
- 2019-01-28 CA CA3089820A patent/CA3089820A1/en active Pending
- 2019-01-28 WO PCT/JP2019/002771 patent/WO2019151189A1/ja not_active Ceased
- 2019-02-01 TW TW108103985A patent/TWI793259B/zh active
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| JP2013107093A (ja) * | 2011-11-18 | 2013-06-06 | Daiwa Can Co Ltd | ボトル型缶の製造方法およびボトル型缶 |
| CN104379687A (zh) * | 2012-05-31 | 2015-02-25 | 东洋制罐集团控股株式会社 | 涂料组合物和涂布有所述涂料组合物的涂装金属板、金属容器和金属盖 |
| TW201718252A (zh) * | 2015-05-21 | 2017-06-01 | 東洋製罐集團控股股份有限公司 | 表面處理金屬板及有機樹脂被覆表面處理金屬板 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201936812A (zh) | 2019-09-16 |
| CA3089820A1 (en) | 2019-08-08 |
| EP3747790A4 (en) | 2021-10-20 |
| WO2019151189A1 (ja) | 2019-08-08 |
| JP2019131275A (ja) | 2019-08-08 |
| JP7355485B2 (ja) | 2023-10-03 |
| US20210031981A1 (en) | 2021-02-04 |
| BR112020015645A2 (pt) | 2020-12-08 |
| EP3747790A1 (en) | 2020-12-09 |
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