CN1032765A - 层压金属片 - Google Patents
层压金属片 Download PDFInfo
- Publication number
- CN1032765A CN1032765A CN88107071A CN88107071A CN1032765A CN 1032765 A CN1032765 A CN 1032765A CN 88107071 A CN88107071 A CN 88107071A CN 88107071 A CN88107071 A CN 88107071A CN 1032765 A CN1032765 A CN 1032765A
- Authority
- CN
- China
- Prior art keywords
- polyester
- metal
- sheet metal
- sheet
- polyester film
- 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
- 239000002184 metal Substances 0.000 title claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 229920000728 polyester Polymers 0.000 claims abstract description 55
- 238000003475 lamination Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 39
- 229920006267 polyester film Polymers 0.000 claims description 39
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 18
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- -1 polybutylene terephthalate Polymers 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000005029 tin-free steel Substances 0.000 claims description 4
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000010030 laminating Methods 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 229920006254 polymer film Polymers 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 6
- 238000000859 sublimation Methods 0.000 description 6
- 230000008022 sublimation Effects 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920001634 Copolyester Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002648 laminated material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical group OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005092 sublimation method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007746 phosphate conversion coating Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920005588 metal-containing polymer Polymers 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
- B32B15/08—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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
- B32B15/08—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
- B32B37/085—Quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
- B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
- B32B37/203—One or more of the layers being plastic
- B32B37/206—Laminating a continuous layer between two continuous plastic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B65D1/00—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, by deep-drawing operations performed on sheet material
- B65D1/22—Boxes or like containers with side walls of substantial depth for enclosing contents
- B65D1/26—Thin-walled containers, e.g. formed by deep-drawing operations
- B65D1/28—Thin-walled containers, e.g. formed by deep-drawing operations formed of laminated material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/02—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/04—Treatment by energy or chemical effects using liquids, gas or steam
- B32B2310/0409—Treatment by energy or chemical effects using liquids, gas or steam using liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/24—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/30—Iron, e.g. steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/66—Cans, tins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12542—More than one such component
- Y10T428/12549—Adjacent to each other
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Abstract
一种层压的金属片,此金属片在其至少一侧主面
上粘合有一层非结晶的聚酯,以及一种制造它的方
法。此种层压金属片特别适用于成型冲拔和薄壁拉
伸的(DWI)罐。这种层压件也适用来形成其它非压
热处理的包装部件。
Description
本发明涉及层压金属片以及生产这种层压金属片的方法。
使聚合物材料在金属带之类的金属片上进行层压成形乃是一种周知的得到普遍确认的技术。这样获得的层压件具有多方面的应用,包括以之来制造冲拔和薄壁拉深的罐(也称作为DWI罐)。
已知可用钢或铝覆以聚烯烃涂层来作为制备DWI罐的坯料。这类材料例如见于美国专利4096815号与英国专利2003415号中所描述的,而就我们所知,这种材料尚未获得商品化应用。
已了解到,聚烯烃涂层并不能象热塑性聚酯那样成形。聚酯涂层对钢与铝的层压结构,例如有英国专利号2123746与2164899所作的描述。但是,这些专利强调,为了使罐壳获得足够的寿命,必须在聚酯涂层中保持着一定的双轴性定向。本发明人等认识到,以上专利中所述的这类层压件,是不能经受制备深冲拔的或DWI罐时不使聚酯涂层发生严重碎裂之成形操作要求的。英国专利2123746或2164899号所述在这种涂层中保持定向的作法,使涂层在断裂值下的延伸率限制到超出DWI罐成形作业所要求的相当低的数值。因而,这样的层压件是不适用来成形DWI罐的。
本发明人等得知,于金属片上粘合一层基本上属非结晶(或无定形)形式的热塑性聚合物,能经受住DWI作业和保持住合格的金属覆盖厚度。这样的涂层在DWI罐的成形中优于聚烯烃涂层,同时保持着更好的连续性与防护性。
据此,本发明在其一个方面是提供一种层压的金属片,此金属片的一面或两面上直接粘附有一层非结晶聚酯膜。
上述的非结晶聚酯(这里也称作为无定形聚酯)经X射线衍射(XRD)或密度测量法测定,应该基本上是无定向的。
由X射线衍射测定结晶度的一种方法已给出在英国专利1566422号中。结晶度能据密度测量法测定如下:
VC=体积分率结晶度
VC=(P-Pa)·(P-Pc)-1
P=聚酯密度
Pa=无定形聚酯密度
Pc=结晶聚酯密度
上述密度测量法可以在氯化锌/水溶液中或正庚烷/四氯化碳中,用密度柱进行。
一般,此种非结晶聚酯为一种聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸丁二醇酯(PBT)。PET材料的特性粘度,按照于邻氯基苯酚中在25℃,5克/升浓度下测量的结果,最好是在0.5与1.1之间。
层压至金属上的这种非结晶聚酯膜是通过下述条件使一种含聚酯的膜层压到金属片上而形成的,即在层压成形过程中要让金属/聚酯层压件中的一或两面上的聚酯膜转变为非结晶(或无定形)形式。
最好使金属片的各主面都载有按以上规定的非结晶聚酯膜。不过,本发明的范围则包答,在一个主面上载有非结晶聚酯膜而在另一主面上载有不同热塑性聚酯膜的金属片。
上面涂敷聚合物膜的金属衬底一般取金属带形式,材料通常为钢或铝或其合金,典型的是包装工业中用的钢基或铝基制品。
上述带的厚度范围,典型的情况是钢从0.05至0.4毫米,而铝从0.02至0.4毫米;对于钢和铝的DWI罐来说,则一般是在0.25至0.35毫米。
钢可用锡镀层,最好通过常规的铬处理法钝化;或者可另行采用镀镍或锌的未镀锡之黑钢板或磷化处理的未镀锡之黑钢板,而在磷化处理之后还再好用铬酸盐液漂洗。
这方面较理想的钢成品乃是用电解法镀有铬的钢(ECCS),上面有着金属铬与氧化铬的双层结构。对这种钢来说,金属铬与氧化铬的面密度可以在广范围内变化。一般,金属铬的含量范围从0.01至0.20克/平方米,而氧化铬的从0.005至0.05克/平方米。ECCS通常是从包括含硫或含氟之催化剂的沉积系统中获取的。
所用的铝最好是那种3004型合金,它具有轧制(“滚轧”)的光洁度、或明亮的与也可用油浸的光洁度、或铬酸盐-磷酸盐处理以及也可经油浸的光洁度。举例来说,AlocromA272便是铝带的一种合适的铬酸盐-磷酸盐处理体系。
有多种不同类型的聚酯膜可用来制备上述的金属聚合物层压件。适用于制备本发明之金属/聚合物层压件的聚酯材料为:
(ⅰ)浇注的热塑性聚酯,例如PET或PBT;
(ⅱ)具有半结晶结构的双轴定向的聚酯膜,典型的有双轴定向的PET;
(ⅲ)浇注的共挤出之复合聚酯膜;
(Ⅳ)如下的一种复合的共挤出之聚酯膜,它包括:
(A1)软化点低于200℃,熔点低于250℃但高于150℃的基本上为非结晶线型聚酯的内层,与
(A2)结晶度大于30%的双轴定向之线型聚酯外层。
采用共挤出的聚酯膜时,最好使用具有较薄内层A1与较厚外层A2的膜。
一般,外层A2是一种PET的均聚物。它的特性粘度对于双轴定向的膜最好介于0.5至1.1之间,更好是在0.6至0.7之间;而对于浇注的膜则最好大于0.9。
较薄的内层A1一般是一种基本上为非结晶性的线型共聚物,有80%的对苯二甲酸乙二醇酯和20%的间苯二甲酸乙二醇酯。另一方面,此内层也可以是一种由对酞酸以及乙二醇与环己烷-二甲醇之类两种二元醇衍生出的,基本上是非结晶的共聚多酯。
如有需要,则这种聚酯层也可以是着色的,例如采用合成石英或能给出彩色或白色外观之颜料(如二氧化钛)的防粘剂。对于能由这种层压件成形的啤酒罐之外表面,以二氧化钛来着色外层A2那是特别理想的。
这种共挤出膜的外层A2最好是PET。在内的无定形层A1则宜用一种线型的共聚多酯,例如一种由约80%的对苯二甲酸乙二醇酯与约20%的间苯二甲酸乙二醇酯组成的无定形共聚物。对酞酸与例如乙二醇和环己烷-二甲醇两种醇组成的共聚多酯,也适用作内部的无定形层A1。
当这种共挤出膜为双轴定向时,外结晶层A2的结晶度一般为50%,但要是减弱此结晶共聚物的双轴定向,则该结晶度可减至40%或更小。
双轴定向膜可按以下方式形成,即在高于聚合物的玻璃转变温度的温度下,按2.2至3.8倍朝前向拉伸之无定形的挤压成形的聚合物膜,且类似地以2.2至4.2倍朝横向拉伸这种膜。
本发明的层压金属片则按下述过程制备,其中包括直接在金属片的一或两个主面上直接粘上一层包含有聚酯的膜,此层压成形的条件是,于层压过程中,在金属/聚合物层压件上的一或两面上的聚酯膜应转变成非结晶的或无定形的形式。
在制备本发明的这种金属/聚合物层压件的一种较佳方法中,是通过把金属片加热到高于聚酯膜熔点的一个温度T1,使聚酯的单层或两层膜粘合到金属片上,此温度T1需在将聚酯膜层压到金属片的过程中,使聚酯膜的外表面保持在其熔点之下,然后将此单层或两层膜层压到金属片上,再用间接方法把层压件重新加热到高于聚酯膜熔点的一个温度T2,经在此高温保持一段时间后,让此聚酯涂层的金属急冷至此种聚酯涂层树脂的玻璃转变温度之下。
在另一种较理想的方法中,这种一面或两面上的聚酯膜乃是包括一内层A1与一外层A2的复合膜,而这样的复合聚酯膜则是同时由下述过程粘合到金属片上的,此过程包括如下步骤:
(ⅰ)将金属加热到高于聚酯内层A1的软化点但低于外层A2的熔点的一温度T1;
(ⅱ)将一面或两面上的膜层压到金属片上;
(ⅲ)通过间接方法重新加热此层压件,使金属片达到聚酯膜或各聚酯膜熔点以上的一个温度;
(Ⅳ)在这样高的温度之上保持一段时间之后,将此聚酯涂层的金属加热到低于聚酯涂层树脂之玻璃转变点下的一个温度。
上述的复合聚酯膜最好是下述形式的共挤出的聚酯膜,包括着:
基本上是非结晶的线型聚酯内层A1,此种聚酯的软化点低于200℃,而熔点低于250℃但高于150℃,
一种聚酯的外层A2,此种聚酯的熔点高于220℃,
以上聚酯于邻氯基苯酚中在25℃,5克/升浓度下测得的特性粘度是在0.5至1.1之间。这样的金属/聚合物层压件最好采用感应加热装置于层压夹的下游重新加热,但也可采用红外加热。
在层压作业前金属所应加热到的温度需取决于待层压之膜的厚度及其化学性质。未涂层的金属则可以采用直接的或例如感应、红外、热空气或热辊等间接的加热方式处理。
140℃至350℃是适用于共挤出的双轴定向之PET膜的温度,130℃至250℃是适用于浇注共挤出之聚酯膜的温度,而260℃至350℃是适用于高结晶度的双轴定向之PET单层膜的温度;另一方面,200℃至300℃则适用于低结晶度的PET膜,而对于铸型的PBT单层膜则需要高于180℃的温度。
一般,于层压夹下游用来重新加热层压件的温度,对于PET在270℃之上,而对于PBT为240℃。在大规模生产中,通常在重新加热作业与急冷之间只要求约2秒的停留时间。急冷是均匀与快速的,可通过把冷水幕导向到此层压带上来实现。为了防止聚酯结晶化,层压件应从190℃以上的温度急冷;而为了防止起泡,涂层应从低于熔点的温度下急冷。
本发明的层压件特别适用于成形DWI罐。从没有有机物涂层之金属片由常规的PWI作业来制造罐时包括以下步骤:
1.润滑镀锡的金属片或铝片;
2.由此金属片切割下一圆盘材料;
3.将此圆盘置于一圆形模具上,并用一圆柱形坯件夹持环使其就位;
4.将一冲头推过此模具,同时用上述坯件夹持环控制金属片的运动;
5.迫使冲头通过模具,直到整个金属片通过模具,而由此金属片形成一浅的杯形件,然后撤除冲头;
6.将此杯状件转移至一直径等于所需容器直径的冲头;
7.重新冲拔此杯状件,并迫使上述冲头与此杯状件通过一组内径逐渐变小的同心环,而使冲头与模具间的间隙小于杯状件的料厚;
8.将杯状件的壁部压薄并拉长;
9.约束住已成形的罐同时撤除冲头;
10.从罐壁顶部修整去余料;
11.洗罐以除去润滑剂,而在铝片情形需腐蚀除去金属屑;
12.将罐漂洗与干燥。
一般在洗涤后,铝质饮料罐可进行下述作业;
13.对表面进行化学处理;
14.于输送机炉子中漂洗并干燥;
15.在外部涂上底膜;
16.固化此底膜;
17.敷贴印刷装饰;
18.固化此装饰;
19.涂敷内涂层(用喷涂法);
20.固化此内涂层;
21.对罐进行颈缩与翻边处理,使颈径减至可与端盖匹配的值,并形成一供二重卷边用的凸缘。
另一方面,要是应用了经选择的外部底膜,则可用英国专利2101530、2145971、2141382、2010529、2141972与2147264号中所述的那种升华印刷法,来取代常规的印刷法。在底膜固化后,将含有可升华之染料的纸标签裹绕到罐上,并在此纸的搭接部分用少量的粘合剂固定住。使此罐通过高于染料升华点的温度的一座炉子,不需采用溶剂而进行转印。这种纸标签可通过空气喷射使之剥离,留下具有优异印刷质量的印有商标之罐。这是一种无溶剂的印刷法,基本上不会有大气排放物。
据本发明层压材料制成的DWI罐,在其成形后可用传统的溶剂基的印油进行装饰与印刷。
热固性聚酯涂层会迅速接受已升华的染料,而由纸标签转移染料到DWI罐上的方法则已工业化。发明人等业已发现,在金属片上的热塑性聚酯涂层会接受升华的染料。但是,由纸标签来获得高质量的装饰仅仅在PET涂层中保持有定向时才可成功。要是这种涂层是无定形的,则会由于它或是在层压过程中熔化,或是由于它是从非取向的膜获得,而使纸标签在升华阶段粘连到涂层上,以致损坏装饰。
由纸标签进行升华时,是在纸与涂层间形成紧密接触,并加热到160℃以上而通常是高达220℃的温度。在上述条件下,无定向的PET在其玻璃转变点(Tg)之上是相当软的,并将粘合到纸上。要是此涂层至少是它的外部保持双轴定向,则纸标签在升华过程中就不会粘连到聚酯上。此外部的有定向的材料在与纸标签接触时的热行为得到了改进,而且在染料升华过程中不会遇到它的有影响的玻璃转变温度。
上面描绘的染料转移到无定形涂层中的问题,似乎不可能使得无定形聚酯涂层之DWI罐上的染料升华。令人惊奇的是,我们已然发现,据本发明无定形聚酯涂层的层压件所形成的DWI罐,能够用标准的标签与升华条件通过升华来成功地进行装饰。
贴标签时最好应略加变动,要避免使标签与罐底有约2毫米的接触(如附图中的图7a中以“d”所指明的)。要是遵循上述方法,纸就不会粘连或接合到涂层上。一般地说,聚酯的无定形涂层在它的Tg之上是会与纸粘连的。但是,这种罐的成形作业则将定向引入到本发明层压件的聚酯涂层内,内而提高了有效的Tg。引入的定向量即使在罐壁的上部也是较少的,而且对于内外涂层又很不相同,这样,出奇的是,此种有益的效应能如此显著地阻止了纸的粘连。
本发明所述的层压件能够出色地加工成DWI罐,同时保持着优越的涂层整体性与粘合性。此外,这种涂层的罐能够用常规的印刷方法或通过染料升华法来装饰。
本发明的层压件还能用于制造其它包装部件,特别是非压热处理的包装部件。其它一些这类部件的典型例子是:
饮料产品用的多级冲拔罐,例如由0.21毫米的ECCS(强度为350牛顿/平方毫米)制造的,54毫米直径×70毫米高的罐;
划线的易开口之饮料罐端部,例如65毫米直径之钢或铝的端部;
椭圆罐的整体颈的椭圆端部;
涂料罐端部件,例如环、端部与盖;
气溶胶的端部件,例如锥形体与拱形顶盖。
本发明的主要优点是:
能切实可行地消除所有的溶剂排放物,因而改进了环境保护;
可用小型漂洗机代替大型的洗罐机,节省了洗涤试剂的成本;
由于削减了为完成这种罐所需通过炉子的次数而降低了能耗;
改进了外底的保护;
改进了复合底的轮廓;
能够不用制罐时所需的润滑剂;
能够减少工厂设备的尺寸与成本,同时降低操作劳务费用;
外部的印刷质料优越。
在整个这份说明书中,特性粘度是在5克/升浓度的邻氯基苯酚溶液中于25℃下测定的。
现在参看附图,对照下述例子,且仅仅以举例方式来进一步详述本发明,在附图中:
图1与2示意地表明了适用于实行本发明之方法的设备;
图3示明通过本发明之层压件截取的一个剖面,其中包括有层压到金属带M的单层聚合物膜A;
图4表明通过类似于图3的层压件截取的一个剖面,但具有层压到金属带M上的复合多层聚合物膜A;
图5表明通过类似于图4的层压件截取的一个剖面,但包含有层压到金属带M相对侧上热塑性聚合物的另一种膜B;
图6表明由本发明之层压件形成的罐端;
图7a与7b分别表明由本发明之层压件形成的DWI罐与多级冲拔罐。
例1至例13
于图1或2所示意表明的设备中,通过层压方法制备了聚合物/金属/聚合物层压件。经红外或感应加热,通过加热器1将金属板予热到一适当的温度T1。此温度T1通常在140至150℃的范围内。聚酯膜A与B由送料辊1与4送入,层压到介于层压辊6、8间的已预热的金属片之两相对侧面上,此种层压辊的直径一般为100至400毫米。层压成形通常是在层压辊间应用200~400牛顿/米的夹力来进行的。
在这里的层压夹中,于金属片与聚合物膜间确立了紧密、均匀与无皱折的接触。在层压辊的下游,形成的层压件最好用感应加热器或通过红外加热,使之加热到聚合物膜A可与之相互作用且与金属片牢牢粘合的一个层压温度T2。此温度T2通常对于PBT在220至270℃的范围内,对于PET在260至300℃范围内。此金属/聚合物夹层件在温度T2或低于T2的一个温度下,保持一段通常不超过2秒的短暂时间,然后用水快速而均匀地急冷到低于膜中聚酯之玻璃转变点之下的一个温度,此温度对PET来说例如约为80℃。可以用任何常规的方式来进行这种急冷,但一般能按下述方式进行,即让此层压件通过图1所示的水槽12,或通过图1与图2所示的急冷水幕14。
通常,最好采用图1所示的按垂直方式进行层压的方法。金属带通过层压阶段的垂直运动常可允许采用较高的急冷速率,同时能给出更好和更均一的急冷效果。
图1还示明了据此图设备所阐明的方法中可能出现的典型温度分布。
根据表Ⅰ中给出的材料,由红外或感应加热予热金属带,使金属带与聚合物膜通入一对夹辊,并使金属带的两立面同时与聚合物膜进行层压,这样便制成了层压件。将这样制备的层压件由红外或感应装置重新加热,于200℃以上保持两秒钟,然后用冷水快速与均匀地急冷。
表Ⅰ
层压件类型
表Ⅱ列出了若干例子,表明由在层压阶段前采用不同的金属温度T1和在层压阶段后采用各种重新加热温度T2下,所制备的这种层压件求得的有关结果。
表Ⅱ
表Ⅰ的注释
PET复合膜一类型Ⅰ:共挤出的铸塑PET复合膜,它具有:
(ⅰ)内层,是对酞酸与乙二醇和环己烷-二甲醇的一种共聚多脂;
(ⅱ)外层,是一种特性粘度大于0.9的PET均聚物。
PET复合膜一类型Ⅱ:同于PET复合膜一类型Ⅰ,但在外层中另加有TiO2颜料。
PET复合膜一类型Ⅲ:共挤出的双轴定向的PET复合膜,它具有
(ⅰ)内层,为对酞酸和异钛酸与乙二醇的共聚物;
(ⅱ)外层,为特性粘度约在0.6至0.7的一种PET均聚物。
PET单层膜:特性粘度约为0.6至0.7的共挤出之双轴定向的单层膜。
PBT单层膜:铸塑的PBT单层膜。
PP复合膜一类型Ⅰ:铸塑的共挤出之聚丙烯复合膜,它具有
(ⅰ)马来酸酐接枝改性之聚丙烯的内层;
(ⅱ)聚丙烯的外层。
PP复合膜一类型Ⅱ:同于PP复合膜一类型Ⅰ,但另有由TiO2与合成石英着色的外层。
Al3004合金:有过铬酸盐-磷酸盐表面处理的铝合金3004(Alocrom A272)。
Al3004合金-轧制的光洁度:冷轧后未清洗与未处理的铝合金3004。
表Ⅱ中述及的层压件可成形性,是根据层压件按以下两个阶段经冲拔和薄壁拉深处理后之涂层的覆盖厚度来评定。
阶段Ⅰ:从此层压件冲拔出一杯状件(高35毫米,直径86毫米),再经适当的润滑处理;
阶段Ⅱ:经再冲拔和薄壁拉伸而形成罐体(直径65毫米,高130毫米)。
成形后,罐于水中漂洗;然后干燥。
评定涂层覆盖厚度时,是将它浸没于酸化硫酸铜中2分钟并目视检验铜的沉淀物,或者根据采用氯化钠溶液的“搪瓷检定”技术,电压为6.3伏而测量电流为毫安级。
由X射线衍射测定了层压温度对聚酯涂层结构与层压件成形性的影响。在这种测量方法中,是将膜或层压件置于一X射线衍射仪中。当平整的样品暴露在基本上是单色的X射线束下时,用合适的探测器测量了计数率。此样品与探测器相对于X射线束成一直线转动,保持着这样的几何结构,使得与通常粉末衍射扫描中的情形相同,让样品与X射线束间角度(θ)以及X射线束与探测器间的角度保持比值1∶2。这种数据给出了有关平行于样品表面之平面的信息。
在双轴定向的PET中,(1,0,0)面在θ=13°给出了高的计数率,但在无定形PET中则没有峰值。层压件与膜的θ=13°峰值高度比与此层压件中所保持的定向有关。我们的结果是作为θ=13°时峰值高度的比值与层压之PET涂层峰值高度而给出的。
根据英国专利2123746中的原理进行层压而保持定向的层压材料B(见例4),它的成形性很差,在制罐中会使金属开裂或使涂层严重碎裂。但当对层压材料B进行处理,消除其定向与结晶性时,如例3所示,则它就具有良好的成形性并在成形后给出优良的防护性。
类似地,双轴定向的共挤出之层压材料C与J要是为无定形时,同样能给出良好的成形性,而要是在此层压件中保持定向,则成形性就很差(将例5与例6,例13与例14进行对比)。
铸塑的未取向的PET或PBT涂层,在它们经层压时能有效地产生一种无定向的而不是结晶性的条件。结晶的条件例如可通过从重新加热的阶段缓慢冷却下来而产生。
例11与12表明,据英国专利2003415所述的那种聚丙烯材料形成的层压件,显示出很差的成形性。这类层压件已发现在罐的形成作业中导致金属断裂。
聚酯涂层的重新取向程龋梢酝ü煅橛烧庵植阊辜肜?中之条件制的DWI罐来加以评定。取得的结果如下:
样品的测定部位 XRD(θ=13°)峰值
罐底-内涂层 <50
罐底-外涂层 <50
罐壁上端-内涂层 100
罐壁上端-外涂层 450
这些XRD数据肯定了此种层压片具有了无定形涂层,而且表明上部的罐部略有定向,且对于罐的外涂层尤其如此。
罐壁外涂层的下部2毫米则未受到罐成形时的显著影响,而基本上保持为无定形的。
由例1至例13之层压件形成的DWI罐的外壁,已用常规的染料升华工艺装饰。获得的装饰质量,当标签不与罐壁下部2毫米处即图7a的区域“d”接触时,可以看出是很优良的。
Claims (21)
1、一种层压的金属片,在它的一或两个主面上直接粘合上了一层非结晶的聚酯膜。
2、如权利要求1所述的层压金属片,其中的金属是钢或其合金、铝或其合金、铝涂层的钢、铬涂层的钢、镀镍或锌的钢、或以铬酸或磷酸进行化学或电解处理的钢。
3、如权利要求2所述的层压金属片,其中的金属片是具有金属铬与铬的氧化物双层结构的,用电解方法镀铬的钢(ECCS)。
4、如权利要求2所述的层压金属片,其中的金属片是铝3004型合金。
5、如以上任一项权利要求所述的层压金属片,其中的非结晶聚酯是聚对苯二甲酸乙二醇酯。
6、如以上任一项权利要求所述的层压金属片,其中的非结晶聚酯是聚对苯二甲酸丁二醇酯。
7、如以上任一项权利要求所述的层压金属片,其中有另一按照权利要求1、5与6所规定的非结晶聚酯膜粘合到金属片的另一主面。
8、权利要求1至7中任一项所述的层压金属片在冲拔和薄壁拉伸法下制得的一种冲拔和薄壁拉伸的罐。
9、按上述任一项权利要求所规定的层压金属片之制造方法,此方法包括在金属片一或两个主面上粘合一层包含聚酯的膜,而进行此层压的条件要使得,在层压过程中,此金属/聚合物层压件中的这一或这些膜要转变为非结晶的或无定形的形式。
10、如权利要求9所述的方法,其中的一面或两面上的聚酯膜为单层膜,而且是在将金属片加热到高于此聚酯膜熔点的一个温度T1下粘合到此金属片上的,此温度T1要使得:在聚酯膜层压到金属片的过程中,聚酯膜的外表面仍处于其熔点之下时才将此种膜层压到金属片上,并通过间接方法将层压件重新加热到高于聚酯膜熔点的一个温度T2,在此高温保持一段时间后,迅速将此已为聚合物涂层的金属急冷至此聚酯涂层树脂的玻璃转变点之下。
11、如权利要求9所述的方法,其中的聚酯膜为包括一内层A1与外层A2的一面或两面上的复合膜,而这些复合聚酯膜是依下述过程同时粘合到金属片上的,此过程包括:
(ⅰ)将金属片加热到高于聚酯内层A1之软化点但低于外层A2之熔点的一个温度T1;
(ⅱ)将这一或这些膜层压到金属片上;
(ⅲ)由间接方式重新加热此层压件,使金属片达到一个高于这一或这些聚酯膜的温度;
(Ⅳ)在上述高温下保持一段时间后,将此聚酯涂层的金属急冷至此聚酯涂层树脂的玻璃转变点之下。
12、如权利要求10或11所述的方法,其中用来使层压件在层压后重新加热的温度是从200至300℃。
13、如权利要求10、11或12所述的方法,其中用于重新加热层压件的间接方式乃是一种感应加热方式。
14、如权利要求9、10、12与13任一项所述的方法,其中的这种或各种聚酯膜乃是一种铸塑的热塑性聚酯。
15、如权利要求14所述的一种方法,其中的铸塑热塑性聚酯是聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯。
16、如权利要求9、10、12与13任一项所述的方法,其中的这种或各种聚脂膜料是具有半结晶结构的双轴定向的聚酯。
17、如权利要求16所述的方法,其中的双轴定向聚酯乃是一种双轴定向的聚对苯二甲酸乙二醇酯。
18、如权利要求11至13中任一项所述的方法,其中的这种或各种聚酯膜乃是一种共挤出的铸塑复合聚酯膜。
19、如权利要求11至13中任一项所述的方法,其中的这种或各各种聚酯膜乃是如下的一种复合的共挤出之聚酯膜,它包括:
内层A1,是软化点低于200℃而熔点低于250℃但高于150℃的一种基本上为非结晶的线型聚酯;
外层A2,为结晶度大于30%的双轴定向的线型聚酯。
20、如权利要求19所述的方法,其中内层A1的线性聚酯是对苯二甲酸乙二醇酯与间苯二甲酸乙二醇酯的一种无定形共聚物,或由对酞酸与两种二元醇形成的一种共聚物。
21、如权利要求19或20所述的一种方法,其中的外层A2是双轴定向的聚对苯二甲酸乙二醇酯。
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CN111479688A (zh) * | 2017-12-15 | 2020-07-31 | 杰富意钢铁株式会社 | 容器用树脂覆膜金属板 |
US11407203B2 (en) | 2017-12-15 | 2022-08-09 | Jfe Steel Corporation | Resin-coated metal sheet for container |
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