GB2123746A - Method for production of metal sheet covered with polyester resin film - Google Patents
Method for production of metal sheet covered with polyester resin film Download PDFInfo
- Publication number
- GB2123746A GB2123746A GB08220583A GB8220583A GB2123746A GB 2123746 A GB2123746 A GB 2123746A GB 08220583 A GB08220583 A GB 08220583A GB 8220583 A GB8220583 A GB 8220583A GB 2123746 A GB2123746 A GB 2123746A
- Authority
- GB
- United Kingdom
- Prior art keywords
- resin film
- polyester resin
- steel sheet
- treatment
- metal sheet
- 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
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 108
- 239000004645 polyester resin Substances 0.000 title claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 74
- 239000002184 metal Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010791 quenching Methods 0.000 claims abstract description 31
- 230000000171 quenching effect Effects 0.000 claims abstract description 31
- 238000010030 laminating Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 65
- 239000010959 steel Substances 0.000 claims description 65
- 239000011651 chromium Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003475 lamination Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000005029 tin-free steel Substances 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 7
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 7
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920006267 polyester film Polymers 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 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
-
- 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
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
-
- 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
- B32B2309/025—Temperature vs time profiles
-
- 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
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- 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
Landscapes
- Laminated Bodies (AREA)
Abstract
A method for the production of a metal sheet covered with polyester resin film which comprises laminating a crystalline and oriented polyester resin film on a metal sheet heated to a temperature above the melting point of polyester resin film and then immediately quenching. This metal sheet is covered with polyester resin film is excellent in corrosion resistance and formability.
Description
SPECIFICATION
Method for production of metal sheet covered with polyester resin film
The present invention relates to a method for the production of a metal sheet covered with polyester resin film produced by laminating a crystalline and oriented polyester resin film on the surface of a metal sheet heated to a temperature above the melting point of polyester resin film and then rapidly quenching the laminate.
At present, organic resin film laminated metal sheets are widely used in various fields such as electrical components, furniture and building materials. In general, there are two well-known methods for continuous lamination of organic resin film on the surface of the metal sheet. The first method is one in which an adhesive coated metal sheet is used. Namely, at first the adhesive in which thermosetting resin is mainly dissolved in a solvent is coated on the surface of the metal sheet. After curing the adhesive, the organic resin film is laminated on the surface of the metal sheet and then heated in an oven with a large capacity for several minutes. After that, the organic resin film laminated metal sheet is cooled.
The second method is one in which an adhesive coated organic resin film is used. In this case, the organic resin film is laminated on the surface of the metal sheet and then is also heated in the same type of oven as in the first method.
However, these methods have some problems because a long time is required for curing the adhesive and heating after lamination of the organic resin film. For example, the production speed is low, e.g. 10 to 30 m/min. In some cases, the characteristics of the organic resin film such as the corrosion resistance are deteriorated by heating for a long time and the laminated organic resin film may be peeled off from the surface of the metal sheet by severe forming because the formability of thermosetting resin used for the adhesive is not good.
Furthermore, in Laid-Open Japanese Patent Application No. Sho 53-81 530, a modified polyester resin film is used for lamination of the organic resin film on the metal sheet without an adhesive such as thermosetting resin.
In the can producing industry, continuous lacquer coating at high speed on the metal sheet has been investigated in order to decrease the production cost. However, such process is very difficult to practice industrially, because a lacquer which can be cured by heating for a few seconds has not yet been developed.
Furthermore, the corrosion resistance after forming of the lacquer coated metal sheet is poor as compared with that of the organic resin film laminated metal sheet.
It is the first object of the present invention to provide a metal sheet covered with polyester resin film having an excellent corrosion resistance after forming as compared with that of the lacquer coated metal sheet and other organic resin film laminated metal sheets. It is the second object of the present invention to provide a method for the continuous lamination of polyester resin film on the surface of the metal sheet at high speeds such as 100 to 600 m/min.
The reason why the metal sheet having an excellent corrosion resistance after forming is obtained according to the method of the present invention is as follows:
In general, polyester resin film having the crystalline and oriented structure has an excellent nonpermeability to water and steam, but it is not adhered to the metal sheet without a thermosetting resin adhesive. On the contrary, polyester resin film having the amorphous structure which is obtained by rapidly cooling the crystalline and oriented polyester resin film heated to a temperature above the melting point of polyester resin for a long time strongly bonds to the metal sheet as shown in Japanese
Patent Publication No. Sho 49-34180, but it is poor in corrosion resistance because water and vapor easily permeates the film.
As described above, both polyester resin films have different properties.
Thus, it is considered that one reason why the metal sheet according to the present invention has excellent corrosion resistance after forming is that the thin amorphous layer of polyester resin film having excellent bonding strength to the metal sheet is formed between the upper layer of crystalline and oriented polyester resin film and the surface of the metal sheet by rapidly quenching after laminating the crystalline and oriented polyester resin film.
The second reason is that the thicker layer of the crystalline and oriented polyester resin film having the excellent non-permeability to water and steam remains after laminating the crystalline and oriented polyester resin film to the surface of the metal sheet.
Therefore, the method of the present invention is characterized by the lamination of the crystalline and oriented polyester resin film on the surface of the metal sheet heated above the temperature of the melting point of the used polyester resin film and then rapidly quenching.
The metal sheet according to the present invention can be used in applications wherein excellent corrosion resistance after severe forming is required, such as drawn cans, drawn and redrawn cans (DR can) in addition to can ends, instead of lacquered electrotinplate and tin free steel having a duplex layer consisting of an upper layer of hydrated chromium oxide and a lower layer of metallic chromium.
Furthermore, it is also used for the can body adhered by polyester resin film instead of the lacquered tin free steel can body seamed by nylon adhesive.
In the present invention, the employed polyester resin film is prepared by processing polyester resin which is produced by the esterification of at least one saturated polycarboxylic acid by at least one saturated polyalcohol selected from the following polycarboxylic acids and polyalcohols.
Saturated polycarboxylic acids are selected from phthalic acid, isophthalic acid, terephthalic acid, succinic acid, azelaic acid, adipic acid, sebacic acid, 1,4-cyclohexane dicarboxylic acid and trimellitic acid anhydride.
Saturated polyalcohols are selected from ethylene glycol, 1 ,4-butane diol, 1 ,5-pentane diol, 1,6hexane diol, propylene glycol, 1,4-dimethanol cyclohexane, trimethylol propane and pentaerythritol.
In some cases, additives such as antioxidants, stabilizers, pigments, antistatic agents and corrosion inhibitors are added during the manufacturing process of the polyester resin film used for the present invention.
In the present invention, the use of polyethylene terephthalate film having biaxial oriented structure is especially desirable from the viewpoint of corrosion resistance and economy.
The thickness of the used polyester resin film should be 5-100 ym, preferably 5-50 ym, although it is not limited to such range. However, if the thickness of the employed polyester resin film is below 5 ym, the excellent corrosion resistance after severe forming in the metal sheet according to the present invention is not obtained.
Moreover, the use of the polyester resin film having a thickness above 100 ym is not economically suitable for the film to be laminated to the metal sheet, because the polyester resin film used for the present invention is expensive as compared with epoxy phenolic lacquers widely used in the can industry and other organic resin films such as polypropylene film.
The metal sheet used in the present invention is steel sheet or aluminum sheet with or without a surface treatment.
Particularly, tin free steel having an upper layer of hydrated chromium oxide and a lower layer of metallic chromium, lightly tin coated steel sheet, Ni plated steel sheet, Cr plated steel sheet, Cu plated steel sheet, steel sheet covered with hydrated chromium oxide and aluminum sheet with chromate treatment and phosphate treatment are suitable as the metal sheet for the present invention, because these metal sheets have excellent bonding strength with respect to the polyester resin film.
Furthermore, the following duplex, triple, composite and alloy plated steel sheets can also be used as the metal sheet in the present invention.
Duplex and triple coated steel sheets are selected from the group consisting of lightly tin coated steel sheet with Ni plating, chromate treatment, phosphate treatment or tin free steel treatment, Ni plated steel sheet with Cr plating, light Sn plating, chromate treatment, phosphate treatment of tin free steel treatment, Cr plated steel sheet with chromate treatment, Cu plated steel sheet with light tin plating, Ni plating, Cr plating, chromate treatment or tin free steel treatment, and Zn plated steel sheet with chromate treatment, phosphate treatment or silicate treatment.
Composite and alloy coated steel sheets are selected from the group consisting of Ni-Sn plated steel sheet with or without chromate treatment and Zn plated steel sheet in which a small amount of at least one metal, hydroxide or oxide of Ni, Co, Fe, Cr and Mo is contained in the plated Zn layer.
In the continuous production of the metal sheet according to the present invention at high speed, tin free steel having below 0.050 g/m2 as chromium in hydrated chromium oxide and below 0.2 g"m2 of metallic chromium, lightly tin coated steel sheet having below 1.0 g/m2 of Sn, Cr plated steel sheet having below 0.2 g/m2 of Cr and Ni plated steel sheet having below 3.0 g/m2 of Ni are suitable for the metal sheet according to the present invention.
The temperature of the metal sheet heated just before the lamination of the polyester resin film which is an important factor in the present invention should be maintained in the range of Tm-Tm +1 600C, in which Tm is the melting point of the polyester resin film which exhibits an endothermic peak in an ordinary differential thermal analysis run at a heating rate of 1 OoC/min., in order to get the excellent bonding strength between the polyester resin film and the metal sheet.
If the temperature of the metal sheet heated just before the lamination of the polyester resin film is above Tm + 1 600C, the corrosion resistance of the polyester resin film laminated metal sheet deteriorates, because the ratio of the non-oriented part to the oriented part in the laminated polyester resin film will perhaps increase. With a temperature below Tm, the polyester resin film laminated metal sheet having excellent bonding strength is not obtained, because the lower side of the employed polyester resin film in contact with the metal sheet is not sufficiently melted.
Furthermore, the quenching conditions after laminating the polyester resin film on the metal sheet is also one of the important factors in the present invention. Namely, the maximum temperature on the surface, which does not contact the surface of the metal sheet, of the laminated polyester resin film should be below TsOC, at which the melting of crystals in the polyester resin film starts, preferably below Ts-200C.
More specifically, Ts represents the temperature at which the endothermic reaction of polyester resin film starts, as determined by ordinary differential thermal analysis which is run at a heating rate of
100C/min.
If the temperature on the surface of the laminated polyester resin film is above Ts, the characteristics of the metal sheet according to the present invention become remarkably poor.
For example, the appearance of the laminated polyester resin film changes from clear to milky and the corrosion resistance after forming becomes poor.
Furthermore, the quenching time for cooling the metal sheet to below Ts after the lamination of the polyester resin film is also an important factor in the present invention. It should be below 10 seconds. In the case where the quenching time is longer, the corrosion resistance of the polyester resin film laminated metal sheet also becomes remarkably poor, because it is considered that the greater part of the crystalline and oriented structure changes to the non-oriented structure in the laminated polyester resin film.
In the present invention, the method for heating the metal sheet to which the polyester resin film is laminated is not limited. However, from the standpoint of continuous and stable production of the polyester resin film laminated metal sheet at high speed, induction heating and/or resistance heating which are used for reflowing tinplate in the conventional process for production of electrotinplate is suitable as the method for heating the metal sheet to be laminated, because the metal sheet to be laminated is rapidly heated and the temperature of the heated metal sheet is easily controlled. Namely, it is desirable in the present invention that the metal sheet to be laminated is heated in the range of from 1-20 seconds.
Furthermore, in the present invention, various methods were considered for quenching the metal sheet heated above the melting point of the polyester resin film after the lamination of the polyester resin film. However, quenching by water spray, water immersion, liquid nitrogen or employing a roller cooled by water or liquid nitrogen are industrially suitable as the method for quenching the heated metal sheet after the lamination of polyester resin film. The temperature of water used for quenching the heated metal sheet should be kept below 900C in consideration of the continuous production of the polyester resin film laminated metal sheet according to the present invention, although it should be kept as low as possible.
The present invention is explained in further detail by reference to the following examples.
EXAMPLE 1
A coid rolled steel sheet having a thickness of 0.23 mm was electrolytically degreased in a solution of 70 g/l sodium hydroxide and then pickled in a solution of 100 g/l sulfuric acid. The steel sheet, after being rinsed with water, was cathodically treated by using an electrolyte consisting of 30 g/l of CrO3 and 1.5 g/l of NaF in water under 20 A/dm2 of cathodic current density at an electrolyte temperature of 300 C. The thus treated steel sheet was rinsed with hot water having a temperature of 800C and dried. After that, a crystalline and oriented polyester resin film (Trade name: Melinex S made by ICI Co., Ltd.) having a thickness of 20 Hm was laminated on the thus treated steel sheet under the following conditions and was quenched.
Conditions of the lamination of the polyester resin film:
Method for heating the treated steel sheet Resistance heating
Temperature of the treated steel sheet just before the lamination 285"C Maximum temperature on the surface of the laminated polyester
resin film between laminating and quenching 1 500C Quenching time to 1 500C on the surface of the laminated
polyester resin film 2 sec.
EXAMPLE 2
The steel sheet was electroplated with 0.3 g/m2 of Sn by using an electrolyte consisting of 25 g/l of stannous sulfate, 1 5 g/l of phenolsulfonic acid (60% aqueous solution) and 2 g/l of ethoxylated anaphthol sulfonic acid in water under 20 A/dm2 of cathodic current density at an electrolyte temperature of 400C after the pretreatment as in Example 1. The tin plated steel sheet was rinsed with water and dried.
After that, a crystalline and oriented polyester resin film (Trade name: Lumirror F made by Tore
Co., Ltd.) having a thickness of 50 Mm was laminated on the thus tin plated steel sheet under the following conditions and quenched.
Conditions for the lamination of the polyester resin film:
Method for heating the tin plated steel sheet Resistance heating
Temperature of the tin plated steel sheet just before the lamination 2700C
Maximum temperature on the surface of the laminated polyester
resin film between laminating and quenching 1 700C Quenching time to 1 700C on the surface of the laminated
polyester resin film 3 sec.
EXAMPLE 3
The steel sheet was electroplated with 0.6 g/m2 of Ni by using a Watt's bath consisting of 40 g/l of NICK, 6H20, 250 girl of NiSO4. 6H20 and 40 g/l of H3BO3 in water under 10 A/dm2 of cathodic current density at a bath temperature of 400 C. The Ni plated steel sheet was rinsed with water after chromate treatment by using 30 g/l of sodium dichromate solution under 10 A/dm2 of cathodic current density at an electrolyte temperature of 450C and dried.
After that, a crystalline and oriented polyester resin film (Trade name: Melinex 377 made by ICI
Co., Ltd.) having a thickness of 50 um was laminated on the treated Ni plated steel sheet under the following conditions and quenched.
Conditions for the lamination of the polyester resin film:
Method for heating the Ni plated steel sheet Induction heating
Temperature of the Ni plated steel sheet just before the lamination 3200C
Maximum temperature on the surface of the laminated polyester
resin film between laminating and quenching 1 850C Quenching time to 1 850C on the surface of the laminated
polyester resin film 4 sec.
EXAMPLE 4
The steel sheet was electroplated with 0.7 g/m2 of Ni containing 0.04 g/m2 of Sn by using a
Watt's bath used in Example 3 added 5 g/l of stannous sulfate under the same conditions as in Example 3 after the pretreatment as in Example 1.
The Ni-Sn plated steel sheet was rinsed with water and dried. After that, a crystalline and oriented polyester resin film (Trade name: W 3030 made by Teijin Co., Ltd.) having a thickness of 30 ym was laminated on the thus Ni-Sn plated steel sheet under the following conditions.
Conditions for the lamination of the polyester resin film:
Method for heating the Ni-Sn plated steel sheet Infrared heating
Temperature of the Ni-Sn plated steel sheet just before the lamination 2800C
Maximum temperature on the surface of the laminated polyester
resin film between laminating and quenching 1 6O0C Quenching time to 1 600C on the surface of the laminated
polyester resin film 2 sec.
EXAMPLE 5
The steel sheet was electroplated with 0.3 g/m2 of Ni by using a Watt's bath used in Example 3.
After rinsing the Ni plated steel sheet was treated by using an electrolyte consisting of 50 g/l of CrO3 and 0.5 g/l of sulfuric acid in water under 10 A/dm2 of cathodic current density at an electrolyte temperature of 550C and then rinsed with water and dried.
After that, a crystalline and oriented polyester resin film (Trade name: E-5000 made by Toyobo
Co., Ltd.) having a thickness of 40 Mm, was laminated on the Ni plated steel sheet having metallic chromium and hydrated chromium oxide under the following conditions and was quenched.
Conditions for the lamination of the polyester resin film:
Method for heating the Ni plated steel sheet Induction heating
Temperature af the Ni plated steel sheet just before the iamination 3000C
Maximum temperature on the surface of the laminated polyester
resin film between laminating and quenching 190 C Quenching time to 1 SO0C on the surface of the laminated
polyester resin film 6 sec.
EXAMPLE 6
An aluminum sheet (JIS 3004) having a thickness of 0.23 mm was cathodically degreased in a solution of 30 g/l sodium carbonate and then treated in a solution containing 30 g/l sodium dichromate at a solution temperature of 650C. The thus chromate treated aluminum sheet was rinsed with water and dried.
After that, a crystalline and oriented polyester resin film (Trade name: Flu mirror S10 made by Tore
Co., Ltd.) having a thickness of 20 Mm was laminated on the treated aluminum sheet under the following conditions and quenched.
Conditions for the lamination of the polyester resin film:
Method-for heating the treated aluminum sheet Resistance heating
Temperature of the treated aluminum sheet just before the lamination 2900C
Maximum temperature on the surface of the laminated polyester
resin film between laminating and quenching 1 800C Quenching time to 1 8O0C on the surface of the laminated
polyester resin film 3 sec.
COMPARATIVE EXAMPLE 1
The same polyester resin film and the same treated steel sheet used for Example 1 were prepared.
This polyester resin film was laminated to the treated steel sheet under the same conditions as in
Example 1.
After lamination, the laminated steel sheet was gradually cooled without water quenching.
COMPARATIVE EXAMPLE 2
The same polyester resin film and the same treated steel sheet used for Example 3 were prepared.
This polyester resin film was laminated to the treated steel sheet under the same conditions asian
Example 3 except for the quenching time to 1850C on the surface of the laminated polyester resin film.
Quenching time to 185PC 45 sec.
COMPARATIVE EXAMPLE 3
An aluminum sheet (JIS 3004) having a thickness of 0.23 mm was treated under the same conditions as in Example 6.
After that, a crystalline and oriented polyester resin film (Trade name: Lumirror S10 made by Tore
Co., Ltd.) having a thickness of 4 ym, was laminated to the treated aluminum sheet under the same conditions as in Example 6.
The characteristics of the resultant metal sheet were evaluated by the following test methods, after the measurement of the coating weight on the resultant metal sheet by the X-ray fluorescent method, the results of which are shown in the Table.
(1) Bonding strength between the metal sheet and the polyester resin film:
The polyester resin film laminated sample was cut to a size of 8 cm x 8 cm, and the polyester resin film laminated side was cut crosswise with a razor. After 6 mm of the sample was extruded by using a conventional Erichsen testing machine, the laminated polyester resin film of the formed part was peeled off by a pincette. Bonding strength was divided into 5 ranks, namely, 5 was excellent, 4 was good, 3 was fair, 2 was poor and 1 was bad.
(2) Corrosion resistance against an acidic solution after forming:
The polyester resin film laminated sample was cut to a circular blank having a diameter of 80 mm by a punch press, and the blank was deeply drawn to form a cup in which the polyester resin film laminated side was inside at a drawing ratio of 2.0.
50 ml of citric acid adjusted to pH 2.2 was filled into the drawn cup, and the iron or aluminum pick up was measured after aging for 30 days at 550C.
(3) Discoloration of the laminated polyester resin film after the retort treatment:
The drawn cup prepared by the method described in (2) above was set in a retort into which steam, heated to 1 25-1 300C under a pressure of 1.6-1.7 kg/cm2, was blown for 6 hours. After that, the discoloration of the laminated polyester resin film was evaluated by the naked eye.
TABLE
Comp. Comp. Comp.
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Base Steel Steel Steel Steel Steel Aluminium Steel Steel Aluminium Ni Metal Coated *1 *2 0.3 Sheet layer Cr *1 ni Ni Cr Cr Ni (g/m) 0.11 Sn 0.6 0.7 0.023 Crox 0.12 Crox Crox 0.3 Crox Sn Crox 0.017 Crox Crox 0.016 0.015 0.004 0.04 0.012 0.015 0.004 Thickness of polyester film 20 m 50 m 50 m 30 m 40 m 20 m 20 m 50 m 4 m Bonding strength 5 4 5 5 5 4 5 5 4 Fe or Al pick up (ppm) 0.05 0.05 0.10 0.23 0.18 0.43 13.5 8.3 3.8 Discoloration No No No No No No Lightly Heavily No of polyester film change change change change change change milky milky change Remarks: *1 The greater parts of plated Sn changes to iron-tin alloy by heating.
*2 The greater parts of plated Ni and Sn may change to Ni-Sn alloy by heating.
*3 Cr is metallic Cr and Crox is Cr in the formed hydrated Cr oxide.
Claims (14)
1. A method for producing a metal sheet covered with a polyester resin film, which comprises
laminating a polyester resin film to a metal sheet heated above the melting point of the polyester resin film and then quenching the laminate.
2. The method according to claim 1, wherein said polyester resin film has a crystalline and oriented structure.
3. The method according to claim 2, wherein said polyester resin film is produced by the esterification of a saturated polycarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, succinic acid, azelaic acid, adipic acid, sebacic acid, diphenyl carboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and trimellitic acid anhydride with a saturated polyalcohol selected from the group consisting of ethylene glycol, 1,4-butane diol, 1,5- pentane diol, 1 ,6-hexane diol, propylene glycol, 1 ,4-dimethanol cyclohexane, trimethylol propane and pentaerythritol.
4. The method according to claim 1, wherein said metal sheet is a sheet or strip of steel or aluminum with or without a surface treatment.
5. The method according to claim 1, wherein said metal sheet is selected from the group consisting of tin free steel having an upper layer of hydrated chromium oxide and a lower layer of metallic chromium, lightly tin coated steel sheet, Ni plated steel sheet, Cr plated steel sheet, Cu plated steel sheet, chromate or phosphate treated steel sheet, Zn plated steel sheet, chromate or phosphate treated aluminum sheet, lightly tin coated steel sheet with Ni plating, chromate treatment, phosphate treatment or tin free steel treatment, Ni plated steel sheet with Cr plating, light tin plating, chromate treatment, phosphate treatment or tin free steel treatment, Cr plated steel sheet with chromate treatment, Cu plated steel sheet with light tin plating, Ni plating, Cr plating, chromate treatment or tin free steel treatment, Zn plated steel sheet with chromate treatment, phosphate treatment or silicate treatment, Ni-Sn alloy plated steel sheet with chromate treatment, phosphate treatment or tin free steel treatment and steel sheet plated with Zn containing a small amount of at least one metal or compound of Ni, Co, Fe, Cr and Mo with or without chromate treatment, phosphate treatment or silicate treatment.
6. The method according to claim 5, wherein an amount of Sn in said lightly tin coated steel sheet is 0.05 to 1.0 g/m2.
7. The method according to claim 5, wherein the amount of metallic chromium and hydrated chromium oxide as chromium is 0.01 to 0.2 g/m2 and 0.005 to 0.050 g/m2, respectively in said tin free steel.
8. The method according to claim 5, wherein the amount of Ni in said Ni plated steel sheet is 0.01 to 3.0 g/m2.
9. The method according to claim 1, wherein the temperature of said metal sheet heated just before the lamination of said polyester resin film is maintained in the range ofTm-Tm+16O0C in which
Tm represents the melting point of said polyester resin film.
10. The method according to claim 1, wherein said metal sheet is heated to TmTm+160 C within 20 seconds by using resistance heating, induction heating or both.
11. The method according to claim 1, wherein the maximum temperature on the surface of the laminated polyester resin film is kept below Ts, between the laminating of polyester resin film and quenching the laminated metal sheet, in which Ts represents the temperature for the start of the endothermic reaction of the polyester resin film.
1 2. The method according to claim 11 , wherein the maximum temperature on the surface of the laminated polyester resin film is kept below Ts-200C.
1 3. The method according to claim 1, wherein the quenching time to Ts, on the surface of the laminated polyester resin film, is below 10 seconds, said quenching being performed by spray of water kept below 900 C, immersion into water kept below 900C or liquid nitrogen or a roller cooled by water or liquid nitrogen.
14. The method according to claim 13, wherein said quenching time is with respect to a temperature between Ts and Ts-200C.
1 5. The method according to claim 1, wherein the thickness of said polyester resin film is 5 to 100 ,um.
1 6. The method according to claim 1 5, wherein the thickness of said polyester film is 5 to 50 um.
1 7. The method according to claim 1, wherein said polyester resin film is polyethylene terephthalate film having a biaxially oriented structure.
1 8. The laminated metal sheet according to any one of claims 1 to 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08220583A GB2123746B (en) | 1982-07-15 | 1982-07-15 | Method for production of metal sheet covered with polyester resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08220583A GB2123746B (en) | 1982-07-15 | 1982-07-15 | Method for production of metal sheet covered with polyester resin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2123746A true GB2123746A (en) | 1984-02-08 |
| GB2123746B GB2123746B (en) | 1986-10-29 |
Family
ID=10531706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08220583A Expired GB2123746B (en) | 1982-07-15 | 1982-07-15 | Method for production of metal sheet covered with polyester resin film |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2123746B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2242159A (en) * | 1990-03-19 | 1991-09-25 | Toyo Kohan Co Ltd | Copolyester resin film - metal sheet laminates |
| US5059460A (en) * | 1987-10-15 | 1991-10-22 | Cmb Foodcan Plc | Laminated metal sheet |
| FR2664532A1 (en) * | 1990-06-26 | 1992-01-17 | Toyo Kohan Co Ltd | Laminate formed by a tin-plated steel sheet, carrying a double layer of chromium, and by a film of copolyester resin, and method for producing it |
| US5238517A (en) * | 1987-10-15 | 1993-08-24 | Cmb Foodcan Plc | Production of laminated materials |
| US5582319A (en) * | 1992-03-06 | 1996-12-10 | Carnaudmetalbox Plc | Can end formed from laminated metal sheet |
| US5585177A (en) * | 1993-10-19 | 1996-12-17 | Toyo Kohan Co., Ltd. | Metal sheet laminated with triple layered thermoplastic resin and a method for production thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB759876A (en) * | 1954-05-21 | 1956-10-24 | Ici Ltd | Coating or laminating process |
| GB1028085A (en) * | 1963-11-06 | 1966-05-04 | Continental Can Co | Improvements in or relating to laminating dissimilar materials |
| GB1422640A (en) * | 1971-12-29 | 1976-01-28 | Union Carbide Corp | Process for preparing laminates p process for preparing laminetes and products |
| GB1501353A (en) * | 1975-02-10 | 1978-02-15 | Toray Industries | Thermoplastic polyester and olefin-copolymer compositions |
| GB1566422A (en) * | 1975-11-26 | 1980-04-30 | Toray Industries | Coated metal sheet and process for production therefor |
-
1982
- 1982-07-15 GB GB08220583A patent/GB2123746B/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB759876A (en) * | 1954-05-21 | 1956-10-24 | Ici Ltd | Coating or laminating process |
| GB1028085A (en) * | 1963-11-06 | 1966-05-04 | Continental Can Co | Improvements in or relating to laminating dissimilar materials |
| GB1422640A (en) * | 1971-12-29 | 1976-01-28 | Union Carbide Corp | Process for preparing laminates p process for preparing laminetes and products |
| GB1501353A (en) * | 1975-02-10 | 1978-02-15 | Toray Industries | Thermoplastic polyester and olefin-copolymer compositions |
| GB1566422A (en) * | 1975-11-26 | 1980-04-30 | Toray Industries | Coated metal sheet and process for production therefor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5059460A (en) * | 1987-10-15 | 1991-10-22 | Cmb Foodcan Plc | Laminated metal sheet |
| US5238517A (en) * | 1987-10-15 | 1993-08-24 | Cmb Foodcan Plc | Production of laminated materials |
| GB2242159A (en) * | 1990-03-19 | 1991-09-25 | Toyo Kohan Co Ltd | Copolyester resin film - metal sheet laminates |
| GB2242159B (en) * | 1990-03-19 | 1994-02-02 | Toyo Kohan Co Ltd | Copolyester resin film-metal sheet laminates |
| FR2664532A1 (en) * | 1990-06-26 | 1992-01-17 | Toyo Kohan Co Ltd | Laminate formed by a tin-plated steel sheet, carrying a double layer of chromium, and by a film of copolyester resin, and method for producing it |
| US5582319A (en) * | 1992-03-06 | 1996-12-10 | Carnaudmetalbox Plc | Can end formed from laminated metal sheet |
| US5585177A (en) * | 1993-10-19 | 1996-12-17 | Toyo Kohan Co., Ltd. | Metal sheet laminated with triple layered thermoplastic resin and a method for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2123746B (en) | 1986-10-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20020714 |