CA1337042C - Polyester resin film laminated steel sheet for drawn and ironed can and method for production thereof - Google Patents
Polyester resin film laminated steel sheet for drawn and ironed can and method for production thereofInfo
- Publication number
- CA1337042C CA1337042C CA000581640A CA581640A CA1337042C CA 1337042 C CA1337042 C CA 1337042C CA 000581640 A CA000581640 A CA 000581640A CA 581640 A CA581640 A CA 581640A CA 1337042 C CA1337042 C CA 1337042C
- Authority
- CA
- Canada
- Prior art keywords
- resin film
- steel sheet
- copolyester resin
- polyester resin
- drawn
- 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.)
- Expired - Fee Related
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
- B21D22/201—Work-pieces; preparation of the work-pieces, e.g. lubricating, 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
- 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
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/02—Sheets of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/10—Applying the material on both sides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/20—Chromatation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/65—Adding a layer before coating 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- 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
- B32B2311/16—Tin
-
- 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
- B32B2311/20—Zinc
-
- 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
- B32B2311/22—Nickel or cobalt
-
- 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
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- 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
Abstract
A polyester resin film laminated steel sheet for a drawn and ironed can which comprises laminating a copolyester resin film prepared by processing according to a known method a polyester resin film consisting of 75 to 95 mole %
of polyethylene terephthalate and 5 to 25 mole % of a polyester resin produced by the esterification of at least one saturated polycarboxylic acid with at least one saturated polyalcohol on the one side of a steel sheet covered with at least hydrated chromium oxide to be employed for the inside of the drawn and ironed can and plating a ductile metal such as tin, nickel, zinc and aluminum on the other side of the steel sheet to be employed for the outside of the drawn and ironed can.
By using this polyester resin film laminated steel sheet, a drawn and ironed can having an excellent corrosion resistance with respect to the packed contents such as carbonated beverages and fruit juices is easily produced.
Furthermore, this drawn and ironed can can be used without an inner lacquer coating after forming.
of polyethylene terephthalate and 5 to 25 mole % of a polyester resin produced by the esterification of at least one saturated polycarboxylic acid with at least one saturated polyalcohol on the one side of a steel sheet covered with at least hydrated chromium oxide to be employed for the inside of the drawn and ironed can and plating a ductile metal such as tin, nickel, zinc and aluminum on the other side of the steel sheet to be employed for the outside of the drawn and ironed can.
By using this polyester resin film laminated steel sheet, a drawn and ironed can having an excellent corrosion resistance with respect to the packed contents such as carbonated beverages and fruit juices is easily produced.
Furthermore, this drawn and ironed can can be used without an inner lacquer coating after forming.
Description
FIELD OF THE INVENTION
The present i~vention relates to a polyester resin film ~A I 337042 laminated steel sheet for a drawn and ironed can ~DI can).
In detail, the polyester resin film laminated steel sheet comprises laminati~g a copolyester resin film on the one side of the steel ~heet to be employed for the inside of the DI can and plating a ductile metal on the other side of the steel sheet to be employed for the outside of the DI can.
~ACKGROUND AND OBJECTIVE
At present, tinplated steel sheet, namely tinplate and aluminum sheet is widely used as a material for DI cans for carbonated beverages and beer. These DI cans are produced by the following p~ocess: cutting to a circular blank -~
drawing -~ redrawing -~ ironing several times -~ washing the coolant oil used f~r forming -~ surface treatment of the formed can by phosphate or zirconium salt -~ rinsing with water -~ drying -~ spray coating of lacquer on the inside of the formed can -~ çolor printing the outside of the formed can.
The production cost of the DI can is expensive because the production process of DI can is complex as described above.
Recently, a p~ecoated material was investigated as a cheaper material for DI cans. For example, the steel sheet coated with polyvinyl chloride organosol (Laid-Open Japanese Patent Application No. Sho. 61-92850), the metal sheet coated with a lacquer of thermosetting resin containing a wax of hydrocarbon type as a lubricant (Laid-Open Japanese Patent Application No. Sho. 62-275172 and polyes.er resin film laminated steel sheet (Laid-Open Japanese Patent Application No. Sho. 60-168643) have been employed.
These precoated metal sheets for use in DI cans reduce costs because the production process of DI cans is simplified. However, the quality of DI cans produced from ~ A 1 3 3 ~ 0 4 2 these precoated metal sheets is inferior to that of the DI
cans produced by the present process. For exampie, the lacquered metal sheets shown in Laid-Open Japanese Patent Application No. ~ho. 61-92850 and Laid-Open Japanese Patent Application No. ~ho. 62-275172 are not used for DI cans in which corrosive b~everages are packed without a spray coating of lacquer on the inside of the formed DI cans because many small cracks are observed in the lacquer film coated on the inside of the formed DI cans even if these precoated metal sheets can be easily formed into DI cans.
The characteristics of DI cans produced from a polyethylene terephthalate film laminated steel sheet shown in Laid-Open Japanese Patent Application No. Sho, 60-168643 deteriorate remarkably by reheating upon curing the color printing ink applied on the outside of the forme~ DI can.
Namely, much filiform corrosion arises from the edge of DI
cans reheated for curing the color printing ink during long storage in the atmosphere having high humidity and high temperature.
It is assumed that the cause of filiform corrosion is due to the deterioration of the adhesion of polyethylene terephthalate film to the steel sheet by recrystallization of polyethylene terephthalate film during reheating at above 160C, although the structure of polyethylene terephthalate film may change to the monoaxial oriented state from the amorphous non-oriented state by ironing.
Accordingly, it is the first objective of the present invention to provide a copolyester ~e~irl film laminated steel sheet or strip as a material for DI cans having excel-lent characteristics in the adhesion of copolyester resin film to the steel sheet after forming into DI cans, filiform co~rosion resistance in the formed part after reheating for curing the color printing ink subjected to the outside of ~ A 1 3 3 7 0 4 2 the formed DI cans at the temperature of 160 to 2Q0C and corrosion resistance to the packed contents such as carbonated beverages and fruit juices.
It is the second objective of the present invention to provide a production method of a material for DI cans having an excellent corra~ion resistance which can be used without an inner lacquer coating after forming of DI cans.
BRIEF DESCRIPTION OF THE INVENTION
The first objective of the present invention can be accomplished by the continuous lamination of a copolyester resin film produced from 75 to 95 mole ~ of polyethylene terephthalate and 5 to 25 mole % of other polyester resin having the restricted chemical and physical properties on the one side of the steel sheet having at least hydrated chromium oxide and the deposition of a ductile metal on the other side of the steel sheet.
The second objective of the present invention can be accomplished by the following two methods. The first method is one in which the copolyester resin film precoated with a small amount of resin composite is laminated on the one side of the steel sheet heated to a melting temperature of copolyester resin film + 50C. The second method is one in which said copolyester resin film is directly laminated on the one side of the steel sheet heated to above melting temperature of said copolyester resin film.
The present invention is characterized by the use of the special copolyester resin film having an exce~lent formability and excellent corrosion resistance described above, in addition to the use of the steel sheet in which the one side is covered with at least hydrated chromium oxlde and the other side is plated with a ductile metal. In the present invention, the presence of a hydrated chromium ~ A 1 3 3 7 C 4 2 oxide and a ductile metal layer on each side of the steel sheet are indispehsable in order to obtain excellent adhesion to the copolyeste~ resin film and excellent formability to DI can.
The copolyester resin film laminated steel ~heet according to the present invention can be also used as a material for drawn cans, drawn and redrawn cans, drawn and thin redrawn cans and can ends.
, .
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the copolyester resin film applied on the inside of the DI can is prepared by processing according to a known method, a copolyester resin which is composed of 75 to 95 mole % of polyethylene terephthalate and 5 to 25 mole % of a polyester resin produced by the esterification of at least one saturated polycarboxylic acid with 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, diphenyl carboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and trimellitic acid anhydride.
Saturated polyalcohols are selected from ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol, 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 copolyester resi~ film used for the present invention.
In the present invention, the use of copolyester resin ~ A 1 3 3 7 0 4 2 film having a biaxial oriented structure is especially desirable from the viewpoint of corrosion resistance, although non-oriented copolyester resin film can be also used.
The thickness of the copolyester resin film used in the present invention should be 10 to 50 ~m, preferably 10 to 30 ~m. If the thickness of the employed copolyester resin film is below 10 ~m, many cracks are observed in the copolyester resin film laminated on the steel sheet according to the present invention after forming into the DI can and the continuous lamination of thin copolyester resin film to the steel sheet at high speed becomes remarkably difficult.
Moreover, use of a copolyester resin film above 50 ~m is not economically suitable for the film to be laminated to the steel sheet, because the copolyester resin film used for the present invention is expensive as compared with lacquers widely used in the can industry.
In the present invention, the softening temperature and the melting temperatu~e of the employed copolyester resin film are also importa~t factors. The softening temperature is defined as the temperature at which the insertion of the needle into the copolyester resin film starts at a heating rate of 10C/min. in the thermal mechanical analyzer. (TMA
100 made by Seiko Den~hi Kogyo Co.) The melting temperature is defined as the temperature at which the endothermic peak is obtained at a heat1ng rate of 10C/min. in the differential scanning calorimeter. (SS10 made by Seiko Denshi Kogyo Co.) In the present ipvention, the copolyester resin ~ilm having a 170 to 235C softening temperature and a 190 to 250C melting temperature should be used. The copolyester resin film having the softening temperature of above 235C becomes poor in formability and bonding strength to the ~ A 1 3 3 7 0 4 2 steel sheet because the copolyester resin film is easily crystallized by reheating to cure the color printing ink subjected to the outside of the DI can. On the other hand, if the copolyester resin film having a softening temperature below 170C is used, the efficiency in the production process of the DI can becomes remarkably poor because the copolyester film becomes soft by reheating to cure the color printing ink applied to the outside of the DI can at a higher temperature l0 than the softening temperature of the copolyester resin film.
The use of the copolyester resin film having a melting temperature above 250C is not suitable in the present invention because this copolyester film is rigid and is poor in formability.
If the copolyester resin film having a melting temperature below 190C is applied to the steel sheet for the DI can according to the present invention, many cracks may be observed in the laminated copolyester resin film after flanging and necking the DI can because the mechanical 20 strength of this copolyester resin film becomes remarkably poor by reheating to cure the color printing ink applied to the outside of the DI can. Therefore, the use of the copolyester resin film having a melting temperature below 190C is not also suitable in the present invention.
Furthermore, the orientation and mechanical properties of the copolyester resin film are also very important factors from the viewpoint of the formability of the copolyester resin film.
Namely, in the copolyester resin film used in the 30 present invention, the orientation coefficient which is defined as the degree of the orientation of the copolyester resin should be in the range of 0 to 0.100. The orientation coefficient defined above is determined by a refraction meter and is shown by the following equation in the present invention.
A=(B+C)/2-D
where, A represents the orientation coefficient of the copolyester resin film, B represents the index of refraction in the lengthwise direction of the copolyester film, C represents the index of refraction in the widthwise direction of the copolyester resin film, D represents the index of refraction in the thickness direction of the copolyester resin film.
If the copolyester resin film having above 0.100 of the orientation coefficient is applied to the steel sheet according to the present invention, many cracks arise in the copolyester resin film laminated to the sheel sheet after forming to DI can, because the formability of this copolyester resin film becomes remarkably poor.
In the present invention, an elongation at break and a strength at break of the employed copolyester resin film, which are determined at the speed of 100 mm/min. at 25C in an ordinary tensile testing machine, should be in the range of 150 to 500 % and 3 to 18 kg/mm2, respectively. If the copolyester resin film having below 150 ~ of elongation at break is used in the present invention, many cracks arise in the copolyester resin film after forming into DI cans, because the formability of this copolyester resin film becomes remarkably poor. On the other hand, if the copolyester resin film having above 500 % of elongation at break is used in the present invention, this film is easily .
- ~Al 337042 damaged by severe forming because the thickness of this copolyester resin film becomes non-uniform during production of this film from the extruder.
- 8a -~ The copolyester resin film having above 18 kg/mm2 of ~ A 1 3 3 7 0 4 2 strength at break is poor in formability and the bonding strength to the steel sheet covered with hydrated chromium oxide. Therefore, if this copolyester resin film is used in the present invention, this film is easily peeled off from the surface of the steel sheet with many cracks. On the other hand, if the cQpolyester resin film having below 3 kg/mm2 of the strength at break is used in the present invention, this copolyester resin film is easily damaged by scratches in the process for making of DI can, because this film has poor toughness.
In the present invention, the copolyester resin film selected by various restrictions described above is laminated on the steel sheet by the following two methods. The first method comprises laminating a copolyester resin film which has been precoated with a small amount of resin composite to a steel sheet. The second method comprises laminating a copolyester resin film directly to a steel sheet which is heated to above a melting temperature of said copolyester resin film.
In the first method, the copolyester resin film which has been precoated with 0.1 to 5 gJm2 of a resin composite containing in its molecular structure at least one radical consisting of epoxy radical, hydroxyl radical, amide radical, ester radical, carboxyl radical, urethane radical, acryl radical and amino radical is laminated to a steel sheet which is heated to a melting temperature of said copolyester resïn film + 50C.
At below 0.1 g/m2 of the resin composite, the bonding strength of he copolyester resin fiim to the steel sheet in the body wall of the formed DI can becomes unstable because the resin composlte is not precoated uniformly and thinly to said copolyester resin film.
_g_ At above 5.0 g/m2 of the resin composite, the copolyester ~A 1 337042 resin film in the body wall of the formed DI can is easily peeled off from the surface of the steel sheet.
Furthermore, if the heating temperature of the steel sheet is below the melting temperature -50C, said polyester resin film is easily peeled off from the surface of the steel sheet or an interface between copolyester resin film and resin composite layer after forming into DI cans.
In the case of the melting temperature of said copolyester resin film +50C in the heating temperature of the steel sheet, the body wall of the obtained DI can is remarkably corroded because said copolyester resin film deterlorates by heating at higher temperature.
In the second method, the copolyester resin film is directly laminated on the steel sheet which is heated to the melting temperature +50C. If the heating temperature of the steel sheet is below the melting temperature of said copolyester resin film, said copolyester resin film laminated on the steel sheet is easily peeled off after forming to DI
can. If the temperature of the heated steel sheet is above the melting temperature of said copolyester resin film +50C, the body wall of the obtained DI can is easily corroded because said copolyester resin film deteriorates by heating at higher temperature as in the first method.
In the first method and the second method of the present invention, it is desirable that the copolyester resin film laminated steel sheet be rapidly cooled compared with gradual cooling, because said copolyester resin film is slightly recrystallized in the cooling stage from the higher temperature than the melting temperature of said copolyester resin film.
Especially, the presence of the resin composite between said copolyester resin film and the steel sheet prevents the growth of filiform corrosion at a severely formed part, ~ A 1 3 3 7 0 4 2 while the formed DI can is kept at an atmosphere having higher temperature and higher humidity for long time before the contents such as carbonated beverage is packed into the formed DI can. Therefore, the copolyester resin film laminated steel sheet by the first method i5 preferable to that by the second method.
In the present invention, a surface treated steel sheet having at least hydrated chromium oxide is used.
Especially, the presence of an optimum amount of hydrated chromium oxide in the one side of the steel sheet wherein the copolyester resin film is laminated is indispensable in order to obtain an excellent adhesion of the steel sheet to the copolyester resin film or the resin composite. The optimum range for the amount of hydrated chromium oxide as chromium is 0.005 to 0.050 g/m2, preferably 0.010 to 0.030 g/m2 on said metal sheet.
If the amount of hydrated chromium oxide as chromium is below 0.005 g/m2 or above 0.050 g/m2, the adhesion of the copolyester resin film may become poor in a severely formed part.
Furthermore, where excellent corrosion resistance is required inside the obtained DI can, the steel sheet covered with at least one metal selected from the group consisting of chromium, nickel, tin, zinc and aluminum under the hydrated chromium oxide layer should be used for the copolyester resin film laminated steel sheet according to the present invention.
The optimum range for the amount of plated chromium, nickel, tin, zinc and alum~num ic '!.01 ~o '! 30 g~m2, U.U~ fn 1.0 g/m2, J.Ol .o 10.0 g/m2, 0.5 to 2.0 g/m2 and 0.1 to 0.7 g/m2, respectively.
If the amount of each plated metal is below the lower limit, the effect of the plated metal on the corrosion resistance in the inside of the DI can is very small, despite further plating. On the other hand, the deposition of each metal above the upper limit is not suitable from the viewpoint of economy, as the corrosion resistance in the inside of the DI can is not remarkably improved.
On the other hand, one side of the steel sheet for the outside of the DI can should be plated with at least one ductile metal selected from the group consisting of tin, nickel, zinc and aluminum.
The optimum range for the amount of a plated ductile metal should be controlled at 0.5 to 11.2 g/m2 in tin, 0.5 to 5.0 g/m2 in nickel, 1.0 to 10.0 g/m2 in zinc and 1.0 to 5.0 g/m2 in aluminum, respectively. If the amount of a ductile metal is below the lower limit, the formability to DI cans becomes remarkably poor. The deposition of each ductile metal of above the upper limit is not suitable from the viewpoint of economy, although the formability does not change.
The surface af the plated ductile metal may be chemically treated by chromate or phosphate solution by electrolytical methods, immersion or spray methods, if these treatments have no bad effects on the formability of the DI -can.
The present invention is explained in further detail by reference to the following examples.
TFS film con~isting of a lower layer of 0.12 g/m2 of metallic chromium and an upper layer of 0.015 g/m2 of hydrated chromium oxide as chromium was formed on the one side of the steel strip having a thickness of 0.30 mm and a temper of T-2.5 by a known electrolytic chromic acid treatment.
After rinsing with water, 5.6 g/m2 of tin was electroplated ~- 1 337042 on the other side of said steel strip by using a known tinplating electrolyte and was rinsed with water and dried.
The obtained surface treated steel strip was heated to 220C by using a roll heater and then a biaxially oriented copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 80 mole % of terephthalic acid and 20 mole % of isophthalic acid having a thickness of 25 ~m, softening temperature of 176C, melting temperature of 215C, elongation at break of 330 %, strength at break of 8.2 kg/mm2 and orientation coefficient of 0.024 was laminated on one side having a TFS
film on said steel strip. After that, said copolyester resin film laminated steel strip was rapidly quenched and then dried.
The thus copolyester resin film laminated steel strip was formed into a DI can in which the copolyester resin film was laminated to the inside of the can under the following conditions:
~ Forming conqitions of a DI can) l.Diameter of sample blank: 123.5 mm 2.Drawing ratio in the first drawing: 1.82 3.Drawing ratio in the second redrawing: 1.29 4.Diameter of an ironing punch: 52.64 mm 5.Total ironing ratio: 64 %
2.8 g/m2 of tin was electroplated on both sides of the same steel strip as in Example 1 by using a known tinplating electrolyte. After rinsing with water, 0.006 g/m2 of hydrated chromium oxide film as chromium was formed on said tin plated steel strip by a known electrolytic chromic acid treatment and then rinsed with water and dried.
The same copolyester resin film as in Example 1 was - ~ ~337042 laminated on the one side of said tin plated steel strip under the same laminating conditions as in Example 1.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same forming conditions as in Example 1.
A copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 85 mole % of terephthalic acid and 15 mole % of isophthalic acid having a thickness of 30 ~Im~ softening temperature of 192C melting temperature of 239C, elongation at break of 210 %, strength at break of 12.3 kg/mmZ and orientation coefficient of 0.065 was laminated on the one side having TFS film of the same steel strip as in Example 1 which is heated to 240C by using a roll heater and then was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
The same copolyester resin film as in Example 3, which is precoated with 0.2 g/m2 ~drying weight) of a resin composite consisting of 80 parts of epoxy resin having an epoxy equivalent of 3000 and 20 parts of resol of paracresol type, was laminated on the one side of the same tin plated steel strip as in Example 2 which was heated to 220C and then was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
1 33704~
A biaxially oriented polyethylene terephthalate film having a thickness of 25 ~m, softening temperature of 242C, melting temperature of 260C, elongation at break of 131 %, strength at break of 23.2 kg/mm2 and orientation coefficient of 0.147 was laminated on the one side having a TFS film of the same steel strip as in Example 1 which was heated to 300C by using a roll heater and then was rapidly quenched and dried.
The thus polyethylene terephthalate film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
A copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 85 mole % of terephthalic acid and 15 mole % of isophthalic acid having a thickness of 30 ~m, softening temperature of 194C, melting temperature of 241C, elongation at break of 190 %, strength at break of 13.6 kg/mm2 and orientation coefficient of 0.129 was laminated on the one side having TFS film of the same steel strip as in Example 1 which was heated to 240C by using a roll heater. After that, said copolyester resin film laminated steel strip was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed to a DI can under the same conditions as in Example 1.
A copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 96 mole % of terephthalic acid and 4 mole % of isophthalic acid 1 3370~
having a thickness of 30 ~m, softening temperature of 235C, melting temperature of 250C, elongation at break of 155 %, strength at break of 20.6 kg/mm2 and orientation coefficient of 0.131, which was precoated with the same resin composite as in Example 4, was laminated on the one side of the same steel strip as in Example 2 which was heated to 220C by using a roll heater. After that, said copolyester resin film laminated steel strip was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
The characteristics of the resultant drawn and ironed can was evaluated by the following methods, after washing the coolant oil for forming a DI can, drying, heating at 190C for 15 minutes which corresponds to conditions for curing the lacquer and printing ink subjected to the outside of the DI can and flange forming.
The results are shown in the Table.
(1) Degree of the exposed metal in the inside of a DI
can.
After 1 % sodium chloride solution was filled in the DI
can, the degree of the exposed metal was evaluated by a current value which was flown between an anode of said DI
can and a cathode of a stainless steel rod inserted in said DI can at constant voltage of 6.3 volts.
(2) Filiform corrosion during storage.
The filiform corrosion which grows near the flange parts in the inside of the DI can was evaluated after storage for 3 months at a relative humidity of 92 % at 27C.
The obtained filiform corrosion resistance was divided into 5 ranks, namely 5 was excellent, 4 was good, 3 was fair, 2 was poor and 1 was bad.
(3) Degree of cracks of polyester resin film in the flange part after seaming.
A lacquered alllm;nllm lid was double-seamed to the DI
can. The degree of cracks of polyester resin film in the flange part near the seaming part was observed after removing the seamed aluminum lid.
(4) Corrosion resistance by pack test.
A lacquered aluminum lid was double-seamed after Coca Cola was filled in the DI can. After the storage for 3 months at 37C, the degree of corrosion was observed by naked eye with measurement of iron pick up.
T~LE
Comp Comp Comp EX. 1 EX. 2 EX. 3 EX. 4 ex. 1 ex. 2 ex. 3 Coating weight in outsid2e Sn 5.6 Sn 2.8 Sn 5.6 ~n 2.8 Sn 5.6 Sn 5.6 Sn 2.8 of the formed ean (g/m ) Cr~0.006 Cr~0.006 CrXO.
Coating weight in inside- Cr 0.12 Sn 2.8 Cr 0.12 Sn 2.8 Cr 0.12 Cr 0.12 Sn 2.8 of the formed can (g/m2) Cr~0.015 CrX0.006 Cr~0.015 Cr~0.006 CrX0.015 Cr~0.015 Cr~0~00 So tening temp.(~) 7 :7. :9 5: 4~ :9~ ~3 Characte- Me_ting temp. (C _1 1 3 3 6 _4: ~5 ristics ~~r entation coeff_cient . 24 ~. 24 ~.~65 ~. 65 . 47 ._29 . 31 of employed longation at break ~%) 3 3 1 ~1 _3_ 9 -5 copolyester trength at break (kg/mm2) .~ .~ _2.3 _2.3 ~3.2 _3.6 ,0.6 resin film Meta: Exposure (mA) ~.03 .01 ~.10 .50 .88 302 Peeloff ~ili orm Corr. resistanee ~ ~ . 2 -----Characte- ~raccs by seaming .o crack :o crack i-o crack o crack ~any micro cracks -----ristics of ron pick up (ppm) .05 .02 .13 .42 1.20 14.8 -----the formed ~orr. by pack test ~-ood ~-ood ~-ood ~-ood Pitting Pitting -----DI can Remarks: *Cr represents metallic chromium and Cr~represents chromium in hydrated chromium oxide.
~*Peel off represents peeling off of the laminated copolyester resin film.
~,
The present i~vention relates to a polyester resin film ~A I 337042 laminated steel sheet for a drawn and ironed can ~DI can).
In detail, the polyester resin film laminated steel sheet comprises laminati~g a copolyester resin film on the one side of the steel ~heet to be employed for the inside of the DI can and plating a ductile metal on the other side of the steel sheet to be employed for the outside of the DI can.
~ACKGROUND AND OBJECTIVE
At present, tinplated steel sheet, namely tinplate and aluminum sheet is widely used as a material for DI cans for carbonated beverages and beer. These DI cans are produced by the following p~ocess: cutting to a circular blank -~
drawing -~ redrawing -~ ironing several times -~ washing the coolant oil used f~r forming -~ surface treatment of the formed can by phosphate or zirconium salt -~ rinsing with water -~ drying -~ spray coating of lacquer on the inside of the formed can -~ çolor printing the outside of the formed can.
The production cost of the DI can is expensive because the production process of DI can is complex as described above.
Recently, a p~ecoated material was investigated as a cheaper material for DI cans. For example, the steel sheet coated with polyvinyl chloride organosol (Laid-Open Japanese Patent Application No. Sho. 61-92850), the metal sheet coated with a lacquer of thermosetting resin containing a wax of hydrocarbon type as a lubricant (Laid-Open Japanese Patent Application No. Sho. 62-275172 and polyes.er resin film laminated steel sheet (Laid-Open Japanese Patent Application No. Sho. 60-168643) have been employed.
These precoated metal sheets for use in DI cans reduce costs because the production process of DI cans is simplified. However, the quality of DI cans produced from ~ A 1 3 3 ~ 0 4 2 these precoated metal sheets is inferior to that of the DI
cans produced by the present process. For exampie, the lacquered metal sheets shown in Laid-Open Japanese Patent Application No. ~ho. 61-92850 and Laid-Open Japanese Patent Application No. ~ho. 62-275172 are not used for DI cans in which corrosive b~everages are packed without a spray coating of lacquer on the inside of the formed DI cans because many small cracks are observed in the lacquer film coated on the inside of the formed DI cans even if these precoated metal sheets can be easily formed into DI cans.
The characteristics of DI cans produced from a polyethylene terephthalate film laminated steel sheet shown in Laid-Open Japanese Patent Application No. Sho, 60-168643 deteriorate remarkably by reheating upon curing the color printing ink applied on the outside of the forme~ DI can.
Namely, much filiform corrosion arises from the edge of DI
cans reheated for curing the color printing ink during long storage in the atmosphere having high humidity and high temperature.
It is assumed that the cause of filiform corrosion is due to the deterioration of the adhesion of polyethylene terephthalate film to the steel sheet by recrystallization of polyethylene terephthalate film during reheating at above 160C, although the structure of polyethylene terephthalate film may change to the monoaxial oriented state from the amorphous non-oriented state by ironing.
Accordingly, it is the first objective of the present invention to provide a copolyester ~e~irl film laminated steel sheet or strip as a material for DI cans having excel-lent characteristics in the adhesion of copolyester resin film to the steel sheet after forming into DI cans, filiform co~rosion resistance in the formed part after reheating for curing the color printing ink subjected to the outside of ~ A 1 3 3 7 0 4 2 the formed DI cans at the temperature of 160 to 2Q0C and corrosion resistance to the packed contents such as carbonated beverages and fruit juices.
It is the second objective of the present invention to provide a production method of a material for DI cans having an excellent corra~ion resistance which can be used without an inner lacquer coating after forming of DI cans.
BRIEF DESCRIPTION OF THE INVENTION
The first objective of the present invention can be accomplished by the continuous lamination of a copolyester resin film produced from 75 to 95 mole ~ of polyethylene terephthalate and 5 to 25 mole % of other polyester resin having the restricted chemical and physical properties on the one side of the steel sheet having at least hydrated chromium oxide and the deposition of a ductile metal on the other side of the steel sheet.
The second objective of the present invention can be accomplished by the following two methods. The first method is one in which the copolyester resin film precoated with a small amount of resin composite is laminated on the one side of the steel sheet heated to a melting temperature of copolyester resin film + 50C. The second method is one in which said copolyester resin film is directly laminated on the one side of the steel sheet heated to above melting temperature of said copolyester resin film.
The present invention is characterized by the use of the special copolyester resin film having an exce~lent formability and excellent corrosion resistance described above, in addition to the use of the steel sheet in which the one side is covered with at least hydrated chromium oxlde and the other side is plated with a ductile metal. In the present invention, the presence of a hydrated chromium ~ A 1 3 3 7 C 4 2 oxide and a ductile metal layer on each side of the steel sheet are indispehsable in order to obtain excellent adhesion to the copolyeste~ resin film and excellent formability to DI can.
The copolyester resin film laminated steel ~heet according to the present invention can be also used as a material for drawn cans, drawn and redrawn cans, drawn and thin redrawn cans and can ends.
, .
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the copolyester resin film applied on the inside of the DI can is prepared by processing according to a known method, a copolyester resin which is composed of 75 to 95 mole % of polyethylene terephthalate and 5 to 25 mole % of a polyester resin produced by the esterification of at least one saturated polycarboxylic acid with 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, diphenyl carboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and trimellitic acid anhydride.
Saturated polyalcohols are selected from ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol, 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 copolyester resi~ film used for the present invention.
In the present invention, the use of copolyester resin ~ A 1 3 3 7 0 4 2 film having a biaxial oriented structure is especially desirable from the viewpoint of corrosion resistance, although non-oriented copolyester resin film can be also used.
The thickness of the copolyester resin film used in the present invention should be 10 to 50 ~m, preferably 10 to 30 ~m. If the thickness of the employed copolyester resin film is below 10 ~m, many cracks are observed in the copolyester resin film laminated on the steel sheet according to the present invention after forming into the DI can and the continuous lamination of thin copolyester resin film to the steel sheet at high speed becomes remarkably difficult.
Moreover, use of a copolyester resin film above 50 ~m is not economically suitable for the film to be laminated to the steel sheet, because the copolyester resin film used for the present invention is expensive as compared with lacquers widely used in the can industry.
In the present invention, the softening temperature and the melting temperatu~e of the employed copolyester resin film are also importa~t factors. The softening temperature is defined as the temperature at which the insertion of the needle into the copolyester resin film starts at a heating rate of 10C/min. in the thermal mechanical analyzer. (TMA
100 made by Seiko Den~hi Kogyo Co.) The melting temperature is defined as the temperature at which the endothermic peak is obtained at a heat1ng rate of 10C/min. in the differential scanning calorimeter. (SS10 made by Seiko Denshi Kogyo Co.) In the present ipvention, the copolyester resin ~ilm having a 170 to 235C softening temperature and a 190 to 250C melting temperature should be used. The copolyester resin film having the softening temperature of above 235C becomes poor in formability and bonding strength to the ~ A 1 3 3 7 0 4 2 steel sheet because the copolyester resin film is easily crystallized by reheating to cure the color printing ink subjected to the outside of the DI can. On the other hand, if the copolyester resin film having a softening temperature below 170C is used, the efficiency in the production process of the DI can becomes remarkably poor because the copolyester film becomes soft by reheating to cure the color printing ink applied to the outside of the DI can at a higher temperature l0 than the softening temperature of the copolyester resin film.
The use of the copolyester resin film having a melting temperature above 250C is not suitable in the present invention because this copolyester film is rigid and is poor in formability.
If the copolyester resin film having a melting temperature below 190C is applied to the steel sheet for the DI can according to the present invention, many cracks may be observed in the laminated copolyester resin film after flanging and necking the DI can because the mechanical 20 strength of this copolyester resin film becomes remarkably poor by reheating to cure the color printing ink applied to the outside of the DI can. Therefore, the use of the copolyester resin film having a melting temperature below 190C is not also suitable in the present invention.
Furthermore, the orientation and mechanical properties of the copolyester resin film are also very important factors from the viewpoint of the formability of the copolyester resin film.
Namely, in the copolyester resin film used in the 30 present invention, the orientation coefficient which is defined as the degree of the orientation of the copolyester resin should be in the range of 0 to 0.100. The orientation coefficient defined above is determined by a refraction meter and is shown by the following equation in the present invention.
A=(B+C)/2-D
where, A represents the orientation coefficient of the copolyester resin film, B represents the index of refraction in the lengthwise direction of the copolyester film, C represents the index of refraction in the widthwise direction of the copolyester resin film, D represents the index of refraction in the thickness direction of the copolyester resin film.
If the copolyester resin film having above 0.100 of the orientation coefficient is applied to the steel sheet according to the present invention, many cracks arise in the copolyester resin film laminated to the sheel sheet after forming to DI can, because the formability of this copolyester resin film becomes remarkably poor.
In the present invention, an elongation at break and a strength at break of the employed copolyester resin film, which are determined at the speed of 100 mm/min. at 25C in an ordinary tensile testing machine, should be in the range of 150 to 500 % and 3 to 18 kg/mm2, respectively. If the copolyester resin film having below 150 ~ of elongation at break is used in the present invention, many cracks arise in the copolyester resin film after forming into DI cans, because the formability of this copolyester resin film becomes remarkably poor. On the other hand, if the copolyester resin film having above 500 % of elongation at break is used in the present invention, this film is easily .
- ~Al 337042 damaged by severe forming because the thickness of this copolyester resin film becomes non-uniform during production of this film from the extruder.
- 8a -~ The copolyester resin film having above 18 kg/mm2 of ~ A 1 3 3 7 0 4 2 strength at break is poor in formability and the bonding strength to the steel sheet covered with hydrated chromium oxide. Therefore, if this copolyester resin film is used in the present invention, this film is easily peeled off from the surface of the steel sheet with many cracks. On the other hand, if the cQpolyester resin film having below 3 kg/mm2 of the strength at break is used in the present invention, this copolyester resin film is easily damaged by scratches in the process for making of DI can, because this film has poor toughness.
In the present invention, the copolyester resin film selected by various restrictions described above is laminated on the steel sheet by the following two methods. The first method comprises laminating a copolyester resin film which has been precoated with a small amount of resin composite to a steel sheet. The second method comprises laminating a copolyester resin film directly to a steel sheet which is heated to above a melting temperature of said copolyester resin film.
In the first method, the copolyester resin film which has been precoated with 0.1 to 5 gJm2 of a resin composite containing in its molecular structure at least one radical consisting of epoxy radical, hydroxyl radical, amide radical, ester radical, carboxyl radical, urethane radical, acryl radical and amino radical is laminated to a steel sheet which is heated to a melting temperature of said copolyester resïn film + 50C.
At below 0.1 g/m2 of the resin composite, the bonding strength of he copolyester resin fiim to the steel sheet in the body wall of the formed DI can becomes unstable because the resin composlte is not precoated uniformly and thinly to said copolyester resin film.
_g_ At above 5.0 g/m2 of the resin composite, the copolyester ~A 1 337042 resin film in the body wall of the formed DI can is easily peeled off from the surface of the steel sheet.
Furthermore, if the heating temperature of the steel sheet is below the melting temperature -50C, said polyester resin film is easily peeled off from the surface of the steel sheet or an interface between copolyester resin film and resin composite layer after forming into DI cans.
In the case of the melting temperature of said copolyester resin film +50C in the heating temperature of the steel sheet, the body wall of the obtained DI can is remarkably corroded because said copolyester resin film deterlorates by heating at higher temperature.
In the second method, the copolyester resin film is directly laminated on the steel sheet which is heated to the melting temperature +50C. If the heating temperature of the steel sheet is below the melting temperature of said copolyester resin film, said copolyester resin film laminated on the steel sheet is easily peeled off after forming to DI
can. If the temperature of the heated steel sheet is above the melting temperature of said copolyester resin film +50C, the body wall of the obtained DI can is easily corroded because said copolyester resin film deteriorates by heating at higher temperature as in the first method.
In the first method and the second method of the present invention, it is desirable that the copolyester resin film laminated steel sheet be rapidly cooled compared with gradual cooling, because said copolyester resin film is slightly recrystallized in the cooling stage from the higher temperature than the melting temperature of said copolyester resin film.
Especially, the presence of the resin composite between said copolyester resin film and the steel sheet prevents the growth of filiform corrosion at a severely formed part, ~ A 1 3 3 7 0 4 2 while the formed DI can is kept at an atmosphere having higher temperature and higher humidity for long time before the contents such as carbonated beverage is packed into the formed DI can. Therefore, the copolyester resin film laminated steel sheet by the first method i5 preferable to that by the second method.
In the present invention, a surface treated steel sheet having at least hydrated chromium oxide is used.
Especially, the presence of an optimum amount of hydrated chromium oxide in the one side of the steel sheet wherein the copolyester resin film is laminated is indispensable in order to obtain an excellent adhesion of the steel sheet to the copolyester resin film or the resin composite. The optimum range for the amount of hydrated chromium oxide as chromium is 0.005 to 0.050 g/m2, preferably 0.010 to 0.030 g/m2 on said metal sheet.
If the amount of hydrated chromium oxide as chromium is below 0.005 g/m2 or above 0.050 g/m2, the adhesion of the copolyester resin film may become poor in a severely formed part.
Furthermore, where excellent corrosion resistance is required inside the obtained DI can, the steel sheet covered with at least one metal selected from the group consisting of chromium, nickel, tin, zinc and aluminum under the hydrated chromium oxide layer should be used for the copolyester resin film laminated steel sheet according to the present invention.
The optimum range for the amount of plated chromium, nickel, tin, zinc and alum~num ic '!.01 ~o '! 30 g~m2, U.U~ fn 1.0 g/m2, J.Ol .o 10.0 g/m2, 0.5 to 2.0 g/m2 and 0.1 to 0.7 g/m2, respectively.
If the amount of each plated metal is below the lower limit, the effect of the plated metal on the corrosion resistance in the inside of the DI can is very small, despite further plating. On the other hand, the deposition of each metal above the upper limit is not suitable from the viewpoint of economy, as the corrosion resistance in the inside of the DI can is not remarkably improved.
On the other hand, one side of the steel sheet for the outside of the DI can should be plated with at least one ductile metal selected from the group consisting of tin, nickel, zinc and aluminum.
The optimum range for the amount of a plated ductile metal should be controlled at 0.5 to 11.2 g/m2 in tin, 0.5 to 5.0 g/m2 in nickel, 1.0 to 10.0 g/m2 in zinc and 1.0 to 5.0 g/m2 in aluminum, respectively. If the amount of a ductile metal is below the lower limit, the formability to DI cans becomes remarkably poor. The deposition of each ductile metal of above the upper limit is not suitable from the viewpoint of economy, although the formability does not change.
The surface af the plated ductile metal may be chemically treated by chromate or phosphate solution by electrolytical methods, immersion or spray methods, if these treatments have no bad effects on the formability of the DI -can.
The present invention is explained in further detail by reference to the following examples.
TFS film con~isting of a lower layer of 0.12 g/m2 of metallic chromium and an upper layer of 0.015 g/m2 of hydrated chromium oxide as chromium was formed on the one side of the steel strip having a thickness of 0.30 mm and a temper of T-2.5 by a known electrolytic chromic acid treatment.
After rinsing with water, 5.6 g/m2 of tin was electroplated ~- 1 337042 on the other side of said steel strip by using a known tinplating electrolyte and was rinsed with water and dried.
The obtained surface treated steel strip was heated to 220C by using a roll heater and then a biaxially oriented copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 80 mole % of terephthalic acid and 20 mole % of isophthalic acid having a thickness of 25 ~m, softening temperature of 176C, melting temperature of 215C, elongation at break of 330 %, strength at break of 8.2 kg/mm2 and orientation coefficient of 0.024 was laminated on one side having a TFS
film on said steel strip. After that, said copolyester resin film laminated steel strip was rapidly quenched and then dried.
The thus copolyester resin film laminated steel strip was formed into a DI can in which the copolyester resin film was laminated to the inside of the can under the following conditions:
~ Forming conqitions of a DI can) l.Diameter of sample blank: 123.5 mm 2.Drawing ratio in the first drawing: 1.82 3.Drawing ratio in the second redrawing: 1.29 4.Diameter of an ironing punch: 52.64 mm 5.Total ironing ratio: 64 %
2.8 g/m2 of tin was electroplated on both sides of the same steel strip as in Example 1 by using a known tinplating electrolyte. After rinsing with water, 0.006 g/m2 of hydrated chromium oxide film as chromium was formed on said tin plated steel strip by a known electrolytic chromic acid treatment and then rinsed with water and dried.
The same copolyester resin film as in Example 1 was - ~ ~337042 laminated on the one side of said tin plated steel strip under the same laminating conditions as in Example 1.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same forming conditions as in Example 1.
A copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 85 mole % of terephthalic acid and 15 mole % of isophthalic acid having a thickness of 30 ~Im~ softening temperature of 192C melting temperature of 239C, elongation at break of 210 %, strength at break of 12.3 kg/mmZ and orientation coefficient of 0.065 was laminated on the one side having TFS film of the same steel strip as in Example 1 which is heated to 240C by using a roll heater and then was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
The same copolyester resin film as in Example 3, which is precoated with 0.2 g/m2 ~drying weight) of a resin composite consisting of 80 parts of epoxy resin having an epoxy equivalent of 3000 and 20 parts of resol of paracresol type, was laminated on the one side of the same tin plated steel strip as in Example 2 which was heated to 220C and then was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
1 33704~
A biaxially oriented polyethylene terephthalate film having a thickness of 25 ~m, softening temperature of 242C, melting temperature of 260C, elongation at break of 131 %, strength at break of 23.2 kg/mm2 and orientation coefficient of 0.147 was laminated on the one side having a TFS film of the same steel strip as in Example 1 which was heated to 300C by using a roll heater and then was rapidly quenched and dried.
The thus polyethylene terephthalate film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
A copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 85 mole % of terephthalic acid and 15 mole % of isophthalic acid having a thickness of 30 ~m, softening temperature of 194C, melting temperature of 241C, elongation at break of 190 %, strength at break of 13.6 kg/mm2 and orientation coefficient of 0.129 was laminated on the one side having TFS film of the same steel strip as in Example 1 which was heated to 240C by using a roll heater. After that, said copolyester resin film laminated steel strip was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed to a DI can under the same conditions as in Example 1.
A copolyester resin film produced from a condensation of ethylene glycol and polycarboxylic acid consisting of 96 mole % of terephthalic acid and 4 mole % of isophthalic acid 1 3370~
having a thickness of 30 ~m, softening temperature of 235C, melting temperature of 250C, elongation at break of 155 %, strength at break of 20.6 kg/mm2 and orientation coefficient of 0.131, which was precoated with the same resin composite as in Example 4, was laminated on the one side of the same steel strip as in Example 2 which was heated to 220C by using a roll heater. After that, said copolyester resin film laminated steel strip was rapidly quenched and dried.
The thus copolyester resin film laminated steel strip was formed into a DI can under the same conditions as in Example 1.
The characteristics of the resultant drawn and ironed can was evaluated by the following methods, after washing the coolant oil for forming a DI can, drying, heating at 190C for 15 minutes which corresponds to conditions for curing the lacquer and printing ink subjected to the outside of the DI can and flange forming.
The results are shown in the Table.
(1) Degree of the exposed metal in the inside of a DI
can.
After 1 % sodium chloride solution was filled in the DI
can, the degree of the exposed metal was evaluated by a current value which was flown between an anode of said DI
can and a cathode of a stainless steel rod inserted in said DI can at constant voltage of 6.3 volts.
(2) Filiform corrosion during storage.
The filiform corrosion which grows near the flange parts in the inside of the DI can was evaluated after storage for 3 months at a relative humidity of 92 % at 27C.
The obtained filiform corrosion resistance was divided into 5 ranks, namely 5 was excellent, 4 was good, 3 was fair, 2 was poor and 1 was bad.
(3) Degree of cracks of polyester resin film in the flange part after seaming.
A lacquered alllm;nllm lid was double-seamed to the DI
can. The degree of cracks of polyester resin film in the flange part near the seaming part was observed after removing the seamed aluminum lid.
(4) Corrosion resistance by pack test.
A lacquered aluminum lid was double-seamed after Coca Cola was filled in the DI can. After the storage for 3 months at 37C, the degree of corrosion was observed by naked eye with measurement of iron pick up.
T~LE
Comp Comp Comp EX. 1 EX. 2 EX. 3 EX. 4 ex. 1 ex. 2 ex. 3 Coating weight in outsid2e Sn 5.6 Sn 2.8 Sn 5.6 ~n 2.8 Sn 5.6 Sn 5.6 Sn 2.8 of the formed ean (g/m ) Cr~0.006 Cr~0.006 CrXO.
Coating weight in inside- Cr 0.12 Sn 2.8 Cr 0.12 Sn 2.8 Cr 0.12 Cr 0.12 Sn 2.8 of the formed can (g/m2) Cr~0.015 CrX0.006 Cr~0.015 Cr~0.006 CrX0.015 Cr~0.015 Cr~0~00 So tening temp.(~) 7 :7. :9 5: 4~ :9~ ~3 Characte- Me_ting temp. (C _1 1 3 3 6 _4: ~5 ristics ~~r entation coeff_cient . 24 ~. 24 ~.~65 ~. 65 . 47 ._29 . 31 of employed longation at break ~%) 3 3 1 ~1 _3_ 9 -5 copolyester trength at break (kg/mm2) .~ .~ _2.3 _2.3 ~3.2 _3.6 ,0.6 resin film Meta: Exposure (mA) ~.03 .01 ~.10 .50 .88 302 Peeloff ~ili orm Corr. resistanee ~ ~ . 2 -----Characte- ~raccs by seaming .o crack :o crack i-o crack o crack ~any micro cracks -----ristics of ron pick up (ppm) .05 .02 .13 .42 1.20 14.8 -----the formed ~orr. by pack test ~-ood ~-ood ~-ood ~-ood Pitting Pitting -----DI can Remarks: *Cr represents metallic chromium and Cr~represents chromium in hydrated chromium oxide.
~*Peel off represents peeling off of the laminated copolyester resin film.
~,
Claims (10)
1. A polyester resin film laminated steel sheet or strip for a drawn and ironed can which comprises:
laminating a copolyester resin film produced from a copolyester resin consisting essentially of 75 to 95 mole %
of polyethylene terephthalate and 5 to 25 mole % of a polyester resin, produced by the esterification of at least one saturated polycarboxylic acid and at least one saturated polyalcohol, said film having a thickness of about 10 to 50 µm, a softening temperature of about 170 to 235°C, melting temperature of about 190 to 250°C, an elongation at break of about 150 to 500 % and strength at break of about 3 to 18 kg/mm2, to one side of said steel sheet or strip which is first covered with at least hydrated chromium oxide, said side to be used for the inside of said drawn and ironed can and said other side of said steel sheet to be used for the outside of said drawn and ironed can being plated with a ductile metal selected from the group consisting of chromium, nickel, tin, zinc and aluminum.
laminating a copolyester resin film produced from a copolyester resin consisting essentially of 75 to 95 mole %
of polyethylene terephthalate and 5 to 25 mole % of a polyester resin, produced by the esterification of at least one saturated polycarboxylic acid and at least one saturated polyalcohol, said film having a thickness of about 10 to 50 µm, a softening temperature of about 170 to 235°C, melting temperature of about 190 to 250°C, an elongation at break of about 150 to 500 % and strength at break of about 3 to 18 kg/mm2, to one side of said steel sheet or strip which is first covered with at least hydrated chromium oxide, said side to be used for the inside of said drawn and ironed can and said other side of said steel sheet to be used for the outside of said drawn and ironed can being plated with a ductile metal selected from the group consisting of chromium, nickel, tin, zinc and aluminum.
2. The polyester resin film laminated steel sheet or strip according to claim 1 wherein 5 to 25 mole % of copolyester resin is produced by the esterification of at least one 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 at least one saturated polyalcohol selected from the group consisting of ethylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol, trimethylol propane and pentaerythritol.
3. The polyester resin film laminated steel sheet or strip according to claim 1 wherein said copolyester resin film has been precoated with about 0.1 to 5 g/m2 of a resin composite containing in its molecule at least one radical selected from the group consisting of epoxy radical, hydroxyl radical, amide radical, ester radical, carboxyl radical, urethane radical, acryl radical and amino radical.
4. The polyester resin film laminated steel sheet or strip according to claim 1 wherein the amount of said hydrated chromium oxide formed on said steel sheet or strip in which said copolyester resin film is laminated is about 0.005 to 0.050 g/m as chromium.
5. The polyester resin film laminated steel sheet or strip according to claim 1 wherein the surface of said steel sheet in which said copolyester resin film is laminated is plated with at least one metal selected from the group consisting of about 0.01 to 0.30 g/m2 of chromium, 0.3 to 1.0 g/m2 of nickel, 0.01 to 10.0 g/m2 of tin, 0.5 to 2.0 g/m2 of zinc and 0.1 to 0.7 g/m2 of aluminum before the formation of hydrated chromium oxide.
6. The polyester resin film laminated steel sheet or strip according to claim 1 wherein the one side of said steel sheet to be used for the outside of said drawn and ironed can is plated with at least one ductile metal selected from the group consisting of about 0.5 to 11.2 g/m2 of tin, 0.5 to 5.0 g/m2 of nickel, 1.0 to 10.0 g/m2 of zinc and 1.0 to 5.0 g/m2 of aluminum.
7. The method for production of the polyester resin film laminated steel sheet or strip according to claim 1 wherein said copolyester resin film is directly laminated to the one side of said steel sheet or strip heated to a melting temperature of said copolyester resin film to a melting temperature + 50°C and then is rapidly quenched.
8. The method for production of the polyester resin film laminated steel sheet or strip according to claim 3 wherein said copolyester resin film precoated with the resin composite is laminated on the one side of said steel sheet or strip heated to a temperature in the range of a melting temperature of said copolyester resin film ? 50°C and then is rapidly quenched.
9. The method for production of the polyester resin film laminated steel sheet or strip according to claim 1 wherein the copolyester resin film has a degree of orientation of between about 0 and 0.100.
10. A drawn and ironed can produced from the polyester resin film laminated steel sheet or strip of claim 1.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000581640A CA1337042C (en) | 1988-10-19 | 1988-10-28 | Polyester resin film laminated steel sheet for drawn and ironed can and method for production thereof |
| DE3836858A DE3836858A1 (en) | 1988-10-19 | 1988-10-28 | Steel sheeting coated with a polyester resin film, in particular for drawn-and-ironed cans, and process for the production thereof |
| GB8825292A GB2224238B (en) | 1988-10-19 | 1988-10-28 | Improvements in polyester resin film laminated steel sheet |
| FR888814174A FR2638429B1 (en) | 1988-10-19 | 1988-10-28 | STEEL SHEET COATED WITH POLYESTER RESIN FILM AND PROCESS FOR PRODUCING THE SAME |
| US07/531,622 US5094924A (en) | 1988-10-19 | 1990-06-01 | Polyester resin film laminated steel sheet for drawn and ironed can |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25970588A | 1988-10-19 | 1988-10-19 | |
| CA000581640A CA1337042C (en) | 1988-10-19 | 1988-10-28 | Polyester resin film laminated steel sheet for drawn and ironed can and method for production thereof |
| DE3836858A DE3836858A1 (en) | 1988-10-19 | 1988-10-28 | Steel sheeting coated with a polyester resin film, in particular for drawn-and-ironed cans, and process for the production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1337042C true CA1337042C (en) | 1995-09-19 |
Family
ID=27168090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000581640A Expired - Fee Related CA1337042C (en) | 1988-10-19 | 1988-10-28 | Polyester resin film laminated steel sheet for drawn and ironed can and method for production thereof |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1337042C (en) |
| DE (1) | DE3836858A1 (en) |
| FR (1) | FR2638429B1 (en) |
| GB (1) | GB2224238B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5071690A (en) * | 1989-02-01 | 1991-12-10 | Diafoil Company, Limited | Moldable biaxially stretched polyester film |
| GB2234704B (en) * | 1989-07-28 | 1993-04-14 | Toyo Kohan Co Ltd | Method for producing steel sheet laminated with a polyester resin film |
| JP2803854B2 (en) * | 1989-08-30 | 1998-09-24 | 新日本製鐵株式会社 | Composite steel sheet excellent in formability of drawn and ironed cans |
| JPH0755552B2 (en) * | 1989-09-18 | 1995-06-14 | 東洋製罐株式会社 | Deep drawing can manufacturing method |
| CA2029943C (en) * | 1989-11-15 | 1999-10-12 | Ryousuke Wake | Resin-coated steel sheet for drawn-and-ironed cans and drawn-and-ironed cans manufactured therefrom |
| GB2242159B (en) * | 1990-03-19 | 1994-02-02 | Toyo Kohan Co Ltd | Copolyester resin film-metal sheet laminates |
| CA2019861C (en) * | 1990-06-26 | 1995-10-17 | Hiroaki Kawamura | Tin-plated steel sheet with a chromium bilayer and a copolyester resin laminate and method |
| DE4023909A1 (en) * | 1990-07-27 | 1992-01-30 | Wild Rudolf Gmbh & Co | REUSABLE PLASTIC CONTAINER AND ITS PRODUCTION AND USE |
| EP0542104B1 (en) * | 1991-11-08 | 1999-04-21 | Nippon Steel Corporation | Coated steel can lid with opening arrangement not requiring repair coating on outer and inner surfaces |
| US5234516A (en) * | 1992-01-28 | 1993-08-10 | Toyo Kohan Co., Ltd. | Method for production of a polyethylene laminated metal sheet |
| CA2077811A1 (en) * | 1992-09-09 | 1994-03-10 | Takaaki Okamura | Polyester laminated metal sheet |
| GB2276347B (en) * | 1993-03-26 | 1997-01-29 | Toyo Kohan Co Ltd | Double layered thermoplastic resin laminated metal sheet |
| NL9301373A (en) * | 1993-08-06 | 1995-03-01 | Toyo Kohan Co Ltd | Polyester laminated metal sheet. |
| CA2108728C (en) * | 1993-10-19 | 2001-02-13 | Takaaki Okamura | Metal sheet laminated with triple layered thermoplastic resin and a method for producing thereof |
| GB2285952B (en) * | 1994-01-19 | 1997-06-25 | Toyo Kohan Co Ltd | Metal sheet covered with polyester resin film for drawn and stretch formed can |
| EP0664209A1 (en) * | 1994-01-24 | 1995-07-26 | TOYO KOHAN Co., Ltd | Metal sheet laminated with resin films |
| DE4447776C2 (en) * | 1994-02-02 | 2002-07-18 | Toyo Kohan Co Ltd | Metal sheet laminated with polyester film, useful for food or beverage container |
| US5686194A (en) * | 1994-02-07 | 1997-11-11 | Toyo Kohan Co., Ltd. | Resin film laminated steel for can by dry forming |
| US6098829A (en) * | 1994-11-30 | 2000-08-08 | Mchenry; Robert J. | Can components having a metal-plastic-metal structure |
| JP3575117B2 (en) * | 1995-06-06 | 2004-10-13 | 東洋製罐株式会社 | Two-piece drawn ironing can with excellent corrosion resistance and flavor resistance and method for producing the same |
| JP5609012B2 (en) * | 2009-05-28 | 2014-10-22 | 東洋製罐株式会社 | Steel drawn iron can and method for producing the same |
| CN102658699A (en) * | 2012-05-25 | 2012-09-12 | 任丘市京开塑业有限公司 | Thin film directly thermally laminated on tinned plate |
| RS62535B1 (en) * | 2017-12-05 | 2021-11-30 | Tata Steel Ijmuiden Bv | Method for producing polymer coated steel sheet for 3-piece cans |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2965613A (en) * | 1954-03-02 | 1960-12-20 | Goodyear Tire & Rubber | Copolyesters |
| LU33680A1 (en) * | 1955-06-16 | 1900-01-01 | ||
| US3382295A (en) * | 1963-08-12 | 1968-05-07 | Goodyear Tire & Rubber | Blend of amorphous polyesters as fluidized bed coating material |
| GB1329723A (en) * | 1970-09-08 | 1973-09-12 | Ici Ltd | Laminated sheets of metals and plastics |
| US3870594A (en) * | 1971-08-16 | 1975-03-11 | Yodogawa Steel Works Limited | Laminated metal-based facing |
| JPS5420940B2 (en) * | 1973-04-03 | 1979-07-26 | ||
| JPS5192739A (en) * | 1975-02-13 | 1976-08-14 | Tairyukaseito taisumatsujiseino suguretadenkiburiki | |
| JPS5323833A (en) * | 1976-08-18 | 1978-03-04 | Toyo Kohan Co Ltd | Surface treated steel sheet for coating |
| AU526377B2 (en) * | 1978-02-23 | 1983-01-06 | Broken Hill Proprietary Company Limited, The | The manufacture of tinplate and tinplate containers |
| JPS56130273A (en) * | 1980-03-19 | 1981-10-13 | Nippon Steel Corp | Manufacture of precoated steel plate |
| GB2118459B (en) * | 1982-03-25 | 1986-03-26 | Koop Wijnbouers Zuid Afrika | Coating of a surface |
| DE3227282A1 (en) * | 1982-07-21 | 1984-01-26 | Toyo Kohan Co., Ltd., Tokyo | Metal sheet coated with polyester resin film and process for manufacture thereof |
| US4551368A (en) * | 1982-09-07 | 1985-11-05 | The Goodyear Tire & Rubber Company | Polyester melt blends having high gas barrier properties |
| DE3401559A1 (en) * | 1984-01-18 | 1985-07-25 | Dynamit Nobel Ag, 5210 Troisdorf | COATING AGENTS |
| GB2164899B (en) * | 1984-09-28 | 1988-01-27 | Toyo Kohan Co Ltd | Method for production of metal sheet covered with polyester resin film |
| DE3436412A1 (en) * | 1984-10-04 | 1986-04-17 | Toyo Kohan Co., Ltd., Tokio/Tokyo | Process for the lamination of metal sheeting with polyester film |
| JPH082950B2 (en) * | 1985-05-31 | 1996-01-17 | 株式会社クラレ | Copolyester film |
| EP0222282A3 (en) * | 1985-11-04 | 1987-08-19 | HENKEL CORPORATION (a Delaware corp.) | Process for coating metal surfaces with organic layers |
| AU583444B2 (en) * | 1986-01-24 | 1989-04-27 | Kawasaki Steel Corporation | Organic coated steel strip having improved bake hardenability and method for making |
| US4808720A (en) * | 1986-06-09 | 1989-02-28 | Stauffer Chemical Company | Certain 3-benzoyl-4-oxolactams |
| US4885215A (en) * | 1986-10-01 | 1989-12-05 | Kawasaki Steel Corp. | Zn-coated stainless steel welded pipe |
| KR910002492B1 (en) * | 1987-03-13 | 1991-04-23 | 닛뽄 고오깐 가부시끼가이샤 | Highly corrosion-resistant multi-layer coated steel sheets |
| DE3882769T2 (en) * | 1987-03-31 | 1993-11-11 | Nippon Steel Corp | Corrosion-resistant plated steel strip and process for its manufacture. |
-
1988
- 1988-10-28 CA CA000581640A patent/CA1337042C/en not_active Expired - Fee Related
- 1988-10-28 FR FR888814174A patent/FR2638429B1/en not_active Expired - Lifetime
- 1988-10-28 DE DE3836858A patent/DE3836858A1/en active Granted
- 1988-10-28 GB GB8825292A patent/GB2224238B/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2638429B1 (en) | 1991-01-25 |
| DE3836858C2 (en) | 1992-12-24 |
| GB2224238B (en) | 1992-06-17 |
| GB2224238A (en) | 1990-05-02 |
| DE3836858A1 (en) | 1990-05-10 |
| FR2638429A1 (en) | 1990-05-04 |
| GB8825292D0 (en) | 1988-11-30 |
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