WO2002076727A2 - Korrosionsstabiles laminat, verfahren zu seiner herstellung und seine verwendung - Google Patents
Korrosionsstabiles laminat, verfahren zu seiner herstellung und seine verwendung Download PDFInfo
- Publication number
- WO2002076727A2 WO2002076727A2 PCT/EP2002/003333 EP0203333W WO02076727A2 WO 2002076727 A2 WO2002076727 A2 WO 2002076727A2 EP 0203333 W EP0203333 W EP 0203333W WO 02076727 A2 WO02076727 A2 WO 02076727A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- roller
- laminate
- film
- rollers
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 70
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000004922 lacquer Substances 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 5
- 239000006120 scratch resistant coating Substances 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920006347 Elastollan Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- -1 Hexamethyldisilane cyclohexene Chemical compound 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001499740 Plantago alpina Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000004924 water-based lacquer Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—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 vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
-
- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/408—Matt, dull surface
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/41—Opaque
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/584—Scratch resistance
-
- 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
- B32B2311/30—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
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
-
- 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
- B32B2605/00—Vehicles
- B32B2605/08—Cars
Definitions
- the present invention relates to a new corrosion-resistant laminate which has at least one layer which contains or consists of at least one metal and at least one layer made of a plasma polymer. Furthermore, the present invention relates to a new method for producing the new corrosion-resistant laminate. Last but not least, the present invention relates to the use of the new laminate for the production of molded parts, in particular automobile body parts.
- Laminates which have a metal layer, a plasma polymer layer applied thereon and a lacquer layer, produced from, for example, customary and known two-component epoxy-amine water-based lacquers, one-component clear lacquers, or cathodically depositable electrocoat materials, are from the dissertation by G. Grundmeier, "interfacial chemistry and corrosion analysis of plasma polymer coatings on steel ", Technical Faculty of the University of Er Weg-Nuremberg, 1997, the patent specifications EP 0 533 606 B1, EP 0 619 847 B1 or EP 0 515 373 B2 or from the articles by Tinghao F.
- Unsupported paint films are known for example from German patent DE 195 35 934 C1.
- Lacquered foils for coating car body parts are known from German patents DE 195 17 069 A1, DE 195 17 067 A1 or DE 195 17 068 A1.
- the parts coated with it have excellent stone chip resistance.
- the good corrosion resistance can, however, be further optimized.
- lacquer films The basic concept of such lacquer films is based on the fact that they only have to be glued onto the substrate.
- the systems required for joining flat materials such as adhesive presses or calenders are comparatively simple and unproblematic to operate.
- the corrosion stability of laminates made from these paint films and metals is still not sufficient for all applications.
- the paint films and foils may be detached or delaminated.
- the object of the present invention is to find a new corrosion-stable laminate which no longer has the disadvantages of the prior art, but rather has a high corrosion stability and excellent interlayer adhesion and can be produced in a simple manner.
- At least one layer which contains or consists of at least one metal
- the new laminate is referred to as “laminate according to the invention” and the new processes for producing the laminate according to the invention as “processes according to the invention”.
- the laminate according to the invention contains at least one layer A) which contains or consists of at least one metal.
- layer A) consists of at least one metal.
- suitable metals to be used according to the invention are titanium, iron, cobalt, nickel, magnesium, aluminum, zinc or their alloys with one another or with other suitable metals such as copper, vanadium, tungsten, molybdenum, chromium, manganese or tin.
- those metals are advantageous which are usually used in automobile construction for the production of bodies. They are therefore preferred.
- suitable metals of this type to be used according to the invention are steels, in particular cold-rolled steels and metal-coated thin steel sheets.
- layer A) can have any shape, for example the shape of a fender, a car door, a bonnet or a trunk lid. According to the invention, it is advantageous if layer A) is planar and in particular is in the form of a sheet or strip.
- the thickness of layer A) can vary widely and depends on the particular use of the laminate according to the invention. Thicknesses of 0.05 mm to 10 mm, as are usually used in automobile construction, are advantageous.
- the further essential component of the laminate according to the invention is at least one layer B) made of a plasma polymer.
- Layer B) can be applied to one side or to both sides of the metal sheets or strips to be used according to the invention. Which variant is chosen depends on the intended use of the metal sheets or strips.
- the plasma polymer B) has a thickness of 5 to 200 nm, preferably 10 to 100 nm and in particular 20 to 60 nm.
- the composition of the plasma polymer B) can be homogeneous or it can change vertically in different ways.
- the concentration of a component within layer B) can decrease or increase continuously or discontinuously.
- the plasma polymer B) is called “gradient plasma polymer B)”.
- This gradient plasma polymer B) is distinguished by the fact that it has special functional groups at the metal A) phase boundary (with or without an oxide layer) / Plasma polymer B), for example organosilicon functional groups, and at the phase boundary plasma polymer B) / - adhesive D) (see below), for example hydroxyl, amino or carboxyl groups, which optimizes the adhesion at the interfaces, which leads to The heteroatom functions at the interface with the metal A) bind to the oxide cover layer of the metal A).
- the functional groups on the surface of the plasma polymer B) form chemical bonds to the adhesive D).
- the plasma polymer B) can also consist of layers of different compositions e are treated with an oxygen plasma before the deposition of the plasma polymer.
- the surface of the plasma polymer can be functionalized by treatment with a non-polymerizing plasma (gases such as oxygen, nitrogen or water).
- the further essential component of the laminate according to the invention is at least one film C) made of organic material.
- film also includes self-supporting lacquer films and foils.
- the foils C) themselves can be constructed in one or more layers. Which structure is chosen depends on the optical and / or technical effect which is to be achieved by the film C). Accordingly, pigmented or unpigmented, colored or uncoloured, matt or clear, transparent or opaque lacquer film or lacquered foils with a smooth, rough or structured surface can be used.
- films C) examples of suitable films C) and their production are known from German patent DE 195 35 934. These films C) consist of a carrier film with a defined surface structure, to which a pigmented lacquer hardened with electron beams is applied. There is an adhesive layer on the lacquer layer, which is covered by a protective film. For the application, the protective film is removed and the film C) is connected to the substrate via the adhesive layer.
- suitable films C) and their production are known from German patents DE 195 17 069, DE 195 17 067 A1 or DE 195 17 068 A1.
- These films C) contain a carrier film made of plastic with a thickness of 10 to 500 ⁇ m, which can also be pigmented.
- An effect layer, a filler layer and / or a pigmented lacquer layer can be applied to its surface.
- These layers can also be coated with a clear lacquer or covered with a peelable film.
- multilayer films are suitable as films C), the clearcoat of which consists of thermoplastic polymers, for. B. polyvinylidene fluoride (PVdF).
- PVdF polyvinylidene fluoride
- Such films are commercially available, for example, as an “In-Mold Surfacing Film” from 3M / REXAM.
- the multilayer films described in patent applications WO94 / 09983 and EP 0361 823 A1 can also be used as films C).
- Their clear layers consist of PVdF / polyacrylate mixtures and their pigmented color layers based on PVdF or polyvinyl chloride are applied via a connecting layer or directly thereon. These foils C) are applied to the molded part to be foiled via an adhesive layer after an optional carrier layer has been removed beforehand.
- clear layers made of thermoplastic polymethyl methacrylate (PMMA), which are preferably obtained by coextrusion with the carrier layer and / or base layer (A. Grefenstein in Kunststoffe 87 (1997), 1332-1343), can also be used.
- a customary and known adhesive and / or a primer D) can be located between layer B) and layer C).
- the laminate according to the invention is produced by I) providing a layer A) containing or consisting of at least one metal,
- Process steps I) to III) can be carried out using customary and known processes and devices.
- the film C) can be applied with the aid of customary and known devices such as adhesive presses or calenders.
- the following method according to the invention for producing the laminate according to the invention proves to be particularly advantageous, which primarily serves for the continuous production thereof.
- FIG. 1 does not reproduce the device (1) to scale, but is intended to explain the essential functions of the device (1) in the form of a schematic diagram.
- the pair of rollers (4) is coupled to a feed roller (8) and, together with a roller of the pair of rollers (4), serves to feed the film C) (9) through the Nip (4b) to the nip (4a).
- the film C) (9) is optionally coated on the side which is connected to the layer A) with an adhesive D).
- the device (1) also contains conventional and known feed devices and discharge devices for the starting compounds of plasma polymerization and for other substances such as inert gases, devices for generating vacuum, heat, cold and plasma, gas-tight locks, mechanical and electric motors, conveying devices, mechanical, pneumatic, magnetic and electronic measuring and regulating devices, sealing devices and calender rolls, presses and winding devices as well as, if necessary, cutting devices for the laminates according to the invention. For the sake of clarity, these devices are not shown in FIG. 1.
- the layer A) (10) is forced through the gap (2a) of the first pair of rollers into the first reaction space (6), in which one of its surfaces (10a) is treated with plasma, so that this surface (10a) is cleaned and / or is provided with an oxidic top layer.
- the layer A) (10) pretreated on one side is forced through the gap (3 a) of the second pair of rollers into the second reaction space (7), in which the plasma polymer B) is formed on the pretreated surface (10a) by plasma polymerization of at least one suitable starting compound.
- the layer A) (10) coated on one side with the plasma polymer B) is conveyed further and its coated side is connected to the film C) (9) in the gap (4a) of the pair of rollers (4), resulting in the laminate (11) according to the invention ,
- the laminate (11) according to the invention can still be pressed hot and can be handled further in a customary and known manner. For example, it can be wound into coils and / or cut into smaller pieces. This can then be suitably shaped into three-dimensional objects.
- the device (1) and the method according to the invention can easily be modified so that the coating of layer A) (10) with the plasma polymers B) and the films C) can be carried out on both sides.
- the same devices as described above need be added to the device (1) of FIG. 1 on the other side of layer A) (10).
- the mutually opposite plasma polymers B) and / or the mutually opposite films C) (9) can each differ from one another in terms of material if this is required by the respective intended use.
- the laminate according to the invention has excellent adhesion of layers A), B) and C) to one another. It is extremely stable against mechanical and chemical influences and exposure to radiation. Even after violent damage to the laminate according to the invention, it proves to be corrosion-stable. Its particular advantage lies in its deep-drawing ability, so that it can be easily formed into molded parts, in particular car body parts.
- Production Example 1 The production of a plasma polymer B) on a steel sheet
- the plasma polymer was used in the plant as described in the articles by G. Grundmeier and M. Stratmann, "Plasma polymerization - a new and pro ising way for the corrosion protection of steel", Materials and Corrosion, Volume 49, pages 150 to 160, 1998, is described.
- a multi-layer plasma polymer was used in accordance with the dissertation by G. Grundmeier, "Interface chemical and corrosion analysis of plasma polymer coatings on steel", Technical Faculty of the University of Er Weg-Nümberg, 1997, pages 140 and 141. The process parameters are shown in Tables 1 and 2.
- a plasma polymer B) with a thickness of 20 nm resulted.
- a white pigmented thermoplastic 60 ⁇ m thick polyurethane film (Elastollan® EL 1184A from Elastogran GmbH) is fixed on a metal sheet and coated with a commercially available white pigmented non-aqueous top coat (dry film thickness: 20 ⁇ m). The basecoat is baked at 130 ° C for 30 minutes.
- a transparent polyester film (Melinex®, ICI) with a 20 ⁇ m thick adhesive layer made of a polyester based on 1,4-butanediol and terephthalic acid / isophthalic acid is applied to the coated side of the film coated in this way (1: 1) has been pressed on at a temperature of 150 ° C and a pressure of 25 bar.
- the laminate obtained in this way is detached from the metal support and laminated at a temperature of 220 ° C. and a pressure of 50 bar onto the side of the steel sheet A) coated with the plasma polymer B) (cf. the manufacturing example).
- the adhesion promoter layer of a white pigmented, thermoplastic 60 ⁇ m thick polyurethane film (Elastollan® EL 1184A from Elastogran GmbH) provided with a 20 ⁇ m thick adhesion promoter layer made of a polyester based on butanediol 1,4 and terephthalic acid / isophthalic acid (1: 1) is coated with a Release paper covered. The uncovered side of the film is then coated with a commercially available white-pigmented, non-aqueous varnish (dry film thickness: 20 ⁇ m). The basecoat is baked at 130 ° C for 30 minutes.
- a white pigmented, thermoplastic 60 ⁇ m thick polyurethane film (Elastollan® EL 1184A from Elastogran GmbH) provided with a 20 ⁇ m thick adhesion promoter layer made of a polyester based on butanediol 1,4 and terephthalic acid / isophthalic acid (1: 1) is coated with a Release paper covered. The
- a transparent polyester film (Melinex®, ICI), which has been provided with a 20 ⁇ m thick adhesive layer made of a polyester based on butanediol 1,4 and terephthalic acid / isophthalic acid (1: 1), is added to the coated side of the film coated in this way a temperature of 150 ° C and a pressure of 25 bar. After the release paper has been removed, the laminate obtained in this way is laminated at a temperature of 220 ° C. and a pressure of 50 bar onto the side of the steel sheet A) coated with the plasma polymer B) (cf. the manufacturing example).
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002256705A AU2002256705A1 (en) | 2001-03-24 | 2002-03-25 | Corrosion-stable laminate, method for the production thereof, and its use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10114468.7 | 2001-03-24 | ||
DE10114468A DE10114468B4 (de) | 2001-03-24 | 2001-03-24 | Verfahren zur Herstellung von beschichteten Formteilen und ihre Verwendung |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002076727A2 true WO2002076727A2 (de) | 2002-10-03 |
WO2002076727A3 WO2002076727A3 (de) | 2002-12-27 |
Family
ID=7678841
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/003333 WO2002076727A2 (de) | 2001-03-24 | 2002-03-25 | Korrosionsstabiles laminat, verfahren zu seiner herstellung und seine verwendung |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU2002256705A1 (de) |
DE (1) | DE10114468B4 (de) |
WO (1) | WO2002076727A2 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1947212A1 (de) * | 2007-01-19 | 2008-07-23 | Xxentria Technology Materials Co., Ltd. | Verfahren zur Herstellung eines Architekturlaminats |
WO2023032958A1 (ja) * | 2021-08-30 | 2023-03-09 | 国立大学法人大阪大学 | 樹脂層と金属層との積層体及びその製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014108187A1 (de) * | 2014-06-11 | 2015-12-17 | Thyssenkrupp Steel Europe Ag | Fahrzeugaußenhautteil |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5290378A (en) * | 1990-03-14 | 1994-03-01 | Bridgestone Corporation | Method for preparing a rubber-based composite material |
US5895723A (en) * | 1993-08-26 | 1999-04-20 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Composite films |
WO2001061069A2 (en) * | 2000-02-18 | 2001-08-23 | University Of Cincinnati | Plasma polymerized primers for metal pretreatment |
WO2002020875A2 (de) * | 2000-09-05 | 2002-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur haftfesten metallbeschichtung |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4980196A (en) * | 1990-02-14 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Method of coating steel substrate using low temperature plasma processes and priming |
FR2681334A1 (fr) * | 1991-09-18 | 1993-03-19 | Siderurgie Fse Inst Rech | Procede et dispositif de revetement d'un produit metallurgique par des couches de polymere et produit obtenu par ce procede. |
US5182000A (en) * | 1991-11-12 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Method of coating metal using low temperature plasma and electrodeposition |
JP3286467B2 (ja) * | 1994-05-25 | 2002-05-27 | 株式会社巴川製紙所 | ポリイミドフイルム−金属薄膜の複合フイルムの製造方法 |
DE19517069A1 (de) * | 1995-05-10 | 1996-11-14 | Basf Lacke & Farben | Folien zur Beschichtung von Formteilrohlingen und deren Verwendung im Automobilbau |
DE19517068A1 (de) * | 1995-05-10 | 1996-11-14 | Basf Lacke & Farben | Mit mehreren Schichten beschichtete Folien und deren Verwendung im Automobilbau |
DE19517067A1 (de) * | 1995-05-10 | 1996-11-14 | Basf Lacke & Farben | Mit mehreren Schichten beschichtete Folien und deren Verwendung im Automobilbau |
DE19535934C2 (de) * | 1995-09-27 | 2002-11-07 | Basf Coatings Ag | Haftfähiger Lackfilm |
-
2001
- 2001-03-24 DE DE10114468A patent/DE10114468B4/de not_active Expired - Fee Related
-
2002
- 2002-03-25 WO PCT/EP2002/003333 patent/WO2002076727A2/de not_active Application Discontinuation
- 2002-03-25 AU AU2002256705A patent/AU2002256705A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5290378A (en) * | 1990-03-14 | 1994-03-01 | Bridgestone Corporation | Method for preparing a rubber-based composite material |
US5895723A (en) * | 1993-08-26 | 1999-04-20 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Composite films |
WO2001061069A2 (en) * | 2000-02-18 | 2001-08-23 | University Of Cincinnati | Plasma polymerized primers for metal pretreatment |
WO2002020875A2 (de) * | 2000-09-05 | 2002-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur haftfesten metallbeschichtung |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch, Week 199606 Derwent Publications Ltd., London, GB; Class A26, AN 1996-056471 XP002214020 & JP 07 316776 A (INAGAKI K), 5. Dezember 1995 (1995-12-05) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1947212A1 (de) * | 2007-01-19 | 2008-07-23 | Xxentria Technology Materials Co., Ltd. | Verfahren zur Herstellung eines Architekturlaminats |
WO2023032958A1 (ja) * | 2021-08-30 | 2023-03-09 | 国立大学法人大阪大学 | 樹脂層と金属層との積層体及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2002076727A3 (de) | 2002-12-27 |
AU2002256705A1 (en) | 2002-10-08 |
DE10114468A1 (de) | 2002-10-02 |
DE10114468B4 (de) | 2005-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102010033082B4 (de) | Verfahren zum Ausbilden einer Schutzkonversionsbeschichtung und einer Elektrotauchlackierung an den Oberflächen einer Mischmetall-Kraftfahrzeugrohkarosserie | |
EP3149224B1 (de) | Verfahren zur herstellung einer sandwichstruktur, die hiermit hergestellte sandwichstruktur und ihre verwendung | |
EP1390564B1 (de) | Verfahren zur beschichtung von metallischen oberflächen und verwendung der derart beschichteten substrate | |
DE3044942A1 (de) | Verbundstoff aus metall und kunstharz und verfahren zu seiner herstellung | |
EP1837091B1 (de) | Verfahren zur Herstellung einer Aluminiumfolie mit einer funktionalen Direktbeschichtung | |
EP0163325B1 (de) | Verfahren und Überzugsmittel zur Behandlung von Metalloberflächen | |
DE69820888T2 (de) | Beschichteter aluminium werkstoff | |
EP2826569B1 (de) | Verfahren zur Passivierung von bandförmigem Schwarzblech | |
EP3408431B1 (de) | Aluminiumlegierungsband für klebstoffverbindung | |
EP0830219B1 (de) | Mit mehreren schichten beschichtete folien und verfahren zur deren herstellung | |
DE2900530A1 (de) | Verfahren zur herstellung von metallgegenstaenden mit einem halbglaenzenden, perlmutterartigen aussehen | |
DE60024889T2 (de) | Säurevorbehandlung für das verkleben von kraftfahrzeugteilen | |
WO2002076727A2 (de) | Korrosionsstabiles laminat, verfahren zu seiner herstellung und seine verwendung | |
DE102015113878B4 (de) | Verfahren zur thermischen Behandlung eines mit einer Konversionsschicht beschichteten Schwarzblechs | |
DE19517069A1 (de) | Folien zur Beschichtung von Formteilrohlingen und deren Verwendung im Automobilbau | |
CH648416A5 (de) | Spiegel und verfahren zur herstellung derselben. | |
DE19517068A1 (de) | Mit mehreren Schichten beschichtete Folien und deren Verwendung im Automobilbau | |
CH687815A5 (de) | Umformbare Verbundplatte. | |
DE102015104887B4 (de) | Rohrprodukt und Verfahren zu dessen Herstellung | |
DE19840807A1 (de) | Mit mehreren Schichten beschichtete Folien und deren Verwendung im Automobilbau | |
EP0770003A1 (de) | Mit mehreren schichten beschichtete substrate und verfahren zur herstellung dieser substrate | |
DE60113137T2 (de) | Mit durchsichtigem harz beschichteter gegenstand aus rostfreiem stahl | |
EP3434807A1 (de) | Stahlblech mit einer konversionsschicht, verfahren zur herstellung eines konversionsbeschichteten stahlblechs und behandlungsmittel zur applizierung einer konversionsschicht auf einem stahlblech | |
DE102012215512A1 (de) | Verfahren und Fertigungsanlage zum Herstellen eines warmumgeformten oder pressgehärteten Blechformteils mit einer metallischen Korrosionsschutzbeschichtung sowie hiermit hergestelltes Blechformteil und Fahrzeugkarosserie mit solchem Blechformteil | |
CH687330A5 (de) | Behandlung von Metalloberflächen mittels Silikaten zur Verbesserung der Haftung von Beschichtungen. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |