Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • 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
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • 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
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • 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
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
• • 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
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249987—With nonvoid component of specified composition
  • Y10T428/249991—Synthetic resin or natural rubbers
  • Y10T428/249992—Linear or thermoplastic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31728—Next to second layer of polyamide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31728—Next to second layer of polyamide
  • Y10T428/31732—At least one layer is nylon type
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31739—Nylon type

Definitions

• the present invention relates to a film which comprises a layer composed of a polyamide blend, and is suitable for decoration of moldings.
• the process of painting plastics components which are components of bodywork can, for example, be carried out on-line, the plastics part being subjected to a paint treatment identical with that for the metallic components.
• identical adhesion of the paint formulation has to be ensured on very different substrates. If the process of painting the plastics parts is carried out in a separate step (known as off-line painting), comprising process conditions more advantageous for plastics, the problem of colormatching arises, meaning that the shade achieved on the metal has to be matched precisely.
• One proposed solution consists in the use of multilayered plastics films, used to cover the components and then requiring no painting.
• the bond between substrate and decorating film can be achieved via a number of manufacturing processes.
• the film can be laminated to the substrate, or it is possible to select a process of reverse coating by an injection-molding process, in which the film is placed in the injection mold during component production.
• the concept of a film as carrier of decoration is also in line with a trend toward individualization of design elements on automobiles. Specifically, this trend leads to a wider range of models in the manufacturing process, but with a reduction in the number of respective components manufactured per series.
• the use of films permits rapid, problem-free design change, and can therefore meet this challenge.
• An important factor here is that the film complies with the standards demanded in the automobile industry with respect to surface properties (class A surface), solvent resistance, and appearance. These films likewise have good capability for use in the design of interior surfaces in automobiles.
• Decorative films of this type are in principle known.
• EP 0 949 120 A1 describes by way of example decorative films with a transparent outer layer composed of polyurethane, polyacrylate, fluoropolymer, or mixtures composed of fluoropolymer and polyacrylate.
• WO 94/03337 and EP 0 285 071 A2 disclose similar decorative films.
• Another application sector for decorative films is as a carrier of decoration, for example for topcoats of sports equipment, e.g. skis or snowboards, or of household items.
• Single-layer films whose topsides or undersides have been printed are often used here.
• the utility model DE 295 19 867 U1 describes a decorable film composed of a copolyamide which is composed of the following monomer units: laurolactam, and also caprolactam and/or hexamethylenediamine/dicarboxylic acid.
• the article by M. Beyer and J. Lohmar, Kunststoffe 90 (2000) 1, pp. 98-101 gives examples of printable films composed of PA12 molding compositions.
• polyamides for example impact resistance and chemical resistance
• polyamides based on PA12 or PA11 good suitability for production of these decorative films.
• the patent literature has descriptions of decorative films or else protective films which comprise an outer layer composed of a polyamide. Examples which may be mentioned here are the specifications JP60155239A, JP2003118055A, EP 1 302 309 A, EP 0 522 240 A, EP 0 694 377 A, EP0734833A, WO9212008A, and EP0568988A.
• the polyamides used and their preparation are known. They are commercially available in a wide variety of marketed grades. According to the invention, the respective homopolyamides are mainly used, but it is also possible to use copolyamides based thereon and incorporating at most 20 mol %, at most 15 mol %, at most 10 mol %, or at most 5 mol %, of comonomers. Suitable comonomers are lactams, the corresponding aminocarboxylic acids, or the combination of diamine and dicarboxylic acid. Diamine and dicarboxylic acid are respectively counted individually in the calculation of the constitution.
• the molding composition is prepared from the individual components according to the prior art via mixing in the melt. It can also comprise the following other components:
• the amount of these other components present in the molding composition is preferably at most 30% by weight, at most 25% by weight, at most 20% by weight, at most 15% by weight, at most 10% by weight, or at most 5% by weight.
• the molding composition comprises at most 50% by weight of the AB polyamide (PA11 or PA12)
• gloss is retained as for the pure AABB polyamides during service life, although this would not be expected in view of the mixing ratio of the polyamides.
• at least 50% by weight of the AABB polyamide is present, it inhibits diffusion of the substances that form deposits and are present in the AB polyamide, possibly cyclic oligomers.
• Another advantage here is that the mixture of the semicrystalline polyamides give blends which are semicrystalline, but sufficiently transparent. Transparency and initial gloss are above the level of the pure components, while resistance to chemicals and environmental effects is retained.
• the film is a single- or multilayer film.
• the nature and number of the other layers depend on the technical requirements of the application; the only decisive factor is that the outer layer is composed of the inventively used molding composition.
• the following embodiments are possible:
• the transparent outer layer may first, like a monofilm, be printed from one side or from both sides and then be bonded in a second step to the other layers to give the multilayer film.
• the transparent outer layer can be printed from above.
• the outer layer may also have transparent or opaque coloring.
• the color layer and/or the carrier layer comprises a molding composition in particular of a polyetheramide or of a polyetheresteramide, and preferably of a polyetheramide or polyetheresteramide based on a linear aliphatic diamine having from 6 to 18, preferably from 6 to 12, carbon atoms, on a linear aliphatic, or an aromatic, dicarboxylic acid having from 6 to 18, preferably from 6 to 12, carbon atoms, and on a polyether having an average of more than 2.3 carbon atoms per oxygen atom and having a number-average molecular weight of from 200 to 2000 for the polyether blocks.
• the molding composition of this layer can comprise other blend components, e.g.
• the polyamide content of the polyamide elastomer it is advantageous here for the polyamide content of the polyamide elastomer to be composed of monomers which are identical with those used in one of the components of the outer layer.
• the color layer and/or the carrier layer can also comprise a conventional impact-modifying rubber alongside a polyamide.
• the thickness of the film or multilayer film with the inventive outer layer is from 0.02 to 1.2 mm, particularly preferably from 0.05 to 1 mm, very particularly preferably from 0.1 to 0.8 mm, and with particular preference from 0.2 to 0.6 mm.
• the thickness of the inventive outer layer in one preferred embodiment is from 0.01 to 0.5 mm, particularly preferably from 0.02 to 0.3 mm, very particularly preferably from 0.04 to 0.2 mm, and with particular preference from 0.05 to 0.15 mm.
• the film is produced by means of known methods, for example via extrusion, or in the case of multilayered systems via coextrusion or lamination. It can then, if appropriate, be subjected to a forming process.
• the film is a decorative film.
• decorative films are films which can be printed and/or comprise a color layer, and moreover are intended for bonding to a substrate in order to decorate its surface.
• the decoration can also be brought about by using a lamination process on visual surface defects, e.g. by hiding surface roughness deriving from fillers or from reinforcing materials.
• Examples of methods of coherent bonding of the film to the substrate are adhesive bonding, pressing, lamination, or coextrusion, or reverse coating by an injection-molding, foaming, or compression-molding method.
• the film can by way of example be previously flame-treated or treated with a plasma.
• the film Prior to formation of the bond between film and substrate, the film can also be subjected to mechanical treatment or forming processes, e.g. via thermoforming or other processes.
• the surface can be structured via embossing, for example.
• the surface can also be pre-structured in the context of film extrusion, for example using specifically designed rolls.
• the resultant composite part can then also be subjected to a forming process.
• suitable substrates are molding compositions based on polyolefins, on polyamides, on polyesters, on polycarbonates, on ABS, on polystyrene, or on styrene copolymers.
• the inventive film is used as outer layer of a film composite for the design or decoration of surfaces on and in automobiles and utility vehicles, the film having been adhesive-bonded to a plastics substrate.
• the correspondingly designed component can be of sheet-like structure, an example being a bodywork part, for example a roof module, wheel surround, engine cover, or door.
• Other possible embodiments are those in which the components produced are elongate, with or without curvature, for example cladding, e.g. the cladding on what are known as A columns of an automobile, or decorative and cover strips of any type.
• Another example is provided by protective cladding for door sills.
• constituents of the interior can also be advantageously decorated via the inventive films, in particular decorative elements such as strips and panels, because impact resistance and resistance to chemicals, such as cleaners, is also required in the interior.
• the inventive film is used as topcoat for snowboard-like equipment of any type, such as skis or snowboards.
• the film can moreover be used by way of example as a protective film to counter soiling, UV radiation, effects of weathering, chemicals, or abrasion, or as a barrier film on vehicles, in the household, on floors, on tunnels, on tents, and on buildings, or as a carrier of decorative effects, for example for topcoats of sports equipment, of boats, of aircraft, in the household, or on buildings.
• the PA12 used was a grade whose relative solution viscosity ⁇ rel , determined to ISO 307, was 2.1 and whose crystallite melting point T m , determined to ISO 11357, was 178° C.
• the PA1012 used was a grade whose relative solution viscosity ⁇ rel was 1.9 and whose crystallite melting point T m was 191° C.
• the molding composition was prepared via mixing in the melt in a Werner+Pfleiderer ZSK M9/2 twin-screw extruder.
• the barrel temperature was 250° C.
• the rotation rate was 250 rpm
• the throughput was 10 kg/h.
• the melt was filtered at 25 ⁇ .
• Injection-molded plaques were produced on an Engel ES 600/150 injection molding machine.
• the melt temperature was 250° C.
• the mold temperature was 80° C.
• Dimensions of the plaques produced were 130 mm ⁇ 130 mm ⁇ 1 mm.
• Monofilms were produced by the calendering process on a Collin 168/400 multilayer film calender at a processing temperature of 240° C.
• the thickness was 400 ⁇ m.
• Monofilms were produced by the calendering process on a Collin 168/400 multilayer film calender at a processing temperature of 240° C. (outer layer) and 240-250° C. (color layer).
• the thickness of the outer layer was 100 ⁇ m, and the thickness of the color layer was 400 ⁇ m.
• Injection-molded plaques were stored in a cabinet under controlled temperature and humidity conditions at 85° C. and 99% relative humidity.
• Transmittance was measured on films of thickness 400 ⁇ m to ISO 13468-2.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Wrappers (AREA)

Applications Claiming Priority (3)

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Citations (68)

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• 2005
  • 2005-02-19 DE DE200510007665 patent/DE102005007665A1/de not_active Withdrawn
• 2006
  • 2006-01-04 BR BRPI0607867A patent/BRPI0607867B1/pt active IP Right Grant
  • 2006-01-04 US US11/816,556 patent/US20080261010A1/en not_active Abandoned
  • 2006-01-04 EP EP06700042A patent/EP1848773B1/de active Active
  • 2006-01-04 DE DE200650001747 patent/DE502006001747D1/de active Active
  • 2006-01-04 WO PCT/EP2006/050038 patent/WO2006087250A1/de active Application Filing
  • 2006-01-04 RU RU2007134536A patent/RU2382796C2/ru not_active IP Right Cessation
  • 2006-01-04 KR KR1020077018827A patent/KR100869430B1/ko active IP Right Grant
  • 2006-01-04 JP JP2007555564A patent/JP4499801B2/ja active Active
  • 2006-01-04 ES ES06700042T patent/ES2316041T3/es active Active
  • 2006-01-04 AT AT06700042T patent/ATE410480T1/de not_active IP Right Cessation
  • 2006-02-13 TW TW95104736A patent/TWI331615B/zh not_active IP Right Cessation
  • 2006-02-20 CN CN200610004112XA patent/CN1821306B/zh active Active
• 2011
  • 2011-12-21 US US13/332,470 patent/US8614005B2/en active Active
• 2013
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