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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • 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
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
• • 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
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
  • B05D7/57—Three layers or more the last layer being a clear coat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
  • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
• • 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
• • 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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
  • B05D5/067—Metallic effect
  • B05D5/068—Metallic effect achieved by multilayers
• • 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
  • 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
  • B32B2398/00—Unspecified macromolecular compounds
  • B32B2398/20—Thermoplastics
• • 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
• • 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
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• • 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
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/259—Silicic material
• • 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]
• • 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]
  • Y10T428/31547—Of polyisocyanurate

Definitions

• the present invention relates to novel color and/or effect films.
• the present invention also relates to a novel process for preparing color and/or effect films.
• the present invention additionally relates to the use of the novel color and/or effect films for coating three-dimensional shaped parts, especially motor vehicle bodies.
• Color and/or effect paint systems on motor vehicle bodies, especially automobile bodies, are nowadays preferably composed of a plurality of coating layers which are applied atop one another and have different properties.
• a substrate will have applied to it successively an electrodeposited electrocoat as primer, a primer-surfacer or antistonechip primer coat, a basecoat, and a clearcoat.
• the electrocoat serves in particular to protect the sheet metal against corrosion.
• the primer By those in the art it is often also referred to as the primer.
• the primer-surfacer coat serves to mask unevennesses in the substrate and, by virtue of its elasticity, ensures stonechip resistance. Where appropriate, the primer-surfacer coat may also serve to strengthen the hiding power and to deepen the shade of the paint system.
• the basecoat contributes the colors and/or the angle-dependent optical effects. Both the brightness (amount) and the color (through wavelength-specific absorption or through interference) of the reflected light may vary depending on the viewing angle, a phenomenon which is also referred to as brightness and/or color flop.
• the clearcoat serves to intensify the optical effects and to protect the paint system against mechanical and chemical damage.
• Basecoat and clearcoat are often also referred to collectively as the topcoat.
• topcoat For further details, refer to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, N.Y., 1998, pages 49 and 51, “automotive finishes”.
• a disadvantage is that these color and/or effect paint systems must often be applied in four separate steps, between each of which the applied films must be flashed off and also, where appropriate, baked, which is very time-consuming and labor-intensive and also leads to increased energy and plant costs.
• a further disadvantage is the environmental burden associated with the use of paints containing solvent.
• multilayer color and/or effect films have been proposed for the coating of motor vehicle bodies, especially exterior parts of motor vehicle bodies.
• These known multilayer color and/or effect films can be prepared under constant conditions and applied to any desired substrates to give, as a result, a substrate- and process-independent color and/or optical effect.
• Application may be carried out by laminating onto metals, injection backmolding with thermoplastics, foam backing, or compression backmolding.
• the corresponding processes and films are known, for example, from the American patents U.S. Pat. No. 4,810,540 A, U.S. Pat. No. 4,931,324 A or U.S. Pat. No.
• the advantages described may be realized with simple colors, such as solid colors, this is not the case with demanding effect paints, such as metallic effects.
• the known films are generally produced by a directed process, such as extrusion to form flat films or the casting of liquid basecoat materials onto carrier films, the color locus and the flop characteristics of the color and/or effect layers are not isotropic; in other words, when the layers are viewed from different angles relative to the preferential direction of the production process, different colors and effects are perceived.
• the reason for this is the orientation of the platelet-shaped effect pigments, such as platelet-shaped aluminum pigments, which have an aspect ratio >1, in the direction determined by the production.
• a further inhomogeneity is generated by the statistically preferred orientation of the surface normals of the platelet-shaped effect pigments relative to the plane of the substrate in said preferential direction.
• the known multilayer color and/or effect films are considerably thicker than the conventional multicoat color and/or effect paint systems.
• the color and/or effect layers of the films are required to be from more than two up to four times thicker than the basecoats of conventional multicoat paint systems in order to retain a sufficiently high hiding power under the conditions of stretching which occur during the coating of three-dimensional articles, and which may amount to more than 200%, and to suffer as little change as possible in color and optical effect.
• novel color and/or effect, single-layer or multilayer films which can be prepared economically and which no longer have the disadvantages of the prior art.
• novel multilayer color and/or effect films should exhibit isotropic flop characteristics and an isotropic color locus, both independently of the viewing angle, so that their processing to coatings for three-dimensional articles, especially motor vehicle bodies, is no longer accompanied by any logistical problems or any large quantities of offcuts.
• the novel coatings produced from the novel single-layer or multilayer color and/or effect films should continue to have a sufficiently high hiding power and to suffer very little if any change in color and effect.
• the novel coatings should exhibit the so-called “automotive quality” (in this respect, cf. also the European patent EP 0 352 298 B1, page 15 line 42 to page 17 line 40).
• the invention accordingly provides the novel single-layer or multilayer color and/or effect films which consist of or comprise at least one color and/or effect layer comprising
• At least one component layer (1) comprising at least one color and/or effect pigment (1) in anisotropic distribution
• At least one component layer (2) comprising the pigment or pigments (1) and/or at least one different color and/or effect pigment (2) in isotropic distribution.
• the invention also provides the novel single-layer or multilayer color and/or effect films which consist of or comprise at least one color and/or effect layer preparable by
• films of the invention are referred to collectively as “films of the invention”.
• the invention further provides the novel process for preparing single-layer or multilayer color and/or effect films which comprises
• the films of the invention surprisingly exhibited an isotropic flop behavior and an isotropic color locus, both of which were independent of the viewing angle, so that their processing to coatings for three-dimensional articles, especially motor vehicle bodies, was no longer accompanied by any logistical problems or any large quantities of offcuts.
• the coatings of the invention produced from the films of the invention surprisingly continued to have a sufficiently high hiding power, even in the extended areas.
• the films of the invention comprise at least one, especially one, color and/or effect layer, or consist thereof.
• the films of the invention may comprise at least two, especially two, color and/or effect layers one above the other, the upper layer(s) fully or partly, especially partly, covering the underlying layer(s).
• the partial coverage is of imagewise configuration. In this way it is possible to combine not only different colors but also different physical and optical effects with one another for the purpose, for example, of information or signaling.
• the films of the invention may be prepared in any of a very wide variety of ways; preferably, they are produced by means of the process of the invention.
• At least one, especially one, basecoat material (A) or at least one, especially one, basecoat material (A) and at least one, especially one, basecoat material (B) different than the basecoat material (A) is used.
• the material composition of the basecoat materials (A) and (B) is not critical;
• the basecoat materials (A) and/or (B) comprise color and/or effect pigments.
• the color and/or effect pigments are preferably selected from the group consisting of organic and inorganic, colored, optical effect-imparting, electrically conductive, magnetically shielding, and fluorescent pigments, metal powders, organic and inorganic, transparent and hiding fillers, and nanoparticles.
• the pigments preferably have an aspect ratio >1.
• suitable effect pigments are metal flake pigments such as commercially customary aluminum bronzes, aluminum bronzes chromated in accordance with DE 36 36 183 A1, and commercially customary stainless steel bronzes, and also nonmetallic effect pigments, such as pearlescent pigments and interference pigments, platelet-shaped effect pigments based on iron oxide with a shade from pink to brownish red, or liquid-crystalline effect pigments.
• metal flake pigments such as commercially customary aluminum bronzes, aluminum bronzes chromated in accordance with DE 36 36 183 A1
• nonmetallic effect pigments such as pearlescent pigments and interference pigments, platelet-shaped effect pigments based on iron oxide with a shade from pink to brownish red, or liquid-crystalline effect pigments.
• suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopones; black pigments such as carbon black, iron manganese black or spinel black; chromatic pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt violet and manganese violet, red iron oxide, cadmium sulfoselenide, molybdate red or ultramarine red; brown iron oxide, mixed brown, spinel phases and corundum phases or chrome orange; or yellow iron oxide, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
• white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopones
• black pigments such as carbon black, iron manganese black or spinel black
• chromatic pigments such
• suitable organic color pigments are monoazo pigments, disazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments or aniline black.
• fluorescent pigments are bis(azomethine) pigments.
• Examples of suitable electrically conductive pigments are titanium dioxide/tin oxide pigments.
• Examples of magnetically shielding pigments are pigments based on iron oxides or chromium dioxide.
• suitable metal powders are powders of metals and metal alloys such as aluminum, zinc, copper, bronze or brass.
• suitable organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide, or organic fillers, such as polymer powders, especially those of polyamide, polyvinylidene difluoride (PVDF) or polyacrylonitrile.
• PVDF polyvinylidene difluoride
• platelet-shaped inorganic fillers such as talc or mica
• nonplatelet-shaped inorganic fillers such as chalk, dolomite, calcium sulfates or barium sulfate
• Suitable transparent fillers are those based on silica, alumina or zirconium oxide.
• Suitable nonoparticles are selected from the group consisting of hydrophilic and hydrophobic, especially hydrophilic, nanoparticles based on silica, alumina, zinc oxide and zirconium oxide and the polyacids and heteropolyacids of transition metals, preferably of molybdenum and tungsten, having a primary particle size ⁇ 50 nm, preferably from 5 to 50 m, in particular from 10 to 30 nm.
• the hydrophilic nanoparticles preferably have no flatting effect Particular preference is given to using nanoparticles based on silica.
• hydrophilic pyrogenic silicas whose agglomerates and aggregates have a chainlike structure and which are preparable by the flame hydrolysis of silica tetrachloride in an oxyhydrogen flame. They are sold, for example, by Degussa under the brand name Aerosil®.
• precipitated waterglasses such as nanohectorites, which are sold, for example, by Südchemie under the brand name Optigel® or by Laporte under the brand name Laponite®.
• the pigments (1) and (2) present in the component layers (1) and (2) may be materially identical with or different than one another.
• a portion or the total amount of at least one, especially one, basecoat material (A) is applied to a carrier by means of a directed application technique (1) in the first step (1).
• the applicator (1) and the carrier are in relative motion with respect to one another.
• the applicator (1) is stationary and the carrier is passed under or over, preferably under, the applicator (1) at a suitable uniform rate of advance, which depends on the requirements of the case in hand and may be set easily by the skilled worker.
• a directed application technique is a technique which gives rise to a certain orientation or preferential direction with the above-described pigments in the basecoat layers, which lead to inhomogeneities and anisotropies in the color and/or effect layers.
• these directed application techniques have the substantial advantage that they can be used to prepare comparatively thick layers without problems.
• Examples of suitable directed application techniques are casting, knife coating, roller coating or extrusion coating. These techniques may be carried out using customary and known devices, such as casting devices, knife coaters, rollers, especially contrarotating rollers, or extruders, especially film extruders.
• step (1) preferably the largest part (1) of the color and/or effect layer (2) is constructed.
• the component layer (1) formed has preferably more than 50%, more preferably more than 60%, with particular preference more than 65%, with very particular preference more than 70%, and in particular more than 75% of the dry film thickness of the color and/or effect layer.
• step (1) a portion of the basecoat material (A) is applied to a carrier. If in step (2) a basecoat material (B) is applied that is different than the basecoat material (A), the entirety of the basecoat material (A) may be applied in step (1).
• the carrier may be permanent or temporary.
• the films of the invention are peeled off from it following their preparation, after which they may be used as single-layer films of the invention or may be joined with other layers or films to form multilayer films of the invention.
• the temporary carriers may comprise circulating metal belts or plastic belts or temporary carrier films, which may have been provided with a release layer.
• the films of the invention remain firmly joined to it following their preparation.
• the permanent carriers comprise polymer films which take on a technical function in the films of the invention.
• the polymer films comprise clearcoat films, adhesion films or comparatively thick, thermoformable carrier films, such as are known, for example, from the European patent EP 0 352 298 B1, page 7 line 54 to page 10 line 51 and page 12 line 55 to page 13 line 53, or from the American patent U.S. Pat. No. 4,810,540 A, column 3 line 37 to column 5 line 15.
• the polymer films used as permanent carriers are thermoplastic.
• the polymer films may be solid or they may be not yet fully solidified and may solidify only after the application of the component layer (1) or of the color and/or effect layer (2), thereby resulting in a particularly high level of interlayer adhesion in the assembly.
• the polymer films may also be pigmented, especially for adjustment toward the brightness of the color and/or effect layer (2).
• step (2) the remainder of the basecoat material (A) and/or the basecoat material (B), which is different than the basecoat material (A), is applied to the component layer (1).
• the remainder of the basecoat material (A) is applied.
• the basecoat material (A) and/or the basecoat material (B) is applied continuously once or at least twice.
• the color and/or effect layer is constructed completely in the first and only step (2).
• the color and/or effect layer is built up further in the first step (2), to give an assembly comprising carrier, component layer (1) and first component layer (2). Complete construction then takes place in at least one further step (2).
• step (2) at least one application technique (2) is employed which gives rise in the resulting component layer (2) to no arrangement of the above-described pigments in a preferential direction, i.e., an anisotropy.
• step or steps (2) is or are carried out in time directly after the step (1), i.e., simultaneously with step (1).
• the step or steps (2) are carried out in time later after the step (1) of the invention, i.e., sequentially.
• the component layer (1) may be dried or partly or fully cured.
• the assembly composed of carrier and component layer (1) is wound up onto rolls and stored in this form until step (2) is implemented.
• the component layer (1) is preferably vented.
• venting is preferably brought about by providing a greater or lesser temporal distance between step (1) and step (2) or the first step (2).
• the temporal distance is also guided by the evaporation characteristics of the component layer (1) and may therefore be set by the skilled worker on the basis of his or her general knowledge in the art, where appropriate with the assistance of simple rangefinding tests.
• the component layer (1) has still not fully dried but instead still has a certain residual moisture and/or organic solvent content.
• step (2) the basecoat materials (A) and/or (B) are applied continuously by at least one application technique (2) to the component layer (1) produced in step (1).
• the application technique (2) does not give rise to an arrangement of the above-described pigments in a preferential direction in the resulting component layer (2); in other words, the pigments are isotropically distributed.
• the applicator(s) (2) and the carrier with the component layer (1) and also, where appropriate, with the first component layer (2) are in relative motion with respect to one another.
• the assemblies comprising carrier and component layer (1) and also, where appropriate, first component layer (2) may be passed in relative motion under or over, preferably under, the applicator(s) (2).
• the application of the basecoat materials (A) and/or (B) may take place once, to give the complete color and/or effect layer.
• the application may take place at least twice, i.e., in at least two component steps (2): in this case, the color and/or effect layer is built up further in the first component step (2) and its construction is concluded in at least one further component step (2).
• the application of at least one further component layer (2) may be carried out simultaneously or sequentially. If it is carried out sequentially, the assembly comprising carrier, component layer (1) and first component layer (2) is preferably wound up onto rolls for storage until the second component step (2) is carried out.
• the application techniques (2) are spray application techniques and the applicators (2) are spray applicators.
• the applicators may be pneumatic sprayers (2) (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, N.Y., 1998, page 165, “compressed air spraying”) or electrostatic sprayers (2) (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, N.Y., 1998, page 186: “electrostatic coating”, page 187: “electrostatic spray guns”, “electrostatic spraying”).
• the applicator(s) (2) is or are disposed directly downstream of the applicator(s) (1).
• the applicator(s) (2) is or are preferably part(s) of a further unit to which the assemblies comprising carrier and component layer (1) and also, where appropriate, first component layer (2) are supplied, preferably in the form of wound-up rolls.
• the applicator(s) (2) may be stationary. Preferably, they span in their entire width the assemblies comprising carrier and component layer (1) and also, where appropriate, first component layer (2). They may be arranged transversely to the direction of motion or at an oblique angle to it. The angle between the edge of an assembly and the main axis of an applicator (2) may be obtuse to acute.
• At least two applicators (2) may be arranged in series. In this case, they may stand parallel to or oblique to one another. Alternatively, the at least two applicators (2) may intersect at obtuse to acute angles.
• one stationary applicator (2) comprises at least two devices for applying the basecoat materials (A) or (B), in particular at least two pneumatically or electrostatically operated spraying heads each with at least one spray nozzle.
• the applicator(s) (2) may be disposed in such a way as to be movable back and forward transversely and/or obliquely to the direction of motion of the assemblies comprising carrier and component layer (1) and also, where appropriate, first component layer (2).
• the movable applicators (2) preferably comprise at least one device for applying the basecoat materials (A) or (B), in particular at least one pneumatically or electrostatically operating spraying head each with at least one spray nozzle.
• the stationary and movable applicators (2) may be combined with one another. Further more, they may be movable in the vertical plane.
• the basecoat materials (A) and/or (B) may be applied at right angles or obliquely, at an acute to obtuse angle, with respect to the plane of the assembly comprising carrier and component layer (1) and also, where appropriate, first component layer (2). They may be applied in or against the direction of motion of the assembly. In the context of the process of the invention, these measures may be combined with one another.
• the basecoat spray jets produced by the spray applicators (2) used with preference may overlap. If so, their areas of impingement may partly or fully coincide.
• the overlap may be achieved, for example, by spraying at least two basecoat spray jets against one another under an acute to obtuse angle.
• overlapping basecoat spray jets may be produced with the aid of spraying heads which comprise at least two spray nozzles in concave or convex arrangement, such as are known, for example, from the patent applications and patents DE 195 38 340 A1, WO 97/14506, U.S. Pat. No. 4,378,386 A or U.S. Pat. No. 5,366,162 A.
• the isotropy of the component layers (2) may be improved further if the pneumatically generated spray jets—or, to be more precise, the spray jet clouds generated—are set in periodic—that is, regularly repeating—motion relative to the spraying direction and relative to the component layer (1).
• any desired periodic motions of the spray jet cloud may be considered.
• Examples of highly suitable periodic motions are
• the wave-form propagation of the coating material in the form of a sinusoidal wave, for example, or
• the customary and known devices for compressed air spraying are modified appropriately by equipping them with movable spray nozzles. Accordingly, preference is given to using rotating spray nozzles, spray nozzles which move backward and forward periodically as viewed in the direction of spraying, or spray nozzles in eccentric disks.
• construction principles may be combined with one another appropriately.
• rotating spray nozzles may be mounted in such a way that they may also be moved backward and forward periodically.
• the construction of these spray guns has no special features; instead, the construction principles, materials, and measurement and control techniques employed are those which are customary and known in the field of moving spray nozzles.
• the frequency, the rate and/or the spatial extent or deflection of the periodic motion which is imposed in accordance with the invention on the propagating spray jet cloud may vary very widely and is guided by the requirements of the case in hand. The skilled worker is able to determine those conditions which are optimum in each case, where appropriate by means of simple preliminary tests.
• the color and/or effect layer is fully constructed. Its wet layer thickness may vary widely and is guided in particular by the dry layer thickness which ensures sufficient hiding power of the color and/or effect layer in the coating of the invention. In the case in hand, therefore, the skilled worker is able to determine the appropriate wet layer thickness on the basis of his or her general knowledge of the art, where appropriate with the assistance of simple preliminary tests.
• the color and/or effect layer is dried or partly or fully cured. Preferably, it is dried. Drying may be carried out using customary and known methods, such as irradiation with IR or microwave radiation or treatment with hot air in countercurrent.
• the resulting films of the invention may be wound up onto rolls before being used further.
• the films of the invention comprise the above-described clearcoat films as permanent carriers
• their color and/or effect layers may be provided, on their side facing away from the clearcoat film, with one of the above-described, comparatively thick, thermoformable carrier films and/or an adhesion film before they are used to produce coatings.
• thermoformable carrier films as permanent carriers
• their color and/or effect layers may be provided, on their side facing away from the thermoformable carrier film, with one of the above-described clearcoat films or with a clearcoat, before they are used to produce coatings.
• an adjustment layer as described, for example, in the European patent application EP 0 949 120 A1.
• the film of the invention may also, however, have a structure which corresponds to that of the customary and known automotive finish, comprising electrocoat or anticorrosion layer, (where appropriate) primer-surfacer coat or antistonechip primer coat, basecoat, and clearcoat (automobile structure).
• Suitable clearcoat materials for producing the clearcoats include all customary and known one-component(1K), two-component(2K) or multicomponent(3K, 4K) clearcoat materials, powder clearcoat materials, powder slurry clearcoat materials or UV-curable clearcoat materials.
• Thermally curable one-component(1K), two-component(2K) or multicomponent(3K, 4K) clearcoat materials are known from the European patent applications DE 42 04 518 A1, 0 594 068 A1, 0 594 071 A1, 0 594 142 A1, 0 604 992 A1 or 0 596 460 A1, the international patent applications WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615 or the American patents U.S. Pat. Nos. 5,474,811 A, 5,356,669 A or 5,605,965 A.
• One-component(1K) clearcoat materials include, as is known, hydroxyl-containing binders and crosslinking agents such as blocked polyisocyanates, tris(alkoxy-carbonylamino)triazines and/or amino resins.
• crosslinking agents such as blocked polyisocyanates, tris(alkoxy-carbonylamino)triazines and/or amino resins.
• they comprise, as binders, polymers containing pendant carbamate and/or allophanate groups, and carbamate- and/or allophanate-modified amino resin crosslinking agents (cf. the American patents U.S. Pat. No.
• Two-component(2K) or multicomponent(3K, 4K) clearcoat materials comprise as essential constituents, as is known, hydroxyl-containing binders and polyisocyanate crosslinking agents, which are stored separately until they are used.
• Thermally curable powder clearcoat materials are known, for example, from the German patent application DE 42 22 194 A1, the BASF Lacke+Farben AG product information literature “Pulverlacke” [powder coating materials], 1990, or the BASF Coatings AG brochure “Pulverlacke, Pulverlacke für von von für von füren” [powder coating materials, powder coatings for industrial applications], January 2000.
• the familiar essential constituents of powder clearcoat materials include binders containing epoxide groups, and polycarboxylic acid crosslinking agents.
• Examples of suitable powder slurry clearcoat materials are known from the U.S. Pat. No. 4,268,542 A1 and from the patent applications DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE 196 13 547 A1, EP 0 652 264 A1, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1 or DE 198 14 471 A1 .
• Powder slurry clearcoat materials contain, as is known, powder clearcoat materials in dispersion in an aqueous medium.
• Clearcoat materials, powder clearcoat materials, and powder slurry clearcoat materials that are curable thermally and with actinic radiation are disclosed, for example, by the patent applications DE 198 18 735 A1, WO 98/40170, DE199 08 013 A1, DE199 08 018 A1, EP0 844 286 A1 or EP0 928 800 A1.
• the clearcoat materials are applied in a wet film thickness such that curing thereof results in clearcoats having the thicknesses which are advantageous and necessary for their functions.
• These thicknesses are preferably from 10 to 100 ⁇ m, more preferably from 15 to 80 ⁇ m, with particular preference from 20 to 75 ⁇ m, and in particular from 25 to 70 ⁇ m.
• the color and/or effect layers (2) are cured together with the clearcoat layers, thermally or both thermally and with actinic radiation.
• Curing may take place after a certain rest period or flash-off time. This may have a duration of from 30 s to 2 h, preferably from 1 min to 1 h, and in particular from 1 min to 45 min.
• the rest period is used, for example, for the leveling and devolatilization of the layers and for the evaporation of volatile constituents such as any water and/or solvent still present.
• Curing with actinic radiation is preferably carried out using a dose of from 1000 to 2000, more preferably from 1100 to 1900, with particular preference from 1200 to 1800, with very particular preference from 1300 to 1700, and in particular from 1400 to 1600 mJ/cm 2 .
• this curing may be supplemented by actinic radiation from other radiation sources.
• actinic radiation from other radiation sources.
• electron beams it is preferred to operate under an inert gas atmosphere. This may be ensured, for example, by supplying carbon dioxide and/or nitrogen directly to the surface of the clearcoat layer.
• curing with UV radiation it is also possible to operate under inert gas in order to prevent the formation of ozone.
• Curing with actinic radiation is carried out using the customary and known radiation sources and optical auxiliary measures.
• suitable radiation sources are flashlamps from the company VISIT, high or low pressure mercury vapor lamps, which may have been doped with lead in order to open up a radiation window up to 405 nm, or electron beam sources.
• thermal curing also has no special features as to its method but instead takes place in accordance with the customary and known methods such as heating in a forced air oven in countercurrent or irradiation using IR and/or NIR lamps.
• thermal curing is effected at temperatures above 90° C. The maximum curing temperatures are dependent on the heat distortion resistance of the carrier or of the carrier film.
• films of the invention especially those prepared by the process of the invention, comprise or consist of
• the films of the invention are outstandingly suitable for producing decorative and/or protective coatings on motor vehicle bodies and parts thereof, the interior and exterior of motor vehicles, the inside and outside of buildings, doors, windows, and furniture, and also in the context of the industrial coating of small parts, coils, containers, packaging, electrical components, and white goods.
• Example 1 the permanent carrier used was a 300 ⁇ m thermoplastic ABS monofilm.
• the film was coated on one side with a metallic aqueous basecoat material (color: “silver metallic”) using a blade coater.
• the parameters set were as follows: Solids content of the aqueous basecoat 19% by weight; material: Viscosity of the aqueous basecoat 200 mPas material: (shear rate: 50 s ⁇ 1 ); Rate of advance of the film: 1 m/min; Wet layer thickness: 200 ⁇ m.
• Atomizer air pressure 5 bar
• Nozzle/film distance 50 cm;
• Rate of advance 1 m/min.
• the resulting wet layer was dried thermally using hot air (120° C. upon entry of the air) in a 3 m nozzle tunnel.
• the resulting film of the invention was wound up onto a roll.
• Example 1 was repeated except that the wet layer produced in the first step was not overcoated with the aqueous basecoat material.
• Example 1 was repeated, but only one aqueous basecoat layer was applied by spray application.
• Example C2 Colorimetric evaluation showed that in terms of color, brightness and flop characteristics, the films of the invention prepared by the process of the invention were fully in accordance with a multicoat automotive OEM finish produced purely by spray application (Example C2). In particular, no strong anisotropies in brightness were observed, which dominate the visual perception in comparison to the color information. However, the coating produced from the noninventive film of Example C2 did not have the necessary hiding power in the extended areas. The noninventive film of Example C1 exhibited severe anisotropies in brightness and in metallic effect, which did not permit its use as a substitute for a conventional automotive OEM finish. In contrast, the inventive films of Example 1 represented a fully equivalent replacement for the automotive OEM finishes of the basecoat/clearcoat type produced by spray application.

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• 2001
  • 2001-08-16 DE DE2001140205 patent/DE10140205A1/de not_active Ceased
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