DD281132A5 - Thermoformable LAMINATE AND METHOD OF USE OF LAMINATE - Google Patents

Abstract

laminate; Paint coating; Outer surface; Body part; plastics; colorless layer; flexible cast film; Dry ink transfer lamination; laminating; Profile; Support material; Spray coating technology; Thermoforming operation; PVDF / acrylic resin paint system

Description

For this 5 pages drawings

Field of application of the invention

This invention relates generally to dry paint application techniques, and more particularly to the use of these techniques to provide the body exterior plastics or body panels with a paint coating applied to the bodywork in a separate operation, thereby incorporating into the Eliminate or largely reduce the manufacturing processes of a conventional production plant for cars resulting color coating process steps.

Characteristic of the known subject of the art

In automotive design and manufacture, there are a remarkable number of problems with the selection of materials and methods of manufacturing bodies. The cars have proven to be incomparable in this form of transportation, as most buyers want a specific look for their vehicle. A current trend in the automotive industry is towards production of vehicles that differ from each other in their external appearance. This is intended to address specific consumer groups. This change has prompted vehicle manufacturers to switch their production from a few large-scale models to a large number of different body styles. This direction of development required the manufacturer to be flexible in manufacturing as well as to provide reasonable service costs for each individual body model.

For many years, body parts and dashboards are mainly made of sheet metal. Vehicle builders have now recognized that the future use of plastic instead of sheet metal on the exterior body panels and frame could be a solution to meet the demand for more distinctive body shapes and lower machining costs. With increased interest in reducing vehicle mass, vehicle manufacturers have now turned their attention to the use of plastics as an alternative to heavier metal parts. For example, in the cars currently on the roads, certain exterior body panels have been made from the lighter plastic. These parts are bumpers, rocker body panels, fender extensions, window and door moldings and more.

As reported in the journal "Plastics World" of November 1986, pp. 30ff, there are a number of collaborative development programs which also seek solutions to the problem of manufacturing larger exterior body parts such as hoods Car roofs, boot lids, and even the entire bodywork, if possible, are made of plastic in a big way.The concept of producing a body from a material other than sheet metal in current production dates back at least to the beginning / middle of the 50s, As the Chevrolet Corvette was the first car to be made with fiberglass bodywork, developments in synthetic resin technology in recent years have resulted in more sophisticated plastic materials with higher impact resistance than fiberglass, with polycarbonates as an example Decade causes v Many manufacturers of plastics are looking for solutions to the problem of making the entire bodywork from these now-developed high-strength plastic materials on a large scale and at a reasonable cost rate. Current development efforts are also directed to the production of plastic bodies through various alternative plastic molding processes, including the use of SMC (film molding compounds) and RIM (reaction injection molding) techniques.

The development of a production process for the production of outer body parts and frames made of plastic requires solutions to a number of technical problems. These parts must be manufactured at a reasonable cost for machining, assembly and materials. The final product must also meet certain quality requirements. For example, the body frame obtained constructive suitability, such. B. impact resistance and resistance to mechanical stress, meet what is required to compete with the plate can. It must also have a color coating with a defect-free and durable outer surface. A car-quality paint overlay must meet certain test specifications with a large number of physical properties in order for it to be used. These properties include surface gloss, clarity of image, hardness, abrasion resistance, weather resistance, e.g. UV resistance, impact resistance, thermal stability, i. Resistance to extremely high and low temperatures, cleanability, paint adhesion to the underlying body frame, resistance to water and exposure to moisture and hiding power or urgency. Transparency of the paint job. In the past, a conventional production method for applying the outer paint coat on sheet metal bodies involved transporting the prefabricated bodies to the paint application lines in the plant where the bodies were dipped in paint, then conveying to a separate place for baking the paint and waiting for the cured paint coat to dry through. Most paint systems today are acrylic-based enamels which crosslink during firing to a hard, glossy and durable paint coat. After the paint coating, the bodies are transported back to the production plant, where further assembly takes place. Conventional paint coatings on sheet metal bodies and plastic parts are touring and pose a significant operational problem with respect to environmental protection, worker safety, corrosion treatment, and waste disposal. It is estimated that about one-third of the total investment in a car production plant today is in the paint of bodywork and frames.

In recent years, metal lamination techniques have been used to form a reflective, weather-resistant metal surface on injection molding plastics for automotive trim parts. These techniques did not result in plastic trim parts with a paint-coated surface that can be used on the outside of the car. Experience has shown that such plastic decorative parts show difficulties in maintaining the reflectivity and in avoiding surface defects during mechanical impact and the exposure to environmental influences.

New body applications for injection molded plastic materials can be developed if the manufacturer could find a way to do that in a large way to produce plastic and painted body frames, from the point of view of durability and appearance all that must be brought along with what is required for use outside the car. Moreover, as an alternative to the conventional car paint coatings, where processes can be developed that already provide moldings or coating for the paint coating, then the assembly equipment for the cars could be even more compact, and it could be at the factory site Saving investment and avoiding environmental and safety issues related to conventional paint coats on cars.

Many collaborative efforts in product wrapping have focused on alternatives to conventional paint coatings for plastic molded body panels and parts thereof, but to date there is still no sign of success in this area. In addition, there are still a number of problems to be overcome until an economical, production-ready color system and a method for applying the color layer has been developed so far that it can be used in the outside of the car and molded from plastic body frames and parts thereof, so that the usual paint spraying operations omitted. For example, the cross-linkable acrylic-based enamelling paint systems that are normally baked on sheet metal bodies to produce a more resistant, glossy finish paint can not be used as a paint coat because of the temperature limitations of the plastic carcasses. One approach, which is the subject of this invention, involves the development of a color-coated laminate to release the usual color finish on the exterior of the body. The laminate with the color layer is produced by applying the paint to a cast film by means of appropriate coating techniques. The dried color layer is then transferred from the cast film to a composite panel using dry-color transfer techniques. The coating process allows the use of paint systems that are resistant to high temperatures and that provide a tough, glossy finishing coat. The laminate is later converted by heat treatment into a complex, three-dimensional shape and then glued or compressed with an underlying body part or frame made of plastic to a total piece or compressed. It is also possible to use spray-coating techniques in which plastic moldings are produced in such a way that they simultaneously bond to the laminate at their surfaces.

Numerous technical problems have to be übowunden to such a laminate of Heat Treatment ¹ ·. Be able to use _(. -R i in a Spritzüberzjgsprozeß, so that it remains. The laminate must for example be in the heat and under vacuum at these operations in an error-free '' RBOB ^ i Λ -he with high gloss and resistance properties.. It is possible to formulate a three-dimensional shape without causing cracking, loss of gloss, discoloration in case of starvation, or other surface imperfections bc "." (+, f) the amount of pigment needed to give the required color density or opaqueness and reproducibility a "picture"

comes. It has been found, however, that the use of pigments in a paint layer can cause the loss of gloss of the paint surface when the paint-coated laminate is subjected to a heat treatment. However, the gloss> -3t may also occur on a non-pigmented colorless coating as a result of the heat treatment.

In addition to the requirements for surface gloss, the finished color coating must be free from defects. Defects must not be caused by the heat treatment step and the laminate must have been bonded or pressed together with the plastic substrate underneath in such a way that any defects which may be present in the support material are masked. _N

In addition, a finished color coat can have a satisfactorily high surface gloss, but still lack the desired and eye-perceivable vision known as the reproducibility of an image. This property refers to the mirror-like character of the topcoat and is measured by the clarity of the image perceived by the reflective surface. It is difficult in a heat treatment process to provide the car with an outer color coat having a high gloss and a high reproducibility of an image.

When creating a color coat that is suitable for outdoor use in the car, the resistance properties are just as critical. The paint coat must not exhibit defects when subjected to mechanical impact and shall not degrade the finish when exposed to chemicals and weather.

A paint system which provides the necessary resistance or hardness for exterior use in automobiles must also possess stretch properties and heat resistance, which is required to heat treat the paint layer to form complex, three-dimensional shapes without cracking, paint loss, stress striation or other surface irregularities or other loss of surface finish. Large pigmented cones also adversely affect the strength and alter the elongation properties of the paint layer. In addition, the reliable bonding of color layer to the laminate and the bonding of the laminate to the underlying support material are essential.

Consequently, the desired color system should be a carefully selected combination of many physical properties to provide a surface suitable for the exterior car of the car so that the desired surface properties are obtained after the film coating, heat treatment and spray coating or compression molding process steps. However, some physical properties tend to preclude each other in such an approach. A color system must z. Have good properties in terms of durability such as hardness, toughness, weather resistance and the like; however, the same color system may not have sufficient extensibility so that it can be complexed by heat treatment without cracking or otherwise losing its resistance properties. Other color systems may lose their luster when they are given a complex form by heat treatment. Other ink systems, in turn, have sufficient elongation to allow heat treatment for the complex shape desired, but are too soft and, as a result, lack the necessary hardness or other resistance properties.

Object of the invention

The aim of the invention is to avoid the disadvantages of the prior art wherever possible.

Presentation of the essence of the invention

It is never an object of the present invention to provide a thermoformable laminate and a method of using a laminate.

The invention is based on the need for an economical production process for producing highly profiled plastic exterior body panels or frames with a film-coated paint coat having both durability and gloss and other appearance properties suitable for outdoor use Car are sufficient. Lamination techniques for applying a coat of paint to such a molded plastic part can be a valuable alternative to conventional masking on exterior body panels. Certain properties, such as Mirror-smooth, defect-free surfaces and uniform color coatings can be achieved better with lamination techniques than with conventional color coatings. Investments can also be reduced and environmental problems can be further reduced. Lamination techniques also require a color system and processing techniques that allow, during processing, to provide the resistance and stretch properties, opacity, gloss and reproduction power for an image, as well as a defect-free surface necessary for outdoor automotive applications maintain.

One embodiment of this invention relates to a process for making a final molded product having a finished paint coating whose surface properties meet the outdoor automotive criteria. These are properties that have been previously defined, and this concerns the durability, gloss and other appearance characteristics of the finished paint coat. In this method, the ink layer is applied to a three-dimensional outer surface of an intermediate laminate by a combination of color coating, dry color transfer lamination and thermoforming techniques. The thermoformed laminate is then glued or compressed with an underlying plastic carrier, e.g. By spray-coating techniques, wherein the paint layer retains its properties which are considered to be sufficient for use during these automotive finishing operations. In this context, the invention herein describes a paint system made of plastic on the surface of a body part or part, but the invention is equally applicable to other products to be provided with a coat of paint. similar in characteristics to those required for outdoor use on the car.

With regard to the use of the invention in a process for producing plastic outer body frames, the paint coating comprises a synthetic resinous material, from which a thin film is applied to a flexible, heat-resistant and temporary cast film. The ink layer is allowed to dry on the film until it has become sufficiently solid, and then it is coated with the previously determined surface glossiness of the cast film on a paint layer. This can consist of a colorless layer and a separate pigmented color layer. The colorless layer and the color layer may have been formed as separate thin film layers which have been dried and then bonded together. The color coat, in conjunction with the colorless coat, provides a composite color coat with the durability, gloss and other exterior appearance characteristics required for exterior automotive use. The ink layer is transferred to a semi-rigid, thermoformable, synthetic and resin-containing laminating film, the ink layer representing the outer surface of the color-coated laminating film. The laminate formed from the liner and the adhered layers of paint is thereafter heat-formed into a three-dimensionally shaped preformed laminate which still has the durability, gloss and other appearance-related properties required for automotive exterior use. The thermoforming step may result in considerable stretching of the ink layer. The ink layer is capable of elongating from about 50% to about 150% or more during thermoforming without appreciable loss of durability, gloss or other appearance on the car. In a subsequent spray coating stage z. B. on the back of the preformed, color-coated laminate, a synthetic, resinous carrier material injection molded to connect the laminate with the carrier. This gives rise to a plastic molded product whose surface has a paint coating that has the properties of exterior surfaces of the car. The carrier material may be the outer body frame of a motor vehicle. Normally, the substrate has a surface quality lower than the standard, but the surface defects in the substrate are masked by the spray-coating step with the liner, leaving only minimal defects on the surface and the gloss corresponding to that of an exterior paint coating on the automobile.

In one embodiment, the color layer is composed of a fluorinated polymer and an acrylic resin-containing color system having thermoplastic properties. The appropriate amounts of fluorinated polymer and the acrylic resin components in the color coat formulation provide sufficient resistance to loss of gloss and corresponding elongation in the laminate so that it can be thermoformed into complex, three-dimensional moldings while providing sufficient durability as well as the external appearance of the finished product, as required in an exterior body panel or frame. In one embodiment, where the color coat consists of an outer, colorless layer and an associated underlying color layer, the colorless layer may be prepared from a fluorinated polymer and an acrylic resin-containing paint. In this case, the colorless layer will mainly provide the durability, gloss and other appearance-related properties required when used as an exterior paint finish on the car. The color coat may also consist of a thermoplastic fluorinated polymer and an acrylic resin-containing paint system. Other color systems that are compatible with both the colorless and laminating films can also be used.

In another embodiment of the invention, the fluorinated polymer component is polyvinylidene fluoride (PVDF) and the acrylic resin component is a polymethyl methacrylate resin or mixtures thereof, including their copolymers. A finished product, which is used as the outer surface in the car, is made from a paint system consisting of about 50 to 70% PVDF and about 30 to 50% acrylic resin, which is Ma ·.%, Based on the total amount of PVDF and the acrylic solids, but without pigments.

This invention also provides a quality exterior car paint finish that has particularly high gloss and reproduction clarity of an image (DOI) in addition to the other durability properties sufficient for outdoor use in the car. This embodiment of the invention utilizes a thermoformable laminate having a colorant layer adhered thereto, which colorant layer was prepared from a solution of vinylidene fluoride in acrylic resin before being cast onto the cast film. The color coat consists at least of a colorless vinylidene fluoride layer and the overcoated acrylic resin derived from the solution to provide thermoformable laminates of high combined gloss and DOI strength. In tests, a good combined gloss and DOI force was obtained when both the colorless layer and the pigmented primer layer were prepared from the same solution of vinylidene fluoride and acrylic resin. In an experimental test on a cover frame provided with a body frame, a gloss of more than 75 gloss units were determined at an angle of 60 ° and reached oine DOI of about 90 units.

The various embodiments of the invention are disclosed herein. One embodiment includes a thermoformable laminate having a color coat whose properties can be used in the formation of a top coat for plastic body frames. Another embodiment of the invention provides a method of applying a paint layer to an exterior body frame of a motor vehicle so that the finish color coat has the durability, gloss and other appearance related properties required for outdoor use in the automobile. Another embodiment of the invention includes a color-coated, self-adhesive backed laminate for use in car paint repairs.

Thus, the present invention provides a process and production products in which a laminated outer color layer simultaneously forms an outer topcoat on a highly shaped surface of a plastic molded article. The ink layer has an appropriate combination of elongation and resistivity against loss of gloss to survive the heat without damage to the original high gloss surface, while preserving its resistance and appearance properties, which is sufficient to provide an outer color coating to be useful on body frames made of plastic.

embodiments

These and other aspects of the invention will be better understood by referring to the following detailed description and accompanying drawings.

Fig. 1 is a semi-schematic perspective view of a motor vehicle, which has one or more outer Body parts or frames may be made of plastic moldings with a color coat, made in accordance with the principles of this Invention was made, are produced. FIG. 2 is an elevational view of a rear window panel portion of a car in which an outer color coating is applied to the Surface of the window panel is applied according to the principles of this invention. FIG. 3 is a cross-sectional view taken along line 3-3 in FIG. 3 to illustrate the complex, three-dimensional shape of the paint layer. FIG

is applied to the outer surface of the window panel.

4 is a schematic representation of a profile illustrating an embodiment of the color-coated cast film

which is used in the dry paint transfer laminating steps of this invention. The ink layer thicknesses have been greatly increased for the sake of simplicity; this was not true to scale.

Fig. 5 is a schematic side elevational view illustrating the color coating step in the process

shall be.

Fig. 6 is a schematic side elevational view intended to illustrate a laminating step in the process. Fig. 7 is a schematic profile view showing how a dry one during the lamination step Composite color layer is applied to a laminating film. The film thicknesses are greatly enlarged and not to scale,

which was for simplicity's sake.

Fig. 8 is a schematic view showing a heat-forming step in the process in which a color-coated Laminate is heated in a vacuum before molding. Fig. 9 is a schematic diagram illustrating another heat forming step in the method. FIG. 10 is a schematic profile view illustrating a preliminary step in the spray coating stage of the process. FIG

shows.

FIG. 11 is a schematic profile view showing a substrate material in an injection mold on the back side of the FIG

thermoformed laminate is sprayed.

Fig. 12 is a schematic profile showing the composite profile structure of the finished plastic molded product

shows that has an outer color layer. For the sake of simplicity, the film thicknesses have been greatly increased and are not,

scale.

Fig. 13 is a graph showing the general relationship between surface gloss and the relative amounts Polyvinylidene fluoride and acrylic resin, which are contained in one embodiment in the color layer. Fig. 14 is a schematic profile view intended to demonstrate an embodiment with a laminate in which a

dry paint film and a self-adhesive film for paint repairs to the car according to the principles of this invention.

A paint layer having a surface suitable for automotive exterior use is applied to a molded plastic product by a combination of paint coating, dry paint transfer lamination and thermal techniques to form a color coated laminate which is then bonded to an underlying plastic substrate or is pressed. The thermoformed laminate can be bonded to the backing by spray-over techniques. The car's external properties, such as durability, gloss and other appearance-related criteria, are produced and maintained during the process. FIGS. 1-3 illustrate an embodiment of the dry paint transfer process and the product in which an exterior paint job for the car is applied to an exterior body panel or frame of a car 20. In the illustrated embodiment, the ink layer is applied to the outer surface of a rear window panel or molding 22 of the vehicle. The rear window molding can be obtained by injection molding on a wood-filled, synthetic, resinous support 24 made of plastic, which delivers the manufacturing element for the field. The color layer 26 may be applied to the outer surface of the support by means of paint coating, dry transfer lamination, thermoforming, and spray coating techniques described below. The ink layer 26 has useful properties for the car exterior paint, and these properties will also be described in more detail below. The use of the method and article of this invention is described in the context of exterior body panels and racks, although other end uses of the method and product are possible without departing from the scope of the invention. For the sake of simplicity, exterior body panels and frames are referred to herein as body panels.

The carrier 24 may contain a large amount of fillers, which may typically cause a surface on the carrier so that it does not meet the standard. In applying the invention, the ink layer 26 is applied to the surface of the carrier so that the laminate obscures all defects in the underlying profile surface and, consequently, provides a truly smooth, flawless color coating with properties that are suitable for outdoor car applications , The rear window molding serves as an example of the type of heavily profiled outer surface on which the paint layer is to be applied. Referring to the rear form-molding part 22 in Figs. 2 and 3, the molding has an elongated, rectangular-shaped window opening 28 with a wide rim 30 which has a heavily profiled outer surface and which extends around the window opening. The complex shaped multi-profiled surface has a curved outer bead 32 of conical profile extending around the periphery of the molding, a longitudinally curved and narrowly recessed region 34 extending within the outer bead, and a wide skirt portion 36 in ascending direction within the recessed region 34 that extends around the entire periphery of the window opening.

The wide edge portion 36 is at the same height as the surface of the wide tail 38 from the window opening. The inner edge 40 of the wide edge portion 36 has a cone-shaped profile thickness and extends around the inside of the window opening. As shown in Figs. 2 and 3, the paint layer 26 of the car adheres to the complex shaped outer surface of the rear window molding, but the paint layer can also provide a durable, highly lustrous outer surface similar to other body frames with various irregularly shaped, three-dimensional surface configurations and may also be useful for other production products. The method comprises first performing the coating step on one or more temporarily used cast films which are provided with a color layer or a portion of a color layer. FIG. 4 illustrates an embodiment of a paint-coated carrier 41 having in connection therewith a flexible, foldable, heat-resistant, and self-supporting carrier film 42, but also relates to the art relating to the cast film; and a transferable, adhesive and flexible paint cover 44 located on one side of the support. The color coat 44 is a non-self-supporting, flexible, synthetic, resinous, dry film-shaped coating. The color coat 44 may be formed from a combination of an outer colorless layer and a color layer; or a combination of outer colorless layer and a tinted layer; or the color layer results from a simple dry-film-formed coating of a pigmented synthetic resinous material having the automobile exterior characteristics described below. In the presently preferred embodiment, the color coat 44 comprises a colorless layer 45 which has been applied to the support and dried, and a color layer 46 on the dried colorless layer. The color layer can be applied to the dried colorless layer. On the other hand, the colorless layer and the color layer can be applied separately to corresponding cast films and dried on the respective carrier. The color layer can then be later connected to the colorless layer. The combination of colorless layer and color layer are referred to here for simplicity as color coat 44 or composite color paint. Optionally, the color-coated carrier may comprise a size coat 47 which is applied to the dried color layer. The size coat provides adhesion to a liner in a subsequent lamination step. In one embodiment described below, a thermoplastic laminating film of a polyolefin is used, and a sizing layer of a thermoplastic chlorinated polyolefin provides excellent adhesion between the ink layer and the kaschiar film.

The carrier film 42 preferably consists of a polyester casting film with a high glossy surface 43. The carrier in the form of a polyester film may consist, for example, of Mylar, of the polyester film 3000 or the like. The preferred film thickness of the cast film is about 50.8 \ im. The polyester films are preferred because the high gloss surface 48 is capable of transferring its high gloss to the surface 49 of the colorless layer 45 when in contact with the substrate.

Carrier material passes, the passed-on gloss is considered sufficient for outdoor use in the car. Alternatively, the coatings can be made on a polished metal band. When the paint layer is cast on a separate cast film, the surface gloss that the substrate imparts to the paint layer is not critical. The polyester base film has sufficient heat resistance so as not to yield to the elongation in the axial direction at the temperatures used in the subsequent paint layer drying and lamination steps. The colorless layer may be applied to the polyester support film without a release layer on the high glossy surface 48 of the support. This makes it possible to avoid a separate coating which could adversely affect the transition of a highly lustrous surface on the substrate to the surface 49 of the colorless layer. The formulation of the colorless layer was chosen to be easily removed from the cast film and assume the highly glossy surface of the support after the colorless layer has dried and used in the subsequent dry-color transfer lamination steps as described below. has been transferred from the carrier to a laminate.

In an optional process step, a thin wax film (not shown) may be applied to the cast film and dried, followed by coating the thin wax film with the colorless layer 45. The wax is coated to a film thickness (less than 0.25 pm, preferably 0.025 μίη) that any adverse effect on the colorless layer in taking over the surface gloss of the support material is avoided.

The colorless layer 45 is a transparent or substantially transparent thermoplastic synthetic resinous coating mixture which is applied in the form of a thin film to the surface of the cast film, in liquid form. Heat is then applied to dry the colorless layer without the resin crosslinking while the colorless layer is on the support. The preferred dry film thickness of the colorless layer is about 12.7 μm to about 38.1 μm. Preferably, the colorless layer is applied to the cast film by a co-rotating roller coating process, as shown in Figure 5, although the colorless layer may also be applied by gravure printing or other conventional coating techniques. Referring to the co-rotating roller application process of Fig. 5, the paint layer 46 is coated in a coating bath 50 having a paint addition point 52 in the center region of the basin and a paint removal point 54 at an opposite location from an overflow 56. An applicator roll 58 rotates take the paint from the bath and thus sweeps the previously uncoated carrier film 42, which is passed over a guide roller 60 and then between the applicator roll and a Gu mm! supporting roller 62 is passed therethrough. A measuring roller 64 in the immediate vicinity of the applicator roll rotates in the same direction as this. A doctor blade 66 passes over the surface of the metering roller to appropriately control the amount of coating on the surface of the applicator roller. The adjustable gap between the metering roll and the applicator roll controls the thickness of the coating on the surface of the applicator roll. The set at the applicator roll layer is then placed on the polyester film 42, as soon as the film comes into contact with the same direction running applicator roll. The coating applied to the film can be seen at 68. The coated film then passes through a drying oven.

The colorless layer is dried at oven temperatures ranging from about 121 to about 204 ^° C. Preferably, the colorless layer is viewed in a plurality of spatially separated zones, in the longitudinal direction of the paint coated carrier and getrockn lying in line with the reverse roll coater - ^ct ne preferred drying method is by the application of three heating zones from wherein, in each subsequent zone. · Ι higher temperature is applied. The solvent vapors contained in the colorless layer are all in the multi-stage drying process

essentially expelled. The same multi-stage drying process is used for the drying of the ink layer 46 and the glue layer 47. The polyester carrier exerts heat at temperatures above 232 ^° C., so that the carrier does not deform during the drying step. The carrier thickness of the polyester film with about 50.8 microns protects the film from stretching in the drying stages. This ensures a high gloss force, which is taken over by the surface 49 of the dried colorless layer of the strong glossy surface of the carrier. This makes it possible to use high-temperature-resistant, high-gloss color systems, which do not apply to plastic substrates and can be dried directly because of the temperature limitations in the plastic material.

The formulation in the colorless layer provides a thin outer layer in the form of a dry film which, in conjunction with the underlying color layer, produces a composite color layer having properties useful for exterior painting on the car. Such a paint coat is substantially a combination of the externally shown the car Beständigkeltseigenschaften, the gloss and the other, the external appearance of relevant properties of the ^finished>: in arbanstrichs. The specifications for a color coating be; Exterior automotive application as defined herein includes the mechanical properties of hardness, abrasion resistance, thermal resistance including heat resistance, resistance to gasoline and acids, cleanability, adhesiveness, certain weatherability properties such. As UV resistance and resistance to exposure to water and moisture and impact resistance. For the sake of simplicity, these properties are collectively referred to herein as 'resistance properties'.

Weatherability, which is determined in part from UV resistance properties, is a durability characteristic commonly used in the art to set standards for exterior painting on the car. To determine the UV resistance, this may require a long-term exposure test on the paint that takes two years for a test method. Certain Long-Term UV Tests The paint of this invention has not been updated but has other accelerated UV resistance and weather resistance short term tests described below.

In addition to the durability properties, the specifications for a car exterior quality paint also include tests to determine the visible appearance of the finished surface. These criteria are the gloss, the reproducibility of an image (DOI), the dry film thickness, and the hiding power or opacity of the color coat. These properties are collectively referred to herein as gloss, gloss and other properties related to the appearance *.

Thus, a paint can have a number of predetermined physical properties which when taken together define whether the paint is suitable for use as a paint finish exterior to the car. In general, in the paint film of this invention, which is in the form of a dry film, a combination of the above-described weatherability and external appearance properties, including gloss, results, allowing it to leave the function of an exterior paint on the car ,

The criteria used to define whether a paint is suitable for outdoor use in the car are not uniformly applied within the automotive industry. Certain standards may vary from one car manufacturer to another, but also vary from model to model at a manufacturer. Most of the criteria used to define a high quality car exterior for the method of the present invention have been adopted from specifications and test methods included in certain test programs of General Motors Fiero and Pontiac Grand AM. These criteria are disclosed herein so that they may be used as an example of techniques to determine if a paint for exterior car painting has the proper characteristics, although other combinations of test criteria and test methods may be used for this purpose as well. The specifications and test methods for determining the properties of the exterior paint on the car according to this invention will be described in detail below.

In addition to the properties of durability and appearance, the formulation of the colorless layer of the composite color layer also gives sufficient elongation at the thermoforming temperatures, allowing the paint to develop complex, three-dimensional shapes without loss of gloss in the colorless layer and without any resistance property below it What is required for an exterior surface of the car, can be heat formed. In one embodiment, the paint is thermoformed at temperatures of about 138 to about 204 ° C. A laminate having a colorless outer surface can be thermoformed at these temperatures and maintains the resistance and appearance characteristics of the composite paint. The stretching of the color layer may be essential in the formation of complex, three-dimensional shapes of a finished product. The elongation of the colorless layer (and the composite color line) can be greater than 50%, often greater than 100%, to produce a highly profiled finished product. Plastic body parts and bodies made of plastic often also require thermoforming. The colorless layer is also capable of resistance and. to maintain the appearance of the paint during a subsequent molding step.

The colorless layer is composed of a transparent, thermoplastic (non-crosslinked), synthetic, resin-containing coating composition. The thermoplastic properties enable a colorless dry-film coating which softens and deforms and molds at thermoforming temperatures in vacuum, yet still preserves the outdoor resistance properties of the car, the gloss, and other properties relating to external phenomena, after the finish and three-dimensionally shaped film coating returns to its stable or cured state. In the form of a dry film, the colorless layer has an extensibility in the range of about 40 to about 150% or more, the film thickness being about 12.5 to 38.1 μm, and the heat forming temperatures being about 138 to about 232 ° C.

In one embodiment, the colorless layer is a mixture of a thermoplastic fluorinated polymer and an acrylic resin. The colorless layer preferably contains the fluorinated polymer and the acrylic resin as its main components. The fluorinated polymer component is preferably a thermoplastic fluorohydrocarbon, such as. As polyvinylidene fluoride (PVDF). The fluorinated polymer may also copolymers and ^T erpolymere of vinylidene included. A thermoplastic fluorohydrocarbon which is suitable for the colorless layer is the polyvinylidene fluoride,

known as Kynar. This polymer has a high molecular weight (400,000) which provides a useful blend of resistance and chemical resistance properties, generally a high molecular weight PVDF resin having an average molecular weight between 200,000 and 600,000 is used.

The acrylic resin component of the colorless layer may be a polymethylmethacrylate or a polyethylmethacrylate resin or mixtures thereof, including methacrylate copolymer resins and small amounts of other comonomers. The colorless bar may also contain minor amounts of block copolymers and / or compatibilizers to stabilize the blended PVDF and acrylic resin system and provide compatibility between the films. In one embodiment, the main component of the acrylic resin contained in the colorless layer is a medium molecular weight polymethyl methacrylate resin, such Elvacite 2010. (In all other references to Elvacite resins, it should be noted that Elvacito as a trade name of DuPont stands for a group of its acrylic resins.) In one embodiment, the major component of the acrylic haze for the colorless layer may be a high molecular weight polyethylmethacrylate resin , z. Elvacite 2042. Dia Acrylkompor.ente the colorless layer may also consist of a mixture of Elvacite 2010 and a medium to high molecular weight polymethyl methacrylate resin, such as. B. Elvacite 2021 exist. In a further embodiment, the acrylic resin component of Elvacite 2042 and a low molecular weight polyethyl methacrylate resin, such as. B. Flvacite 2043. Further, similar combination 'n of acrylic resins, their homopolymers and copolymers can be used as a component in the colorless layer. In general, the acrylic resin component has a relatively high average molecular weight of 50,000 to about 400,000.

The formulation for the PVDF and AcH-based colorless layer can be prepared as a solution of PVDF in acrylic resin and a solvent Experimental experiments on finished body frames in which the paint was made from a solution of PVDr in the acrylic resin give high gloss and rendering power of an image The experimental test results are described below in Example 11.

The formulation of a colorless PVDF based and acrylic resin based coating can also be prepared as a dispersion of PVDF in a solution of acrylic resin. In one embodiment, the formulation for the colorless layer may be made by mixing the acrylic resin with a suitable organic solvent and applying heat to dissolve the resin. The mixture is then allowed to cool sufficiently long before the PVDF component is added so that the PVDF does not dissolve but is present as a dispersion in the acrylic resin-solvent mixture. By leaving the PVDF component in the undissolved state in the colorless layer, the evaporation of the solvent during drying of the colorless layer can be improved.

A preferred composition in the dried colorless layer comprises about 50 to 70% PVDF and about 30 to 50% by weight of acrylic resin. In some cases, the maximum content of the PVDF component is about 65%, the remainder being essentially the acrylic resin. These solids ranges are based on relative proportions of the PVDF and acrylic resin components within the colorless layer formulation. Other smaller solid quantities, such as. As UV stabilizers, block copolymers and compatibilizers may also be included in the formulation for the colorless layer. In one embodiment, in a successful attempt at a body frame, exterior car paint properties have been provided with a paint system in which the dried colorless layer consists essentially of about 50% by weight PVDF and about. 50% by mass of folymethyl methacrylate resin. This colorless layer provided high gloss (after thermoforming) and good properties related to the car's exterior appearance and durability. In another successful experiment on a body shop, which had good car appearance and durability characteristics and high gloss, the dried colorless layer consisted essentially of about 65% by PVDF and about 3% by weight of polyethyl methacrylate resin.

The acrylic resin component in the colorless layer is desirable because of its compatibility with the PVDF in the dry film profile. The acrylic resin component is added to the PVDF in an amount to prevent loss of gloss during thermoforming of the final colorless layer. The acrylic resin is also added in such an amount as to give a transparent, colorless layer in the dry-roughened profile. In general, the transparency and reproducibility of an image in the composite color paint increase in proportion to the amount of acrylic resin added to the PVDF acrylic resin system. It has been found that a colorless layer of pure PVDF has fairly good resistance and elongation properties, but such a layer of 100% PVDF is usually transparent and loses much of its gloss when heated to normal thermoforming temperatures. When sufficient PVOF resin component is added to the PVOF component, the resulting colorless layer becomes acceptably transparent and no loss of gloss occurs at the thermoforming temperatures. Increasing transparency in the colorless layer improves the gloss of the finished colorless layer. The combination of acrylic resin with the PVDF in such amounts is also done so as to provide sufficient elongation to allow the colorless layer (and associated paint layer) to form complex, three-dimensional (as part of the laminate described below) Profiles heat molds, wherein the outside of the car attached finished paint on the permanence characteristics and the appearance of the appearance-related properties, including the gloss are retained. It has been found that with a colorless PVDF-acrylic resin-based dry film-based film lying on the total solids of PVDF and acrylic resin, more than about 35 mole% of acrylic resin and less than about 65-70ma. -% PVL-F contains, the Glartzverlu & t is avoided as a result of thermoforming heat and is still provided for a sufficient elongation.

It is believed that in some of the cases, the loss of gloss in a PVDF-acrylic resin-based colorless layer is caused by the precipitation crystallization in the colorless layer upon cooling after heat-forming. Stronger crystallization in the arblosen layer on PVDF-acrylic resin-based, so it is believed, at least partially, due to relatively higher thermoforming temperatures. The addition of acrylic resin to the PVDF for colorless layer formulation can prevent the PVDF from crystallizing on cooling after the application of normal heat forming temperatures. The use of polymethylmethacrylate as the defining component of the acrylic resin in the colorless layer may be desirable because it results in a higher glossing power over the polyethylmethacrylate. It is believed that the higher gloss results from a lower crystallization rate of the polymethylmethacrylate on cooling. It is further believed that in certain instances the gloss loss due to microcracking on the surface of the colorless

Layer caused during thermoforming v - '. Rd. The use of a certain amount of a softer acrylic resin than the polymethyl methacrylate, e.g. For example, the F olyethyl- methacrylate, in some cases, after heat-forming, especially in the context of lower Wärmaformungetemperaturr «n, u u can cause a strong shiny surface in the colorless layer.

Referring to the extent of gloss loss from the colorless layer, which may be caused by non-uniform coalescence of the PVDF component within the resin system, it is believed that this problem is due to more uniform mixing in the dispersion, namely the PVDF in the acrylic resin , or overcome by using a solution-based system. ""

The PVDF component in the colorless layer is desirable because of the exterior durability properties of the automobile and because of the stretch properties that it provides in the final colorless layer, particularly in conjunction with the acrylic resin component. The PVDF component also provides good weatherability properties in the final paint. It has been found that a colorless layer of the pure thermoplastic acrylic resin gives good hardness and toughening characteristics, but lacks weatherability. A colorless layer of pure acrylic resin also results in difficulty in dissolving out of the injection mold near the spray coating calls. A crosslinked acrylic resin which is predominantly used as an exterior paint in a car is not advantageous in the process of the present invention. In the heat-forming process, it breaks and tears as soon as vacuum is applied to the laminate coated therewith. A PVDF and acrylic resin-containing colorless dry film layer containing about 30 to 50% by weight of acrylic resin (based on total PVDF and acrylic resin solids mass) has a sufficient dwell to allow for proper heat forming and overspray while leaving the exterior of the car regarding!) durability, gloss and other appearance related properties in the final composite paint finish.

The color layer 46 is bonded to the colorless layer after this colorless layer is dried on the cast film. The color layer can be applied to the dried colorless layer or else the color layer is applied to a separate cast film made of polyester, dried and late tr then transferred from the cast film to the colorless layer. In both cases, the ink layer is preferably applied by co-rolling techniques similar to those shown in Figure 5 to the cast film. The preferred dry film thickness of the ink layer ranges from about 12.7 to 38.1 μm. The paint layer consists of a thermoplastic, synthetic, resinous paint mixture that contains a sufficient amount of pigment to provide external appearance to the car for outdoor appearance on the finished product. Specifically, the ink layer has a sufficient amount of pigment so that the bond coat retains its corresponding opacity and reproducibility of image, and the whiteness is avoided under stress in the thermoforming process and thus can be used as exterior paint on the car. The resinous material, which is contained in the color layer, in conjunction with the colorless layer ensures that ' in the finished paint and the required outdoor car surface created. That is, although the colorless layer is the Ben. At the finished surface, the properties of the exterior of the car are determined not only in front of the formulation for the colorless layer. The color layer underneath can, for example, influence the besting properties of the finished paint. The abrasion resistance is an example of a mechanical property that can be increased from the combination of a tougher color layer and the colorless outer layer. The weatherability of the finished paint is also influenced by the formulation for the color coat for the colorless layer. The paint layer also has a resinous material, which is capable of sufficient elongation at the thermal bonding temperatures, so that the properties of the finished paint paint on the outside of the car are affected. The ink layer is preferably dried by passing it through the same multiple heating zones as are used in drying the colorless layer. The drying temperatures are increased in steps and can have approximately the same temperatures as are used in drying the colorless layer. Preferably, in the colorless layer, similar resinous components with mutually compatible solvents are used in the color layer to provide adhesion between the colorless layer and the color layer, without the need for additional stabilizers or additives. The composition for the color layer is preferably made of a synthetic, resinous paint mixture with thyrmoplastic properties which are comparable to those of the colorless layer. Although the paint layer per se does not necessarily have to have all the properties required for the exterior of the car in terms of durability and appearance to have a useful composite paint coat, composition is preferred for the paint coat (of which this is in the paint) excepted pigment), which has most of the desired outdoor durability properties. In one embodiment, the color layer consists of a thermoplastic fluorinated polymer blended together and an acrylic resin-containing color system. This color system can be comparable to the coating of PVDF and acrylic resin used in the colorless layer. The fluorinated polymer component may also include copolyesters and terpolymers of vinylidene fluoride. The formulation for the color layer can be prepared by mixing the acrylic component with suitable organic solvents and applying heat to dissolve the acrylic resin. In a preferred embodiment, the PVDF component is solubilized in the acrylic resin solution b, although the PVDF may also be left as a dispersion in the acrylic resin based system. Subsequently, the pigment is added to the PVDF-acrylic resin composition. The composition of the dried ink layer (of the PVDF and the acrylic resin solids but without the pigment) preferably comprises about 50 to 70% PVDF by weight and about 30 to 50% by weight of acrylic resin, based on the total mass PVDF and acrylic resin solids. In a preferred dispersion formulation, the dried color layer consisted of about 65% PVDF and about 35% acrylic resin by weight. For the ink layer, a polyethylmethacrylate resin such as Elvacite 2042 or Elvacite 2043 or mixtures thereof is the preferred acrylic resin component. The relatively large amounts of PVDF present in the ink layer results in a further film and thus increases its elongation properties.

The color layer may have a substantial level of pigment to provide sufficient opacity and to give the finished product the desired color. In a heavily profiled, three-dimensional

A large amount of pigment may be required to make the finished article opaque in the end after heat-forming. For most colors, based on the solids contained in the layer, a pigment content of about '; to 30Ma .-% necessary to achieve the desired opacity in the finished paint. In this case, too, one speaks of the pigment-binder ratio. The amount of pigment used varies depending on the color. For example, in an experiment on a body frame provided with a red paint, the pigment level was about 23 mass%, based on the total solids. In a body frame used for experimental purposes, for a black paint, about 3 to 5 mass% of carbon black was used. iment required. The pigment contained in the ink layer can affect the properties that affect the exterior of the car. If z. B. in a laminate, the color layer is applied as Einzelelfarbschicht or comes in the laminate as an external paint application for use, during the heat molding of the laminate, the pigment contained in the coating in the ink layer lead to a loss of gloss. (Under these circumstances, no loss of gloss can occur in the same coating with a colorless layer and during the same thermoforming step.) It has been found that high gloss power is provided in a finished paint when an outer colorless layer is applied to the ink layer does not suffer any loss of gloss, which would otherwise occur during thermoforming of the color layer. In other words, a color coat, which normally undergoes a loss of gloss as a topcoat, may be under an outer colorless coat if, after heat-forming, this colorless coat provides the shine required for outdoor use on the finish.

With respect to the loss of luster phenomenon, it has been found that an otherwise glossy outer surface of a paint layer, applied to a laminate in a flat (even) coating of uniform thickness, usually undergoes loss of gloss when the laminate is heat formed into a complex, three-dimensional profile. It is believed that such a loss of gloss is caused by the particles added to the layer, which pigment penetrates into the outer layer during softening and stretching upon thermoforming. It has also been found that such a loss of gloss can be overcome by coating (or laminating) the outer colorless layer which is on the color layer with a sufficient film thickness so that the colorless layer acts as a barrier layer and prevents the pigment particles from precipitating migrate the color layer through the colorless layer and penetrate to the surface of the colorless layer in the heat-forming step.

The high pigment content in the paint layer may also be due to mechanical properties of the paint, e.g. As the resistance and elongation adversely affect. In general, the high pigment level present in the ink layer reduces the elongation of the paint. The pigment may also reduce the strength or hardness of the coating. A paint coat, which by itself may not have all the durability properties of an exterior paint finish for the car, may still be useful in the finished product. The elongation properties, however, prove to be critical because during heat-forming the color layer must not hinder the stretching of the colorless layer. In the ink layer, when the amount of the PVDF component is at least equal to or greater than that of the acrylic resin component, the stretching properties of the ink layer increase. In addition, the acrylic resin component in the formulation for the color layer may have a high molecular weight, which gives the color layer through the high-strength resin, the hardness or strength properties that it lost by the addition of the pigment. The greater amount of PVDF in the color coat can also improve the resistance to stain of the finished paint.

Consequently, the desired formulation in the color layer provides the appearance-related properties as well as the resistance properties which, in conjunction with the colorless layer, provide a composite color coat whose properties are suitable for outdoor use in the car. The ink layer also has sufficient elongation to be thermoformed together with the colorless layer, so that during the thermoforming, the resistance and the external appearance of the property including gloss in the finished paint are not degraded. In a Ausfohrungsfo'm a test was carried out on a body frame with a Faibanstrich which PVDF between about 50 and 70Ma .-% and a high molecular weight polyethylene methacrylate resin between 30 and 50Ma .-%, based on the total (non-pigmented) Solids, exhibited. This combination created the endurance and exterior appearance characteristics of the finished paint finish, which are sufficient for outdoor use on the car.

As an alternative to the combination of PVDF and acrylic resin, the ink layer may also contain other formulations. It is believed that a flexible pure acrylic resin having the required elongation properties or certain softer acrylic resin co-dispersible or acrylic dispersing paints having sufficient elongation and resistance properties (especially in resistance to weathering) could also be envisaged for a paint coat formulation. It is also believed that hateirated urethanes and vinyl compositions, e.g. Polyvinyl chloride, binders for acceptable paints submit grains. The use of a separate color coat containing no fluorinated polymer such as the PVDF can reduce the cost of the finished paint.

Although the color scheme has been described in terms of a colorless coat and a separate color coat, this inventive paint finish can also be obtained in a simple, pigmented, thermoplastic, synthetic, and resinous coating, with the pigment being highly dispersed in the coating, so that with her after the heat forming no loss of gloss occurs. Alternatively, a colorless layer having the required resistance and appearance characteristics may be used together with an underlying layer or anode substrate, thereby promoting color and the other, in conjunction with the creation of a finished article Paint properties necessary properties is provided and thus suitable for outdoor use in the car.

Next, the size coat 47 is applied to the dried color layer, either when the color layer is applied to the colorless layer or when the color layer is only spread on a separate cast film. The size coat bonds the color coat to the liner used in the lamination step, which will be described below. The size coat is a synthetic resinous material which is heat activated in the subsequent lamination step to bond the color coat to the liner. The preferred dry film thickness of the size coat is between 2.54 and about 25.4 μm. The glue layer is preferably used in the form of a thermoplastic and dried in the same multistage drying plant, as it is also used for the colorless layer and the color layer.

The size coat is dried at a temperature such that the solvent evaporates, but the resin is not yet cross-linked. The composition for the glue layer may vary depending on the composition of the paint layer and the laminating film to which the paint layer is bonded. For a paint on PVDF acrylic resin bases, an acrylic resin-based size coat is preferred for proper adhesion of the color coat to the liner. In one embodiment, where the ink layer adheres to a liner made of acrylonitrile butadiene styrene (ABS), the size coat is a polymethyl methacrylate resin, e.g. Acryloid A-101, which was dissolved in a suitable solvent. In another embodiment in which the laminating film consists of a thermoplastic polyolefin, the size coat is preferably used as the chlorinated polyolefin.

The ink-coated carrier shown in Figure 4 is next coated with a thermoformable laminating film by dry-color transfer lamination techniques. The lamination step is made clear by FIG. Figure 7 shows a schematic of a thermoformable laminate 70 resulting from a dry color transfer lamination step. The laminate 70 has a composite color coating 44 (consisting of the colorless layer and the color layer), which adheres to the laminating film 72 by means of the glue layer 47. The laminating film preferably consists of a semi-rigid, self-supporting, thin and flat film of a synthetic, resinous material. The laminating film is made of a material which is compatible with the plastic material used later in injection molding and serving as a support for the mold carrier in the finished product. The laminating film is preferably produced from the same or essentially the same polymer material from which the carrier substrate of the finished product is made. The laminating film is also made of the material whose thickness allows the thermoforming together with the adherent composite color layer to a complex, three-dimensional shape, without the properties of the outside of the car to be applied paint painting affected. The material from which the carrier is injection molded may contain a substantial amount of filler capable of producing a flawed surface which will be visible on the substrate of the injection molded article. The laminate is adhered to the malformed top surface of the injection-molded carrier to improve the surface properties of the carrier rack and to provide an outstandingly smooth, inspectable exterior painting on the car. The multi-layered product, in its finished form, has a high quality, substantially defect-free, three-dimensionally formed paint on the exterior of the car, including the laminating film 72 combined therewith, which provides the buffer layer between the surface that does not meet the requirements represents the carrier and the finished color layer. The material of the laminating film minimizes the surface defects that can be transferred to the paint. In this case, ABS is the preferred material from which laminating films are produced. One of the preferred ABS materials is Cycolac L. S. Thermoplastic polyolefins (TPO's), such as polypropylene and polyethylene, can be used as well as'

Polyester or an amorphous nylon, e.g. Bexloy C-712, use. The incorporation of laminating films and TPO substrates within a composite structure will be described in more detail below. The thickness of the liner may vary, but in general the liner must be sufficiently thick to be able to mend or mask the imperfections on the surface of the underlying support so as to have a perfectly smooth surface beneath the paint. The laminating film must also not be so thick that the stretching properties of the laminate suffer disadvantages in the subsequent thermoforming step. A desired thickness range for the laminating film is between about 254 and 762-1016pm, e.g. 508pm is the preferred thickness for an ABS film.

The lamination step is best understood when referring to the schematic diagram of FIG. 6 where the color coated backing 41 is on the upper unwind roll 74 and a flexible 508 μm ABS backing film 72 rests against the lower unwind roll 76. The color-coated carrier in one embodiment consists of the colorless layer and the color layer which are on a simple, flexible cast film. The color-coated cast film 41 is guided over a belt roll 77 and the laminating film 72 over a belt roll 78. The backing and liner are then passed between a heated lamination drum 79 and a rubber backing roll 80. The lamination drum 79 is preferably made of steel and operated at a preferable temperature of 204.4 to 218 ^° C. It brings by pressure the overlapping foils in contact with each other, so that they are heated to the appropriate temperature, the adhesive is activated in the glue layer and connects the ink layer with the laminating film when pressure contact of the two films. The rubber support roller 80 is pressed against the lamination drum with a preferably applied pressure of about 44 kg / cm in the longitudinal direction. The slow rate at which the film is moved during lamination ensures that the resulting laminate 70 has been heated to a temperature approaching the temperature of the lamination drum. This slightly softens the laminating film material and also activates the heat-sensitive glue layer, ensuring complete adhesion between the ink layer and the laminating film. The polyester cast film of the color coated carrier is heat resistant to well above the lamination temperatures, so that the cast film resists stretching during the lamination step. After the adhesion process step, the flexible color coated laminate 70 passes one or more chill rolls 82 to achieve? Laminate back to room temperature to cool. The laminate 70 then passes onto a laminate rewind drum 84. The cast film is stripped from the laminate prior to the subsequent thermoforming step. This leaves a smooth, flawless, highly glossy outer surface in the colorless layer which takes over the highly lustrous surface present on the cast film. The thermoformable laminate 70 shown in FIG. 7 can also be produced by separate lamination steps, each being comparable to the lamination step shown in FIG. In this embodiment, a separate color layer is first transferred from a cast film to the laminating portfolio. The color layer may have a glue layer, with which the color layer is connected to the laminating film. The Gioßfolie is removed after lamination. The dried colorless layer is then applied by a separate cast film to the top of the paint layer, which is located on the opposite side of the laminating film. In the Heißlaminieruny stage, no glue layer is required to bring the colorless layer with the color layer to adhere.

In the next process step, the laminate 70 shown in Figure 7 is thermoformed to the desired three-dimensional profile. Figures 8 and 9 illustrate an example of a thermoforming step wherein the initially flat laminate is converted to a three-dimensional shape with a pronounced profile which is used as the surface of a body frame. Referring to Figs. 8 and 9, here are shown individually

separate laminate films inserted into a clamping frame 106 of a vacuum forming machine. The chipping can be moved on a guideway 108 back and forth. The laminate film is initially inserted into the position shown by dashed lines at 106 in Figure 8 from the clamping frame.

The clamping frame is then slid into the oven 110 on the guideway to heat the laminating film to the thermoforming temperature. The laminating film of ABS is heated to a temperature ranging from about 138 to 193 ⁰ C, while the film of Bexloy nylon undergoes heat in the range of about 138 to 216 ⁰ C. These temperatures are the actual film temperatures, not those of the oven. The actual thermoforming temperatures used in these areas can be a factor in that the colorless layer does not lose its gloss during thermoforming. In some cases, in the examples described below, a lower heat-forming temperature may prevent the loss of gloss or the formation of small cracks in the surface of the paint. These phenomena can otherwise occur at higher thermoforming temperatures. In the thermoforming stage, a pressure booster can be used to reduce the thermoforming temperature. A lower thermoforming temperature of about 132 ° C can help create high gloss and high reproducibility of an image on the finished surface. At the thermoforming temperatures, the laminate 70 bends, as shown by the dashed lines on the right side in FIG. After the laminate has been heated to the desired temperature in the oven 110, the chuck frame on the guideway is retrieved from the oven 110 and moved to its original position, which is above a vacuum forming furnace 112. The working surface of the vacuum forming furnace 112 is shown as a curved surface in Figs. 8 and 9, but this is only by way of example. So you can use other configurations. This depends on the desired three-dimensional shape that is to take the surface of the finished product. The preheated laminate is next given the desired three-dimensional shape by vacuum forming by first applying a vacuum to the vacuum forming furnace 112 via the joint 114 with a vacuum pump. The vacuum forming furnace 112 is then moved up to the position shown in Figure 9, where it enters the clamping frame. The vacuum is maintained through holes in the oven to force the molten plastic to accept the mold from the working surface of the oven. Increased air pressure can be applied to the free surface of the colorless layer on the opposite side of the support body to increase the molding pressure. The oven remains in this position for a sufficient time to cool the plastic to solid state before the oven returns to the position shown in FIG. This leaves the plastic in the form that the oven has. In the preferred vacuum forming step, a vacuum mold is used in which the vacuum forming furnace 112 is in direct contact with the laminating film and does not contact the outer colorless layer 45 on the opposite side of the Kascier foil. In this way, most of the possible defects in the working surface of the oven are obscured; and the surface * of the colorless layer is not adversely affected but can expand freely.

In an alternative applicable thermoforming stage (not shown here), the laminate 70 can be supplied as a continuous sheet of the heat mold. The laminate first passes through the oven and then passes through the thermoforming oven, which is in series with the upstream end of the oven. The continuous film is stopped to heat the laminate to the thermoforming temperature at predetermined intervals while a previously heated portion of the film is given the desired shape in vacuum.

The thermoforming stage produces a three-dimensionally shaped, preformed laminate 116, which is shown in FIGS. 10 and 11. For simplicity, the preformed laminate will be illustrated as being composed of the liner 72 and the multi-layer paintcoat 44 associated therewith. The laminate is shown in a three-dimensional shape after the heat-forming step, this being only one example of a possible three-dimensional shape. Other complex, three-dimensional forms are also possible. The composite paint layer resists elongation of greater than 40% in heat molding without loss of gloss, cracking, whitening under load, or other significant losses in the car exterior performance and appearance related properties that were present in the composite paint finish prior to thermoforming ,

Figures 10 and 11 schematically illustrate the steps in a subsequent spray-coating operation in which the preformed laminate 116 is adhered to a plastic carrier frame thereunder. The spray-coating step exemplifies one possible way to bond the laminate to the carrier. Following the thermoforming step, the laminate is placed in an injection mold 117 and fused to the front of an injection carrier 118. FIG. 10 depicts the first step in the spray coating stage where a plastic injection mold is in the open position and the preformed laminate 116 is in the injection molding stage Mold cavity between front and rear mold half 120 and 122 is introduced. The inner surface 124 of the mold half 120 imparts an identical outer profile to the paint-coated surface of the preformed laminate. The inner surface 124 of the mold has a rigid, high gloss and highly polished surface on which there are no defects, so that they can not be transferred to the glossy, provided with a colorless layer surface of the laminate. After the laminate has been preformed to its desired shape, it is cut to the appropriate size and ready for spray coating. The vacuum-formed, punched-out film is placed in the injection mold and the mold halves 120 and 122 are closed, leaving behind the laminate a space of the desired size for receiving the Spritzguismasse. This is best illustrated in Figure 11 where the injection molding material 118 flows past the preformed laminate 116 into the mold cavity via a channel 126 located in the rear mold half 122. The mold conforms to the shape of the mold cavity and permanently fuses with the laminating film of the laminate. The injection molding compound does not come into contact with the ink layer. As already described above, the molding compounds from which the carrier 118 and the laminating film 72 are produced are mutually compatible, so that the two materials fuse together to form a solid mold carrier in which the color layer has a flawless surface finish. The temperature at which the injection molding is carried out, is substantially below the melting temperature of the molding composition. In one embodiment with ABS as Kaschierfolie has z. B. the molten material at a temperature of about 232 ⁰ C. It can also use a water jacket to cool the top of the mold. During injection molding, the laminating film material softens on fusion with the molding compound, and the surface of the colorless layer takes on the surface of the molding due to the pressure during the molding process. Both tops

the mold are cooled to a temperature which is in the range of 71 to 76 ⁰ C, so that the ink layer 44 remains stable on the laminate during injection molding. The material of the colorless layer has already delivered all solvent vapors at the time of injection molding, so that the formation of vapors in injection molding is largely excluded. As a result, the colorless layer continues to have high gloss surface properties after injection molding.

FIG. 12 shows a schematic representation of the finished product 130 which has been produced according to the inventive method. For the finished product, the preformed laminate and laminating film were fused to the mold carrier 118. In one embodiment, the product may be a body exterior or frame. The outer colorless layer 45 and the color layer 45 are combined on the surface of the carrier to a paint with the outside of the car encountered properties. All defective areas on the carrier material are covered by the 508 pm thick laminating film 72, so that a faultless color coating is provided.

Alternatively, in some cases, one can eliminate the color layer or reduce the pigmentation, in which case the pigments provide the pigments contained in the laminating film or in the molding composition for the carrier. In these cases, the colorless layer is thermoformed together with the laminating film and then adhered to the support according to the previously described processing techniques. An advantage deriving from the coloring present in the laminating film is that the effects can be obscured when the paint peels off. Although the invention has been described with reference to the injection molding operations illustrated in FIGS. 10 and 11, other techniques may be employed in forming the finished product depicted in FIG. These include, but are not limited to, the use of preimpregnated glass fiber (SMC), compression and reaction foam injection molding (RIM), and self-adhesive or adhesive techniques. Instead of ABS, it is also possible to use other plastic molding compounds for fusing the support frame with the color-coated laminating film. These can be thermoplastic polyolefins (TPO's), z. As polypropylenes and polyethylenes, but also be polyester or amorphous nylon. In these cases, the laminating film is preferably made of the same polymer material as that used in the injection molding composition.

The following list contains the physical properties used for the test to determine whether the finished colorant is useful as an exterior paint on the car:

(1) gloss

(2) Rendering clarity of an image

(3) color uniformity (hiding power)

(4) Dry Film Thickness Uniformity ·

(5) Petrol resistance

(6) Solvent resistance

(7) Resistance to acid stain

(8) hardness

(9) abrasion resistance

(10) Impact Strength

(11) Adhesive strength of the paint

(12) artificial UV resistance

(13) Resistance to water and exposure to moisture.

The properties (1) to (4) are regarded as the appearance-related properties, and those of (5) to (13) are regarded as the resistance properties. Specifications and test methods for each of these physical properties are described below. Certain specifications and test methods shown below are generally available, industry standardized specifications and test methods. They were incorporated here and with reference to it.

(1) The gloss is measured by remission of a light beam at angles of 20 "and 60 'The desired remission on an exterior paint on the car should be at least about 60 to 65 gloss units at an angle of 20" and at least 75 to 80 gloss units at 60 ° respectively. The remission and other criteria were measured here before the finished painted surface is buffered and waxed. A preferred test method is described in GM Test Specification TM-204-A. To determine the mirror gloss of a finished surface, the gloss meters "multigloss" and "single gloss" can be used. These gloss meters provide values comparable to those obtained according to ASTM Method D-523-67. Each Glanzmeeser works with gloss standards that cover the expected measurement range, as well as with a piece of polished black glass plate with a known refractive index. The glossmeter is calibrated by adjusting it to read the gloss in a well-polished standard and then the value at a working standard, preferably the latter in the range of the frame to be tested. The second standard should exactly match the assigned value except for one unit. At least two readings are made on the test rig in a particular area. These values are summarized as an average, provided that they match exactly to one unit. If the area continues to diverge as one unit, additional areas are surveyed and an average is calculated.

(2) The reproduction clearness of an image (DOI) is a measurement of the clarity of an image reflected from the finished surface. The DOI can be determined from the reflection angle of a light beam on a spherical surface. The desired DOI for an exterior paint job for the car is at least about 60 units, with the maximum being at the DO1100 units. The DOI is determined using the Hunterlab Model No. D47 R-6F of a Dorigon Glossmeter. A test rack is placed on the sensor of the device and the sharpness of the reflected image is measured. The details of the DOI test procedure are described in GM Test Specification TM-204-M, incorporated herein by reference.

(3) Color uniformity is a test of whether the color of the ink layer remains uniform after heat-forming and spray-coating. The coloring is checked after the color layer has been applied to the cast film,

however, before transfer to the laminating film. A rechecking is done after a deep drawing corner to simulate the elongation during the heat forming, to determine if the color has changed. When measuring on the calorimeter, the required color uniformity should not exceed a color deviation of about one to two McAdam units.

(4) The dry film thickness (DFT) represents the film thickness of the final paint layer, which is the industry standard to determine if the ink layer thickness reaches the required film thickness as determined by the automaker. With the current exterior car specifications, uniformity of the finished paint proves to be a useful parameter in determining whether the paint meets the appearance requirements. The unit thickness uniformity of the finished paint can be determined at several locations on the finished product, including the areas provided with a high profile, to find out if the variations in the thickness of a finished paint coat exceed a required level.

(5) Petrol resistance requires that no color change, deterioration, stickiness, damage or loss of paint adhesion occurs on the plastic parts used at or near fuel filler ports after immersing them in a specified calibration fuel for ten times ten seconds between each dipping a drying period of 20 seconds was. Immediately after the tenth dip, the painted surface is checked and must pass the thumbnail hardness test according to GM Test Specification TM 55-6, which is incorporated herein by reference.

(6) Cleanability is tested in accordance with GM Test Specification TM 31-11, which has been incorporated herein by reference. According to this test, it is required that the painted plastic part survive ten rubs with gauze saturated with 9981062 heavy gasoline without evidence of staining, discoloration or softening of the painted surface. This test does not require proof of the color transition from the test piece to the fabric. A friction consists of a forward and backward movement.

(7) The resistance to acid stain requires that the test piece withstand exposure to 0.1 N sulfuric acid for 16 hours without evidence of staining, discoloration or softening of the painted surface.

(8) The hardness is determined according to the standardized Knopp hardness test. The required hardness must reach at least the Knopp hardness number four.

(9) The abrasion resistance is tested with a gravelometer under the standardized test method specified in the SAE J-400. According to this test, the painted part should withstand the gravelometer test at -23 ° C with a minimum score of eight (according to the F.B. Fravelometer rating chart). The test specimen to be tested shall pass the gravelometer test on delivery and after exposure under the Florida conditions described below. A Fisher specification for covering the FBMS 26-7 material (which has been incorporated herein by reference) also defines a minimum level of abrasion resistance in the finished paint.

(10) The impact strength is tested at room temperature using Gardener Tf .st and at -29 ⁰ C by means of Rosand test. The paint should be removed from the test in a direct impact of at least 18961 cmg without damage.

(11) The adhesion of the paint is tested by a standardized adhesive adhesion test described in GM Test Specification TM 55-3 and incorporated herein by reference. According to this test, an adhesive tape is printed on an X-shaped cut in the ink layer, and thereafter the adhesive tape is removed to check the peeling amount of the film. The adhesion test requires that at least 99% of the paint can not be removed in the pre-treatment area of the adhesive tape.

(12) Artificial UV resistance, also referred to as accelerated weathering or QUV, uses short-term test methods to determine the weathering resistance of a paint, which is designed to give an accurate indication of long-term UV stability or otherwise Properties for weathering resistance can be made. For the dom QUV test, which proves to be beneficial in determining UV short-term stability, the test panel should not show any significant deterioration in the surface after approx. 500 to 1000 hours exposure to UV light, no loss of adhesion to the paint, none impermissible shrinkage and no noticeable changes in gloss or b <. have the color, wherein in the condensation apparatus according to ASTM G-53 cycles of eight hours UV irradiation at 7O ⁰ C and four hours of moisture load at 5O ⁰ C are used.

(13) The resistance to water and exposure to moisture is determined by several tests. In the first humidity exposure test of the device under test to 96 hours 100% relative humidity and 37 ⁰ C in a Feuchtraun, as defined in GM test specification TM 55-3, and a two-hour water immersion test at 37 ⁰ C according to GM test specification TM 55-12 resist. The test panel obtained shall not show any signs of blistering when subjected to a test every minute from the test chamber and shall also pass the paint adhesion test described above. The paint adhesion test is performed within one minute of removal from the test chamber. In a second test, the finished part shall survive 15 cycles of a humidity-cold cycle test as defined in GM Test Specification TM 45-61A (and incorporated herein by reference) without any visible signs of cracking or blistering. After the 15 cycles, the part will withstand the above-described exposure to moisture for 96 hours and then also the above paint adhesion test. The paint adhesion test is performed within one minute after removal from the foamed environment. One cycle consists of 24 hours at 100% relative humidity, 20 hours at -23 ° C and four hours at room temperature. Other durability tests can also be used to determine the usefulness of a paint application for outdoor use in the car. These tests may be long-term exposure tests with ultraviolet irradiation and heat exposure tests. These two forms of test require long-term exposure of the board in a particular environment. For example, a UV long-term test may require two years exposure to determine the long-term resistance to ultraviolet irradiation in a paint application. In a long term weathering and heat resistance test, the painted plastic part is required to withstand biennial testing at a test site in Florida and Arizona without significant color or gloss change, loss of adhesion, and other deleterious effects on surface or substrate deterioration , After long-term exposure to Florida and / or Arizona, the painted specimens must pass the Tape Adhesion, Abrasion, Gravelometer, and Wet-Wet Circulation tests. The test sites in Florida and Arizona may also be exposed for five years

be used. Other test methods may include sulfide stain, detergent resistance, solvent resistance, compatibility, cyclic tests, moisture and adhesion, moisture and abrasion resistance. Exposure to cold and exposure in Florida and Arizona, as outlined in FBMS 26-7.

example 1

A high gloss, deep black, painted exterior paint finish was applied to the exterior surface of a trial plast molded part for the back window of a Pontiac Grand AM. The window molding was comparable to that shown in FIG. The ink layer was first applied to the surface of a cast film of flexible polyester film. The flexible carrier consisted of the 50.8 μm thick, high-gloss polyester film. The color layer was composed of a colorless layer, a color layer and a size layer, which were applied to the polyester cast film in this order. First, a thin wax film was applied to the polyester film. The wax coating formulation consisted of 40% by weight of xylene, 59.4% by weight of cyclohexanone and 0.6% by weight of carnauba wax. The wax was dissolved in the solvents at 12O ⁰ F and cast using a gravure cylinder on the polyester film. The wax coating was in the form of a thin film of about 0.025 pm thickness. The wax-coated casting sheet was then passed through a drying oven and dried at 121 ⁰ C at a moving speed of 7.6mm per minute. If necessary, the wax-coated cast film can be moved in a separate run with higher forward movement. The wax film does not interfere with the adoption of the polyester surface by the colorless layer. The colorless layer was then formulated with the following formulation:

component proportion of BLO (butyrolactone) 15.00 DIBK (di-isobutyl-ketone) 27.00 Polymethyl methacrylate (Elvacite 2010) 18,00 PVDF (Kynar301F) 18,00 BLO 6.28 cyclohexanone 15.00 Silicone Fluid (Dow Corning DC-11) 0.72

The acrylic resin Elvacite 2010 was mixed with the solvents BLO and DIBK with heating to about 54 ⁰ C and finally dissolved therein. The resulting mixture was then allowed to cool overnight. The PVDF was mixed together with the remaining solvent BLO and the cyclohexanone and the silicone fluid at room temperature so that the PVDF component remained as a dispersion in the mixture and did not dissolve. The dried colorless layer contained about 50 wt% PVDF and 50 wt% polymethyl methacrylate, based on the total solids of PVDF and the acrylic resin.

The colorless layer was applied to the cast film at a dry film thickness of about 20.3 μm. The colorless layer was applied to the film by means of a co-rotating roll coater (illustrated in Figure 5) preceded by the engraving oven to dry the wax film so that the colorless layer can be applied immediately after drying the wax. The colorless layer was thereby dried on the cast film to be passed through a multi-stage drying oven with air admission, wherein seen in the longitudinal direction of the carrier, three spatially separate heating zones are present and each drying zone has an increasingly higher temperature. The carrier provided with the colorless layer moves through the heating zones with a forward movement of 7.6 m per minute, each heating zone being 12.2 m long. The temperatures in the three heating zones were: zone 1 = 126 ^° C., zone 2 = 166 ^° C., zone 3 = 199 ^° C. When passing through the three heating zones, essentially all the solvent vapors contained in the colorless layer were removed, which was a dry one , produces a colorless layer of uniform film thickness. Next, a deep black ink layer having a dry film thickness of about 0.8 mil was applied to the dried colorless layer. The formulation for the color layer was as follows:

component proportion of cyclohexanone 9.27 DIBK 18.54 BLO 8.34 Polyethyl methacrylate (Elvacite 2042) 10.02 Dispersant (Solsperse 17,000) 0.10 PVDF <Kynar301F) 24,04 BLO 14.14 carbon black dispersion 15.00

The carbon black dispersion included carbon black in the binder Elvacite 2043, which may be purchased as Gibraltar 438-39110 pigment. The formulation for the ink layer was prepared in a similar manner as in the color clear layer, by first mixing the acrylic resin in the solvents cyclohexanone, DIBK and BLO was dissolved at a temperature of about 54 ⁰ C, then allowed to cool before the to the mixture PVDF component was added to give a dispersion of PVDF in the acrylic resin. The pigment was then added to the resulting mixture to produce a deep black color. The amount of pigment contained in the ink layer formulation accounts for about 4 to 5 mass%. The dried paint layer consists of about 65% by weight of PVDF and about 35% by weight of acrylic resin, based on the total solids amount of PVDF and acrylic resin without the pigments. The acrylic resin component contains polyethylmethacrylate, which in turn consists of about 90% Elvacite 2042 and about 10% Elvacite 2043. The ink layer is applied in liquid form to the dried colorless layer and then sent to dry the ink layer through the three-zone oven described above.

Next, a glue layer is prepared for the use of an ABS laminating film. The size coat consists of 50 parts of methyl methacrylate resin, known by the name Acryloid A-101, dissolved in SO parts of the solvent methyl ethyl ketone. The size coat was applied to the dried color layer at a dry film thickness of about 2.54 μm and using a one-piece gravure coating roll. The size coat was then dried by passing a single stage drying oven at a temperature of about 135 ° C.

The resulting color-coated support was then fed to the lamination process, which is similar to that illustrated in Figure 6, where the color layer of the polyester support material is transferred to a 508 μηη thick ABS lamination film. During this lamination process, the laminating film and the color-coated substrate run at a longitudinal speed of 4.6 m per liter. Minute and the laminating roller was operated at a temperature of 204 ⁰ C. The size coat was heat-activated and transferred to the top of the ABS lamination film during lamination, with the hot steel roll exerting a pressure of about 44 kg / cm. The support in the form of a polyester film is peeled from the surface of the laminate and leaves a color layer bonded to the ABS film, the colorless layer on the outer skin of the ABS laminating film providing a highly lustrous surface. The paint-coated laminate was then thermoformed into a complex, three-dimensional profile to form the window molding of plastic. The laminate was thermoformed by first heating the planar laminate in an oven to a temperature of about 182 ° C to soften the laminate. After the laminate had been heated, it was transferred to a vacuum forming furnace comparable to that shown in Figs. 8 and 9, and vacuum was applied to the holding device on the ABS side of the laminate to place the heated laminate in the laminate bring three-dimensional shape of the window molding.

The thermoformed laminate is then trimmed to match the mold cavity of the plastic injection molding machine. A plastic molding compound of ABS for forming the support base for the window molding is injected into the mold behind the thermoformed laminate to fuse the ABS molding compound to the laminate. The mold was operated at normal melt temperatures for the ABS resin. This gives rise to a window molding as an integral part with a defect-free ink layer on the outside surface of the field. The window panel was tested and the tests demonstrated the utility of the paint coating as an exterior paint job on the car. The test results showed that the required appearance characteristics including gloss were produced. The gloss was determined at 2O ⁰ C with 62 units and 60 "with 79 units. The measurement of the DOI yielded 64 units. The color uniformity was good. The test results also provided a desired combination of the durability characteristics. The test rack was the Benzinbeständigkeits-, Acid Resistance, Abrasion Resistance, (Gravelometer Reading at 8), Impact Resistance (from 80 in-lb in the Gardner Test), QUV, and the 96-hour Moisture Exposure Test according to the test methods described above.

Example 2

A bright, red-laminated exterior paint finish was provided on the car, on the outside surface of a high-profile plastic body frame. The laminate was adapted to the red body color of the Fiero and used to create a prototype of the rear back wall at the Fiero. The ink layer was first applied to a cast film consisting of the two mil thick, high gloss polyester film. On the cast film, a colorless layer, a paint layer and a size coat were applied in the following order. The colorless layer was prepared in the following formulation:

component proportion of cyclohexanone 15.47 BLO (butyrolactone) 7.52 DIBK (di-isobutyl-ketone) 21.66 Polyethyl methacrylate (Elvacite 2042) 12.95 UV absorbers 1.1 PVDF {Kynar301F) 24.05 BLO 17.24

The acrylic resin Elvacite was dissolved in the solvents BLO, DIBK and cyclohexanone while stirring and heating to about 54 ⁰ C. The resulting mixture was allowed to cool overnight. Then, the UV absorbers were added to the mixture and the PVDF dispersed in the resin. The remaining solvent BLO was then added to dilute the final mixture. The PVDF component is present as a dispersion in the mixture and does not dissolve. The dried colorless layer contained about 65% PVDF and 35% acrylic resin based on the total solids of PVDF and the acrylic resin. The colorless layer was applied to the cast film at a dry film thickness of 15.2 μm. The wax layer described in Example 1 was omitted in this test. The colorless layer was dried on the cast film by feeding it to the three-zone drying oven described in Example 1. The linear velocity and temperatures in the three zones were the same. When passing through the drying oven, substantially all the solvent vapors contained therein were stripped from the colorless layer to produce a dry colorless film of uniform film thickness. Next, a red paint layer having a film thickness of about 20.3 μm was applied to the dried colorless layer. The color coat formulation is composed as follows:

component proportion of cyclohexanone 10.61 Polyethyl methacrylate (Elvacite 2042) 2.99 Dispersant (Solsperse 17,000) 0.10 PVDF (Kynar301F) 19,95 BLO 4.02 Solvent (M-Pyrol) 8.45 red dispersion 57.9

The dispersi 'consists of several pigments, which are powdered with a binder consisting of 16% solids of polyeth / -. lrylat resin Elvacite 2043 and 84% of the solvent cyclohexanone are mixed together. The formulation for the color layer was made in a manner similar to that for the colorless layer by first dissolving the acrylic resin at a temperature of about 54 ^° C. in the solvents. The dispersant and a portion of the red dispersion were added. The mixture was allowed to cool to room temperature and the PVDF component was dispersed using a high speed stirrer. The remainder of the red dispersion was then added to the resulting mixture to produce a matched red color. The dried ink layer is made to approximately 65mA .-% of PVDF and about 35mA .-% of acrylic ^resin,% based on the total mass of non-pigmented PVDF and acrylic resin together. The acrylic resin component is a polyethylmethacrylate and consists of about 80% Elvacite 2043 and about 20% Elvacite 2042. The pigment had a ratio of three parts pigment to ten parts resin binder or about 23% total solids. The ink layer was applied in liquid form to the dried colorless layer and then passed through the three-stage oven described above to dry the ink layer. Next, a glue layer was prepared for the use of a laminating film of ABS. The size coat consisted of 75 parts of the methyl methacrylate resin Acryloid A-101 and dissolved in 25 parts of the solvent toluene, stirring to homogeneity. (The Acryloid A-101 is composed of 40% PMMA solids in the solvent MEK.) The size coat was then applied to the dried ink layer at a film thickness of about 2.64pm. The glue layer was applied in accordance with the co-rotating roll coating machine described in FIG. 5 and then dried in the same three-stage drying oven as in the colorless layer and the color layer. The resulting color-coated support was subjected to the lamination process illustrated in Figure 6, where the color layer from the polyester support was transferred to a 508 μm thick ABS laminating film. The backing film was peeled from the surface of the laminate leaving the red paint with a high gloss finish on the outside of the ABS liner.

The laminate was then heat formed into the complex, three-dimensional profile of a rear wall. The laminate in the form of a continuous film was passed through an oven during thermoforming in order to heat the laminate to a temperature of about 143 ^° C. After the continuous film has reached this temperature, it is passed through a vacuum forming machine, the vacuum applied, and the laminate formed into the three-dimensional profile from the rear wall. At the free area of the film provided with the colorless layer, an overpressure of 103.4 kPa is applied and vacuum is drawn on the ABS side of the film.

The thermoformed laminate was placed in a die cavity of a plastic injection mold and an ABS-based plastic molding compound for forming the backing backing backing behind the thermoformed laminate was injected into the die to fuse the ABS-side molding compound to the laminate. This resulted in the rear end wall as a unitary whole plastic part with a flawless, glossy paint on the outside surface of the field. The field was tested and the tests showed the usefulness of the paint as an exterior paint job on the car. The test results proved that the required appearance characteristics, including gloss, were present. The gloss was determined to be 65 units at 20 ° and 80 units at 60 °. At DOI, 65 units were determined. The color uniformity was good. The test results also demonstrated a desirable combination in resistance properties. The test rack met tests for gasoline resistance, cleanability, acid resistance, hardness {from 7 to 8 on the Knoop hardness scale readings), abrasion resistance (gravelometer reading of 8), impact resistance (of 80 in-lb in the Gardner test), QUV and gh-hr humidity exposure according to the test methods described above. The Florida exposure was passed after three months.

Example 3

Tests were carried out to determine the relative proportions of the PVDF and the aoyl resin components in the colorless layer and in the paint layer, with which one can produce a composite paint which can be cast as a film with which a laminating film laminated, thermoformed and injection-molded to obtain a finished product having an exterior paint surface for the car. In this example, standard acrylic-based car spray enamel paints were used as the paint in this method of the present invention. These types of paint systems are currently used as common automotive exterior paints. These paints were heat-cured and, when dried on the support, they crosslink at low temperatures. These color layers were then transferred from the support to a 508 μm ABS laminating film, which was subsequently mounted on a vacuum forming machine. The color layer proved too brittle to stretch adequately; At the stress points of the laminate, cracks and fractures formed during heat forming.

Similarly, the urethane-based car paints commonly used in rubber shock absorbers and which failed equally in thermoforming. These color systems were stable at room temperature, but cracks occurred during high temperature vacuum forming.

Example 4

In a test comparable to that described in Example 3, a paint coat of a non-thermosetting acrylic paint was evaluated. The paint layer was composed of a lucite dispersion paint and a thermoplastic acrylic resin. The ink layer was applied to the cast film, dried and laminated with a 508 μm ABS laminating film. This paint system heat-set but was difficult to process. When applied as a paint with many solids (low solvent), the drying of the paint took too long. When stabilizers were added to improve the dryness, cracking occurred during thermoforming. She also tended to stick to the injection mold.

example

There have also been other pure thermoplastic acrylic resin color systems such. Example, a polymethyl methacrylate and a solvent-based paint with dispersed pigments. Such pure acrylic paint systems were characterized primarily by their difficulty in processing, as they have a low solvent evaporation rate on drying

and tended to adhere to the surface of the injection mold. With acrylic pigment systems provided with considerable amounts of pigment, their gloss was lost during heat-forming. Pure thermoplastic acrylic paint systems also showed deficiencies in certain mechanical properties, including inadequate abrasion (in the gravelometer), so that they did not meet the criteria applicable to the exterior of the car. Moreover, these pure acrylic resin formulations do not pour well into film molds, white! they tend to stick too strongly to the cast film.

Example β

A pure PVOF (Kynar 301 F) Fa / b system was tested by the method according to the invention. The PVDF paint system exhibited sufficient elongation upon thermoforming so that cracking did not occur, but excessive thermally loss was associated with thermoforming.

Example 7

According to the process of the invention, an acrylic-vinyl thermoplastic color system was experimentally tested. The color system also contained a dispersed black pigment of about 3% by mass based on the total solids mass. The paint system was previously successfully installed in Ir isren the. \ Utos on equipment such as dashboards u.a. used. The paint system could be laminated with an ABS-Xaschierfolie, but when it was heat-formed, excessive gloss loss occurred. This interior trim system did not create an exterior paint surface for the car that meets the minimum requirements for gloss and the CiOI for outdoor use in the car. Also, when applied to the automotive interior, this paint layer was not applied with a film thickness that would be necessary to meet the exterior durability specifications of a car. The use of a higher level of pigment required on the exterior finish of a car resulted in extreme loss of gloss on thermoforming. Other mechanical properties necessary for outdoor use were also absent.

Example 8

A thermoplastic paint system mixed together from PVDF and acrylic resin was experimentally tested by the method according to the invention. This mixed paint system consisted of a dispersion of 72% by PVDF and 28% by weight of acrylic resin, based on the total solids of PVDF and acrylic resin. This paint system was applied analogously to a commercial one on metallic exterior trim parts in automobiles where the metal was spray coated and then cold formed to produce the desired trim part. This mixed paint system contained about 3% by weight of a black pigment in the form of a dispersion, based on the total solids mass. This paint system was not suitable for outdoor use in the car. The paint system was laminated with an ABS laminating film, but excessively lost its gloss during heat molding. In addition to the low gloss, this paint system also did not have the DOI requirements for the exterior finish of the car.

Example 9

A colorless layer of PVDF and acrylic resin was tested in conjunction with an acrylic resin based paint layer. Each paint layer was placed on a cast film, the coatings dried and transferred to an ABS backing film to form a composite paint layer, and the film thermoformed. In one test, the acrylic resin component in the paint layer was a weather-resistant acrylate known as Korad D. Other tests were done with pure acrylic color layer formulations of PMMA and ΡΕΜΑ copolymers. In one test, the paint layer was pure Elvacite 2042, a polyethyl methacrylate. Visual observations on the thermoformed laminates showed that good appearance properties including gloss and DOI could be achieved. One observation was that a colorless layer of PVDF and acrylic resin can be used in conjunction with a colorant layer which does not have a PVDF component, resulting in a less expensive composite color layer with which the expensive fluorohydrocarbon component in some of the finished Arw'richsschicht is eliminated.

Beitplul 10

Tests were conducted on a composite paint layer consisting of an outer colorless layer bonded to a paint layer. The solids in the paint layer and in the colorless layer are essentially a mixed PVDF and acrylic resin thermoplastic paint system. The paint film was applied to a cast film, thermoformed, and injection molded with an ABS substrate. It has been found that certain PVDF / acrylic resin ratios in the colorless layer do not provide a sufficient combination of resistance and appearance characteristics in the finished laminate to be suitable for outdoor automotive use. For example, 100% PVDF in heat-forming led to loss of gloss, whereas 100% of acrylic resin created processing problems, including sticking to the injection mold and slow solvent evaporation. Figure 13 is a graph showing a performance curve for a PVDF and acrylic resin based composite paint. This graph reflects the relationship between gloss (in glosses at 60 °) of the colorless layer on the finished product and the ratio of PVDF to acrylic resin in the dried colorless layer based on the PVDF and acrylic resin solids. This curve is based on experimental evaluations of colorless layer formulations resulting from various combinations of acrylic resins, particularly polymethylmethacrylate and polyethylmethacrylate or mixtures thereof, with the PVDF, including a range of low to high molecular weight acrylic resins. This curve indicates that a transition point between acceptable gloss and unacceptable gloss loss exists above about 65 to 70% PVDF in the colorless layer formulation. When the PVDF contained in the formulation is more than 70%, it causes excessive loss of gloss in the heat molding. The performance curve testing also revealed that a ratio of 50:50 PVDF to acrylic resin is about the same as where the addition of a larger proportion of acrylic resin would increase the processability of the acrylic resin

Painting system designed as too cumbersome. The dashed line portion of the curve represents the combination of PVDF and acrylic resin that can be processed in this particular combination of resins to produce a colorless layer of the desired gloss. As a minimum, specifically in this example, a required gloss of 75 units at a remission angle of 60 ° was selected. These tests have shown that the polymethyl methacrylate in the PVDF and acrylic paint system generally results in a higher glossiness than the polyethylene methacrylate; and therefore, the curve civi shown in Fig. 13 tends to increase as more polymethyl methacrylate is used. The curve will go deeper as more Polyethvlmethacrylat is used. In addition, the tests have shown that pigment addition to the underlying paint layer can cause greater loss of gloss in the outer colorless layer during thermoforming; and therefore the curve shown in Figure 13 will be deeper as the pigment content in the color layer increases. Likewise, the tests have shown that the loss of gloss in the colorless layer can be caused by various factors. If z. For example, if the colorless layer is too thin, the pigment particles may migrate from the underlying paint layer over the interface to the colorless layer in thermoforming. bring about at least a little loss of gloss. In certain cases, a thicker colorless layer can prevent this form of loss of gloss. In other cases, however, a thicker colorless layer can not avoid the occurrence of loss of gloss. In one test, in a relatively thick 30.5 μπι colorless layer consisting of 50% PVDF and 50% polymethyl methacrylate, loss of gloss occurred when the heat forming was carried out at 177 ⁰ C. The underlying paint layer had a significant pigment level of 23%. By increasing PVDF in the colorless layer to 65% solids and by changing the acrylic component to 35% polyethylene methacrylate and the application of a lower thermoforming temperature of 143 ⁰ C, the loss of color was prevented in the colorless layer.

Example 11

Experiments were conducted to compare the physical properties of PVDF / acrylic resin coatings prepared as a solution of PVDF in acrylic resin and applied externally to the car with similar dispersion systems. These tests were performed on both the colorless layer and the color layer to compare the image reproducibility (DOI) and glossiness of the> / poorly-formed areas, with the PVDF / Auyl resin films coming out of solution as well as through Dispersion casting were prepared. For the colorless layers and the color layers, the following dispersion and solution formulations were prepared:

Colorless layer as dispersion: ·

Component share

Polymethyl methacrylate (Elvacite 2010) 50

PVDF (Kynar301F) 50

high-boiling acetate solvent (Exxate700) 74

Solvent (M-Pyrol) 55.5

Cyclohexanone 55.5

Colorless layer as a solution:

Component share

Polymethyl methacrylate (Elvacite 2010) 50

PVDF (Kynar301F) 50

Solvent (M-Pyrol) 225

Methyl ethyl ketone 225

Color layer as dispersion:

Component share

DIBK (di-isobutyl ketone) 18.55 BLO (butyrolactone) 8.34

Polyethylene methacrylate (Elvacite 2042) 10,20 Cyclohexanone 9,27

Dispersant (Solspeiere 17,000) 0.10

PVDF (Kynar301F) 24.40

BLO 14,14

Carbon black lock.on 15

Color coat as solution:

Component share

Polyethylmethacrylate (Elvacite 2042) 10,20

Dispersant (Solsperre 17,000) 0.10

PVDF (Kynar301F) 24.4 "

Carbon black dispersion 15.00

Solvent (M-Pyrol) 86.00

Methyl ethyl ketone 74.30

The colorless layer as a dispersion was prepared by initially dissolving Elvacite 2010 in Exxate 700 and cyclohexanone. Then the Kynar 301F was disperged in the resulting mixture using a high-speed mixer (Cowles mixer). Subsequently, the M-pyrol was added to the resulting mixture. The mixing was done at room temperature so that the PVDF component was present as a dispersion in the mixture and not dissolved

has been. The present as a dispersion colorless layer was applied to a cast film, which is a polyester film, by means of a co-rotating roller coating machine. The colorless layer was then passed through on the cast film

Drying techniques dried, as already described here. The colorless layer as a solution was prepared by dissolving both resin 3 in the mixed solvent and using

a high-speed Cowles mixer were added, wherein the mixture sufficient heat was supplied to completely dissolve the resin. The colorless layer present as a solution had significantly less solids (less than about 20% PVDF / acrylic resin solids) than the colorless layer dispersion, with stronger solvents being used to form a colorless PVDF / acrylic resin solution coating.

The color layer as a dispersion was prepared by treating the Elvacite 2042 in the solvents DIBK and cyclohexanone

and the first part of α9m solvent BLO was dissolved. The Kynar 301 F was dispersed in the resulting mixture, which was then diluted with the remaining BLO before adding the carbon black dispersion. The carbon black dispersion consisted of carbon black dispersed in Elvacite 2042 and cyclohexanone.

The color layer as a solution was prepared by dissolving both resins in the solvent and then the Carbon black dispersion was added. The paint layers were cast on separate polyester cast films and not on the

applied dried colorless layer. When the base layer is poured over a dried colorless layer, the solvents of the base layer will attack the colorless layer, especially when in solution form

Base layer with its stronger solvents. Both layers of paint were then applied to their respective cast films

dried.

Four thermoformable laminates were then made for testing gloss and DOI. There were different Combinations of colorless layer as dispersion, color layer as dispersion, colorless layer as solution and color layer

as a solution to the PVDF / acrylic resin laminates as described below. Each thermoformable laminate comprised a paint layer and a colorless layer laminated with a 457 μm thick ABS film. First, the

Color layer laminated with the ABS laminating film, the cast film peeled off polyester, then the colorless layer on the Applied color layer and then removed the casting film made of polyester for the colorless layer, which is an ABS

existing, thermoformable laminate with on the top of the laminating film associated colorless layer as a cover layer and the color layer results. The backing sheet was then subjected to deep draw thermoforming using pressure assistance exposed (the Wärmeformungstemparaturen were about 132-138 ⁰ C) to provide test areas, the DOI and then to

Glanzkraft were measured. The comparative tests for gloss and DOI for the coating layers present as dispersion and solution gave the

following results: *

laminate Shine at 20 ° Shine at 60 ° DC colorless layer as dispersion / Color layer as a dispersion 66 82 72 colorless layer as solution / Color layer as a dispersion 69 82 82 colorless layer as dispersion / Color layer as a solution 65 81 70 colorless layer as solution / Color layer as a solution 70 81 89

The test results show that a higher level of DOI can be achieved by using the solution form in the PVDF / acrylic resin coatings as compared to the coatings used as the corresponding dispersion. Moreover, the DOI levels are then high, i. greater than about 80 units, and in one case even approached 90 units when the laminate has at least one colorless layer of PVDF / acrylic resin in solution form. In the case of the coatings with the solution and with the dispersion, the gloss intensity at 60 ° was approximately the same and sufficiently large to meet the requirements imposed on the exterior of the car. At 20 ", the gloss of the colorless films was somewhat higher with the solution, and the best results were obtained when the paint was applied to both the colorless layer and the ink layer underneath with the PVDF / acrylic resin solution.

Thermoplastic polyolefins (TPO's), such as. As polypropylene and polyethylene, are useful as body support material because of their impact resistance, corrosion resistance and their formability in various complex designs. Initially, TPO's proved to be difficult to paint, and this limited their use in the automotive industry. In particular, the adhesion of the paint layer on the TPO support turned out to be a problem. The method of the invention can be used to apply a high quality paint on the TPO body frame to the car and provide good adhesion between the paint layer and the TPO composite structure as the underlying body frame.

Briefly, in this embodiment of the present invention, a thin layer of thermoplastic chlorinated polyolefin (CPO) is applied between the paint layer on a flexible carrier film and the flexible laminating film of TPO. This composite structure is then thermoformed and bonded to a thick, rigid layer of TPO resin, providing the backing for the bodywork composite frame.

The size coat is preferably made from a coating composition containing the CPO in solution. The composition for the coating comprises about 10-60% by weight of CPO and accordingly about 40-90% by weight of solvent. Any conventional solvent, such as toluene or xylon, which solubilizes CPO can be used. The CPO is preferably a chlorinated polypropylene or chlorinated polyethylene containing up to about 50 mole percent chlorine, preferably about 15-50 mole percent chlorine. A preferred chlorinated polypropylene is a propylene / maleic anhydride copolymer having a chlorine content of about 15-50 wt%. A particularly preferred chlorinated polypropylene is that of polypropylene and maleic acid having 18-35Ma% chlorine and an acid number of about 15.

The flexible laminating film and the rigid support layer of the bodywork composite frame are made of cars standardized, quality TPO resins, which is typically a polypropylene resin.

The TPO composite of this invention offers automakers many advantages over current prior art compositions. Adhesion problems with recessed portions at a part are minimized, solvent emissions associated with Sprühanstrichen, the need for expensive towing devices and racks to maintain the shape of a plastic part during baking and the requirement füre · ¹ on base coat, which is necessary for a conventional Farbsprühverfahrsn everything that will be eliminated. In addition, the composite has a unique set of characteristics that make it superior to the usual injection molded and spray painted parts.

The color coat / color clear layer of the composite material according to this invention can be used at temperatures of about 200 ⁰ C cure as compared to it is at the üblichon injection molded and painted by spraying plastic parts of a maximum of 125 ° C. This allows the use of paints that can not otherwise be used in the conventional TPO parts. For example, according to this invention, the polymers of fluorocarbons can be used and they are much more durable and more resistant to chemicals than the stoving paints commonly used at low temperature.

The TPOs used for the flexible laminating film and for the rigid carrier as a composite layer may differ in terms of quality. At present, the TPO resins used in the manufacture of injection molded automotive parts must be of the highest quality, i. H. free of gel particles and any foreign matter, to ensure that a defect-free part with a quality surface for the car is created. However, because according to this invention, the surface quality of the composite is determined by the surface of the flexible laminating film, only the laminating film needs a high quality TPO resin, while the rigid carrier layer of the composite requires, for example, a lower quality TPO resin which may contain gel particles and thereby not adversely affecting the external appearance of the obtained part or its structural integrity.

The ability to separate the surface characteristics of the composite injection-molded plastic used to form a rigid composite layer allows the manufacture of significantly improved automotive parts. For example, glass fiber reinforced or other filler reinforced TPO's may be used as the injection molding resin for the rigid composite layer, and it is possible to make stronger and more rigid parts that have heretofore been impossible. The following example demonstrates the use of the TPO composite structure in a body.

Example 12 The rear panel for a Pontiac Fiero was made from a thermoformed thermoplastic polyolefin (TPO) with a strong

shiny, deep black exterior color made for the car. The color layer was first placed on the surface of a film of sterile acrylic film. The film is in 50 micron thick, high gloss Mylar 200A polyester film Die

Film layers were coated on the film as a colorless layer, a color coat, and a chlorinated polyolefin sizing layer

applied. Each time, the polyester film was coated in this order.

A composition for the colorless coating was prepared as follows:

component proportion of methyl ethyl ketone 40.85 butyrolactone 40.85 Elvacite 2021 (polymethylmethacrylate with an average molecular weight of 200,000) 6.22 UV absorber (Tinuvin 900 = 2-hydroxy-3,5-di- (1,1-dimethyl (benzyl) phenyl) -2K-benzo-triazole) 0.35 UV stabilizer with hindered amine (Tinuvin 292 = bis (1,2,2,6,6-pentamethyl) 4-piperidinyl) sebacate) 0.18 Kynar301F 11.15

The solid ingredients were added to the solvents methyl ethyl ketone and butyrolactone with stirring and stirring continued until dissolved. The film-forming binder of the coating contained about 65% PVDF and 35% polymethyl methacrylate. The application of the colorless layer on the polyester film was carried out with the same direction rolling applicator. The colorless layer was dried on the polyester film by passing it through a multi-zone drying oven with air admission, with three spatially separated zones relative to the longitudinal guide of the carrier, with each drying zone having an increasingly higher temperature. The colorless polyester film migrated through the heating zones at a speed of about 7.5 meters per minute; each heating zone was about 12 meters long. The tempering doors in the three heating zones were: Zone 1 = 125 ° C; Zone 2 = 165 ⁰ C; Zone 3 = 200 ^° C. By passing through the three heating zones, the colorless layer on the polyester film had substantially all of the solvent vapors de-fused to give a dry, colorless, uniform film thickness of about 20 microns thick

 The composition for a deep black color coating was set up as follows:

component proportion of cyclohexanone 9.27 Di-isobutyl ketone 18.54 butyrolactone 8.34 Elvacite 2042 (polyethylmethacrylate with an average molecular weight of 300,000) 10.02 Solsperse 17,000 as dispersant χ 0.10 Kynar301F 24,04 butyrolactone 14.14 black pigment dispersion 15.00

The black pigment dispersion included carbon black in the binder Elvacite 2043 (polyethylmethacrylate), which is commercially available as Gibraltar 438-39110 pigment.

The composition for the color coating was first made so that the acrylic resin in the solvents cyclohexanone, di-isobutyl ketone and butyrolactone is dissolved at a temperature of about 55 ⁰ C, then allowed to cool before the polyvinyl fluoride component is added to the mixture so that a dispersion of PVDF is formed in the acrylic resin. The black pigment dispersion was then added to the present mixture to provide the deep black color layer composition. Based on the mass basis, the amount of pigment contained in the paint was about 4-5%. The paint binder was about 65% by weight of PVDF and about 35% by weight of acrylic resin. The acrylic resin component comprised about 90% Elvacite 2042 and about 10% Elvacite 2043. The paint composition was applied to the dried colorless layer as above and then passed through the three-stage oven described above to dry the paint. which resulted in a dry coating of about 20 microns thickness in the paint.

The composition for a glue layer of CPO (chlorinated polyolefin) for use in the TPO laminating film was prepared as follows:

Component share

Xylene 24.60

chlorinated polyolefin (CPO) as a solution

(CP-343-1 from Eastman = 25% solids in xylene

of the chlorinated polypropylene / maleic acid polymer,

Acid number about 15, chlorine content about 18-23%) 25.00

Toluene 42.50

Acrylic resin dispersion (60% solids of a Acrylic vinyl oxyzolinester polymer described

by Miller in U.S. Patent 3,844,993 in Example 1) 6,90

N-methylpyrrolidone 1.00

The binder for the size coat composition contained about 60% by weight of CPO and about 40% by weight of acrylic resin. The size coat composition was applied to the dried paint layer to a dry film thickness of about 2.5 microns using the co-rotating roller applicator. The three temperature zones were left at the same temperatures as applied to the colorless layer and the color layer, but the carrier speed reached 30 meters per minute.

The resulting paint-coated polyester film was then subjected to the lamination operation illustrated in Figure 2, wherein the paint layer of the polyester film was transferred to a 500 micron TPIE lamination film of TPIE-1000, a thermoplastic olefinic elastomer, to give a topcoat film. The RPIE-1000 has a flexural modulus of about 690MPa and a melt flow rate of about 0.8g / 10min. In the lamination process, the liner and paint-coated polyester film support were moved at a linear speed of 5 meters per minute and the lamination drum was operated at a temperature of 177 ° C. The glue layer of CPO was heat-activated and the paint layer of the polyester film on top of the TPO In this lamination operation, the hot steel drum exerted a force of about 54 kg per centimeter of length to give the topcoat film The polyester film was peeled from the surface of the topcoat film leaving behind the paint layer associated with the TPO film Layer provides a strong shiny surface on top of the TPO laminating film.

The resulting composite sheet was then heat-formed into a complex, three-dimensional profile to give a backside plastic molding. In the thermoforming process, the composite sheet was first heated to a temperature of about 121X to soften it. The heated composite sheet was then placed in a pressure-assisted vacuum forming oven, a vacuum applied to the TPO side of the composite sheet and an air pressure of 2.1 kg / cm ² set on the side of the colorless layer of the laminate to form the three-dimensional sheet Form profile of the back wall.

The resulting thermoformed laminate was then trimmed to conform it to the die cavity of a plastic injection molding machine. It was then formed the back wall. An elastomeric thermoplastic injection resin with additive, RTA-3263, having a flexural modulus of about 1725 MPa, was used to form the backwall pad. The resin was injected behind the thermoformed laminate into the mold, merging with the TPO underlayer from the laminate, and creating the back wall of about 2.5-3.75 mm thickness. The mold was operated at normal melting temperatures for the resin. There was a back wall, d. H. a self-consistent plastic composite having a defect-free paint layer on the outer surface of the cladding.

The back panel was tested and the tests showed the usefulness of the paint coating as a top coat on the outside of the car. The test results showed that the desired appearance-related properties including gloss were present. The remission was measured at 20 ° with 70 units and the DOI with 85 units. The color uniformity was good. The test results also showed a desirable combination of resistance properties. The test rig passed the tests for gasoline resistance, acid resistance, chip resistance (gravelometer reading at 9), impact strength (80in / lb. in the Gardner test) and passed the QUV and SB hour moisture exposure tests. As previously disclosed, a thin wax film may be applied to the flexible support film prior to casting the colorless layer on the support. The wax film can serve as a protective layer for the finished painted body frame. In addition, in the colorless layer (or in the wax film on the colorless layer) during processing, a separate, water-soluble protective coating can be applied, so that the water-soluble layer for a scratch-resistant outer protective layer for the finished body frame during assembly of the car and when shipping to Buyer cares. The layer preferably consists of a low molecular weight material, which adheres to the colorless layer during processing and can be modified to a glossy surface protection.

From time to time, the water-soluble protective coating is applied as an insulating film on the dried colorless layer. As already described above, the colorless layer and the color layer are cast on a carrier film made of polyester and connected to the flexible laminating film. Separately, on a flexible carrier film made of polyester oins water-soluble layer, for. B. of polyvinyl alcohol (PVA), applied and dried. After the carrier film has been removed from the surface of the colorless layer, the PVA film is pressed onto the surface of the colorless layer, preferably by means of a pressure roller technique. The PVA is cast separately so as not to be exposed to the solvent attack of the colorless layer, and accordingly, the glossiness of the surface of the colorless layer can not be deteriorated when transferring the colorless layer from the polyester cast film. The polyester support film is then removed from the PVA layer and leaves on the outer surface of the colorless layer an adherent water-soluble protective film of PVA. The resulting liner is then subjected to further processing, including thermoforming and injection coating, to yield a finished body frame with the water-soluble outer protective layer. This layer can then be easily buffered or removed with water, either by the car dealer or the buyer.

The color layers used according to this method may contain metallic, shingled pigments. When a metallic flake pigment dries on a support surface, the flakes orient themselves generally parallel to the surface of the support. However, these orientations may vary, especially in spray painting, which can lead to significant disorientation, resulting in differences in visible color in the finished paint. Visual color comparisons on metallic paints can be made directly from above (HOB) by means of known procedures for measuring such parameters as the flop index and surface haze. (These measurements are described by Kelly in U.S. Patent No. 4,692,481 and are incorporated herein by reference.) A finished paint layer having low-profile metallic flakes had the desired high flop and HOB values. The process according to the invention can be used to produce a finished coat of paint with metallic flakes having high flop and HOB values. You can apply the metallic shingled color layer separately on a carrier film made of polyester and allowed to dry slowly on the film so that the metallic scales align carefully parallel to each other and so high flop and HOB values can be achieved. The pre-oriented, metallic-skinned pigment is then subjected to further processing (e.g., transfer to the liner, thermoforming, and spray coating) to produce a finished body frame with high flop and HOB values. The linear orientation of the flakes is not disturbed during further processing and is thought to be increased by the strain encountered in thermoforming. The high flop and HOB values are considerably greater than in the case of spray-coating a comparable carrier.

Improvements can be achieved in the method according to the invention by the use of a pigmented laminating film. Experiments have shown that the transparency of a color coated laminate is reduced when a pigmented liner is used in the process as compared to a colorless liner. These experiments involved measuring the light transmittance on a white paint layer laminated with a black laminating film (the color layer consisted of a colorless layer and a white color layer below), in comparison with the measurement of the light transmittance on the same white color layer laminated with a colorless laminating foil .vorden. The pigmented liner significantly increases the opacity, which can reduce the amount of pigment needed for the ink layer to mask defects in the underlying support. In this method according to the invention, printed graphic representations can also be incorporated. Thus, in a process for the use of graphic representations on the finished ink layer, the colorless layer is first cast onto the flexible polyester carrier film. The colorless layer is then dried on its carrier film. The pattern of the graphic image is then printed on the surface of the dried colorless layer, on the opposite side of the carrier film. The pattern of the graphical representation may e.g. B. be any desired pattern. The color layer is also cast on the colorless layer and over the pattern of the graphic and dried. This gives the colorless layer on its carrier film with the previously applied graphics and the color layer visible through the colorless layer. Alternatively, the ink layer may be cast onto a separate carrier sheet and then applied in the dry film form to the preprinted patterns of the graphic representation as well as to the dried colorless layer. A suitable size coat is then applied to the surface of the dried paint layer and the resulting laminate transferred to a flexible liner using the techniques previously described. In this process, the carrier sheet is removed and the resulting color-coated laminate is thermoformed to the desired profile to give the press-mold insert. The resulting mold insert is then injection molded with the required substrate to yield the finished body frame. An advantage of this method η is that the patterns for the graphics are printed under the colorless paint for the car, which provides a smooth outer surface in the finished body frame and protects the underlying graphic representation. The plots are therefore not exposed to wax or debris accumulation, as is currently the case with graphic representations applied to the surface of a finished exterior paint.

Thus, the present invention provides a dry paint process and a paint system that provides a useful blend of resistance, chemical, and visual appearance properties. The paint layer has a combination of durability, gloss, gloss loss and elongation, which creates and preserves the paint properties of the exterior of the car during processing stages. From the invention, there is an advantage in using the high molecular weight PVDF in an OEM exterior paint for plastic body, namely that despite the temperature limitations of the plastics molding compounds and the fact that the PVDF normally requires the use of strong solvents and high temperatures Polymer 'make additional films. The addition of acrylic resin polymers to the PVDF polymers results in a paint layer having excellent mechanical properties, including outdoor durability, chemical resistance and toughness. The low surface energy characteristic of the fluoropolymer surfaces also provides for improved washability and, through a large contact angle, provides a "permeable" surface requiring little or no ingrowth and the coating, which coincides with other manufacturing operations in a car manufacturing plant, becomes possible by transferring the quality control, the problems of solvent emission and the control of the color to a foreign supplier, thus allowing the car factory to perform the usual coating operations, including the job lines As an additional advantage of the dry paint process, there is an extension to making a flexible pressure sensitive laminate for use in automotive refinishing work an embodiment of such a laminate 140, the rapid refinishing work on an exterior painting on the car are possible without great demands are made in the surface preparation. The flexible laminate consists of a removable cover 141, the colorless layer 45, which is bonded to the paint layer 46 (although a simple paint layer having the corresponding exterior automotive properties may be used as an alternative to the separate colorless layer and the paint layer), a flexible liner 142 adhered to the ink layer 46, a self-adhesive 144 on the flexible liner, and a release liner 146 covering the pressure-sensitive adhesive. This laminate proves to be resistant to rough surfaces and, due to its adaptability, due to its flexibility and self-adhesive lamination, it develops good adhesion. By offering a self-adhesive, self-adhesive film for large and small areas, there are applications both by the skilled practitioner of repairs and for use in the consumer market, eliminating the need for large paint booths and furnaces, saving investment and environmental issues the issue and usually occur in the external renewal of the car, be dismantled. ·

Although the described invention relates to automotive quality paints and has been applied to body frames, it is to be understood that the invention is not limited solely to use with the automobile and its exterior body panels. The invention is also applicable to other vehicles in which exterior color paints are required of the quality as in the car. Examples include lorries, motorcycles, boats, dune buggies and others. In addition, the invention can be applied to a variety of exterior body parts or automotive parts. Examples of other substrates to which paint can be applied and which are present alongside conventional exterior body panels or vehicle superstructures include bumpers, fender extensions, trim disks, hubcaps, wheel trim rings, lamp housings, grills, and other business elements or components.

Claims (45)

A thermoformable laminate for use in forming an outer part of an exterior body panel, characterized in that the laminate consists of a thin, semi-rigid laminating film made of a synthetic resinous material and a high quality paint layer for the car facing the top the lamination film, wherein the color layer includes a synthetic, resinous coating in the form of a dry, thin film whose outer surface has a predetermined glossiness imparted to it by a high gloss cast film, the ink layer having sufficient elongation and Resistance to loss of gloss has, so that the laminate is thermoformable into a contoured, three-dimensional profile while the ink layer substantially maintains its predetermined gloss during the thermoforming process and for the previously festgel eg, outer appearance and durability properties that are sufficient after the thermoforming of the laminate to be useful as an exterior paint finish on the car. 2. Laminate according to claim 1, characterized in that the laminate can be thermoformed at a temperature of at least about 132 ° C and the color layer during the heat forming at this thermoforming temperature by more than about 40% and thereby still the gloss and the outer Appearance and preservation properties. 3. Laminate according to claim 1, characterized in that the color coating consists of a fluorinated polymer and acrylic resin-containing paint system having thermoplastic properties, wherein the ink layer is applied to a cast film and dried and then transferred from the cast film to the laminating film. 4. Laminate according to claim 1, characterized in that the color layer comprises a thermoplastic paint system consisting of polyvinylidene fluoride and an acrylic resin. A laminate according to claim 4, characterized in that the dried paint layer contains less than about 70% by weight of polyvinylidene fluoride and less than about 50% by weight of acrylic resin, based on the total weight of the PVDF and acrylic resin components disclosed in U.S. Pat Color layer are present. 6. Laminate according to claim 1, characterized in that the color coating comprises a pigmented, synthetic, resinous material having thermoplastic properties. 7. Laminate according to claim 1, characterized in that the color coating consists of an outer colorless layer and an underlying color layer associated with dt> r colorless layer. 8. Laminate according to claim 7, characterized in that the color layer contains a highly dispersed pigment, and the colorless layer is a thermoplastic coating containing mainly a fluorinated polymer and an acrylic resin. 9. A laminate according to claim 8, characterized in that the colorless layer is a thermoplastic paint system consisting essentially of about 50 to about 70% polyvinylidene fluoride and about 30 to about 50% acrylic resin and the acrylic resin component polymethylmethacrylate, polyethylmethacrylate or mixtures including the copolymers thereof. 10. A laminate according to claim 9, characterized in that the color layer consists essentially of about 50 to about 70% polyvinylidene fluoride and about 30 to about 50% acrylic resin and thereby comprises the acrylic resin component polymethylmethacrylate, polyethylene methacrylate or mixtures thereof including their copolymers , A laminate according to claim 1, characterized in that the color coat on the thermoformed laminate achieves at least the gloss gloss, image reproducibility, QUV, hardness, impact resistance, cleanability, acid resistance, gasoline resistance, and abrasion resistance, such as they are essentially defined in motor vehicle specifications for exterior paint finishes on automobiles and described herein. 12. A laminate according to claim 1, characterized in that the color coat comprises a fluorinated polymer selected from the group consisting of polyvinylidene fluoride and the copolymers and terpolymers of vinylidene fluoride. 13. A laminate according to claim 1, characterized in that the color coating at an angle of 60 ° has a gloss of more than about 75 gloss units and a level of reproducibility of an image of more than about 80 units. 14. Laminate according to claim 1, characterized in that the laminating film is a semi-rigid film having a thickness in the range of about 254μηη to about 1016Mm. 15. Laminate according to claim 1, characterized in that the laminating film is made of a material selected from the group consisting of ABS, polyester, amorphous nylon, thermoplastic polyolefins, including polypropylene and polyethylene. 16. Laminate according to claim 1, characterized in that, based on the outside of the colorless layer, a wax film is applied to the cast film. 17. Laminate according to claim 1, characterized in that between the color coat and the liner a pattern of a graphic representation is printed, which is visible through the color coating. 18. Laminate according to claim 1, characterized in that a pigment is contained in the laminating film. 19. Laminate according to claim 1, characterized in that in the color coating, a metallic, scaly color layer is included. 20. Laminate according to claim 1, characterized in that a water-soluble protective coating is applied to the outer surface of the color coatings. 21. A method for using a laminate as a color coat, which is suitable for outdoor use in cars, in a plastic outer body frame for a motor vehicle, characterized in that the method comprises the following steps: a) applying a colorless layer of a synthetic resinous material in the form of a thin film on the surface of a flexible cast film and drying the colorless layer on the cast film, wherein the surface of the film has a specular remission. to transfer to the surface of the dried colorless layer a glossiness sufficient for outdoor use in the car; the formation of a colored layer of a pigmented, synthetic, resinous material which is dried and adhered to the colorless layer; transferring the dried colorless layer and color layer to a semi-rigid laminating film of a synthetic resinous material to form a composite color layer bonded to an upper surface of the laminating film, the colorless layer forming the outer surface of the transferred color coating and the color layer between the color layer colorless layer and the top of the laminating film is incorporated, while the outer surface of the colorless layer when transferring their cast film substantially preserves the gloss obtained thereby; thermoforming the liner and the composite color coat thereon to form a three-dimensionally shaped preformed laminate; and inserting the preformed laminate into a mold and injection molding a synthetic resinous carrier mass onto the preformed laminate to form an exterior body panel with a finished exterior paint finish for the automobile; the colorless layer is made of a material which substantially retains the glossiness during the heat-forming step; the liner has a sufficient thickness and sufficient elongation to mask the defects present in the substrate and, in the subsequent adhesion of the laminate to the substrate, maintains a substantially defect-free, glossy surface in the colorless layer; the finished composite paint coating provides sufficient exterior appearance and durability properties for use as an exterior paint finish in a car, or b) applying a colorless layer of a solution of vinylidene fluoride and acrylic resin in the form of a thin layer on a surface of a flexible casting sheet and dasTrocknen the fai Blosen layer on de ^r cast film, wherein the surface of the film has a specular reflectance in which eir.e Glossiness is transferred to the surface of the dried colorless layer, which suffices for outdoor use in the car; casting a paint film with a pigmented solution of vinylidene fluoride and acrylic resin in the form of a thin film and drying the paint film; transferring the dried colorless layer and color layer to a semi-rigid laminating film of a synthetic resinous material to form a composite color layer which is bonded to an upper side of the laminating film in which the colorless layer is the outer surface of the transferred color layer and the color layer itself is sandwiched between the colorless layer and the upper side of the laminating film, while the outer surface of the colorless layer substantially retains the sheen she took from the cast film; thermoforming the liner and the composite color layer disposed thereon to form a three-dimensionally shaped, imagined laminate; and adhering the laminate to a synthetic, resinous substrate to form an outer body frame; while the colorless layer essentially retains its brilliance in the heat-forming process; the laminating film has sufficient strength and sufficient elongation to obscure the defects present in the substrate, so that after adhesion of the laminate to the substrate a substantially flawless, glossy surface is present in the colorless layer; The composite color coating provides the appropriate exterior appearance and durability applications as an automotive exterior coating layer. 22. The method of claim 21a, characterized in that the laminate is thermoformed at a temperature greater than about 132 ⁰ C and the composite color layer is stretched during the heat-forming step by more than about 40%, while still the gloss and the appearance of the concerned and durability properties. 23. The method according to claim 21 a, characterized in that the colorless layer consists of a fluorinated polymer and a acrylic resin-containing material. A method according to claim 23, characterized in that the colorless layer consists of a thermoplastic paint system in which the fluorinated polymer is selected from the group consisting of polyvinylidene fluoride and copolymers and terpolymers of vinylidene fluoride. 25. A process according to claim 24, characterized in that the dried colorless layer comprises less than 70% by weight of polyvinylidene fluoride (PVDF) and less than about 50% by weight of acrylic resin, based on the total solids of acrylic resin and PVDF used in the colorless layer are present. 26. A method according to claim 21, characterized in that the color coat has the minimum values of gloss, reproducibility of an image, QUV, gasoline resistance, cleanability, acid resistance, hardness, abrasion resistance and impact resistance, as described essentially in US Pat Automotive specifications for exterior paint finishes are defined and described herein. 27. The method according to claim 21 a, characterized in that the preformed laminate with the carrier material by injection molding, Reaktionssspritzguß- or Duroplastplattenform techniques is press-formed. 28. The method of claim 21, characterized in that the colorless layer is applied to the cast film and thereby comprises a thermoplastic paint system comprising polyvinylidene fluoride and an acrylic resin, wherein the polyvinylidene fluoride is dispersed in a solution of acrylic resin. 29. The method according to claim 21 a, characterized in that the applied to the cast film colorless layer is a thermoplastic paint system, which consists of a solution of polyvinylidene fluoride and acrylic resin. 30. The method of claim 29, characterized in that the final color coat at an angle of 60 ° has a gloss of greater than about 75 gloss units and a reproducibility level of an image greater than about 80 units. 3. '. A method according to claim 21, characterized in that the laminating film is a semi-rigid film having a thickness in the range of about 254 to about 1016pm. 32. The method of claim 21, characterized in that the liner is made of a material selected from the group consisting of ABS, polyester, amorphous nylon, and thermoplastic polyolefins including polypropylene and polyethylene. 33. The method of claim 21 a, characterized in that on the cast film, a thin wax film is applied before it comes to apply the colorless layer on the cast film. 34. ancestors according to claim 21 a, characterized in that a pattern of a graphical representation between the colorless layer and the color layer is imprinted. 35. The method of claim 21 a, characterized in that in the laminating film, a pigment is contained. 36. The method of claim 21 a, characterized in that in the color layer metallic flakes are included, which line up in the Schichi when the flakes are applied to a carrier film. 37. The method according to claim 21a, characterized in that on the outer surface of the paint coating, a water-soluble protective layer is applied. 38. The method according to claim 37, characterized in that the protective layer is pressed onto the colorless layer. 39. The method according to claim 21a, characterized in that the heat-forming process is carried out while a contact between the thermoforming apparatus and the side of the laminating film is avoided, on which the colorless layer is located. 40. The method of claim 21 b, characterized in that the color layer on the thermoformed laminate has a gloss of more than evva 75 gloss units and a reproducibility of an image of more than about HO units. 41. The method according to claim 21b, characterized in that the carrier adheres to the laminate by the Spritzgußüberzugs-, the reaction injection molding or Duroplastplattenform technique. 42. The method of claim 21 b, characterized in that the laminating film is a semi-rigid film having a thickness in the range of about 254 to about 1016μηη. 43. The method of claim 21b, characterized in that the laminating film is made of a material selected from the group consisting of ABS, polyester, amorphous nylon, thermoplastic polyolefins including polypropylene and polyethylene. 44. The method of claim 21 b, characterized in that the color coating is cast as a solution of polyvinylidene fluoride and acrylic resin. 45. The method of claim 21 b, characterized in that the finished color coat reaches the minimum gloss, image reproducibility, QUV, gasoline resistance, cleanability, acid resistance, hardness, abrasion resistance, and impact resistance, as described in US Pat Automotive specifications for exterior color finishes are set forth in cars and described herein.