Decorative Antique Copper Coating with HTL Compatibility and Novel Interlayer Adhesion Mechanism

Abstract

The present invention relates to an article having a decorative coating, comprising a plastic substrate having a front surface; a base hard coating located on the front surface; one or more intermediate layers located on the hard coating; a TiN layer located on the one or more intermediate layers; a SiO 2 layer or a PECVD HMDSO+O 2 etching layer; and a protective hard coating located on the PECVD HMDSO+O 2 etching layer, and is directed to an article.

Description

Technical Field

[0001]

[0001] The present invention relates to a decorative coating for a substrate, and more particularly to a stable and durable coating that is spectrally adjustable to allow for a variety of appearance choices, particularly an (antique) copper-like metallic finish. The present invention also provides a novel interlayer adhesion mechanism for providing a more cost-effective and technically appropriate preparation process.

Background Art

[0002]

[0002] Decorative coatings, particularly decorative metallic finishes, are increasingly desired as designer surfaces on a variety of consumer goods, including premium automotive interior and exterior trim parts, consumer goods and household items, and fashionable home electronics, and as either partial or complete surfaces for those items.

[0003]

[0003] While bulk metal can be used for such applications, it is not only heavy and difficult to handle, but also difficult and costly to machine and polish into common complex shapes across these types of parts. In addition, bulk metal does not support "surprise and delight" hidden lighting, or generally backlighting, and is not suitable for forming surfaces where one part of the surface has a different appearance from another part of the surface. Therefore, it is more desirable to utilize lightweight substrates such as plastic substrates. Such plastic parts further have many attractive properties, including fracture resistance, low cost, the ability to be shaped and molded, and its transparency in some applications. However, such plastic parts do not necessarily meet the visual and wear requirements required for automotive applications. By coating a plastic substrate (with a metal coating), parts can be provided that satisfy the desired visual beauty while also improving the wear resistance of the underlying plastic substrate.

[0004]

[0004] The metal coating should have adjustable properties to provide a durable decorative finish that also allows light transmission. Such a coating should be capable of converging the need for spectral and optical tunability for a metallic finish that produces a customizable surface, from (for example) bright to deep black colors, that is functional, highly durable, and optionally has a backlighting function.

[0005]

[0005] OEMs are constantly looking for ways to make their vehicles stand out from the crowd. This can mean, from a styling perspective, the use of certain color trims throughout the vehicle to give it a different and / or premium feel. For example, the provision of (antique) copper color may be desirable for certain applications such as in vehicles. PVD coatings using Cu are not satisfactory in this regard as the coating can have a dull and cloudy copper appearance. Such coatings are often affected by significant color changes during the heat curing operation of the protective topcoat (both temperature and time are important), and furthermore, are also affected by corrosion during the neutral salt spray test. Also, conventional combinations of Si and Cr-based materials can result in a similar copper color, but the color is overly angle-dependent, i.e., such a coating changes color when rotated at different viewing angles, which is undesirable, i.e., the appearance is different from what is desired. Therefore, it is necessary to use a combination of several metals or mixtures thereof to achieve a desired color such as (antique) copper color.

Summary of the Invention

Problems to be Solved by the Invention

[0006]

[0006] However, the preparation of coatings from different metals or mixtures of metals makes it difficult to simultaneously prepare an additional adhesion layer, which may be necessary for applying and adhering a protective topcoat.

[0007]

[0007] Thus, there is a need for a plastic substrate that can be easily prepared by enabling a wide range of selections of appearances such as copper color, can be substantially transparent to enable hidden lighting functionality if necessary, and obtaining excellent adhesion of the applied layers, with a durable spectrally tunable surface.

Means for Solving the Problem

[0008]

[0008] The above background discussion is included to explain the context of the present invention. None of the materials mentioned should be construed as an admission that any of them was published, known, or part of common general knowledge as of the priority date of any one of the claims.

[0009]

[0009] The above object is achieved by an article having a decorative coating: · A plastic substrate having a front surface; · Any base hard coating located on the front surface; · One or more intermediate layers located on the hard coating; · A TiN layer located on the one or more intermediate layers; · SiO 2 layer or a PECVD HMDSO + O 2 etching layer; and · SiO 2 or a PECVD HMDSO + O 2 etching layer, and a protective hard coating located on the etching layer, provided by the present invention.

[0010]

[0010] The present invention also provides an article for use in automotive applications.

[0011] Also, a method of manufacturing an article, comprising: a) forming a plastic substrate having a front surface; b) optionally coating a hard coating on the front surface of the substrate; c) forming one or more intermediate layers on the hard coating; d) Coating a TiN layer on one or more intermediate layers; e) On the TiN layer, coating a SiO 2 layer or a layer using PECVD HMDSO + O 2 etching technology; and f) Coating a protective hard coating layer on the layer prepared in step e). A method is provided that includes the above steps.

[0011]

[0012] In the present invention, the "desired optical effect" should be achieved. The desired optical effect affects how the decorative coating is spectrally adjusted to endow the coated substrate with its desired optical effect.

[0012]

[0013] The desired optical effect will result in the desired appearance of the surface or a part of the surface of a product (when viewed from the front) including the coated substrate. The desired optical effect is composed of a combination of the desired transmission color, the desired specular reflection color, and the desired diffuse reflection color, taking into account the combined effects of the decorative coating, the plastic substrate, and the presence or absence of a backlight. In this regard, it should be taken into account that the plastic substrate can be colored or transparent itself, or can contain embedded particles to give the uncoated substrate a dull appearance, or can have one or both of its (uncoated) surfaces with a texture that can be employed to provide a "brush metal" appearance. While all of these characteristics contribute to the overall appearance of the final product, it should be recognized that what can be adjusted in the present invention to enable the achievement of the desired optical effect is specifically the decorative coating.

[0013]

[0014] Regarding the measurement of the desired transmission color, the desired specular reflection color, and the desired diffuse reflection color, references to "color" throughout this specification are measured according to the 1976 CIE L * a * b * space (or CIELAB) color model, where L * , a* and b * It is a reference to a color defined by values and is a substantially uniform color scale configured in the form of a cube. Orthogonal a * and b * On the color axis, a positive a * value is red, a negative a * value is green, a positive b * value is yellow, a negative b * value is blue, while the vertical axis for lightness (or grayscale) L * ranges from 0 (black) to 100 (white) and enables positioning the full color E at three points. The chroma of the color (C * ) is defined as √(a *2 +b *2 ) and is used to quantify the magnitude of the color regardless of its lightness.

[0014]

[0015] It will also be recognized that references to "transmitted" color and "reflected" color are references to the color of light after passing through an object ("transmitted color") or after being reflected by the surface of an object ("reflected color"). Further, with respect to the reflected color, "specular reflection" is a reference to the specular reflection of light from the surface of an object, where light from a single incident direction is reflected in a single exit direction, while "diffuse reflection" is of course a reference to the fact that incident light is reflected in a wide range of directions.

[0015]

[0016] The present invention also provides a method of applying a decorative coating to a plastic substrate, wherein the decorative coating causes the coated substrate to have a desired optical effect, a) determining the desired optical effect; b) determining an appropriate system to provide the desired optical effect; c) coating the appropriate system on the substrate; d) thereby forming a coated plastic substrate having the desired optical effect.

[0016]

[0017] Embodiments of the present disclosure will be considered by way of example with reference to the accompanying drawings.

Brief Description of the Drawings

[0017]

Figure 1

[0018] Figures 1a - 1c show schematic views of a coated plastic substrate according to the first to third preferred embodiments of the present invention, and show an article of the present invention having a decorative coating that provides an antique copper color.

Figure 2

[0019] Figure 2 shows a color matching diagram for an antique copper coating.

Mode for Carrying Out the Invention

[0018]

[0020] The present invention relates to an article having a decorative coating, comprising: · a plastic substrate having a front surface; · any base hard coating located on the front surface; · one or more intermediate layers located on the hard coating; · a TiN layer located on the one or more intermediate layers; · SiO 2 layer or a PECVD HMDSO + O 2 etching layer; and · a protective hard coating located on the SiO 2 or PECVD HMDSO + O 2 etching layer.

[0019]

[0021] The substrate of the present invention may be formed from any suitable plastic material. For example, the plastic substrate may be, but is not limited to, acrylonitrile ethylene styrene (AES), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylate (ASA), polyamide (PA), polybutylene terephthalate (PBT), polycarbonate (PC), polyethylene (PE), polyethylene terephthalate (PET), poly(methyl methacrylate) (PMMA), polyoxymethylene (POM), polypropylene (PP), polyurethane (PU), polyvinyl chloride (PVC), high flow AES, acrylonitrile-(ethylene-propylene-diene)-styrene (AEPDS), a blend of thermoplastic plastics, or a PC-ABS blend thermoplastic, and may be formed from a material selected from the group consisting of these. In one preferred embodiment, the plastic substrate is made of polycarbonate. In a preferred form, the substrate typically has a physical thickness in the range of 0.1 mm to 20 mm, more preferably in the range of 1 mm to 5 mm, and most preferably in the range of 2 mm to 3 mm, but is not limited thereto.

[0020]

[0022] In some embodiments, the provided plastic substrate may include visible texturing prior to the deposition of the decorative coating. In some embodiments, the present invention further includes providing visible texturing to the plastic substrate. In certain embodiments, the plastic substrate comprises or includes two or more visually different textures.

[0021]

[0023] An article having the decorative coating of the present invention may optionally further include a base hard coating between the decorative coating and the substrate. The base hard coating may be a protective layer that does not contribute to the overall desired optical effect. On the other hand, in other embodiments, the external protective layer on the decorative coating itself becomes a hard coating. Alternatively, the base hard coating may also contribute to the desired optical effect. The base hard coating can be used to prevent UV radiation damage. This blocks the UV generated during plasma processing, thereby enabling the advantages of plasma pretreatment without UV degradation. In one embodiment, there is no base hard coating. In further embodiments, there is a base hard coating.

[0022]

[0024] In this regard, a coating referred to as a "hard coating" is a coating that is harder and more rigid than the substrate, whereby the coating increases the abrasion resistance of the substrate. Such an abrasion-resistant hard coating reduces damage due to impact and scratching. Abrasion resistance can be measured by tests such as ASTM F735 "Standard Test Method for Abrasion Resistance of Transparent Plastics and Coatings Using the Oscillatory Sand Method", ASTM D4060 "Standard Test Method for Abrasion Resistance of Organic Coatings" using a Taber Abraser, or by using the well-known steel wool test.

[0023]

[0025] Furthermore, some plastic substrates may be damaged by certain solvents. For example, polycarbonate is damaged by acetone. That many products are "chemically resistant" is a requirement for many products suitable for the decorative coating of the present invention, and it refers to the ability to withstand exposure to common solvents such as diesel fuel, petroleum, battery acid, brake fluid, antifreeze, acetone, alcohol, automatic transmission fluid, hydraulic oil, and ammonia-based window cleaners. In this regard, it is recognized that a hard coating ideally results in a product having the decorative coating of the present invention with such chemical resistance.

[0024]

[0026] The hard coating is preferably formed from one or more wear-resistant layers and may include a primer layer that bonds well to the plastic substrate and forms a preferred material for subsequent wear-resistant layers. The primer layer may be provided by any suitable material, for example, an organic resin such as an acrylic polymer, a copolymer of an acrylic monomer and methacryloxysilane, or a copolymer of a methacrylic monomer and an acrylic monomer having a benzotriazole group or a benzophenone group. These organic resins may be used alone or in combination of two or more.

[0025]

[0027] The wear-resistant layer is preferably an organosilicon, acrylic, urethane, melamine, or amorphous SiO x C y H zIt is formed from one or more materials selected from the group consisting of. Most preferably, the wear-resistant layer is an organosilicon layer due to its excellent wear resistance and compatibility with physical vapor deposition films. For example, a wear-resistant layer containing an organosilicon polymer can be formed by methods such as dip coating with the following compounds: trialkoxysilanes or triacyloxysilanes, such as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, gamma-chloropropyltrimethoxysilane, gamma-chloropropyltriethoxysilane, gamma-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-(beta-glycidoxyethoxy)propyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N-beta(aminoethyl)-gamma-aminopropyltrimethoxysilane, beta-cyanoethyltriethoxysilane, etc.;and a dialkoxysilane or a diacyloxysilane, such as dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropylphenyldimethoxysilane, gamma-glycidoxypropylphenyldiethoxysilane, gamma-chloropropylmethyldimethoxysilane, gamma-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, gamma-mercaptopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc., selected from the group consisting of compounds, and then forming a layer and curing the layer.;

[0026]

[0028] The wear-resistant layer may be coated on the plastic substrate by dip coating in a liquid, subsequent solvent evaporation, or plasma chemical vapor deposition (PECVD) with a suitable monomer. Alternative deposition techniques such as flow coating and spray coating are also suitable. To improve the wear resistance of the hard coating, the coating after the wear-resistant layer may preferably be added within a period of 48 hours so as to avoid the aging deterioration and contamination of the previous coating.

[0027]

[0029] The thickness of the wear-resistant layer is preferably selected to provide suitable wear resistance. In this regard, suitable wear resistance is considered herein to be a Taber abrasion rate of 5 with respect to an uncoated plastic substrate (such as polycarbonate), or alternatively, after testing with a 500 g load and a CS10F wheel for 500 cycles, a Delta haze of less than 15% as determined by a Taber abrasion test (% haze measured in accordance with ASTM D1003). When these requirements are met, the thickness of the hard coating is preferably in the range of about 1 to about 15 microns, such as about 2 to about 10 microns, and most preferably 2 to 7 microns. In one embodiment, the minimum thickness is about 1 micron. In another embodiment, the minimum thickness is about 2 microns.

[0028]

[0030] The article of the present invention further includes one or more intermediate layers that can adjust the properties of the decorative coating. In such embodiments, the decorative coating can include a "stack" of layers of different materials. For example, additional layers can adjust the overall residual stress of the decorative coating, change the appearance of the decorative coating, or facilitate the adhesion of the decorative coating to a post-treatment or layer such as the aforementioned base hard coating. In certain embodiments, the decorative coating further includes an adhesion control layer (also referred to herein as an adhesion promotion layer). In some embodiments, the decorative coating further includes an optical modification layer.

[0029]

[0031] One or more intermediate layers are located on the base hard coating. In one embodiment, there are two or more intermediate layers. In a preferred embodiment, there is one intermediate layer. One or more intermediate layers may be independently selected from the group consisting of: metals, metalloids, and alloys including chromium (Cr), aluminum (Al), titanium (Ti), nickel (Ni), molybdenum (Mo), zirconium (Zr), tungsten (W), silicon (Si), niobium (Nb), tantalum (Ta), vanadium (V), cobalt (Co), manganese (Mn), silver (Ag), zinc (Zn), indium (In), germanium (Ge), tin (Sn), and mixtures thereof; and their oxides, nitrides, borides, fluorides, or carbides, and mixtures thereof. In one embodiment, at least one or more intermediate layers are formed from chromium, titanium, zirconium, or mixtures thereof. In a preferred embodiment, the article of the present invention includes one layer consisting of Cr-Zr or Ti. In one embodiment, the article of the present invention includes only one intermediate layer consisting of Cr-Zr. In one embodiment, the article of the present invention includes only one intermediate layer consisting of Ti.

[0030]

[0032] The CrZr layer can provide strong adhesion to the base hard coating and can also achieve a wide range of film stresses (when adjusted). In one embodiment, CrZr can be used without a base hard coating. The Ti layer can also be adjusted to an acceptable and strong level of stress.

[0031]

[0033] One or more intermediate layers may each have a thickness of about 10 nm to about 50 nm, such as about 15 nm to 45 nm, 15 nm to 40 nm, or 15 nm to 35 nm. In one embodiment, the total thickness of all the deposited intermediate layers may be within the above range for the individual layers.

[0032]

[0034] In addition, the coated substrate can provide an illumination pattern to the product and is sometimes generally referred to as "hidden til lit" (HTL) and, in appropriate circumstances, as a backlight. In this regard, the desired optical effect can be achieved by selecting the correct %R and %T such that light can be emitted through the coating to provide the illumination pattern. However, in the absence of rear illumination, the appearance of the product appears uniform so that no visible pattern is present.

[0033]

[0035] For example, the use of a CrZr or Ti layer can both achieve HTL compatibility (e.g., a transmittance of 6 - 15% is possible). Since the light transmission can be too high for the correct reflected color, an intermediate layer, such as a CrZr and / or Ti layer, can also provide some opacity.

[0034]

[0036] It may also be desirable to enable selective light transmission through the coated plastic article. Thus, in some embodiments, the method further includes providing a mask to the plastic substrate to provide a portion of controlled light transmission. This mask can be provided on the surface of the substrate under the decorative coating. The mask may include an opaque coating (PVD, ink, or paint), an adhesive masking film, film insert molding, or two - component injection molding. Thus, this can provide a visual symbol within a manufactured plastic article that can be illuminated via a backlight.

[0035]

[0037] According to the present invention, the TiN layer is located on one or more intermediate layers. The TiN layer can have a thickness of about 10 nm to about 50 nm, such as about 15 nm to 45 nm, 15 nm to 40 nm, or 15 nm to 35 nm. In one embodiment, the layer thickness is about 15 nm to about 30 nm. In a further embodiment, the layer thickness is about 15 nm to about 25 nm. The latter can result in light transmission of 46 - 60%. The TiN layer has a specific antique or discolored copper appearance. In such an embodiment, the TiN layer may have the following color ranges (Table 1):

[0036]

Table 1

[0038] The color of the TiN layer is affected by the thickness of the TiN and the nitrogen gas concentration. According to the present invention, the TiN layer contains not only stoichiometric TiN but also other ratios of Ti:N. In one embodiment, the TiN layer may be a gradient layer. According to the present invention, a gradient layer means that the concentration of either Ti or N increases from a portion directly located on one or more intermediate layers towards the outer portion of the TiN layer, while the concentration of the other component decreases in the same direction. The gradient may progress uniformly throughout the layer. In another embodiment, the gradient progresses non-uniformly. For example, the gradient can be achieved by continuously reducing or increasing the flow of nitrogen gas into the reaction chamber. Those skilled in the art will know how to change the nitrogen flow to achieve the desired gradient. The TiN layer may have a refractive index of approximately 1.35 and an extinction coefficient of 2.76 at 632.8 nm.

[0037]

[0039] According to the present invention, the SiO 2 layer or PECVD HMDSO + O 2The etching layer is located on the TiN layer. Since the protective hard coating, which is the outermost layer of the layer stack, generally does not adhere to layers such as Cr, CrZr, Ti, TiN, etc., these layers are required to adhere such a protective hard coating to the article. Therefore, in the layer design of the present invention, the protective hard coating can be fixedly and permanently attached to the underlying layer. In one embodiment, SiO 2 The layer is located on the TiN layer. In a preferred embodiment, PECVD HMDSO + O 2 The etching layer is located on the TiN layer.

[0038]

[0040] Generally, the execution of the sputtering process in the same PVD chamber is limited with respect to the number of target materials. For example, an industry-standard PVD apparatus can only be suitable for two target materials at a given time. It can, for example, flow both SiO 2 and Ti / TiN (for example, in a sputtering apparatus, the Si target is usually replaced with the Ti target), but this means that CrZr becomes unavailable afterwards. Therefore, a split process needs to be applied for further sputtering of the CrZr layer. Therefore, the system needs to be evacuated and reloaded later for CrZr deposition.

[0039]

[0041] To avoid the above preparation problems, a PECVD HMDSO process with oxygen post-etching can be used to replace the sputtered SiO 2 layer with PECVD HMDSO + O 2 etching. This achieves excellent adhesion and passes all external medium tests (or a UV accelerated test equivalent to a 1-year cycle). The etched HMDSO layer may be used as an adhesion promoter between the TiN layer and the top coat. Also, the HMDSO layer can be used as a stress control layer similar to SiO 2 The layer or PECVD HMDSO + O

[0040]

[0042] SiO 2 layer or PECVD HMDSO + O 2The etching layer is overcoated with a protective hard coating. The protective hard coating forms the outermost coating of the article manufactured during use. Thus, the protective coating is exposed to the elements. This layer can further improve abrasion resistance, fingerprint resistance, and "easy clean" functionality. For example, the protective layer can be formed from a material exhibiting properties including, but not limited to, the following hydrophobic, hydrophilic, oleophobic, lipophilic, oil-repellent properties, or combinations thereof, and may include a hard coating (with or without a matte additive (particles)) such as those described above. The abrasion-resistant hard coating reduces damage due to impact and scratching. Abrasion resistance can be measured through tests such as ASTM F735 "Standard Test Method for Abrasion Resistance of Transparent Plastics and Coatings Using the Vibratory Abrasion Method", ASTM D4060 "Standard Test Method for Abrasion Resistance of Organic Coatings" by a Taber Abraser, or by using a well-known steel wool test.

[0041]

[0043] Suitable materials for such protective hard coatings may be the materials described above for the base hard coatings. In one embodiment, the protective hard coating may be a fluoropolymer-based coating deposited by evaporation or liquid transfer techniques, or a liquid hard coating applied by spin, dip, spray, or flow coating techniques, with or without particulate additives for haze control (matting additives). In one embodiment, spray coating techniques are used to apply the protective hard coating. Commercially available hard coats include, but are not limited to, Momentive hard coats such as UVHC3000, UVHC5000, PHC587B / C, PHCXH100P, and AS4700F, Mitsubishi hard coats such as PH-800, or KCC hard coats such as KUV-5000. Each of these coatings has different abrasion resistance, weather resistance performance, and deposition parameters. Thus, one of ordinary skill in the art can select a coating appropriate for the intended purpose of the plastic article. In some preferred embodiments, the hard coating is Momentive PHC587B or AS4700F. In the most preferred embodiment, the hard coating is Momentive PHC587B.

[0042]

[0044] In one embodiment, the article is: · A polycarbonate substrate; · Any base hard coating located on the substrate; · A CrZr layer located on the hard coating; · A TiN layer located on the CrZr layer; · A PECVD HMDSO+O 2 etching layer; and · A protective hard coating located on the PECVD HMDSO+O 2 etching layer comprising.

[0043]

[0045] In one embodiment, the article is: · Polycarbonate substrate; · Any base hard coating located on the substrate; · Ti layer located on the hard coating; · TiN layer located on the Ti layer; · PECVD HMDSO+O 2 etching layer; and · PECVD HMDSO+O 2 protective hard coating located on the PECVD HMDSO+O etching layer including.

[0044]

[0046] In one embodiment, the article includes a base hard coating.

[0047] Improvements to the appearance can also be achieved by patterning the substrate. For example, through the use of a patterned injection mold, the pattern can be formed on the front surface of the substrate. An example of a desired optical effect is to reproduce brushed stainless steel, and it has been found that this appearance can be achieved when parallel lines of random length (1 - 5 cm) arranged closely adjacent to each other are subsequently coated in the present invention.

[0045]

[0048] The application of the protective coating may affect the stress of the decorative coating. Thus, in some embodiments, the residual stress of the decorative coating is the residual stress prior to any further processing of the decorative coating and in particular prior to the application of the protective coating. Further, one of ordinary skill in the art will recognize that the application of the protective coating can be modified to affect any further stress applied to the coated plastic article as a result of the protective coating. As is known in the art, a protective coating can have residual stress when cured on its own, which can be modified during the application of the protective coating. Some examples of parameters that can be adjusted during the application of the protective coating include the means of application (e.g., dip coating or spray coating), application on one or both sides of the coating, the thickness of the applied coating, the use of a primer prior to the application of the coating, the curing temperature of the protective coating, and the cooling rate of the coating (depending on the nature of the applied coating). Each of these factors can be modified based on what is known in the art, and the results can be evaluated based on known methods for evaluating residual stress, including the methods exemplified herein.

[0046]

[0049] The protective coating can change the appearance of the coating when applied over the decorative coating. In some embodiments, the protective coating includes a matting additive applied to the coated plastic article. In this regard, it is known that the matting effect is achieved by the diffusion effect provided by small (typically ~5 μm) particles of the matting additive. By modifying the protective coating by adding a matting additive, a "satin" appearance can also be achieved. This is characterized by a significant diffuse reflection component (e.g., 10% - 30% diffuse reflection, preferably 16%, and specular reflection ~8%). For example, Tospearl 2000B loading may be used at 1.5% w / w for both PHC587B and AS4700F, for example. In one embodiment, the loading is 3.5%.

[0047]

[0050] In one embodiment, an antique copper coating having HTL compatibility should be provided. As can be seen from FIGS. 1a - 1c, the TiN layer and SiO 2 or PECVD HMDSO + O 2 The use of an etching layer and a CrZi or Ti intermediate layer results in a close match of the antique copper color. FIG. 2 provides a color match diagram of these articles, showing that the color target (indicated by the black triangle) and the colors of the articles of FIGS. 1a - 1c (indicated by the circles) completely overlap and match.

[0048]

[0051] Preferred deposition methods that can be employed to apply the multi - layers of the articles of the present invention can be selected from any suitable vacuum deposition system such as thermal evaporation, electron beam evaporation (with or without ion beam assist), or sputter deposition. Sputter deposition is the preferred method. Additionally, the surface of the plastic substrate may first be subjected to a surface treatment to improve adhesion. The surface treatment can be selected from any of plasma discharge, corona discharge, glow discharge, and UV radiation.

[0049]

[0052] The preferred optical thickness of each individual layer of the articles of the present invention naturally depends on the desired optical effect. Thus, for different individual products, what can be expected is that there are different sets of "preferred optical thicknesses".

[0050]

[0053] In some embodiments, the overall residual stress of the decorative coating is compressive (when measured without a protective hard coating).

[0054] The residual stress within the film can be measured and is typically reported as pressure (e.g., MPa). Also, the residual stress can be reported as the displacement representing the deflection of the underlying substrate after the coating is applied. The displacement is determined by the stress within the coating, the thickness of the coating, and the properties of the underlying substrate. Thus, a thick coating having a lower stress profile (measured in MPa) can exert the same stress displacement on the substrate as a thinner coating with a higher stress profile. Accordingly, in some preferred embodiments, the residual stress of the decorative coating is measured as stress displacement. In some embodiments, the stress displacement is measured using a slide glass as the substrate. In some embodiments, the thickness of the slide glass is about 150 μm.

[0051]

[0055] In some embodiments, the decorative coating, when deposited, is deposited under conditions where a residual film stress displacement of -50 μm or less occurs. In some further embodiments, the decorative coating, when deposited, is deposited under conditions where a residual film stress displacement of -240 μm or less occurs. In some further embodiments, the decorative coating, when deposited, is deposited under conditions where a residual film stress displacement of less than -765 μm occurs.

[0052]

[0056] In this regard, in this stress range, it has been found that the coated substrate exhibits sufficient performance through durability tests such as salt spray, thermal shock, dry heating, immersion, and humidity tests. Throughout this specification, this range is referred to as the "desired stress window". Therefore, alternative ranges for the desired stress window are less than -6 MPa, or less than -63 MPa, or less than -76 MPa, or less than -100 MPa, or less than -110 MPa, or less than -112, or less than 160 MPa. Further, the lower limit of the stress window may be -360 MPa or more, -359 MPa or more, -300 MPa or more, -250 MPa or more, or -200 MPa or more. Further combinations of these ranges are also contemplated by the present invention. For example, the stress window may be 0 MPa to -300 MPa; -63 MPa to -300 MPa, -75 MPa to -300 MPa, -110 MPa to -300 MPa, or 0 MPa to -250 MPa, etc.

[0053]

[0057] In one embodiment, the residual stress can also be compressive.

[0058] In one form, the system can be adjusted to achieve the desired stress window by optimizing the deposition parameters of one or more of its layers. These parameters include sputter power, gas pressure, nitrogen gas doping, and coating thickness. The stress can also be adjusted to be more compressive (or less tensile) by introducing a thermal stress component by substrate heating or by performing a pretreatment process immediately before deposition of the stress control system. The interaction of the stress control system with the spectral control system is complex, and the adjustment of the overall residual stress is ideally performed on the entire decorative coating, which is a complete coating "stack".

[0054]

[0059] In this regard, the overall residual stress is the measured stress profile of the layers as a complete stack deposited on a glass microscope coverslip. The stress measurement is obtained by placing the slide glass in a stress measuring device (such as Sigma Physik SIG-500SP) before and after coating deposition.

[0055]

[0060] The article of the present invention can be used in several different applications. In one embodiment, the article is used in automotive applications. In one embodiment, the article is used for automotive badges, door finishers, instrument panels, automotive mirrors, etc., but is not limited thereto.

[0056]

[0061] In terms of the possible uses of the decoratively coated plastic substrate according to the present invention, as described above, the coated plastic substrate can be used as a designer aspect on various consumer goods including premium automotive interior and exterior trim parts, consumer goods and household items, and fashionable household electronic products, and as either a partial or complete surface for those articles.

[0057]

[0062] In one aspect, the present invention is a method of manufacturing an article, comprising: a) forming a substrate having a front surface; b) optionally coating a hard coating on the front surface of the substrate; c) forming one or more intermediate layers on the hard coating; d) coating a TiN layer on the one or more intermediate layers; e) coating a SiO 2 layer or a layer using PECVD HMDSO+O 2 etching technology; and f) coating a protective hard coating layer on the layer prepared in step e) is provided.

[0058]

[0063] In one embodiment, step b) is present.

[0064] The above modifications and variations are within the scope of the present disclosure. It is understood that the present disclosure as disclosed and defined herein extends to all alternative combinations of two or more of the individual features that are either recited or apparent from the text and / or drawings. All such various combinations constitute alternative aspects of the present disclosure. The embodiments described herein illustrate the best known mode of carrying out the teachings of the present disclosure and enable those skilled in the art to utilize the teachings of the present disclosure. The claims should be construed to include alternative embodiments to the extent permitted by the prior art. The present invention is capable of other embodiments and of being practiced or carried out in various ways. Also, it is understood that the language and terminology used herein are for the purpose of description and should not be regarded as limiting. The use of "including", "comprising", and their variations herein is intended to encompass the recited items and their equivalents as well as additional items and their equivalents.

Example

[0059]

[0065] Example 1 - Desired Optical Effect - Copper Spectral Reflection Appearance with High %T Preparation of Substrate

[0066] The injection-molded polycarbonate substrate is first cleaned using a detergent in a commercially available ultrasonic cleaning system. A final rinse in distilled water is required in a clean (dust-free) environment. The substrate is then dip-coated with Momentive PHC-587B at a withdrawal rate of 10 mm / s. A flash-off time of 10 minutes allows the solvent to evaporate slowly and enables the portion to generally be non-stick. The substrate is then moved to a curing oven at 130 °C for 45 minutes. Subsequent coating is performed within a period of 48 hours to avoid the aging degradation / contamination of the hard coating.

[0060] Decorative Coating

[0067] The substrate was loaded into a batch vacuum sputter coater (PylonMET VXL), which consists of a single coating chamber where the sample is placed, evacuated, and coated. Inside this chamber, the sample was evacuated to a pressure below 8×10-5 mbar. The distance from the target to the substrate was 110 mm, and the following were the deposition conditions:

[0061]

Table 2

[0062]

Table 3

[0063] Protective satin coating - internal deformation

[0068] To achieve a satin metal appearance, a protective hard coat containing an additive that causes diffusion of visible light was applied. Specifically, the following parameters were used.

[0064]

Table 4

[0069] To achieve a satin metal appearance, a protective hard coat containing an additive that causes diffusion of visible light was applied. Specifically, the following parameters were used.

[0065]

Table 5

[0066] Example 2: Stress test

[0070] The test was conducted and the results are summarized in Table 5 below.

[0067]

Table 6-1

[0068]

Table 6-2

[0071] As can be seen from Table 5, the prepared articles passed all the required tests.

Claims

1. Articles having a decorative coating: • Plastic substrate with a front surface; - An optional base hard coating, the base hard coating located directly above the front surface; - One or more intermediate layers located directly above the base hard coating or directly above the front surface of the plastic substrate; - A TiN layer located directly above one or more of the aforementioned intermediate layers; SiO located directly above the TiN layer ２ Layer or PECVD HMDSO+O ２ Etched layer; and - The aforementioned SiO ２ Or PECVD HMDSO+O ２ Protective hard coating located directly above the etching layer Articles including.

2. The article according to claim 1, wherein the plastic substrate is formed from a material selected from the group consisting of polyacrylate, polyester, polystyrene, polyethylene, polypropylene, polyamide, polyimide, polycarbonate, epoxy, phenol, acrylonitrile butadiene-styrene, acetyl material, poly(2,2'-dihydroxyphenylpropane)carbonate, polydiethylene glycol, bis(allyl carbonate), polymethyl methacrylate, and polystyrene polycarbonate and blends thereof.

3. The article according to claim 1 or claim 2, wherein the base hard coating is formed from one or more wear-resistant layers, and the wear-resistant layers are formed from a material selected from the group consisting of organosilicon, acrylic, urethane, melamine, and SiOxCyHz.

4. The article according to claim 3, wherein the base hard coating has a thickness in the range of about 1 micron to about 15 microns.

5. The article according to claim 1, wherein the one or more intermediate layers are layers selected from the group consisting of chromium, aluminum, titanium, nickel, molybdenum, zirconium, tungsten, silicon, niobium, tantalum, vanadium, cobalt, manganese, silver, zinc, and mixtures thereof; as well as oxides, nitrides, borides, or carbides thereof, alloys thereof, and mixtures thereof.

6. The article according to claim 5, wherein one or more intermediate layers are formed from chromium, titanium, zirconium, or a mixture thereof.

7. The article according to claim 6, comprising one intermediate layer made of CrZr or Ti.

8. The article according to claim 1, wherein one or more intermediate layers have a thickness in the range of about 20 nm to about 80 nm, preferably in the range of about 20 nm to about 80 nm, or preferably about 40 nm.

9. The article according to claim 1, wherein the TiN layer has a thickness of about 15 nm to about 50 nm.

10. The article according to claim 1, wherein the protective hard coating is Momentive AS4700F or Momentive PHC587B.

11. PECVD HMDSO+O ２ The article according to claim 1, wherein the etching layer is located directly above the TiN layer.

12. The article according to claim 1, wherein the article is intended for automotive use.

13. A method for manufacturing an article: a) Step of forming a plastic substrate having a front surface; b) Optionally, a step of applying a hard coating to the front surface of the plastic substrate; c) The step of forming one or more intermediate layers on the front surface of the plastic substrate or on the hard coating; d) The step of coating one or more intermediate layers with a TiN layer; e) SiO on the TiN layer ２ Layer or PECVD HMDSO+O ２ A step of coating a layer using etching technology; and f) A step of coating a protective hard coating layer onto the layer prepared in step e). Methods that include...

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