Milky white

Abstract

The present disclosure relates to multi-layer coatings that are be applied to substrates such as automotive substrates and methods of preparing and applying such coatings.

Description

MILKY WHITEFIELD OF THE DISCLOSURE

[0001] The present disclosure relates to multi-layer coatings that are be applied to substrates such as automotive substrates and methods of preparing and applying such coatings.BACKGROUND OF THE DISCLOSURE

[0002] Multi-layer coatings are applied to a wide variety of substrates to provide color and other visual effects, corrosion resistance, abrasion resistance, chemical resistance, and the like. For example, multi-layer coatings often include a basecoat layer that provides color or other visual special effects and a clear coat layer that provides an abrasion and scratch resistant layer. With respect to multilayer coatings applied to substrates such as automotive substrates, a primer layer and primer surfacer layer are also typically included.

[0003] Typical special effect coatings provide a flop, wherein a change in reflectance of a metallic color is observed as the coating is rotated through the range of viewing angles. In the CIELAB color space (L*a*b*), the lightness L* value changes depending on the viewing angle that is expressed as the flop index.

[0004] However, it is desired to provide coatings having a new color impression.SUMMARY OF THE DISCLOSURE

[0005] The aforementioned problem could be solved by a multi-layer coating comprising: (a) a substrate, (b) a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, (c) a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0006] A method for preparing a multi-layer coating, particularly a multi-layer coating according to the present disclosure, is provided comprising in thefollowing order: (A) forming a basecoat layer over at least a portion of a substrate by depositing a basecoat composition over at least a portion of the substrate, wherein the basecoat composition comprises a goniochromatic pigment, (B) optionally drying and / or curing the basecoat layer, (C) forming a clear coat layer over at least a portion of the basecoat layer by depositing a clear coat composition over at least a portion of the substrate, wherein the clear coat composition comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition, and (D) drying and / or curing the clear coat layer or both the basecoat and clear coat layers, wherein the dry thickness of the clear coat layer is in the range of 15 to 80 pm and the dry thickness of the basecoat layer in the range of 5 to 35 pm.

[0007] Moreover, the present disclosure relates to the use of a clear coat coating composition comprising 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition, to form a clear coat layer over a basecoat layer, wherein the basecoat layer has a flop index of at least 1 .

[0008] Furthermore, a laminate is provided comprising a protective film, particularly a removable protective film (I) a clear coat layer applied over at least a portion of the protective film, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm, (ii) an optional basecoat layer applied over at least a portion of the clear coat, wherein particularly the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer particularly comprises a goniochromatic pigment (iii) an optional carrier film applied over at least a portion of the basecoat layer, (iv) an optional adhesive layer applied over at least a portion of the clear coat, basecoat layer and / or carrier film, and (v) an optional liner applied over at least a portion of the adhesive film.

[0009] Moreover, a method for applying a laminate onto a substrate is provided, comprising (I) providing a laminate according to the present disclosure, (II) contacting the substrate with the laminate, wherein the substrate particularlycomprises a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment (III) optionally applying an adhesive on the substrate before contacting the substrate with the laminate so that the laminate is applied onto the adhesive.

[0010] It has been surprisingly found that a multi-layer coating according to the present disclosure reveals a huge color travel and particularly a huge delta b* shift. Additionally, a milky white effect is achieved without negatively affect the color of the multi-layer coating such as the color of the basecoat.BRIEF DESCRIPTION OF THE DRAWINGSFigure 1 : A multi-layer coating according to the present disclosure is shown.Figure 2a: A further multi-layer coating according to the present disclosure is shown.Figure 2b: A method to apply a laminate onto a coated substrate is shown.Figure 3: A laminate according to the present disclosure is shown.DESCRIPTION OF THE DISCLOSURE

[0011] It is to be understood that the disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary.

[0012] It should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0013] In this application, the use of "or" means "and / or" unless specifically stated otherwise, even though "and / or" may be explicitly used in certain instances. Further, in this application, the use of "a" or "an" means "at least one" unless specifically stated otherwise. For example, "a" multi-layer coating, "a" basecoat, "a" clear coat, and the like refer to one or more of any of these items. For example, the expression "a” goniochromatic pigment includes the plural, namely goniochromatic pigments. Moreover, for example, the expression goniochromaticpigments means that one type of goniochromatic pigments can be present or multiple different types of goniochromatic pigments can be present.

[0014] As used herein, the term “aqueous” refers to a carrier or solvent wherein the solvent comprises water and up to 50 wt. % of water miscible organic solvents, such as alkyl ethers.

[0015] As used herein, the term “basecoat” refers to a coating layer that provides protection, color, hiding (also known as “opacity”) or visual appearance. The term “basecoat coating composition” refers to a coating composition that contains pigments and / or colorants, and that can be used to form a basecoat.

[0016] The term “clear coat” refers to a coating layer that can be substantially transparent rather than opaque. However, a clear coat can comprise pigments and / or colorants but should comprise pigments and / or colorants only in such as an amount that the coating layer is not opaque.

[0017] As used herein, the term “coating” (as well as “coat”) refers to the finished product resulting from applying coating compositions to a substrate and forming the coating, such as by curing. A basecoat and clear coat layer may all be coatings, and any of these coatings can be formed in accordance with the methods of the present disclosure.

[0018] The present disclosure relates to a multi-layer coating comprising: (a) a substrate, (b) a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, (c) a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0019] The basecoat layer can have a flop index of at least 1 . Thus, a flop of the basecoat can be achieved by a basecoat comprising a goniochromatic pigment.

[0020] The indication of weight percent in the present disclosure based on the respective coating, such as clear coat or basecoat, can be also considered as the solid content of the coating composition used to obtain the respective coating.

[0021] It is intended that the basecoat layer (b) and the clearcoat layer in the context of the multi-layer coating refer to cured coating layers.

[0022] Goniochromatic pigments are used, for example, in automotive coatings, decorative coatings, plastic pigmentation, printing inks (security inks in particular), textiles, and cosmetics. Their optical effect results from the directional reflection of light from predominantly sheet-like particles that conventionally are metallic or that have a structured refractive index contrast, the length scale of which is comparable to the wavelength of light. According to the nature of the pigment particles, the pigments are known as metallic effect pigments (for example, aluminum, zinc, copper or alloys thereof) or interference pigments (for example, based on titanium dioxide-coated mica, such as muscovite, phlogopite, and biotite).

[0023] As a result of the incident light being reflected directionally by the predominantly sheet-like particles, color effect pigments that are oriented, for example, in a coating, exhibit goniochromaticity; that is, their perceived color (lightness and / or hue and / or chroma) varies with the angle of illumination or observation.

[0024] Interference pigments may comprise a single plate-like layer, or a multilayer structure. The color perceived is affected by, for example, interference in the thin layer or layers, and optionally also by absorption by a chromophore (an organic moiety or inorganic complex that absorbs wavelengths of light in the visible and / or UV ranges) or a color center. A color center is an electron hole pair that results from a lattice defect in a crystalline solid-state material and which absorbs wavelengths in the visible and / or UV ranges. Interference, with or without absorption, results in a multiplicity of hue variations that are dependent on the thickness of the thin layer or layers and the effective refractive index of the layer or layers.

[0025] A suitable goniochromatic pigment is a flake pigment, such as an aluminum flake pigment, zinc flake pigment, copper flake pigment or a flake pigment ofalloys thereof. It is desired that the goniochromatic pigment comprises an aluminum flake pigment, or a flake pigment comprising aluminum. Accordingly, (b) the basecoat layer can comprise a flake pigment (as the goniochromatic pigment). A flake pigment generally includes a flake that is coated with one of the aforementioned metals, such as metal oxides.

[0026] The thickness of the flake pigments can be between 10 and 1000 pm, such as 10 to 80 pm, 20 to 80 pm, or 100 to 1000 pm. The volume average particle diameter Dv50 can be 5 to 50 pm, such as 5 to 35 pm, 8 to 32 pm, or 12 to 30 pm. The Dv50 and the thickness of the flake pigments can be derived from the technical documents of manufacturers of the flake pigments.

[0027] The Dv50 can be determined by laser diffraction. The Dv50 can be determined by a laser diffraction measuring device Microtrac MT3300EXII, manufactured by MicrotracBEL Corp, particularly following the user manual. The Dv50 can also be determined by dynamic light scattering. The Dv50 can be determined by a dynamic light scattering measuring device SZ-100V2 nanoPartica Dynamic Light Scattering (DLS), manufactured by HORIBA, particularly following the user manual. Dynamic light scattering is particularly useful for low particle sizes such as 0.3 nm to 10 pm and laser diffraction is particularly useful for particles sizes of 10 nm to up to 5 mm. The Dv50 using dynamic light scattering set out, for example, in ASTM E3247-20. Generally, it is possible to convert from an intensity to a volume or number distribution.

[0028] A commercially available aluminum flake pigment is, for example, STAPA® HYDROLAN 2154 and HYDROLAN 8154 sold by the firm Eckart.

[0029] Moreover, goniochromatic pigments according to the disclosure of US 6,894,086 B2 can be used, which is incorporated by reference.

[0030] The optical properties (such as the flop index, L*, a*, b*) of coatings (particularly the multilayer-coating stack according to the disclosure or a basecoat) can be measured with a multiangle spectrophotometer BYK-mac I (manufactured by BYK) and particularly following the instructions of the instrument manual. BYK-mac I performs a 5-angle color measurement for light / dark travel evaluation: 15° 125° 145° / 75° / 110°. Color calculation and measurement can be found in DIN EN ISO 1 1664 (2020-03) standards (1 -4).

[0031] A flop index of 0 indicates a solid color, while a very high flop metallic or pearlescent basecoat / clear coat color may have a flop index of 15-17. The flop index can be calculated as follows:2.69Flop index =

[0032] It is desired that the basecoat layer has a flop index of at least 1 , such as at least 2, at least 3, at least 4, or at least 5. The basecoat layer can have a flop index of 1 to 20, such as 2 to 18, 3 to 15, 4 to 12, or 5 to 10.

[0033] It is desired that the multi-layer coating according to the disclosure has a flop index of at least 0.1 , such as at least 0.5, at least 1 , at least 1 .5, or at least 2. The multi-layer coating can have a flop index of 0.1 to 15, such as 0.5 to 10, 0.8 to 8, 1 to 7, or 1.5 to 6.

[0034] It is desired that the flop index of the multi-layer coating according to the disclosure is lower than the flop index of the basecoat layer.

[0035] A goniochromatic pigment is generally considered as a pigment exhibiting a flop index of at least 1 in a coating. For instance, the flop index can be measured by using a basecoat mentioned in the examples, wherein the desired measured pigment is the sole pigment in the desired content in the basecoat, and a clear coat is applied over said basecoat without pigments.

[0036] Generally, the basecoat layer is formed from a basecoat coating composition. Generally, the clear coat layer is formed from a clear coat coating composition.

[0037] The dry thickness (or dry film thickness) of the basecoat layer can be in the range of 7 to 28 pm, such as 8 to 26 pm, 9 to 25 pm, or 10 to 20 pm.

[0038] The dry thickness (or dry film thickness) of the clear coat layer can be in the range of 20 to 70 pm, such as 30 to 65 pm, 35 to 60 pm, or 45 to 57 pm. It is particularly desired that the dry thickness of the clear coat layer is 20 to 30 pm, such as 35 to 45 pm, 44 to 48 pm, 49 to 52 pm, or 53 to 56 pm.

[0039] The dry coating thickness of the multi-layer coating can be in the range of 70 to 200 pm, such as 80 to 160 pm, 90 to 150 pm, or 100 to 130 pm.

[0040] The coating thickness can be measured with non-destructive coating thickness measurements device “LAYERCHECK 750 USB” (ERICHSEN GmbH & Co. KG, Germany) with the magnetic-inductive method. Determination of Film build thickness generally follows DIN EN ISO 2808.

[0041] The basecoat can have a total pigment content of at least 10 wt. %, such as at least 15 wt. %, at least 20 wt. %, or at least 25 wt. %, based on the total weight of the basecoat. For instance, the basecoat has a total pigment content of 10 wt. % to 30 wt. %, such as 15 wt. % to 30 wt. %, 20 wt. % to 30 wt. %, or 25 wt. % to 30 wt. %, based on the total weight of the basecoat.

[0042] The basecoat composition can have a total pigment content of at least 10 wt. %, such as at least 15 wt. %, at least 20 wt. %, or at least 25 wt. %, based on the total solid content of the basecoat composition. For instance, the basecoat composition can have a total pigment content of 10 wt. % to 30 wt. %, such as 15 wt. % to 30 wt. %, 20 wt. % to 30 wt. %, or 25 wt. % to 30 wt. %, based on the total solid content of the basecoat composition.

[0043] The basecoat can comprise further pigment. Further pigment with respect to the basecoat means pigment(s) different from a goniochromatic pigment(s). The further pigment can comprise a colorant or a mixture of colorants. The colorant can be used to provide the desired color of the multi-layer coating.

[0044] As used herein, the term "colorant" means any substance that imparts color and / or other opacity and / or other visual effect to the composition. The colorant can be added in any suitable form, such as discrete particles, dispersions, solutions and / or flakes.

[0045] The further pigment in the basecoat may comprise carbazole dioxazine pigments, azo pigments, monoazo pigments, disazo pigments, naphthol AS pigments, salt type (lakes) pigments, benzimidazolone pigments, metal complex pigments, isoindolinone pigments, isoindoline pigments, polycyclic phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, diketopyrrolo pyrrole pigments, thioindigo pigments, anthraquinone pigments, indanthrone pigments, anthrapyrimidine pigments, flavanthrone pigments, pyranthrone pigments, anthanthrone pigments, dioxazine pigments,triarylcarbonium pigments, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures thereof.

[0046] The further pigment in the basecoat may comprise Violet Mica, Blue Mica, Green Mica, Mica Copper, Alizarin Crimson(PR83), Lamp Black (PBk 7), Chrome Iron Brown (PBr29), Alizarin Crimson (PR83), Perylene Violet (PV29), Yellow Iron Oxide (PY42), Nickel Azo Yellow (PY150), Bismuth Vanadate Orange (PO86), Iron Oxide Red (PR101 ), Phthalocyanine Blue (PB15), Phthalocyanine Blue RS (PB15:1 ), Phthalocyanine Blue (PB15:2), Phthalocyanine Blue BGS (PB15:3), Phthalocyanine Blue NCF (PB15:4), Phthalocyanine Blue (PB15:5), Phthalocyanine Blue (PB15:6), Cobalt Blue (PB28), Indanthrone Blue (PB60), Phthalocyanine Green BS (PG7), Phthalocyanine Green YS (PG36), Cobalt Titanate Green (PG50), Carbon Black (PBk6), Titanium White (PW6) that has a particle size over 250 nm, red iron oxide (PR101 :1), Transparent Red Iron Oxide (PR1011), Yellow Iron Oxide (PY42t), Transparent Yellow Iron Oxide (PY42t), mica, glass flakes, and / or a combination thereof. The pigments can be found in The Color of Art Pigment Database: Pigment Orange, PO (artiscreation.com, David G. Myers).

[0047] However, it is possible that the goniochromatic pigment(s) is / are the sole pigment(s) present in the basecoat. In other words, no further pigments may be present in the basecoat.

[0048] The clear coat can have a total pigment content of up to 3 wt. %, such as up to 2 wt. %, up to 1 .5 wt. %, up to 1 wt. %, up to 0.9 wt. %, up to 0.8 wt. %, up to 0.7 wt. %, up to 0.6 wt. %, based on the total weight of the clear coat. For instance, the clear coat has a total pigment content of 0.1 wt. % to 3 wt. %, suchas at least 0.5 wt. % to 2 wt. %, at least 0.6 wt. % to 1 .5 wt. %, or at least 0.7 wt. % to 1 wt. %, based on the total weight of the clear coat.

[0049] The clear coat composition can have a total pigment content of up to 3 wt. %, such as up to 2 wt. %, up to 1 .5 wt. %, up to 1 wt. %, up to 0.9 wt. %, up to 0.8 wt. %, up to 0.7 wt. %, up to 0.6 wt. %, based on the total solid content of the clear coat composition. For instance, the clear coat composition has a total pigment content of 0.1 wt. % to 3 wt. %, such as 0.5 wt. % to 2 wt. %, 0.6 wt. % to1 .5 wt. %, or 0.7 wt. % to 1 wt. %, based on the total solid content of the clear coat composition.

[0050] The clear coat layer can comprise titanium dioxide having a volume average particle size Dv50 in the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, or 35 to 55 nm.

[0051] The clear coat layer can comprise titanium dioxide having a particle size the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, or 35 to 55 nm.

[0052] Accordingly, the clear coat layer can comprise 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, wherein clear coat layer comprises titanium dioxide having a volume average particle size Dv50 in the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, or 35 to 55 nm.

[0053] Moreover, the clear coat layer can comprise 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, or 35 to 55 nm, based on the total weight of the clear coat layer.

[0054] The Dv50 can be determined by laser diffraction. The Dv50 can be determined by a laser diffraction measuring device Microtrac MT3300EXII, manufactured by MicrotracBEL Corp, particularly following the user manual. The Dv50 can also be determined by dynamic light scattering. The Dv50 can be determined by a dynamic light scattering measuring device SZ-100V2 nanoPartica Dynamic Light Scattering (DLS), manufactured by HORIBA, particularly following the user manual. Dynamic light scattering is particularly used for low particle sizes such as 0.3 nm to 10 pm and laser diffraction is particularly used for particles sizes of 10 nm to up to 5 mm. The Dv50 using dynamic light scattering set out, for example, in ASTM E3247-20. Generally, it is possible to convert from an intensity to a volume or number distribution.

[0055] Accordingly, the Dv50 can be determined by laser diffraction and / or by dynamic light scattering.

[0056] Suitable titanium dioxide used in the clear coat is the commercially available titanium dioxide MT-700HD from TAYCA Co., Ltd. MT-700HD has volume average particle size Dv50 of 50 nm

[0057] The clear coat layer can comprise 0.04 wt. % to 1 .30 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, such as 0.09 wt. % to 1 .10 wt. %, 0.14 wt. % to 1 .00 wt. %, 0.20 wt. % to 0.90 wt. %, 0.25 wt. % to 0.80 wt. %, 0.35 wt. % to 0.70 wt. %, 0.40 wt. % to 0.70 wt. %, 0.50 wt. % to 0.70 wt. %, or 0.50 wt. % to 0.60 wt. %, based on the total weight of the clear coat layer.

[0058] Accordingly, the clear coat layer can comprise 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, such as 0.04 wt. % to 1 .30 wt. %, 0.09 wt. % to 1 .10 wt. %, 0.14 wt. % to 1 .00 wt. %, 0.20 wt. % to 0.90 wt. %, 0.25 wt. % to 0.80 wt. %, 0.35 wt. % to 0.70 wt. %, 0.40 wt. % to 0.70 wt. %, 0.50 wt. % to 0.70 wt. %, or 0.50 wt. % to 0.60 wt. %, based on the total weight of the clear coat layer, wherein clear coat layer comprises titanium dioxide having a volume average particle size Dv50 in the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, or 35 to 55 nm.

[0059] Moreover, the clear coat layer can comprise 0.01 wt. % to 1 .50 wt. %, such as 0.04 wt. % to 1 .30 wt. %, 0.09 wt. % to 1 .10 wt. %, 0.14 wt. % to 1 .00 wt. %, 0.20 wt. % to 0.90 wt. %, 0.25 wt. % to 0.80 wt. %, 0.35 wt. % to 0.70 wt. %, 0.40 wt. % to 0.70 wt. %, 0.50 wt. % to 0.70 wt. %, or 0.50 wt. % to 0.60 wt. %, titanium dioxide having a volume average particle size Dv50 in the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, 35 to 55 nm, based on the total weight of the clear coat layer.

[0060] The pigment weight concentration (PWC) of the clear coat layer can be 0.01 % to 2 %, such as 0.05 % to 1 .8 %, 0.1 % to 1 .3 %, 0.2 % to 1 .1 %, 0.25 % to 1 %, 0.40 % to 0.90 %, or 0.50 % to 0.80 %. Moreover, the pigment weight concentration of the clear coat layer can be 0.15 % to 0.30 %, such as 0.2 % to 0.6 %, 0.3 % to 0.5 %, 0.5 % to 0.6 %, 0.6 % to 0.7 %, 0.8 % to 0.9 %, or 1 .2 % to 1 .4 %. The pigment weight concentration is the total pigment content divided by the sum of the total pigment content and the binder content. The binders includeall film-forming resins as well as all crosslinking agents. Crosslinking agents are for example polyisocyanates.

[0061] The pigment weight concentration (PWC) can be calculated as follows pi mentPWC = - — - - - — pigment + binder wherein pigment is the total weight of the pigments in the coating composition and binder is the total weight of the binders in the coating composition. The binders include all film-forming resins as well as all crosslinking agents. Crosslinking agents are for example polyisocyanates.

[0062] The ratio of the total pigment weight to the total binder weight can be 0.0001 to 0.1 , such as 0.0005 to 0.08, 0.0009 to 0.04, 0.001 to 0.03, 0.002 to 0.02, 0.003 to 0.01 , 0.004 to 0.009, or 0.005 to 0.008.

[0063] The ratio of the total pigment weight to the total binder weight can be as follows pigment P / B binder wherein pigment is the total weight of the pigments in the coating composition and binder is the total weight of the binders in the coating composition. The binders include all film-forming resins as well as all crosslinking agents. Crosslinking agents are for example polyisocyanates.

[0064] The BET surface area of the titanium dioxide in the clear coat (i.e. titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm) layer can be 20 to 80 m2 / g, such as 25 to 70 m2 / g, 25 to 50 m2 / g, or 30 to 45 m2 / g. The BET surface area can be measured by Brunauer-Emmert-Teller Theory / DIN ISO 9277:2003-05.

[0065] The titanium dioxide in the clear coat (i.e. titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm) can have a rutile structure.

[0066] The oil absorption (g / 100g pigment) of the titanium dioxide in the clear coat(i.e. titanium dioxide having a volume average particle size Dv50 in the range of 1to 250 nm) can be 15 to 50, such as 20 to 45, 25 to 45, or 30 to 40. The oil absorption can be measured according to DIN ISO 787-10.

[0067] The clear coat (c) can comprise further pigment, such as Violet Mica, Blue Mica, Green Mica, Mica Copper, Alizarin Crimson(PR83), Lamp Black (PBk 7), Chrome Iron Brown (PBr29), Alizarin Crimson (PR83), Perylene Violet (PV29), Yellow Iron Oxide (PY42), Nickel Azo Yellow (PY150), Bismuth Vanadate Orange (PO86), Iron Oxide Red (PR101), Phthalocyanine Blue (PB15), Phthalocyanine Blue RS (PB15:1 ), Phthalocyanine Blue (PB15:2), Phthalocyanine Blue BGS (PB15:3), Phthalocyanine Blue NCF (PB15:4), Phthalocyanine Blue (PB15:5), Phthalocyanine Blue (PB15:6), Cobalt Blue (PB28), Indanthrone Blue (PB60), Phthalocyanine Green BS (PG7), Phthalocyanine Green YS (PG36), Cobalt Titanate Green (PG50), Carbon Black (PBk6), Titanium White (PW6) that has a particle size over 250 nm, red iron oxide (PR101 :1), Transparent Red Iron Oxide (PR1011), Yellow Iron Oxide (PY42t), Transparent Yellow Iron Oxide (PY42t), mica, glass flakes, and / or a combination thereof. Further pigment with respect to the clear coat means pigments different from the titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm.

[0068] The further pigments can be present in the clear coat (c) in an amount of 0.1 wt. % to 1 .5 wt. %, based on the total weight of the clear coat, such as 0.2 wt. % to 1 .1 wt. %, 0.3 wt. % to 0.9 wt. %, or 0.4 wt. % to 0.7 wt. %.

[0069] However, it is desired that the titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm are the sole pigments present in the clear coat. In other words, no further pigments may be present in the clear coat.

[0070] It is desired that the clear coat is a transparent coating. In order to determine the transparency of a coating, the respective coating composition may be applied in a wedge shape onto a black and white chart and dried or hardened. Black and white charts are typically used when determining black / white opacity of coating compositions. If the underlying black / white chart is visible in the desired coating thickness, the coating is transparent. The black / white opacity can be determined by a user e.g. with the eyes.

[0071] The multi-layer coating can further comprise an electrodeposited coating layer applied over at least a portion of the substrate, wherein the electrodeposited coating layer is positioned between the basecoat layer and the substrate.

[0072] The multi-layer coating can further comprise a primer or a second basecoat layer applied over at least a portion of the substrate, wherein the primer or a second basecoat layer is positioned between the basecoat layer (b) and the substrate, or the primer or a second basecoat layer is positioned between the basecoat layer (b) and the electrodeposited coating layer.

[0073] The substrate can be any suitable substrate. The respective coating composition (or laminate) can be applied to a wide range of substrates, known in the coatings industry. For example, the substrate, specifically a part of the surface of the substrate, can comprise at least one material selected from metals, plastics, ceramics, such as boron carbide or silicon carbide, glass, wood, paper, cardboard, rubber, leather, textiles, fiberglass composite, carbon fiber composite, an existing coating, or mixtures thereof.

[0074] Metals may include, but are not limited to, ferrous metals, tin steel, aluminum, aluminum alloys, zinc-aluminum alloys, titanium, titanium alloys, magnesium, magnesium alloys, copper, copper alloys and mixtures. The ferrous metal may include iron, steel, and alloys thereof. Non-limiting examples of useful steel materials may include rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, pickled steel, zinc-iron alloy, and combinations thereof. Combinations or composited of ferrous and non-ferrous metals can also be used. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX or 8XXX series as well as clad aluminum alloys and cast aluminum alloys of the A356, 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X or 8XX.X series also may be used as the substrate. Magnesium alloys of the AZ31 B, AZ91C, AM60B or EV31 A series also may be used as the substrate. The substrate may be pretreated with pretreatment solution including a zinc phosphate pretreatment solution such as, e.g., those described in US 4,793,897 and US 5,588,989, or a zirconium containing pretreatment solution such as, e.g., those described in US 7,749,368 and US 8,673,091 .

[0075] The substrate can be vehicles, storage tanks, windmills, packaging substrates, wood flooring and furniture, apparel, electronics, glass and transparencies, sports equipment, buildings, bridges, and the like. According to the present disclosure, the substrate of the present disclosure can be a vehicle part.

[0076] The term “vehicle” is used in its broadest sense and includes (without limitation) all types of aircraft, spacecraft, watercraft, and ground vehicles. For example, a vehicle can include, aircraft such as airplanes including private aircraft, and small, medium, or large commercial passenger, freight, and military aircraft; helicopters, including private, commercial, and military helicopters; aerospace vehicles including, rockets and other spacecrafts. Vehicles can include ground vehicles such as, for example, trailers, cars, trucks, buses, coaches, vans, ambulances, fire engines, motorhomes, caravans, go-karts, buggies, fork-lift trucks, sit-on lawnmowers, agricultural vehicles such as, for example, tractors and harvesters, construction vehicles such as, for example, diggers, bulldozers and cranes, golf carts, motorcycles, bicycles, trains, and railroad cars. Vehicles can also include watercraft such as, for example, ships, submarines, boats, jet-skis and hovercraft.

[0077] Parts of vehicles may include vehicular body parts (e.g. , without limitation, doors, body panels, trunk deck lids, roof panels, hoods, roofs and / or stringers, rivets, wheels, landing gear components, and / or skins used on an aircraft), hulls, marine superstructures, vehicular frames, chassis, and vehicular parts not normally visible in use, such as engine parts, motorcycle fairings and fuel tanks, fuel tank surfaces and other vehicular surfaces exposed to or potentially exposed to fuels, aerospace solvents and aerospace hydraulic fluids. Any vehicular parts which may benefit from coating as defined herein may undergo coating, whether exposed to or hidden from view in normal use.

[0078] The multi-layer coating according to the present disclosure can have a color travel AC* of at least 2, such as at least 5, at least 8, at least 10, at least 20, or at least 30. The color travel can be calculated according to the following formulaColor travelThe color travel AC* can be measured with a multiangle spectrophotometer BYK- mac I (manufactured by BYK), particularly following DIN EN ISO 1 1664 (2020-03) standards (1 -4).

[0079] The multi-layer coating according to the present disclosure can have a Ab* between the angles 750and 150of 4.5 to 50, such as 5 to 40, 6 to 40, or10 to 35. The Ab* can be measured with a multiangle spectrophotometer BYK-mac i (manufactured by BYK), particularly following DIN EN ISO 1 1664 (2020-03) standards (1 -4). The color shift Ab* can be calculated as followsAb* = £?I5O — by5.

[0080] The multi-layer coating according to the present disclosure can have a Aa* between the angles 750and 150of 0.5 to 15, such as 0.8 to 10, 1 to 8, or 1 .5 to 5. The Aa* can be measured with a multiangle spectrophotometer BYK-mac I (manufactured by BYK), particularly following DIN EN ISO 1 1664 (2020-03) standards (1 -4). The color shift Aa* can be calculated as follows

[0081] A method for preparing a multi-layer coating, particularly a multi-layer coating according to the disclosure, is provided comprising in the following order: (A) forming a basecoat layer over at least a portion of a substrate by depositing a basecoat composition over at least a portion of the substrate, wherein the basecoat composition comprises a goniochromatic pigment, (B) optionally drying and / or curing the basecoat layer, (C) forming a clear coat layer over at least a portion of the basecoat layer by depositing a clear coat composition over at least a portion of the substrate, wherein the clear coat composition comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition, and (D) drying and / or curing the clear coat layer or both the basecoat and clear coat layers, wherein the dry thickness of the clear coat layer is in the range of 15 to 80 pm and the dry thickness of the basecoat layer in the range of 5 to 35 pm.

[0082] The basecoat composition generally further comprises a film-forming resin, and a crosslinking agent suitable for crosslinking the film-forming resin. Thus, thebasecoat composition can comprise a film-forming resin, a crosslinking agent suitable for crosslinking the film-forming resin, and a goniochromatic pigment.

[0083] The clear coat composition generally comprises a film-forming resin, a crosslinking agent suitable for crosslinking the film-forming resin, and 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition.

[0084] The coating compositions can be applied to at least a part of a surface of a substrate by any means standard in the art, such as by electrocoating, spraying, electrostatic spraying, dipping, rolling, brushing, and the like.

[0085] As used herein, the term “film-forming resin” refers to resins that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers present in the composition or upon curing at ambient conditions, e.g., at a temperature in the range of 20 to 25 °C, or at elevated temperatures, e.g., at a temperature in the range of 40 to 200 °C. The terms “resin” and “resinous” and the like are used interchangeably with the terms “polymer” and “polymeric” and the like. Further, the term "polymer" is used herein in its common meaning in the art, referring to macromolecular compounds, i.e., compounds having a relatively high molecular weight (e.g., 500 Da or more), the structure of which comprises multiple repetition units (also referred to as “mers”) derived, actually or conceptually, from chemical species of relatively lower molecular mass. Unless indicated otherwise, molecular weights are on a weight average basis (“Mw”) and are determined by gel permeation chromatography using polystyrene standards.

[0086] By ambient conditions is meant that the composition is cured without the aid of heat, for example, without baking in an oven, use of forced air, or the like.

[0087] Examples of film-forming resins comprise acrylic resins, vinylic resins, polyester resins, polysiloxane resins, epoxy resins, polyurethane resins, polyamide resins, copolymers thereof, and mixtures thereof.

[0088] The acrylic resins may be homopolymers or copolymers, which can be obtained by polymerizing one or more monomers comprising substituted or unsubstituted (meth)acrylic acids and (meth)acrylates. Herein, the terms“(meth)acrylic acid” and “(meth)acrylate” and similar terms refer both to the acrylic acid or acrylate and the corresponding methacrylic acid or methacrylate, respectively. Suitable (meth)acrylates can include, but are not limited to, alkyl (meth)acrylates, cycloalkyl (meth)acrylates, alkylcycloalkyl (meth)acrylates, aralkyl (meth)acrylates, alkylaryl (meth)acrylates, aryl (meth)acrylates and functional groups-containing (meth)acrylates. As used herein, the term “functional group” refers to a group that includes one or a plurality of atoms other than hydrogen and sp3carbon atoms. Examples of functional groups include, but are not limited to, hydroxyl, carboxylic acid, amido, isocyanate, urethane, thiol, amino, sulfone, sulfoxide, phosphine, phosphite, phosphate, halide, and the like. Non-limiting examples of acrylic resins may include acrylic resins derived from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, iso-butyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, iso-octyl (meth)acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 3,3,5-trimethyl-cyclohexyl (meth)acrylate, 3-methylphenyl (meth)acrylate, 1 -naphtyl (meth)acrylate, 3-phenyl-n-propyl (meth)acrylate, 2-phenyl-aminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate or combinations thereof. According to the present disclosure, the acrylic resins may have a hydroxyl value in a range of 20 to 400, such as of 30 to 350, or of 40 to 300, or of 50 to 250. The hydroxyl value may be determined according to DIN EN ISO 4629-1 :2016. Suitable acrylic resins include, but are not limited to acrylic resins under the trademark SETALUX®, such as SETALUX® 1776 VS-65, SETALUX® 1774 SS-70, SETALUX® 1797 SS-70, SETALUX® 1762 W-70, SETALUX® 1760 VB-64, SETALUX® 1795 VX-74, SETALUX® D A 870 BA, commercially available from Allnex Germany GmbH (Germany) and acrylic resins under the trademark VIACRYL®, such as VIACRYL SC 370 / 75SNA, commercially available from Allnex Germany GmbH (Germany).

[0089] Vinylic resins may be homopolymers or copolymers, which can be obtained by polymerizing one or more monomers comprising vinyl aromatic compounds, such as styrene and vinyl toluene; nitriles, such as (meth)acrylonitrile; vinyl andvinylidene halides, such as vinyl chloride and vinylidene fluoride; and vinyl esters, such as vinyl acetate. Suitable vinylic resins can be exemplified by vinylic resins under the trademark LUMIFLON™ available from AGC Chemicals Europe, Ltd. (Netherlands).

[0090] Polyester resins may be prepared in a known manner, e.g., by condensation of a polyol and a polyacid or by ring-opening polymerization of lactones. As used herein, the term “polyol” refers to a compound having more than one hydroxyl group per molecule, e.g., 2, 3, 4, 5, 6 or more hydroxyl groups per molecule, and the term “polyacid” refers to a compound having more than one carboxylic acid group per molecule, e.g., 2, 3, 4, 5, 6 or more carboxylic acid groups per molecule, and includes anhydrides of the corresponding acid. Suitable polyols include, but are not limited to, alkylene glycols, such as ethylene glycol, propylene glycol, butylene glycol, 1 ,6-hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight in the range of 200 to 10.000 g / mol, polypropylene glycol having a molecular weight in the range of 200 to 10.000 g / mol, polybutylene glycol having a molecular weight in the range of 300 to 10.000 g / mol and neopentyl glycol; bisphenol A; hydrogenated bisphenol A; bisphenol F; hydrogenated bisphenol F; cyclohexandiol; propanediols such as 1 ,2-propanediol,1.3-propanediol, butyl ethyl propanediol, 2-methyl-1 ,3-propanediol and 2-ethyl-2- butyl-1 ,3-propanediol; butanediols such as 1 ,4-butanediol, 1 ,3-butanediol,2.3-butanediols, 1 ,2-butanediols, 3-methyl-1 ,2-butanediol and 2-ethyl- 1 ,4- butanediol; pentanediols such as 1 ,2-pentanediol, 1 ,5-pentanediol,1 .4-pentanediol, 3-methyl-4,5-pentanediol and 2,2,4-trimethyl-1 ,3-pentanediol; hexandiols such as 1 ,6-hexanediol, 1 ,5-hexanediol, 1 ,4-hexanediol and2.5-hexanediol; poly(caprolactone)diols having a molecular weight in the range of 400 to 10.000 g / mol; polyether glycols, such as poly(oxytetramethylene) glycol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; dimethylolcyclohexane and glycerol. Suitable polyacids may include, but are to limited to, maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid,hexahydrophthalic acid; methyl hexahydrophthalic acid; dimethyl terephthalic acid; cyclohexane dicarboxylic acid, 1 ,3-cyclohexane dicarboxylic acid; 1 ,4- cyclohexane dicarboxylic acid; tricyclodecanepolycarboxylic acid, endomethylenetetrahydrophthalic acid; endoethylenehexahydrophthalic acid; cyclohexane tertracarboxylic acid; cyclobutanetetracarboxylic acid and anhydrides of all the aforementioned polyacids. Suitable lactones may include, but are not limited to, p-propiolactone; y-butyrolactone; 5-valerolactone; e-caprolactone; a-angelica lactone; and mixtures thereof. Suitable polyester resins include, but are not limited to polyester resins under the trademark SETAL®, such as SETAL® 1715 VX-74, SETAL® 91703 SS-53, and SETAL® 91715 SS-55 commercially available from Allnex Germany GmbH (Germany).

[0091] Polysiloxane resins may include, but are not limited to, alkyl substituted polysiloxanes, aryl polysiloxanes, copolymers, blends and mixtures thereof. The alkyl substitution may be selected from short chain alkyl groups of 1 to 4 carbon atoms, such as methyl or propyl. The aryl substitution may comprise phenyl groups. Suitable polysiloxane resins include, but are not limited to, Silres® 601 or Silres® M 50 E, both commercially available from Wacker Chemie AG (Germany), and DOWSIL™ RSN-6018, commercially available from Dow Chemical Company (USA).

[0092] Epoxy resins may be prepared in a known manner, e.g., by reacting a compound comprising at least one epoxide functionality and a cyclic co-reactant comprising at least two hydroxyl groups. Examples of suitable compounds comprising one epoxide functionality include, but are not limited to, glycidol; epichlorohydrin; glycidol amines and mixtures thereof. As used herein, the terms “epoxy” and “epoxide” are used interchangeably. Examples of suitable cyclic co-reactants comprising at least two hydroxy groups include, but are not limited to, bisphenol A; hydrated bisphenol A; bisphenol F; hydrated bisphenol F; novolac resins such as phenolic novolac, cresol novolac; and mixtures thereof. Suitable epoxy resins include, but are not limited to, Eponex 1510, Eponex 1513, Epikote Resin 862 and Epikote Resin 828 commercially available from Hexion (USA); Epodil 757 commercially available from Evonik Corporation (Germany); Araldite GY 2600, Araldite GY 281 and Araldite EPN 1138 commercially available from Huntsman (USA).

[0093] Polyurethane resins can be prepared in a known manner, e.g., by reacting a polyisocyanate and a polyol. As used herein, the term “polyisocyanate” refers to a compound having more than one isocyanate group per molecule, e.g., 2, 3, 4, 5, 6, or more isocyanate groups per molecule. Suitable polyisocyanates include aliphatic polyisocyanates, such as 2,2,4-trimethyl hexamethylene diisocyanate,2,4,4-trimethyl hexamethylene diisocyanate, 1 ,6-hexamethylene diisocyanate; cycloaliphatic polyisocyanates, such as isophorone diisocyanate and 4,4’- methylene-bis(cyclohexyl isocyanate); aromatic polyisocyanates such as 4,4’- diphenylmethane diisocyanate, toluene diisocyanate, 1 ,2,4-benzene triisocyanate, tetramethyl xylylene diisocyanate and polymethylene polyphenyl isocyanate. Nonlimiting examples of suitable polyols may be the polyols described above for producing the polyester resins. Suitable polyurethane resins include, but are not limited to the reaction product of Desmodur N 3300 (commercially available from Covestro (Germany)) with an alkylene glycol, such as ethylene glycol or propylene glycol.

[0094] Suitable polyamide resins may be prepared in a known manner, e.g., by polymerizing a polyamine and a polyacid or by ring-opening polymerization of lactams. Herein, the term “polyamine” refers to a compound having more than one amine group per molecule, e.g., 2, 3, 4, 5, 6, or more amine groups per molecule. Suitable polyamines include, but are not limited to, aliphatic diamines such as1.2-ethanediamine, 1 ,2-propanediamine, 1 ,3-propanediamine, 1 ,2-butanediamine,1.3-butanediamine, 1 ,4-butanediamine, 1 ,3-pentanediamine, 1 ,5-pentanediamine,1 .6-hexanediamine, 2-methyl-1 ,5-pentanediamine, 2,5-dimethylhexane-2,5- diamine, 2,2 ,4-trimethyl- 1 ,6-hexanediamine, 2,4 ,4-trimethyl- 1 ,6-hexanediamine,1.7-heptanediamine, 1 ,8-octanediamine, 1 ,9-nonanediamine and1 ,10-decanediamine; cycloaliphatic diamines such as 2,4'-diamino dicyclohexylmethane, 4,4'-diamino dicyclohexylmethane, 3,3’-di methy l-4,4'- diamino dicyclohexylmethane and 3,3'-diethyl-4,4'-diaminodicyclohexylmethane; and aromatic diamines such as 1 ,2-benzenediamine, 1 ,3-benzenediamine,1 .4-benzenediamine, 1 ,5-naphthalenediamine, 1 ,8-naphthalenediamine,2.4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, and 3,3'-dimethyl- 4,4'-biphenyldiamine. Non-limiting examples of suitable polyacids may include those listed above for preparing polyesters. Suitable lactams may include, but arenot limited to, p-propiolactam; y-butyrolactam; 8-valerolactam; e-caprolactam; and mixture thereof. Suitable polyamide resins include, but are not limited to polyamide resins under the trademark Flex-Rez™, such as Flex-Rez™ 0080CS, Flex-Rez™ 1060CS, Flex-Rez™ 1074 CS A, commercially available from Lawter (USA).

[0095] In particular, the film forming resin may comprise acrylic polyols, acrylic polyesters, or a combination thereof.

[0096] The film-forming resin may be present in an amount of at least 25 wt. %, such as at least 30 wt. %, such as at least 40 wt. %, such as at least 50 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition). The film-forming resin may be present in an amount of no more than 95 wt. %, such as no more than 90 wt. %, such as no more than 85 wt. %, such as no more than 80 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition). Ranges of film-forming resins may include, for example, from 25 to 95 wt. %, such as from 25 to 90 wt. %, such as from 25 to 85 wt. %, such as from 25 to 80 wt. %, such as from 30 to 95 wt. %, such as 30 to 90 wt. %, such as 30 to 85 wt. %, such as 30 to 80 wt. %, such as 40 to 95 wt. %, such as 40 to 90 wt. %,such as 40 to 85 wt. %, such as 40 to 80 wt. %, such as 50 to 95 wt. %, such as 50 to 90 wt. %, such as 50 to 85 wt. %, such as 50 to 80 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition). The film-forming resin may be present in the coating composition in the range between any of the above-mentioned values such as from 25 to 95 wt. %, such as from 30 to 90 wt. %, such as from 35 to 85 wt. %, such as from 40 to 80 wt. %, such as from 50 to 80 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition).

[0097] The coating composition disclosed herein may further comprise a crosslinking agent suitable for crosslinking the film-forming resin. As used herein, the term “crosslinking” refers to the formation of covalent bonds between polymer chains of the constituent polymer molecules. The terms "crosslinking agent", "curing agent" and "crosslinker" are herein used interchangeably. Curing or crosslinking reactions may be induced, for example, by exposing the coatingcomposition to heat or radiation, but may also be carried out at ambient conditions to form a cured coating. The crosslinking agent may comprise at least one of a polyepoxide, a polyisocyanate and an amino resin. The crosslinking agent may comprise an amino resin. The crosslinking agent may often comprise a melamine resin.

[0098] Suitable polyepoxides may include, but are not limited to, low molecular weight polyepoxides, e.g., polyepoxides having a molecular weight in the range of from 200 to 500 g / mol, as well as higher molecular weight polyepoxides, e.g., polyepoxides having a molecular weight in the range of from 500 to 10.000 g / mol. Suitable low molecular weight polyepoxides include, but are not limited to, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate and bis(3,4-epoxy- 6-methylcyclohexyl-methyl) adipate, bisphenol A diglycidyl ether, bisphenol E diglycidyl ether and bisphenol F diglycidyl ether. Suitable higher molecular weight polyepoxides may include, but are not limited to, polyglycidyl ethers of cyclic polyols, for example, polyglycidyl ethers of polyhydric phenols such as bisphenol A, bisphenol F, resorcinol, hydroquinone, benzenedimethanol, phloroglucinol, and catechol; or polyglycidyl ethers of polyhydric alcohols such as aliphatic polyols, particularly cycloaliphatic polyols such as 1 ,2-cyclohexane diol, 1 ,4-cyclohexane diol, 2,2- bis(4-hydroxycyclohexyl)propane, 1 ,1-bis(4-hydroxycyclohexyl)ethane, 2-methyl-1 ,1-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-hydroxy-3- tertiarybutylcyclohexyl)propane, 1 ,3-bis(hydroxymethyl)cyclohexane and 1 ,2-bis(hydroxymethyl)cyclohexane. Examples of aliphatic polyols may include, but are not limited to inter alia, trimethylpentanediol and neopentyl glycol. Suitable polyepoxides include, but are not limited to EPONEX™ 1510, Epon® 828, EPIKOTE™ Resin 828, commercially available from Hexion Inc. (USA).

[0099] Suitable polyisocyanates can be aliphatic, aromatic, or a mixture thereof. As used herein, the term "polyisocyanate" is intended to include blocked polyisocyanates as well as unblocked polyisocyanates. As used herein, the term “blocked polyisocyanate” refers to adducts derived from the equilibrium reaction of an isocyanate with a blocking agent, whereby the adduct is thermally instable and dissociates (unblocks) at elevated temperatures, such as temperatures above 120 °C. The term “unblocked isocyanate” refers to a polyisocyanate without blocking agents. The polyisocyanate may be prepared from a variety ofisocyanate-containing materials. Examples of suitable polyisocyanates include trimers prepared from, but not limited to, toluene diisocyanate, 4,4'-methylene- bis(cyclohexyl isocyanate), isophorone diisocyanate, an isomeric mixture of 2,2,4- and 2,4,4-trimethyl hexamethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, tetramethyl xylylene diisocyanate and 4,4'- diphenylmethylene diisocyanate. Isocyanate groups of the polyisocyanates may be blocked or unblocked as desired. Examples of suitable blocking agents include those materials which would unblock at elevated temperatures, e.g., at temperatures above 120 °C, such as lower aliphatic alcohols having 1 to 6 carbon atoms including methanol, ethanol, and n-butanol; cycloaliphatic alcohols such as cyclohexanol; aromatic alkyl alcohols such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds such as phenol itself and substituted phenols wherein the substituents do not affect coating operations, such as cresol and nitrophenol. Glycol ethers may also be used as blocking agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether. Other suitable blocking agents include oximes such as methyl ethyl ketoxime, acetone oxime and cyclohexanone oxime, lactams such as epsilon-caprolactam, pyrazoles such as dimethyl pyrazole, and amines such as dibutyl amine. Suitable polyisocyanates include, but are not limited to Desmodur ultra grade polyisocyanates, such Desmodur ultra DN, Desmodur ultra N 3300, Desmodur ultra IL EA and Desmodur Ultra N 3300 BA / SN commercially available from Covestro (Germany).

[0100] Suitable amino resins can be obtained from the condensation reaction of an aldehyde, such as formaldehyde, with a compound comprising at least two amine or amide groups per molecule. Suitable examples of aldehydes include, but are not limited to, formaldehyde, acetaldehyde, crotonaldehyde and benzaldehyde. Suitable examples of compounds comprising at least two amine or amide groups include, but are not limited to, melamine, urea and benzoguanamine. Suitably, the amino resins may be etherified, typically, with an alcohol, such as methanol, ethanol, butanol or mixtures thereof. Suitable amino resins include, but are not limited to Maprenal® Amino Resin, such as Maprenal MF 612 / 70B, Maprenal MF 613 / 71 B and Maprenal MF 650 / 55IB commercially available from Prefere Resin Holding GmbH (Germany), Cymel® AminoCrosslinkers, such as Cymel 303, Cymel 202, Cymel 1 161 , Cymel 325 and Cymel 1133 commercially available from Allnex Industries (Germany); Setamine® aminoresins, such as Setamine US-138 BB-70, and Setamine US-146 BB-72 commercially available from Allnex (Germany).

[0101] The crosslinking agent may be present in an amount of at least 5 wt. %, such as at least 10 wt. %, such as at least 15 wt. %, such as at least 20 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition). The crosslinking agent may be present in an amount of no more than 75 wt. %, such as no more than 70 wt. %, such as no more than 60 wt. %, such as no more than 50 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition). Ranges of crosslinking agent may include, for example, from 5 to 75 wt. %, such as from 5 to 70 wt. %, such as from 5 to60 wt. %, such as from 5 to 50 wt. %, such as from 10 to 75 wt. %, such as 10 to 70 wt. %, such as 10 to 60 wt. %, such as 10 to 50 wt. %, such as 15 to 75 wt. %, such as 15 to 70 wt. %,such as 15 to 60 wt. %, such as 15 to 50 wt. %, such as 20 to 75 wt. %, such as 20 to 70 wt. %, such as 20 to 60 wt. %, such as 20 to 50 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition). The crosslinking agent may be present in the coating composition in range between any of the above- mentioned values such as from 5 to 75 wt. %, such as from 10 to 70 wt. %, such as from 15 to 60 wt. %, such as from 20 to 50 wt. %, based on the total weight of solids in the respective coating composition (i.e. basecoat composition or clear coat composition).

[0102] The respective coating composition (i.e. basecoat composition or clear coat composition) may further comprise a solvent or a mixture of solvents. Suitable solvents include water, organic solvents and a mixture thereof. The organic solvent may comprise any suitable organic solvents known in the art. Non-limiting examples of suitable organic solvents may include, but are not limited to, alcohols, glycol ethers, esters, ether esters and ketones, aliphatic and / or aromatic hydrocarbons, such as, for example, methanol, ethanol, isopropanol, n-butanol, 2- butanol, tridecyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, 3-butoxy-2- propanol, ethyl 3-ethoxypropionate, butyl glycol, butyl glycol acetate, butanol,dipropylene glycol methyl ether, diethylene glycol monobutyl ether, butyl glycolate, hexane, heptane, octane, toluene, xylene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, 2-butoxyethyl acetate, amyl acetate, isoamyl acetate, diethylene glycol butyl ether acetate, acetone, xylene, toluene and the like. The solvent may be present in the coating composition in an amount of 5-70 wt. %, such as 10-65 wt. %, such as 15-60 wt. %, such as 20-55 wt. %, such as 30-50 wt. %, based on the total weight of the respective coating composition (i.e. basecoat composition or clear coat composition).

[0103] The respective coating composition (i.e. basecoat composition or clear coat composition) may be a water-borne coating composition or a solvent-borne coating composition.

[0104] The respective coating composition (i.e. basecoat composition or clear coat composition) may be a solvent-borne coating composition. As used herein, the term “solvent-borne coating composition” refers to a coating composition comprising a solvent mixture comprising an organic solvent and less than50 wt. % of water, such as less than 40 wt. % of water, such as less than 30 wt. % of water, such as less than 20 wt. % of water, such as less than 10 wt. % of water, such as less than 5 wt. % of water, such as less than 2 wt. % of water, such as less than 1 wt. % of water, based on the total weight of the solvent mixture. The solvent-borne coating composition may be free of water, i.e., the solvent-borne coating composition may comprise less than 0.5 wt. % of water, such as less than 0.2 wt. % of water, such as less than 0.1 wt. % of water, based on the total weight of the solvent mixture. The solvent-borne coating composition may be completely free of water, i.e., the solvent-borne coating composition may comprise 0 wt. % of water based on the total weight of the solvent mixture.

[0105] Moreover, the respective coating composition (i.e. basecoat composition or clear coat composition) may be a water-borne coating composition. The term “water-borne coating composition” refers to a coating composition comprising a solvent mixture comprising water and less than 50 wt. % of an organic solvent, such as less than 40 wt. % of an organic solvent, such as less than 30 wt. % of an organic solvent, such as less than 20 wt. % of an organic solvent, such as less than 10 wt. % of an organic solvent, such as less than 5 wt. % of an organic solvent, such as less than 2 wt. % of an organic solvent, such as less than 1 wt. %of an organic solvent, based on the total weight of the solvent mixture. The waterborne coating composition may be free of an organic solvent, i.e. , the water-borne coating composition may comprise less than 0.5 wt. % of an organic solvent, such as less than 0.2 wt. % of an organic solvent, such as less than 0.1 wt. % of an organic solvent. The water-borne coating composition may be completely free of water, i.e., the water-borne coating composition may comprise 0 wt. % of an organic solvent, based on the total weight of the solvent mixture.

[0106] The respective coating composition (i.e. basecoat composition or clear coat composition) may further comprise at least one additional ingredient selected from colorants such as pigments, dyes and tints; plasticizers; anti-oxidants; hindered amine light stabilizers; UV light absorbers and stabilizers; surfactants; flow control agents; fillers; reactive diluents; catalysts; grind vehicles, such as an acrylic grind vehicle; defoamers; dispersants; adhesion promoters; antistatic agents; and mixtures thereof. When used, the coating composition may comprise a total of from 0.1 to 45 wt. % of these additional ingredients, such as from 1 to 40 wt. %, such as from 1 .5 to 35 wt. %, based on the total solids weight of the respective coating composition (i.e. basecoat composition or clear coat composition).

[0107] Suitable dyes include, but are not limited to, acid dyes, azoic dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example, bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenyl methane.

[0108] Suitable plasticizers include, but are not limited to, phthalate esters, such as dibutylphthalate, butyl benzyl phthalate, diisooctyl phthalate and decyl butyl phthalate; chlorinated paraffins; and hydrogenated terphenyls.

[0109] Suitable examples of anti-oxidants to, e.g., prevent oxidation of resins from heat exposure that extends from production and application or to prevent yellowing of the coating, include, but are not limited to, phenolic anti-oxidants, phosphite anti-oxidants and the like. Suitable anti-oxidants include, but are not limited to Irganox® antioxidants, such as Irganox 245, Irganox 1010, and Irganox 1076 commercially available from BASF SE (Germany).

[0110] As used herein, a “hindered amine light stabilizer” (“HALS”) refers to compounds comprising an amine functional group and which are added to polymeric materials to inhibit or retard their degradation by, e.g., photo-oxidation. Typically, derivatives of tertramethylpiperidine are used. Examples of suitable hindered amine light stabilizers (HALS) include, but are not limited to, Tinuvin® light stabilizers, such as TINUVIN® 292, TINUVIN® 123, TINUVIN® 328, TINUVIN® 622, TINUVIN® 783, and TINUVIN® 770 available from BASF (Germany). As used herein, “UV light absorbers and stabilizers” refer to compounds used to absorb UV radiation to reduce the UV degradation of a polymeric material. Examples of suitable UV light absorbers and stabilizers include, but are not limited to, CYASORB light stabilizers, such as CYASORB UV- 1164L available from Solvay (Germany) and TINUVIN® 1 130 available from BASF (Germany).

[0111] Surfactants may be added to the respective coating composition (i.e. basecoat composition or clear coat composition) in order to aid, e.g., in flow and wetting of the substrate. Suitable surfactants include, but are not limited to alkyl sulphates (e.g., sodium lauryl sulphate); ether sulphates; phosphate esters; sulphonates; and their various alkali, ammonium, and amine salts; aliphatic alcohol ethoxylates; alkyl phenol ethoxylates (e.g., nonyl phenol polyether); salts and / or combinations thereof.

[0112] As used herein, the term “flow control agent” refers to a compound, which controls the rheological behavior of the coating composition during application, drying and / or curing, including controlling viscosity, thixotropic properties under shear stress and leveling when applied to a surface of a substrate. The flow control agent may comprise sag control agents. As used herein, the term “sag control agent” refers to a compound which minimizes sagging, i.e., defects such as tear drops caused by gravity-driven flow of wet coating compositions when applied to a substrate, in particular a substrate comprising a non-horizontal, e.g., a vertical surface. Suitable flow control agents, especially sag control agents may include, but are not limited to those compounds described in US 4,31 1 ,622 A, EP 0 192 304 A1 and EP 3 728 482 A1 .

[0113] As used herein, a “reactive diluent” refers to a monomer or oligomer which reduces the viscosity of the respective coating composition (i.e. basecoatcomposition or clear coat composition) and can be co-polymerized during curing of the respective coating composition. A suitable reactive diluent may have a molecular weight in the range of 100 to 350 g / mol. Suitable examples of reactive diluents include, but are not limited to, epoxy functional compounds, vinyl functional compounds, (meth)acrylate compounds, and combinations thereof.

[0114] The respective coating composition (i.e. basecoat composition or clear coat composition) may contain a catalyst to facilitate any desired curing reaction. Any curing catalyst typically used to catalyze crosslinking reactions may be used, and there are no particular limitations on the catalyst. Non-limiting examples of catalysts include phenyl acid phosphate, sulfonic acid functional catalysts such as dodecylbenzene sulfonic acid (DDBSA), dinonyl naphthalene sulfonic acid, dinonyl naphthalene disulfonic acid, complexes of organometallic compounds including tin, zinc or bismuth, such as stannous octoate, butyl stannoic acid, dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin mercaptide, dibutyltin diacetate, dibutyltin dimaleate, dimethyltin diacetate, dimethyltin dilaurate, 1 ,4- diazabicyclo[2.2.2]octane and bismuth carboxylates, and the like.

[0115] Alternatively, the respective coating composition (i.e. basecoat composition or clear coat composition) may be essentially free of a catalyst. As used throughout this specification, including the claims, by “essentially free” is meant that a compound is not intentionally present in the respective coating composition; and if a compound is present in the respective coating composition, it is present incidentally in an amount less than 0.1 wt. %, usually less than trace amounts, i.e., in an amount less than 100 ppm, based on the total weight of the respective coating composition (i.e. basecoat composition or clear coat composition).

[0116] As used herein, the term “adhesion promoter” refers to any material that, when included in the coating composition, enhances the adhesion of the respective coating composition to a substrate in comparison to suitable examples of an adhesion promoter include, but are not limited to, a free acid, a phosphatized epoxy resin or an alkoxysilane. As used herein, the term "free acid" is meant to encompass organic and / or inorganic acids that are included as a separate component of the compositions as opposed to any acids that may be used to form a polymer that may be present in the respective composition. The free acid may comprise tannic acid, gallic acid, phosphoric acid, phosphorousacid, citric acid, malonic acid, a derivative thereof, or a mixture thereof. Suitable derivatives include esters, amides, and / or metal complexes of such acids.

[0117] The respective coating composition (i.e. basecoat composition or clear coat composition) may be a one-component (1 K) coating composition or a two-part (2K) coating composition. Suitably, the respective coating composition (i.e. basecoat composition or clear coat composition) may be a two-component (2K) coating composition. As used herein, a “one-component” or “1 K” coating composition is a composition in which all the ingredients may be premixed and stored in one container and wherein the reactive components do not readily react at ambient temperatures, e.g., temperatures in the range of from 20 to 25 °C, or slightly elevated temperatures, e.g., temperatures in the range of 25 ° to 60 °C, but instead only react upon activation by an external energy source. External light source that may be used to promote the curing reaction include, for example, radiation (i.e., actinic radiation) and / or heat. As used herein, a “two-component” or “2K” coating composition is a composition in which at least a portion of the reactive components readily react and at least partially cure without activation from an external energy source, such as at ambient temperatures, e.g., temperatures in the range of from 20 to 25 °C, or slightly elevated temperatures, e.g., temperatures in the range of 250to 60 °C, when mixed. One of skill in the art understands that the two components of the coating composition are stored separately from each other and mixed just prior to application of the coating composition.

[0118] The terms “cure”, “cured” or similar terms, as used in connection with the coating compositions described herein, means that at least a portion of the components that form the coating composition is crosslinked to form a coating. Cure, or the degree of cure, can also be determined by dynamic mechanical thermal analysis (DMTA) using a Polymer Laboratories MK III DMTA analyzer conducted under nitrogen in which the degree of cure can for example be at least 10%, such as at least 30%, such as at least 50%, such as at least 70%, or at least 90% of complete crosslinking as determined by DMTA.

[0119] The basecoat composition and the clear coat composition can be applied to the substrate and cured together. It is beneficial to dry the basecoat before applying the clear coat composition.

[0120] Thus, the drying in steps (A) and / or (B) can be carried out at a temperature in the range of 30 to 80 °C, and / or the curing in steps (A) and / or (B) are carried out at a temperature in the range of 80 to 140 °C.

[0121] The method may further comprises forming an electrodeposited coating layer over at least a portion of a substrate by depositing an electrodeposited coating composition over at least a portion of the substrate, wherein the electrodeposited coating layer is positioned between the basecoat layer and the substrate.

[0122] The method may further comprises forming a primer or a second basecoat over at least a portion of a substrate by depositing a primer composition or a second basecoat composition over at least a portion of the substrate, wherein the primer or a second basecoat layer (e) is positioned between the basecoat layer (b) and the substrate (a), or the primer or a second basecoat (e) is positioned between the basecoat layer (b) and the electrodeposited coating (d).

[0123] The clear coat composition comprising the titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm can be used to provide a multi-layer coating composition which reveal a new milky white effect and a huge color travel compared to a standard clear coat without said titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm.

[0124] Accordingly, the use of a clear coat coating composition comprising 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition, is provided to form a clear coat layer over a basecoat layer, wherein the basecoat layer has a flop index of at least 1 .

[0125] The aforementioned basecoat composition and clear coat composition can also be provided as a kit suitable to form a multi-layer coating over a substrate.

[0126] Furthermore, the multi-layer coating can be provided by applying a laminate onto a substrate. Accordingly, a protective film, particularly a removable protective film, can be coated with a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the drythickness of the clear coat layer is in the range of 15 to 80 pm and then optionally coated with a basecoat layer. The laminate can then be applied onto a substrate such as a surface particularly a surface of a car. The surface can be a coated surface that comprises a basecoat layer and a clear coat layer, wherein said basecoat layer has a dry thickness in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment. In other words, the laminate can be used on an already coated surface or already coated car. It is also possible that the basecoat layer of the laminate already has a dry thickness in the range of 5 to 35 pm and comprises a goniochromatic pigment.

[0127] The definitions, such as the definitions of the basecoat layer(s) and / or clear coat, mentioned for the multi-layer coating also applies for the laminate. For instance, the definitions of the titanium dioxide mentioned above also apply for the clear coat of the laminate. Thus, the basecoat layer can be a basecoat layer as described for the present disclosure. Thus, the clear coat layer can be a clear coat layer as described for the present disclosure.

[0128] The laminate can be applied onto a substrate, such as a coated substrate, a multilayer coated substrate or substrate without a coating (for instance a surface of a vehicle). The laminate can be applied onto a substrate by using an adhesive. Otherwise, an adhesive layer can be present. Particularly the adhesive layer is present between the substrate and the basecoat layer. Particularly the adhesive layer is present between a liner and the basecoat layer. Particularly the adhesive layer is present between the second protective film and the basecoat layer. It is also possible that the basecoat layer comprises an adhesive.

[0129] A liner can be applied over at least a portion of the adhesive layer. Generally, a laminate is applied by removing a liner (such as a removable liner) so that the remaining basecoat layer and clear coat layer is applied to the surface to be laminated (i.e. a substrate). It is desired that basecoat layer is applied to the surface to be coated, particularly using an adhesive applied onto the basecoat layer and / or onto the surface to be coated or using an adhesive layer applied over at least a portion of basecoat layer.

[0130] Furthermore, it is possible that a second protective film, particularly a second removable protective film, is applied over at least a portion of a basecoatlayer. Furthermore, it is possible that a second protective film, particularly a second removable protective film, is applied over at least a portion of the adhesive layer.

[0131] It is also possible that the multi-layer coating is a multi-layer coating in which the laminate is already applied onto a coated surface.

[0132] Accordingly, the multi-layer coating can comprise in the following order, a substrate, a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, a second clear coat, and a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0133] Accordingly, the multi-layer coating can comprise in the following order, a substrate, a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, a second clear coat, an adhesive layer, and a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0134] Accordingly, the multi-layer coating can comprise in the following order, a substrate, a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, a second clear coat, an adhesive layer, a further basecoat layer, and a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of theclear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0135] Accordingly, the multi-layer coating can comprise in the following order, a substrate, an adhesive layer, a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, a second clear coat, and a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0136] Accordingly, the multi-layer coating can comprise in the following order, a substrate, an adhesive layer, a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, and a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0137] Accordingly, the multi-layer coating can comprise in the following order, a substrate, an adhesive layer, a carrier film, a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment, and a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

[0138] The further basecoat layer and the second clear coat can be any conventional basecoat layer or clear coat layer, or a basecoat layer and clear coat layer as described according to the present disclosure.

[0139] The multi-layer coating can comprise a second clear coat and the second clear coat is applied over at least a portion of the basecoat layer (b) so that the second clear coat is positioned between the basecoat layer (b) and the clear coat layer (c). The multi-layer coating can comprise an adhesive layer and the adhesive layer is applied over at least a portion of the second clear coat so that the adhesive layer is positioned between the second clear coat and the clear coat layer (c).

[0140] It is desired that the adhesive or the adhesive layer, and / or the further basecoat layer is transparent. The dry film thickness of the further basecoat layer can be 5 to 35 pm. The dry film thickness of the adhesive layer can be 2 to 35 pm.

[0141] Furthermore, a laminate is provided comprising (i) a protective film, particularly a removable protective film (ii) a clear coat layer applied over at least a portion of the protective film, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm, (iii) an optional basecoat layer applied over at least a portion of the clear coat, wherein particularly the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer particularly comprises a goniochromatic pigment (iv) an optional carrier film applied over at least a portion of the basecoat layer, (v) an optional adhesive layer applied over at least a portion of the clear coat, basecoat layer and / or carrier film, and (vi) an optional liner applied over at least a portion of the adhesive layer.

[0142] Furthermore, a laminate can be provided comprising in the following order (i) a protective film, particularly a removable protective film (II) a clear coat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm, (iii) an optional basecoat layer, wherein particularly the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment (iv) an optional carrier film, (v) an optional adhesive layer, and (vi) an optional liner.

[0143] Furthermore, a laminate can be provided comprising a protective film, particularly (I) a removable protective film (II) a clear coat layer applied over at least a portion of the protective film, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm, (iii) an optional basecoat layer applied over at least a portion of the clear coat, wherein particularly the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer particularly comprises a goniochromatic pigment (iv) an optional carrier film applied over at least a portion of the basecoat layer, (v) an optional adhesive layer applied over at least a portion of the clear coat, basecoat layer and / or carrier film, and (vi) an optional second protective film, particularly a second removable protective film applied over at least a portion of the adhesive layer.

[0144] A laminate can be provided comprising a protective film, particularly (I) a removable protective film (II) a clear coat layer applied over at least a portion of the protective film, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm, (iii) a basecoat layer applied over at least a portion of the clear coat, wherein particularly the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer particularly comprises a goniochromatic pigment (iv) a carrier film applied over at least a portion of the basecoat layer, (v) an adhesive layer applied over at least a portion of the clear coat, basecoat layer and / or carrier film, and (vi) an optional liner applied over at least a portion of the adhesive layer.

[0145] The liner is generally a removeable liner. The liner is usually removed before applying the laminate onto a substrate.

[0146] A laminate can be provided comprising (i) a removable protective film (ii) a clear coat layer applied over at least a portion of the protective film, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in therange of 15 to 80 pm, (iii) a basecoat layer applied over at least a portion of the clear coat, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer particularly comprises a goniochromatic pigment (iv) an optional carrier film applied over at least a portion of the basecoat layer, (v) an adhesive layer applied over at least a portion of the clear coat, basecoat layer and / or carrier film, and (vi) an optional liner applied over at least a portion of the adhesive layer. The liner is generally a removeable liner. The liner is usually removed before applying the laminate onto a surface.

[0147] The thickness of the carrier film can be 20 pm to 150 pm, such as 30 to 40 pm or 120 to 140 pm. The carrier film can be a plastic film, such as polypropylene.

[0148] The carrier film of the laminate can be a plastic, particularly the plastic is selected from fluoropolymers such as ethylene-tetrafluoroethylene (ETFE), polyethylene terephthalate, polyolefin, polycarbonate, aery Ion itrile-butad iene- styrene (ABS), acrylic styrene-acrylonitrile (ASA), acrylonitrile-butadiene- styrene / polycarbonate (ABS / PC), acrylic-styrene-acrylic nitrile / polycarbonate (ASA / PC), polycarbonate / polybutylene terephthalate (PC / PBT), polyacrylate, polystyrene and / or polymethyl methacrylate.

[0149] The (removable) protective film of the laminate can be a plastic, particularly the plastic is selected from fluoropolymers such as ethylene-tetrafluoroethylene (ETFE), polyethylene terephthalate, polyolefin, polycarbonate, acrylonitrile- butadiene-styrene (ABS), acrylic styrene-acrylonitrile (ASA), acrylonitrile- butadiene-styrene / polycarbonate (ABS / PC), acrylic-styrene-acrylic nitrile / polycarbonate (ASA / PC), polycarbonate / polybutylene terephthalate (PC / PBT), polyacrylate, polystyrene and / or polymethyl methacrylate.

[0150] The second (removable) protective film of the laminate can be a plastic, particularly the plastic is selected from fluoropolymers such as ethylene- tetrafluoroethylene (ETFE), polyethylene terephthalate, polyolefin, polycarbonate, acrylonitrile-butadiene-styrene (ABS), acrylic styrene-acrylonitrile (ASA), acrylonitrile-butadiene-styrene / polycarbonate (ABS / PC), acrylic-styrene-acrylic nitrile / polycarbonate (ASA / PC), polycarbonate / polybutylene terephthalate (PC / PBT), polyacrylate, polystyrene and / or polymethyl methacrylate.

[0151] Moreover, a method for applying a laminate onto a substrate is provided, comprising (I) providing a laminate according to the present disclosure, (II) contacting the substrate with the laminate, wherein the substrate particularly comprises a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment (III) optionally applying an adhesive on the substrate before contacting the substrate with the laminate so that the laminate is applied onto the adhesive. For instance, the substrate can be a coated surface of a vehicle or an uncoated surface of a vehicle.

[0152] An example for a laminate can be found in WO 2009 / 024310 A1 .

[0153] The disclosure will now be described with reference to the accompanying figures which do not limit the scope and ambit of the disclosure. The description provided is purely by way of example and illustration.

[0154] Figure 1 shows a multi-layer coating (100) comprising a substrate (101 ), a basecoat layer (102) and a clear coat layer (103) each coating layer according to the present disclosure. The basecoat layer (101 ) generally comprises a goniochromatic pigment and may have a flop index of at least 1 . The clear coat layer (103) comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer. As can be seen from said figure, the basecoat layer (102) is directly applied over the substrate. However, a second basecoat layer (not shown), or a primer (not shown) can be present between the substrate (101 ) and the basecoat layer (102).

[0155] Figure 2a shows a multi-layer coating (200a) that comprises a substrate (101), a basecoat layer (102) and a clear coat layer (103) each according to the disclosure. Furthermore, a second clear coat (104) is present between the basecoat layer (102) and an adhesive layer (105). On top of the clear coat layer (103), a removable protective film (106) is present. Generally, the finished multilayer coating does not comprise the removable protective film anymore. The removable protective film (106), the clear coat layer (103) and the adhesive layer (105) according to Figure 2a represents a laminate that is applied onto a coatedsubstrate comprising a substrate (101 ), a basecoat layer (102) and a second clear coat (104).

[0156] Figure 2b shows a method in which a laminate comprising a removable protective film (106), a clear coat layer (103), an adhesive layer (105) and a liner (107) is applied on a coated substrate comprising a substrate (101), a basecoat layer (102) and a second clear coat (104). The liner (107) is removed and then, the laminate is applied on top of the second clear coat (104). The removable protective film (106) can be removed.

[0157] Figure 3 reveals a further laminate comprising a removable protective film (106), a clear coat layer (103), a basecoat layer (102), a carrier film (108), an adhesive layer (105) and a liner (107).EXAMPLES

[0158] The following examples are used to illustrate the present disclosure without limiting it to those examples. Unless otherwise indicated, all temperatures are 22°C, all pressures are 1 atmosphere and relative humidity was 30%.Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. All parts and percentages in the examples are by weight unless otherwise indicated.

[0159] Specific features exemplified in the examples can be used to further restrict the scope of the disclosure.

[0160] The dry film thickness was measured with non-destructive coating thickness measurements device “LAYERCHECK 750 USB” (ERICHSEN GmbH & Co. KG, Germany) with the magnetic-inductive method. Determination of Film build thickness follows DIN EN ISO 2808.

[0161] The optical properties (such as the flop index, L*, a*, b*) of coatings (particularly the multilayer-coating stack according to the disclosure or a basecoat) were measured with a multiangle spectrophotometer BYK-mac I (manufactured by BYK) and particularly following the instructions of the instrumentmanual. BYK-mac i performs a 5-angle color measurement for light / dark travel evaluation: 15° 125° 145° / 75° / 110°. Color calculation and measurement are following DIN EN ISO 1 1664 (2020-03) standards (1-4). The flop index was calculated as follows: i

[0162] The color travel was calculated according to the following formulaColor travel AC* =

[0163] The color shift Ab* was calculated as followsAb — Z?15» b75

[0164] The color shift Aa* was calculated as follows

[0165] The pigment weight concentration (PWC) was calculated as follows pigmentPWC pigment + binder wherein pigment is the total weight of the pigments in the coating composition and binder is the total weight of the binders in the coating composition. The binders include all film-forming resins as well as all crosslinking agents. Crosslinking agents are for example polyisocyanates.A. Preparation of the basecoat compositions

[0166] A basecoat composition according to the present disclosure was prepared by mixing the components listed in Table 1 under agitation.

[0167] Table 1 : Basecoat compositions for preparing the basecoat layer1Polyurethane acrylic latex - Polymer of Example II A described in U.S. Pat. No. 5,972,809.2Acrylic dispersion made of 30.0 wt % Styrene, 35.0 wt % n-Butyl Acrylate, 18.0 wt % n-Butyl Methacrylate, 8.5 wt % 2- Hydroxyethyl Acrylate and 8.5 wt % Acrylic Acid made at 26.1% weight solids in a 84.5 wt % deionized water / 15.5 wt % Butyl Carbitol solvent mixture and 54% neutralized with Dimethyl Ethanolamine.3Polyester resin - Polymer of Example 2 described in U.S. Pat. No. 5,468,802.4Dimethyl ethanolamine (50% aqueous solution)5Phosphatized Epoxy prepared from Epon 828, polyglycidyl ether of Bisphenol A, avaialable from Shell Chemical Co; reacted with phosphoric acid at an 83:18 weight ratio.6Additive available from Byk Chemie.7Polyether polyol available from Bayer Material Science.8Melamine curing agent commercially available from INEOS Melamine.9’10Solvents available from Dow Co.11Solvent available from Shell Chemical Co.12Surfactant available from Air Products & Chemicals.13Respective basecoat tint paste as mentioned below having a solids content of 46%. Basecoat “silver” was prepared by using the silver tint paste. Basecoat “violet” was prepared by using the violet tint paste. Basecoat “blue” was prepared by using the blue tint paste. Basecoat “blue 2” was prepared by using the blue 2 tint paste. Basecoat “beige” was prepared by using the beige tint paste. Basecoat “dark green” was prepared by using the dark green tint paste. Basecoat “brown” was prepared by using the brown tint paste. Basecoat “green” was prepared by using the green tint paste. Basecoat “dark blue” was prepared by using the dark blue tint paste.14Dispersion of 9% Aerosil R812 commercially available from Evonik Degussa in 21 % acrylic polymer blend and having a solids content of 31%.

[0168] The tint pastes were prepared using “Disperser DAS H [ / A] 200-K mit Kuhleinrichtung - SYSTEM LAU” (LAU GmbH, Germany, Prufgerate fur Oberflachenschutz, lau-hemer.de).

[0169] The silver tint paste has a solid content of 46 % and aluminum flakes as the sole pigments.

[0170] The aluminum flakes provide the desired flop index of the basecoat layer. In comparative example 43, the optical properties of the silver basecoat are shown, wherein a standard clear coat without pigments is applied over the silver basecoat.

[0171] The violet tint paste has a solid content of 46 % and comprises 18 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, violet mica, and TiO? having a Dv50 of 20 pm.

[0172] The blue tint paste has a solid content of 46 % and comprises 16 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, and blue mica.

[0173] The blue 2 tint paste has a solid content of 46 % and comprises 80 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, blue mica, and Iron Oxide Red (PR101 ).

[0174] The beige tint paste has a solid content of 46 % and comprises 44 wt. % (based on the total pigment content) aluminum flakes that is a goniochromaticpigment, mica copper, TiC>2 having a Dv50 of 20 pm, and Iron Oxide Red (PR101 ).

[0175] The dark green tint paste has a solid content of 46 % and comprises 23 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, and green mica.

[0176] The brown tint paste has a solid content of 46 % and comprises 40 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, blue mica, and Iron Oxide Red (PR101 ).

[0177] The green tint paste has a solid content of 46 % and comprises 33 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, and green mica.

[0178] The dark blue tint paste has a solid content of 46 % and comprises 15 wt. % (based on the total pigment content) aluminum flakes that is a goniochromatic pigment, blue mica, and TiO2 having a Dv50 of 20 pm.B. Preparation of the tint pasts for the clear coat composition

[0179] The tint pastes were prepared using “Disperser DAS H [ / A] 200-K mit Kuhleinrichtung - SYSTEM LAU” (LAU GmbH, Germany, Prufgerate fur Oberflachenschutz, lau-hemer.de).

[0180] White clear coat tint paste 1 was formed from 67 wt. % titanium dioxide having a Dv50 of 20 pm dispersed in 10.3 wt % polyester resin, and 4.4 wt % melamine resin blend having a solids content of 84 wt. %. The solvent was butylacetat. The titanium dioxide in tint paste 1 has a rutil crystal structure, an oil absorption according to DIN ISO 787-10 (g / 100g pigment) of 18 and a BET surface area (m2 / g) (measured by Brunauer-Emmert-Teller Theory / DIN ISO 9277:2003-05) of 13 to 14. The titanium dioxide in tint paste 1 was the commercially available titanium dioxide Tiona 595 from Tronox US Holdings Inc.

[0181] The clear coat tint paste 2 was formed from 40 wt. % titanium dioxide having a Dv50 of 50 nm dispersed in 20.2 wt. % polyester resin, 8.5 wt. % Melamine resin blend having a solids content of 75 wt. %. The solvent was butylacetat. The titanium dioxide in tint paste 2 has a rutil crystal structure, an oil absorbtion according to DIN ISO 787-10 (g / 100g pigment) of 30 to 40 and a BETsurface area (m2 / g) (measured by Brunauer-Emmert-Teller Theory I DIN ISO 9277:2003-05) of 35. The titanium dioxide in tint paste 2 was the commercially available titanium dioxide MT-700HD from TAYCA Co., Ltd.

[0182] The above-mentioned materials with one half of the solvent and without the melamine resin for the respective tint paste was added in a glass bottle in addition to glass beads with a diameter of 2 mm. The mixture was shaken for 60 min with the above-mentioned disperser. Melamine resin and the second half of the solvent was added and shaken again for 2 min. The ratio of the materials and the glass beads should be in a ratio of 1 :2.25. The grinding fineness of the respective tine pastes size should be around 5-8 Microns (For tint paste 1 : 7.5 pm and for tint paste 2: 8 pm). The resulting tint pastes were filtered and used in the following examples.

[0183] The aforementioned grinding fineness was measured with Grindometer of Hegman Model 232-25 (from Erichsen, ERICHSEN GmbH & Co. KG, Germany). The grinding fineness was obtained according to DIN 53 203, DIN EN 21 524 and ISO 1524. A liquid wedge of the test substance is generated on the testing device. If the grain dimensions are larger than the local wedge thickness, this is easily detected visually. At the boundary between the disturbed and smooth liquid surface, the operator can read the associated wedge thickness, this value refers to the fineness of grinding.C. Preparation of two-component (2K) clear coat composition

[0184] A 2K clear coat coating composition according to the present disclosure were prepared by preparing Component A and Component B as listed in table 2. The 2K coating composition prepared by mixing Component A and Component B of table 2 (weight ratio Component A to Component B 2:1). In table 2, the weight percentages based on the total composition is indicated for the final and mixed clear coating compositions.

[0185] Table 2: 2K Coating composition15Hydroxyl number: 150, OH%: 4.55, Solid content: 60, Tg [°C]: -518Setalux 91767 VX-60 commercially available from Allnex (Germany), OH%: 4.5, solid content: 6017Hydroxyl number: 290, OH%: 8.79, Solid content: 78, Tg [°C]: -1618Cymel 1156 commercially available from Allnex (Germany)19Tinuvin 928 commercially available from BASF (Germany)20Tinuvin 1 3 commercially available from BASF (Germany)21Byk 322 commercially available from Byk (Germany);22Byk 390 commercially available from Byk (Germany)23Nacure 5528 commercially available from King Industries Inc. (USA), solid content: 2524Aromatic 100 commercially available from ExxonMobil (USA); isoamyl actetate, n-butylacetate; ethyl 3-ethoxypropionate; diethylene glycol butyl ether acetate, 2-butoxyethyl acetate25Tint paste 1 as mentioned under item B.26Tint paste 2 as mentioned under item B.27Desmodur ultra N 3390 BA / SN commercially available from Covestro (Germany), solid content: 9028Solvesso 100 commercially available from ExxonMobil (USA)

[0186] The hydroxyl value and the hydroxy content (OH%) of the acrylic resins was determined according to DIN EN ISO 4629-1 :2016. The glass transition temperature (Tg) was determined according to DIN EN ISO 16805:2005.D. Preparation of multi-layer coatings

[0187] According to table 3, in each example the basecoat composition as indicated in table 1 was spray applied with a Satajet 100BFRP spray gun available from SATA GmbH&Co (Germany) onto E-coated steel substrates available from ACT Test Panels LLC (USA). The film thickness of basecoatcomposition was chosen so that the dry film thickness was in the indicated range as mentioned in table 3. The basecoat composition was then dried for 10 min at 80 °C. The clear coat composition as indicated in table 2 was spray applied with a Satajet 100BFRP spray gun available from SATA GmbH&Co (Germany) onto the basecoat so that the dry film thickness was in the indicated range as mentioned in table 3. The substrates coated with the coating composition were cured using heated air in an oven (HORO Dr. Hofmann GmbH (Germany)). The substrates were cured at 140 °C for 20 min.

[0188] Table 3: Multi-layer coatings using a 2 K clear coat composition29Standard TiC>2, Tiona 595 / Tronox, added as tint paste 130nTiO2: Micro MT-700HD from TAYCA Co., Ltd, added as tint paste 231Basecoat Violet additionally comprises 4.73 wt. % nTiO2

[0189] Comparative Examples 1 shows that the mere addition of titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm into the basecoat requires a very high amount of said titanium dioxide in order to show a at least a weak color travel. However, a high amount of titanium dioxide in the basecoat results in a strong white coloring of the color of the basecoat.

[0190] In Comparative Example 2 to 4, a standard titanium dioxide is used in the clear coat. A milky white effect is not observed but a mere white color change of the multi-layer coating.

[0191] Examples 5 to 14 reveal that the addition of titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm in the clear coat result in a strong color travel, strong Ab* change and a milky white effect.

[0192] According to table 4, in each example the basecoat composition as indicated in table 1 was spray applied with a Satajet 100BFRP spray gun available from SATA GmbH&Co (Germany) onto E-coated steel substrates available from ACT Test Panels LLC (USA). The film thickness of basecoat composition was chosen so that the dry film thickness was in the indicated range as mentioned in table 4. The basecoat composition was then dried for 10 min at 80 °C. A 1 K clear coat composition was spray applied with a Satajet 100BFRP spray gun available from SATA GmbH&Co (Germany) onto the basecoat so that the dry film thickness was in the indicated range as mentioned in table 4. Each 1 K clear coat composition shown in table 4 comprises the required amount (0.01 wt. % to 1 .50 wt. %) of titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm. The substrates coated with the coatingcomposition were cured using heated air in an oven (HORO Dr. Hofmann GmbH (Germany)). The substrates were cured at 140 °C for 20 min.

[0193] Table 4: Multi-layer coatings using a 1 K clear coat composition30nTiO2: Micro MT-700HD from TAYCA Co., Ltd, added as tint paste 2

[0194] Examples 15 to 32 also reveal the relation of the PWC and the dry film thickness of the clear coat layer. There should be a balance between film build and pigment concentration in the clearcoat to achieve a maximum of the color travel. If a high pigment concentration in the clear coat is desired, the dry film thickness should be reduced.

[0195] In table 5, standard clear coats without pigments are applied over effect basecoats comprising a goniochromatic pigment are directly compared with clear coatings according to the present disclosure comprising 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to250 nm.

[0196] As can be seen in table 5, the flop index is reduced but a strong color travel, particularly a strong Ab* shift, and a milky white effect is observed by using the clear coat according to the present disclosure (see Examples 12, 34, 36, 38, 40, and 42).

[0197] Table 5: Comparison of multi-layer coatings comprising a standard clear coat

[0198] Whereas particular examples of this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from what is defined in the appended claims.

Claims

Claims1 . A multi-layer coating comprising:(a) a substrate,(b) a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment,(c) a clear coat layer applied over at least a portion of the basecoat layer, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm.

2. The multi-layer coating according to claim 1 , wherein the dry thickness of the basecoat layer is in the range of 7 to 28 pm, such as 8 to 26 pm, 9 to 25 pm, or 10 to 20 pm, and / or wherein basecoat layer has a flop index of at least 1 , and / or wherein the dry thickness of the clear coat layer is in the range of 30 to 70 pm, such as 33 to 65 pm, 35 to 60 pm, or 40 to 50 pm, and / or wherein the multi-layer coating has a flop index of at least 0.1 , and / or wherein the dry coating thickness of the multi-layer coating is in the range of 70 to 200 pm, such as 80 to 160 pm, 90 to 150 pm, or 100 to 130 pm.

3. The multi-layer coating according to any one of the preceding claims, wherein the multi-layer coating comprises a second clear coat and the second clear coat is applied over at least a portion of the basecoat layer (b) so that the second clear coat is positioned between the basecoat layer (b) and the clear coat layer (c), and / or wherein the multi-layer coating comprises an adhesive layer and the adhesive layer is applied over at least a portion of the second clear coat so that the adhesive layer is positioned between the second clear coat and the clear coat layer (c) and / or wherein the multi-layer coating comprises an adhesive layer and the adhesive layeris applied over at least a portion of the substrate (a) so that the adhesive layer is positioned between the substrate (a) and the basecoat layer (b).

4. The multi-layer coating according to any one of the preceding claims, wherein the clear coat layer comprises titanium dioxide having a volume average particle size Dv50 in the range of 12 to 80 nm, such as 20 to 70 nm, 30 to 60 nm, or 35 to 55 nm, and / or wherein the clear coat layer comprises 0.04 wt. % to 1 .30 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, such as 0.09 wt. % to 1.10 wt. %, 0.14 wt. % to 1.00 wt. %, 0.20 wt. % to 0.90 wt. %, 0.25 wt. % to 0.80 wt. %, 0.35 wt. % to 0.70 wt. %, 0.40 wt. % to 0.70 wt. %, 0.50 wt. % to 0.70 wt. %, or 0.50 wt. % to 0.60 wt. %, based on the total weight of the clear coat layer.

5. The multi-layer coating according to any one of the preceding claims, wherein the pigment weight concentration (PWC) of the clear coat layer is 0.01 % to 2 %, such as 0.05 % to 1 .8 %, 0.1 % to 1 .3 %, 0.2 % to 1 .1 %, 0.25 % to 1 %, 0.40 % to 0.90 %, or 0.50 % to 0.80 %, and / or wherein the ratio of the total pigment weight to the total binder weight is 0.0001 to 0.1 , such as 0.0005 to 0.08, 0.0009 to 0.04, 0.001 to 0.03, 0.002 to 0.02, 0.003 to 0.01 , 0.004 to 0.009, or 0.005 to 0.008.

6. The multi-layer coating according to any one of the preceding claims, wherein the BET surface area of the titanium dioxide in the clear coat is 20 to 80 m2 / g, such as 25 to 70 m2 / g, 25 to 50 m2 / g, or 30 to 45 m2 / g.

7. The multi-layer coating according to any one of the preceding claims, wherein the multi-layer coating further comprises an electrodeposited coating layer applied over at least a portion of the substrate, wherein the electrodeposited coating layer is positioned between the basecoat layer and the substrate.

8. The multi-layer coating according to any one of the preceding claims, wherein the multi-layer coating further comprises a primer or a secondbasecoat layer applied over at least a portion of the substrate, wherein the primer or a second basecoat layer is positioned between the basecoat layer (b) and the substrate, or the primer or a second basecoat layer is positioned between the basecoat layer (b) and the electrodeposited coating layer.

9. A method for preparing a multi-layer coating, particularly a multi-layer coating according to any one of the preceding claims, comprising in the following order:(A) forming a basecoat layer over at least a portion of a substrate by depositing a basecoat composition over at least a portion of the substrate, wherein the basecoat composition comprises a goniochromatic pigment,(B) optionally drying and / or curing the basecoat layer,(C) forming a clear coat layer over at least a portion of the basecoat layer by depositing a clear coat composition over at least a portion of the substrate, wherein the clear coat composition comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition, and(D) drying and / or curing the clear coat layer or both the basecoat and clear coat layers, wherein the dry thickness of the clear coat layer is in the range of 15 to 80 pm and the dry thickness of the basecoat layer in the range of 5 to 35 pm.

10. The method according to any one of claim 9, wherein the drying in steps(A) and / or (B) are carried out at a temperature in the range of 30 to 80 °C, and / or the curing in steps (A) and / or (B) are carried out at a temperature in the range of 80 to 140 °C.11 . The method according to any one of claims 9 or 10, wherein the method further comprises forming an electrodeposited coating layer over at least a portion of a substrate by depositing an electrodeposited coating composition over at least a portion of the substrate, wherein theelectrodeposited coating layer is positioned between the basecoat layer and the substrate, and / or wherein the method further comprises forming a primer or a second basecoat over at least a portion of a substrate by depositing an primer composition or a second basecoat composition over at least a portion of the substrate, wherein the primer or a second basecoat layer (e) is positioned between the basecoat layer (b) and the substrate (a), or the primer or a second basecoat (e) is positioned between the basecoat layer (b) and the electrodeposited coating (d).

12. Use of a clear coat coating composition comprising 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total solid content of the clear coat composition, to form a clear coat layer over a basecoat layer, wherein the basecoat layer has a flop index of at least 1.

13. A laminate comprising(i) a protective film, particularly a removable protective film,(ii) a clear coat layer applied over at least a portion of the protective film, wherein the clear coat layer comprises 0.01 wt. % to 1 .50 wt. % titanium dioxide having a volume average particle size Dv50 in the range of 1 to 250 nm, based on the total weight of the clear coat layer, and the dry thickness of the clear coat layer is in the range of 15 to 80 pm,(iii) an optional basecoat layer applied over at least a portion of the clear coat, wherein particularly the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer particularly comprises a goniochromatic pigment,(iv) an optional carrier film applied over at least a portion of the basecoat layer,(v) an optional adhesive layer applied over at least a portion of the clear coat, basecoat layer and / or carrier film, and(vi) an optional liner applied over at least a portion of the adhesive layer.

14. The laminate according to claim 13, wherein the carrier film of the laminate is a plastic, particularly the plastic is selected from fluoropolymers such as ethylene-tetrafluoroethylene (ETFE), polyethylene terephthalate, polyolefin, polycarbonate, acrylonitrile-butadiene-styrene (ABS), acrylic styreneacrylonitrile (ASA), acrylonitrile-butadiene-styrene / polycarbonate (ABS / PC), acrylic-styrene-acrylic nitrile / polycarbonate (ASA / PC), polycarbonate / polybutylene terephthalate (PC / PBT), polyacrylate, polystyrene and / or polymethyl methacrylate.

15. A method for applying a laminate onto a substrate, comprising(I) providing a laminate according to any one of claims 13 to 14,(II) contacting the substrate with the laminate, wherein the substrate particularly comprises a basecoat layer applied over at least a portion of the substrate, wherein the dry thickness of the basecoat layer is in the range of 5 to 35 pm and wherein the basecoat layer comprises a goniochromatic pigment(III) optionally applying an adhesive on the substrate before contacting the substrate with the laminate so that the laminate is applied onto the adhesive.

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