Metal effect coating composition and application thereof

Abstract

The present invention relates to a coating composition comprising (A) a pigment composition comprising: (A-1) a yellow red pigment; (A-2) a magenta pigment; and (A-3) a green blue pigment, (B) a binder; (C) carbon black, preferably gas black; and (D) aluminum wherein the sum of the weight percentages of components (A-1), (A-2) and (A-3) is at least 80% by weight, preferably at least 95% and more preferably 100%, based on the total weight of component (A), the coating composition providing a unique gray color transmission. The invention further relates to a coating film having a unique gray color transmission and to the use of the coating composition. The unique gray color transmission obtained by the invention is a unique gray color transmission from the blue-gray-red tone with a change in viewing angle.

Description

Technical Field

[0001] The present invention relates to a coating composition and more particularly to a metallic effect coating composition for automobiles, which is capable of forming a coating film having color-travel properties. Background Art

[0002] Coating compositions capable of forming coating films exhibiting color-transmitting properties (also referred to as color-transmitting coating compositions) are known and widely used in a variety of applications. For example, in the automotive field, color-transmitting coating compositions are primarily used for high-end customization of luxury brand vehicles, enabling these vehicles to have unique colors. The color-transmitting properties of the resulting color-transmitting coating films are imparted by a specific type of pigment composition contained in the color-transmitting coating composition, referred to as a color-transmitting pigment composition.

[0003] Traditionally, color-transmitting pigment compositions, such as those suitable for automotive applications, are made from a class of pigments with specialized optical effects. These effects are developed by strictly controlling the pigment particle size and the diameter-to-thickness ratio of the substrate used, precisely controlling the coating thickness across multiple layers, and using a variety of metal oxides to achieve the desired color intensity and color-transmitting properties. However, due to the use of such optical-effect pigments, these color-transmitting pigment compositions suffer from several drawbacks, primarily due to: 1) the hiding power of the optical-effect pigments is poor, and the thickness uniformity of the resulting coating affects the color of the finished product; 2) various factors affect the orientation of the optical-effect pigment particles during spray application, leading to color deviations; 3) controlling the optical effect is difficult and complex; and 4) color-transmitting pigment compositions made from optical-effect pigments have a high tendency to settle. These drawbacks often result in issues with color quality and color stability. For example, color variations can occur between batches of the pigment composition, and when a color-transmitting coated product (such as a color-transmitting coated automobile) is damaged, such as by cuts or scratches, it can be difficult to repair it to its original appearance.

[0004] Therefore, there is a need to provide a new type of coating composition capable of forming a coating film having color transmission properties, which comprises a color transmission pigment composition, wherein the coating films of these coating compositions have a unique color and have greatly improved color quality and batch-to-batch color stability compared to those formed by using optical effect pigments. Summary of the Invention

[0005] In one aspect, the present invention provides a metal effect coating composition comprising

[0006] (A) a pigment composition comprising:

[0007] (A-1) yellow-red pigment;

[0008] (A-2) magenta pigment; and

[0009] (A-3) green-blue pigment,

[0010] (B) adhesive;

[0011] (C) carbon black, preferably gas black; and

[0012] (D) aluminum, wherein the sum of the weight percentages of components (A-1), (A-2) and (A-3) based on the total weight of component (A) is at least 80%, preferably at least 95% and more preferably 100% by weight.

[0013] In another aspect, the present invention provides a coating film obtained from the coating composition of the present invention having a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV and V, preferably at least four of conditions I, II, III, IV and V, and more preferably all of conditions I, II, III, IV and V:

[0014]

[0015]

[0016] In another aspect, the present invention provides a coating film obtained from the coating composition of the present invention having a CIEHLC color space, wherein the C*, h° values ​​are as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0017]

[0018] In another aspect, the present invention provides use of the coating composition of the present invention in the fields of construction, industry, automobiles, home appliances, leather, inks, textiles and paper.

[0019] The coating films obtained from the coating compositions of the present invention exhibit a unique gray color transition from bluish-gray to reddish hues at varying viewing angles. The coating compositions of the present invention achieve the desired properties without optical effect pigments, thus avoiding disadvantages such as poor color quality and batch-to-batch color fluctuations. DETAILED DESCRIPTION

[0020] The present invention will now be described more fully hereinafter, in which some, but not all, embodiments of the invention are shown. Indeed, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.

[0021] In the context of the present disclosure, the expressions “a / an”, “the” when used to define a term include both the plural and singular forms of the term.

[0022] In the context of this disclosure, the terms "comprise," "comprising," and the like are used interchangeably with "contain," "containing," and the like and are to be interpreted in a non-limiting, open-ended manner. That is, for example, additional components or elements may be present. If used, the expression "consisting of" or "consisting essentially of" or cognates may be included in "comprises" or cognates.

[0023] In the context of this disclosure, for convenience, "resin" is used in this disclosure to encompass resins, oligomers, and polymers. "Binder" refers to the film-forming component of the coating composition. Thus, resins, crosslinkers, and other film-forming agents are part of the binder, but solvents, pigments, additives like antioxidants, light stabilizers (e.g., hindered amine light stabilizers, HALS), UV absorbers, etc. are not part of the binder.

[0024] In the context of this disclosure, the "CIELAB color space" (also known as L*a*b*) is a color space defined by the International Commission on Illumination (abbreviated as CIE) in 1976. It represents color as three values: L* represents perceived lightness; a* and b* represent the four unique colors of human vision: red, green, blue, and yellow.

[0025] In the context of this disclosure, "CIEHLC color space" is a color space based on CIELAB, which uses polar coordinates C* (chroma, relative saturation) and h° (hue angle, the angle of the hue on the CIELAB color wheel) instead of Cartesian coordinates a* and b*. CIELAB lightness L* remains unchanged. The conversion of a* and b* to C* and h° is performed as follows: C* = (a* 2 +b* 2 ) 1 / 2 ; h°=atan(b* / a*).

[0026] Coating composition

[0027] The present invention provides a metal effect coating composition comprising

[0028] (A) a pigment composition comprising:

[0029] (A-1) yellow-red pigment;

[0030] (A-2) magenta pigment; and

[0031] (A-3) green-blue pigment,

[0032] (B) adhesive;

[0033] (C) carbon black, preferably gas black; and

[0034] (D) aluminum, wherein the sum of the weight percentages of components (A-1), (A-2) and (A-3) based on the total weight of component (A) is at least 80%, preferably at least 95% and more preferably 100% by weight.

[0035] The coating composition of the present invention is capable of forming a coating film having a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV, and V, preferably at least four of conditions I, II, III, IV, and V, and more preferably all of conditions I, II, III, IV, and V:

[0036]

[0037] The coating composition of the present invention is capable of forming a coating film having a CIEHLC color space, wherein the C* and h° values ​​are as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0038]

[0039] In an embodiment, the coating film has a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in three of conditions I, II, III, IV, and V (such as conditions I, II, and III, or conditions I, II, and IV, or conditions I, II, and IV, or conditions I, III, and IV, or conditions I, III, and V, or conditions II, III, and IV, or conditions II, III, and V, or conditions III, IV, and V, preferably conditions I, III, and IV).

[0040] In an embodiment, the coating film has a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in four of conditions I, II, III, IV, and V (such as conditions I, II, III, and IV, or conditions I, II, III, and V, or conditions I, III, IV, and V, or conditions II, III, IV, and V).

[0041] In an embodiment, the coating film has a CIELAB color space, where the L*, a*, b* values ​​are as defined in all of conditions I, II, III, IV, and V.

[0042] In an embodiment, the coating film has a CIEHLC color space, wherein the C*, h° values ​​are as defined in three of conditions VI, VII, VIII, IX and X (such as conditions VI, VII and VIII, or conditions VI, VII and IX, or conditions VI, VII and IX, or conditions VI, VIII and IX, or conditions VI, VIII and IX, or conditions VII, VIII and X, or conditions VIII, IX and X, preferably conditions VI, VIII and IX).

[0043] In an embodiment, the coating film has a CIEHLC color space, wherein the C*, h° values ​​are as defined in four of conditions VI, VII, VIII, IX, and X (such as conditions VI, VII, VIII, and IX, or conditions VI, VII, VIII, and X, or conditions VI, VIII, IX, and X, or conditions VII, VIII, IX, and X).

[0044] In an embodiment, the coated film has a CIEHLC color space, wherein the C*, h° values ​​are as defined in all of conditions VI, VII, VIII, IX, and X.

[0045] Pigment composition

[0046] The pigment composition in the coating composition of the present invention comprises:

[0047] (A-1) yellow-red pigment;

[0048] (A-2) magenta pigment; and

[0049] (A-3) Greenish blue pigment.

[0050] The term "pigment" is well known in the art and refers to a class of materials suitable for coloring a substrate and that are insoluble in solvents and water. The particle size of the pigment can be determined by a skilled artisan based on the actual application. Preferably, the pigment may have a primary particle size in the range of 0.01 μm to 1 μm, more preferably in the range of 0.3 μm to 1 μm.

[0051] Preferably, the amount of component (A-1) is in the range of 20% to 60% by weight, or 30% to 60% by weight, or 20% to 50% by weight, or 30% to 50% by weight, based on the weight of the pigment composition of the present invention, preferably in the range of 40% to 60% by weight. For the purpose of the present invention, component (A-1) is selected from CI Pigment Red 101 or CI Pigment Red 254.

[0052] Preferably, the amount of component (A-2) is in the range of 10% to 40% by weight, or 10% to 30% by weight, or 20% to 40% by weight, or 15% to 40% by weight, based on the weight of the pigment composition of the present invention, preferably in the range of 10% to 20% by weight. For the purpose of the present invention, component (A-2) is selected from CI Pigment Red 122, CI Pigment Red 202, CI Pigment Violet 19, or a combination of CI Pigment Red 177 and CI Pigment Violet 23, preferably in a combination ratio of 10:1 to 1:10, more preferably 10:1 to 1:2.

[0053] Preferably, the amount of component (A-3) is in the range of 20% to 50% by weight, or 25% to 50% by weight, or 30% to 50% by weight, or 25% to 40% by weight, based on the weight of the pigment composition of the present invention, preferably in the range of 20% to 40% by weight. For the purpose of the present invention, component (A-3) is selected from CI Pigment Blue 15; a combination of CI Pigment Blue 15 and CI Pigment Green 7, preferably in a combination ratio of 2:1 to 1:2, more preferably 1.2:1 to 1:1.2; or a combination of CI Pigment Blue 15 and CI Pigment Green 36, preferably in a combination ratio of 25:1 to 1:1, more preferably 20:1 to 1:1, preferably component (A-3) is selected from a combination of CI Pigment Blue 15 and CI Pigment Green 7 or a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0054] Preferably, components (A-1), (A-2) and (A-3) account for at least 80% by weight, more preferably at least 90% by weight, and even more preferably at least 95% by weight of the pigment composition of the present invention. Most preferably, components (A-1), (A-2) and (A-3) account for 100% by weight of the pigment composition of the present invention.

[0055] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (1), wherein:

[0056] Component (A-1) is CI Pigment Red 101,

[0057] Component (A-2) is CI Pigment Red 122, and

[0058] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0059] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (2), wherein:

[0060] Component (A-1) is CI Pigment Red 101,

[0061] Component (A-2) is CI Pigment Red 122, and

[0062] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0063] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (3), wherein:

[0064] Component (A-1) is CI Pigment Red 101,

[0065] Component (A-2) is CI Pigment Red 122, and

[0066] Component (A-3) is CI Pigment Blue 15.

[0067] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (4), wherein:

[0068] Component (A-1) is CI Pigment Red 101,

[0069] Component (A-2) is CI Pigment Red 202, and

[0070] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0071] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (5), wherein:

[0072] Component (A-1) is CI Pigment Red 101,

[0073] Component (A-2) is CI Pigment Red 202, and

[0074] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0075] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (6), wherein:

[0076] Component (A-1) is CI Pigment Red 101,

[0077] Component (A-2) is CI Pigment Red 202, and

[0078] Component (A-3) is CI Pigment Blue 15.

[0079] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (7), wherein:

[0080] Component (A-1) is CI Pigment Red 101,

[0081] Component (A-2) is CI Pigment Violet 19, and

[0082] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0083] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (8), wherein:

[0084] Component (A-1) is CI Pigment Red 101,

[0085] Component (A-2) is CI Pigment Violet 19, and

[0086] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0087] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (9), wherein:

[0088] Component (A-1) is CI Pigment Red 101,

[0089] Component (A-2) is CI Pigment Violet 19, and

[0090] Component (A-3) is CI Pigment Blue 15.

[0091] In an embodiment of the present invention, the pigment composition of the present invention is a pigment composition (10), wherein:

[0092] Component (A-1) is CI Pigment Red 101,

[0093] Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and

[0094] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0095] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (11), wherein:

[0096] Component (A-1) is CI Pigment Red 101,

[0097] Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and

[0098] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0099] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (12), wherein:

[0100] Component (A-1) is CI Pigment Red 101,

[0101] Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and

[0102] Component (A-3) is CI Pigment Blue 15.

[0103] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (13), wherein:

[0104] Component (A-1) is CI Pigment Red 254,

[0105] Component (A-2) is CI Pigment Red 122, and

[0106] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0107] In an embodiment of the present invention, the pigment composition of the present invention is a pigment composition (14), wherein:

[0108] Component (A-1) is CI Pigment Red 254,

[0109] Component (A-2) is CI Pigment Red 122, and

[0110] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0111] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (15), wherein:

[0112] Component (A-1) is CI Pigment Red 254,

[0113] Component (A-2) is CI Pigment Red 122, and

[0114] Component (A-3) is CI Pigment Blue 15.

[0115] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (16), wherein:

[0116] Component (A-1) is CI Pigment Red 254,

[0117] Component (A-2) is CI Pigment Red 202, and

[0118] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0119] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (17), wherein:

[0120] Component (A-1) is CI Pigment Red 254,

[0121] Component (A-2) is CI Pigment Red 202, and

[0122] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0123] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (18), wherein:

[0124] Component (A-1) is CI Pigment Red 254,

[0125] Component (A-2) is CI Pigment Red 202, and

[0126] Component (A-3) is CI Pigment Blue 15.

[0127] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (19), wherein:

[0128] Component (A-1) is CI Pigment Red 254,

[0129] Component (A-2) is CI Pigment Violet 19, and

[0130] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0131] In an embodiment of the present invention, the pigment composition of the present invention is a pigment composition (20), wherein:

[0132] Component (A-1) is CI Pigment Red 254,

[0133] Component (A-2) is CI Pigment Violet 19, and

[0134] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0135] In an embodiment of the present invention, the pigment composition of the present invention is a pigment composition (21), wherein:

[0136] Component (A-1) is CI Pigment Red 254,

[0137] Component (A-2) is CI Pigment Violet 19, and

[0138] Component (A-3) is CI Pigment Blue 15.

[0139] In an embodiment of the present invention, the pigment composition of the present invention is a pigment composition (22), wherein:

[0140] Component (A-1) is CI Pigment Red 254,

[0141] Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and

[0142] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0143] In an embodiment of the present invention, the pigment composition of the present invention is pigment composition (23), wherein:

[0144] Component (A-1) is CI Pigment Red 254,

[0145] Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and

[0146] Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0147] In an embodiment of the present invention, the pigment composition of the present invention is a pigment composition (24), wherein:

[0148] Component (A-1) is CI Pigment Red 254,

[0149] Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and

[0150] Component (A-3) is CI Pigment Blue 15.

[0151] In an embodiment of the present invention, the pigment composition of the present invention is any combination of two or more compositions selected from the group consisting of pigment composition (1) to composition (24).

[0152] According to the present invention, the coating composition may not contain optical effect pigments. Typically, effect pigments are laminate substrates, such as natural mica or glass flakes, that have been coated with a metal oxide layer. A description of the properties of effect pigments can be found in the Pigment Handbook, Volume 1, Second Edition, pp. 829-858, John Wiley & Sons, New York, 1988.

[0153] The pigment composition of the present invention can be prepared by a skilled person using methods known in the art.

[0154] Preferably, the amount of the pigment composition as component (i) in the coating composition of the present invention is in the range of 0.3% to 3% by weight (e.g. 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5% or 3% by weight), preferably in the range of 0.5% to 2% by weight, based on the weight of the coating composition.

[0155] Adhesives

[0156] The coating composition of the present invention comprises a binder as component (ii).

[0157] The adhesive can be any adhesive suitable for the coating composition. For example, the adhesive can be selected from the group consisting of polyester resins, polyurethane resins, acrylic resins, cellulose acetate butyrate resins, and melamine resins. The adhesive can be heat-curable, including self-crosslinking, curable with a curing agent or crosslinking agent, or those resins that are curable by exposure to actinic radiation such as UV or EB radiation, and crosslinking agents for such resins. The adhesive can include any one or combination of a variety of resins or polymers. Non-limiting examples of suitable curable polymers include vinyl polymers, such as acrylic polymers (poly (meth) acrylates) and modified acrylic polymers, including branched, grafted ones, and copolymers with polyesters, polyethers, or other blocks, polyesters, polyurethanes, polyurethanes prepared using macromonomers such as polyester diols, polyether diols, and polycarbonate diols; alkyd resins, epoxy resins, polycarbonates, polyamides, polyimides, polysiloxanes, alkyd resins, and unsaturated oligomers and resins, and mixtures thereof, all of which are known in the art. In various embodiments, curable polymers have the group reacted with the crosslinking agent.The limiting examples of polymer functional groups comprises carboxyl, hydroxyl, silanol groups, aminoplast functional group, urea, carbamate, isocyanate (blocked or unblocked), epoxy group(ing), cyclic carbonate, amine, aldehyde radical, thiol group, hydrazide group, activated methylene and any combination thereof, and these groups can be made in heat curable polymers.In various embodiments, polymer functional groups is hydroxyl, primary carbamate, isocyanate, aminoplast functional group, epoxy group(ing), carboxyl and mixture thereof.In certain embodiments, polymer functional groups is hydroxyl, carboxyl, silanol groups, epoxy group(ing) and mixture thereof.

[0158] In one embodiment of the invention, the polymer is an acrylic polymer. The acrylic polymer preferably has a number average molecular weight of 500 to 20,000 and more preferably 1500 to 10,000. The number average molecular weight is determined by gel permeation chromatography of a sample dissolved in tetrahydrofuran using polystyrene or poly(methyl methacrylate) standards. Such polymers are well known in the art and can be prepared from monomers such as methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3,3,5-trimethylhexyl acrylate, 3,3,5-trimethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate or lauryl methacrylate, cycloalkyl acrylate and / or cycloalkyl methacrylate, such as cyclopentyl acrylate, cyclopentyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate, and vinyl aromatic hydrocarbons, such as vinyl toluene, α-methylstyrene and styrene, as well as amides or nitriles of acrylic acid or methacrylic acid, vinyl esters and vinyl ethers. Any crosslinkable functional group, such as hydroxyl, amine, glycidyl, carbamate, etc., can be incorporated into the ester portion of the acrylic monomer. Non-limiting examples of hydroxyl-functional acrylic monomers that can be used to form such polymers include hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and hydroxypropyl acrylate. Amino-functional acrylic monomers will include tert-butylaminoethyl methacrylate and tert-butylaminoethyl acrylate. Glycidyl groups can be incorporated, for example, by copolymerizing glycidyl methacrylate or allyl glycidyl ether.Other acrylic monomers having crosslinkable functionality in the ester portion of the monomer are also within the skill in the art.

[0159] Modified acrylic polymers can also be used as film-forming curable polymers in coating compositions. Such acrylic polymers can be polyester-modified acrylic polymers or polyurethane-modified acrylic polymers, as are well known in the art. Polyester-modified acrylic polymers modified with e-caprolactone are described in U.S. Patent No. 4,546,046 to Etzell et al., the disclosure of which is incorporated herein by reference. Polyurethane-modified acrylic polymers are also well known in the art. They are described, for example, in U.S. Patent No. 4,584,354, the disclosure of which is incorporated herein by reference.

[0160] Polyester can also be used as a binder resin in coating compositions. Polyester resins can be formulated as acid-functional or hydroxy-functional resins. The polyester can have an acid number of 20 to 100, or 20 to 80, or 20 to 40 mg KOH per gram. In another embodiment, the polyester can have a hydroxyl number of 25 to 300, or 25 to 150, or 40 to 100 mg KOH per gram. Methods for making polyester resins are well known. Typically, a polyol component and an acid and / or anhydride component or a polymerizable derivative such as a methyl ester are heated together, optionally with a catalyst, and usually accompanied by the removal of by-product water or methanol to drive the reaction to completion. The polyol component has an average functionality of at least two. The polyol component can contain monofunctional, difunctional, trifunctional, and higher functional alcohols. Diols are preferred, but when some branching of the polyester is desired, higher functional alcohols are included. Illustrative examples include, without limitation, alkylene glycols and polyalkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and hydroxyalkylated bisphenols. Alternatively, small amounts of trifunctional and higher functional alcohols such as glycerol, trimethylolpropane, trimethylolethane, or pentaerythritol may be used. The acid and / or anhydride component comprises a compound having an average of at least two carboxylic acid groups and / or anhydrides or lower alkyl (C1-C4, particularly methyl) esters of these. Dicarboxylic acids or anhydrides of dicarboxylic acids are preferred, but when some branching of the polyester is desired, higher functional acids and anhydrides can be used. Suitable polycarboxylic acids or anhydride compounds include, but are not limited to, those having 3 to 20 carbon atoms. Illustrative examples of suitable compounds include, but are not limited to, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, malonic acid, maleic acid, succinic acid, azelaic acid, glutaric acid, adipic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, dodecane-1,12-dicarboxylic acid, citric acid, trimellitic acid, and anhydrides thereof. Alternatively, monocarboxylic acids such as octanoic acid, nonanoic acid, stearic acid, and cyclohexanoic acid; and hydroxycarboxylic acids such as dimethylolpropionic acid; and combinations of these compounds.

[0161] Polyurethanes with crosslinkable functional groups such as hydroxyl groups are also well known in the art. They are prepared by chain extension reactions of polyisocyanates (e.g., hexamethylene diisocyanate, isophorone diisocyanate, MDI, etc.) and polyols (e.g., 1,6-hexanediol, 1,4-butanediol, neopentyl glycol, and any other substances mentioned as being useful for preparing polyesters and combinations thereof) and macromolecular diols such as polyester diols, polyether diols, and polycarbonate diols. They can be provided with crosslinkable functional groups by terminating the polyurethane chain with an excess of diols, polyamines, amino alcohols, etc.

[0162] Carbamate-functional polymers and oligomers may also be used as curable polymers, especially those having at least one primary carbamate group.

[0163] The carbamate functional example of the curable polymer used in the coating composition can be prepared in a variety of ways. For example, and using the situation of acrylic polymers, a kind of mode of preparing such polymers is to prepare monomers with carbamate functionality in the ester portion of the monomer, such as acrylic monomers. Such monomers are well known in the art and are described in, for example, U.S. Patents 3,479,328, 3,674,838, 4,126,747, 4,279,833 and 4,340,497, 5,356,669 and WO 94 / 10211, the disclosure of which is incorporated herein by reference. A kind of synthetic method relates to the reaction of hydroxy ester and urea, to form carbamoyloxy carboxylate (that is, carbamate-modified acrylic polymer). Another synthetic method makes α, β-unsaturated acid ester react with hydroxy carbamate to form carbamoyloxy carboxylate. Yet another technique involves forming a hydroxyalkyl carbamate by reacting a primary or secondary amine or a diamine with a cyclic carbonate, such as ethylene carbonate. The hydroxyl groups on the hydroxyalkyl carbamate are then esterified by reacting with acrylic acid or methacrylic acid to form a monomer. Other methods for preparing carbamate-modified acrylic monomers are described in the art and may also be used. If desired, the acrylic monomer can then be polymerized with other ethylenically unsaturated monomers using techniques well known in the art.

[0164] An alternative approach to preparing curable polymers for adhesives is to react an already formed polymer such as an acrylic polymer, a polyester polymer, or a polyurethane polymer with another component to form carbamate functional groups pendant to the polymer backbone, as described in U.S. Pat. No. 4,758,632. One technique for preparing such polymers involves thermally decomposing urea (to release ammonia and HNCO) in the presence of a hydroxyl functional acrylic polymer to form a carbamate functional polymer. Another technique involves reacting the hydroxyl groups of a hydroxyalkyl carbamate with the isocyanate groups of an isocyanate functional polymer to form a carbamate functional polymer. Isocyanate functional acrylic polymers are known in the art and are described, for example, in U.S. Pat. No. 4,301,257, the disclosure of which is incorporated herein by reference. Isocyanate vinyl monomers are well known in the art and include unsaturated m-tetramethylxylene isocyanate (available from American Cyanamid as (sold). Isocyanate-functional polyurethanes can be formed by using an equivalent excess of diisocyanates or by capping hydroxyl-functional prepolymers with polyisocyanates. Yet another technique is to react the cyclic carbonate groups on a cyclic carbonate-functional acrylic polymer with ammonia to form a carbamate-functional acrylic polymer. Cyclic carbonate-functional acrylic polymers are known in the art and are described, for example, in U.S. Patent No. 2,979,514, the disclosure of which is incorporated herein by reference. Another technique is to transcarbamylate the hydroxyl-functional polymer with an alkyl carbamate. A more difficult but feasible way to prepare such a polymer would be to transesterify it with a hydroxyalkyl carbamate.

[0165] The binder of the coating composition may further comprise a crosslinker.The crosslinker may be used in an amount of 10% to 60%, typically 15% to 55%, or 25% to 50%, all based on the total binder of the coating composition.

[0166] In certain embodiments, the reaction between the crosslinking agent and the polymer may be preferred to form an irreversible linkage. Examples of functional group "pairs" that produce thermally irreversible linkages are hydroxyl / isocyanate (blocked or unblocked), hydroxyl / epoxy, carbamate / aminoplast, carbamate / aldehyde, acid / epoxy, amine / cyclic carbonate, amine / isocyanate (blocked or unblocked), urea / aminoplast, and the like. Non-limiting examples of crosslinking agent binder resins include aminoplasts, blocked or unblocked polyisocyanates, polyepoxides, polycarboxylic acid or anhydride compounds, oligomers, or polymers, and polyurea compounds or oligomers.

[0167] In certain embodiments, the coating composition comprises an aminoplast as a crosslinking agent. Aminoplasts for the purposes of the present invention are materials obtained by reacting activated nitrogen with a relatively low molecular weight aldehyde, optionally further reacted with an alcohol (preferably a monoalcohol having one to four carbon atoms) to form an ether group. Preferred examples of activated nitrogen are activated amines such as melamine, benzoguanamine, cyclohexylcarboguanamine, and acetoguanamine; ureas, including urea itself, thiourea, ethyleneurea, dihydroxyethyleneurea, and guanylurea; glycolurils; amides such as dicyandiamide; and carbamate-functional compounds having at least one primary carbamate group or at least two secondary carbamate groups.

[0168] The activated nitrogen is reacted with a relatively low molecular weight aldehyde. The aldehyde may be selected from formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde, or other aldehydes used in the manufacture of aminoplast resins, although formaldehyde and acetaldehyde are preferred, especially formaldehyde. The activated nitrogen groups are at least partially alkanolated with the aldehyde and may be fully alkanolated; preferably, the activated nitrogen groups are fully alkanolated. This reaction may be acid-catalyzed, for example, as taught in U.S. Patent No. 3,082,180, the contents of which are incorporated herein by reference.

[0169] The hydroxyalkyl group formed by the reaction of activated nitrogen with the aldehyde can be partially or completely etherified with one or more monofunctional alcohols. Suitable examples of monofunctional alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butyl alcohol, benzyl alcohol, etc. Monofunctional alcohols having one to four carbon atoms and mixtures thereof are preferred. Etherification can be carried out, for example, by the methods disclosed in U.S. Patent Nos. 4,105,708 and 4,293,692, the disclosures of which are incorporated herein by reference.

[0170] Aminoplast can be at least partially etherified, and in various embodiments, aminoplast is fully etherified. For example, these aminoplast compounds can have a plurality of methylol and / or etherified methylol, hydroxybutyl or hydroxyalkyl, which can exist in any combination together with unsubstituted nitrogen and hydrogen. A non-limiting example of fully etherified melamine-formaldehyde resin is hexamethoxymethyl melamine. Aminoplast crosslinking agents can be used as crosslinking agents for carbamates, terminal ureas and hydroxy-containing polymers.

[0171] In certain embodiments, the coating composition comprises a polyisocyanate or a blocked polyisocyanate crosslinking agent. Useful polyisocyanate crosslinking agents include, but are not limited to, isocyanurates, biuret, allophanate, uretdione compounds, and isocyanate functional prepolymers, such as the reaction product of one mole of triol and three moles of diisocyanate. Polyisocyanates can be blocked with lower alcohols, oximes, or other such materials that volatilize to regenerate isocyanate groups at the curing temperature.

[0172] The isocyanate or blocked isocyanate may be used in an equivalent ratio of 0.1 to 1.1, or in an equivalent ratio of 0.5 to 1.0, per equivalent of the functional group reactive therewith available from the cross-linkable binder resin.

[0173] Epoxide-functional crosslinking agents can be used with carboxyl or amine-functional crosslinkable resins. Illustrative examples of epoxide-functional crosslinking agents are all known epoxide-functional polymers and oligomers. Non-limiting examples of epoxide-functional crosslinking agents are polyglycidyl ethers, polyglycidyl esters, glycidyl methacrylate polymers, and isocyanurate-containing epoxide-functional materials such as triglycidyl isocyanurate and the reaction products of trimers of glycidol with isocyanate-functional isocyanurates such as isophorone diisocyanate (IPDI).

[0174] Preferably, the amount of component (ii) in the coating composition of the present invention is in the range of 10% to 30% by weight (e.g., 10%, 15%, 20%, 25% or 30% by weight), preferably in the range of 12% to 20% by weight, based on the weight of the coating composition.

[0175] carbon black

[0176] The coating composition of the present invention comprises carbon black as component (iii).

[0177] Carbon black is usually produced by thermal decomposition of hydrocarbons (liquid and gaseous hydrocarbons) under controlled conditions, i.e., by oxidative pyrolysis process, most commonly by incomplete combustion of raw materials. The most common source of raw materials for the production of carbon black is a heavy stream of hydrocarbons derived from coal or crude oil processing, which is referred to as carbon black oil (CBO). CBO usually mainly contains polycyclic aromatic hydrocarbon feedstock oil. Natural gas, distillates from coal tar (carbon chemical oil) or residual oil produced by catalytic cracking of petroleum fractions and olefins manufactured by thermal cracking of naphtha or gasoline (petrochemical oil) are the key sources of this raw material. Production methods are different based on the mode of arranging heat and decomposition stage. The gained carbon black product (for example, lamp black, gas black or furnace black) is filtered from the exhaust gas of production process. Manufacturing methods include furnace black, gas black, lamp black and thermal cracking carbon black method.

[0178] Over 98% of the world's annual carbon black production is achieved through the furnace black process. The furnace black process is continuous and uses liquid and gaseous hydrocarbons as feedstock. The heated liquid feedstock is sprayed into a heat source generated by the combustion of natural gas or fuel oil and preheated air. Because it occurs at very high temperatures, the reaction is confined to a refractory-lined furnace. After the carbon black is formed, the process mixture is quenched by injecting water. This also prevents any unwanted secondary reactions. The carbon black-laden gas then passes through a heat exchanger for further cooling while simultaneously heating the preheated air required for process combustion. Bag filters separate the carbon black particles from the gas stream. The gases produced by this reaction are flammable and, in most cases, are burned in boilers to generate steam and / or electricity, or alternatively, are flammable. The carbon black collected by the filter has a very low bulk density and, depending on the application, is often pelletized or further densified to facilitate onward processing.

[0179] The gas black process uses vaporized oil as a feedstock. The oil is heated and the resulting vapor is carried by hydrogen-rich gas into a tube equipped with multiple burners. These individual particles impact the surface of a water-cooled rotating drum. A portion of the resulting carbon black is deposited on the rollers, while the remainder enters a filter system. The two carbon black streams are then combined. Onward processing is similar to the furnace black process. The thermal cracking carbon black process for producing carbon black is a semi-batch process, with natural gas being the most common feedstock, although higher hydrocarbon oils can also be used. It involves thermal decomposition of the feedstock in a refractory-lined vessel, which breaks down the natural gas into carbon black and hydrogen.

[0180] Lamp black is a specialty carbon black produced by the incomplete combustion of carbon black oil similar to the furnace black process, except that the combustion occurs in large, open, shallow vessels. Lamp black is the oldest industrial-scale carbon black production method still in use.

[0181] Carbon black suitable for coating compositions can be used in the present invention. A skilled person can select appropriate carbon black according to the actual application.

[0182] In a preferred embodiment of the present invention, the carbon black used in the coating composition of the present invention is gas black.

[0183] In a preferred embodiment of the present invention, the carbon black used in the present invention has an oil absorption rate measured according to GB / T5211.15-2014 within the range of 100 to 200 mL / 100 g, preferably 130 to 170 mL / 100 g, more preferably 140 to 160 mL / 100 g.

[0184] In a preferred embodiment of the present invention, the carbon black used in the coating composition of the present invention is CI Pigment Black 7, such as FW2 from Evonik Industries AG, Germany.

[0185] Preferably, the amount of component (iii) in the coating composition of the present invention is in the range of 0.05% to 0.3% by weight (e.g., 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25% or 0.3% by weight), preferably in the range of 0.05% to 0.2% by weight, based on the weight of the coating composition.

[0186] aluminum

[0187] The coating composition of the present invention comprises aluminum as component (iv). Aluminum can be used in any suitable form, and this form is suitable as the component of coating composition and can be selected by technical personnel according to actual application. Preferably, aluminum can be used in the present invention in powder form. More preferably, the D50 particle size of the aluminum used in the present invention is in the range of 5 to 40 μm, preferably in the range of 10 to 35 μm. For example, aluminum can be commercially available those, such as Stapa Hydrolan 2154 from ECKART, Germany.

[0188] Preferably, the amount of component (iv) in the coating composition of the present invention is in the range of 0.5% to 2.0% by weight, preferably in the range of 0.8% to 1.8% by weight, based on the weight of the coating composition.

[0189] water

[0190] The coating composition of the present invention comprises water as component (v). Component (v) may be selected from the group consisting of deionized water, distilled water, and pure water. Preferably, component (v) is deionized water.

[0191] Preferably, the amount of component (v) in the coating composition of the present invention is in the range of 20% to 70% by weight (e.g., 20%, 30%, 40%, 50%, 60% or 70% by weight), preferably in the range of 30% to 60% by weight, more preferably in the range of 50% to 65% by weight, based on the weight of the coating composition.

[0192] solvent

[0193] The coating composition of the present invention may further comprise one or more solvents as component (vi). Non-limiting examples of suitable solvents include aromatic hydrocarbons, ketones, esters, glycol ethers, and glycol ether esters. Specific examples include, but are not limited to, methyl ethyl ketone, methyl isobutyl ketone, n-amyl acetate, ethylene glycol butyl ether and ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, xylene, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, N-methyl pyrrolidone, N-ethyl pyrrolidone, aromatic hydrocarbons 100, aromatic hydrocarbons 150, naphtha, mineral spirits, butyl glycol, and the like.

[0194] In the present invention, the term "solvent" does not include water.

[0195] Preferably, the amount of component (vi) in the coating composition of the present invention is in the range of 10% to 30% by weight (e.g., 10%, 15%, 20%, 25% or 30% by weight), preferably in the range of 10% to 16% by weight, based on the weight of the coating composition.

[0196] additive

[0197] The coating composition of the present invention may further comprise an additive as component (vii), preferably, the additive is selected from the group consisting of defoamers, UV absorbers, rheology control agents, antioxidants, surface conditioners, dispersants, anti-settling agents, and pH adjusters.

[0198] The pH adjuster can be selected from the group consisting of: bases and amines, such as ammonia, triethylamine, and alcohol amines, preferably alcohol amines with no or light odor. In a preferred embodiment of the present invention, the pH adjuster in the coating composition of the present invention is AMP-95 from ANGUS Chemical Company, USA.

[0199] The amount of component (vii) in the coating composition of the present invention can be determined by a skilled person according to actual application. Preferably, the amount of component (vii) in the coating composition of the present invention can be in the range of 0-10% by weight, preferably in the range of 0-8% by weight, based on the weight of the coating composition.

[0200] In an embodiment, the coating composition of the present invention comprises the following components:

[0201] (i) a pigment, wherein the pigment is a pigment composition of the present invention, which is contained in an amount of 0.3% to 3% by weight, preferably 0.5% to 2% by weight, based on the weight of the coating composition;

[0202] (ii) a binder, which is contained in an amount of 10 to 30% by weight, preferably 12 to 20% by weight, based on the weight of the coating composition;

[0203] (iii) carbon black, preferably gas black, contained in an amount of 0.05 to 0.3% by weight, preferably 0.05 to 0.2% by weight, based on the weight of the coating composition;

[0204] (iv) aluminum, which is contained in an amount of 0.5 to 2.0% by weight, preferably 0.8 to 1.8% by weight, based on the weight of the coating composition; and

[0205] (v) water, which is contained in an amount of 20 to 70% by weight, preferably in an amount of 30 to 60% by weight, more preferably in the range of 50-65% by weight, based on the weight of the coating composition,

[0206] Preferably, the composition has a pH in the range of 7.5 to 8.5, preferably 7.8 to 8.2.

[0207] In another embodiment, the coating composition of the present invention comprises the following components:

[0208] (i) a pigment, wherein the pigment is a pigment composition of the present invention, which is contained in an amount of 0.3% to 3% by weight, preferably 0.5% to 2% by weight, based on the weight of the coating composition;

[0209] (ii) a binder, which is contained in an amount of 10 to 30% by weight, preferably 12 to 20% by weight, based on the weight of the coating composition;

[0210] (iii) carbon black, preferably gas black, contained in an amount of 0.05 to 0.3% by weight, preferably 0.05 to 0.2% by weight, based on the weight of the coating composition;

[0211] (iv) aluminum, which is contained in an amount of 0.5 to 2.0% by weight, preferably in an amount of 0.8 to 1.8% by weight, based on the weight of the coating composition;

[0212] (v) water, which is contained in an amount of 20% to 70% by weight, preferably in an amount of 30% to 60% by weight, more preferably in the range of 50%-65% by weight, based on the weight of the coating composition; and

[0213] (vi) a solvent, which is contained in an amount of 10 to 30% by weight, preferably 10-16% by weight, based on the weight of the coating composition,

[0214] Preferably, the composition has a pH in the range of 7.5 to 8.5, preferably 7.8 to 8.2.

[0215] In another embodiment, the coating composition of the present invention comprises the following components:

[0216] (i) a pigment, wherein the pigment is a pigment composition of the present invention, which is contained in an amount of 0.3% to 3% by weight, preferably 0.5% to 2% by weight, based on the weight of the coating composition;

[0217] (ii) a binder, which is contained in an amount of 10% to 30% by weight, preferably 12% to 20% by weight, based on the weight of the coating composition;

[0218] (iii) carbon black, preferably gas black, contained in an amount of 0.05% to 0.3% by weight, preferably 0.05% to 0.2% by weight, based on the weight of the coating composition;

[0219] (iv) aluminum, which is contained in an amount of 0.5% to 2.0% by weight, preferably in an amount of 0.8% to 1.8% by weight, based on the weight of the coating composition;

[0220] (v) water, which is contained in an amount ranging from 20% to 70% by weight, preferably from 30% to 60% by weight, more preferably from 50% to 65% by weight, based on the weight of the coating composition;

[0221] (vi) a solvent, which is contained in an amount of 10% to 30% by weight, preferably 10% to 16% by weight, based on the weight of the coating composition; and

[0222] (vii) additives, which are contained in an amount of 0-10% by weight, preferably 0-8% by weight, based on the weight of the coating composition; preferably, the additives are selected from the group consisting of defoamers, UV absorbers, rheology control agents, antioxidants, surface conditioners, dispersants, anti-settling agents, and pH adjusters,

[0223] Preferably, the composition has a pH in the range of 7.5 to 8.5, preferably 7.8 to 8.2.

[0224] The coating composition of the present invention can be prepared by a skilled person using methods known in the art. For example, the coating composition of the present invention can be prepared by adding all components simultaneously under stirring.

[0225] Preferably, before forming coating composition of the present invention, when pigment, carbon black and / or aluminium are used in the form of dry powder or granules, they are pre-dispersed in a binder and / or solvent respectively to form a pre-dispersion. The binder and solvent for forming the pre-dispersion are those that are applicable to the present invention. For example, they can be the binder and solvent disclosed above. Preferably, the binder and solvent for forming the pre-dispersion are a part of the binder and solvent in the coating composition of the present invention. In a preferred embodiment, coating composition of the present invention is prepared by a method comprising the following steps:

[0226] Taking a portion of the binder for the coating composition and a portion of the solvent for the coating composition to form a mixture and pre-dispersing aluminum into the mixture under stirring to form an aluminum pre-dispersion, wherein the weight ratio of aluminum:binder:solvent is preferably 1:1:1;

[0227] Prepare carbon black predispersion and pigment predispersion in the same manner;

[0228] The remaining binder and solvent are added to the aluminum pre-dispersion with stirring to form a dispersion; and then

[0229] A carbon black predispersion and a pigment predispersion are added to the dispersion to form a coating composition.

[0230] The coating composition of the present invention produces or can produce a coating film having color transfer properties. The coating film has a unique gray color transfer from blue to gray to red when the viewing angle is changed. Specifically, the coating film has a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV, and V, preferably at least four of conditions I, II, III, IV, and V, and more preferably all of conditions I, II, III, IV, and V:

[0231]

[0232] The coating film obtained from the coating composition of the present invention has a CIEHLC color space, wherein the C*, h° values ​​are as defined in at least three of conditions VI, VII, VIII, XI and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0233]

[0234] coating

[0235] The present invention further provides a coating film having a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV, and V, preferably at least four of conditions I, II, III, IV, and V, and more preferably all of conditions I, II, III, IV, and V:

[0236]

[0237] The present invention further provides a coating film having a CIEHLC color space, wherein the C* and h° values ​​are as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0238]

[0239] In an embodiment of the present invention, the coating film of the present invention is obtained from the pigment composition of the present invention.

[0240] Colored products

[0241] The present invention further relates to a colored article, wherein the colored article has a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV and V, preferably at least four of conditions I, II, III, IV and V, and more preferably all of conditions I, II, III, IV and V:

[0242]

[0243] The present invention further relates to a colored article, wherein the colored article has a CIEHLC color space, wherein the C* and h° values ​​are as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0244]

[0245] The colored article of the present invention is an article obtained by coating an article with the coating composition of the present invention or an article having the coating film of the present invention.

[0246] In an embodiment, the colored article of the present invention comprises a basecoat, a coating film, and optionally a clearcoat.

[0247] The colored article of the present invention can be obtained by a skilled person using conventional procedures. In an embodiment of the present invention, the colored article of the present invention is prepared by a method comprising the following steps:

[0248] Provide products,

[0249] applying a primer on the surface of the article, and then drying the primer to form a primer film, preferably drying the primer at room temperature for, for example, 5 minutes, to form a primer film preferably having a thickness in the range of, for example, 12 to 15 μm; and

[0250] The coating composition of the present invention is applied to the formed primer film, and then the coating composition is dried to form a coating film, preferably the coating composition is dried at room temperature for, for example, 5 minutes and then at, for example, 80° C. for, for example, 5 minutes to form a coating film preferably having a thickness in the range of, for example, 12 to 15 μm, thereby obtaining the colored article of the present invention.

[0251] Preferably, a clear coating is further applied on the formed coating film, and then the clear coating is preferably dried at room temperature for, for example, 7 minutes, and then at, for example, 140° C. for 30 minutes to form a clear coating film preferably having a thickness in the range of 40 to 45 μm.

[0252] In an embodiment of the present invention, the colored article is prepared by a method comprising the steps of:

[0253] (1) applying a primer on the surface of an article, and then drying the primer at room temperature for 5 minutes to form a primer film preferably having a thickness in the range of 12 to 15 μm; and

[0254] (2) The coating composition of the present invention is applied to the primer film formed in step (1), and the coating composition is then dried at room temperature for 5 minutes and then at 80° C. for 5 minutes to form a coating film preferably having a thickness in the range of, for example, 12 to 15 μm, thereby forming a colored article.

[0255] In an embodiment of the present invention, the colored article is prepared by a method comprising the steps of:

[0256] (1) applying a primer on the surface of an article, and then drying the primer at room temperature for 5 minutes to form a primer film preferably having a thickness in the range of 12 to 15 μm;

[0257] (2) applying the coating composition of the present invention on the primer film formed in step (1), and then drying the coating composition at room temperature for 5 minutes and then at 80° C. for 5 minutes to form a coating film preferably having a thickness in the range of 12 to 15 μm; and

[0258] (3) A clear coating is applied on the coating film formed in step (2), and then the clear coating is dried at room temperature for 7 minutes and then at 140° C. for 30 minutes to form a clear coating film preferably having a thickness in the range of 40 to 45 μm, thereby forming a colored article.

[0259] Many different types of articles can be used in the present invention, including metal or metal articles, such as bare steel, phosphated steel, galvanized steel, or aluminum; and non-metal articles, such as plastics and composites.

[0260] The primer used in the present invention may be an electrodeposition (electrocoating) primer. The electrodeposition composition may be any electrodeposition composition used in, for example, motor vehicle coating operations. Non-limiting examples of electrocoating compositions include those sold by BASF Corporation. Electrocoating compositions, such as 500. The electrodeposition coating bath typically comprises an aqueous dispersion or emulsion comprising a primary film-forming epoxy resin having ionic stability (e.g., salt-forming amine groups) in water or a mixture of water and an organic solvent. Emulsified with the primary film-forming resin is a crosslinking agent that can react with functional groups on the primary resin under appropriate conditions (e.g., under the application of heat) and thereby cure the coating. Suitable examples of crosslinking agents include, but are not limited to, blocked polyisocyanates. The electrodeposition coating composition typically comprises one or more pigments, catalysts, plasticizers, coalescing aids, defoaming aids, flow control agents, wetting agents, surfactants, UV absorbers, HALS compounds, antioxidants, and other additives.

[0261] The clear coating suitable for the present invention can be selected by a skilled person. For example, it can be the clear coating composition FF99-0345 commercially available from BASF.

[0262] The present invention provides a unique gray color transmission using a combination of the following specific pigments: 1) a high-chroma blue pigment with a light green hue that is the primary color contributor at a 15° viewing angle; 2) a magenta pigment with medium chroma and translucency that dilutes the blue at a 45° viewing angle without affecting the color at a 15° viewing angle; and 3) an iron oxide red opaque pigment that provides a maroon hue without haze at a 75° viewing angle. This does not rely on optical effect pigments, thus avoiding the drawbacks caused by optical effect pigments, such as pigment orientation issues, color quality issues, and batch-to-batch color stability issues, and enables stable and widespread application of the pigment and coating compositions of the present invention, such as in the mass production of target products (e.g., automobiles and household appliances). Furthermore, when a product coated with the coating composition of the present invention is damaged, such as by being cut or scratched, it can be easily repaired with the coating composition to restore its original appearance.

[0263] Example

[0264] Example 1

[0265] A metallic effect coating composition comprising

[0266] (A) a pigment composition comprising:

[0267] (A-1) yellow-red pigment;

[0268] (A-2) magenta pigment; and

[0269] (A-3) green-blue pigment,

[0270] (B) adhesive;

[0271] (C) carbon black, preferably gas black; and

[0272] (D) aluminum, wherein the sum of the weight percentages of components (A-1), (A-2) and (A-3) based on the total weight of component (A) is at least 80%, preferably at least 95% and more preferably 100% by weight.

[0273] Example 2

[0274] The coating composition according to embodiment 1, wherein the component (A) comprises

[0275] 20 to 60%, preferably 40 to 60%, by weight of component (A-1),

[0276] 10 to 40%, preferably 10 to 20%, by weight of component (A-2), and

[0277] 20 to 50%, preferably 20 to 40% by weight of component (A-3).

[0278] Example 3

[0279] The coating composition according to any one of embodiments 1 to 2, wherein

[0280] The component (A-1) is one selected from the following: CI Pigment Red 101 and CI Pigment Red 254,

[0281] The component (A-2) is one selected from the following: CI Pigment Red 122, CI Pigment Red 202, CI Pigment Violet 19, and a mixture of CI Pigment Red 177 and CI Pigment Violet 23 in a weight ratio of 1:10 to 10:1 and preferably 1:10 to 2:1, and

[0282] The component (A-3) is one selected from the group consisting of CI Pigment Blue 15, a mixture of CI Pigment Blue 15 and CI Pigment Green 7 in a weight ratio of 1:2 to 2:1, more preferably 1:1.2 to 1.2:1, and a mixture of CI Pigment Blue 15 and CI Pigment Green 36 in a weight ratio of 1:1 to 25:1 and preferably 1:1 to 20:1, wherein the component (A-3) is preferably selected from a mixture of CI Pigment Blue 15 and CI Pigment Green 7 or a mixture of CI Pigment Blue 15 and CI Pigment Green 36.

[0283] Example 4

[0284] The coating composition according to any one of embodiments 1 to 3, comprising 0.3% to 3% and preferably 0.5% to 2% by weight of component (A), based on the total weight of the coating composition.

[0285] Example 5

[0286] The coating composition according to any one of embodiments 1 to 4, wherein the binder is at least three selected from the group consisting of polyester, polyurethane, poly(meth)acrylate, cellulose acetate butyrate resin, and melamine resin.

[0287] Example 6

[0288] The coating composition according to any one of embodiments 1 to 5, wherein the coating composition comprises

[0289] 10% to 30%, preferably 12% to 20% by weight of component (B);

[0290] 0.05% to 0.3%, preferably 0.05% to 0.2% by weight of component (C); and

[0291] 0.5% to 2.0%, preferably 0.8% to 1.8% by weight of component (D).

[0292] Example 7

[0293] The coating composition of any one of embodiments 1 to 6, further comprising 20% ​​to 70%, preferably 30% to 65%, and more preferably 50% to 65% by weight of water based on the total weight of the coating composition.

[0294] Example 8

[0295] The coating composition of any one of embodiments 1 to 7, further comprising 10% to 30%, preferably 10% to 16% by weight of a solvent based on the total weight of the coating composition.

[0296] Example 9

[0297] The coating composition according to any one of embodiments 1 to 8, further comprising at least three additives selected from the group consisting of a defoamer, a UV absorber, a rheology control agent, an antioxidant, a surface conditioner, a dispersant, an anti-settling agent, and a pH adjuster, wherein the amount of the additives is no more than 10% by weight and preferably no more than 8% by weight based on the total weight of the coating composition.

[0298] Example 10

[0299] The coating composition according to any one of embodiments 1 to 9, wherein it has a pH value in the range of 7.5 to 8.5 and preferably 7.8 to 8.2.

[0300] Example 11

[0301] The coating composition according to any one of embodiments 1 to 10, wherein the coating composition is capable of forming a coating film having a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV, and V, preferably at least four of conditions I, II, III, IV, and V, and more preferably all of conditions I, II, III, IV, and V:

[0302]

[0303] Example 12

[0304] The coating composition according to any one of embodiments 1 to 11, wherein the coating composition is capable of forming a coating film having a CIEHLC color space, wherein the C*, h° values ​​are as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0305]

[0306]

[0307] Example 13

[0308] A coating film obtained from the coating composition according to any one of embodiments 1 to 10, wherein the CIELAB color space of the coating film has L*, a*, b* values ​​as defined in at least three of conditions I, II, III, IV and V, preferably at least four of conditions I, II, III, IV and V, and more preferably all of conditions I, II, III, IV and V:

[0309]

[0310] Example 14

[0311] A coating film obtained from the coating composition according to any one of embodiments 1 to 10, wherein the CIEHLC color space of the coating film has C*, h° values ​​as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

[0312]

[0313]

[0314] Examples

[0315] The present invention will be better understood in view of the following non-limiting examples. The examples do not limit the scope of the invention as described and claimed.

[0316] Preparation of staining plates

[0317] In order to measure the CIELAB color space, a series of color plates were prepared.

[0318] In the examples, the prepared coating composition was used as a primer. In the method for preparing the tinted panels, the primer (if any) and the undercoat were applied by a Bell-bell spray primer and undercoat application method with the following parameters:

[0319]

[0320] The clearcoat (if any) is applied by a process having the following parameters:

[0321]

[0322] Measurement of CIELAB and CIEHLC color spaces

[0323] The CIELAB and CIEHLC color spaces of each tinted plate were measured by a BYK mac i from BYK-Chemie GmbH with 45° illumination using a D65 illuminant and observation angles of 15°, 25°, 45°, 75° and 110°.

[0324] Materials used in the examples

[0325] The materials used in the examples are listed as follows:

[0326]

[0327]

[0328]

[0329] Example 1-16

[0330] A series of coating compositions were prepared according to the components and amounts provided in Tables 1 and 2, wherein the pH of each resulting coating composition was adjusted to 8.2. The resulting coating compositions were applied as basecoats.

[0331] Table 1

[0332]

[0333]

[0334] Table 2

[0335]

[0336] The colored plate in this example was prepared by a method comprising the following steps:

[0337] (1) applying a primer on a substrate plate, and then drying the primer at room temperature for 5 minutes to form a primer film having a thickness of 12 μm on the substrate plate;

[0338] (2) applying the obtained coating composition on the primer film, and then drying the coating composition at room temperature for 5 minutes, and then at 80° C. for 5 minutes to form a coating film having a thickness of 12 μm; and

[0339] (3) A clear coating material was applied on the coating film, and then the clear coating material was dried at room temperature for 7 minutes and then at 140° C. for 30 minutes to form a clear coating film having a thickness of 40 μm, thereby forming a colored plate.

[0340] The coating film obtained from each of the obtained coating compositions completely hid the color of the underlying basecoat film.

[0341] The measured CIELAB and CIEHLC color spaces for each of the tinted plates prepared from Examples 1 to 16 are provided below:

[0342]

[0343]

[0344]

[0345]

[0346] Example 17

[0347] To test the effect of clear coating, tinted panel 1-C# was prepared by a process comprising the following steps:

[0348] (1) applying a primer on a substrate plate, and then drying the primer at room temperature for 5 minutes to form a primer film having a thickness of 12 μm on the substrate plate; and

[0349] (2) Coating composition 1 in Table 1 was applied on the primer film, and then the coating composition was dried at room temperature for 5 minutes and then at 80° C. for 5 minutes to form a coating film having a thickness of 12 μm, thereby obtaining a colored plate 1-C#.

[0350] The measured CIELAB and CIEHLC color spaces of the tinted plate 1-C# and the tinted plate 1# prepared in Example 1 are compared as follows:

[0351]

[0352] The measured CIELAB and CIEHLC color spaces of Color Plate #1 are provided below.

[0353]

[0354] It can be seen that the CIELAB and CIEHLC color spaces of the obtained tint plates I and II remain essentially identical to each other regardless of the presence or absence of a clear coating.

Claims

1. A metal effect coating composition comprising (A) a pigment composition comprising: (A-1) yellow-red pigment; (A-2) magenta pigment; and (A-3) greenish blue pigment, (B) adhesive; (C) carbon black, preferably gas black; and (D) aluminum, wherein the sum of the weight percentages of components (A-1), (A-2) and (A-3) based on the total weight of component (A) is at least 80%, preferably at least 95% and more preferably 100% by weight.

2. The coating composition according to claim 1, wherein The component (A) comprises based on the total weight of the component (A) 20 to 60%, preferably 40 to 60%, by weight of component (A-1), 10 to 40%, preferably 10 to 20%, by weight of component (A-2), and 20 to 50%, preferably 20 to 40% by weight of component (A-3).

3. The coating composition according to any one of claims 1 to 2, wherein The component (A-1) is one selected from the following: CI Pigment Red 101 and CI Pigment Red 254, The component (A-2) is one selected from the group consisting of CI Pigment Red 122, CI Pigment Red 202, CI Pigment Violet 19, and a mixture of CI Pigment Red 177 and CI Pigment Violet 23 in a weight ratio of 1:10 to 10:1 and preferably 1:10 to 2:1, and The component (A-3) is one selected from the group consisting of CI Pigment Blue 15, a mixture of CI Pigment Blue 15 and CI Pigment Green 7 in a weight ratio of 1:2 to 2:1, more preferably 1:1.2 to 1.2:1, and a mixture of CI Pigment Blue 15 and CI Pigment Green 36 in a weight ratio of 1:1 to 25:1 and preferably 1:1 to 20:1, wherein the component (A-3) is preferably selected from a mixture of CI Pigment Blue 15 and CI Pigment Green 7 or a mixture of CI Pigment Blue 15 and CI Pigment Green 36.

4. The coating composition according to any one of claims 1 to 3, wherein It contains 0.3 to 3% and preferably 0.5 to 2% by weight of component (A), based on the total weight of the coating composition.

5. The coating composition according to any one of claims 1 to 4, wherein The binder is at least three selected from the group consisting of polyester, polyurethane, poly(meth)acrylate, cellulose acetate butyrate resin, and melamine resin.

6. The coating composition according to any one of claims 1 to 5, wherein It comprises based on the total weight of the coating composition 10% to 30%, preferably 12% to 20% by weight of component (B); 0.05% to 0.3%, preferably 0.05% to 0.2% by weight of component (C); and 0.5% to 2.0%, preferably 0.8% to 1.8% by weight of component (D).

7. The coating composition according to any one of claims 1 to 6, further comprising 20% ​​to 70%, preferably 30% to 65% and more preferably 50% to 65% by weight of water based on the total weight of the coating composition.

8. The coating composition according to any one of claims 1 to 7, further comprising 10 to 30%, preferably 10 to 16% by weight of a solvent, based on the total weight of the coating composition.

9. The coating composition according to any one of claims 1 to 8, further comprising at least three additives selected from the group consisting of a defoamer, a UV absorber, a rheology control agent, an antioxidant, a surface conditioner, a dispersant, an anti-settling agent, and a pH adjuster, wherein the amount of the additives does not exceed 10% by weight and preferably does not exceed 8% by weight based on the total weight of the coating composition.

10. The coating composition according to any one of claims 1 to 9, wherein The coating composition has a pH value in the range of 7.5 to 8.5 and preferably 7.8 to 8.

2.

11. The coating composition according to any one of claims 1 to 10, wherein The coating composition is capable of forming a coating film having a CIELAB color space, wherein the L*, a*, b* values ​​are as defined in at least three of conditions I, II, III, IV, and V, preferably at least four of conditions I, II, III, IV, and V, and more preferably all of conditions I, II, III, IV, and V: 。 12. The coating composition according to any one of claims 1 to 11, wherein The coating composition is capable of forming a coating film having a CIEHLC color space, wherein the C* and h° values ​​are as defined in at least three of conditions VI, VII, VIII, IX, and X, preferably at least four of conditions VI, VII, VIII, IX, and X, and more preferably all of conditions VI, VII, VIII, IX, and X:

13. A coating film obtained from the coating composition according to any one of claims 1 to 10, wherein The CIELAB color space of the coating film has L*, a*, b* values ​​as defined in at least three of conditions I, II, III, IV and V, preferably at least four of conditions I, II, III, IV and V, and more preferably all of conditions I, II, III, IV and V: 。 14. A coating film obtained from the coating composition according to any one of claims 1 to 10, wherein The CIEHLC color space of the coating film has C*, h° values ​​as defined in at least three of conditions VI, VII, VIII, IX and X, preferably at least four of conditions VI, VII, VIII, IX and X, and more preferably all of conditions VI, VII, VIII, IX and X:

Images