Metallic effect coating compositions and their applications

Abstract

The present invention relates to a coating composition that provides characteristic gray color travel, comprising (A) a pigment composition containing the following components: (A-1) a yellowish red pigment, (A-2) a magenta pigment, and (A-3) a greenish blue pigment; (B) a binder; (C) carbon black, preferably gas black; and (D) aluminum, wherein the sum of the mass percentages of components (A-1), (A-2), and (A-3) is at least 80 mass %, preferably at least 95 mass %, and more preferably 100 mass %, based on the total mass of component (A). The present invention also relates to a coating film having the characteristic gray color travel and application of the coating composition. The characteristic gray color travel obtained by the present invention is a characteristic gray color travel of blue-gray-red hues as the observation angle changes.

Description

[Technical Field]

[0001] The present invention relates to coating compositions, and more particularly to metallic effect coating compositions for use on automobiles that are capable of forming coating films with color travel properties. [Background technology]

[0002] Coating compositions capable of forming coating films having color travel properties (also referred to as color-traveling coating compositions) are known and widely used in various applications. For example, in the automotive field, color-traveling coating compositions are mainly applied to high-end customization of luxury brand cars, allowing the cars to have distinctive colors. The color travel properties of the formed color-traveling coating films are produced by a specific type of pigment composition, called a color-traveling pigment composition, contained in the color-traveling coating composition.

[0003] Traditionally, color travel pigment compositions (e.g., those applicable to automobiles) are made with pigments with special optical effects, developed based on strict control of the particle size of the pigment particles and the diameter-to-thickness ratio of the substrate used, precise control of the coating thickness through multiple layers, and the use of multiple metal oxides, to achieve the desired color intensity and color travel properties. However, by using such optical effect pigments, these color travel pigment compositions have several drawbacks, mainly including: 1) poor hiding power of the optical effect pigments; the uniformity of the thickness of the formed coating layer 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 deviation; 3) difficult and complicated control of the optical effect; and 4) a color travel pigment composition made from optical effect pigments is likely to settle. These drawbacks generally result in problems in terms of color quality and color stability. For example, there may be color differences between batches of pigment compositions, and if a color travel coating product (e.g., a color travel coated car) is damaged, such as cut or scratched, it is almost impossible to repair and restore the original appearance. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need to provide a new type of coating composition that includes a color travel pigment composition and is capable of forming coating films with color travel properties, which coating films have distinctive colors and significantly improved color quality and batch-to-batch color stability compared to those formed using optical effect pigments. [Means for solving the problem]

[0005] In one aspect, the present invention provides a composition comprising the following components: (A) a pigment composition comprising: (A-1) a yellowish red pigment, (A-2) magenta pigment, and (A-3) a greenish blue pigment, (B) a binder; (C) carbon black, preferably gas black, and (D) Aluminum Including, A metallic effect coating composition is provided, wherein the sum of the mass percentages of components (A-1), (A-2) and (A-3) is at least 80 mass %, preferably at least 95 mass %, and more preferably 100 mass %, relative to the total mass of component (A).

[0006] In another aspect, the present invention provides a coating film obtained from the coating composition of the present invention, having a CIELAB color space having L*, a*, b* values ​​defined by at least three of conditions I, II, III, IV, and V, preferably at least four of conditions I, II, III, IV, and V, more preferably all of conditions I, II, III, IV, and V:

[0007] [Table 1]

[0008] In another aspect, the present invention provides a coating film obtained from the coating composition of the present invention, having a CIE HLC color space having C*, h° values ​​as defined by 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:

[0009] [Table 2]

[0010] In a further aspect, the present invention provides uses of the coating compositions of the present invention in areas such as construction, industry, automotive, appliances, leather, ink, textiles and paper.

[0011] The coating film obtained from the coating composition of the present invention has a characteristic gray color travel of blue-gray-red hues as the observation angle changes. The coating composition of the present invention achieves the required color travel properties without using optical effect pigments, thereby avoiding drawbacks such as poor color quality and batch-to-batch color variation. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will now be described in more detail, illustrating some, but not all, embodiments of the invention. Indeed, the present 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.

[0013] In the context of this disclosure, the terms "a," "an," and "the," when used to define a term, include both the plural and the singular form of that term.

[0014] In the context of the present disclosure, the terms "comprise," "comprising," and the like are used interchangeably with "contain," "containing," and the like, and are to be interpreted openly and without limitation. That is, for example, additional components or elements may be present. The expressions "consists of" or "consists essentially of" or equivalent terms, when used, may be encompassed within "comprise" or equivalent terms.

[0015] In the context of this disclosure, for convenience, "resin" is used to encompass resins, oligomers, and polymers. "Binder" refers to the film-forming component of the coating composition. Thus, resins, crosslinkers, and other film-formers are part of the binder, but solvents, pigments, additives such as antioxidants, light stabilizers (e.g., hindered amine light stabilizers, HALS), UV absorbers, etc. are not part of the binder.

[0016] 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 CIE) in 1976. It describes color using three values: L*, the perceived lightness, and a* and b*, the four colors native to human vision: red, green, blue, and yellow.

[0017] In the context of this disclosure, a "CIE HLC 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 rectangular coordinates a* and b*. The CIELAB lightness L* remains unchanged. The conversion from a* and b* to C* and h° is done as follows: C* = (a* 2 +b* 2 ) 1 / 2 , h o =atan(b* / a*).

[0018] Coating Composition The present invention relates to a composition comprising the following components: (A) a pigment composition comprising: (A-1) a yellowish red pigment, (A-2) magenta pigment, and (A-3) a greenish blue pigment, (B) a binder; (C) carbon black, preferably gas black, and (D) Aluminum Including, A metallic effect coating composition is provided, wherein the sum of the mass percentages of components (A-1), (A-2) and (A-3) is at least 80 mass %, preferably at least 95 mass %, and more preferably 100 mass %, relative to the total mass of component (A).

[0019] The coating composition of the present invention is capable of forming a coating film having a CIELAB color space having L*, a*, b* values ​​defined by 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:

[0020] [Table 3]

[0021] The coating composition of the present invention is capable of forming a coating film having a CIE HLC color space having C* and h° values ​​as defined by 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:

[0022] [Table 4]

[0023] In one embodiment, the coating film has a CIELAB color space having L*, a*, b* values ​​defined by three of conditions I, II, III, IV, and V, for example, 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.

[0024] In one embodiment, the coating film has a CIELAB color space with L*, a*, b* values ​​defined by four of conditions I, II, III, IV, and V, for example, conditions I, II, III, and IV, or conditions I, II, III, IV, and V, or conditions II, III, IV, and V.

[0025] In one embodiment, the coating has a CIELAB color space with L*, a*, b* values ​​defined by all of conditions I, II, III, IV, and V.

[0026] In one embodiment, the coating film has a CIE HLC color space having C* and h° values ​​as defined by three of conditions VI, VII, VIII, IX, and X, for example, conditions VI, VII, and VIII, or conditions VI, VII, and IX, or conditions VI, VIII, and IX, or conditions VI, VIII, and IX, or conditions VI, VIII, and X, or conditions VII, VIII, and IX, or conditions VIII, IX, and X, preferably conditions VI, VIII, and IX.

[0027] In one embodiment, the coating film has a CIE HLC color space having C* and h° values ​​defined by four of conditions VI, VII, VIII, IX, and X, for example, 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.

[0028] In one embodiment, the coating has a CIE HLC color space with C*, h° values ​​defined by all of conditions VI, VII, VIII, IX, and X.

[0029] pigment composition The pigment composition in the coating composition of the present invention is (A-1) a yellowish red pigment, (A-2) magenta pigment, and (A-3) Greenish blue pigment Includes.

[0030] The term "pigment" is well known in the art and refers to a type of material that can be applied to color a substrate and is insoluble in solvents and water. The particle size of the pigment can be determined by a person skilled in the art depending on the actual application. Preferably, the pigment has 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.

[0031] 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, or preferably in the range of 40 to 60% by weight, based on the weight of the pigment composition of the present invention. For the purposes of the present invention, component (A-1) is selected from CI Pigment Red 101 or CI Pigment Red 254.

[0032] 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, preferably in the range of 10 to 20% by weight, based on the weight of the pigment composition of the present invention. For the purposes 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 ratio of 10:1 to 1:10, more preferably 10:1 to 1:2.

[0033] Preferably, the amount of component (A-3) is 20 to 50% by weight, or 25 to 50% by weight, or 30 to 50% by weight, or 25 to 40% by weight, preferably 20 to 40% by weight, based on the weight of the pigment composition of the present invention. For the purposes 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 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 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.

[0034] Preferably, components (A-1), (A-2), and (A-3) constitute at least 80% by weight of the pigment composition of the present invention, more preferably at least 90% by weight, and even more preferably at least 95% by weight. Most preferably, components (A-1), (A-2), and (A-3) constitute 100% by weight of the pigment composition of the present invention.

[0035] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (1), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Red 122, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0036] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (2), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Red 122, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0037] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (3), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Red 122, and Component (A-3) is CI Pigment Blue 15.

[0038] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (4), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Red 202, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0039] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (5), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Red 202, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0040] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (6), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Red 202, and Component (A-3) is CI Pigment Blue 15.

[0041] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (7), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Violet 19, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0042] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (8), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Violet 19, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0043] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (9), Component (A-1) is CI Pigment Red 101, Component (A-2) is CI Pigment Violet 19, and Component (A-3) is CI Pigment Blue 15.

[0044] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (10), Component (A-1) is CI Pigment Red 101, Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0045] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (11), Component (A-1) is CI Pigment Red 101, Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0046] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (12), Component (A-1) is CI Pigment Red 101, Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and Component (A-3) is CI Pigment Blue 15.

[0047] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (13), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Red 122, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0048] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (14), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Red 122, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0049] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (15), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Red 122, and Component (A-3) is CI Pigment Blue 15.

[0050] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (16), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Red 202, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0051] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (17), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Red 202, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0052] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (18), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Red 202, and Component (A-3) is CI Pigment Blue 15.

[0053] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (19), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Violet 19, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0054] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (20), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Violet 19, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0055] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (21), Component (A-1) is CI Pigment Red 254, Component (A-2) is CI Pigment Violet 19, and Component (A-3) is CI Pigment Blue 15.

[0056] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (22), Component (A-1) is CI Pigment Red 254, Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 7.

[0057] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (23), Component (A-1) is CI Pigment Red 254, Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and Component (A-3) is a combination of CI Pigment Blue 15 and CI Pigment Green 36.

[0058] In one embodiment of the present invention, the pigment composition of the present invention is pigment composition (24), Component (A-1) is CI Pigment Red 254, Component (A-2) is a combination of CI Pigment Red 177 and CI Pigment Violet 23, and Component (A-3) is CI Pigment Blue 15.

[0059] In an embodiment of the present invention, the pigment composition of the present invention is any combination of two or more compositions selected from pigment compositions (1) to (24).

[0060] According to the present invention, the coating composition may not contain optical effect pigments. Typically, effect pigments are layered platy substrates, such as natural mica or glass flakes, coated with a metal oxide layer. A description of the properties of effect pigments can be found in Pigment Handbook, Vol. I, 2nd Edition, pp. 829-858, John Wiley & Sons, NY 1988.

[0061] The pigment compositions of the present invention can be prepared by those skilled in the art using methods known in the art.

[0062] Preferably, the amount of the pigment composition in the coating composition of the present invention as component (i) 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.

[0063] binder The coating composition of the present invention comprises a binder as component (ii).

[0064] The binder may be any suitable binder for coating compositions. For example, the binder may be selected from the group consisting of polyester resins, polyurethane resins, acrylic resins, cellulose acetate butyrate resins, and melamine resins. The binder may be thermosetting, including resins that are self-crosslinking, curable with a curing or crosslinking agent, or curable by exposure to actinic radiation, such as UV or EB radiation, and crosslinkers for such resins. The binder may comprise any one or combination of a wide 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 those that are branched, grafted, and copolymers with polyester, polyether, or other blocks); polyurethanes prepared using macromonomers such as polyesters, polyurethanes, polyester diols, polyether diols, and polycarbonate diols; alkyds; epoxy resins; polycarbonates; polyamides; polyimides; polysiloxanes; alkyds; and unsaturated oligomers and resins, and mixtures thereof, all of which are known in the art. In various embodiments, the curable polymer has groups that are reactive with a crosslinker. Non-limiting examples of polymer functional groups include carboxyl, hydroxyl, silanol groups, aminoplast functional groups, urea, carbamate, isocyanate (blocked or unblocked), epoxy, cyclic carbonate, amine, aldehyde groups, thiol groups, hydrazide groups, activated methylene groups, and any combination thereof that can be produced in a thermosetting polymer. In various embodiments, the polymer functional groups are hydroxyl, primary carbamate, isocyanate, aminoplast functional groups, epoxy, carboxyl, and mixtures thereof. In certain embodiments, the polymer functional groups are hydroxyl, carboxyl, silanol groups, epoxy, and mixtures thereof.

[0065] In one embodiment of the present 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 measured 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 include 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-trimethyl acrylate, methyl methacrylate, ... The polymers can be prepared from hydroxyl, methyl, methyl, methylhexyl, methylhexyl, methylhexyl acrylate, methylhexyl methacrylate ...Amino-functional acrylic monomers include t-butylaminoethyl methacrylate and t-butylamino-ethyl acrylate. Glycidyl groups may be incorporated, for example, by copolymerizing glycidyl methacrylate or allyl glycidyl ether. Other acrylic monomers with crosslinkable functionality in the ester portion of the monomer are within the skill of those skilled in the art.

[0066] Modified acrylics can also be used as film-forming curable polymers in coating compositions. Such acrylics can be polyester-modified acrylics or polyurethane-modified acrylics, as is well known in the art. Polyester-modified acrylics 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 acrylics are also well known in the art. These are described, for example, in U.S. Patent No. 4,584,354, the disclosure of which is incorporated herein by reference.

[0067] Polyesters can also be used as binder resins in coating compositions. The polyester resins may be formulated as acid- or hydroxyl-functional resins. The polyesters have an acid value of 20 to 100, or 20 to 80, or 20 to 40 mg KOH per gram. In other embodiments, the polyesters have a hydroxyl value of 25 to 300, or 25 to 150, or 40 to 100 mg KOH per gram. Methods for preparing 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 the reaction is usually completed by removing by-product water or methanol. The polyol component has an average functionality of at least 2. The polyol component may contain mono-, di-, tri-, and higher-functional alcohols. Diols are preferred, although higher-functional alcohols may be included if a degree of branching of the polyester is desired. Examples include, but are not limited to, 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. Optionally, small amounts of trifunctional and higher functional alcohols, such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol, may be used. The acid and / or anhydride component includes compounds having an average of at least two carboxylic acid groups and / or anhydrides or lower alkyl (C1-C4, especially methyl) esters thereof.Dicarboxylic acids or dicarboxylic acid anhydrides are preferred, although more highly functional acids and anhydrides can be used if a degree of branching of the polyester is desired. Suitable polycarboxylic acid or anhydride compounds include, but are not limited to, those having 3 to 20 carbon atoms. 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 their anhydrides. Optionally, 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.

[0068] Polyurethanes with crosslinkable functional groups, such as hydroxyl groups, are also well known in the art. They are prepared by the chain extension reaction of polyisocyanates (e.g., hexamethylene diisocyanate, isophorone diisocyanate, MDI, etc.) with polyols (e.g., 1,6-hexanediol, 1,4-butanediol, neopentyl glycol, and any other of those mentioned as useful in preparing polyesters, and combinations thereof), and macrodiols such as polyesterdiols, polyetherdiols, and polycarbonatediols. Crosslinkable functional groups can be imparted to these by capping the polyurethane chains with excess diols, polyamines, aminoalcohols, etc.

[0069] Carbamate-functional polymers and oligomers, particularly those having at least one primary carbamate group, can also be used as the curable polymer. Carbamate-functional examples of curable polymers used in coating compositions can be prepared in a variety of ways. For example, using the case of acrylic polymers, one method of preparing such polymers is to prepare a monomer, e.g., an acrylic monomer, having carbamate functionality in the ester portion of the monomer. Such monomers are well known in the art and are described, for example, in U.S. Pat. Nos. 3,479,328, 3,674,838, 4,126,747, 4,279,833, 4,340,497, 5,356,669, and WO 94 / 10211, the disclosures of which are incorporated herein by reference. One synthesis method involves reacting a hydroxy ester with urea to form a carbamyloxy carboxylate (i.e., a carbamate-modified acrylic). Another synthesis method involves reacting an α,β-unsaturated acid ester with a hydroxy carbamate ester to form a carbamyloxy carboxylate. Yet another technique involves reacting a primary or secondary amine or diamine with a cyclic carbonate such as ethylene carbonate to form a hydroxyalkyl carbamate. The hydroxyl group on the hydroxyalkyl carbamate is then esterified by reacting with acrylic acid or methacrylic acid to form the monomer. Other methods for preparing carbamate-modified acrylic monomers are described in the art and can be used as well. The acrylic monomer can be polymerized, if desired, with other ethylenically unsaturated monomers by methods well known in the art.

[0070] An alternative route to preparing the curable polymer for the binder is to react an already formed polymer, such as an acrylic polymer, polyester polymer, or polyurethane polymer, with another component to form a carbamate functional group attached to the polymer backbone, as described in U.S. Pat. No. 4,758,632. One technique for preparing such polymers involves pyrolyzing urea (producing ammonia and HNCO) in the presence of a hydroxy-functional acrylic polymer to form the carbamate-functional polymer. Another technique involves reacting the hydroxyl group of a hydroxyalkyl carbamate with the isocyanate group of an isocyanate-functional polymer to form the carbamate-functional polymer. Isocyanate-functional acrylics 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 (sold by American Cyanamid under the trademark TMI®). Isocyanate-functional polyurethanes can be formed by using an equivalent excess of diisocyanate or by end-capping a hydroxyl-functional prepolymer with a polyisocyanate. Yet another technique involves reacting the cyclic carbonate group of a cyclic carbonate-functional acrylic with ammonia to form a carbamate-functional acrylic. 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 a hydroxy-functional polymer with an alkyl carbamate. A more difficult, but viable method of preparing the polymer would be transesterification with a hydroxyalkyl carbamate.

[0071] The binder of the coating composition may further comprise a crosslinking agent, which may be used in an amount of 10 to 60%, typically 15 to 55%, or 25 to 50%, based on the total binder content of the coating composition.

[0072] In certain embodiments, forming an irreversible linkage may be preferred for the reaction between the crosslinker and the polymer. Examples of functional group "pairs" that form thermally irreversible linkages include hydroxy / isocyanate (blocked or unblocked), hydroxy / epoxy, carbamate / aminoplast, carbamate / aldehyde, acid / epoxy, amine / cyclic carbonate, amine / isocyanate (blocked or unblocked), urea / aminoplast, etc. Non-limiting examples of crosslinker binder resins include aminoplasts, blocked or unblocked polyisocyanates, polyepoxides, polycarboxylic acid or anhydride compounds, oligomers, or polymers, and polyurea compounds or oligomers.

[0073] In certain embodiments, the coating composition includes an aminoplast as a crosslinker. For purposes of the present invention, an aminoplast is a material obtained by reacting an activated nitrogen with a low molecular weight aldehyde, optionally further reacting with an alcohol (preferably a monoalcohol having 1 to 4 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; glycoluril; amides such as dicyandiamide; and carbamate-functional compounds having at least one primary carbamate group or at least two secondary carbamate groups.

[0074] The activated nitrogen is reacted with a low molecular weight aldehyde. The aldehyde may be selected from formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde, or other aldehydes used in the production of aminoplast resins, with formaldehyde and acetaldehyde, especially formaldehyde, being preferred. The activated nitrogen group is at least partially alkylolated with the aldehyde, and may be fully alkylolated, preferably fully alkylolated. This reaction may be acid-catalyzed, as taught, for example, in U.S. Pat. No. 3,082,180, the contents of which are incorporated herein by reference.

[0075] The alkylol group formed by the reaction of the activated nitrogen with the aldehyde may 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, and the like. Monofunctional alcohols having 1 to 4 carbon atoms and mixtures thereof are preferred. Etherification can be carried out, for example, by the methods disclosed in U.S. Pat. Nos. 4,105,708 and 4,293,692, the disclosures of which are incorporated herein by reference.

[0076] The aminoplast may be at least partially etherified, and in various embodiments, the aminoplast is fully etherified. For example, the aminoplast compound may have multiple methylol groups and / or etherified methylol, butyrol, or alkylol groups, which may be present in any combination with unsubstituted nitrogen hydrogen. A non-limiting example of a fully etherified melamine-formaldehyde resin is hexamethoxymethylmelamine. Aminoplast crosslinkers can be used as crosslinkers for carbamate, terminal urea, and hydroxyl-containing polymers.

[0077] In certain embodiments, the coating composition includes a polyisocyanate or blocked polyisocyanate crosslinker. Useful polyisocyanate crosslinkers include, but are not limited to, isocyanurates, biurets, allophanates, uredione compounds, and isocyanate-functional prepolymers, such as the reaction product of one mole of a triol with three moles of a diisocyanate. The polyisocyanate may be blocked with a lower alcohol, oxime, or other such material that volatilizes at cure temperatures to regenerate the isocyanate group.

[0078] The isocyanate or blocked isocyanate can be used in an equivalent ratio of 0.1 to 1.1, or 0.5 to 1.0 for each equivalent of functional groups reactive with the isocyanate or blocked isocyanate available from the crosslinkable binder resin.

[0079] Epoxide-functional crosslinkers can be used with carboxyl- or amine-functional crosslinking resins. Examples of epoxide-functional crosslinkers include any known epoxide-functional polymers and oligomers. Non-limiting examples of epoxide-functional crosslinkers include polyglycidyl ethers, polyglycidyl esters, glycidyl methacrylate polymers, and isocyanurate-containing epoxide-functional materials, such as trisglycidyl isocyanurate and the reaction product of glycidol with an isocyanate-functional isocyanurate, such as the trimer of isophorone diisocyanate (IPDI).

[0080] Preferably, the amount of component (ii) in the coating composition of the present invention is in the range of 10 to 30% by weight (for example, 10, 15, 20, 25 or 30% by weight), preferably 12 to 20% by weight, based on the weight of the coating composition.

[0081] carbon black The coating composition of the present invention comprises carbon black as component (iii).

[0082] Carbon black is typically produced by the thermal decomposition of hydrocarbons (liquid and gaseous hydrocarbons) under controlled conditions, i.e., the oxidative pyrolysis process, most commonly by incomplete combustion of the feedstock. The most common feedstock for carbon black production is heavy hydrocarbon streams derived from coal or crude oil processing, called carbon black oil (CBO). CBO typically contains primarily polycyclic aromatic hydrocarbon feedstocks. Natural gas, distillates from coal tar (carbochemical oils), or residual oils resulting from catalytic cracking of petroleum fractions, and olefins (petrochemical oils) produced by the thermal cracking of naphtha or diesel are the primary sources of this raw material. Production methods vary based on the arrangement of the thermal and cracking stages. The resulting carbon black product (e.g., lamp black, gas black, or furnace black) is filtered from the off-gas of the production process. Production methods include furnace, gas, lamp, and thermal black processes.

[0083] 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 feedstocks. The heated liquid feedstock is sprayed into a heat source generated by the combustion of natural gas or heavy oil and preheated air. Because the reaction occurs at very high temperatures, it is confined within a refractory-lined furnace. After the carbon black is formed, the process mixture is quenched by the injection of water, which 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. A bag filter separates the carbon black particles from the gas stream. The gas produced by the reaction is flammable and is most often burned in a boiler to generate steam and / or electricity, or flared. The carbon black recovered by the filter has a very low bulk density and, depending on the application, is typically pelletized or further densified for easier subsequent handling.

[0084] The gas black process uses vaporized oil as the feedstock. The oil is heated, and the resulting vapor is carried by hydrogen-rich gas through a tube equipped with multiple burners. Individual particles collide with the surface of a water-cooled drum. Some of the resulting carbon black is deposited on rollers, while the remainder enters a filter system. The two carbon black streams are then combined. Subsequent processing is similar to that of the furnace black process. The thermal black process for producing carbon black is a semi-batch process, and natural gas is the most commonly used feedstock, although higher-grade hydrocarbon oils can also be used. The feedstock is pyrolyzed in a refractory-lined vessel, where the natural gas is split into carbon black and hydrogen.

[0085] Lampblack is a special type of carbon black produced by the incomplete combustion of carbon black oil, similar to the furnace black process, except that the combustion takes place in a large, open, shallow vessel. Lampblack is the oldest industrial-scale method of producing carbon black still in use today.

[0086] In the present invention, any carbon black that can be used in a coating composition can be used. Those skilled in the art can select an appropriate carbon black depending on the actual application.

[0087] In a preferred embodiment of the present invention, the carbon black used in the coating composition of the present invention is gas black.

[0088] In a preferred embodiment of the present invention, the carbon black used in the present invention has an oil absorption measured in accordance with GB / T5211.15-2014 in the range of 100 to 200 mL / 100 g, preferably 130 to 170 mL / 100 g, and more preferably 140 to 160 mL / 100 g.

[0089] 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, e.g., FW2 from Evonik Industries AG, Germany.

[0090] 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.

[0091] aluminum The coating composition of the present invention contains aluminum as component (iv). Aluminum may be used in any suitable form applicable as a component of a coating composition, and a person skilled in the art can select the form depending on the actual application. Preferably, aluminum can be used in the present invention in the form of powder. More preferably, the D50 particle size of the aluminum used in the present invention is in the range of 5 to 40 μm, preferably 10 to 35 μm. For example, the aluminum may be commercially available, such as Stapa Hydrolan 2154 from ECKART, Germany.

[0092] 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 mass, preferably in the range of 0.8 to 1.8% by mass, based on the mass of the coating composition.

[0093] water 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 purified water. Preferably, component (v) is deionized water.

[0094] Preferably, the amount of component (v) in the coating composition of the present invention is in the range of 20 to 70% by mass (e.g., 20, 30, 40, 50, 60, or 70% by mass), preferably in the range of 30 to 60% by mass, more preferably in the range of 50 to 65% by mass, based on the mass of the coating composition.

[0095] solvent 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 esters of glycol ethers. Specific examples include, but are not limited to, methyl ethyl ketone, methyl isobutyl ketone, m-amyl acetate, ethylene glycol butyl ether and ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, xylene, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, N-methylpyrrolidone, N-ethylpyrrolidone, Aromatic 100, Aromatic 150, naphtha, mineral spirits, butyl glycol, and the like.

[0096] In the present invention, the concept of the term "solvent" does not include water.

[0097] Preferably, the amount of component (vi) in the coating composition of the present invention is in the range of 10 to 30% by weight (for example, 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.

[0098] additives The coating composition of the present invention may further comprise an additive as component (vii), and preferably the additive is selected from the group consisting of an antifoaming agent, an ultraviolet absorber, a rheology control agent, an antioxidant, a surface conditioner, a dispersant, an anti-settling agent, and a pH adjuster.

[0099] The pH adjuster can be selected from the group consisting of bases and amines, such as ammonia, triethylamine, and alcohol amines, preferably odorless or weak-odor alcohol amines. 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.

[0100] The amount of component (vii) in the coating composition of the present invention may be determined by those skilled in the art depending on the actual application. Preferably, the amount of component (vii) in the coating composition of the present invention may be in the range of 0 to 10% by mass, preferably 0 to 8% by mass, based on the mass of the coating composition.

[0101] In one embodiment, the coating composition of the present invention comprises the following components: (i) a pigment composition of the present invention, which is contained in an amount of 0.3 to 3 mass %, preferably 0.5 to 2 mass %, relative to the mass of the coating composition; (ii) a binder, which is contained in an amount of 10 to 30% by mass, preferably 12 to 20% by mass, based on the mass of the coating composition; (iii) carbon black, preferably gas black, 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; (iv) aluminum, in an amount of 0.5 to 2.0% by mass, preferably 0.8 to 1.8% by mass, based on the mass of the coating composition; and (v) water, contained in an amount ranging from 20 to 70% by mass, preferably from 30 to 60% by mass, more preferably from 50 to 65% by mass, based on the mass of the coating composition; Including, Preferably, the composition has a pH in the range of 7.5 to 8.5, preferably 7.8 to 8.2.

[0102] In a further embodiment, the coating composition of the present invention comprises the following components: (i) a pigment composition of the present invention, which is contained in an amount of 0.3 to 3 mass %, preferably 0.5 to 2 mass %, relative to the mass of the coating composition; (ii) a binder, which is contained in an amount of 10 to 30% by mass, preferably 12 to 20% by mass, based on the mass of the coating composition; (iii) carbon black, preferably gas black, 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; (iv) aluminum, in an amount of 0.5 to 2.0% by mass, preferably 0.8 to 1.8% by mass, based on the mass of the coating composition; and (v) water, contained in an amount ranging from 20 to 70% by mass, preferably from 30 to 60% by mass, more preferably from 50 to 65% by mass, based on the mass of the coating composition; (vi) a solvent, which is contained in an amount of 10 to 30% by mass, preferably 10 to 16% by mass, based on the mass of the coating composition; Including, Preferably, the composition has a pH in the range of 7.5 to 8.5, preferably 7.8 to 8.2.

[0103] In a further embodiment, the coating composition of the present invention comprises the following components: (i) a pigment composition of the present invention, which is contained in an amount of 0.3 to 3 mass %, preferably 0.5 to 2 mass %, relative to the mass of the coating composition; (ii) a binder, which is contained in an amount of 10 to 30% by mass, preferably 12 to 20% by mass, based on the mass of the coating composition; (iii) carbon black, preferably gas black, 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; (iv) aluminum, in an amount of 0.5 to 2.0% by mass, preferably 0.8 to 1.8% by mass, based on the mass of the coating composition; and (v) water, contained in an amount ranging from 20 to 70% by mass, preferably from 30 to 60% by mass, more preferably from 50 to 65% by mass, based on the mass of the coating composition; (vi) a solvent, present in an amount of 10 to 30% by weight, preferably 10 to 16% by weight, based on the weight of the coating composition; and (vii) an additive contained in an amount of 0 to 10% by mass, preferably 0 to 8% by mass, based on the mass of the coating composition; Including, Preferably, the additive is selected from the group consisting of an antifoaming agent, an ultraviolet absorber, a rheology control agent, an antioxidant, a surface conditioner, a dispersant, an anti-settling agent, and a pH adjuster; Preferably, the composition has a pH in the range of 7.5 to 8.5, preferably 7.8 to 8.2.

[0104] The coating compositions of the present invention can be prepared by those skilled in the art using methods known in the art. For example, the coating compositions of the present invention can be prepared by adding all of the ingredients simultaneously with stirring.

[0105] Preferably, before forming the coating composition of the present invention, when the pigment, carbon black, and / or aluminum are used in the form of dry powder or particles, they are pre-dispersed in a binder and / or solvent to form a pre-dispersion, respectively. The binder and solvent used to form the pre-dispersion are those applicable to the present invention. For example, they may be the binders and solvents disclosed above. Preferably, the binder and solvent used to form the pre-dispersion are part of the binder and solvent in the coating composition of the present invention. In a preferred embodiment, the coating composition of the present invention is prepared by the following steps: taking a portion of the binder and a portion of the solvent used in the coating composition to form a mixture, and pre-dispersing aluminum in the mixture with stirring to form a pre-dispersion, preferably in a 1:1:1 weight ratio of aluminum:binder:solvent; Similarly, preparing a carbon black pre-dispersion and a pigment pre-dispersion; adding the remaining binder and solvent to the aluminum pre-dispersion with stirring to form a dispersion; and adding a carbon black pre-dispersion and a pigment pre-dispersion to the dispersion to form a coating composition. It is prepared by a method comprising:

[0106] The coating composition of the present invention provides or can provide a coating film having color travel characteristics. The coating film exhibits a characteristic gray color travel of blue-gray-red as the observation angle changes. Specifically, the coating film has a CIELAB color space with L*, a*, and b* values ​​defined by 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:

[0107] [Table 5]

[0108] The coating film obtained from the coating composition of the present invention has a CIE HLC color space having C*, h° values ​​as defined by 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:

[0109] [Table 6]

[0110] coating film The present invention further provides a coating film having a CIELAB color space having L*, a*, b* values ​​defined by 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:

[0111] [Table 7]

[0112] The present invention further provides a coating film having a CIE HLC color space having C* and h° values ​​as defined by 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:

[0113] [Table 8]

[0114] In an embodiment of the present invention, the coating film of the present invention is obtained from the pigment composition of the present invention.

[0115] colored articles The present invention further relates to a colored article, the colored article having a CIELAB color space with L*, a*, b* values ​​defined by 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:

[0116] [Table 9]

[0117] The present invention further relates to a colored article, the colored article having a CIE HLC color space having C* and h° values ​​defined by 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:

[0118] [Table 10]

[0119] The colored article of the present invention is obtained by coating an article with the coating composition of the present invention, or is an article having a coating film of the present invention.

[0120] In one embodiment, the colored article of the present invention comprises a primer, a coating film, and optionally a clear coat.

[0121] The colored article of the present invention can be obtained by a person skilled in the art by conventional procedures. In one embodiment of the present invention, the colored article of the present invention is obtained by the following steps: providing the article; applying a primer to the surface of the article, and then drying the primer to form a primer film, preferably drying the primer at room temperature for e.g., 5 minutes to form a primer film preferably having a thickness in the range of e.g., 12 to 15 μm; applying a coating composition of the present invention onto the formed primer film, and then drying the coating composition to form a coating film, preferably drying the coating composition at room temperature for, for example, 5 minutes, and then drying 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; It is prepared by a method comprising:

[0122] Preferably, a clear coat is further applied onto the formed coating film, and then the clear coat is dried, preferably at room temperature, for example, for 7 minutes, and then at 140°C for 30 minutes, to form a clear coat film preferably having a thickness in the range of 40 to 45 μm.

[0123] In one embodiment of the present invention, a colored article is prepared by the following steps: (1) applying a primer to the surface of the 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 (2) applying the coating composition of the present invention onto 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, for example, 12 to 15 µm, thereby forming a colored article; It is prepared by a method comprising:

[0124] In one embodiment of the present invention, a colored article is prepared by the following steps: (1) applying a primer to the surface of the 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 (2) applying the coating composition of the present invention onto 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 (3) applying a clear coat onto the coating film formed in step (2), and then drying the clear coat at room temperature for 7 minutes and then at 140°C for 30 minutes to form a clear coat film preferably having a thickness in the range of 40 to 45 μm, thereby forming a colored article; It is prepared by a method comprising:

[0125] Many different types of articles can be used in the present invention, including metals or metallic articles such as bare steel, phosphated steel, galvanized steel, or aluminum, and non-metallic articles such as plastics and composites.

[0126] The primer used in the present invention may be an electrodeposition (electrodeposition coating) primer. The electrodeposition composition may be, for example, any electrodeposition composition used in automotive vehicle coating operations. Non-limiting examples of electrodeposition compositions include CATHOGUARD® electrodeposition compositions, such as CATHOGUARD® 500, available from BASF Corporation. Electrodeposition coating baths typically contain an aqueous dispersion or emulsion containing a primary film-forming epoxy resin with ionic stabilization (e.g., amine chloride groups) in water or a mixture of water and an organic solvent. A crosslinking agent emulsified with the primary film-forming resin can react with functional groups on the primary resin under appropriate conditions, such as the application of heat, to cure the coating. Suitable examples of crosslinking agents include, but are not limited to, blocked polyisocyanates. Electrodeposition coating compositions typically contain one or more pigments, catalysts, plasticizers, coalescents, defoamers, flow control agents, wetting agents, surfactants, UV absorbers, HALS compounds, antioxidants, and other additives.

[0127] The clear coat applicable to the present invention can be selected by those skilled in the art, and may be, for example, clear coat composition FF99-0345 commercially available from BASF.

[0128] The present invention provides a characteristic gray color travel by using a specific pigment combination: 1) a high-chroma blue pigment with a greenish hue (which primarily contributes to the color at an observation angle of 15°), 2) a magenta pigment with medium chroma and translucency (which dilutes the blue at an observation angle of 45° and does not affect the color at an observation angle of 15°), and 3) an iron oxide red opaque pigment (which provides a maroon hue at an observation angle of 75° without haze and without relying on optical effect pigments). This avoids the drawbacks caused by optical effect pigments, such as pigment orientation problems, color quality problems, and batch-to-batch color stability problems, and realizes stable and widespread use of the pigment composition and coating composition of the present invention in mass production of target products, such as automobiles and home appliances. Furthermore, if a product coated with the coating composition of the present invention is damaged, for example, if it is cut or scratched, the product can be easily repaired with the coating composition to restore its original appearance.

[0129] Embodiment Embodiment 1 The following ingredients: (A) a pigment composition comprising: (A-1) a yellowish red pigment, (A-2) magenta pigment, and (A-3) a greenish blue pigment, (B) a binder; (C) carbon black, preferably gas black, and (D) Aluminum Including, 1. A metallic effect coating composition, wherein the sum of the mass percentages of components (A-1), (A-2) and (A-3) is at least 80 mass%, preferably at least 95 mass%, and more preferably 100 mass%, relative to the total mass of component (A).

[0130] Embodiment 2 The component (A) contains, relative to the total mass of the component (A), 20% by mass to 60% by mass, preferably 40% by mass to 60% by mass, of component (A-1); 10% to 40% by mass, preferably 10 to 20% by mass, of component (A-2), and 20% by mass to 50% by mass, preferably 20% by mass to 40% by mass of component (A-3) 2. The coating composition of embodiment 1, comprising:

[0131] Embodiment 3 the component (A-1) is one selected from CI Pigment Red 101 and CI Pigment Red 254, the component (A-2) is one selected from 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 mass ratio of 1:10 to 10:1, and preferably 1:10 to 2:1; and the component (A-3) is one selected from CI Pigment Blue 15, a mixture of CI Pigment Blue 15 and CI Pigment Green 7 in a mass 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 mass ratio of 1:1 to 25:1, preferably 1:1 to 20:1, and 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; 3. The coating composition of any one of embodiments 1-2.

[0132] Embodiment 4 4. The coating composition of any one of embodiments 1 to 3, comprising 0.3% to 3% by weight, and preferably 0.5% to 2% by weight, of component (A), based on the total weight of the coating composition.

[0133] Embodiment 5 5. The coating composition of any one of the preceding claims, 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.

[0134] Embodiment 6 based on the total weight of the coating composition, 10% to 30% by weight, preferably 12% to 20% by weight, of component (B); 0.05% to 0.3% by weight, preferably 0.05% to 0.2% by weight, of component (C), and 0.5% to 2.0% by mass, preferably 0.8% to 1.8% by mass of component (D) 6. The coating composition of any one of the preceding embodiments, comprising:

[0135] Embodiment 7 7. The coating composition of any one of embodiments 1 to 6, further comprising 20% ​​to 70% by weight, preferably 30% to 65% by weight, and more preferably 50% to 65% by weight, of water, relative to the total weight of the coating composition.

[0136] Embodiment 8 8. The coating composition of any one of embodiments 1 to 7, further comprising 10% to 30% by weight, preferably 10% to 16% by weight, of a solvent, based on the total weight of the coating composition.

[0137] Embodiment 9 9. The coating composition of any one of the preceding embodiments, further comprising at least three additives selected from the group consisting of antifoaming agents, ultraviolet absorbers, rheology control agents, antioxidants, surface conditioners, dispersants, anti-settling agents, and pH adjusters, wherein the amount of said additive(s) is 10% by weight or less, preferably 8% by weight or less, based on the total weight of the coating composition.

[0138] Embodiment 10 10. The coating composition of any one of the preceding embodiments, having a pH value in the range of 7.5 to 8.5, and preferably 7.8 to 8.2.

[0139] Embodiment 11 11. The coating composition of any one of embodiments 1 to 10, wherein the coating composition is capable of forming a coating film having a CIELAB color space with L*, a*, b* values ​​as defined by 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:

[0140] [Table 11]

[0141] Embodiment 12 12. The coating composition of any one of embodiments 1 to 11, wherein the coating composition is capable of forming a coating film having a CIE HLC color space having C*, h° values ​​as defined by 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:

[0142] [Table 12]

[0143] Embodiment 13 11. 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 by 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:

[0144] [Table 13]

[0145] Embodiment 14 11. A coating film obtained from the coating composition according to any one of the preceding claims, wherein the CIE HLC color space of the coating film has C*, h° values ​​as defined by 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:

[0146] [Table 14] [Example]

[0147] The present invention will be better understood by consideration of the following non-limiting examples, which are not intended to limit the scope of the invention as described and claimed.

[0148] Preparing the coloring plates To measure the CIELAB color space, a series of colored plates were prepared. In the examples, the prepared coating compositions were used as base coats. In the process of preparing the color plates, the primer (if any) and base coat were applied by a Ber-Ber spray primer and base coat application process with the following parameters:

[0149] [Table 15]

[0150] The clear coat (if any) was applied by a process with the following parameters:

[0151] [Table 16]

[0152] Measurement of CIELAB and CIE HLC color spaces The CIELAB and CIE HLC color spaces of each colored plate were measured with a BYK mac i from BYK-Chemie GmbH under 45° illumination with a D65 light source and observation angles of 15°, 25°, 45°, 75°, and 110°.

[0153] Materials used in the examples The materials used in the examples are listed below:

[0154] [Table 17]

[0155] Examples 1 to 16 A series of coating compositions were prepared according to the ingredients and amounts shown in Tables 1 and 2, and the pH of each resulting coating composition was adjusted to 8.2. The resulting coating compositions were applied as base coats.

[0156] [Table 18]

[0157] [Table 19]

[0158] The colored plate of this example was prepared by the following steps: (1) applying a primer onto 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; (2) applying the resulting coating composition onto the primer film, then drying the coating composition at room temperature for 5 minutes, and then drying at 80°C for 5 minutes to form a coating film having a thickness of 12 μm; and (3) applying a clear coat onto the coating film, then drying the clear coat at room temperature for 7 minutes, and then drying at 140°C for 30 minutes to form a clear coat film having a thickness of 40 μm, thus forming a colored plate; It was prepared by a method including:

[0159] The coating film obtained from each of the resulting coating compositions completely hid the color of the underlying primer film.

[0160] The measured values ​​in the CIELAB and CIE HLC color spaces for each of the colored plates prepared in Examples 1 to 16 were as follows:

[0161] [Table 20]

[0162] [Table 21]

[0163] [Table 22]

[0164] [Table 23]

[0165] [Table 24]

[0166] [Table 25]

[0167] [Table 26]

[0168] [Table 27]

[0169] [Table 28]

[0170] [Table 29]

[0171] [Table 30]

[0172] [Table 31]

[0173] [Table 32]

[0174] [Table 33]

[0175] [Table 34]

[0176] [Table 35]

[0177] Example 17 To test the effect of the clear coat, the colored plate 1-C# was subjected to the following steps: (1) applying a primer onto 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 (2) applying coating composition 1 of Table 1 onto the primer film, then drying the coating composition at room temperature for 5 minutes, and then drying at 80°C for 5 minutes to form a coating film having a thickness of 12 μm, thus obtaining colored plate 1-C#; It was prepared by a method including:

[0178] The measured values ​​of the CIELAB and CIE HLC color spaces of the colored plate 1-C# and colored plate 1# prepared in Example 1 were compared as follows:

[0179] [Table 36]

[0180] The measured values ​​of the CIELAB and CIE HLC color spaces of colored plate 1# were as follows:

[0181] [Table 37]

[0182] It can be seen that the CIELAB and CIE HLC color spaces of the resulting colored plates I and II, with and without the clear coat layer, are substantially identical to each other.

Claims

1. The following ingredients: (A) a pigment composition comprising: (A-1) a yellowish red pigment, (A-2) a magenta pigment, and (A-3) a greenish blue pigment, (B) a binder; (C) carbon black, preferably gas black, and (D) Aluminum Including, the sum of the mass percentages of components (A-1), (A-2) and (A-3) is at least 80 mass%, preferably at least 95 mass%, and more preferably 100 mass%, based on the total mass of component (A); Metallic effect coating compositions.

2. The component (A) contains, relative to the total mass of the component (A), 20% to 60% by weight, preferably 40% to 60% by weight, of component (A-1); 10% to 40% by weight, preferably 10 to 20% by weight, of component (A-2), and 20% to 50% by weight, preferably 20% to 40% by weight, of component (A-3) The coating composition of claim 1 comprising:

3. The component (A-1) is one selected from C.I. Pigment Red 101 and C.I. Pigment Red 254, The component (A-2) is one selected from C.I. Pigment Red 122, C.I. Pigment Red 202, C.I. Pigment Violet 19, and a mixture of C.I. Pigment Red 177 and C.I. Pigment Violet 23 in a mass ratio of 1:10 to 10:1, and preferably 1:10 to 2:1, and The component (A-3) is one selected from C.I. Pigment Blue 15, a mixture of C.I. Pigment Blue 15 and C.I. Pigment Green 7 in a mass ratio of 1:2 to 2:1, more preferably 1:1.2 to 1.2:1, and a mixture of C.I. Pigment Blue 15 and C.I. Pigment Green 36 in a mass ratio of 1:1 to 25:1, and preferably 1:1 to 20:1; The component (A-3) is preferably selected from the mixture of C.I. Pigment Blue 15 and C.I. Pigment Green 7 or the mixture of C.I. Pigment Blue 15 and C.I. Pigment Green 36; The coating composition according to claim 1 or 2.

4. 3. The coating composition of claim 1, comprising 0.3% to 3% by weight, and preferably 0.5% to 2% by weight, of component (A) relative to the total weight of the coating composition.

5. 3. The coating composition according to claim 1, 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. based on the total weight of the coating composition, 10% to 30% by weight, preferably 12% to 20% by weight, of component (B); 0.05% to 0.3% by weight, preferably 0.05% to 0.2% by weight, of component (C), and 0.5% to 2.0% by weight, preferably 0.8% to 1.8% by weight, of component (D) 3. The coating composition of claim 1 or 2, comprising:

7. 3. The coating composition of claim 1 or 2, 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. 3. The coating composition of claim 1, further comprising 10% to 30% by weight, preferably 10% to 16% by weight, of a solvent, based on the total weight of the coating composition.

9. 3. The coating composition according to claim 1 or 2, further comprising at least three additives selected from the group consisting of antifoaming agents, ultraviolet absorbers, rheology control agents, antioxidants, surface conditioners, dispersants, anti-settling agents, and pH adjusters, wherein the amount of the additives is 10% by weight or less, and preferably 8% by weight or less, based on the total weight of the coating composition.

10. 3. The coating composition according to claim 1 or 2, having a pH value in the range of 7.5 to 8.5, and preferably 7.8 to 8.

2.

11. 3. The coating composition according to claim 1 or 2, wherein the coating composition is capable of forming a coating film having a CIELAB color space having L*, a*, b* values ​​defined by 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: Table 1

12. 3. The coating composition of claim 1 or 2, wherein the coating composition is capable of forming a coating film having a CIE HLC color space having C*, h° values ​​as defined by 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: Table 2

13. 3. A coating film obtained from the coating composition according to claim 1 or 2, wherein the CIELAB color space of the coating film has L*, a*, b* values ​​defined by 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: Table 3

14. 3. A coating film obtained from the coating composition according to claim 1 or 2, wherein the CIE HLC color space of the coating film has C*, h° values ​​as defined by 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: Table 4

Images