Surface-treated metallic effect pigments, their preparation and use - Patents.com

Abstract

A metal effect pigment, which is surface-treated with A) phosphoric acid (H3PO4), B) tetraethyl orthosilicate (TEOS), and C) at least one organic coupling agent, and which exhibits excellent humidity resistance without affecting the chroma, gloss, and color of the base metal effect pigment, its manufacturing method, and its use.

Description

[Technical field]

[0001] The present invention relates to surface-treated metallic effect pigments, their preparation process and uses. [Background technology]

[0002] Highly corrosion-resistant thin platelet-shaped metal pigments that have high corrosion resistance and good dispersibility without impairing the original surface smoothness of the thin platelet-shaped metal substrate such as aluminum flakes are well known (for example, JP 2003-41150 A). The corrosion resistance of the highly corrosion-resistant thin platelet-shaped metal substrate pigment is achieved by treating the surface of the thin platelet-shaped metal substrate with a phosphoric acid compound and / or a boric acid compound in a non-aqueous system (first layer), and then coating a hydrated metal oxide thereon by a sol-gel method in a non-aqueous system (second layer). Furthermore, the outer layer of the highly corrosion-resistant thin platelet-shaped metal pigment used as the base is coated with one or more hydrated metal oxide layers (third layer or more) by a wet method in an aqueous system to obtain a metallic luster interference color pigment (JP 2003-41150 A, paragraph

[0034] ). When effect pigments are used in a number of different application media, such as paints and coatings, they have to meet completely different requirements. Firstly, they not only need to be compatible with the application media surrounding them, but also must be sufficiently stable, possibly even over long periods of time. Surface coating layers for outdoor applications are often exposed to extreme weather conditions and to persistent and intense water and light over long periods of time, which often leads to aging of the material. Effect pigments with titanium dioxide, iron oxide or other metal oxide layers can exhibit significant changes in their properties due to external influences such as water and light, which is evident from discoloration, embrittlement and reduced mechanical and chemical stability.

[0003] To avoid the above problems, it has been proposed to subject effect pigments to post-treatments aimed at improving their applicability, which often involve coating the effect pigments with polymers, various metal oxides / hydroxides, and / or silanes. For example, WO 99 / 57204 describes the use of reactive surface modifiers to prepare effect pigments that exhibit good orientation and distribution in surface coatings, and WO 94 / 01498 describes the use of three layers of metal oxides applied on top of each other. WO 98 / 13426, DE 10348174, and U.S. Pat. No. 4,544,415 describe pigments having layers comprising metal oxides and monomeric, oligomeric, and polymeric coupling agents. For example, treatment for light resistance, water resistance, and weather resistance required for application as an automobile paint (for example, JP-A-63-130673, JP-A-01-292067, etc.), high orientation (leafing effect) treatment required in the paint field and printing field (for example, JP-A-2001-106937, JP-A-11-347084), aqueous treatment for aqueous paint or aqueous printing ink (for example, JP-A-8-283604), silicone treatment for improving dispersibility in applications in the cosmetics field, and hydrogen polysiloxane treatment for improving water and oil repellency properties, weld line prevention surface treatment when used as a resin (for example, JP-A-03-100068, JP-A-03-93862), and various treatments for improving dispersibility can be performed. However, state-of-the-art effect pigments have disadvantages in terms of light stability and / or compatibility with application media. Moreover, none of the above additional surface treatments provide metal effect pigments with significantly improved moisture resistance performance. In other words, metal effect pigments without surface treatment or with only insufficient surface treatment show deterioration of appearance quality over time and have unstable moisture resistance in customer's aqueous systems. Thus, there continues to be a need for metal effect pigments that have improved humidity resistance without affecting the chroma, gloss, and color of the base metal effect pigment, and for the easy preparation of such metal effect pigments. Summary of the Invention

[0004] It is therefore an object of the present invention to provide surface-treated metal effect pigments which achieve good moisture resistance performance, important for outdoor applications, without affecting the chroma, gloss and color of the base metal effect pigment.

[0005] In order to solve the above problems, the inventors of the present invention have conducted extensive research and have found that the moisture resistance performance of metal effect pigments can be surprisingly improved by subjecting the base metal effect pigment to a surface treatment with A) phosphoric acid (H3PO4), B) tetraethyl orthosilicate (TEOS), and C) at least one organic coupling agent. Furthermore, the present invention provides the possibility to stabilize metal effect pigments by a surface treatment that does not affect the chroma, gloss and color of the base metal effect pigment.

[0006] The present invention therefore relates to metal effect pigments surface treated with A) phosphoric acid (H3PO4), B) tetraethyl orthosilicate (TEOS), and C) at least one, preferably two or more organic coupling agents. In a highly preferred embodiment, three organic coupling agents are used. The present invention also relates to the above metallic effect pigments, in which at least three organic coupling agents are used. The present invention also relates to the above metal effect pigments, wherein the organic coupling agent(s) is / are selected from alkylsilanes, epoxysilanes, (meth)acrylicsilanes, aminosilanes, and vinylsilanes. The present invention further relates to the above metallic effect pigments, wherein the amount of C) organic coupling agent(s) is in the range of 0.3 to 3.0% by weight, calculated as carbon content, based on the total weight of the metallic effect pigment. The present invention further relates to the above metal effect pigments, wherein the amount of A) phosphoric acid compound (H3PO4) is in the range of 0.01 to 1.0% by weight, calculated as P2O5, based on the total weight of the metal effect pigment. The present invention further relates to the above metal effect pigments, wherein the amount of B) tetraethyl orthosilicate (TEOS) is in the range of 0.1 to 1.5% by weight, calculated as SiO2, based on the total weight of the metal effect pigment.

[0007] The present invention further relates to metal effect pigments comprising a thin platelet-shaped metal substrate coated with one or more layers of a metal compound selected from metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal sulfides, metal carbides, metal nitrides, metal oxynitrides, and mixtures thereof; wherein the thin platelet-shaped metal substrate is selected from at least one metal or metal alloy selected from aluminum, titanium, gold, silver, iron, stainless steel, copper, zinc, tin, nickel, and chromium. The present invention further relates to such metallic effect pigments, in which the platelet-shaped metal substrate is coated with one or more metal oxides and / or metal sulfides of one or more metals selected from the group consisting of iron, titanium, aluminum, zirconium, tin, zinc, bismuth, calcium, manganese, cerium, chromium, cobalt, silicon and boron. In a preferred embodiment, the platelet-shaped metal substrate is coated with one or more metal oxides selected from Fe2O3 and TiO2. The present invention further relates to metal effect pigments as described above, which further comprise a layer resulting from a step of treating the surface of the platelet-shaped metal substrate with a phosphate compound and / or a borate compound and then coating by a sol-gel process with one or more hydrous metal oxide layers of one or more metals selected from the group consisting of silicon, aluminum, zirconium and titanium.

[0008] The present invention also relates to a method for preparing said metallic effect pigments, comprising the following steps: Dispersing / suspending metal effect pigments in water and / or one or more solvents, Carrying out a surface treatment by adding A) phosphoric acid (H3PO4), B) tetraethyl orthosilicate (TEOS), and C) at least one organic coupling agent to water and / or solvent(s); Drying the metal effect pigment. The present invention further relates to said process for the preparation of said metallic effect pigments, wherein the surface treatment can be carried out by wet-chemical methods and / or by sol-gel methods.

[0009] The present invention also relates to an aqueous coating system comprising the above-mentioned metallic effect pigments. The present invention also relates to the use of said metal effect pigments in paints, coatings, automotive coatings, industrial coatings, pigment preparations, pigment pastes, radar-transparent coatings, lidar applications, painted materials, inks, printed materials, plastics, moldings, laser marking, or cosmetics.

[0010] The metal effect pigments of the present invention comprise a platelet-shaped metal substrate coated with one or more layers of metal compounds selected from metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal sulfides, metal carbides, metal nitrides, metal oxynitrides, and mixtures thereof. On the basis of the metal effect pigments, a surface treatment is carried out on the substrate comprising A) phosphoric acid (H3PO4), B) tetraethyl orthosilicate (TEOS), and C) at least one organic coupling agent. The surface-treated metal effect pigments show superior moisture resistance and compatibility with the application medium compared to no surface treatment or only insufficient surface treatment, i.e., for example, only with organic coupling agents. Furthermore, the present invention offers the possibility to stabilise metal effect pigments without affecting the chroma, gloss and colour of the base metal effect pigment. Furthermore, the surface treatment can be carried out by utilizing a so-called wet method, which makes the procedure simple and the operation easy, while reducing the production cost. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below together with the production method. The platelet-shaped metal substrate used in the present invention can be selected from at least one metal or metal alloy selected from aluminum, titanium, gold, silver, iron, stainless steel, copper, zinc, tin, nickel, and chromium. On the platelet-shaped metal substrate, one or more layers of metal compounds selected from metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal sulfides, metal carbides, metal nitrides, metal oxynitrides, and mixtures thereof can be coated. For example, the platelet-shaped metal substrate can be coated with one or more metal oxides and / or metal sulfides of one or more metals selected from the group consisting of iron, titanium, aluminum, zirconium, tin, zinc, bismuth, calcium, manganese, cerium, chromium, cobalt, silicon, and boron. The highly corrosion-resistant thin platelet-shaped metal substrate used in the present invention has a layer formed by a corrosion-resistant treatment in a non-aqueous system. The thin platelet-shaped metal substrate as the core of the highly corrosion-resistant thin platelet-shaped metal substrate is made of metal and metal alloy. The flake-like metal substrate used in the present invention has an average particle size of 2 to 100 μm and an average thickness of 0.02 to 5 μm, preferably an average particle size of 5 to 50 μm and an average thickness of 0.02 to 2 μm, more preferably an average particle size of 5 to 30 μm and an average thickness of 0.05 to 1 μm. Specific examples of the flakes include aluminum flakes, titanium flakes, iron flakes, bronze flakes, stainless steel flakes, aluminum bronze flakes, various aluminum alloy flakes, various titanium alloy flakes, etc. Preferred flakes include aluminum flakes, titanium flakes, stainless steel flakes, bronze flakes, etc.; even more preferred flakes include aluminum flakes (supplied, for example, by Silver Line Co. Ltd., Showa Aluminum Co., Ltd., Toyo Aluminum Co., Ltd., Asahi Kasei Metals Co., Ltd., Eckart-Werke, etc.), titanium flakes, stainless steel flakes, etc., which are commercially available as brilliant metallic pigments and are stably supplied. In particular, aluminum flakes having an average particle size of 5 to 50 μm are preferred. Among the above, flake-like metal substrates available on the market in various states may be used, for example, substrates already suspended in an organic solvent to prevent oxidation corrosion due to moisture in the air (e.g., pigment paste suspended in mineral spirits, etc.), substrates treated with various surface treatment agents for leafing or to improve dispersibility and suspended in an organic solvent, and substrates on whose surface an oxidation protection film (passivation film, i.e., a thin surface oxide layer) has been applied in advance can be used. With respect to the subject matter of the present invention, the effects of the present invention are achieved by particularly highly corrosive flake-like metals, as long as the majority of the surface is not oxidized, and therefore their use is preferred. For example, highly corrosive substrates such as aluminum flakes available on the market already suspended in an organic solvent before handling, and substrates treated with various surface treatment agents and suspended in an organic solvent are particularly recommended for use in the present invention. It is also possible to use flake-like metal substrates and flake-like alloy substrates that have been previously subjected to corrosion resistance (passivation) treatment.

[0012] The metal substrate having a layer formed by a non-aqueous corrosion-resistant treatment used in the present invention includes a thin platelet-shaped metal substrate whose surface is treated with a phosphoric acid compound and / or a boric acid compound and further coated with one or more hydrated metal oxide layers of one or more metals selected from the group consisting of silicon, aluminum, zirconium, and titanium by a sol-gel method (for example, as described in JP-A-2003-41150). In consideration of its good surface smoothness, dispersibility, and inherent surface gloss, and good adhesion between the intermediate binder layer and the hydrated iron oxide layer further formed thereon, the above corrosion-resistant thin platelet-shaped metal substrate containing a layer of a phosphoric acid compound and / or a boric acid compound and one or more hydrated metal oxide layers of one or more metals selected from silicon, aluminum, etc., formed by a sol-gel method, is adopted. The treatment of the highly corrosion-resistant platelet-like metal substrate with a phosphoric acid compound and / or a boric acid compound may be carried out according to the description in JP-A-2003-41150. The metal used in the subsequently formed hydrated metal oxide layer may be selected from the group consisting of silicon, aluminum, zirconium, and titanium. Of these, silicon and aluminum are preferred due to their excellent transparency and low refractive index. Silicon is particularly preferred due to its ease of handling. The sol-gel process (described in JP 2003-41150 A) is preferred among the non-aqueous reactions for coating the second layer of this highly corrosion-resistant treatment in order to maintain surface smoothness.

[0013] In the description of this specification, for example, the thin platelet-shaped metal treated with a phosphoric acid compound and / or a boric acid compound and further combined with a hydrated metal oxide layer in a non-aqueous system as described in JP 2003-41150 A is defined as a "thin platelet-shaped metal substrate having a layer formed by a non-aqueous corrosion-resistant treatment", on which a layer containing hydrated tin oxide is coated as an "intermediate binder layer" (first layer), and an outer layer, a hydrated iron oxide layer, is coated as a "second layer". Furthermore, in the present invention, the term "hydrated oxide" in "hydrated metal oxide" generally refers to metal "oxide", "hydroxide", "hydrate of oxide", "hydrated oxide", and "mixtures thereof" unless otherwise specified. The term "oxide" in "metal oxide" is also based on the definition of "hydrated oxide". Furthermore, when such "hydrated metal oxide" is expressed by a chemical formula (for example, as described in one embodiment, etc.), it is convenient to express it in the form of oxide.

[0014] Next, the intermediate binder layer (first layer) for improving the adhesion and compactness of the second layer will be described. The intermediate binder layer is the outer layer immediately following the highly corrosion resistant flake metal substrate and can be obtained as follows: A suitable material for the intermediate binder layer (first layer) is hydrated tin oxide. The highly corrosion-resistant thin platelet-like metal substrate is dispersed in water maintained at a temperature of 60 to 90°C so as to easily control a uniform coating layer, and a tin salt aqueous solution and a basic aqueous solution are simultaneously added to the suspension while maintaining a constant pH, thereby coating a hydrated tin oxide layer (intermediate binder layer) on the highly corrosion-resistant metal substrate. The pH is preferably less than 4.7. More preferably, a pH value of 0.5 to 3.0 can be adopted. The amount of hydrated tin oxide in the intermediate binder layer (first layer) of a thin platelet-shaped metal substrate having a layer formed by a non-aqueous corrosion-resistant treatment must be sufficient so that the substrate (the layer treated by a non-aqueous treatment) is not exposed; that is, this amount must be more than the amount required to form a monolayer. 2 The amount of hydrated tin oxide per unit area is approximately 0.0008 g or more in terms of metal oxide (SnO2). Specifically, the amount of hydrated tin oxide used in the intermediate binder layer (first layer) must be appropriately adjusted according to the type, particle size, and particle size distribution of the flaky corrosion-resistant metal substrate. Considering the unit surface area of ​​the highly corrosion-resistant metal substrate, it is natural that the amount must be reduced when the particle size is large and increased when the particle size is small. The amount of hydrated tin oxide is adjusted within a feasible range in which sufficient adhesion and improved compactness of the second layer are achieved, and the hue of the interference color can be controlled; therefore, the unit area (m 2 ) of the platelet-like metal substrate having a layer formed by the anti-corrosion treatment in a non-aqueous system can be adjusted. 2 The amount per 1000 μm2 is preferably 0.0008 g to 0.3 g, more preferably 0.0009 g to 0.2 g, and even more preferably 0.01 g to 0.1 g, calculated as metal oxide (SnO2). For example, a highly corrosion-resistant substrate (specific surface area: 3.01 m2) containing metallic aluminum as a thin platelet metal 2 / g (as described in Table 3 of JP 2003-41150 A), the preferred amount is 2 ) is 0.001g to 0.06g. The aqueous solution of the tin salt used is a water-soluble tin(II) salt or tin(IV) salt, such as tin(II) chloride, tin(IV) chloride, tin(II) sulfate, tin(II) acetate, tin(II) oxalate, etc.

[0015] The coating of the hydrated iron oxide (second layer) after the intermediate binder layer is formed will be described below. The coating of the hydrated iron oxide (second layer) on the surface of the intermediate binder layer (first layer) can be carried out by a gas phase method, a sol-gel method, or the like, but the wet method (see JP 2003-41150 A for the definition) is more preferably adopted because, in contrast to the gas phase method and the sol-gel method, there are no restrictions on raw materials and production equipment, a uniform coating layer is easily obtained, it has a wide range of uses, and it is easy to operate in a simple manner. The wet method preferably used in the present invention has been defined above. More specifically, in an aqueous system, the method comprises: (1) in the case of neutralization hydrolysis, a desired water-soluble metal salt (such as nitrates, sulfates, chlorides, acetates, and further metal acid salts, etc.) and a predetermined amount of the aqueous solution thereof are selected, while separately preparing an alkaline aqueous solution (an acidic aqueous solution in the case of a metal acid salt), which is dropped into a suspension of a highly corrosion-resistant thin platelet-like metal pigment as a base obtained in advance while maintaining a predetermined pH, forming a hydrolysis product layer on the surface, which is then washed, filtered, dried, and optionally calcined; and (2) in the case of thermal hydrolysis, a predetermined amount of a desired water-soluble metal salt is added to a suspension of a highly corrosion-resistant thin platelet-like metal pigment as a base obtained in advance, which is heated to form a hydrolysis product layer, which is then washed, filtered, dried, and optionally calcined. Furthermore, as a variant of the method by neutralization hydrolysis (1), a method using urea and acetamide that become alkaline by heating instead of an alkaline aqueous solution (so-called "homogeneous precipitation method") can also be used.

[0016] As the iron (III) salt to be used, a water-soluble salt such as a chloride, sulfate, or nitrate can be selected. After coating the intermediate binder layer (first layer), an aqueous iron salt solution is successively added while keeping the pH constant (4 or less) using an alkaline aqueous solution. Specific examples of the alkaline aqueous solution used in the present invention include aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, aqueous solutions of alkali metal carbonates such as sodium carbonate and potassium carbonate, aqueous solutions of alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, aqueous solutions of ammonium carbonate, ammonium hydrogen carbonate, or aqueous ammonia. In order to obtain a reddish color and to sufficiently improve the color development, the amount of hydrated iron oxide is adjusted to 100% by weight per unit area (m2) of the flaky metal substrate having a layer formed by the corrosion-resistant treatment in a non-aqueous system. 2 The amount is preferably 0.01 g to 1.0 g in terms of metal oxide (Fe2O3) per 1000 g of water. Therefore, the amount can be appropriately changed depending on the hue and surface smoothness of each thin metal substrate, and the properties of the highly corrosion-resistant metal substrate obtained and treated in a non-aqueous system. From the viewpoint of efficiency, the temperature during this coating step is preferably the same as the temperature during coating of the intermediate binder layer (first layer). The suspension containing the colored thin platelet-shaped interference pigment having a reddish metallic luster thus obtained is then filtered, washed, dried, and calcined. The metallic luster interference color pigment having a reddish color obtained as described above has an intermediate binder layer, which improves the adhesion and denseness of the hydrated iron oxide layer (second layer) coated thereon, and exhibits a reddish body color having an interference color.

[0017] In the following, surface treatments are described which are carried out on the base metal effect pigments according to the invention in order to improve their humidity resistance performance without affecting the chroma, gloss and color of the pigments. The surface treatments performed on the metallic effect pigments include treatment with A) phosphoric acid (H3PO4), B) tetraethyl orthosilicate (TEOS), and C) at least one organic coupling agent. Such surface treatments can be carried out by wet chemical and / or sol-gel methods, the former being easy to operate and cost effective, while the latter providing the treated pigment with better moisture resistance, but may be slightly more expensive. One of the essential components of the surface treatment according to the invention is A) phosphoric acid (H3PO4). After the anti-corrosive treatment of the metal effect pigments with a phosphoric acid (H3PO4) solution, phosphates (e.g. aluminum phosphates) are formed on the surface of the metal effect pigments. Another essential component of the surface treatment according to the invention is B) tetraethyl orthosilicate (TEOS). After the metal effect pigments are treated and hydrolyzed with tetraethyl orthosilicate (TEOS) solution, silicon hydroxide (Si(OH)4) is formed on the surface of the metal effect pigment, which facilitates further surface treatment and makes the fixation of the organic coupling agent(s) much easier. The metal effect pigments are dried after the surface treatment. After the drying step, the silicon hydroxide (Si(OH)4) becomes silicon dioxide (SiO2). Another essential component of the surface treatment according to the invention is C) at least one organic coupling agent, which is preferably immobilized within the surface coating and / or to the phosphates (e.g. aluminum phosphates) from A) phosphoric acid (H3PO4) treatment of the surface, and / or to silicon hydroxides (Si(OH)4) from B) tetraethyl orthosilicate (TEOS) treatment, and / or to the substrate (i.e. via siloxanes).

[0018] Suitable and preferred organic coupling agents for the present invention are organosilanes, -aluminates, -titanates and / or -zirconates of the general formula: X 4-n-m ZR n (-BY) m In the formula, X=OH, halogen, alkoxy, aryloxy Z=Si, Al, Ti, Zr R=alkyl, phenyl, or hydrogen B = at least difunctional organic group (alkylene, alkyleneoxyalkylene) Y=amino, substituted amino, hydroxyl, hydroxyalkyl, siloxane, acetoxy, isocyanate, vinyl, acryloyl, epoxide, epoxypropyloxy, imidazole, or ureido group. n,m=0,1,2,3, where n+m<3. The organic coupling agent is preferably a compound with Z=Si. The organic coupling agent preferably contains an alkoxysilane group, which can be converted into the corresponding hydroxy group by hydrolysis reaction conditions. The latter can result in fixation via oxygen bridges. Furthermore, mixtures of different coupling agents can also be used, in particular mixtures of two or three, most preferably three, coupling agents, which can be applied as a mixture or individually. By suitable selection of the coupling agent, the metal effect pigments of the present invention can be adapted to various application systems. The organic coupling agent can be adapted to the application medium by selecting a suitable functional group. Furthermore, a bond with the medium can be formed via the organic coupling agent by reaction between the functional group and a corresponding functional group in the application medium. In a particularly preferred embodiment, the surface of the metal effect pigments of the invention is modified by the combination of a mixture of different organic coupling agents adapted to the application medium. The hydrophobicity of the metal effect pigment surface can be adapted by incorporating alkyl-containing organic coupling agents, such as, for example, alkylsilanes. In addition to organosilanes, the use of hydrolysates and their homogeneous and heterogeneous oligomers and / or polymers is also preferred, which can be used as organic coatings, either alone or in combination with silanes, zirconates, aluminates, zircoaluminates and / or carboxyzircoaluminates. Mixtures of different organic coupling reagents, in particular those with different functional groups Y, are particularly preferred, which ensure a certain range of applications. Particularly preferred are mixtures of organosilanes, in particular mixtures comprising at least two, preferably at least three, organosilanes with different functional groups.

[0019] Examples of organosilanes are propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, vinyltrimethoxysilane. Suitable oligomeric alcohol-free organosilane hydrolysates are in particular the products sold by Sivento under the trade name "Dynasylan®", such as Dynasylan HS2926, Dynasylan HS2909, Dynasylan HS2907, Dynasylan HS2781, Dynasylan HS2776, Dynasylan HS2627. Furthermore, oligomeric vinylsilanes and aminosilane hydrolysates are also suitable as organic coatings. The functionalized organosilanes are, for example, 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3,-tetramethyldisiloxane, ureidopropyltriethoxysilane, preferably 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane. Examples of polymeric silane systems are described in WO 98 / 13426 and are sold, for example, by Sivento under the trade name Hydrosil®. Particular preference is given to alkylsilanes, epoxysilanes, (meth)acrylicsilanes, aminosilanes and / or vinylsilanes, in particular mixtures of such silanes. Particular preference is given to hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and / or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, in particular mixtures of such silanes, in particular mixtures of at least three or more of these silanes.

[0020] It is essential for the metal effect pigments of the invention to have a carbon content of >0.3% by weight, based on the total weight of the metal effect pigment. The upper limit is preferably fixed at a quantity that starts to impair the effect of the pigment. Typically, this amount is about 3.0%. Preferably, the carbon content is in the range of 0.5-3.0% by weight, in particular in the range of 0.5-1.5% by weight, based on the total weight of the metal effect pigment. The carbon content is determined by elemental analysis of the dry pigment, preferably with a CHN analyzer UNICUBE from Elementar. The outer coating may not have a layered structure, but may be a mixture of phosphate, silicon dioxide and organic compounds. Advantageously, the outer coating shows a non-uniform distribution of compounds, especially oxidizing compounds. If desired, the outer coating may be structured to have a multi-layer structure. Preferably, the concentration of the organic coupling agent is greatest at the outer surface of the metal effect pigment and decreases towards the base substrate. On the other hand, the decrease in the concentration of the phosphate and silicon dioxide compounds preferably starts from the inner surface of the metal effect pigment towards the outer surface. In other words, the concentration of the phosphate and silicon dioxide compounds is greatest at the inner surface of the metal effect pigment and decreases towards the outer surface of the metal effect pigment.

[0021] A) The treatment with the phosphoric acid compound is carried out by adding the phosphoric acid compound to the suspension of the metal effect pigment. The amount of phosphoric acid compound used is preferably an amount corresponding to 0.01 to 1.0% by weight, more preferably an amount corresponding to 0.02 to 0.8% by weight, even more preferably an amount corresponding to 0.02 to 0.5% by weight, calculated as P2O5, based on the total weight of the metal effect pigment. After A) the treatment with the phosphoric acid compound, B) the treatment with tetraethyl orthosilicate (TEOS) is carried out by adding TEOS to the suspension of the metal effect pigment. The amount of TEOS used is preferably an amount corresponding to 0.1 to 1.5% by weight, more preferably an amount corresponding to 0.1 to 1.0% by weight, even more preferably an amount corresponding to 0.15 to 0.6% by weight, calculated as SiO2, based on the total weight of the metal effect pigment.

[0022] All weight percentages are based on the total weight of the metallic effect pigment. C) The treatment with at least one organic coupling agent can be described as follows: First, the reaction for the application of C) at least one organic coupling agent is preferably carried out for a time of 10 to 120 minutes, but can be extended if necessary. The obtained metal effect pigments are then purified and isolated by methods widely used by those skilled in the art, for example by filtration, drying and sieving. The drying step can be carried out in commercially available dryers, ovens or kilns, under air or under nitrogen gas or other inert gas. The drying temperature is in the range of 110 to 180 ° C, preferably in the range of 120 to 160 ° C. The drying time is in the range of 15 to 360 minutes, preferably in the range of 30 to 180 minutes, depending on the amount of material to be dried. With the above surface treatment, A) phosphate (e.g. aluminum phosphate) generated from phosphoric acid (H3PO4), B) silicon dioxide (SiO2) from tetraethyl orthosilicate (TEOS), and C) organic carbon from at least one organic coupling agent have a synergistic effect to improve the humidity resistance performance. Furthermore, the mixture of phosphate, silicon dioxide and organic compound forms a very thin layer(s) on the surface of the metal effect pigment, thus stabilizing the metal effect pigment without affecting the chroma, luster and color of the base metal effect pigment.

[0023] The present invention further relates to pigment pastes made from the above metal effect pigments pasted with a solvent such as mineral spirits, light aromatic solvents, ethylene glycol monobutyl ether (Butyl Cellosolve), dibutyl phthalate (DBP), diethylene glycol monoethyl ether (Carbitol), diethylene glycol monobutyl ether (Butyl Carbitol) or propylene glycol methyl ether (PGM), preferably with mineral spirits, and / or diethylene glycol monoethyl ether (Carbitol). The pigment paste with solvent provides phlegmatization of the metal effect pigments and avoids dust emission during handling and transportation.Furthermore, the pigment paste is easy to handle when used in compositions that may additionally contain further pigments, resin components and / or oil components for various applications such as paints, coatings, automotive coatings, industrial coatings, pigment preparations, pigment pastes, radar transparent coatings, lidar applications, painted materials, inks, printed materials, plastics, moldings, laser marking, or cosmetics. The metal effect pigments obtained according to the present invention may be used in compositions, which may additionally comprise further pigments, resin components and / or oil components, for various applications, such as paints, coatings, automotive coatings, industrial coatings, pigment preparations, pigment pastes, radar-transparent coatings, lidar applications, painted materials, inks, printed materials, plastics, moldings, laser marking, or cosmetics. The present invention relates to painted materials having at least one paint layer comprising the above-mentioned resin / oil and pigment composition. Specific examples thereof are described below. Although not specifically mentioned, the "pigment of the present invention" used in the following examples refers to "metal effect pigments", including those prepared by applying the above-mentioned various treatments as described in paragraph

[0003] of this application.

[0024] Use in paints Examples of the use in paints include organic solvent-based paints, NAD-based (non-aqueous dispersion) paints, water-based paints, emulsion paints, colloidal paints, and powder paints. The pigment of the present invention can be mixed in a ratio of 1 to 100% by mass with respect to the paint resin solids. A ratio of 1 to 70% by mass is preferred. A ratio of 1 to 20% by mass is particularly preferred. In order to improve dispersibility, the surface of the pigment of the present invention can be treated with a silane coupling agent and a titanium coupling agent. Examples of the resin component of the paint in the present invention include acrylic resins, alkyd resins, unsaturated polyester resins, amino resins, melamine resins, polyurethane resins, epoxy resins, polyamide resins, phenolic resins, cellulose resins, vinyl resins, silicone resins, and fluororesins. These resins may be used alone or in combination of two or more. Examples of water-based paints include emulsion-based resins containing crosslinked resins based on acrylic melamine resins. Examples of mixtures and blends include further pigments such as organic pigments and inorganic pigments, as well as antisagging agents, viscosity modifiers, antisettling agents, crosslinking accelerators, hardeners, leveling agents, defoamers, plasticizers, preservatives, mildew inhibitors, UV stabilizers, etc. Examples of further pigments that can be used in combination with the pigments of the present invention include titanium dioxide; calcium carbonate; clay; talc; barium sulfate; white carbon; chromium oxide; zinc oxide; zinc sulfide; zinc powder; metal powder pigments (e.g., aluminum flakes, colored aluminum flakes, stainless steel flakes, titanium flakes, etc.); iron black; yellow iron oxide; red iron oxide; yellow lead; carbon black; molybdate orange; iron blue; ultramarine; cadmium-based pigments; fluorescent pigments; soluble azo dyes; insoluble azo dyes; condensed azo dyes; phthalocyanine pigments; condensed polycyclic pigments; composite oxide-based pigments; graphite; mica (e.g., muscovite, phlogopite, synthetic mica, tetrafluoroethylene ... metal oxide-coated mica (e.g., titanium oxide-coated mica, titanium dioxide-coated mica, (hydrated) iron oxide-coated mica, iron oxide and titanium oxide-coated mica, low-order titanium oxide-coated mica, etc.); metal oxide-coated graphite (e.g., titanium dioxide-coated graphite, etc.); flaky alumina; metal oxide-coated alumina (e.g., titanium dioxide-coated alumina, iron oxide-coated flaky alumina, Fe2O3-coated flaky alumina, Fe3O4-coated flaky alumina, interference color metal oxide-coated flaky alumina, etc.); micaceous iron oxide (MIO); metal oxide-coated MIO; metal oxide-coated silica flakes, and metal oxide-coated glass flakes. By combining these pigments with each other, new colors can be obtained and color development can be improved. This paint can be applied to wood, plastics, metal plates, glass, ceramics, paper, films, sheets, translucent films of reflectors for LC displays, etc. Examples of applications of paints include automobiles, construction, ships, home appliances, canned goods, industrial equipment, road markings, plastics, and household goods.

[0025] Examples of coating structures of painted materials include, but are not limited to, layered structures such as, for example, a base layer, an intermediate coat layer, a pigment-containing layer of the present invention, and a clear coat in that order; or a base layer, a pigment-containing intermediate coat layer of the present invention, and a clear coat in that order. Coating film formation methods for forming coated materials include 1 coat / 1 bake, 2 coat / 1 bake, 2 coat / 2 bake, 3 coat / 1 bake, 3 coat / 2 bake, 3 coat / 3 bake, etc. Examples of coating methods include electrostatic coating, spray coating, airless coating, roll coater coating, dip coating, etc. Examples of the use in radar-transparent coatings include water-based OEM or refinish automotive coatings on plastic substrates. The plastic substrates are automotive bumpers, radiator grilles, automotive back panels, door trim strips, rearview mirror casings, or handy casings. The plastic substrates may be thermoplastics such as polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS) copolymers, acrylonitrile-ethylene-styrene (AES) copolymers, and polypropylene (PP). The radar-transparent coatings on plastic substrates are preferably on automotive bumpers and are made from coating formulations containing metallic effect pigments and / or mixtures with other pearlescent effect pigments. The coatings on plastic substrates preferably have a dry film thickness of 15 μm or less and a percentage of metal (aluminum) moiety mass concentration (PWC) of 5% or less by weight. Examples of lidar applications include lidar transparent pigments and lidar reflective layers, both in lidar compatible paint systems. The pigments of the present invention, like metallic gray colors, can be formulated with lidar reflective materials, such as functional black, to enhance lidar reflectivity and detectability.

[0026] Use in printing inks Examples of use in printing inks include letterpress ink, lithographic printing ink, intaglio printing ink, metal plate ink, radiation curable ink, UV ink, EB ink, flexographic ink, screen ink, offset ink, gravure ink, and the like, as well as water-based inks thereof. The pigment of the present invention can be mixed in a ratio of 1 to 100% by mass with respect to the resin as the solid content of the ink. A ratio of 1 to 70% by mass is preferred. A ratio of 1 to 20% by mass is particularly preferred. The pigment of the present invention can be treated on the pigment surface with a silane coupling agent, a titanium coupling agent, or the like. Examples of the resin component include, for example, maleic rosin resin, maleic resin, alkyd resin, polyamide resin, phenolic resin, petroleum resin, urethane resin, epoxy resin, acrylic resin, butyral resin, melamine, epoxy resin, vinyl chloride resin, vinylidene chloride resin, cellulose resin, vinyl resin, unsaturated polyester resin, cellulose resin, and the like. These resins may be used alone or in combination of two or more. Examples of mixtures include further pigments such as organic pigments, inorganic pigments, and additives such as varnishes, reducers, compounders, extra-print varnishes, gelling agents, drying accelerators, antioxidants, anti-offset agents, lubricants, surfactants, etc. Further examples include anti-sagging agents, viscosity modifiers, anti-settling agents, crosslinking accelerators, hardeners, leveling agents, defoamers, plasticizers, preservatives, mildew inhibitors, UV stabilizers, etc. Examples of further pigments which can be used in combination with the pigments of the present invention include extender pigments; precipitated barium sulfate; precipitated calcium carbonate; alumina white; magnesium carbonate; white carbon; white pigments such as titanium oxide and zinc oxide; black pigments such as carbon black; yellow pigments such as chrome yellow, disazo yellow, and Hansa yellow; red pigments such as brilliant carmine 6B, lake red C, permanent red F5R, and rhodamine lake; blue pigments such as phthalocyanine blue, Victoria blue lake, and Prussian blue; orange pigments such as chrome vermilion and disazo orange; green pigments such as phthalocyanine green; purple pigments such as methyl violet lake and dioxazine violet; isoindolinone, benzimidazoline, condensed azo, and cyan. Other pigments include porcelain, composite oxide pigments, graphite, mica (e.g., muscovite, gold mica, synthetic mica, fluorine tetrasilicic mica, etc.), metal oxide-coated mica (e.g., titanium oxide-coated mica, titanium dioxide-coated mica, (hydrated) iron oxide-coated mica, iron oxide and titanium oxide-coated mica, low-order titanium oxide-coated mica, etc.), metal oxide-coated graphite (e.g., titanium dioxide-coated graphite, etc.), flaky alumina, metal oxide-coated alumina (e.g., titanium dioxide-coated alumina, iron oxide-coated flaky alumina, Fe2O3-coated flaky alumina, Fe3O4-coated flaky alumina, interference color metal oxide-coated flaky alumina, etc.), MIO, metal oxide-coated MIO, metal oxide-coated silica flakes, and metal oxide-coated glass flakes. These inks can be printed on wood, plastic, metal steel sheets, glass, ceramics, paper, cardboard, films, sheets, cans, translucent films of reflectors for LC displays, etc. When the pigment according to the present invention is combined with these pigments, etc., new hues, colors, and functions can appear. In particular, when appropriately combined with a play-of-color pigment, the pigment according to the present invention can be suitable for preventing counterfeiting of securities, tickets, travel tickets, train tickets, etc. Furthermore, when used in printing inks, it is particularly preferable to subject the pigment of the present invention to high orientation treatment (described above). The pigment thus surface-treated can be mixed into various printing inks and used in offset printing, gravure printing, screen printing, UV curing printing, letterpress printing, and lithographic printing. By using the pigment that has been subjected to high orientation treatment in inks, the color development of interference colors on the printing surface is improved.

[0027] Use in plastics In the present invention, when incorporated into plastics, the pigment can be mixed with the resin either directly or after forming pellets in advance, and then incorporated into various molded products by extrusion molding, calendar molding, blow molding, etc. As the resin component, any of polyolefin-based thermoplastic resins, epoxy-based, polyester-based, and polyamide (nylon)-based thermosetting resins can be used. A small amount of pigment can be sufficient to effectively produce the coloring effect of the pigment of the present invention. For example, when molding a multi-layer plastic bottle, the appearance of the bottle can be made effective by incorporating the pigment into the resin of the outer layer. In particular, the pigment obtained by the present invention is preferably further subjected to a surface orientation treatment (as described above) for the purpose of improving coloring. Of course, it is also possible to use the pigment of the present invention that has been subjected to a weld line prevention surface treatment (for example, encapsulation treatment, etc.). The pigment of the present invention can be used in combination with other pigments. Examples of such pigments include titanium dioxide, calcium carbonate, clay, talc, barium sulfate, white carbon, chromium oxide, zinc oxide, zinc sulfide, zinc powder, metal powder pigments, iron black, yellow iron oxide, red iron oxide, yellow lead, carbon black, molybdate orange, iron blue, ultramarine, cadmium pigments, fluorescent pigments, soluble azo dyes, insoluble azo dyes, condensed azo dyes, phthalocyanine pigments, condensed polycyclic pigments, composite oxide pigments, graphite, mica (e.g., muscovite, phlogopite, synthetic mica, fluorine tetrasilicic mica, etc.), metal oxide-coated mica (e.g., titanium oxide, metal oxide coated mica, titanium dioxide coated mica, (hydrated) iron oxide coated mica, iron oxide and titanium oxide coated mica, low titanium oxide coated mica, etc.); metal oxide coated graphite (e.g., titanium dioxide coated graphite, etc.); flaky alumina; metal oxide coated alumina (e.g., titanium dioxide coated alumina, iron oxide coated flaky alumina, Fe2O3 coated flaky alumina, Fe3O4 coated flaky alumina, interference color metal oxide coated flaky alumina, etc.); MIO; metal oxide coated MIO; metal oxide coated silica flakes, and metal oxide coated glass flakes.

[0028] Use for laser marking The pigment of the present invention can be used in various molded products by kneading it into the above-mentioned plastics not only for design purposes but also to facilitate laser printing and increase the transparency.

[0029] Use in cosmetics The use of the pigment in cosmetics in the present invention includes makeup cosmetics, hair care products, cosmetic packs, etc. The pigment can be used, for example, in gels, lipsticks, foundations (emulsions, liquids, oil-type emulsions, etc.), blushers, mascaras, nail enamels, eyebrow creams, eyeshadows, eyeliners, hair agents, etc. These pigments can be used in a proportion of 1 to 100% by mass based on the blend. For example, the pigment can be used in a proportion of 1 to 50% by mass for foundations, 1 to 80% by mass for eyeshadows, 1 to 40% by mass for lipsticks, and 0.1 to 20% by mass for nail enamels. Examples of the mixed components are shown below. Examples of pigments that can be used in combination with the pigment of the present invention include titanium dioxide, calcium carbonate, clay, talc, barium sulfate, white carbon, chromium oxide, zinc oxide, zinc sulfide, zinc powder, metal powder pigments, iron black, yellow iron oxide, red iron oxide, yellow lead, carbon black, molybdate orange, iron blue, ultramarine, cadmium pigments, fluorescent pigments, soluble azo dyes, insoluble azo dyes, condensed azo dyes, phthalocyanine pigments, condensed polycyclic pigments, composite oxide pigments, graphite, metal powder pigments, mica (e.g., muscovite, phlogopite, synthetic mica, fluorine tetrasilicic mica, etc.), metal oxide-coated mica (e.g., titanium oxide-coated mica, titanium dioxide-coated mica, (hydrated) iron oxide-coated mica, oxide iron and titanium oxide coated mica, low titanium oxide coated mica, etc.); metal oxide coated graphite (e.g., titanium dioxide coated graphite, etc.); flaky alumina; metal oxide coated alumina (e.g., titanium dioxide coated alumina, iron oxide coated flaky alumina, Fe2O3 coated flaky alumina, Fe3O4 coated flaky alumina, interference color metal oxide coated flaky alumina, etc.); MIO; metal oxide coated MIO; metal oxide coated silica flakes, and metal oxide coated glass flakes, sericite, magnesium carbonate, silica, zeolite, hydroxyapatite, chromium oxide, cobalt titanate, glass beads, nylon beads, silicone beads, etc. Examples of organic pigments are Red Nos. 2, 3, 102, 104, 105, 106, 201, 202, 203, 204, 205, 206, 207, 208, 213, 214, 215, 218, 219, 220, 221, 223, 225, 226, 227, 228, 230(1), 230(2), 231, 232, and 405; Yellow Nos. 4, 5, 201, 202(1), 202(2), 203, and 204. , 205, 401, 402, 403, 404, 405, 406, 407; green, 3, 201, 202, 204, 205, 401, 402; blue, 1, 2, 201, 202, 203, 204, 205, 403, 404; orange, 201, 203, 204, 205, 206, 207, 401, 402, 403; brown, 201; purple, 201, 401; and black, 401. Examples of natural dyes include salol yellow, carmine, β-carotene, hibiscus pigment, capsaicin, carminic acid, laccaic acid, glucumin, riboflavin, and shikonin. Further, examples of other components include fats and oils, surfactants, hydrocarbons such as squalane, liquid paraffin, palmitic acid, stearic acid, beeswax, and myristyl myristate, oil components such as acetone, toluene, butyl acetate, acetate esters, and polyhydric alcohols, and other organic solvents, waxes, antioxidants, UV absorbers, vitamins, hormones, preservatives, and fragrances. By combining the pigment of the present invention with the above pigments and components, new effect colors and functions can be found. When used in cosmetics, the pigment of the present invention can be used, for example, in compact cakes, creams, lipsticks, etc., but is particularly effective when used in make-up cosmetics where color is particularly important. Of course, the pigment of the present invention can be used after surface treatment (see above) has been performed in advance.

[0030] Other uses The pigment of the present invention can be used by being blended in color toners for copying machines. EXAMPLES

[0031] The present invention will be described in more detail below with reference to examples and comparative examples, but these are not intended to limit the present invention.

[0032] Example 1 Preparation of metallic luster interference color pigment (Fe2O3 / SnO2 / [SiO2 / Al(P)]) with reddish color 100 g of a flake-like metal substrate (e.g., aluminum) having a mass median diameter D50 of about 13.5 μm and a layer formed by a corrosion-resistant treatment ([SiO2 / Al(P)] obtained according to Example 4-b of paragraph

[0061] of JP 2003-41150 A) is suspended in 2 liters of water. The suspension is heated to 75 °C under stirring. 186 mL of a 50 g / L SnCl4·5H2O solution is dripped into the suspension while keeping the pH at 1.8 using a 20% by mass aqueous sodium carbonate solution (preparation of the first layer "intermediate binder layer"). Then, 4540 g of a 87.75 g / L FeCl3(III) aqueous solution is dripped until the desired hue is reached while keeping the pH at 3.0 using a 20% by mass aqueous sodium carbonate solution (preparation of the second layer). The solid portion is filtered from the suspension, washed, dried, and calcined at 350°C for 30 minutes to obtain a reddish metallic luster interference color pigment.

[0033] Example 2 Example of surface treatment of metallic luster interference color pigment (Fe2O3 / SnO2 / [SiO2 / Al(P)]) with reddish color according to the present invention A 10% slurry of Example 1 (mass ratio 100g / 1000g of Example 1 / ion-exchanged water) is prepared, and the temperature is kept at room temperature while stirring. After adding phosphoric acid (H3PO4) solution, the slurry is kept for 30 minutes. Then, a solution of tetraethyl orthosilicate (TEOS) is dripped. Then, the pH of the slurry is adjusted to 6.0, and the temperature is raised to 75°C. Two types of silane coupling agents, methacrylsilane (Z6030: methacryloxypropyltrimethoxysilane) and epoxysilane (Z6040: 3-glycidoxypropyltrimethoxysilane), are dripped into the solution. After holding for 1 hour, a silane coupling agent, aminosilane (Z6020: N-(β-aminoethyl)-y-aminopropyltrimethoxysilane) solution, is added to the solution. After holding for 1 hour, the slurry is filtered and washed with ion-exchanged water. The cake is dried at 130°C for 2.5 hours. The dried sample is sieved through a 32 μm sieve. The resulting metal effect pigment has a P2O5 content of 0.025% by weight, a SiO2 content of 0.5% by weight, and a carbon content of 1.0% by weight. All percentages are measured by weight based on the total weight of the metal effect pigment. The carbon content is measured by Elementar's UNICUBE CHN analyzer.

[0034] Example 3 Example of surface treatment of metallic luster interference color pigment (Fe2O3 / SnO2 / [SiO2 / Al(P)]) with reddish color according to the present invention Meoxal® Victoria Red (Fe2O3 / SnO2 / [SiO2 / Al(P)] from Merck KGaA) with a mass median diameter D50 of about 18 μm is obtained according to JP 2004-004811, JP 2005-264144, and JP 3987067. A 10% slurry of the above Meoxal® Victoria Red (100 g / 1000 g of the above Meoxal® Victoria Red / ion-exchanged water by mass ratio) is prepared and the temperature is kept at room temperature while stirring. After adding a phosphoric acid (H3PO4) solution, the slurry is kept for 30 minutes. Then, a solution of tetraethyl orthosilicate (TEOS) is added dropwise. The pH of the slurry is then adjusted to 6.0 and the temperature is increased to 75°C. Two silane coupling agents, methacrylsilane (Z6030: methacryloxypropyltrimethoxysilane) and epoxysilane (Z6040: 3-glycidoxypropyltrimethoxysilane), are dropped into the solution. After holding for 1 hour, a silane coupling agent, aminosilane (Z6020: N-(β-aminoethyl)-y-aminopropyltrimethoxysilane) solution, is added to the solution. After holding for 1 hour, the slurry is filtered and washed with ion-exchanged water. The cake is dried at 130°C for 2.5 hours. The dried sample is sieved through a 32 μm sieve. The resulting metal effect pigment has a P2O5 content of 0.15 wt%, SiO2 content of 0.5 wt%, and a carbon content of 1.8 wt%. All percentages are measured by weight based on the total weight of the metal effect pigment. The carbon content is measured by Elementar's UNICUBE CHN analyzer.

[0035] Comparative Example 1 Example of insufficient surface treatment of metallic luster interference color pigment (Fe2O3 / SnO2 / [SiO2 / Al(P)]) with reddish color A 10% slurry of Example 1 (mass ratio 100g / 1000g of Example 1 / ion-exchanged water) is prepared, and the temperature is kept at room temperature while stirring. Then, the pH of the slurry is adjusted to 6.0, and the temperature is raised to 75°C. Then, two types of silane coupling agents, methacrylsilane (Z6030: methacryloxypropyltrimethoxysilane) and epoxysilane (Z6030: methacryloxypropyltrimethoxysilane), are dropped into the solution. After holding for 1 hour, a silane coupling agent, aminosilane (Z6020: N-(β-aminoethyl)-y-aminopropyltrimethoxysilane) solution, is added to the solution. After holding for 1 hour, the slurry is filtered and washed with ion-exchanged water. The cake is dried at 130°C for 2.5 hours. The dried sample is sieved through a 32 μm sieve.

[0036] Comparative Example 2 Example of insufficient surface treatment of metallic luster interference color pigment (Fe2O3 / SnO2 / [SiO2 / Al(P)]) with reddish color Meoxal® Victoria Red (Fe2O3 / SnO2 / [SiO2 / Al(P)] from Merck KGaA) with a mass median diameter D50 of about 18 μm is obtained according to JP 2004-004811, JP 2005-264144, and JP 3987067. A 10% slurry of the above Meoxal® Victoria Red (100 g / 1000 g of the above Meoxal® Victoria Red / ion-exchanged water by mass ratio) is prepared and the temperature is kept at room temperature while stirring. The pH of the slurry is then adjusted to 6.0 and the temperature is increased to 75° C. Two silane coupling agents, methacrylsilane (Z6030: methacryloxypropyltrimethoxysilane) and epoxysilane (Z6030: methacryloxypropyltrimethoxysilane), are then dropped into the solution. After holding for 1 hour, a silane coupling agent of aminosilane (Z6020: N-(β-aminoethyl)-y-aminopropyltrimethoxysilane) solution is added to the solution. After holding for 1 hour, the slurry is filtered and washed with ion-exchanged water. The cake is dried at 130°C for 2.5 hours. The dried sample is sieved through a 32 μm sieve.

[0037] Moisture resistance evaluation The metallic effect pigments according to the invention and the comparative metallic effect pigments were investigated in a wet test as follows and the corresponding test results are shown in Table 1. Wet Test: The humidity test evaluates the behavior of the coating or pigments embedded in the coating after storing the coated panels for 10 days in a chamber at 100% humidity and 40°C according to DIN EN ISO 6270-2 in a HYGROTHERM 519 from ERICHSEN INC. The test is carried out on water-based coating systems. After completion of the wet test, the panels were removed and left for 1 hour and 4 hours. The performance (humidity resistance) was evaluated by the clarity of image (DOI) {test scale 10 (good) to 0 (bad)} The results of the wet test are shown in Table 1.

[0038] [Table 1] When the metal effect pigments have no surface treatment, for example, the metal effect pigments obtained from Example 1 show very poor moisture resistance performance, which is almost unusable for outdoor applications. As shown in Comparative Examples 1 and 2, when the surface treatment is insufficient, the resulting metal effect pigments still have poor moisture resistance performance (see Table 1). When only the surface treatments disclosed in this application (for example, Examples 2 and 3) are used, the resulting metal effect pigments can achieve excellent moisture resistance performance (see Table 1).

[0039] Examples of use are given below: The surface-treated metallic effect pigments according to the invention show very good application medium compatibility. Usage example 1 Examples of use in paints: Pearlescent pigment-based paints: (Composition A) Acrydic 47-712 70 parts by mass Super Beckamine G821-60 30 parts by mass (Composition B) Sample of Example 2 10 parts by weight Pearlescent pigment 10 parts by weight (Composition C) Ethyl acetate 50 parts by weight Toluene 30 parts by weight n-Butanol 10 parts by mass Solvesso #150 40 parts by mass 100 parts by weight of composition A is mixed with 20 parts by weight of composition B, and the resulting mixture is diluted to obtain a viscosity suitable for spray coating using composition C (12 to 15 seconds with Ford Cup #4), which is then spray coated to form a base layer. Clear Paint: Acrydic 44-179 14 parts by mass Super Beckamine L117-60 6 parts by mass Toluene 4 parts by mass MIBK (methyl isobutyl ketone) 4 parts by weight Butyl cellosolve 3 parts by mass This composition is coated onto the pearlescent base, dried at 40° C. for 30 minutes, air dried at room temperature, and baked (130° C. for 30 minutes). The resulting coating exhibits a vivid reddish metallic interference color with high chroma.

[0040] Usage example 2 Examples of applications in plastics: High density polyethylene (pellets) 100 parts by weight Sample of Example 2 1 part by weight Magnesium stearate 0.1 parts by weight Zinc stearate 0.1 parts by weight The above ingredients are dry blended and molded by injection molding. The molded product containing the sample of Example 2 exhibits a vivid reddish interference color having a metallic luster.

[0041] Usage example 3 Examples of use in inks: CCST medium (nitrocellulose resin) 10 parts by weight Sample of Example 2 8 parts by weight Solvent NC102 is added to the ink composition blended from the above components to prepare an ink having a viscosity of 20 seconds in Zahn Cup No. 3. Prints obtained with this ink, including the sample of Example 2, show interference colors with a bright reddish color and metallic luster.

[0042] Usage example 4 Examples of use in cosmetics Compact powder application example: Talc 50 parts by weight Sample of Example 2 25 parts by weight Color pigment 5 parts by weight Isopropyl myristate (appropriate amount) Magnesium stearate 2 parts by weight Foundation Formulation: Talc 38 parts by weight Sample of Example 2 25 parts by weight Mica (8μm) 10 parts by mass Magnesium stearate 3 parts by weight Nylon powder 12 8 parts by weight Yellow iron oxide 1.9 parts by weight 0.8 parts by weight of red iron oxide Titanium oxide 1.0 parts by mass Mineral oil (oil component) Appropriate amount (Caprylic acid, capric acid) triglyceride (oil component) 3.3 parts by mass Butylparaben 0.1 parts by weight [Industrial Applicability]

[0043] The metal effect pigments of the present invention are pigments in which a platelet-shaped metal substrate is coated with one or more layers of metal compounds selected from metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal sulfides, metal carbides, metal nitrides, metal oxynitrides, and mixtures thereof. Based on the metal effect pigments, a surface treatment is carried out on the substrate, which comprises phosphoric acid (H3PO4), tetraethyl orthosilicate (TEOS), and at least one organic coupling agent. The surface-treated metal effect pigments show excellent moisture resistance without affecting the chroma, gloss, and color of the base metal effect pigment. Thus, the pigments can be used in paints, coatings, automotive coatings, industrial coatings, pigment preparations, pigment pastes, radar-transparent coatings, lidar applications, painted materials, inks, printed materials, plastics, moldings, laser marking, or cosmetics, etc.

Claims

1. A) Phosphoric acid (H 3 P.O. 4 ), B) tetraethyl orthosilicate (TEOS), and C) metal effect pigments surface treated with at least one organic coupling agent.

2. 10. The metallic effect pigment of claim 1, wherein three organic coupling agents are used.

3. 2. The metallic effect pigment of claim 1, wherein the organic coupling agent is selected from alkylsilanes, epoxysilanes, (meth)acrylicsilanes, aminosilanes, and vinylsilanes.

4. 2. The metallic effect pigment of claim 1, wherein the amount of C) organic coupling agent is in the range of 0.3 to 3.0% by weight, calculated as carbon, based on the total weight of the metallic effect pigment.

5. A) Phosphate compound (H 3 P.O. 4 ) is based on the total weight of the metallic effect pigments. 2 O 5 2. The metallic effect pigment of claim 1, wherein the total amount of the metallic effect pigment is in the range of 0.01 to 1.0% by weight.

6. B) The amount of tetraethyl orthosilicate (TEOS) is based on the total weight of the metal effect pigment. 2 2. The metallic effect pigment of claim 1, wherein the total amount of the metallic effect pigment is in the range of 0.1 to 1.5% by weight.

7. The metallic effect pigments comprise a platelet-shaped metal substrate coated with one or more layers of metal compounds selected from metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal sulfides, metal carbides, metal nitrides, metal oxynitrides, and mixtures thereof; 2. The metallic effect pigment of claim 1, wherein the platelet-shaped metal substrate is selected from at least one metal or metal alloy selected from aluminum, titanium, gold, silver, iron, stainless steel, copper, zinc, tin, nickel, and chromium.

8. 8. The metallic effect pigments according to claim 7, wherein the platelet-shaped metal substrate is coated with one or more metal oxides and / or metal sulfides of one or more metals selected from the group consisting of iron, titanium, aluminum, zirconium, tin, zinc, bismuth, calcium, manganese, cerium, chromium, cobalt, silicon, and boron.

9. 8. The metal effect pigments according to claim 7, further comprising a layer obtained from a step of treating the surface of the platelet-shaped metal substrate with a phosphate compound and / or a borate compound, followed by a step of coating with one or more hydrous metal oxide layers of one or more metals selected from the group consisting of silicon, aluminum, zirconium and titanium by a sol-gel process.

10. A method for preparing the metallic effect pigments according to any one of claims 1 to 9, comprising the steps of: dispersing / suspending said metallic effect pigments in water and / or one or more solvents, A) Phosphoric acid (H 3 P.O. 4 ), B) tetraethyl orthosilicate (TEOS), and C) at least one organic coupling agent are added to water and / or said solvent to perform a surface treatment; drying the metallic effect pigment; A preparation method comprising:

11. 11. A method for preparing metallic effect pigments according to claim 10, wherein the surface treatment can be carried out by wet chemical methods and / or by sol-gel methods.

12. A water-based coating system comprising the metallic effect pigments according to any one of claims 1 to 9.

13. 10. Use of the metal effect pigments according to any one of claims 1 to 9 in paints, coatings, automotive coatings, industrial coatings, pigment preparations, pigment pastes, radar-transparent coatings, lidar applications, painted materials, inks, printed materials, plastics, moldings, laser marking, or cosmetics.