Effect pigments

Abstract

Effect pigments that have high stability and high gloss, and are less prone to aggregation during application. Provided. [Solution] Al2O3 flakes are coated with one or more layers of metal oxide or a mixture of metal oxides. The amount of Al2O3 in the Al2O3 flake and the total amount of metal oxide in the coating layer are coated. Effect pigments with a ratio ranging from 27:73 to 83:17.

Description

[Technical Field]

[0001] This invention relates to an Al2O3 flake-based effervescence with high weather resistance and low photoactivity. Pigments, as well as paints, industrial coatings, automotive coatings, printing inks, chemicals Regarding their use in cosmetic formulations. [Background technology]

[0002] The imparting of pearly luster, metallic luster, color flop, or multicolor effect is achieved through natural or synthetic transparency. This can be achieved by using pearlescent pigments based on light-colored flakes. α- Pearlescent pigments based on Al2O3 flakes are well known in the literature, and Xiralli It is sold commercially by Merck KGaA under the trademark c(registered trademark).

[0003] Based on titanium dioxide-doped aluminum oxide flakes, this metal oxide is Coatings of Al2O3 are known from US5,702,519.

[0004] WO 2006 / 101306 A1 and WO 2008 / 026829 A1 are zinc-doped Al2O3 flakes. and relating to pearlescent pigments based on these Al2O3 flakes. These zincs The processed Al2O3 flakes are not stable under acidic conditions and therefore are not suitable for all applications. That is inappropriate.

[0005] Conventional effect pigments based on Al2O3 flakes are often very insufficient. It does not have high chemical and weather stability, sometimes exhibits a grayish color texture, and / or chemical It has the disadvantage of being prone to aggregation when added to cosmetics and paints. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The objective of the present invention is to provide a product that does not exhibit the drawbacks of the prior art and is characterized by high stability and high gloss. Furthermore, Al2O3 flakes that do not show any tendency to aggregate when incorporated into the application examples are used. The objective is to provide an improved effect pigment.

[0007] Surprisingly, the alumina flakes coated with one or more metal oxides are based on The properties of the pigment depend on the amount of Al2O3 in the Al2O3 flake (substrate) and the coating layer. By using alumina flakes with a precisely defined ratio to the total amount of all metal oxides, Therefore, it was finally discovered that it can be increased.

[0008] For details, the aggregation behavior and weather resistance stability of the effect pigments are specified for Al2O3 / gold It may be affected by the ratio of group oxides. Furthermore, the effect has a defined ratio. The pigments exhibit improved gloss, saturation, and exceptionally clear colors. [Means for solving the problem]

[0009] Therefore, the present invention relates to Al2O3 flakes being one or more metal oxides or mixtures of metal oxides. It is coated with a layer of Al2O3, and the amount of Al2O3 in the Al2O3 flake and the metal oxidation of the coating layer The ratio of the total amount of material to the total effect pigments is in the range of 27:73 to 83:17. This relates to an effect pigment based on alumina flakes, characterized by the following features.

[0010] The effect strips according to the present invention include, for example, inks, coatings, preferably automotive coatings. - coatings, industrial coatings, plastics, cosmetic formulations, etc., the effect pigments can be used in all formulations commonly used. It can be used in all formulations commonly used.

[0011] Compared with the prior art, the effect pigments according to the present invention exhibit improved weather stability and improved adhesion properties such that the tendency to agglomerate and turn grayish is reduced, and at the same time, exhibit improved optical properties, particularly high chroma, higher gloss, lower haze, and excellent finish, and at the same time exhibit high chemical stability.

Embodiments for Carrying out the Invention

[0012] An essential feature of the effect pigments according to the present invention is the ratio of Al2O3 (substrate) to the total amount of metal oxides on the surface of the Al2O3 substrate. The term "metal oxides" includes mixtures of metal oxides.

[0013] In this patent application, the term "amount" is the weight of the Al2O3 flakes and the weight of the total metal oxides including the mixture of metal oxides of the entire coating layer on the surface of the Al2O3 flakes.

[0014] Coatings of Al2O3 substrates with one or more metal oxides are well-known, and suitable metal oxides are preferably selected from TiO2, Fe2O3, Fe3O4, SnO2, ZrO2, ZnO, Cr2O3, FeTiO5, or mixtures thereof. A preferred mixture of metal oxides is selected from TiO2 / Fe2O3.

[0015] The term metal oxides in this patent application also includes SiO2.

[0016] The effect pigments preferably have Al2O3 flakes with a thickness of 130 - 500 nm as the basis. - Make it into flakes. Preferred Al2O3 flakes preferably have a thickness of 130 - 400 nm, especially 150 - 350 nm.

[0017] Preferred Al2O3 flakes are characterized by a particle size distribution having a Gaussian distribution in which the volume size fraction is distributed as follows: - D is in the range of 15 - 30 μm, preferably 15 - 25 μm, 50 - D is in the range of 30 - 45 μm, preferably 30 - 40 μm. 90 In this patent application, D

[0018] of the alumina flakes, D 10 D 50 and D 90 are evaluated by using Malver n MS 2000.

[0019] The particle size distribution D 50 is also known as the median diameter or the median value of the particle size distribution; this is the value of the particle size at 50% of the cumulative distribution and is one of the important parameters characterizing the particle size of the pigment. Accordingly, the D

[0020] value is determined again in the form of the equivalent spherical diameter using laser particle size analysis 90 as the maximum longitudinal dimension of the Al2O3 flakes, meaning the maximum longitudinal dimension at which 90% of all the Al2O3 particles reach or are below that value. In a preferred embodiment, the D value of the alumina flakes according to the present invention is less than 9.5 μm

[0021] and preferably 9.0 μm or less. 10 The D value is determined for the Al2O3 flakes in the form of the equivalent spherical diameter using laser particle size analysis

[0022] 10 ​This is the vertical dimension value, and 10% of all Al2O3 flakes reach this maximum value. This refers to a vertical dimension value that is less than that.

[0023] In a preferred embodiment, the standard deviation of the thickness distribution of the Al2O3 flakes according to the present invention is less than 80. Full, preferably 50-60, especially 10-50.

[0024] In this patent application, the average thickness is such that the Al2O3 flakes are substantially parallel to the substrate in a planar manner. The orientation is determined based on the cured coating. For this purpose, the cross-section of the cured coating is The thickness of 100 Al2O3 thin sections was confirmed and measured under a scanning electron microscope (SEM). To average something out.

[0025] The desired size and thickness distribution can be determined by classifying through a selected screen, etc. It can be obtained by appropriate classification of the thin sections.

[0026] The Al2O3 flakes according to the present invention preferably have an aspect ratio of 30 to 200, particularly 50 to 150. It has a diameter-to-thickness ratio.

[0027] In a preferred embodiment, the Al2O3 flake of the present invention is an α-Al2O3 flake.

[0028] Al2O3 thin sheets are prepared by methods that are known, as described in the literature. It can be manufactured.

[0029] Doped Al to control grain size, thickness, optical properties, and / or surface morphology. Using 2O3 can sometimes be helpful. Dopants are a group of compounds including: TiO 2. From ZrO2, SiO2, In2O3, SnO2, ZnO, and combinations thereof, Preferably selected. The Al2O3 flake contains one or more dopants, preferably Al2 It can be contained in an amount of 0.01 to 5% by weight relative to the O3 flakes. In a preferred embodiment... Al2O3 flakes contain only one type of dopant.

[0030] In a preferred embodiment, the dopant is 0.05 to 3% by weight relative to the Al2O3 flake. The substances most commonly used are TiO2, ZrO2, or ZnO.

[0031] Al2O3 flakes are layers of metal oxides, such as TiO2, ZrO2, SnO2, ZnO, Fe2O3, Fe3O 4、 Layers such as FeTiO5, Cr2O3, CoO, and Co3O4 The TiO2 layer is preferably coated with at least one high refractive index layer. It may be in the chill or anatase form. Generally, it is of the highest quality and luster, and at the same time... The most suitable effect pigment is obtained when TiO2 is in the rutile form. To achieve this, an additive can be used that can convert TiO2 to the rutile form. Rutile derivatives are disclosed in US4,038,099, US5,433,779, and EP 0 271 767. The preferred rutile inducer is SnO2.

[0032] Preferred effect pigments based on Al2O3 flakes are formed by one or more layers of metal oxide. Preferably, only one metal oxide layer, particularly TiO2, Fe2O3, Fe3O4, Sn Coated with O2, ZrO2, or Cr2O3. TiO2 or Fe2O3 In particular, Al2O3 flakes coated with these mixtures are preferred.

[0033] The thickness of each high refractive index layer depends on the desired interference color. The wavelength is 20-400 nm, preferably 30-300 nm, and particularly 30-200 nm.

[0034] The number of layers on the surface of the Al2O3 flake is preferably 1 or 2 layers, and more preferably 3, 4, 5, or 6 layers. Alternatively, it has 7 layers.

[0035] In particular, interference packages consisting of high and low refractive index layers on the surface of Al2O3 flakes have a glossy finish. This increases the interference color or color flop, resulting in an effect pigment with even greater interference.

[0036] A suitable colorless, low refractive index material for coating is preferably a metal oxide or a corresponding material. Oxide hydrates, such as SiO2, Al2O3, AlO(OH), B2O3, MgO· It is a compound such as SiO2 or MgF2, or a mixture of the aforementioned metal oxides.

[0037] In the case of multilayers attached to the surface of Al2O3 flakes, the interfering system is particularly TiO2-SiO2-T This is the layer order of iO2.

[0038] Furthermore, the effect pigment according to the present invention may have a translucent metal layer as an outer layer. This type of coating is known, for example, from DE 38 25 702 A1. The metal layer is preferred The layer is a chromium or aluminum layer with a thickness of 5 to 25 nm.

[0039] Furthermore, the Al2O3 flake-based effect pigment is used as a final top coat. The area is coated with an organic or inorganic dye, preferably Prussian blue or carmine red. It can be done.

[0040] A particularly preferred effect pigment based on Al2O3 flakes according to the present invention is the following layer It has an order: Al2O3 flake +TiO2 Al2O3 flake +TiO2 / Fe2O3 Al2O3 flake + Fe2O3 Al2O3 flake + Fe3O4 Al2O3 flake+TiO2+Fe2O3 Al2O3 flake+TiO2+Fe3O4 Al2O3 flake+TiO2+SiO2+TiO2 Al2O3 flake+TiO2+MgO・SiO2+TiO2 Al2O3 flake+Fe2O3+SiO2+TiO2 Al2O3 flake+TiO2 / Fe2O3+SiO2+TiO2 Al2O3 flake+TiO2+SiO2+TiO2 / Fe2O3 Al2O3 flakes+TiO2 / Fe2O3+SiO2+TiO2 / Fe2O3 Al2O3 flake+TiO2+SiO2 Al2O3 flake+TiO2+SiO2 / Al2O3 Al2O3 flake+TiO2+Al2O3 Al2O3 flake + SnO2 Al2O3 flake+SnO2+Fe2O3 Al2O3 flake+SnO2+TiO2 Al2O3 flake + ZrO2 Al2O3 thin section + TiO2 + Prussian blue or Al2O3 thin section + TiO2 + carmine red

[0041] In the preferred embodiment described above, the TiO2 layer is made rutile or anatase. This is possible. In a preferred embodiment, the TiO2 layer is rutile-type. In a preferred embodiment, In the rutile type, first a thin SnO2 layer having a thickness in the range of 1 to 20 nm is attached, The material is then prepared by attaching a TiO2 layer.

[0042] The Al2O3 flakes described above in a preferred embodiment can be doped or doped. You don't have to do it.

[0043] In this application, the terms “coating” or “layer” refer to the Al2O according to the present invention. This is interpreted as meaning complete coverage by three thin layers.

[0044] Effect pigments based on doped or undoped Al2O3 flakes Preferably, 27-83% by weight of Al2O3 flakes and 17-7% of the total effect pigment. It consists of a 3% by weight coating layer.

[0045] If the interference color and / or texture color of the effect pigment is silver, then the Al2 of the Al2O3 flake The ratio of O3 to the amount of metal oxide in the coating layer is 60:40, based on the total effect pigment. A ratio of approximately 80:20 is preferable.

[0046] If the interference color and / or texture color of the effect pigment is blue, then the Al2 of the Al2O3 flake The ratio of O3 to the amount of metal oxide in the coating layer is 35:65, based on the total effect pigment. A ratio of approximately 60:40 is preferable.

[0047] If the interference color and / or texture color of the effect pigment is red, then the Al2 of the Al2O3 flake The ratio of O3 to the amount of metal oxide in the coating layer is 35:65, based on the total effect pigment. A ratio of ~65:35 is preferable.

[0048] Al2O3 flakes are wet chemically coated by CVD or PVD processes. It can be coated.

[0049] α-Al2O3 by one or more layers, preferably one or more metal oxide layers The coating of the flakes is preferably carried out by a wet chemical method, which produces a pearly finish. It is possible to use a wet chemical coating method developed for the preparation of this material. The type can be, for example, DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191、DE 22 44 298、DE 23 13 331、DE 15 22 572、DE 31 37 808、DE 31 37 8 09, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017, or This is described in other patent documents and other publications known to those skilled in the art.

[0050] In the case of wet coating, Al2O3 flakes are suspended in water, and one or more hydrolyzable metals are added. The salt is added at a pH appropriate for hydrolysis, but this value depends on the metal oxide or the hydrolysis of the metal oxide. The solution is selected so that it precipitates directly onto the thin section without causing secondary precipitation. pH is Normally, this is kept constant by the simultaneous addition of a base and / or acid. Then the pigment is separated. Separate, wash, dry at 50-150°C for 1-18 hours, and pre-bake for 0.5-3 hours, but this The calcination temperature can be optimized for each existing coating. Generally, The calcination temperature is 500-1000°C, preferably 600-900°C. If desired, The pigments are separated after the individual coatings have been applied, dried, optionally calcined, and then again It can be resuspended to allow for the attachment of additional layers.

[0051] SiO2 layer on Al2O3 flakes and / or already coated Al2O3 flakes Adhesion can generally be removed by adding a potassium or sodium aqueous glass solution at the appropriate pH. It will be carried out by [company name].

[0052] Furthermore, the coating can also be carried out in a fluidized bed reactor by gas-phase coating. This coating allows for, for example, the preparation of a suitable pearlescent pigment using EP 0 045 851. It is also possible to use the method presented in EP 0 106 235.

[0053] The hue and saturation of the effect pigment based on Al2O3 flakes according to the present invention are It can be varied over a very wide range through different selections of the amount of coating or the resulting layer thickness. It is possible to make subtle adjustments to a certain hue or saturation, either visually or through measurement techniques. By approaching the desired color under controlled conditions, it is possible to achieve something beyond mere quantity selection. ru.

[0054] The effect pigments according to the present invention can be used indoors and outdoors. Outdoor application For example, effect pigments are in high demand. In this case, the effect pigments are affected. Various factors can contribute to this, including exposure to light, high atmospheric humidity, and high and low temperatures. Furthermore, plastic parts and coatings used in outdoor applications are often subjected to extreme weather conditions. Furthermore, prolonged exposure to intense light causes the material to age over extended periods.

[0055] To improve weather resistance, dispersibility, and / or compatibility with user media, for example, A functional coating of Al2O3 or ZrO2 or a mixture thereof is applied to the pigment surface. It is possible to attach them. Furthermore, for example, EP 0090259, EP 0 634 459, WO 99 / 57204 、WO 96 / 32446、WO 99 / 57204、US5,759,255、US5,571,851、WO 01 / 92425、US RE41,858 E , or JJ Ponjee, Philips Technical Review, Vol. 44, No. 3, 81 ff. and PH Harding JC Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp. 471-493. For example, organic post-coating with silane is possible.

[0056] The after-coating layer or functional coating layer contains one or more layers of metal oxide. If present, the amount of metal oxide in the functional coating layer is the amount of Al2O3 in the Al2O3 flakes. The ratio of the amount to the amount of metal oxide in the coating layer must be considered, and this ratio is 27: It must be 83 to 83:17.

[0057] The present invention provides a pre-treated material containing a small amount of oxide or hydroxide of a rare earth metal compound. The effect pigments exhibit improved weather resistance and a low grayish effect, especially rare earth A metal oxide or hydroxide of a metal-like compound in an amount of 0.01 to 3%, particularly 0.05 to 2% by weight. The effect pigments contained in the present invention have further improved photostability and weather resistance. This indicates.

[0058] Therefore, the present invention further relates to oxides and hydroxides of rare earth metal compounds to all pigments. This relates to an effect pigment based on Al2O3 flakes containing 0.01 to 3% by weight of [a specific substance]. .

[0059] Preferred rare earth metal compounds are Ce2O3, La2O3, and Y2O3.

[0060] In addition to rare earth metal compounds, such as Ce2O3, other preferred metal oxides present in the protective layer are also desirable. The materials are Al2O3, SiO2, and ZrO2. Furthermore, the protective layer is an organic coupling. Organic components specifically selected from silanes, organic functional silanes, amino compounds, and organophosphorus compounds. It can contain.

[0061] Suitable coupling reagents include, for example, organosilanes, organoaluminates, and organosilanes. The coupling agent is preferably notitanate and / or zirconate. It is a type of orchid called Ganoishira.

[0062] Examples of organosilanes include propyltrimethoxysilane and propyltriethoxysilane. n-Hexyltrimethoxysilane, Isobutyltrimethoxysilane, n-Octyltrimethyl Toxysilane, i-octyltrimethoxysilane, n-octyltriethoxysilane, n - Decyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxy Silane, vinyltrimethoxysilane, preferably n-octyltrimethoxysilane, and It is n-octyltriethoxysilane. Suitable oligomeric alcohol-free organelle. Nosilane hydrolysates, in particular, Dynasylan® Hydrosil and Products sold by Evonik Industries under the product name, for example, D ynasylan (registered trademark) Hydrosil 2926, Dynasylan (registered trademark) Trademark) Hydrosil 2909, Dynasylan (Registered Trademark) Hydrosil 2907, Dynasylan® Hydrosil 2781, Dynas ylan® Hydrosil 2776, Dynasylan® H ydrosil 2627, etc. Furthermore, oligomeric vinylsilanes and amino-sil ane hydrolyzates are also suitable as organic coatings. Functionalized organic silanes include, for example, 3 -aminopropyltrimethoxysilane (AMMO), 3-methacryloxytrimethoxy silane (DAMO), 3-glycidoxypropyltrimethoxysilane (GLYMO) , β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-isocyanato propyltrimethoxysilane, 1,3-bis(3-glycidoxypropyl)-1,1, 3,3,-tetramethyldisiloxane, ureidopropyltriethoxysilane, preferably 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-glycidoxypropyl-trimethoxysilane, β-(3,4-epoxycyclohe xyl)ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane. Examples of polymer silanes are described in WO 98 / 13426 and are sold, for example, under the trademark Dynasylan® Hydrosil by Evonik I ndustries. The amount of the organic coating can be between 0.2 and 5 wt% with respect to the effect pigment, preferably 0.5 to 2 wt%. ndustries under the trademark Dynasylan® Hydrosil . The amount of the organic coating can be between 0.2 and 5 wt% with respect to the effect pigment, preferably 0.5 to 2 wt%. .

[0063] Suitable coupling agents include, inter alia, the following structures

[0064] [Chemical formula]

[0065] (In the formula, X is NH2, COOH, -COO - hydroxyphenyl, methacrylate, carboxy Siphenyl, alkyl, mercapto, phenyl, H, vinyl, styryl, melamine, epoxy Represents xy, aryl, or alkyl, (n represents 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) It is zirconium aluminate.

[0066] Other suitable coupling reagents have the following structure M n (OR) y (In the formula, M represents Zr, Ti, or Al. N represents the valence of the metal. y is 1, 2, or 3 depending on the valence of the metal. R is (i) Alkyl or aryl compounds with 1 to 12 carbon atoms, (ii) -N(alkyl)3, -NH(alkyl)2, -NH2(alkyl), -NH 3, N(aryl)3, -NH(aryl)2, or -NH2(aryl) Substituted alkyl or aryl (aryl is a halogen, nitro, amino, or water) (May be substituted by an element), (iii) C-aryl or C-alkyl (Indicates) It is a metal acid ester.

[0067] Particularly suitable metal acid esters, such as acrylate-functional and methacrylamide-functional. Titanate and methacrylamide-functionalized zirconate are commercially available.

[0068] Effect pigments composed of a protective layer on the surface of coated Al2O3 flakes The total percentage is 2 to 20% by weight, preferably 2 to 10% by weight, and especially 2 to 5% by weight. Yes. The protective layer itself contains 0.2 to 2% by weight of a rare earth metal oxide, preferably Ce2O3. 0.2-2 wt% SiO2, 0.2-4 wt% Al2O3 and / or ZrO2 , and also containing 1 to 10% by weight of organic components. In preferred embodiments, the organic components are cup It is a ring agent.

[0069] In a preferred embodiment, the protective layer is Ce2O3 0.4-1.5% by weight, SiO2 0.4-1 wt%, Al2O3 and / or ZrO2 0.5-2.5 wt%, and It consists of 2-5% by weight of a plucking agent.

[0070] This product contains a protective layer in which the amount of Ce2O3 relative to the total effect pigment is 2% by weight or less. The effect pigments produced by the invention are particularly preferred.

[0071] Effect pigment according to the present invention, containing a protective layer with a cerium oxide content of 2% by weight or less. It exhibits further advantages, namely, it does not yellow in the dark, and does not contain phenolic antioxidants (e.g., BH T) results in less or no yellowing under UV irradiation and humidity, and high lightfastness. It also exhibits high weather resistance and stability.

[0072] According to the present invention, a protective coating on an effect pigment is prepared by a method known to those skilled in the art. It is manufactured. In a preferred embodiment, the effect pigment is pre-coated by wet chemical coating. It will be processed.

[0073] In a preferred embodiment, the effect pigment is suspended in water and the pH is adjusted to a value between 3 and 5. Afterwards, an aqueous salt solution or solid salt of a rare earth metal, and metallic aluminum and zirconium A solution of the aqueous salt or solid salt, or a mixture thereof, is applied to the oxide of the protective layer in a 1 to 4-degree Celsius manner. Add to the pigment suspension at a concentration of % by weight. Raise the pH value to 9 and maintain a constant pH value. Then add a dilute sodium silicate or potassium solution. In the final step, the effect To the pigment, add at least one coupling reagent in an amount of 1 to 10% by weight, preferably two. Add 5% by weight of the suspension, stir, and adjust the pH value to a value between 5 and 8. The finished effect pigment is post-treated by a method conventional to those skilled in the art, for example, by filtration. Isolate by drying and sieving.

[0074] Drying is preferably done at a temperature of 80 to 180°C, usually for 10 minutes or more, and 6 minutes if necessary. It can be carried out for up to 18 hours.

[0075] The present invention provides a protective layer containing 2% by weight or less of Ce2O3 relative to the total content. The pigments further excel in terms of dispersibility, stability, color properties, microbubble formation, swelling, and gloss. Improved properties, such as improved photostability, reduced grayish tint, and very good performance. Excellent suitability for weather-resistant, water-dilutable surface coating systems, especially automotive paint systems. This indicates.

[0076] The thickness of the protective layer on the effect pigment is, in a preferred embodiment, 0.5 to 10 nm, The range is 1 to 5 nm.

[0077] In a preferred embodiment, the effect pigment according to the present invention is obtained by the BET method (DIN ISO 12m (measured by 9277:2003-05) 2 / g or less, preferably 8m 2 It has a specific surface area of ​​less than or equal to / g.

[0078] The Al2O3 flake-based effect pigment according to the present invention has a large number of color systems, preferably These include paints, automotive coatings, industrial coatings, and printing inks, as well as cosmetic coatings. It can be adapted to a wide range of color systems from the realm of composite materials. For example, gravure printing, flexographic printing. , preparing printing inks for offset printing and offset overburning. In some cases, numerous binders are used, especially water-soluble grade binders, such as BASF, Marabu, and P. roll, Sericol, Hartmann, Gebr. Schmidt, Sicpa , Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco. , or those sold by Coates Screen INKS GmbH are suitable. It is correct. Printing inks should be water-based or solvent-based. It can do this. The pigment has applications in laser marking of paper and plastic, and in the agricultural sector. It is also more suitable for coloring greenhouse sheets, for example, and tent canopies.

[0079] Needless to say, in various application examples, the effect pigments according to the present invention are organic dyes, organic Pigments, or other pigments, such as transparent and opaque white, colored, and black pigments, Iron oxide in flake form, holographic pigments, LCP (liquid crystal polymer), and conventional transparent A colored, black glossy pigment, which is mica coated with a metal oxide and It can also be advantageously used by blending it with materials based on SiO2 flakes, etc. The Al2O3 flake-based effect pigments developed by this invention can be used with commercially available pigments and fillers. They can be mixed in any ratio.

[0080] Examples of fillers include natural and synthetic mica, nylon powder, pure or filler. Melamine resin, talc, SiO2, glass, kaolin, aluminum, magnesium Aluminum, calcium, or zinc oxides or hydroxides, BiOCl, barium sulfate, sulfuric acid Calcium, calcium carbonate, magnesium carbonate, carbon, and the physical properties of these substances Or it is a chemical combination. There are no restrictions regarding the particle shape of the filler. For example, according to requirements They may be flaky, spherical, or needle-shaped.

[0081] The Al2O3 flake-based effect pigment according to the present invention is easy to handle and use. Yes. Al2O3 flakes and effect pigments based on Al2O3 flakes are simply By stirring, it can be added to the system in which it is used. Al2O3 requires labor. Powdering and dispersion of the flakes and effect pigments are not necessary.

[0082] The Al2O3 flake-based effect pigment according to the present invention is used as a coating material, marking For coloring inks, plastics, agricultural films, button pastes, and seeds. It can be used for coloring food, and for coating pharmaceutical or cosmetic formulations. The concentrations of Al2O3 flakes and effect pigments in the system used for coloring are: Generally between 0.01 and 50% by weight, preferably between 0.1 and 5% by weight, relative to the total solids content of the system. It is between weight percent. This concentration generally depends on the individual application.

[0083] The effect pigment of the present invention is contained in an amount of 0.1 to 50% by weight, particularly 0.5 to 7% by weight. The plastics that possess this quality often exhibit a noteworthy glossy effect.

[0084] In the field of coatings, particularly automotive coatings and automotive finishes, the present invention The effect pigment is used in an amount of 0.5 to 10% by weight.

[0085] In coating materials, the effect pigment according to the present invention includes a single-layer coating (1 (As a base coat in a two-coat system) to achieve the desired color and gloss. This has the advantage of providing [something].

[0086] In binder-based pigment coloring, for example, paints for intaglio, offset, or screen printing... In the case of printing inks, Stapa®-Aluminium manufactured by Eckart GmbH. Effect pigments based on Al2O3 flakes containing um and gold bronze paste are particularly It has been proven to be appropriate. The effect pigment should be 2-50% by weight, preferably 5- It is added to printing inks in amounts of 30% by weight, especially 8-15% by weight. (Metallic effect pigment) In combination with the present invention, the printing ink containing the effect pigment exhibits a clear hue. Furthermore, the printability has been improved due to the favorable viscosity value.

[0087] Similarly, the present invention relates to effect pigments and other effect pigments, binders, The present invention provides pigment preparations containing additives as needed, wherein the preparations are substantially solvent It takes the form of easily flowable granules that do not contain [unclear]. Such granules are the effect face according to the present invention. It contains up to 95% by weight of the material. Al2O3 flakes and Al2O3 flakes according to the present invention are used as a base. The effect pigments, when combined with or without additives, with a binder and water, It has been paste-processed with a syrup / or organic solvent, and the paste has been subsequently dried. They are made into compacted fine particle forms, such as granules, pellets, briquettes, masterbatches, and The pigment preparation, which is in tablet form, is particularly suitable as a precursor for printing inks.

[0088] Therefore, the present invention relates to paints, coatings, automotive coatings, automotive finishes, Industrial coatings, paints, powder coatings, printing inks, security printing inks Also used as an effect pigment in formulations in the fields of plastics, ceramic materials, and cosmetics. Regarding coated and uncoated Al2O3 flakes, For use in paper, paper coatings, toners for electrophotographic printing processes, seeds, greenhouse screens. Thermally conductive, self-supporting, electrically insulating flexible material for insulating machinery or devices, and waterproof fabric. Plastic sheets are used as absorbents in laser marking of paper and plastic. Pigment base containing water, organic and / or aqueous solvents as an absorbent in laser welding of bucks. In addition, pigment preparations and dried preparations, such as granules, are used, for example, in the industrial and automotive sectors. As a clear coat, sunscreen, filler, especially for automotive coatings and It can also be used for automotive finishing. [Examples]

[0089] All percentage data in this application are weight percentages unless otherwise specified. That is the case.

[0090] The following examples illustrate the present invention in more detail, but without limiting it. That is the case. Example 1 Preparation of Al2O3 flakes Aluminum sulfate 18-hydrate 74.6g, polyaluminum chloride (PAC:Centr Al Glass Co., LTD (10% solution as Al2O3) 57.1g, anhydrous Heat 57.3g of sodium sulfate and 46.9g of potassium sulfate to over 60°C. Dissolve it in 300 ml of deionized water. Add 34.4% titanyl sulfate to this solution. Add 3.0 g of the solution. The resulting solution will be denoted as aqueous solution (a).

[0091] 0.45 g of trisodium phosphate dodecahydrate and 55.0 g of sodium carbonate are removed from the ash. Add to 300 ml of aqueous solution. The resulting solution is denoted as aqueous solution (b).

[0092] Add aqueous solution (b) to aqueous solution (a) while stirring, and maintain the temperature at approximately 60°C. Stir for 1 hour. Continue. The mixture of solution (a) and solution (b) obtained is a slurry. This slurry Evaporate to dryness, and heat the dried product at 1150°C for 6 hours. Add water to the heated product. Add to dissolve the free sulfate. Filter off the insoluble solids and wash with water. Finally, the product Dry it.

[0093] The obtained alumina thin section is examined by X-ray diffraction measurement. The diffraction pattern is obtained by colander It exhibits only peaks caused by the α-alumina structure.

[0094] The resulting Al2O3 thin section is its D 50 The value is 16.0 μm, D 90 The value is 30.8 The unit is μm, and the thickness is 200 nm.

[0095] The standard deviation of the thickness distribution of α-Al2O3 thin sections is 28. Example 2 Preparation of Al2O3 flakes Aluminum sulfate 18-hydrate 74.6g, polyaluminum chloride (PAC:Centr Al Glass Co., LTD (10% solution as Al2O3) 57.1g, anhydrous Heat 57.3g of sodium sulfate and 46.9g of potassium sulfate to over 60°C. Dissolve it in 300 ml of deionized water. Add 34.4% titanyl sulfate to this solution. Add 3.0 g of the solution and 5.5 g of a 5.0% indium(III) chloride solution. The resulting solution is denoted as aqueous solution (a).

[0096] 0.45 g of trisodium phosphate dodecahydrate and 55.0 g of sodium carbonate are removed from the ash. Add to 300 ml of aqueous solution. The resulting solution is denoted as aqueous solution (b).

[0097] Add aqueous solution (b) to aqueous solution (a) while stirring, and maintain the temperature at approximately 60°C. Stir for 1 hour. Continue. The mixture of solution (a) and solution (b) obtained is a slurry. This slurry Evaporate to dryness, and heat the dried product at 1200°C for 4 hours. Add water to the heated product. Add to dissolve the free sulfate. Filter off the insoluble solids and wash with water. Finally, the product Dry it.

[0098] The obtained alumina thin section is examined by X-ray diffraction measurement. The diffraction pattern is obtained by colander It exhibits only peaks caused by the α-alumina structure.

[0099] The resulting Al2O3 thin section is its D 50 The value is 19.0 μm, D 90 The value is 35.6 It is μm in thickness and 250 nm in diameter.

[0100] The standard deviation of the thickness distribution of α-Al2O3 thin sections is 32. Example 3 Preparation of Al2O3 flakes 1.3g of 27% Al2(SO4)3 solution, 45g of Na2SO43, K2SO42 Add 80g of the solution and 6g of ZnSO4·7H2O to 1,205ml of water and heat at 70°C. Heat in water. 900ml of water contains 320g of Na2CO3 and 62.7g of (NaPO3). Add the alkaline solution consisting of at 70°C. Add the aluminum sulfate mixture solution to pH 6.8 Titrate with an alkaline solution while stirring. Gel mixture of pseudo-boehmite and flux. The following is obtained. The gel mixture is aged at 90°C for 20 hours, then distilled in a vacuum at 60°C, and 11 Dry at 0°C for 20 hours. Grind the dried gel mixture into pieces smaller than 5 mm in size and pour into 2 liters of water. Moisture is removed by calcining in an alumina crucible at 500°C for 1 hour. The temperature is then increased to 930°C. The temperature is raised to ℃ and maintained for 0.5 hours, so that a homogeneous molten salt is formed, and needle-shaped alumina The particles solidify, forming flaky crystals. Crystallization occurs at 1,150°C for 5 minutes. This process is carried out for 0.5 hours, and filtration yields flaky α-alumina crystals. - Suspend the alumina crystals in 3,000 L of 0.5% sulfuric acid solution. Allow the particles to rise at 60°C for 48 hours. Stir to complete dispersion. Filter the mixture again, wash with water, and dry at 100°C. Transparent, flaky α-alumina with a thickness of 255 nm and an average particle size of 15.6 μm is obtained. Example 4 Coating of Al2O3 flakes Suspend 20 g of the alumina flakes from Example 1 in 250 ml of deionized water. The resulting suspension The pH is adjusted to 1.8-1.9 by adding 10% HCl, and throughout the entire procedure... Maintain at approximately 75°C. After stirring for 10 minutes, add 40.8g of SnCl to 15ml of deionized water. The solution and a 32% NaOH solution are added dropwise simultaneously while maintaining a pH of 1.8-1.9. After stirring for 30 minutes, prepare a solution containing 429g of TiCl in 50ml of deionized water. Add the 10% NaOH solution simultaneously while maintaining the pH at 1.8-1.9. Stir for 15 minutes. After mixing, adjust the pH to 7.5 by adding a 32% sodium hydroxide solution. After stirring for 10 minutes, 25 ml of deionized water contains 4.8 g of Na2SiO3. Add the solution to the suspension. At the same time, add a 10% HCl solution to maintain the pH at 7.5. After stirring for 10 minutes, the pH is adjusted to 1.8 by adding a 10% HCl solution. To reduce the suspension, allow it to settle, and partially remove the clear solution from the top of the settled particles. Therefore, adjust the volume to approximately 280 ml.

[0101] While stirring, add the solution of 0.8g of SnCl in 15ml of deionized water and sodium hydroxide. By adding the 32% solution while maintaining the pH at 1.8-1.9, simultaneous dropwise addition is possible. An additional layer of SnO2 was deposited by this process. After stirring for 30 minutes, 50 ml of deionized water was added. A solution containing 21.9g of TiCl4 is maintained at a pH of 1.8-1.9 while adding Na Add the 10% OH solution simultaneously. After stirring for 30 minutes, adjust the pH to 5.0-5.3. Filter. Wash the filter cake with water and dry it. Finally, heat the dried solids at 850°C. By calcining for 30 minutes, a very bluish, lustrous, pearly pigment is obtained. At a glossy angle, you can see the strong bluish tint and extremely glossy appearance from a wider angle. It is possible. Example 5 Coating of Al2O3 flakes Suspend 20 g of alumina flakes from Example 2 in 400 ml of deionized water. The resulting suspension Add a solution containing 125 g of TiCl4 per liter to the solution (maintained at approximately 65°C). At the same time, add a 10% NaOH solution to maintain the pH at 2.1. Add TiCl4 solution. Stop when the resulting product has a yellowish color. Then add Na2 per liter. A solution containing 350g of SiO3 is added to the resulting suspension. At the same time, 10% of HCl is added. Add a % solution to maintain the pH at 7. Next, add a solution containing 125g of TiCl4 per liter. Add the solution to the resulting suspension. At the same time, add a 10% NaOH solution to adjust the pH. Maintain the temperature at 2.1. Add TiCl4 solution when the resulting product has a bluish color. Stop. Filter out the suspended solids, wash with water, and dry. Finally, remove the dried solids from the 85°C container. By calcining at 0°C for 30 minutes, a very bluish, lustrous, pearly pigment can be obtained. It has a strong bluish tint and a very glossy appearance at a wide angle. You can see it. Example 6 Coating of Al2O3 flakes Suspend 20 g of the alumina flakes from Example 2 in 250 ml of deionized water. The resulting suspension The pH is adjusted to 1.8-1.9 by adding 10% HCl, and throughout the entire procedure... Maintain at approximately 75°C. After stirring for 10 minutes, add 40.8g of SnCl to 15ml of deionized water. The solution and a 32% NaOH solution are added dropwise simultaneously while maintaining a pH of 1.8-1.9. After stirring for 30 minutes, prepare a solution containing 429g of TiCl in 50ml of deionized water. Add the 10% NaOH solution simultaneously while maintaining the pH at 1.8-1.9. Stir for 15 minutes. After mixing, adjust the pH to 7.5 by adding a 32% sodium hydroxide solution. After stirring for 10 minutes, 25 ml of deionized water contains 4.8 g of Na2SiO3. Add the solution to the suspension. At the same time, add a 10% HCl solution to maintain the pH at 7.5. After stirring for 10 minutes, the pH is adjusted to 1.8 by adding a 10% HCl solution. To reduce the suspension, allow it to settle, and partially remove the clear solution from the top of the settled particles. Therefore, adjust the volume to approximately 280 ml.

[0102] While stirring, add the solution of 0.8g of SnCl in 15ml of deionized water and sodium hydroxide. By adding the 32% solution while maintaining the pH at 1.8-1.9, simultaneous dropwise addition is possible. An additional layer of SnO2 was deposited by this process. After stirring for 30 minutes, 50 ml of deionized water was added. A solution containing 21.9g of TiCl4 is maintained at a pH of 1.8-1.9 while adding Na Add the 10% OH solution simultaneously. After stirring for 30 minutes, adjust the pH to 5.0-5.3. Filter. Wash the filter cake with water and dry it. Finally, heat the dried solids at 850°C. By calcining for 30 minutes, a very bluish, lustrous, pearly pigment is obtained. At a glossy angle, you can see the strong bluish tint and extremely glossy appearance from a wider angle. It is possible. Example 7 Coating of Al2O3 flakes Suspend 20 g of the alumina flakes from Example 3 in 400 ml of deionized water. The resulting suspension Add a solution containing 125 g of TiCl4 per liter to the solution (maintained at approximately 65°C). At the same time, add a 10% NaOH solution to maintain the pH at 2.1. Add TiCl4 solution. Stop when the resulting product has a yellowish color. Then add Na2 per liter. A solution containing 50 g of SiO3 is added to the resulting suspension. At the same time, 10% of the HCl Add the solution to maintain a pH of 7. Next, add a solution containing 125g of TiCl4 per liter. Add the solution to the resulting suspension. At the same time, add a 10% NaOH solution to adjust the pH. Maintain the temperature at 2.1. Stop adding TiCl4 solution when the resulting product has a bluish tint. Stop. Filter out the suspended solids, wash with water, and dry. Finally, the dried solids are 850 By calcining at ℃ for 30 minutes, a very bluish, lustrous, pearly pigment can be obtained. At a wide angle, the strong bluish tint and extremely glossy appearance are visible. It is possible. Example 8 Coating of Al2O3 flakes Suspend 20 g of the alumina flakes from Example 3 in 250 ml of deionized water. The resulting suspension The pH is adjusted to 1.8-1.9 by adding 10% HCl, and throughout the entire procedure... Maintain at approximately 75°C. After stirring for 10 minutes, add 40.8g of SnCl to 15ml of deionized water. The solution and a 32% NaOH solution are added dropwise simultaneously while maintaining a pH of 1.8-1.9. After stirring for 30 minutes, prepare a solution containing 429g of TiCl in 50ml of deionized water. Add the 10% NaOH solution simultaneously while maintaining the pH at 1.8-1.9. Stir for 15 minutes. After mixing, adjust the pH to 7.5 by adding a 32% sodium hydroxide solution. After stirring for 10 minutes, 25 ml of deionized water contains 4.8 g of Na2SiO3. Add the solution to the suspension. At the same time, add a 10% HCl solution to maintain the pH at 7.5. After stirring for 10 minutes, the pH is adjusted to 1.8 by adding a 10% HCl solution. To reduce the suspension, allow it to settle, and partially remove the clear solution from the top of the settled particles. Therefore, adjust the volume to approximately 280 ml.

[0103] While stirring, add the solution of 0.8g of SnCl in 15ml of deionized water and sodium hydroxide. By adding the 32% solution while maintaining the pH at 1.8-1.9, simultaneous dropwise addition is possible. An additional layer of SnO2 was deposited by this process. After stirring for 30 minutes, 50 ml of deionized water was added. A solution containing 21.9g of TiCl4 is maintained at a pH of 1.8-1.9 while adding Na Add the 10% OH solution simultaneously. After stirring for 30 minutes, adjust the pH to 5.0-5.3. Filter. Wash the filter cake with water and dry it. Finally, heat the dried solids at 850°C. By calcining for 30 minutes, a very bluish, lustrous, pearly pigment is obtained. At a glossy angle, you can see the strong bluish tint and extremely glossy appearance from a wider angle. It is possible. Example 9 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 4 are placed in 1000ml of deionized water. Suspend in HCl. Maintain the resulting suspension at approximately 70°C and adjust the pH to 7 with 10% HCl. Then, 100 ml of a water glass solution containing 3.05 g of Na2SiO3 was added over a period of 90 minutes. At the same time, add a 10% HCl solution to maintain the pH at 7. Then, aluminum sulfate 100 ml of a solution containing 6.5 g of um(Al2(SO4)3·18H2O) is divided into 10% Add to the suspension over 90 minutes while maintaining pH 7 with NaOH. After increasing it to 7.5, 3-aminopropyl-trimethoxysilane (CAS No. 1 3822-56-5) 1.5g and 3-glycidyloxypropyl-trimethoxysilamine 1.5g of (CAS No. 2530-83-8) in 10% HCl or 10% NaO Add each component to the suspension over a 15-minute interval while maintaining the pH at 7.0 with H. The contents are filtered, washed with water, dried at 140°C, and sieved (325 mesh).

[0104] Surface-treated effect pigments exhibit good moisture resistance (wetness test) and remaining photoactivity. It exhibits moderate weather resistance. Example 10 Surface treatment of coated Al2O3 flakes Contains 2.55g of sodium hypophosphite (NaH2PO2·H2O) in a 2% by weight aqueous solution. While stirring the liquid at room temperature, add 3.90g of zirconium chloride (ZrOCl2·8H2O). To a 5% by weight aqueous solution containing [the substance], slowly add it so that no white precipitate forms. To the clear solution obtained in this way, 4.1 g of 35% by weight hydrochloric acid was added, and zirconoxide was added. A mixed solution of nium and sodium hypophosphite was obtained.

[0105] 100g of alumina flakes coated according to Example 4 are placed in 1000ml of deionized water. The resulting suspension is suspended in a container kept at approximately 70°C and adjusted to pH 2.5 with 10% HCl. Add 2.95 g of cerium(III) chloride (CeCl3·7H2O) to the turbid solution. A solution of zirconium oxide and sodium hypophosphite is maintained at pH 2.5 with 10% NaOH. Add it over a 60-minute period. Then, adjust the pH by adding 10% NaOH. Raise to 7.0 within 60 minutes. 3-aminopropyl-trimethoxysilane (CAS (No. 13822-56-5) 1.5g, 3-glycidyloxypropyl-trimethoxy Silane (CAS No. 2530-83-8) 1.5g, and n-hexyl trimethoquinol 0.5g of sisilane (CAS No. 3069-19-0) in 10% HCl or 10% The substances were added to the suspension over a 15-minute interval while maintaining the pH at 7.0 with NaOH. The turbid solids are filtered off, washed with water, dried at 140°C, and sieved (325 mesh).

[0106] Surface-treated effect pigments exhibit good moisture resistance and weather resistance. Example 11 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 4 are placed in 1000ml of deionized water. Suspend in HCl. The resulting suspension is kept at approximately 70°C and adjusted to pH 3.0 with 10% HCl. Add 1.70 g of cerium(III) chloride (CeCl3·7H2O) and aluminum sulfate to the turbid solution. Add 3.27g of nium(Al2(SO4)3·18H2O). Adjust the pH to 10% Na Using OH, the level is raised to 7.5 over 90 minutes. Then, 3.03 g of Na2SiO3 is added. Add 50 ml of the water glass solution over 90 minutes while maintaining the pH at 7.5 with 10% HCl. 3-aminopropyl-trimethoxysilane (CAS No. 13822-56-5) 1.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 2 Maintain 1.5g of (530-83-8) at pH 7.5 with 10% HCl or 10% NaOH. Each substance was then added to the suspension over a 15-minute interval. The suspended solids were filtered off and washed with water. Then, dry at 140°C and sift (325 mesh).

[0107] The effect pigment surface-treated according to Example 11, with reduced cerium content, is an example of Example 11. Compared to 9 and 10, it exhibits superior humidity characteristics (very good humidity) and weather resistance. Example 12 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 5 are placed in 1000ml of deionized water. Suspend in HCl. Maintain the resulting suspension at approximately 70°C and adjust the pH to 7 with 10% HCl. Add 100 ml of a water glass solution containing 3.05 g of Na2SiO3 over a period of 90 minutes. Add. At the same time, add a 10% HCl solution to maintain the pH at 7. Then, aluminum sulfate 100 ml of a solution containing 6.5 g of nium (Al2(SO4)3·18H2O) is divided into 10 Add to the suspension over 90 minutes while maintaining pH 7 with %NaOH. After increasing it to 7.5, 3-aminopropyl-trimethoxysilane (CAS No. 1 3822-56-5) 1.5g and 3-glycidyloxypropyl-trimethoxysilamine 1.5g of (CAS No. 2530-83-8) in 10% HCl or 10% NaO While maintaining the pH at 7.0 with H, the substances were added to the suspension over a 15-minute interval. (Suspension solids) The pulp is filtered, washed with water, dried at 140°C, and sieved (325 mesh).

[0108] Surface-treated effect pigments exhibit good moisture resistance (wetness test) and remaining photoactivity. It exhibits excellent weather resistance. Example 13 Surface treatment of coated Al2O3 flakes Contains 2.55g of sodium hypophosphite (NaH2PO2·H2O) in a 2% by weight aqueous solution. While stirring the liquid at room temperature, add 3.90g of zirconium chloride (ZrOCl2·8H2O). To a 5% by weight aqueous solution containing [the substance], slowly add it so that no white precipitate forms. To the clear solution obtained in this way, 4.1 g of 35% by weight hydrochloric acid was added, and zirconoxide was added. A mixed solution of nium and sodium hypophosphite was obtained.

[0109] 100g of alumina flakes coated according to Example 5 are placed in 1000ml of deionized water. The resulting suspension is suspended in a container kept at approximately 70°C and adjusted to pH 2.5 with 10% HCl. Add 2.95 g of cerium(III) chloride (CeCl3·7H2O) to the turbid solution. A solution of zirconium oxide and sodium hypophosphite is maintained at pH 2.5 with 10% NaOH. Add it over a 60-minute period. Then, adjust the pH by adding 10% NaOH. Raise to 7.0 within 60 minutes. 3-aminopropyl-trimethoxysilane (CAS (No. 13822-56-5) 1.5g, 3-glycidyloxypropyl-trimethoxy Silane (CAS No. 2530-83-8) 1.5g, and n-hexyl trimethoquinol 0.5g of sisilane (CAS No. 3069-19-0) in 10% HCl or 10% The substances were added to the suspension over a 15-minute interval while maintaining the pH at 7.0 with NaOH. The turbid solids are filtered off, washed with water, dried at 140°C, and sieved (325 mesh).

[0110] Surface-treated effect pigments exhibit good moisture resistance and weather resistance. Example 14 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 5 are placed in 1000ml of deionized water. Suspend in HCl. The resulting suspension is kept at approximately 70°C and adjusted to pH 3.0 with 10% HCl. Add 1.70 g of cerium(III) chloride (CeCl3·7H2O) and aluminum sulfate to the turbid solution. Add 3.27g of nium(Al2(SO4)3·18H2O). Adjust the pH to 10% Na Using OH, the level is raised to 7.5 over 90 minutes. Then, 3.03 g of Na2SiO3 is added. Add 50 ml of the water glass solution over 90 minutes while maintaining the pH at 7.5 with 10% HCl. 3-aminopropyl-trimethoxysilane (CAS No. 13822-56-5) 1.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 2 Maintain 1.5g of (530-83-8) at pH 7.5 with 10% HCl or 10% NaOH. Each substance was then added to the suspension over a 15-minute interval. The suspended solids were filtered off and washed with water. Then, dry at 140°C and sift (325 mesh).

[0111] The effect pigment surface-treated according to Example 14, with reduced cerium content, is an example of Example 14. Compared to 12 and 13, it exhibits superior humidity characteristics (very good humidity) and weather resistance. Example 15 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 6, in 1000ml of deionized water. Suspend in HCl. Maintain the resulting suspension at approximately 70°C and adjust the pH to 7 with 10% HCl. Then, add 100 ml of a water glass solution containing 3.05 g of Na2SiO3 over a period of 90 minutes. Add. At the same time, add a 10% HCl solution to maintain the pH at 7. Then, aluminum sulfate 100 ml of a solution containing 6.5 g of um(Al2(SO4)3·18H2O) is divided into 10% Add to the suspension over 90 minutes while maintaining pH 7 with NaOH. After raising it to 7.5, 3-aminopropyl-trimethoxysilane (CAS No. 13 822-56-5) 1.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 2530 - 83 - 8) 1.5 g was successively added to the suspension within 15 minutes each while maintaining the pH at 7.0 with 10% HCl or 10% NaOH. The suspended solids were filtered off, washed with water, dried at 140 °C, and sieved (325 mesh). The surface - treated effect pigment exhibits good moisture resistance (moisture test) and adequate weather resistance due to the remaining photoactivity.

[0112] The surface - treated effect pigment exhibits good moisture resistance (moisture test) and adequate weather resistance due to the remaining photoactivity. The surface - treated effect pigment exhibits good moisture resistance (moisture test) and adequate weather resistance due to the remaining photoactivity. Example 16 Surface Treatment of Al2O3 Flakes with Coating A 2 wt% aqueous solution containing 2.55 g of sodium hypophosphite (NaH2PO2·H2O) was slowly added to a 5 wt% aqueous solution containing 3.90 g of zirconium oxychloride (ZrOCl2·8H2O) while stirring at room temperature so that no white precipitate was formed. A 2 wt% aqueous solution containing 2.55 g of sodium hypophosphite (NaH2PO2·H2O) was slowly added to a 5 wt% aqueous solution containing 3.90 g of zirconium oxychloride (ZrOCl2·8H2O) while stirring at room temperature so that no white precipitate was formed. A 2 wt% aqueous solution containing 2.55 g of sodium hypophosphite (NaH2PO2·H2O) was slowly added to a 5 wt% aqueous solution containing 3.90 g of zirconium oxychloride (ZrOCl2·8H2O) while stirring at room temperature so that no white precipitate was formed. 4.1 g of 35 wt% hydrochloric acid was added to the thus - obtained transparent solution to obtain a mixed solution of zirconium oxychloride and sodium hypophosphite. 4.1 g of 35 wt% hydrochloric acid was added to the thus - obtained transparent solution to obtain a mixed solution of zirconium oxychloride and sodium hypophosphite.

[0113] 100 g of alumina flakes coated according to Example 6 was suspended in 1000 ml of deionized water. 2.95 g of cerium(III) chloride (CeCl3·7H2O) was added to the obtained suspension maintained at about 70 °C and adjusted to pH 2.5 with 10% HCl. 2.95 g of cerium(III) chloride (CeCl3·7H2O) was added to the obtained suspension maintained at about 70 °C and adjusted to pH 2.5 with 10% HCl. The solution of zirconium oxychloride and sodium hypophosphite was added over 60 minutes while maintaining the pH at 2.5 with 10% NaOH. The solution of zirconium oxychloride and sodium hypophosphite was added over 60 minutes while maintaining the pH at 2.5 with 10% NaOH. Then the pH was raised to 7.0 over 60 minutes by adding 10% NaOH (CAS No. 13822 - 56 - 5) 1.5 g, 3 - glycidoxypropyl - trimethoxysilane (CAS No. 2530 - 83 - 8) 1.5 g, and n - hexyltrimethoxy silane (CAS No. 2530 - 83 - 8) 1.5 g, and n - hexyltrimethoxysilane 0.5g of sisilane (CAS No. 3069-19-0) in 10% HCl or 10% The substances were added to the suspension over a 15-minute interval while maintaining the pH at 7.0 with NaOH. The turbid solids are filtered off, washed with water, dried at 140°C, and sieved (325 mesh).

[0114] Surface-treated effect pigments exhibit good moisture resistance and weather resistance. Example 17 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 6, in 1000ml of deionized water. Suspend in HCl. The resulting suspension is kept at approximately 70°C and adjusted to pH 3.0 with 10% HCl. Add 1.70 g of cerium(III) chloride (CeCl3·7H2O) and aluminum sulfate to the turbid solution. Add 3.27g of nium(Al2(SO4)3·18H2O). Adjust the pH to 10% Na The concentration is raised to 7.5 over 90 minutes using OH. Then, 3.03 g of Na2SiO3 is added. Add 50 ml of water glass solution over 90 minutes while maintaining the pH at 7.5 with 10% HCl. 3-Aminopropyl-trimethoxysilane (CAS No. 13822-56-5) 0.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 25 Maintain 1.5g of (30-83-8) at pH 7.5 with 10% HCl or 10% NaOH. Then, each was added to the suspension at intervals of 15 minutes. The suspended solids were filtered off and washed with water. Then, dry at 140°C and sift (325 mesh).

[0115] The surface-treated effect pigment according to Example 17, with reduced cerium content, is an example of Example 17. Compared to 15 and 16, it exhibits superior humidity characteristics (very good humidity) and weather resistance. Example 18 Surface Treatment of Coated Al2O3 Flakes 100 g of alumina flakes coated according to Example 7 are suspended in 1000 ml of deionized water The resulting suspension, maintained at about 70 °C and adjusted to pH 7 with 10% HCl To this, 100 ml of a water glass solution containing 3.05 g of Na2SiO3 is added over 90 minutes At the same time, a 10% solution of HCl is added to maintain the pH at 7. Then, 100 ml of a solution containing 6.5 g of aluminum sulfate (Al2(SO4)3·18H2O) is added to the suspension over 90 minutes while maintaining the pH at 7 with 10% NaOH. After raising the pH to 7.5 with 10% NaOH, 1.5 g of 3-aminopropyl-trimethoxysilane (CAS No. 13 822-56-5) and 1.5 g of 3-glycidoxypropyl-trimethoxysilane (CAS No. 2530-83-8) are successively added to the suspension over 15 minutes each while maintaining the pH at 7.0 with 10% HCl or 10% NaOH The suspended solids are filtered off, washed with water, dried at 140 °C, and sieved (325 mesh). (CAS No. 2530-83-8) are successively added to the suspension over 15 minutes each while maintaining the pH at 7.0 with 10% HCl or 10% NaOH The suspended solids are filtered off, washed with water, dried at 140 °C, and sieved (325 mesh). The surface-treated effect pigment exhibits good moisture resistance (moisture test) and moderate weather resistance due to the remaining photoactivity

[0116] The surface-treated effect pigment exhibits good moisture resistance (moisture test) and moderate weather resistance due to the remaining photoactivity The surface-treated effect pigment exhibits good moisture resistance (moisture test) and moderate weather resistance due to the remaining photoactivity Example 19 Surface Treatment of Coated Al2O3 Flakes A 2 wt% aqueous solution containing 2.55 g of sodium hypophosphite (NaH2PO2·H2O) is slowly added to a 5 wt% aqueous solution containing 3.90 g of zirconium oxychloride (ZrOCl2·8H2O) while stirring at room temperature so that no white precipitate is formed A 2 wt% aqueous solution containing 2.55 g of sodium hypophosphite (NaH2PO2·H2O) is slowly added to a 5 wt% aqueous solution containing 3.90 g of zirconium oxychloride (ZrOCl2·8H2O) while stirring at room temperature so that no white precipitate is formed A 2 wt% aqueous solution containing 2.55 g of sodium hypophosphite (NaH2PO2·H2O) is slowly added to a 5 wt% aqueous solution containing 3.90 g of zirconium oxychloride (ZrOCl2·8H2O) while stirring at room temperature so that no white precipitate is formed To the transparent solution thus obtained, 4.1 g of 35 wt% hydrochloric acid is added, and zirconium oxychloride A mixed solution of nium and sodium hypophosphite was obtained.

[0117] 100g of alumina flakes coated according to Example 7, in 1000ml of deionized water. The resulting suspension is suspended in a container kept at approximately 70°C and adjusted to pH 2.5 with 10% HCl. Add 2.95 g of cerium(III) chloride (CeCl3·7H2O) to the turbid solution. A solution of zirconium oxide and sodium hypophosphite is maintained at pH 2.5 with 10% NaOH. Add it over a 60-minute period. Then, adjust the pH by adding 10% NaOH. Raise to 7.0 within 60 minutes. 3-aminopropyl-trimethoxysilane (CAS (No. 13822-56-5) 1.5g, 3-glycidyloxypropyl-trimethoxy Silane (CAS No. 2530-83-8) 1.5g, and n-hexyl trimethoquinol 0.5g of sisilane (CAS No. 3069-19-0) in 10% HCl or 10% The substances were added to the suspension over a 15-minute interval while maintaining the pH at 7.0 with NaOH. The turbid solids are filtered off, washed with water, dried at 140°C, and sieved (325 mesh).

[0118] Surface-treated effect pigments exhibit good moisture resistance and weather resistance. Example 20 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 7, in 1000ml of deionized water. Suspend in HCl. The resulting suspension is kept at approximately 70°C and adjusted to pH 3.0 with 10% HCl. Add 1.70 g of cerium(III) chloride (CeCl3·7H2O) and aluminum sulfate to the turbid solution. Add 3.27g of nium(Al2(SO4)3·18H2O). Adjust the pH to 10% Na The concentration is raised to 7.5 over 90 minutes using OH. Then, 3.03 g of Na2SiO3 is added. Add 50 ml of water glass solution over 90 minutes while maintaining the pH at 7.5 with 10% HCl. 3-Aminopropyl-trimethoxysilane (CAS No. 13822-56-5) 0.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 25 Maintain 1.5g of (30-83-8) at pH 7.5 with 10% HCl or 10% NaOH. Then, each was added to the suspension at intervals of 15 minutes. The suspended solids were filtered off and washed with water. Then, dry at 140°C and sift (325 mesh).

[0119] The surface-treated effect pigment according to Example 20, with reduced cerium content, is an example of Example 20. Compared to 18 and 19, it exhibits superior humidity characteristics (very good humidity) and weather resistance. Example 21 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 8, in 1000ml of deionized water. Suspend in HCl. Maintain the resulting suspension at approximately 70°C and adjust the pH to 7 with 10% HCl. Then, add 100 ml of a water glass solution containing 3.05 g of Na2SiO3 over a period of 90 minutes. Add. At the same time, add a 10% HCl solution to maintain the pH at 7. Then, aluminum sulfate 100 ml of a solution containing 6.5 g of um(Al2(SO4)3·18H2O) is divided into 10% Add to the suspension over 90 minutes while maintaining pH 7 with NaOH. After raising it to 7.5, 3-aminopropyl-trimethoxysilane (CAS No. 13 822-56-5) 1.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 2530-83-8) 1.5g in 10% HCl or 10% NaOH While maintaining the pH at 7.0, each substance was added to the suspension over a 15-minute interval. Suspended solids The contents are filtered, washed with water, dried at 140°C, and sieved (325 mesh).

[0120] Surface-treated effect pigments exhibit good moisture resistance (wetness test) and remaining photoactivity. It exhibits excellent weather resistance. Example 22 Surface treatment of coated Al2O3 flakes Contains 2.55g of sodium hypophosphite (NaH2PO2·H2O) in a 2% by weight aqueous solution. While stirring the liquid at room temperature, add 3.90g of zirconium chloride (ZrOCl2·8H2O). To a 5% by weight aqueous solution containing [the substance], slowly add it so that no white precipitate forms. To the clear solution obtained in this way, 4.1 g of 35% by weight hydrochloric acid was added, and zirconoxide was added. A mixed solution of nium and sodium hypophosphite was obtained.

[0121] 100g of alumina flakes coated according to Example 8, in 1000ml of deionized water. The resulting suspension is suspended in a container kept at approximately 70°C and adjusted to pH 2.5 with 10% HCl. Add 2.95 g of cerium(III) chloride (CeCl3·7H2O) to the turbid solution. A solution of zirconium oxide and sodium hypophosphite is maintained at pH 2.5 with 10% NaOH. Add it over a 60-minute period. Then, adjust the pH by adding 10% NaOH. Raise to 7.0 within 60 minutes. 3-aminopropyl-trimethoxysilane (CAS (No. 13822-56-5) 1.5g, 3-glycidyloxypropyl-trimethoxy Silane (CAS No. 2530-83-8) 1.5g, and n-hexyl trimethoquinol 0.5g of sisilane (CAS No. 3069-19-0) in 10% HCl or 10% The substances were added to the suspension over a 15-minute interval while maintaining the pH at 7.0 with NaOH. The turbid solids are filtered off, washed with water, dried at 140°C, and sieved (325 mesh).

[0122] Surface-treated effect pigments exhibit good moisture resistance and weather resistance. Example 23 Surface treatment of coated Al2O3 flakes 100g of alumina flakes coated according to Example 8, in 1000ml of deionized water. Suspend in HCl. The resulting suspension is kept at approximately 70°C and adjusted to pH 3.0 with 10% HCl. Add 1.70 g of cerium(III) chloride (CeCl3·7H2O) and aluminum sulfate to the turbid solution. Add 3.27g of nium(Al2(SO4)3·18H2O). Adjust the pH to 10% Na The concentration is raised to 7.5 over 90 minutes using OH. Then, 3.03 g of Na2SiO3 is added. Add 50 ml of water glass solution over 90 minutes while maintaining the pH at 7.5 with 10% HCl. 3-Aminopropyl-trimethoxysilane (CAS No. 13822-56-5) 0.5g and 3-glycidyloxypropyl-trimethoxysilane (CAS No. 25 Maintain 1.5g of (30-83-8) at pH 7.5 with 10% HCl or 10% NaOH. Then, each was added to the suspension at intervals of 15 minutes. The suspended solids were filtered off and washed with water. Then, dry at 140°C and sift (325 mesh).

[0123] The surface-treated effect pigment according to Example 23, with reduced cerium content, is an example of Example 23. Compared to 21 and 22, it exhibits superior humidity characteristics (very good humidity) and weather resistance.

Claims

1. Al ２ O ３ A flake-based effect pigment, Al ２ O ３ The flakes were doped. Al ２ O ３ The flakes consist of one or more layers of a metal oxide or a mixture of metal oxides. Coated, Al ２ O ３ The amount of Al flakes ２ O ３ and the metal oxide of the coating layer The ratio of the amount of monster to the total amount of effect pigment is in the range of 27:73 to 83:

17. An effect pigment characterized by the following:

2. Al ２ O ３ The surface of the flake is coated with one or two metal oxide layers. The effect pigment according to claim 1, characterized by the following:

3. Al ２ O ３ The thin sheet is TiO ２ , ZrO ２ , SiO ２ , SnO ２ , In ２ O ３ , ZnO, The claim according to claim 1 or 2, characterized in that it is doped with a combination of these or Effect pigments.

4. The amount of doping is Al ２ O ３ The characteristic is that it is 0.01 to 5% by weight relative to the thin slice. An effect pigment as described in any one of the requirements 1 to 3.

5. TiO ２ or characterized by being doped with ZnO, any one of claims 1 to 4 The effect pigments listed in item 1.

6. Al ２ O ３ The thin flakes are characterized by having a particle thickness in the range of 130 to 500 nm. An effect pigment as described in any one of the requirements 1 to 5.

7. Al ２ O ３ Claim 1, characterized in that the standard deviation of the thickness distribution of the thin section is less than 80. The effect pigments described in any one of items 6 to 6.

8. Al ２ O ３ The thin sections are arranged in the following layer order: Al ２ O ３ Thin film + TiO ２ Al ２ O ３ Thin piece + TiO ２ / Fe ２ O ３ Al ２ O ３ Thin piece + Fe ２ O ３ Al ２ O ３ Thin piece + Fe ３ O ４ Al ２ O ３ Thin piece + TiO ２ +Fe ２ O ３ Al ２ O ３ Thin piece + TiO ２ +Fe ３ O ４ Al ２ O ３ Thin film + TiO ２ +SiO ２ +TiO ２ Al ２ O ３ Thin film + TiO ２ +MgO·SiO ２ +TiO ２ Al ２ O ３ Thin film + Fe ２ O ３ +SiO ２ +TiO ２ Al ２ O ３ Thin piece + TiO ２ / Fe ２ O ３ +SiO ２ +TiO ２ Al ２ O ３ Thin piece + TiO ２ +SiO ２ +TiO ２ / Fe ２ O ３ Al ２ O ３ Flake + TiO ２ / Fe ２ O ３ + SiO ２ + TiO ２ / Fe ２ O ３ Al ２ O ３ Thin film + TiO ２ +SiO ２ Al ２ O ３ Thin piece + TiO ２ +SiO ２ / Al ２ O ３ Al ２ O ３ Thin piece + TiO ２ +Al ２ O ３ Al ２ O ３ Thin film + SnO ２ Al ２ O ３ Thin piece + SnO ２ +Fe ２ O ３ Al ２ O ３ Thin film + SnO ２ +TiO ２ Al ２ O ３ Thin piece + ZrO ２ Al ２ O ３ Thin piece + TiO ２ + Prussian Blue or Al ２ O ３ Thin piece + TiO ２ +Carmine Red The E according to any one of claims 1 to 7, characterized in that it is coated with Pigments.

9. Al ２ O ３ The flakes are rutile or anatase-type TiO ２ It is coated with An effect pigment according to any one of claims 1 to 8, characterized by the following:

10. Al ２ O ３ The thin section is a rutile-type TiO ２ A feature that is coated with The effect pigment according to any one of claims 1 to 9.

11. The method according to any one of claims 1 to 10, characterized in that it contains a protective layer on its surface. Effect pigments.

12. The protective layer contains at least one rare earth metal oxide and silicon, aluminum, or d A metal oxide selected from tulconium or a mixture thereof, and an organic Effer according to any one of claims 1 to 11, characterized in that it contains a compound. Pigments.

13. The organic components include organic coupling agents, organic functional silanes, amino compounds, and organophosphorus compounds. The effect according to any one of claims 1 to 12, characterized by being selected from Pigment.

14. Claims 1 to 1 are characterized in that the rare earth metal oxide in the protective layer is cerium oxide. The effect pigment described in any one of item 13.

15. The effect pigment is characterized by having a content of 2% by weight or less of rare earth metal oxides. The effect pigment according to any one of claims 1 to 14.

16. The protective layer contains at least one rare earth metal oxide in an amount of 0.2 to 2% by weight, SiO ２ 0.2 ~2% by weight, Al ２ O ３ and / or ZrO ２ 0.2 to 4% by weight of the organic component The following is a characteristic of containing 1 to 10% by weight, according to any one of claims 1 to 15. Pigments.

17. The protective layer is characterized by having a thickness of 0.5 to 10 nm, according to claims 1 to 16. A different effect pigment as described in item 1.

18. Paints, coatings, automotive coatings, automotive finishes, industrial coatings, Paints, powder coatings, printing inks, security printing inks, plastics, ceramics Mick materials, cosmetics, glass, paper, paper coatings, toners for electrophotographic printing processes, Thermally conductive freestanding electric for seed, greenhouse sheeting material and waterproofing cloth, and insulation for machinery or devices. Laser-molded paper and plastic in formulations for gas-insulating flexible sheets. As an absorbent in King, as an absorbent in plastic laser welding, water, organic In pigment pastes containing and / or aqueous solvents, in pigment preparations and dried preparations The use of an effect pigment according to any one of claims 1 to 17.

19. Add one or more effect pigments according to any one of claims 1 to 17 to the entire composition In contrast, formulations containing the substance in an amount ranging from 0.01 to 95% by weight.

20. Water, polyols, polar or nonpolar oils, fats, waxes, film-forming agents, polymers, etc. Polymers, surfactants, free radical scavengers, antioxidants, stabilizers, odor enhancers Strengthening agents, silicone oil, emulsifiers, solvents, preservatives, thickeners, rheological additives, fragrances, colorants , effect pigments, UV absorbers, surfactants, and / or active ingredients for cosmetics, filling At least one selected from the group consisting of fillers, binders, pearlescent pigments, color pigments, and organic dyes. A type according to any one of claims 1 to 17, characterized in that it contains one component. A formulation containing the above-mentioned effect pigments.

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