TW200831617A - Black pearl shiny powder and method for making such powder - Google Patents

Abstract

This invention provides a black pearl-shiny titanium suboxide powder and a method for easily making such powder. It is a pearl-shiny black powder having thin-plate shaped powder of which the surface is coated with a titanium suboxide, wherein the titanium suboxide substantially free of nitrogen and is Ti0x (X= 1.56 to 1.75).

Description

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The present invention relates to a black pearlescent powder and a method for producing the same, and more particularly to a hue improvement of a black pigment using titanium oxide. Eight [Previous Technology] " Originally, color is a very important factor for human beings to cause physical and psychological effects. Today, color modulation technology is used in various fields to create a safe and functional working environment or a healthy and comfortable living environment. This is a high-quality sensation created by the achromatic black fairy: the uncolored color is required to be able to cross the entire wavelength of the visible light to play the line. Therefore, the desire to obtain "black" and the use of excellent 里 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ For example, although the blackness of carbon black is high, it is dull = two high (four): shortcomings, so it has been developed for years, and the degree of black pearl gloss powder system has been developed for many years.疋 疋 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠 珍珠, boasting in various fields 'but the black pearl of the past 319711 5 200831617 'The gloss pigment is coated with iron oxide black, because it is ferromagnetic, it is not well dispersed in the base of the coating, and it cannot obtain sufficient luster. Further, when the tree H is mixed, there is a disadvantage that the iron oxide black is oxidized by the temperature to become brown. In addition, the method disclosed in the publication J is a method for producing a dark pearlescent pigment by reducing the methane gas stream by the mica of the titanium oxide. • The color of this dark pearlescent pigment is also close to black and has good color and luster. However, due to the use of toxic ammonia gas flow during the manufacturing process, it is extremely difficult to manage. The reduction method of titanium dioxide is also contained in Patent Documents 2 and 4^, which have different purposes. Patent Document 2 discloses a method of obtaining a colored mica titanium-based pigment by mixing titanium metal in titanium dioxide-coated mica. Patent Document 3 discloses that titanium dioxide is deposited in the original state by using Xi Shi, titanium hydride, calcium chloride, and slave. A method of obtaining a colored mica titanium pigment. These patent documents relate to a method for producing a colored mica titanium-based pigment by reducing a titanium oxide of a mica titanium-based pigment by a metal and forming a low-titanium oxide to cause the titanium oxide to be gray to dark reddish brown. The titanium oxide causes absorption of light, and a colored mica titanium-based pigment having an appearance color which interferes with color development is produced. Further, Patent Document 4 discloses a method for producing a colored mica titanium-based pigment obtained by reducing titanium dioxide by oxidation. Further, Patent Document 5 discloses a method for producing a colored mica titanium-based pigment obtained by reducing titanium dioxide with metal aluminum, manganese, iron, cobalt, nickel, and zinc. Thus, although a method of reducing titanium dioxide without using ammonia is well known, 319711 6 200831617 • There is no mention of a method for producing a black pearlescent pigment. This is because when titanium oxide is formed by using titanium or the like, black is blue or red, and "black paint" cannot be obtained. [Patent Document 1] JP-A-58-164653 [Patent Document 2] Japanese Patent No. 173281 No. [Patent Document 3] Japanese Patent Laid-Open No. Hei 6-211521 [Patent Document 4] 曰本特开平8-6783 〇 参 [ [Patent Document 5] Japanese Patent No. 3542388 [Explanation] The present invention has been made in view of the above-described prior art, and the problem to be solved is to provide an excellent color tone. A low-titanium oxide black pearlescent powder, and a method of easily producing the black powder. (Means for Solving the Problem) The inventors of the present invention attempted to produce a powder having a color tone and gloss equivalent to or higher than the black pearl luster pigment reduced by the above-mentioned ammonia reduction without using ammonia gas. As described above, 'Since titanium oxide has a dark color to a black color, although it is attempted to reduce it with metallic titanium, it will become a dark brown or reddish hue, and it has not been possible to obtain the "black" obtained by the reduction of ammonia. Color. / As a result, it was found that when ammonia reduction was carried out, a titanium oxynitride compound was formed, and therefore, it was investigated in this point that ammonia nitrogen enters the titanium compound and its blackness is high. 319711 7 200831617

« Ti 〇2 + Nils—Ti ON On the other hand, when it is reduced by titanium metal, it is difficult to obtain “paint black” because of the darkness and unique color of these compounds. "." (4) The inventors of the present invention conducted further research and found that even if the metal is used for the reduction of the degree of reduction, the reduction degree can be obtained by adjusting the degree of reduction of the titanium oxide. The present invention is completed by the pearlescent powder of the chrome, and also: 'The black pearlescent powder of the present invention is a black pearlescent powder which is coated with a low-oxidation coating on the surface of the enamel-like powder. The pot is characterized in that the low cerium oxide does not actually contain nitrogen and is Ti〇x (x=i.5u 1.75). Further, in the above powder, the titanium oxide is preferably a method for producing at least the black pearlescent powder of the present invention, which is characterized in that the pearl is formed of a (four) plate-shaped base powder of titanium dioxide. The metal titanium is mixed in the powder and then 'reduced under low oxygen conditions until ^TiGxO^U') and then oxidized in an oxidizing atmosphere until it becomes TiOx (X; 1.56 to 1.75). Further, in the above method, it is preferred to mix the titanium metal in the pearly luster powder obtained by coating the thin plate-like base powder with titanium dioxide, and to be under the oxygen condition. Reduction is carried out in c, and then oxidative firing is carried out in 200 to 5001 in an i-ring. <Glowing property> 319711 8 200831617 In the present invention, shining is evaluated as follows. That is, the powder lg was added to 15 g of nitron clear lacquer 6341 manufactured by Musashi Paint Co., Ltd., and thoroughly mixed, and the concealing rate of the coating of 4 宓 = (^ · thickness unit) was applied to the white and black bottom. Paper 2 Then, the gloss of the coating film on the self-quality substrate was measured by a Gloss Checker IG-300 manufactured by Tsukaku Seisakusho Co., Ltd.丨 "Black pearlescent powder of the present invention, 6 (r and 2 〇 60 or more. 阻 乂 1 soil < blackness > In the present invention, the degree of blackness is evaluated in the following manner. That is, the powder lg was added to 15 g of nit_ca 6 = made by Musashi Paint Co., Ltd., thoroughly mixed, and coated on a concealing rate test paper of white black beard with a 4 mil spreader. Then, white And 7 «The color of the film on the shell is measured by the spectrophotometer CM_25〇〇d made by Minolta Co., Ltd. The color measurement is expressed by the L, a, b color values of the Chinese characteristic difference meter. The black pearl of the present invention For the gloss powder, the [value (brightness) is preferably hereinafter or less, and the value of a is preferably 1.5 or less.] The b value is preferably - 〇 5 < concealing force > In the present invention, the concealing force is as follows The method was evaluated. That is, the powder lg was added to 15 g of nitr〇n dear law·* manufactured by Musashi Paint Co., Ltd., and thoroughly mixed, and coated on a concealed test paper of white and black bottom with a 4 mil spreader. Then, the color of the coating on the white matter and the black matter on the bottom of the black matter is measured by the spectrophotometer of the Min 〇 1 ta company. 319711 9 200831617 • The black pearlescent powder of the present invention is represented by the color values of l, a, b of the Chinese characteristic difference meter, and the color difference Δ£ on the white matter base and the black matter bottom is preferably 1 · 0 In the present invention, TiOx is measured in the following manner. Titanium coated on a powder substrate is dissolved in hot sulfuric acid, and reduced by metal aluminum to quantify the amount of titanium, and then the titanium is used. The amount of the gas enthalpy in the titanium oxide compound is quantified from the amount of weight increase in the atmosphere and (10) the oxidation of the oxidized powder. The black pearlescent powder of the present invention preferably has Ti0x2X.丨56 to 1.75. Further, when the compound for reducing the oxidized powder was measured by a rifling diffraction apparatus Mini flex manufactured by Rigaku Co., Ti2〇3 and Ti3〇5 which are compounds of titanium oxide were confirmed.

Further, the thin plate-shaped base powder system is selected from the group consisting of natural mica, synthetic mica, alumina, and cerium oxide, and the base powder is preferably made of titanium dioxide. complex

Further, the base material powder is coated with titanium dioxide and the pearl gloss is preferably silvery. The particles of the aforementioned black pearlescent powder can be coated with a colorless metal oxide and/or a colorless metal hydroxide. The metal of the colorless metal vapor and/or the colorless metal hydroxide is preferably selected from the group consisting of cerium oxide, aluminum oxide, and cerium oxide. Further, the inventors of the present invention provide a composition comprising the above-mentioned black pearl light and a pen on 319711 10 200831617 and/or coated black pearl luster ^ ^ ^ ^ ^ ^. The "grey composition for coloring and coloring" of the color of the sapphire is a variety of physical composition, for example, makeup: one thing, printing oil _η (4) external composition, paint Composition, soil, and, and the composition of the composition and adhesion. Second, after the 'color of this color with the color of the 沴砝 籾 籾 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便 便On the coated surface of the tile, you can use the light to interfere with the specific light-absorbing text of the titanium oxide compound to form a black pearl luster. (Effects of the Invention) As described above, the black system according to the present invention provides a kind of zt w 7 ball, the filial piety body, which does not actually contain nitrogen due to no money reduction, and

Metal titanium adjustment is also thick and I female dazzle ^ g A ^ has k /, blackness, brightness, the sound of the sound of the powder. ", has no beads, and the right method of manufacturing the black pearlescent powder according to the present invention i can be used to reoxidize and adjust the reduction of the titanium dioxide-coated powder by the titanium metal once and for all. Therefore, it is possible to adjust the originality in an open environment, which not only makes the manufacturing easy, but also has good blackness and pearl light. [Embodiment] The following describes a preferred embodiment of the present invention. The black pearl luster of the present invention The powdered and/or coated black pearlescent powder and the method for producing the same are obtained by mixing titanium metal in a pearly luster powder coated with a thin plate-like base powder of titanium dioxide, and then repelling the original under low oxygen conditions. Then, in the oxidizing environment, the oxidative firing is performed by 319711 11 200831617 • The light interference effect of the specific titanium oxide compound is obtained by the light interference effect, and the color of the pearl pearl powder is obtained. It is a colored pearlescent powder which is colored in silver to interference color, and it is considered that one of the characteristics of the present invention is black pearlescent powder is black. The pearlescent powder of the present invention, the black pearlescent powder of the present invention and/or the base particle coated with the black pearlescent powder is a so-called silver pearlescent powder which is coated with a thin plate-like powder. For the silver pearlescent powder, commercially available silver pearlescent powders such as the Ir1〇dln series manufactured by Merck, the red enamel series manufactured by Engelhard, and the Ref lex series manufactured by CQV can be used. Alternatively, it may be produced by a generally known method. For example, a synthetic mica made by τ〇ργ Industrial Co., Ltd. is used to produce a silver-coated pearlescent powder coated with titanium dioxide in a usual manner, and in addition, the above-mentioned base particle may be used. ... Ming ~ 汲 汲 powder, is mica, synthetic mica, oxidized Ming, oxygen cut. In these, = shape and surface of the self-sufficiency or expected to control the difficult cloth, and then on its particles On the surface, it is preferred to make silver pearlescent powder. The choice ===cheng mica as the base material is the best material. —”: Metal oxide such as titanium dioxide or iron oxide is oxidized. The pearl luster of the pearly _, the system is all ^ = Glossy: the material is due to natural mica, and the mica contains miscellaneous color, the color of the head is poor, and there is a complementary color (C0mplementary c〇1〇r 319711 12 200831617 . Also mixed: 蜀之=: Therefore, a pearlescent pigment made of synthetic mica or platy alumina which has been decontaminated, and platy cerium oxide as a rabbit is used as post-dioxide or iron oxide. ..., the particle size of the base particle is not specified, but it is preferable that the average particle diameter is 3 = or less. When the particle size is above 3 〇, the mixture is fully recorded: "The reduction under the condition is sufficient but the concealing force (shadowing and not filling (4) is black); ^,, == affected by the color of the bottom, Powder = Si: The silver pearl luster formed by breaking these base particles _ is based on the amount of granules mixed with 5 mass 2 22, but the metal titanium ", due to dioxane Good. When it is not reached, it is sufficient, so even if it is more than 18:v in the oxidizing environment, it forms a black pearlescent powder. In addition, if it is 18%, then 2/Bu, Du, I, Block— Titanium telluride in the face of the original will make the condensation = strong ^ and lose the brightness of the pearl material, so it is not good. Warm production = according to: Under the hypoxic conditions of the reduction, although the reduction / degree For example, depending on the amount of metal titanium mixed, 1000 C is preferred. If it is less than 7 〇〇. 钕 reduction, even if the oxidized ring is produced, 隹- 钦 can not fully color the pearl gloss powder. If it is a surface. If it is above C, then it will be reduced by 1 and =, and it will be condensed with the metal form, and it will become the luster of pearl luster. Therefore, it is not good. Therefore, the loss is further improved. When the reduction is carried out under the above-mentioned low-oxygen conditions, for the purpose of 319711 13 200831617, the efficiency is avoided, the flow is inert, and the heat is improved by the gas, argon. Gas or helium and its mixed under the above-mentioned low-oxygen conditions will reduce the reduced 吏:= rate. The environment is oxidized and fired, and the titanium dioxide is fired, and the titanium oxide is different in oxygen, but at 2G ( Rc to 5GGt for ^1 according to the degree of reduction

. . 'Do not cause oxidation of low-titanium dioxide two-color two; if less than 200 c, the oxidation of low-oxidation will be excessive color:. In the case of the melamine powder, the color tone is also silvery pearlescent powder, so that the black pearl lustre obtained under the above conditions can be surface-treated in the same manner. ^如! 1 By 糸 = to improve the treatment, the light resistance or dispersibility of the line is turned into a black pearlescent powder. In addition, it is also hydrophobized by the erroneous or titanium coupling agent. For example, 〒矽 =, a fatty acid metal salt, a hospital-based scaly acid, a gasification with a perfluoroalkyl group, and a hydrophobization treatment of a compound temple may be mentioned. The black pearly luster powder of the present invention having such excellent properties is very suitable as a blending component of the "glossing composition for coloring" which is a gloss composition which is a basic definition of the color of the object. The gloss composition for coloring according to the present invention (hereinafter referred to as the colored gloss composition of the present invention) is colored not only by the "coloring pigment" but also by the use of light in the concept of coloring the object as described above. The gloss that interferes with it. The colored luster composition of the present invention is a composition defined by the above definition, and the specific aspect thereof is not particularly limited, and an external composition such as a makeup cosmetic, a coating composition, and a printing ink set can be used. 200831617 Composition of the composition of the object and the adhesive composition. That is, the colored luster composition of the present invention is applied to a coated surface, and a gloss composition which causes light drying and forms a black gloss in the composite powder layer formed on the coated surface. The content of the black pearlescent powder in the colored luster composition of the present invention is appropriately selected depending on the specific aspect or purpose of the composition, and is not particularly limited. The following is a description of the composition which can be used for the colored glossy composition of the present invention. ^ (1) Even in the external composition such as cosmetics, especially when it is used as a makeup, it is considered to have a beautifying appearance and to maintain the cosmetic effect, to enhance the "psychological effect" of the mood, and to protect the muscles and protect the body. effect". ^ In order to fully achieve these effects, in addition to improving the color of the makeup cosmetics, it is also necessary to improve the usability or the last name. The powder system of the present invention is suitable for use as such a composition. Among the makeup cosmetics, a powder component can be cited as a component responsible for the main action. Among these powder components, the pigment component is further improved by the use of a knife and the use of a good touch when using the makeup of the blouse, or the persistence of the makeup, and the ultraviolet shielding effect due to the type thereof. The above; role". At the same time, the direct relationship between the desire to make a good color, so that the color elements of the pigment component are improved, the use of the cosmetic material and the sustainability of the elements of the cosmetics, the main subject of makeup and cosmetics. 319711 15 200831617 This month's external composition, By formulating the dip composition, the blending amount of the black pearl luster powder of the present invention in the external antimony composition having a large increase in sustainability can be adapted to the dosage form or type of the composition, and the invention can be formulated accordingly. The coloring gloss composition is appropriately selected and is not particularly limited, and is usually formulated in a range of from about 0.0.i to about 80.0% by weight in the composition. • In addition, the external composition of the present invention does not impair the present invention. Within the scope of the desired effect, the other ingredients formulated in the general cosmetic composition can be adjusted. For example, petroleum jelly, lanolin, ceresin, Brazilian brown wax, and candelabra wax can be appropriately blended (CandeHlla catches)乂), solid fatty acids, higher alcohols, and other solid or semi-solid oil components; squalane, mobile paraffin, ester oil, triglyceride, etc. Ingredients; oil components such as bismuth oxygen; humectants such as sodium hyaluronate and glycerin; surfactants such as cationic interface/tongue agent, nonionic surfactant; pigment, art preservative, perfume, activator (activat〇 r), ultraviolet shielding agent, etc. Further, the external composition of the present invention may be in the form of a powder, a mass, a pen, a rod, a liquid, or the like, such as a foundation, a lipstick, an eye shadow, a blush, an eyeliner ( Eyeliner), makeup cosmetics such as eucalyptus oil and mascara, and hair cosmetics such as hair lotion, hair liquid, and set lotion, etc., may be applied to the external composition of the present invention. In particular, among these, the excellent composition of the colored luster composition of the present invention can be maximized by blending in a makeup cosmetic. The external composition of the present invention is applied to the skin of the coated surface or the hair. 16 319711 200831617 On the composite powder layer formed on the skin or hair, black pearl luster can be confirmed by light interference and light absorption of a specific titanium oxide compound. The pearly luster pigment, the black luster of the black pearl luster is particularly strong. ^ (2) When the colored luster composition of the present invention is a coating composition (hereinafter, the inventive coating composition), the majority of the color is applied to the object. In most cases, the use of colored "flooding composition" is used. The coating composition initially has fluidity, is applied to the surface of the material, and is spread and adhered, and then subjected to a drying process to form a composition of the continuous film. ^ =, in the case of the paint composition, it is also required to apply a colorful color to the object = 'for this pigment' to exert the switching effect (1) ip_n〇p ur also requires the use of pearl light which can impart more color interference color. The colored luster composition is such that the light absorption of the f-titanium compound imparts a black pearl = the gloss which has not been obtained in the past.如此 Thus, the present invention also provides a coating composition of the article. The present invention relates to the use of the gloss composition of the pearly luster powder as the above-mentioned composition, which comprises the black pearl luster powder of the invention of the invention, which is suitable for the specific type and purpose of the composition of the coating composition of the invention; Depending on the coating group of the present invention, in particular, because the powder of the present invention is defined by black cherries, the enamel pearl powder, compared to 319711 17 200831617 = 3:: zein pigment, even if more is formulated, It can be painted on both sides, and it can easily make black more intense color. In addition to the desired effect of the present invention, in addition to the =(tetra) bead gloss powder, it can be formulated in the coating composition as well as in the coating composition of the present invention. (2) In the case of 'coating film forming elements', the following can be formulated in a composition of a coating: a polymer film, a natural or synthetic resin, a polymer material such as cellulose or rubber bamboo, and the like. Plasticizing, desiccant, hardener, antiskinning agent, fluidity regulator (tackifier, flattening agent, etc.), anti-sagging agent (anti _ saggmg agent), preservative, anti A mold, a rust preventive agent, an ultraviolet absorbing agent, a coating film forming auxiliary element, a pigment other than the black pearlescent powder of the present invention, and the like. Further, a solvent for dissolving the coating film forming element may be appropriately selected and used. In the fourth aspect of the present invention, the composition towel is applied to the coated surface, and is confirmed by light interference and light absorption of a specific compound of the oxidized compound in the composite powder layer formed on the coated surface. To black pearl luster. The coating composition of the invention can be widely used in various coatings, such as building (four), stone #coating, vehicle coating, ship and/or ship bottom coating, wood coating, machine coating, standard coating, electric insulating coating, conductive and / or semi-conductive coatings, chemical resistant coatings, anti-corrosive coatings, heat-resistant coatings, fire retardant coatings, temperature coatings, luminescent coatings, insecticidal coatings, etc. (3) When the & gloss composition of the present invention is a printing ink composition (hereinafter referred to as a printing ink composition of the present invention): the printing ink composition means a chart prescribed by 319711 18 200831617 T or a warp plate or the like. A set of filaments that are formed on the surface of the object to be brushed by a printing means and are fixed and used privately. Material (four) material

The production of the HI! ink composition has the characteristics "printing and color development" required for the printed matter in the printing step, and in this regard, the above coating composition can be distinguished. After the ninth, in the printing ink composition, it is necessary to use a pearlescent pigment as a coloring material in the same manner as the above coating composition, in order to provide a further P brush. The black pearl luster pigment of the present invention is as described above, and is suitable as a printing ink set and a coloring material even in view of the characteristics imparted to the object by the gloss, and further, since it is a black luster. Therefore, the printed matter provided by using the printing ink composition as the coloring material is also excellent in terms of the black gloss which can effectively obtain the strong hiding power. Thus, the present invention also provides a printing ink composition as the aforementioned gloss composition. The printing ink composition of the present invention contains the black pearlescent powder of the present invention as the above coloring material. The blending amount of the black pearlescent powder of the present invention in the printing ink composition of the present invention can be appropriately selected according to the specific kind, purpose, and the like of the printing ink composition of the present invention, and is not limited thereto, but especially the black pearl of the present invention. The gloss powder system makes the concealing power strong due to the black gloss powder, so that the pearl pearl luster can be more easily obtained than the pearl pearl pigment in the past. In addition to the initial effect of the present invention, in addition to the black pearlescent powder of the invention of 319711 19 200831617 4, the elements which can be generally formulated in the printing ink composition can also be formulated in the printing ink of the present invention. In the composition. Specifically, in the case of a color material, the following may be formulated in the printing ink composition of the present invention: a pigment or a dye other than the black pearlescent powder of the present invention; in the case of a vehicle, such as a vehicle Oil (vegetable oil such as linseed oil, tung oil, mineral oil such as printing ink oil and solvent oil), resin (natural resin such as hard asphalt and rosin, rosin modified phenol resin, maleic acid resin, petroleum tree citric acid, acid alcohol) Resin (alkyd resin, ester rubber and other synthetic resins), plasticizers, waxes, solvents, etc.; in the case of adjuvants, such as drying control agents (hair dryer, anti-,,, skin, special), viscosity control agent ( Compound (c〇), tackifier, thixotropic agent, etc.), dispersibility control agent (dispersant, anti-separator, stabilizer, etc.), color adjuster (toner), matting agent Etc.), reactants (photopolymerization start] catalyst, parent-linked agent), other such as wetting agent, defoamer, rust inhibitor. In the printing ink composition of the present invention, it is coated on the coated surface, and after the printing step, in the composite powder layer formed on the coated surface, by light interference and titanium oxide Light absorption of a specific compound, and black pearl luster can be confirmed. The printing ink composition of the invention can be widely used in various printing inks, such as lithographic inks, gravure inks, embossing inks, screen printing inks, flexographic printing inks, gravure printing inks, Various special printing inks, etc. Thus, the colored luster composition of the present invention has various aspects, but the aspect of the colored luster composition of the present invention is not limited to the above. For example, 319711 20 200831617 2 describes a solid coloring matter obtained by kneading a black pearl light-transferring body of the present invention into a plastic. (Example)

The invention is more specifically disclosed by the following examples, but the technical scope of the invention is not limited by the embodiments. Further, the amount of the preparation in the present embodiment is not particularly limited, that is, parts by weight. Further, the method of numerical values shown in the production examples and the like is as follows. a) Gloss measurement method This black material gloss powder lg is added to the nitron clear iac (luer 6341 manufactured by Musashi Paint Co., Ltd.), which is fully mixed with the experimental disperser, and then 4 mils (〇.丨The spreader of 01 mm) was applied to the concealment rate test paper of the white-black bottom. Then, the glossiness of the coating film on the white matter bottom was measured by using Gloss Checker IG-300 manufactured by Horiba, Ltd. at 60 and 20. The measured values are displayed. b) Measurement of colorimetric values L, a, b 1 g of this black pearlescent powder was added to 1 nitron clear lacquer 6341 manufactured by Musashi Paint Co., Ltd., and thoroughly mixed and dispersed by an experimental disperser. Then, it was coated on a concealing rate test paper of white black bottom with a 4 mil (〇·i〇imm) spreader. Then, the color tone of the coating film on the white matter bottom was measured by a spectrophotometer cM-2500d manufactured by Minolta Co., Ltd., and the values indicated by the L, a, and b color values of the Chinese characteristic difference meter were displayed. c) Determination of concealment rate This black pearlescent powder lg is added to 15g of nitron clear laCquer 6341 manufactured by Musashi Paint Co., Ltd., with a sample disperser full of 21 319711 200831617, mixed and dispersed, and then 4 mils (〇 The spreader of &, 1Uimm is applied to the concealment rate test paper of white and black background. Then, the color tone of the coating film on the white matter bottom and the black matter bottom is measured by a spectrophotometer CM_25〇〇d manufactured by Minolta Co., Ltd., and expressed by the L, a, b color values of the Chinese characteristic difference meter, and displayed. The color difference ΔΕ on the bottom of the white matter and the bottom of the black matter. The color difference ΔE value is obtained by the following formula. ΔΕ= { (Lw-Lb)2+(aw-ab)2+(bw-bb)2} 1/2......Formula φ w: value on the white matter bottom b: on the black bottom Value d) Oxygen content measurement in the titanium oxide compound The black pearlescent powder was accurately taken in about 3 § cm 3 and baked in the air at 750 ° C for 2 minutes. After cooling, the weight of the scale was measured, and the weight change of titanium oxide black to titanium dioxide was determined. Correctly take the 75 〇〇c of the black pearlescent powder, 〇·2g, and transfer it to a 2 〇〇cm3 flask. Add a small amount of pure water and shake it to make it milky, then add concentrated sulfuric acid 3〇cm3, and ammonium sulfate! &, heated by electric heating. It starts to slowly heat and finally dissolves with strong heat. After cooling, 80 cm 3 of pure water and 80 cm 3 of hydrochloric acid were added, and the mixture was shaken well. Metallic aluminum 3g was washed with hydrochloric acid (1 + 5). The washed aluminum metal was placed in a triangular flask and heated while being heated by a heater to generate hydrogen. After the metal aluminum is completely dissolved and the liquid becomes transparent purple, it is left for a few minutes and then cooled to 5 〇 DC or less with running water. A saturated solution of potassium thiocyanate (3 cm3) was used as an indicator and immediately titrated with a solution of 〇·lm〇1/1 ammonium iron sulfate (ΠΙ). The point where the liquid pale brown does not disappear within 3 seconds is used as the end point. 319711 200831617 ^ Titanium dioxide (%) was obtained by the following formula. A=(〇.〇0799Bf/S)100........................Form 2 A: Titanium dioxide (%) B·Sulfuric acid required for titration Ammonium iron (ΙΠ) solution amount (cm3) f · Sulfuric acid iron (ΠΙ) solution factor (fact〇r) S : sample weight (g) Dan from the A value to determine the amount of titanium dioxide (set ag) and thin plate Shape of the base disk powder. Furthermore, the amount of the titanium oxide black was determined by subtracting the amount of the thin plate-shaped substrate from the amount of the black pearlescent powder (bg), and the relationship between the weight increase rate of a/b and TiOx was obtained by the following formula. Y=—〇· 39X 十1·1698.........................3 γ : Weight gain rate X : Ti 〇x X value e) Crystal structure analysis method This black pearlescent powder is used by Rigaku X-ray diffraction device Mini flex and Cu to cathode 3〇Kv · 15 minus · κ stone filter powder The body was measured by the το method. Identification of titanium oxide compounds from the ray. (Manufacturing Example 1) The silver type of Ultimica SC-100 having an average particle size of 2 〇 # m sold by Nippon Kogyo Kogyo Co., Ltd. was weighed to 15 kg, and metal titanium 1·95 Kg was added thereto, and a schel mixer was used. (jjenschei mixer) mixed. The mixed powder was filled in a reaction vessel, which was vacuumed by a vacuum apparatus, and heating was started when the degree of vacuum reached 10-iPa, and was 85 Torr. 〇 React 10%. After the completion of the reaction, argon gas was passed to accelerate the cooling. 319711 23 200831617 After confirming that the internal temperature is below 200t, the original powder is taken from the reaction vessel. The reduced powder was pulverized by a pulverizer, and the titanium sieving was fractionated to remove titanium metal. Further, the classified reduced powder was oxidized and fired in a gas atmosphere for 3 hours. Made of 14. 5Kg and has a black pearl luster. In the black Π Mg obtained, G. Kawasaki Isopropyl Alcohol and G., called Shinko eKF_99Q9, manufactured by Shin-Etsu Chemical Industry Co., Ltd., were added for a five-hour gathering (4). . The black pearlescent powder UKg coated with oxygen is obtained. 2' The inventor (4) observed the appearance of the material according to the manufacturer's various materials. The results are shown in the table. Test case

Reduction - oxidation only reduction reduction - oxidation Xianze ◎ χ χ

Ammonia reduction ◎ color lacquer black lacquer black lacquer black lacquer black enamel lacquer black is: Li s two to carry out ί also! The case (test case 5), although the use of toxic gas is satisfied, but due to manufacturing steps The mother's milk is so difficult to manage. 1-2, 1 4 4\' When the degree of reduction is adjusted by metal reduction only (test example, although it is satisfied in terms of lacquer black, it is not possible to obtain 319711 24 200831617 • sufficient gloss, and due to the degree of reduction The adjustment system must be carried out in the poor and the poor, and it is difficult to obtain reproducibility. Sealing, in contrast, after the full metal reduction, reoxidation is carried out: (Test Example H, Bu 3), in the dark At the same time, it is also possible to obtain = good: ^ Zeze, and because the degree of reduction can be adjusted in the oxidizing environment (atmosphere), it can be manufactured with excellent reproducibility. Thus, even if the degree of reduction is about the same, When the reduction step is performed in the reduction step, and the re-oxidation phase is performed after performing an excessive reduction, the difference is in the gloss. Therefore, the inventor of the present invention causes the reduction to proceed to Ti〇x^X. After 15 〇, it was reoxidized to adjust the black pearlescent powder. The inventors of the present invention have studied the degree of reduction in the case of reoxidation and the research into the field. The manufacturing method is based on the above-mentioned production example 1. Sure in Table 2. [Table 2]

• 72 1. 74 1. 77 ◎ 〇 〇 ◎ 〇 Blue Black 1. 50 1. 56

1. 63 ◎ ◎ s type test case

2-6 2-7 2-8 △ 〇 Appearance color red black 〇

Right, you can see Table 2, not as long as the X of Ti〇X becomes! · 56 to h75 left to get the lacquer black, ^ If you want the corpse of the corpse, the eyes [right to receive the special excellent paint black and light,] is 1 · 58 to 1 · 72. Especially JL 3 production, seat; s production, especially when the normality is high (Test Example 2-1) 319711 25 200831617 will turn red and black, and only improve the degree of reduction, it can be known that the degree of reduction is low (★猞 9 9 , ... 邑 邑 邑 邑 邑 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Table 3. (Production Example 2) A silver type of Iriodin 111 having a δ 卞9 particle size of 8#m manufactured by Merck was weighed to 12 Kg, and a metal illusion was taken thereto, and a Henschel mixer was used. Mixing. The mixed powder is filled into the reaction vessel, and vacuumed to make it a vacuum. When the degree of vacuum reaches 1 〇, a is started, and heating is started, and the reaction is completed immediately after the reaction is completed. The cooling is accelerated. After confirming that the internal temperature is 20 (TC or less, the reduced steroid is taken out from the reaction vessel. The pulverized powder is pulverized by a pulverizer, and the titanium metal is fractionated by a wind sieve. Further, the grading is reduced. The powder is oxidized and fired in the atmosphere at 32 〇t: for 2 hours. The powder produced was 11 Kg and had a pearl luster of black. The black pearlescent powder UKg was placed in a reactor of 2 〇〇dm3, and aluminum sulfate 0 55 kg, urea 11 kg, and tap water 150 kg were added thereto while stirring. While raising the temperature, it was subjected to a ripening reaction for 3 hours at 95. After cooling, it was washed with water, and then sodium sebacate dissolved therein was added thereto. 21 Kg of tap water 40 dm3, and dissolved aerobic chlorination. 185 kg of tap water 40 dm3 'Adding tap water to make i50dm3, and performing the ripening reaction for 6 hours at 6/cm or more. After washing with water, drying, the surface treatment is carried out with the hydroxide of Ming·Shi Xixi 酉·鍅. Black pearly powder UKg, which is coated with a hydroxide of yoshiyoshi and yoshi. 26 319711 200831617 I (Manufacturing example 3) The average particle size of Enge 1 hard company! 8 # m Magna 丄, 1100 The silver type is weighed 14Kg, and the metal titanium is added to the 96Kg, and mixed with a Henschel mixer. The mixed powder is filled into the reaction vessel, and vacuumed to make it vacuum, when the vacuum reaches !lpa Time When the reaction was completed, the reaction was completed, and the reaction was completed. After the completion of the reaction, the nitrogen gas was passed through and the temperature was accelerated to 0. After confirming that the internal temperature was 200 t: or less, the reduced powder was taken out from the reaction vessel. 5克克和黑黑的, The smelting was carried out by a sifting, and the smelting of the smelt was carried out in the air at a temperature of 31 ° C for 2 hours. Pearl luster. The black pearlescent powder i 3Kg was placed in a reaction dad of 200 dm, and aluminum sulfate 〇. 65 Kg, urea 卯 Kg, tap water 150 kg, and the temperature was raised while stirring, and the mixture was aged at 95 t > c for 3 hours. reaction. After cooling, it was washed with water, and then dried at 15 (rc for 1 hr, to obtain 13 Kg of the alumina-treated powder. In the 13 Kg of the alumina powder, the Ajinomoto Fine_Techn〇 was added. Company's Plenact 055 (coupling agent) 0.26Kg, and xylene (xyl〇1) l3,

Kg' is mixed with a Shel mixer and placed at 〇5〇. 〇 〇 之 hours of processing. A black pearlescent powder coated with an alumina/coupler was obtained. (Production Example 4) A silver type of Iri〇din 121 having an average particle diameter of 15/cm manufactured by Merck Co., Ltd. was weighed and weighed at a level of 13 kg, and a metal titanium h 82 kg was added thereto, and mixed by a Henschel mixer. The mixed powder was filled in a reaction vessel, and vacuumed to make it vacuum. When the degree of vacuum reached 1 ()-ipa, heating was started, and 319711 27 200831617 1 and a_ °C reaction was 10 /J. After the reaction was completed, argon gas was passed to accelerate the cooling. After confirming that the internal temperature became 2 〇〇 t: or less, the reduced powder was taken out from the reaction vessel. The reduced powder was pulverized by a pulverizer, and the titanium metal was classified by a wind sieve. Further, the fractionated reduced powder was oxidized and fired in the air at 290 Torr for 3 hours to produce a powder of 12. 5 kg and having a black pearl luster. The black pearlescent powder 12Kg was placed in a reaction crucible of 200 dm3, and tap water of 150 dm3 was added thereto, and AsahiGuard AG-530 (fluorine treatment agent) 2·2 Kg manufactured by Asahi Glass Co., Ltd. was added while stirring, and then dropped therein. A 1% aqueous hydrochloric acid solution brought the pH to 4. The ripening reaction was carried out for 1 hour while stirring. After filtration and washing with water, it was added to C over 16 hours to obtain a fluorine-coated black pearlescent powder of 12 kg. (Production Example 5) A silver type of lri〇din 1〇3 having an average particle diameter of 22//m manufactured by Merck was weighed to 16 kg, and metal titanium 2·〇8 kg was added thereto, and mixed by a Henschel mixer. . The mixed powder was filled in a reaction vessel, and vacuumed to make it vacuum. When the degree of vacuum reached i 〇-lpa, heating was started, and the reaction was carried out at 850 Torr for 10 hours. After the reaction was completed, argon gas was passed to accelerate the cooling. Confirm that the internal temperature is 2〇〇. (: After the following, the reduced powder was taken out from the reaction vessel. The reduced powder was pulverized by a pulverizer, and the metal qing was fractionated by a wind sieve. Further, the fractionated reduced powder was placed in the atmosphere at 3 Torr (rc) The powder was oxidized and fired for 3 hours, and the obtained powder was 15.5 kg and had a pearl luster of black. The powder of the black pearlescent powder produced in the above production example was shown in Table 3 for the powder value of 319711 28 200831617. It can be seen from the table that the powders produced by any of the production examples have a black pearly powder having a low gloss, a low brightness, a small hue and a small b value, and a small concealing rate (a strong hiding power). The results of the measurement of the black line of the pearly powder before the surface treatment are shown in Fig. 1. It can be seen from the figure that the black pearl gloss powder system can confirm the mica and Ti203i Ti305. [Table 3] /,

Item Manufacturing Example 1 --------- Manufacturing Example 2 Production Example 3 Production Example 4 Production Example 5 Glossiness----- 73. 4 66· 1 72. 6 70. 7 75. 2 White texture Hue L : 19· 9 a · 0. 48 b : -1·35 L : 20. 2 a: 1.10 b : -1.92 L : 19. 6 a: 0.64 b : -2· 35 L · 19· 8 a: 1.05 b :~2· 40 ITT 21. 1 a: 0. 02 b : —? Fi? Concealment rate △ E 0. 91 0. 45 0. 85 〇. 68 U Ll m \JL· 0. 98 T i Ox value 1. 65 1. 58 1. 63 1. 59 1· 68 X-ray diffraction —————————J Ti2〇3 T 1 3〇5 Tl2〇3 Tl3〇5 Τΐ2〇3 TisOs Τΐ2〇3 Τΐ2〇3 T i 3〇5 Use this black pearlescent powder for the following blending Example [Preparation Example 1] Powder solid-state eyebrow cosmetic compounding component L Production Example 2. Talc dose (parts by weight) Polyester oxygen-coated black pearl gloss powder 〇 52· 8 10· 0 4. 0 Appropriate amount of 3 · lanolin equine 4 · mobile paraffin 5 · 对 曱 319 319 319 319 711 711 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 311 In the mixture of Henscher-mixer mixer, add + to dissolve and mix 3 to knead. Use pulverizer powder, knife... 仃 off (4) Middle plate for pressure forming. If you use a wet brush, you can use it as an eyeliner, use cocoa as an eyebrow pencil (eyeb(10)), or use eyelashes with a brush ==. In addition, for the sake of comparison, the first term is made into a polyaluminum oxide treated iron oxide black. [Preparation Example 2] The amount of the mascara formulated with the ingredients (parts by weight) 50· 0 1. 0 3· 0 12. 0 28. 0 Appropriate amount of 5. 0 1 · Refined water methyl cellulose sodium 1, Fluoride-coated black pearly luster vinyl acetate resin emulsion of 2-pentanediol production example 4: Ethyl p-hydroxybenzoate perfume 8. Ethanol <Preparation method> Adding the second and third components to the above first component The component was heated and dissolved, and the fourth item was added to be treated with a colloid mill (c〇11 〇idm丨11). Then, the fifth component is added and stirred, and after homogenization, the third component of the sixth and seventh components is dissolved in 319711 30 200831617 and mixed. Further, in the case of the parent example 2, the component of the fourth item is a fluorine-treated iron oxide black.

Formulation amount (parts by weight) 8· 〇20· 〇10· 0 10. 0 8.0 4· 0 28· 〇 [Preparation example 3] Pencil type eyebrow cosmetic preparation 1 · Carnauba wax 2. Honey wax 3. Sacrifice 〇 〇 〇 i After the first to eighth ingredients are heated and dissolved, the ninth item is added to the octagonal grinding machine for kneading. This was carried out using an extruder, and the knife was extruded into a diameter of 5 mm. The wood portion having the groove is formed by pressing the joint D. This product is cut into a shape to shape the outer shape into a wrong pen type, and is applied to the wood portion by painting, marking, or the like. Further, in Comparative Example 3, the component of the ninth item was set as iron oxide black. 〃 Regarding the above-described blending examples and comparative examples of the present invention, the degree of coating (4) was evaluated. The evaluators are evaluated according to 10 panelists from ι to 5 from 4 3 temple level 319711 31 200831617', and are shown in Table 4 with the following symbols ◎ 4· 5 and above and 5. 0 The following 〇3·5 or more and less than 4·5 Δ 2· 5 or more and less than 3·5 X 1· 5 or more and less than 2. 5 XX 1· 0 or more and less than 1·5 [Table 4]

m As can be seen from Table 4, the powder solid-type eyebrow cosmetic of Formulation Example 1, the film-type eyelash of the second example, and the wrong type of eyebrow cosmetic of Formulation Example 3 have the effect of improving the gloss and finish of the coating. The natural color of the time, and the effect of eliminating color unevenness and beautifying when finishing makeup. Formulation amount (parts by weight) 78. 3 [Preparation Example 4] Coating composition preparation component 1 · Thermoplastic propionic acid resin 2 · Production example 2 Aluminium • 矽•鍅 coated 32 319711 200831617 _ Black pearl gloss powder 8 7 3 · Acetic acid butyl | PCT 13: 〇 < Preparation method> The above-mentioned items 1 to 3 were uniformly dispersed in a disperser to obtain a coating composition.

The coating composition of the preparation example 4 was spray-coated on a steel plate having a thickness of 2 mm to make the film thickness of about 3 〇#, placed at 2 $ t for 3 minutes, and then painted at U (rc). Spraying (bakingfinish) treatment for 2 minutes. The obtained coating film has a strong black gloss. [Preparation Example 5] Printing ink composition preparation component 1 · Production example formulation (parts by weight) Oxidized and coupled agent coated

Black pearlescent powder 2·ethylene-vinyl acetate copolymerized resin 3. Chlorinated polypropylene 4·butyl acetate 5. Ethyl acetate G·isopropyl alcohol 7·polyethylene wax 8 ·Antistatic agent <Preparation method&gt The above-mentioned first to the printing ink composition was used to mix and disperse in the bead mill using the compound of the formula 5, and the obtained printing ink composition was printed on a white paper 319711 33 200831617 I for drying. After the thickness became 60 // m, the resulting coated body had a strong black gloss. [Preparation Example 6] Preparation amount of the ink composition for printing (parts by weight) 1. Black pearlescent powder coated with polyoxynitride of Production Example 15. 〇20· 0 35· 0 30. 0 2 · C Dilute acid resin 3 · naphtha

4. Butyl cellosolve <Production Method> The components of the above items 1 to 4 were weighed and mixed and dispersed by a bead mill to obtain a printing ink composition. The printing ink composition of this Formula 6 was printed on a white paper so that the thickness after drying became 50 / / m, and the resulting coated body had a strong gloss of specific color. ^ ... [Preparation Example 7] Preparation of the adhesive sheet for coatings ^ Formulation amount (parts by weight) • Acrylic adhesive (u 〇9, manufactured by Toyo Ink Co., Ltd.) 8g ^ 2· Hardener (8515, manufactured by Toyo Ink Co., Ltd.) ^3. The fluorine-coated black pearlescent powder of the coating example 4 is only <Production Method> = the above-mentioned m-th component is taken and dispersed by a disperser, and the cloth (4) is placed on the sheet to be dried. After the thickness becomes =, it is bonded to a releasenner, and the adhesive sheet for coating obtained by the coating is "II97I1 34 200831617 r." The coating adhesive sheet has a strong black gloss. [Simplified illustration] Fig. 1 shows the basis of the powder. A diagram of the ray of the manufacturing examples 1 to 5 obtained by the X-ray diffraction method. This ray system is used to identify a compound.

35 319711

Claims (1)

200831617 Γ 》 Ten, the scope of application for patents: 1. Two kinds of black pearlescent powder, which is a black pearlescent powder made of titanium oxide coated on the surface of a thin plate-like powder, wherein the titanium oxide actually Contains no nitrogen and is Ti〇x (X = 1.56 to 1.75). 2. A black pearlescent powder having a patent application range of 帛μ, wherein the low titanium oxide contains at least Ti2〇3 and Ti3〇5. - 3) A method for producing a black pearlescent powder, characterized in that metal titanium is mixed in a pearly luster powder coated with a thin plate-shaped base powder of titanium dioxide, and then under low oxygen conditions The reduction was carried out until it became TiakXg 1.5), and then oxidative firing was carried out in an oxidizing atmosphere until it became Ti〇x (X = 1.56 to 1.75). 4. The method for producing a black pearlescent powder according to the third aspect of the patent application, wherein the titanium metal is mixed in a pearly luster powder coated with a thin plate-like base powder of titanium dioxide, and then under low oxygen conditions. The reduction is carried out at 7 Torr to 100 ° C and then oxidized in an oxidizing atmosphere at 2 Torr to 5 〇〇 ° ° °. 319711 36