WO2008059828A1

WO2008059828A1 - Black pearlescent powder and process for producing the same

Info

Publication number: WO2008059828A1
Application number: PCT/JP2007/071998
Authority: WO
Inventors: Masahiro Hashimoto; Shingo Okubo; Fukuji Suzuki; Asa Kimura
Original assignee: Nihon Koken Kogyo Co., Ltd.; Shiseido Company Ltd.
Priority date: 2006-11-13
Filing date: 2007-11-13
Publication date: 2008-05-22
Also published as: TW200831617A; JP2008120914A

Abstract

[PROBLEMS] To provide a low-dimensional titanium oxide black pearlescent powder excelling in color, and provide a process for easily producing the black powder. [MEANS FOR SOLVING PROBLEMS] There is provided a black pearlescent powder having a thin-plate powder at its surface coated with a low-dimensional titanium oxide, characterized in that the low-dimensional titanium oxide contains substantially no nitrogen and is represented by the formula TiOX (X = 1.56 to 1.75).

Description

Specification

Black nacreous powder and method for producing the same

Related applications

[0001] This application claims the priority of Japanese Patent Application No. 2006-306171 filed on November 13, 2006, and is incorporated herein.

Technical field

[0002] The present invention relates to a black pearly luster powder and a method for producing the same, and more particularly to an improvement in the color of a black pigment using low-order titanium oxide.

Background art

[0003] Originally, color is a very important factor that has a physiological and psychological impact on humans. In fact, there are methods to create a safe and functional working environment and a healthy and comfortable living environment by utilizing the physiological and psychological effects that color can have on humans. It ’s been used!

[0004] Here, black, which is an achromatic color, is in great demand due to its high-quality feeling, but is required to exhibit uniform absorption over the entire wavelength range of visible light. For this reason, it was extremely difficult to produce a pigment that can produce “black” and has good strength and usability. For example, carbon black has a high blackness, but it has a matte texture and lacks a high-class feeling, and there is a drawback that it is possible to obtain a black pearl glaze powder with gloss, particularly pearly luster, and high blackness. It was a long-standing development issue.

[0005] By the way, pearlescent pigments such as titanium dioxide-covered mica, which are pigments utilizing the interference phenomenon of light in addition to colored pigments, are provided.

This pearlescent pigment is used in various fields such as paints, cosmetics, adhesives, printing inks, resin kneading, etc., but conventional black pearlescent pigments are coated with black iron oxide and are strong. Since it is magnetic, it has poor dispersion in a substrate such as a paint, so that sufficient gloss cannot be obtained, and when kneaded into a resin, black iron oxide is oxidized by the temperature and turns brown.

[0006] On the other hand, titanium dioxide-coated mica is reduced in a stream of ammonia to produce a dark pearlescent pigment. A manufacturing method is disclosed in Patent Document 1!

The dark pearl luster pigment has a good color tone and luster that is close to true black and has a problem that it is extremely difficult to manage because it uses a toxic ammonia stream in the manufacturing process.

[0007] The method of reducing titanium dioxide is also described in Patent Documents 2, 3, 4, and 5, although the purpose is different. Patent Document 2 discloses a method of obtaining a colored mica titanium pigment by mixing metallic titanium with titanium mica coated with titanium dioxide. Patent Document 3 discloses a method for obtaining a colored mica titanium-based pigment by reducing titanium dioxide with silicon, titanium hydride, calcium hydride, and carbon. In these patent documents, titanium dioxide, which is a mica titanium-based pigment, is reduced to a low-order titanium oxide by reducing the titanium dioxide into a gray to reddish-brown color, which causes light absorption and interference. The present invention relates to a method for producing a colored mica titanium-based pigment that is colored as an appearance color. Patent Document 4 discloses a method for producing a colored mica titanium-based pigment obtained by reducing titanium dioxide with aluminum oxide. Further, Patent Document 5 discloses a method for producing a colored mica titanium pigment obtained by reducing titanium dioxide with metallic aluminum, manganese, iron, cobalt, nickel, and zinc. Thus, there is no mention at all of a method for producing a force black pearlescent pigment, which is known as a method for reducing titanium dioxide without using ammonia. This is because when low-order titanium oxide is produced using titanium metal or the like, “black” is bluish or red is strong, and “true black” cannot be obtained.

[0008] Patent Document 1: JP-A-58-164653

Patent Document 2: Patent No. 1732810

Patent Document 3: Japanese Patent Laid-Open No. 6-211521

Patent Document 4: JP-A-8-67830

Patent Document 5: Patent No. 3542388

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention has been made in view of the above prior art, and the problem to be solved is to easily produce a low-order titanium oxide black pearly luster powder excellent in color and the black powder. It is to provide a method.

Means for solving the problem

[0010] The present inventors have attempted to produce a powder having a color tone and luster equivalent to or higher than those of the black pearl luster pigment obtained by ammonia reduction without using ammonia gas.

[0011] As described above, low-order titanium oxide has a dark blue or black color, so the power of reduction using metallic titanium has a dark brown or reddish tone, and is "black" as obtained by ammonia reduction. Nearly! /, The color has been obtained! / ,!

As a result of further investigation on this point, when ammonia reduction is performed, nitrogen derived from ammonia is incorporated into the titanium compound to form a titanium oxynitride compound.

, It was found that the blackness is high.

TiO + NH TiON

twenty three

On the other hand, when reduction is performed with metallic titanium, Ti 2 O 3, Ti 2 O 3, etc., depending on the degree of reduction

2 3 3 5 are produced, each of which is amber, but has a unique color, so it is difficult to obtain “true black”.

As a result of further studies by the present inventors, even when reduction was performed with metallic titanium, the reduction degree of low-order titanium oxide was adjusted by simply adjusting the degree of reduction of the lower-order titanium oxide as in the conventional case. It was found that a pearly luster powder was obtained, and the present invention was completed.

[0013] That is, the black pearly luster powder according to the present invention is a black pearly luster powder having a surface of a thin plate powder coated with low-order titanium oxide,

The low-order titanium oxide is substantially free of nitrogen and is composed of TiO (X = l. 56-; 1.75).

X

It is characterized by being.

In the powder, low-order titanium oxide contains at least Ti 2 O 3 and Ti 2

Including 2 3 3 o

5 is preferred.

[0014] Further, the method for producing a black pearly luster powder according to the present invention includes:

Metallic titanium is mixed with pearly luster powder coated with titanium dioxide on a thin plate-like base powder, and reduced under low oxygen conditions until TiO (X≤l.5) is obtained.

X

After that, it is oxidized and fired until it becomes TiO (X = l. 56-1.75) in an oxidizing atmosphere. Features.

[0015] Further, in the above method, metallic pearl luster powder in which the thin plate-like base powder is coated with titanium dioxide is mixed, reduced at 700 1000 ° C under low oxygen conditions, and then in an oxidizing atmosphere. It is preferable to oxidize and fire at 200 to 500 ° C.

[0016] <Brightness>

In the present invention, the glitter was evaluated as follows. That is, the powder lg was added to 15 g of Nitron Riya Lacquer Lacquer 6341 manufactured by Musashi Paint Co., Ltd., mixed well, and applied to a black and white underlayer concealment rate test paper with a 4 mil applicator. Then, the glossiness of the coating film on the white ground was measured with Daros Checker IG-300 manufactured by Horiba.

It is preferable that the black pearly luster powder that is useful in the present invention has a value of 60 ° and 20 ° of 60 or more.

[0017] <Blackness>

In the present invention, the blackness was evaluated as follows. That is, the powder lg was added to 15 g of 2 Toronto Tariya Lacquer 6341 manufactured by Musashi Paint Co., Ltd., mixed well, and applied to a black and white underlayer concealment rate test paper with a 4 mil applicator. The black pearly luster powder according to the present invention, in which the color tone of the coating film on the white ground was measured with a spectrocolorimeter CM-2500d manufactured by Minolta and represented by Hunter's L, a, b color values, It is preferable that the L value (lightness) is 25 or less, the a value is 1.5 or less, and the b value is 0.5 2.9.

[0018] <Hiding power>

In the present invention, the hiding power was evaluated as follows. That is, the powder lg was added to 15 g of Nitron Riya Lacquer Lacquer 6341 manufactured by Musashi Paint Co., Ltd., mixed well, and applied to a black and white underlayer concealment rate test paper with a 4 mil applicator. The color tone of the paint film on the white ground and the black ground was measured with a spectrocolorimeter CM-2500d manufactured by Minolta.

The black pearly luster powder that is suitable for the present invention preferably has a color difference ΔE between white ground and black ground of 1.0 or less when expressed by Hunter's L, a, b color values. .

[0019] <TiO>

X

In the present invention, TiO was measured as follows. Titanium coated on powder substrate Is dissolved in hot sulfuric acid and reduced with metallic aluminum to quantify the amount of titanium. From the amount of titanium and the weight increase when the reduced oxidized powder is oxidized at 700 ° C in the atmosphere, The amount of oxygen was quantified.

[0020] The black pearly luster powder that is effective in the present invention has a TiO X of 1.56 to 1.75.

X

The compound of the reduced oxide powder is recognized as Ti 2 O and Ti 2 as a titanium oxide compound when measured with a Rigaku X-ray diffractometer Miniflex.

2 3 3 o is sure

Five

The thin plate-like substrate powder is preferably selected from natural mica, synthetic mica, aluminum oxide, and silicon oxide, and it is preferable to use a material obtained by coating this substrate powder with titanium dioxide.

[0021] Further, the pearly luster powder in which the raw material base powder is coated with titanium dioxide is preferably silver-glossy.

Moreover, it is possible to coat | cover the particle | grain surface of the said black pearl luster powder with a colorless metal oxide and / or a colorless metal hydroxide. Suitably, the metal of the colorless metal oxide and / or the colorless metal hydroxide is selected from silica, alumina and zircoure.

Furthermore, the present inventor provides a “coloring gloss composition” comprising the above black pearly luster powder and / or coated black pearly luster powder as a coloring component. This “coloring gloss composition” is a composition that can take various specific embodiments, for example, external compositions such as makeup cosmetics, coating compositions, printing ink compositions, adhesive compositions, and the like. .

As a method of using the glossy composition for coloring, a black pearly luster composition is applied on a coated surface, and light interference and light of a specific titanium oxide compound are formed on the powder layer formed on the coated surface. It is preferable to make it black pearl luster by absorption.

The invention's effect

[0023] As described above, the black pearly luster powder according to the present invention does not substantially contain nitrogen because it has not undergone ammonia reduction, and has excellent blackness and brightness by adjusting the reduction degree with metallic titanium. A black pearly luster powder can be provided.

[0024] Further, according to the method for producing a black pearly luster powder according to the present invention, the titanium dioxide-coated powder is once reduced to strength with metallic titanium and then re-oxidized to adjust the degree of reduction. As a result, the reduction degree can be adjusted in an open atmosphere, facilitating manufacturing. , Blackness and pearl luster are also good.

BEST MODE FOR CARRYING OUT THE INVENTION

[0025] Hereinafter, preferred embodiments of the present invention will be described.

The black pearly luster powder and / or the coated black pearly luster powder according to the present invention and the method for producing the same are obtained by mixing metallic titanium with pearly luster powder obtained by coating a thin plate-like substrate powder with titanium dioxide, and under low oxygen conditions. It is reduced below and then oxidized and fired in an oxidizing atmosphere, and a black pearly powder is obtained by the light interference action and the light absorption action of a specific titanium oxide compound.

[0026] The black pearly luster powder of the present invention is a black pearly luster powder compared to the colored pearly luster powder in which the color tone of the conventional pearly luster powder is colored from silver to an interference color. New features are recognized.

[0027] The base particles of the black pearly luster powder and / or coated black pearly luster powder of the present invention,

V, a so-called thin plate-like powder coated with titanium dioxide, is a silvery pearlescent powder. As this silver pearly luster powder, commercially available silvery pearly luster powder, for example, Iriodin series made by Merck, Madana Pearl series made by Engelhard, Reflex series made by CQV, etc. In addition, those produced using a generally known method can be used. For example, by using a synthetic My power manufactured by Toby Industries, a silver pearly luster powder coated with titanium dioxide can be produced by a conventional method and used.

[0028] The base particles, V, and the so-called thin plate-like powder are selected from natural mica, synthetic mica, aluminum oxide, and key oxide. Among these, natural mica and synthetic mica are relatively easy to control the shape and surface uniformity, particle size and distribution, and further, the surface of the particles is uniformly coated with titanium dioxide to give a silvery color. In terms of producing pearly luster powder! /, It is the preferred material to select as a base particle.

[0029] A pearlescent pigment that has a nacreous appearance by coating natural mica with a metal oxide such as titanium dioxide or iron oxide has been conventionally known. Since this type of pearlescent pigment is a natural mica, it contains impurities in the mica, so that it has the disadvantage that the color of the color is poor and the extra color is cloudy. Therefore, it is used as a nacreous pigment coated with titanium dioxide, iron oxide, etc. based on synthetic mica, plate-like aluminum oxide, and plate-like oxide that have been free of impurities. It was.

[0030] Although the particle diameter of the base particles is not particularly specified, the average particle diameter is preferably 30 m or less. When this particle size is 30 m or more, metal titanium is mixed and reduction under low oxygen conditions is sufficiently reduced, but the hiding power (covering power: power to hide the ground) becomes weak and the ground This is not preferable because it is easily affected by the color and a sufficient black gloss cannot be obtained.

[0031] These base particles are mixed with silver pearly luster powder coated with titanium dioxide, and metallic titanium is mixed and reduced under low oxygen conditions. The mixing amount of titanium metal is somewhat different depending on the size of the base particles. The mixing amount of titanium metal is preferably 5 mass% to 18 mass%. When the amount is less than 5% by mass, the reduction of titanium dioxide is insufficient, so that even when fired in an oxidizing atmosphere, a black pearlescent powder is not obtained. On the other hand, when the content is 18% by mass, the reduction of titanium dioxide proceeds, and at the same time, the aggregation due to the solid solution becomes strong, and the luster as pearl luster is lost, which is not preferable.

[0032] When the reduction is performed under the above-described low oxygen condition, the reduction temperature varies depending on the amount of metallic titanium mixed, but is preferably 700 ° C to 1000 ° C. Titanium dioxide cannot be reduced sufficiently below 700 ° C, so even if it is oxidized and fired in an oxidizing atmosphere, it does not become a black pearlescent powder. If the temperature is 1000 ° C or higher, reduction is too advanced, and aggregation due to a solid solution with titanium metal becomes strong, and the glitter as pearl luster is lost.

[0033] Further, in the case of reduction under the above-mentioned low oxygen condition, in order to increase the reduction efficiency, by flowing an inert gas such as argon or helium gas and a mixed gas thereof, heat conduction is improved. Reduction efficiency is improved.

[0034] Low-order titanium oxide obtained by reducing titanium dioxide under the above-mentioned low-oxygen conditions is oxidized and fired in an oxidizing atmosphere. The firing temperature varies depending on the degree of reduction. The ability to fire at 200 ° C to 500 ° C preferable. Below 200 ° C, oxidation of low-order titanium oxide does not occur and there is no change in color tone. Above 500 ° C, the oxidation of low-order titanium oxide proceeds excessively, and the low-order titanium oxide returns to titanium dioxide and the color tone becomes silvery pearlescent powder, which is not preferable.

[0035] The black pearly luster powder obtained under the above conditions can be surface treated in the same manner as conventional pearly luster powder. For example, the light resistance and dispersibility improvement treatment with silica, alumina, zirconia and a mixture thereof was used as the coated black pearl luster powder. Also aluminum Hydrophobic treatment with titanium or titanium coupling agent. Examples thereof include hydrophobization treatment with a silicone oil, a fatty acid metal salt, an alkyl phosphate, a fluorine compound having a perfluoroalkyl group, and the like.

[0036] The black pearly luster powder of the present invention having such extremely excellent properties is very useful as a compounding component of a "coloring glossy composition" which is a glossy composition whose primary purpose is coloring of an object. Are better.

[0037] The coloring composition for coloring according to the present invention (hereinafter referred to as the coloring composition for coloring according to the present invention! /) Is! In addition to coloring by "", it also includes imparting gloss using light interference. This is a composition having the primary meaning, and its specific embodiment is not particularly limited. For example, a composition for external use such as makeup cosmetics, a coating composition, a printing ink composition, an adhesive composition, etc. A composition that can take the form of

[0038] That is, the colored gloss composition of the present invention is a gloss composition that can be applied on a coated surface and blackened by causing light interference in a composite powder layer formed on the coated surface. is there.

[0039] The content of the black pearly luster powder in the colored glossy composition of the present invention can be appropriately selected depending on the specific mode and purpose of the composition, and is not particularly limited.

Hereinafter, the composition of typical embodiments that the colored gloss composition of the present invention can take will be described.

[0040] (1) Among the compositions for external use such as cosmetics, the makeup cosmetics have a particularly beautiful role, an “aesthetic role” that keeps the makeup lasting, a “psychological role” that tightens the mood, and The "protective role" that protects the skin is recognized.

In order to fully fulfill these roles, it is essential to improve the color elements of makeup cosmetics and improve usability and sustainability.

The powder which is suitable for the present invention is suitably used for such an external composition.

[0041] In the makeup cosmetics, a powder component may be mentioned as a component that plays a central role. Among these powder components, the pigment component is used for makeup cosmetics and has a good feel. In addition, the above-mentioned “protective role” is fulfilled by providing makeup with persistence, coloring, and, depending on the type, providing an ultraviolet shielding effect.

Therefore, improving the color elements of the pigment component and improving the elements directly linked to the usability and sustainability of the cosmetics are central issues in creating an excellent makeup cosmetic.

[0042] By adding the colored gloss composition of the present invention to the composition for external use of the present invention, an external composition having good black gloss and drastically improved cosmetic durability is provided. The blending amount of the black pearly luster powder of the present invention in the composition for external use can be appropriately selected according to the dosage form and form of the composition and the purpose of blending the colored glossy composition of the present invention, and is particularly limited. Usually, it is blended in the composition in the range of about 0.;! To 80.0% by weight.

In addition, in the composition for external use of the present invention, other components which are usually blended in cosmetics can be blended as long as the desired effects of the present invention are not impaired.

[0043] For example, solid or semi-solid oils such as petrolatum, lanolin, ceresin, carnauba wax, candelillaro, higher fatty acids, higher alcohols, fluid oils such as squalane, liquid paraffin, ester oil and triglyceride, oils such as silicone oil, hyaluronic acid Moisturizers such as sodium and daricerine, surfactants such as cationic surfactants and nonionic surfactants, pigments, preservatives, fragrances, activators, UV screening agents and the like can be appropriately blended.

[0044] The composition for external use of the present invention can take the form of powder, cake, pencil, stick, liquid, etc. For example, foundation, lipstick, eye shadow, scarlet, eyeliner , Makeup cosmetics such as nail enamel and mascara, hair cosmetics such as hair treatment, hair liquid, and set lotion can be applied to the composition for external use of the present invention. By blending, it is possible to maximize the excellent characteristics of the colored gloss composition of the present invention.

[0045] The composition for external use of the present invention is applied on the skin or hair as the application surface, and in the composite powder layer formed on the skin or hair, light interference and light absorption of a specific titanium oxide compound. Thus, black pearl luster is recognized. Its black pearly luster is much stronger than conventional pearlescent pigments. [0046] (2) The colored gloss composition of the present invention is a coating composition (hereinafter referred to as the present coating composition)

In many cases of coloring an object, a colored “paint composition” is often used. The coating composition is a composition that initially has fluidity, spreads and adheres to the surface of an object, and then forms a continuous film through a drying process.

[0047] And, in the present age when it is required to apply more various colors to the coating composition, this pigment also exhibits the above-mentioned flip-flop effect. There is also a need to use pearlescent pigments that can impart more diverse interference colors. As described above, the colored gloss composition of the present invention imparts a black pearl luster to an object by light interference and light absorption of a specific titanium oxide compound, and a gloss that has never been obtained can be obtained. It ’s so good!

[0048] As described above, the present invention also provides a coating composition as the above-described coloring gloss composition. The coating composition of the present invention contains the black pearl luster powder of the present invention as a luster pigment as described above. The blending amount of the black pearly luster powder of the present invention in the coating composition of the present invention can be appropriately selected according to the specific type, purpose, etc. of the coating composition of the present invention, and is not limited at all. Although the powder that is particularly effective in the present invention is a black pearlescent powder, even if it is added in a larger amount than a conventional pearlescent pigment, it is uniformly applied to the object. It is easy to develop a stronger black color.

[0049] In addition to the black pearly luster powder of the present invention, the paint composition of the present invention usually contains elements that can be blended in the paint composition to the extent that the intended effect of the present invention is not impaired. Specifically, coating film forming elements such as polymer oils, natural or synthetic resins, polymer materials such as cellulose and rubber derivatives, etc .; plasticizers, desiccants, curing agents, skin prevention Film formation aids such as agents, fluidity modifiers (thickeners, leveling agents, etc.), sagging inhibitors, antiseptics, antifungal agents, rust inhibitors, UV absorbers, etc .; the black pearl luster powder of the present invention Facial materials other than these can be blended in the coating composition of the present invention.

[0050] A solvent for dissolving the coating film-forming element can also be appropriately selected and used.

In the coating composition of the present invention, the composite formed on the coated surface is formed on the coated surface. Black pearl luster is observed in the powder layer due to light interference and light absorption by specific compounds of titanium oxide.

[0051] This paint composition of the present invention comprises various paints such as architectural paints, stone paints, vehicle paints, ships and ship bottom paints, wood paints, equipment paints, marker paints, electrical insulation paints, conductive and semiconductive paints, It can be applied to a wide range of quality paints, anticorrosion paints, heat resistant paints, fireproof paints, temperature indicating paints, luminescent paints, and insecticidal paints.

[0052] (3) When the colored gloss composition of the present invention is a printing ink composition (hereinafter referred to as the printing ink composition of the present invention): The printing ink composition is an image defined on a manuscript or a plate. The composition is used as an image-forming material that is formed and fixed on the surface of a printing material by a printing method.

[0053] This printing ink composition is distinguished from the above-described coating composition in that it has "printing color", which is a characteristic necessary for producing a printed material without any trouble in the printing process.

Also, in the printing ink composition, the use of pearlescent pigments as a colorant has been studied in the same manner as the above-mentioned coating composition because of the need to provide more various printings.

[0054] As described above, the black pearly luster powder of the present invention is excellent as a colorant for a printing ink composition in that it imparts a black luster to an object, and is also a black glossy powder. Therefore, the printed matter provided using the printing ink composition using this as a colorant is also excellent in that a black gloss having a strong hiding power can be effectively obtained.

Thus, the present invention also provides a printing ink composition as the aforementioned coloring composition.

[0055] The printing ink composition of the present invention contains the black pearly luster powder of the present invention as a colorant as described above. The amount of the black pearl luster powder of the present invention in the printing ink composition of the present invention can be appropriately selected according to the printability required according to the specific type and purpose of the printing ink composition of the present invention. In particular, the black pearly luster powder of the present invention has a black concealing power because it is a black glossy powder, so that the black pearly luster is higher than that of conventional pearly luster pigments. It became easy to obtain.

In addition to the black pearly luster powder of the present invention, the printing ink composition of the present invention is usually printed. Elements that can be incorporated into the ink composition can be incorporated as long as the initial effects of the present invention are not impaired.

[0056] Specifically, pigments and dyes other than the black pearl luster powder of the present invention as a coloring material; as a vehicle, oil (vegetable oil such as flaxseed oil and drill oil, mineral oil such as ink oil and solvent) Etc.), resins (natural resins such as gilsonite and rosin, rosin-modified phenolic resins, maleic resins, petroleum resins, alkyd resins, ester resins, etc.), plasticizers, waxes, solvents, etc .; as auxiliary agents , Drying control agents (dryers, anti-skinning agents, etc.), viscosity control agents (compounds, thickeners, waist-cutting agents, etc.), dispersibility control agents (dispersants, anti-coloring agents, stabilizers, etc.), color Conditioning agents (toners, matting agents, etc.), reactive agents (photopolymerization initiators, catalysts, crosslinking agents, etc.), other ingredients, wetting agents, antifoaming agents, fungicides, etc. are incorporated into the printing ink composition of the present invention. I can do it.

[0057] In the printing ink composition of the present invention, the composite powder layer formed on the coated surface is coated on the coated surface and then subjected to a printing process. Black pearl luster is recognized by light absorption.

This printing ink composition of the present invention is widely used as various printing inks, for example, lithographic printing ink, gravure printing ink, relief printing ink, screen printing ink, flexographic printing ink, intaglio printing ink, various special printing inks, etc. It is possible.

[0058] Thus, the colored gloss composition of the present invention has many aspects,

The embodiment of the colored gloss composition of the present invention is not limited to the embodiment described above! /. For example, the “colored plastic product” obtained by kneading and mixing the black pearl luster powder of the present invention in plastic as shown in the examples described later is also the colored gloss composition of the present invention.

Example

[0059] In the following, the ability to disclose the present invention more specifically by way of examples, the technical scope of the present invention is not limited by these examples.

In addition, unless otherwise indicated, the compounding quantity in a present Example is a weight part. The number of measurement methods shown in the production examples is as follows.

[0060] a) Glossiness measurement method

This black pearl luster powder lg is converted to 15g of Nitron Riya Lacquer 6341 made by Musashi Paint Co., Ltd. The mixture was thoroughly mixed and dispersed with a lab disperser, and applied to a black and white underlayer concealment rate test paper with a 4 mil (0.101 mm) applicator. And the glossiness of the coating film on the white ground was measured at 60 ° and 20 ° with a daros checker IG-300 manufactured by Horiba.

[0061] b) Measurement method of colorimetric values L, a, b

Add this black pearl luster powder lg to 15g of Nitron Riya Lacquer 6341 made by Musashi Paint Co., Ltd. It was applied with an applicator. Then, the color tone of the coating film on the white ground was measured with a spectrocolorimeter CM-2500d manufactured by Minolta Co., Ltd., and the values represented by Hunter's L, a, b color values were shown.

[0062] c) Measuring method of concealment rate

Add this black pearl luster powder lg to 15g of Nitron Riya Lacquer 6341 made by Musashi Paint Co., Ltd. It was applied with an applicator. Then, the color tone of the paint film on the white ground and the black ground is measured by the spectrophotometer CM-2500d manufactured by Minolta Co., Ltd., and expressed by Hunter's L, a, b color values. E value is shown.

The color difference ΔΕ was determined by the following equation.

AE = {(L -L) ² + (a-a) ² + (b — b) ² } ^1/2 '' l

w b w b w b

w: Value on white background, b: Value on black background

[0063] d) Method for measuring oxygen content in titanium oxide compound

About 3 g of this black pearl luster powder was accurately weighed into a 50 cm ³ crucible and baked at 750 ° C for 2 hours in the atmosphere. After standing to cool, the weight is measured, and the increase in weight of black titanium oxide changed to titanium dioxide is determined.

Accurately measure 0.2 g of this black pearl luster powder baked at 750 ° C and transfer it to 500 cm ³ Erlenmeyer flask. Add a small amount of pure water and shake to make milky. Add 30cm ^{3 of} concentrated sulfuric acid and 12g of ammonium sulfate and heat with an electric heater. Heat slowly at the beginning and ignite at the end to dissolve. After cooling, add 80cm ³ of pure water and 80cm ³ of hydrochloric acid, and shake well. Wash 3g of metallic aluminum with hydrochloric acid (1 + 5). Add washed metal aluminum to the Erlenmeyer flask and generate hydrogen while warming with a heater. The metal aluminum is completely dissolved and the liquid After it becomes clear purple, leave it for a few minutes and cool it down to 50 ° C or below with running water. Titrate immediately with 0.1 lmol / 1 ammonium iron (III) sulfate solution using 3 cm of saturated potassium thiocyanate solution as an indicator. Liquid dullness, brown color disappears for 30 seconds! /, Point is the end point.

Titanium dioxide (%) was determined from the following formula.

[0064] A = (0.0000Bf / S) 100 2 formula

A: Titanium dioxide (%)

B: Amount of ammonium iron (III) sulfate solution required for titration (cm)

f: Factor of ammonium iron (III) sulfate solution

S: Sample weight (g)

From the A value, calculate the amount of titanium dioxide (assumed to be ag) and the amount of thin base powder. In addition, the amount of black titanium oxide (bg) is obtained by subtracting the amount of the thin plate-like substrate powder from the amount of the black pearl luster powder, and the relationship between the weight increase rate of a / b and TiOx is obtained by the following equation. .

[0065] Y = -0. 39X + 1. 1698 3 formulas

Υ: Weight increase rate

: Value of 1 0

[0066] e) Crystal structure analysis measurement method

This black pearly luster powder is measured by an X-ray diffractometer miniflex manufactured by Rigaku Corporation using a Cu counter cathode 30 Kv l 5 mA-K β filter. Titanium oxide compounds are identified from diffraction lines.

[0067] (Production Example 1) Artemica SC with an average particle size of 20 m, sold by Nippon Koken Kogyo Co., Ltd.

100K silver color 15Kg was weighed, 1 · 95Kg of titanium metal was added to this, and mixed with Henschel mixer. The mixed powder was filled into a reaction vessel, evacuated with a vacuum apparatus, and when the degree of vacuum reached 10, heating was started and the reaction was carried out at 850 ° C. for 10 hours. After the reaction was completed, argon gas was flowed to speed up the cooling.

After confirming that the internal temperature was 200 ° C. or lower, the reduced powder was taken out from the reaction vessel. The reduced powder was pulverized with a pulverizer and the titanium metal was removed by wind classification. The classified reduced powder was oxidized and fired at 300 ° C. for 3 hours in the atmosphere. The powder produced was 14.5 kg and had a black pearly luster! /. Manufactured black pearl luster powder 14Kg in isopropyl Alconole 0.45 kg and Shin-Etsu Chemical Co., Ltd. Silicone KF-9909 were mixed in a Henschel mixer and silicone-treated at 140 ° C for 5 hours. Silicone-covered black pearl luster powder of 14 kg was obtained.

First, the present inventors prepared black pearly luster powder by various production methods according to Production Example 1, and observed the appearance. The results are shown in Table 1 below.

[table 1]

Test example 1-1 1-2 1-3 1-4 1-5

τ io _x 1. 9 1-6 1 1. 6 5 1. 6 4

Recipe ^→ Acid IS 兀 only 逯^→ Acid is 兀 only Nonmoni / IS 兀 Gloss ◎ X ◎ X 〇

Appearance color True black Straightness color True blackness Straightness color As shown in Table 1, when ammonia reduction was performed (Test Example 15), both gloss and true black were satisfactory. Manufacturing process Because of the use of toxic ammonia gas, management was extremely difficult.

[0069] In addition, when the reduction degree was adjusted only by metal reduction (Test Examples 1, 2, 1 to 4), the black color was satisfactory, and gloss was not sufficiently obtained. However, since the reduction degree must be adjusted in a high temperature sealed container, it was difficult to obtain reproducibility.

In contrast, when re-oxidation was performed after sufficient metal reduction (Test Examples 1-1 and 1-3), extremely good gloss was obtained with true black color, and the strength and degree of reduction were also reduced. Since adjustment can be performed in an oxidizing atmosphere (in the air), it was possible to manufacture with good reproducibility.

[0070] Even if the degree of reduction is substantially the same as described above, there is a difference in gloss between the case where the reduction degree is adjusted in the reduction step and the case where reduction is excessively advanced and reoxidized once. Arise.

Accordingly, the present inventors decided to adjust the reduction to 1.50 or less and then reoxidize to adjust the black pearl luster powder.

Next, the present inventors conducted a detailed study on the reduction degree adjustment during reoxidation. The production method was the same as in Production Example 1. The results are shown in Table 2.

[0071] [Table 2] Test example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 io _x 1. 50 1. 56 1. 58 1. 59 1. 63 1. 72 1. 74 1 77 Gloss Δ 〇 ◎ ◎ ◎ ◎ 〇 Appearance color Red black 〇 ◎ ◎ ◎ ◎ Black As is clear from Table 2, true black is 1.56 ~; A true black color and gloss were obtained from 1.58 to 1.72. In particular, when the degree of reduction is high (Test Example 2-1), the color is reddish black. Simply increasing the degree of reduction does not yield true black. On the other hand, when the degree of reduction is low (Test Example 2-8), it turns out to be blue-black, and it is understood that true black cannot be obtained.

Furthermore, the present inventors conducted various production tests shown below, and the evaluation is shown in Table 3.

(Production Example 2) A silver color of 12 kg of ilidine 111 having an average particle diameter of 8 am manufactured by Merck & Co. was measured, and 1.8 kg of titanium metal was added thereto and mixed with a Henschel mixer. The mixed powder was filled into a reaction vessel and evacuated with a vacuum device. When the vacuum reached 10-, heating was started and the reaction was carried out at 800 ° C for 10 hours. After completion of the reaction, argon gas was passed to accelerate the cooling. After confirming that the internal temperature was 200 ° C. or lower, the reduced powder was taken out from the reaction vessel. The reduced powder was pulverized with a pulverizer and the titanium metal was removed by wind classification. The classified reduced powder was oxidized and fired at 320 ° C. for 2 hours in the air. The powder produced was 1 lKg and had a black pearly luster! Add 1 lKg of the black pearl luster powder to a 200 dm ³ reaction kettle, add 0.5 Kg of aluminum sulfate, 1. lKg of urea and 150 Kg of tap water, and stir without power. Aged reaction was carried out. It was allowed to cool and then washed with water. To this was added 40 dm of clean water in which 0.21 kg of sodium metasilicate was dissolved and 40 dm of clean water in which 0.185 kg of zirconium oxychloride was dissolved. Incubate for 3 hours at the above temperature. After washing with water and drying, the surface was treated with hydroxides of aluminum, silicic acid and zirconium. Aluminum silicate-zirconium hydroxide-coated black pearlescent powder l lKg was obtained.

(Production Example 3) 14 kg of Magna Pearl 1100 silver with an average particle size of 18 m manufactured by Engelhard Co., Ltd. 14 kg was measured, and 1.96 kg of metal titanium was added thereto and mixed with a Henschel mixer. The mixed powder is filled into the reaction vessel and evacuated with a vacuum device, reaching a vacuum of 10- Then, heating was started and the reaction was carried out at 780 ° C for 10 hours. After completion of the reaction, argon gas was flowed to accelerate cooling. After confirming that the internal temperature was 200 ° C or lower, the reduced powder was taken out from the reaction vessel. The reduced powder was pulverized with a pulverizer, and metal titanium was removed by wind classification. The classified reduced powder was oxidized and fired at 310 ° C. for 2 hours in the atmosphere. The produced powder had a black pearl luster at 13.5 kg. Add 13 kg of this black pearl luster powder to a 200 dm ³ reaction kettle, add 0 to 65 kg of aluminum sulfate, 0 to 98 kg of urea, 150 kg of tap water, and warm to 95 ° C for 3 hours with stirring. Reacted. After standing to cool, it was washed with water and dried at 150 ° C. for 10 hours to obtain 13 kg of alumina-treated powder. Add Ajinomoto Fine Techno Co., Ltd. Preact KR55 (coupling agent) 0 · 26 Kg and Xylol 1.3 Kg to the alumina-treated powder 13 Kg, mix with a Henschel mixer and mix at 150 ° C. Time processed. 13 kg of alumina powder-coated black pearl luster powder was obtained.

(Production Example 4) A silver color of 13 kg of Iriodin 121 having an average particle diameter of 15 m manufactured by Merck & Co. was measured, and 1.82 kg of metal titanium was added thereto and mixed with a Henschel mixer. The mixed powder was filled into a reaction vessel, evacuated with a vacuum device, and when the vacuum reached 10-, heating was started and the reaction was carried out at 800 ° C for 10 hours. After completion of the reaction, argon gas was supplied to accelerate the cooling. After confirming that the internal temperature force was ¾00 ° C. or less, the reduced powder was taken out from the reaction vessel. The reduced powder was pulverized with a pulverizer, and metal titanium was removed by wind classification. The powder obtained by oxidizing and baking the classified reduced powder at 290 ° C. for 3 hours in the atmosphere had a black pearly luster at 12.5 kg. Add 12 kg of this black pearl luster powder into a 200 dm reaction kettle and add 2.2 kg of Asahi Guard AG-530 (fluorine treatment agent) manufactured by Asahi Glass Co., Ltd. A 10% aqueous hydrochloric acid solution was added dropwise to adjust the pH to 4. The mixture was aged for 1 hour with stirring. After filtration and washing with water, it was dried at 150 ° C. for 16 hours to obtain 12 kg of fluorine-coated black pearl luster powder.

(Production Example 5) A silver color of 16 kg of Iriodin 103 having an average particle diameter of 22 m manufactured by Merck & Co. was measured, and 2.08 kg of metal titanium was added thereto and mixed with a Henschel mixer. The mixed powder was filled into a reaction vessel and evacuated with a vacuum device. When the degree of vacuum reached 10−, heating was started and the reaction was carried out at 850 ° C. for 10 hours. After completion of the reaction, argon gas was supplied to accelerate the cooling. After confirming that the internal temperature force was ¾00 ° C. or less, the reduced powder was taken out from the reaction vessel. The The reduced powder was pulverized with a pulverizer and the titanium metal was removed by wind classification. The classified reduced powder was oxidized and fired at 300 ° C. for 3 hours in the atmosphere. The powder produced was 15.5 kg and had a black pearly luster!

[0076] Table 1 shows the powder characteristic values of the black pearl luster powder produced in the above production example. As can be seen from the table, the powders produced from any of the production examples are glossy, have low lightness, low a and b values, and low concealment ratio (strong concealment power). Black pearl luster powder It was a body. Figure 1 shows the X-ray diffraction measurement results of the black pearl luster powder before the surface treatment. As can be seen from the figure, the black nacreous powder can be confirmed by My strength, Ti O and Ti O.

2 3 3 5

[0077] [Table 3]

These black pearly luster powders were used in the following formulation examples.

: Formulation example 1] Powdered solid type eyebrow cosmetics

Blending ingredients Blending amount (

1-Silicone-coated black nacreous powder from Production Example 1 3 2.0

2 Talc 5 2 8

3 Lanolin wax 1 0. 0

4. Moody, 'Raffin 4.0

5. Appropriate amount of propyl baroxybenzoate

6 Antioxidant suitability

7. Fragrance

<Manufacturing Method> The above 1 2 was mixed with a Henschel mixer, and 3 7 mixed with heating and dissolution was added and kneaded. It was pulverized with a pulverizer, passed through a sieve, and pressed into an intermediate dish. Power and eyebrow cosmetics should be used as an eyeliner when wet with a brush, as an eyebrow when using a dry brush, and as a mascara when using a brush for mascara. I can do it. Further, as Comparative Example 1, the component 1 was a silicone-treated black iron oxide.

[0080]: Formulation Example 2] Film type mascara

Compounding ingredients Compounding amount (parts by weight)

1 Purified water 5 0. 0

2. Carboxymethyl senorelose sodium 1.0

3.1, 2 pentanegiore 3.0

4. Fluorine-coated black pearl luster powder from Production Example 4 1 2.0

5 Emmanoresin of vinyl acetate resin 2 8.0

6. Appropriate amount of methyl paraoxybenzoate

7. Appropriate amount of fragrance

8.

<Manufacturing Method> Add 2.3 to 1. above and dissolve with heating, add 4. and process with a colloid mill. Five

Add and agitate to homogenize, then dissolve 6.7 in 8. Add to it and mix. Further, as Comparative Example 2, the component 4 was fluorinated black iron oxide.

[0082]: Formulation Example 3] Pencil-type eyebrow cosmetic

Compounding ingredients Compounding amount (parts by weight)

1 Canorenanoru 8.0

2. Beeswax 2 0. 0

3 Ozokerite 1 0. 0

4. Microcrystalline wax 1 0. 0

5 ヮ Serine 8.0

6 Lanolin 5.0

7 Percussion Norraffin 7.0

8 Myristin Isopropinore 4.0

9. Black pearly luster powder from Production Example 5 2 8.0

<Production Method> The above components 1 to 8 are dissolved by heating, 9 is added, and the mixture is kneaded with a roll mill. This is extruded to a diameter of 5 mm using an etastruder. At the wood part with a groove, the molded core is sewn and crimped. This is cut and the outer shape is molded into a pencil shape, and the wood is painted and engraved to make a product. Moreover, as Comparative Example 3, the component of 9. was black iron oxide

Yes

With respect to the blending examples and comparative examples of the present invention, evaluation was made on wrinkles, the naturalness of the finished color, and the uneven color of the finished product. The evaluator performed a five-step evaluation of 1 to 5 by 10 expert panels, and the average value was displayed in Table 4 with the following symbols. : 4.5 or more, 5.0 or less

○: 3.5 or more, less than 4.5

Δ: 2.5 or more, less than 3.5

X: 1.5 or more, less than 2.5

X X: 1.0 or more, less than 1.5

[Table 4]

[0085] From Table 4, the powder solid eyebrow cosmetics of Formulation Example 1, the coating type masker of Formulation Example 2, and the pencil type eyebrows cosmetic of Formulation Example 3 are wrinkles at the time of application, the naturalness of the finished color, and the finish It has become clear that it has the effect of improving beautifully without uneven color.

[0086]: Formulation Example 4] Coating composition

Compounding ingredients Quantity (parts by weight)

1 Thermoplastic acrylic resin 7 8. 3

2. Anolemi, Siri force, Zirco coating of Production Example 2

Black nacreous powder 8.7

3. Butyl acetate 1 3. 0

<Production Method> The above components !! to 3 were uniformly dispersed with a disperser to obtain a coating composition.

The paint composition of Formulation Example 4 was applied to a mild steel plate with a thickness of 2 mm with a spray gun so that the coating thickness was about 30 μm, left at 25 ° C for 30 minutes, and then at 140 ° C for 20 minutes. Burned. The resulting coating film had a strong black color! [0088]: Formulation Example 5] Ink composition for printing

Blending ingredients Blending J t (:

1. Anolemina / force-strengthening coating of production example 3

Black nacreous powder 1 4.0

2. Ethylene acetate butyl copolymer resin 7.5

3. Salty polypropylene 5. 5

4. Ptyl acetate 40. 0

5. Acetic acid chill 2 9. 0

6. Isopropyl 'anoreconor 3.0

7. Polyethylene wax 0.8

8. Antistatic agent 0.2

<Production Method> The above components !! to 8 were weighed and mixed and dispersed by a bead mill to obtain a printing ink composition.

Using this printing ink composition of Formulation Example 5 and printing on white paper to a thickness of 60 m after drying, the coated body has strong black color and gloss! /, It was.

[0090]: Formulation Example 6] Ink composition for printing

Compounding ingredients Compounding amount (parts by weight)

1. Silicone-coated black pearlescent powder from Production Example 1 1 5.0

2. Acrylic resin 20. 0

3. Naphtha 3 5. 0

4. Butinorece r 30. 0

<Production method> The above components !! to 4 were weighed and mixed and dispersed by a bead mill to obtain a printing ink composition.

Using the printing ink composition of Formulation Example 6 and printing on white paper so that the film thickness after drying was 50 m, the coated body had a strong black gloss.

[0092] [Composition Example 7] Adhesive sheet for coating

Compounding ingredients Compounding amount (parts by weight)

1. Ataryl adhesive (Toyo Inkki 1 1 0 9) 8 9. 3

2. Curing agent (Toyo Inki 8 5 1 5) 1. 8

3. Fluorine-coated black pearl luster powder from Production Example 4 8.9

<Manufacturing method> The above components !! to 3 were weighed and mixed and dispersed with a disper, and this was applied to a polyester sheet with a thickness of 50 am so that the film thickness after drying was 30 am. After drying, a thin ij liner was bonded to obtain an adhesive sheet for coating.

The obtained pressure-sensitive adhesive sheet for coating had a strong black color!

Brief Description of Drawings

[FIG. 1] The diffraction lines of Production Examples 1 to 5 by the X-ray diffraction method of the powder are shown. This curve is the figure used to identify the compound.

Claims

The scope of the claims

[1] A black pearly luster powder having a surface of a thin plate-like powder coated with low-order titanium oxide, wherein the low-order titanium oxide does not substantially contain nitrogen, and TiO (X = l. 1.75)

X

A black pearl luster powder characterized by being.

[2] In the powder according to claim 1, the low-order titanium oxide contains at least Ti 2 O and Ti 2 O.

2 3 3 5 Black pearlescent powder characterized by having

[3] Metallic titanium is mixed with pearly luster powder coated with titanium dioxide on a thin plate-like base powder, and reduced under low oxygen conditions until TiO (X≤l.5) is obtained.

X

After that, it is oxidized and fired until it becomes TiO (X = l. 56-1.75) in an oxidizing atmosphere.

X

A method for producing black pearl luster powder, which is characterized.

[4] In the method according to claim 3, titanium metal is mixed with pearly luster powder coated with titanium dioxide on a thin plate-like base powder, reduced at 700 to 1000 ° C under low oxygen conditions, and thereafter A method for producing a black pearly luster powder, characterized by oxidizing and baking at 200 to 500 ° C. in an oxidizing atmosphere.