JPH05156174A - Pigment coated with titanium and zinc, its production and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To provide a cosmetic containing a coated flaky pigment, having a low surface gloss and a nonbluish gloss, and excellent spread on the skin and adhesion to the skin. CONSTITUTION:A flaky pigment composition containing a flaky powder such as mica as a base and prepared by coating this base with hydrated oxide of titanium and a hydroxide and/or a hydrated oxide of zinc by hydrolysis and firing the coated base at 300-900 deg.C; and a cosmetic containing the composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pigment in which the particle surface of a scaly powder is coated with titanium oxide or a composite oxide of titanium and zinc as an inner layer and further with a zinc oxide as an outer layer, and a method for producing the pigment. And cosmetics containing the same.

More specifically, it has optical characteristics such that surface gloss is low and glossy light does not show a bluish color tone.
Moreover, the present invention relates to a novel flake pigment that exhibits good spreadability and adhesiveness when applied to the skin, a method for producing the same, and a cosmetic containing the same.

[0003]

2. Description of the Related Art Cake-like makeup cosmetics are prepared by using scaly powder such as mica or sericite as an extender pigment and adding a white pigment, a coloring pigment, an oily substance or the like thereto. It is known.

However, among the scaly powders of mica and sericite, those obtained by only crushing natural minerals have a color such as gray or brown due to impurities in the crystal lattice. However, when the scaly powder as described above is mixed in a cosmetic, there is a drawback that the color of the scaly powder itself remains. In addition, there is a drawback that the extensibility and the adhesiveness are insufficient in the feeling of use when the scale-like powder is blended in a cosmetic.

Therefore, various improvements have been attempted so far, and many proposals have been made, in order to eliminate the above-mentioned drawbacks.

[0006] With respect to the drawback that the color of the scale-like powder remains, for example, Japanese Patent Publication No. 51-6172 discloses a pearl pigment that can be incorporated into makeup cosmetics, and the surface of the mica is in the form of fine particles. Titanium oxide coated mica titanium is disclosed.

Further, JP-A-58-149959 discloses a pearlescent pigment having improved transparency and tinting strength by coating the surface of mica with titanium oxide, silica and alumina.

Further, in order to improve the drawback that the extensibility and adhesion are insufficient, for example, Japanese Patent Publication No. 2-42.
Japanese Patent No. 388 discloses a flaky pigment having good adhesion to skin, spreadability and transparency by coating an inner layer with barium sulfate and an outer layer with a metal oxide such as titanium oxide. ..

Further, in JP-A-63-254169, by coating the inner layer with titanium oxide and the outer layer with aluminum oxide, the surface gloss is low and the glossy light does not show a bluish color tone. It is described that a scale-like powder having extensibility and transparency is obtained.

[0010]

The objects of the present invention are as follows: (1) Surface gloss is small and gloss light does not show bluish tint. (2) Extensibility on the skin and adhesion to the skin are excellent. It is to provide a novel and useful flake pigment having both of the above characteristics, a method for producing the same, and a cosmetic containing the same.

JP-B-51-6172 and JP-A-5-
In the improvement described in JP-A-8-149959, pearl luster due to the titanium oxide thin film coated on the mica surface is generated, or interference color due to preparation conditions is generated and the surface gloss is increased, so the surface It is unsuitable for the purpose of the present invention, which is to obtain a scaly powder having optical characteristics that have low gloss and do not show a bluish color tone of gloss light.

Further, in the improvements disclosed in Japanese Patent Publication No. 2-42388 and Japanese Patent Application Laid-Open No. 63-254169,
The drawback of exhibiting a bluish surface gloss has not been fully resolved.

[0013]

The present invention solves the above-mentioned drawbacks of the prior art, that is, 2 to 5% by weight of titanium based on the scale-like powder is added to the surface of the scale-like powder. The decomposition product is coated, and further, the hydrolysis product of zinc of 5 to 30% by weight based on the scale-like powder is coated,
Then, by calcining at 300 to 900 ° C., the surface of the scaly particles is coated with titanium oxide or a composite oxide of titanium and zinc, and further, a scaly pigment coated with zinc oxide is obtained, It has achieved its purpose.

In the present invention, the titanium oxide which coats the surface of the particles of the scale-like powder means titanium oxide hydroxide or oxide formed by calcining titanium hydroxide or titanium oxide hydroxide produced by hydrolysis of titanium. Means titanium.

Similarly, the zinc oxide means zinc oxide hydroxide or zinc oxide formed by firing zinc hydroxide or zinc oxide hydroxide produced by hydrolysis of zinc.

The scaly pigment of the present invention is obtained by coating the particle surface of the scaly powder with the hydrolysis product of titanium, subsequently coating the hydrolysis product of zinc, and calcining at 300 to 900 ° C. Manufactured. By this firing, hydrous titanium oxide or hydrous zinc oxide gradually loses water and gradually changes to titanium oxide or zinc oxide. As the firing temperature becomes higher, the titanium oxide coated on the particle surface of the flaky powder is at least In the boundary area, it starts to react with zinc oxide to form a complex oxide.

The amount of the complex oxide formed and the ratio thereof to titanium oxide and zinc oxide differ depending on the coating amount of the hydrolysis products of titanium and zinc, the temperature and time during firing, but usually 300 At a calcination temperature of ~ 600 ° C, a scaly pigment coated with titanium oxide and further coated with zinc oxide is obtained, and as the calcination temperature becomes higher than the above temperature, titanium oxide and zinc oxide in the boundary region are oxidized. The amount of the complex oxide formed with the product increases, and at a firing temperature of 700 to 900 ° C., a scaly pigment coated with the complex oxide of titanium and zinc and further coated with zinc oxide is obtained.

As the scale-like powder that can be used in the present invention,
For example, mica, sericite, talc, kaolin, barium sulfate, boron nitride, and flaky alumina are preferably used, and among them, those having a particle diameter of 1 to 100 μm are preferable.

As a raw material for coating the surface of the particles of the scale-like powder with a hydrolysis product of titanium, for example, water-soluble titanium salts such as titanyl sulfate, titanium sulfate and titanium tetrachloride can be used. Is particularly preferable.

The amount of titanium oxide coating the particle surface of the scale-like powder is preferably ₂ to 5% by weight as TiO ₂ with respect to the scale-like powder. Since titanium oxide has a high refractive index, if the coating amount is 5% by weight or more, optical interference occurs in the coating layer, and pearl luster and a bluish color tone appear, which is not preferable. On the other hand, when the coating amount is 2% by weight or less, sufficient whiteness cannot be obtained when wet with oil, water, and solvent, giving a dull color tone when blended in cosmetics and paints, and spreading on the skin. And the adhesion to the skin deteriorate.

As a raw material for coating the particle surface of the scale-like powder coated with the hydrolysis product of titanium with the hydrolysis product of zinc, for example, zinc such as zinc sulfate, zinc chloride and zinc hydroxide can be used. Although compounds can be used, zinc sulfate is particularly preferred.

The reason why the zinc hydrolysis product is coated after coating the titanium hydrolysis product is that zinc oxide formed on the surface of the flaky powder after firing has a higher refractive index than titanium oxide. This is because it is low and has excellent extensibility on the skin and excellent adhesion to the skin, and thus gives a soft feeling when applied to the skin.

The coating amount of zinc oxide is preferably 5 to 30% by weight as ZnO with respect to the untreated scale-like powder. When the coating amount is 5% by weight or less, the extensibility on the skin and the adhesion to the skin are poor, and when the coating amount is 30% by weight or more, the adhesiveness to the skin is poor, which is not preferable.

The outline of the method for producing the scaly pigment of the present invention described above is as follows.

First step: The scaly powder is suspended in water, a water-soluble titanium salt is added to the suspension, and the suspension is heated to the boiling point to
Keep boiling for ~ 8 hours. As a result, the surface of the scale-like powder is coated with the hydrolysis product of titanium, and thus the suspension is filtered and washed with water to obtain a scale-like powder coated with the hydrolysis product of titanium. Second step: The scale-like powder coated with the hydrolysis product of titanium obtained in the first step is suspended again in water. Continuing,
The suspension is adjusted to pH 10-12 with an aqueous alkaline solution. Ammonia water is added to the zinc compound to adjust the pH to 10, and a zinc-ammonia complex ion aqueous solution is separately prepared, and the aqueous solution is adjusted to 5 to 30% by weight as ZnO with respect to the untreated scale-like powder. After adding to the suspension, heat and boil. As a result, the surface of the scale-like powder is coated with the hydrolysis product of zinc, so this suspension is filtered, washed with water, coated with the hydrolysis product of titanium, and further coated with the hydrolysis product of zinc. A scaly powder is obtained. Second step (alternate method): The flaky powder coated with the hydrolysis product of titanium obtained in the first step is suspended again in water. Then, the above suspension was adjusted to pH 10 to 12 with an alkaline aqueous solution.
Adjust to. Ammonia water is added to the zinc compound to adjust the pH.
A zinc-ammonia complex ion aqueous solution obtained by adjusting to 10 was separately prepared, and the aqueous solution was added to the above suspension so that ZnO was 5 to 30% by weight with respect to the untreated scale-like powder. Heat to 40 ° C, pH of suspension
Dilute sulfuric acid is added over 4-5 hours until a pH of 6.5-8.5. As a result, the surface of the scale-like powder is coated with the hydrolysis product of zinc, so this suspension is filtered, washed with water, coated with the hydrolysis product of titanium, and further coated with the hydrolysis product of zinc. A scaly powder is obtained. 3rd step: The flaky powder coated with the hydrolysis product of titanium and zinc obtained by the method of any of the 2nd steps was added to 3
Bake at 00-900 ° C. At this time, 300-600
When calcined at ° C, a scale-like pigment coated with titanium oxide and further coated with zinc oxide is obtained, which is 700 to 90.
When calcined at 0 ° C., a flaky pigment coated with a complex oxide of titanium and zinc and further coated with zinc oxide is obtained.

The particle surface of the scaly powder obtained by the process for producing the scaly pigment of the present invention described above is coated with titanium oxide or a composite oxide of titanium and zinc, and further with zinc oxide. Compared with conventional pigments, the scale-like pigments that are coated have less surface gloss and have the optical characteristics that glossy light does not show a bluish color tone, and have extensibility and transparency when blended into cosmetics. It is possible to obtain an excellent product having properties.

[0027]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. Example 1 100 g of mica having an average particle size of 5 μm was suspended in 300 ml of water, and titanyl sulfate containing 5.0 g of titanium as TiO ₂ was added to the suspension. The suspension is heated to the boiling point in 30 minutes while stirring and kept boiling for 3 hours,
The suspension was filtered, washed and collected. The recovered mica was suspended again in 500 ml of water, and aqueous ammonia was added to adjust the pH to 10 to 10.5. On the other hand, as ZnO, 10.
After dissolving zinc sulfate containing 0 g of zinc content in 300 ml of water, ammonia water was added to adjust the pH to 10 to separately prepare a zinc-ammonia complex ion aqueous solution.
After the entire amount of this zinc-ammonium complex ion aqueous solution was added to the suspension, it was heated and continued to boil to adjust the pH of the suspension.
When the value reached 7, the heating was stopped and the scale-like powder coated with the hydrolysis product of titanium and zinc was recovered by filtering and washing. The recovered flaky powder is heated and dried, and then calcined at 500 ° C. for 2 hours to obtain 112 of the flaky pigment coated with titanium oxide and zinc oxide.
g was obtained. As a result of measuring the obtained pigment by fluorescent X-ray,
_3. Titanium oxide as TiO ₂ for untreated mica.
3% by weight, zinc oxide was coated as ZnO at 8.7% by weight.

Example 2 After adding the entire amount of the zinc-ammonium complex ion aqueous solution to the suspension in Example 1, instead of continuing heating and boiling, the entire amount of the zinc-ammonium complex ion aqueous solution was added to the suspension. After that, the mixture was heated to 40 ° C., a sulfuric acid aqueous solution having a concentration of 100 g / L was added dropwise over 4.5 hours, and when the pH of the suspension reached 7, the addition of the sulfuric acid aqueous solution was stopped, filtration, The scaly powder coated with the hydrolysis products of titanium and zinc was recovered by washing. The same treatment as in Example 1 was performed except that the above operation was changed. The obtained scaly pigment was the same as in Example 1.

Example 3 The same treatment as in Example 1 was carried out except that the firing temperature in Example 1 was changed from 500 ° C to 800 ° C. As a result of measuring the obtained flaky pigment by X-ray diffraction, zinc oxide and zinc titanate were confirmed from the diffraction profile.

Example 4 The coating amount of the hydrolysis product of zinc in Example 1 was changed to Z
The same treatment as in Example 1 was performed except that the nO content was changed to 25% by weight.

Example 5 The same treatment as in Example 1 was carried out except that the average particle diameter of the mica used in Example 1 was changed to 10 μm.

Comparative Example In an aqueous solution of 13 L in which 100 g of titanyl sulfate as TiO ₂ , 100 g of aluminum sulfate as Al ₂ O ₃ and 650 g of urea were dissolved, the same average particle diameter as in Example 1 was 5 μm.
1 kg of mica of m was suspended and heated to the boiling point in 30 minutes while stirring. The pH of the suspension at that time was 1.5. Continue boiling for 6 hours, stop heating when the pH of the suspension reaches 6, collect the suspension by filtration and washing with water, and
After drying at 20 ° C. for 4 hours, it was baked at 500 ° C. for 2 hours to obtain 1.16 kg of titanium oxide-aluminum oxide-coated mica. As a result of analysis by fluorescent X-ray, the mass of the above-mentioned pigment coating was 8.3 wt% as TiO _{2 with} respect to mica, and Al ₂
It was 8.3% by weight as O ₃ .

Next, the gloss and color tone of the pigments shown in Examples 1 to 5 and Comparative Example were measured and comparative evaluation was performed. Furthermore, a sunscreen foundation was prepared and the feeling of use was evaluated.

<Glossiness> 1 g of each sample and 9 g of cellulose lacquer (NV = 20%) were weighed and mixed with a paint conditioner for 20 minutes to uniformly disperse each sample. The disperse paste was applied to a hiding rate test paper with a doctor blade of 10 mil, and after statically drying, 20 ° -20 ° gloss value was measured with a gloss meter UGV-4D (manufactured by Suga Test Instruments). The measurement results are shown in Table 1. The 20 ° -20 ° gloss value obtained by the measurement with this gloss meter means the reflectance when the incident angle and the light receiving angle are respectively 20 ° with respect to the coating surface, and the reference surface of the specular gloss is obtained. Is expressed as a percentage with the glossiness of 100 being 100, and the higher the value, the higher the gloss of the coating film.

<Measurement of Color Tone> The lacquer coating film used for the gloss measurement was color-measured using a color difference meter CR-200 (manufactured by Minolta) in the Lab color system specified by JIS Z 8730. The larger the negative value of the b value obtained by the Lab color system by colorimetry with this colorimeter, the stronger the blue tint of the coating film. Therefore,
The smaller the absolute value of the negative b value,
It means that it has optical characteristics not showing a bluish color tone. The measurement results (b value) are shown in Table 1.

[0036]

[Table 1]

As is clear from Table 1, the scaly pigments of Examples 1 to 5 of the present invention have a smaller 20 ° -20 ° gloss value than the pigments of Comparative Examples, and the minus value of b value. Since the absolute value at is also small, it can be seen that the present invention provides a scaly pigment having optical characteristics such that the surface gloss is low and the glossy light does not exhibit a bluish tone.

<Evaluation of feeling of use> Preparation of sunscreen solid foundation sample 45.0% talc 35.0% titanium dioxide pigment 10.0% iron oxide pigment (red) 1.4% iron oxide pigment (black) 0 .2% Iron oxide pigment (yellow) 2.9% Isostearyl alcohol 2.0% Lanolin 2.0% Sorbitan fatty acid ester 0.5% Triethanolamine 1.0% Perfume
Appropriate amount

Lanolin, sorbitan fatty acid ester, triethanolamine, and fragrance in the above mixture were heated and mixed at 70 ° C., the remaining powder which had been thoroughly mixed in advance was added thereto, and then they were sufficiently mixed and pressed. Molded to obtain a solid foundation. The feeling of use was evaluated by a sensitivity test.

[0040]

[Table 2]

As is apparent from Table 2, the cosmetics containing the flaky pigments of Examples 1 to 5 of the present invention are superior in extensibility and adhesiveness as compared with the cosmetics containing the pigments of Comparative Examples. ing.

[0042]

As described above, the scaly pigment composition of the present invention has optical characteristics such that the surface gloss is low and the glossy light does not show a bluish color tone, and is incorporated into a cosmetic composition. In this case, the extensibility and adhesion to the skin are excellent.

Claims (4)

[Claims] 1. A scaly pigment composition characterized in that the particle surface of scaly powder is coated with titanium oxide or a composite oxide of titanium and zinc, and further coated with zinc oxide. 2. The coating amount of titanium oxide is ₂ to 5% by weight of scaly pigment in terms of TiO ₂ , and the coating amount of zinc oxide is 5 to 30% by weight of flake pigment in terms of ZnO. %
The scaly pigment composition according to claim 1, wherein 3. A scaly powder is prepared by suspending a scaly powder in water, adding a predetermined amount of a water-soluble titanium salt, heating the suspension, and maintaining the boiling state for 1 to 8 hours. The body surface is coated with a hydrolysis product of titanium, filtered and washed, and then the obtained powder is suspended again in water to adjust the pH of the suspension to 10 to 1
After adjusting to 2, and adding a predetermined amount of a separately prepared aqueous solution of zinc-ammonium complex ion thereto, heating the suspension,
After boiling or adding a predetermined amount of an aqueous solution of zinc-ammonium complex ion, the mixture is heated to 40 ° C. to dilute sulfuric acid 4 times.
The titanium oxide is further coated with a hydrolysis product of zinc by addition over 5 hours until the pH of the suspension is 6.5-8.5 and the resulting suspension is filtered. ,
A method for producing a scaly pigment, which comprises rinsing at 300 to 900 ° C. after washing and drying. 4. A cosmetic comprising the flaky pigment composition according to claim 1.