JPH0643566B2 - Method for producing colored aluminum pigment - Google Patents

Description

The present invention relates to an improved method for producing a colored aluminum pigment, and more specifically, it has an infrared ray cut effect, is excellent in coloring properties, and is a pigment itself that causes precipitation, segregation, and color components. Accordingly, the present invention provides a colored aluminum pigment that is suitable for cosmetics and does not cause color unevenness.

Conventionally, as a color pigment having an infrared ray cutting effect which is generally used for cosmetics, there is a lame agent which is said to be shredded after aluminum deposition is applied to a resin,
When this is used in makeup cosmetics, for example, there is a problem with the safety of the resin itself, a problem with dispersibility due to the difference in specific gravity from other components, and a strong metallic luster, which causes a glaring feeling when applied to the face, and is especially a base. There is a problem that the cosmetics are not suitable for make-up, and the cosmetics are limited in production and dosage form.

On the other hand, uncolored aluminum powder having an infrared cut effect exhibits gray to gray-black color, and when blended into makeup cosmetics, appearance color and coating color are liable to cause dullness, and high quality with high saturation. I didn't get anything. Similarly, aluminum powder is difficult to be pulverized due to the danger of dust explosion, and usually has a large average particle size of 13 to 50 μm. Therefore, it has metallic luster and clearly feels the infrared cut effect, and has a warmth. When added to make-up cosmetics at a concentration that does not give a feeling, the color development of make-up on the face is poor and an unusual luster appears, which greatly impairs the make-up effect and can be inevitably used. The concentration remains at a low compounding concentration of about 0.1-0.5%,
It did not contribute to the infrared cut effect.

On the other hand, there has been a technique of converting aluminum into a color pigment in order to obtain a colorant such as paint. For example, JP-B-53-4004 and JP-B-55-5780 have already disclosed a method of obtaining a colored aluminum pigment by preferably treating a boehmite-treated aluminum powder with a weakly alkaline treatment liquid.

However, when aluminum is used as a colored pigment by such a method, since aluminum is an amphoteric substance and has a very high reactivity, rapid dissolution and bumping occur in the alkaline treatment liquid, and the degree of coloring (metal hydroxide) is increased. It is almost impossible to control the coating rate), and the surface area per unit weight becomes larger as the particle size becomes smaller. Therefore, if one having a small particle size (for example, 13 μ or less) is used, There is a problem that the coloring treatment itself becomes difficult due to the problem of solubility. Further, regarding the obtained colored aluminum, the boehmite treatment causes a reduction in the infrared cut effect of aluminum, and further, the colored aluminum treated with a metal hydroxide under alkaline conditions is liable to change in black and has a beautiful tint of high saturation. However, there are drawbacks in that it is difficult to control the color tone, and it is difficult to control the color tone, and the infrared ray cutting effect is further reduced.

Therefore, the present inventors do not impair the infrared ray cutting effect of aluminum, are excellent in colorability, and are also excellent in dispersibility with other powders and pigments, so that precipitation, segregation, color separation, color unevenness, etc. As a result of intensive studies aimed at obtaining a colored aluminum pigment that does not occur, the present invention has been completed.

That is, the present invention, the aluminum powder alone metal aluminum or aluminum-coated inorganic powder is immersed in a solution having a weakly acidic to neutral PH region containing a metal salt, an organic compound having a chelating ability, and a dispersant, The present invention relates to a method for producing a colored aluminum pigment, which comprises depositing a metal oxide layer on the surface of aluminum powder or aluminum-coated inorganic powder. In the production method of the present invention, after the metal oxide layer is deposited on the surface of the aluminum powder or the aluminum-coated inorganic powder, water repellent treatment with a water repellent can be performed.

Hereinafter, the present invention will be described in detail.

As the aluminum powder applied to the method of the present invention,
Mineral spirit or higher fatty acid treated,
Or a metal aluminum powder from which they have been removed,
As described above, the boehmite-treated product is not preferable because the infrared ray cutting effect is reduced and the tint becomes black. Similarly, as the aluminum-coated inorganic powder, aluminum-coated talc, aluminum-coated sericite, aluminum-coated titanium oxide, aluminum-coated muscovite,
Aluminum-coated kaolin or the like can be used as the substrate as long as it is a generally used inorganic powder, and is not particularly limited thereto. The method of coating aluminum on the substrate may be appropriately selected according to the desired film thickness and the like in the usual methods such as vacuum deposition method, sputtering method, and ion beam method.

The average particle size of the aluminum powder or the aluminum-coated inorganic powder (hereinafter referred to as aluminum powder) is not particularly limited, but the range of 5 to 18 μ is preferable in that the features of the method of the present invention can be effectively utilized. preferable.

Next, as the metal salt, a water-soluble salt such as cobalt, manganese, iron, for example, hydrochloride, sulfate, nitrate, etc., specifically, cobalt chloride, manganese chloride, iron chloride, cobalt sulfate, manganese sulfate, iron sulfate, nitric acid, etc. Cobalt, manganese nitrate, iron nitrate and the like are exemplified, but when a hydrochloride or a sulfate is used, nitrate is advantageously used because the by-product dilute hydrochloric acid or sulfuric acid slowly reacts with aluminum. This is because, when a nitrate is used, the by-product nitric acid and aluminum are likely to passivate, and the dissolution rate of aluminum is expected to be suppressed as compared with the case where a hydrochloride or a sulfate is used.

As the organic compound having a chelating ability, generally, various organic compounds capable of forming a complex with a metal ion may be used, and for example, oxalic acid, malonic acid, succinic acid, tartaric acid,
O-coordinating chelating agents including citric acid, phthalic acid, glycerin and their derivatives, methylamine, ethylamine, N-coordinating chelating agents including ethylenediaminetetraacetic acid (Fe-EDTA), monoethanolamine, O-coordinating groups including diethanolamine, triethanolamine, glutamic acid and their derivatives, and N
A chelating agent having a coordinating group and the like. One or more of these organic compounds having chelating ability are selected, depending on the type and concentration of the metal salt used and the amount of the metal oxide layer deposited on the surface of the target aluminum powder or the like. The necessary amount is added to stabilize the metal ions in the step of converting the metal salt to the metal oxide.

On the other hand, as for the dispersant, aluminum powder etc. to be immersed in the solution are dispersed in the solution to form a uniform metal oxide layer on the surface of the aluminum powder etc., and the treatment time is shortened in order to shorten the treatment time. It is used for reducing the problem of dissolution of the above, and any ordinary water-soluble surfactant can be used and is not particularly limited. Further, as other dispersants, lower alcohols such as methanol, ethanol and isopropanol may be used.

In the method of the present invention, a treatment solution containing the above metal salt, an organic compound having a chelating ability, and a dispersant is treated in a weakly acidic to neutral pH region, specifically PH5 or more and less than 8 and preferably PH6 or more and less than 8 inclusive. It is important to keep it within the range. By keeping the treatment solution in the above range, a pigment with high saturation can be obtained, and the control of the degree of coloring becomes possible, and the average particle diameter of aluminum powder etc. is small (for example, 13μ or less). Can also be used. Therefore, if a pH adjusting agent is required, alkali hydroxide, ammonia, amine, alkali carbonate, alkali salt of aluminate, etc. may be added. When the pH is higher than the above range, that is, in the alkaline region, the solubility of aluminum powder or the like remarkably progresses,
Occasionally, bumping etc. may occur and workability deteriorates, and the obtained colored aluminum pigment does not have a vivid color with a black tint, and the infrared cutoff effect is remarkably reduced, which is very suitable for cosmetics. Is hard to be. On the contrary, PH
Is small, that is, in the acidic region, the solubility of the metal oxide in the treatment solution increases, the degree of coloring on aluminum powder etc. is low, and it is difficult to expect particularly high colorability (high degree of deposition of metal oxide). .

Next, the conditions of immersion in a treatment solution such as aluminum powder can be changed according to the type and concentration of the metal salt, the degree of deposition of the target metal oxide, etc. Based on the reactivity from the to the metal oxide, etc., it is appropriately selected within the range of a solution temperature of 60 to 100 ° C. and an immersion time of 5 to 60 minutes. If the immersion time is shorter than 5 minutes, uncolored aluminum powder or the like will remain in part, so it should be avoided.

Here, in the colored aluminum pigment obtained by the method of the present invention, it is desirable to maintain the content of the deposited metal oxide layer in the range of 10 to 80% by weight based on the entire colored aluminum pigment. The reason is the lower limit of 10
If the content is less than wt%, the metallic luster of aluminum powder, etc. does not disappear, and a grayish black color remains, and the makeup effect is impaired when used in cosmetics.
If it exceeds the range, it is converted into a metal oxide pigment and the tint is emphasized, but the infrared ray cutting effect of the aluminum powder or the like is significantly reduced.

Although various components, conditions and the like relating to the method of the present invention have been described above, a typical production flow is shown below in order to explain the method of the present invention in more detail.

(1) A chelating agent of 0.
002 to 0.2 mol, 0.001 to 0.1 mol of metal salt and 0.001 to 1.3 mol of dispersant are dissolved (P of the solution is
H is about 0.7 to 2.0), and amine is added to this to adjust PH to 5
After adjusting between ~ 8, add aluminum powder etc.
After heating and stirring for 60 minutes (PH is kept below 8), 100 to 1000 ml of purified water is added, followed by filtration, washing with water and drying.

(2) A chelating agent of 0.
0001 to 0.08 mol and 0.001 to 0.1 mol of metal salt are dissolved (pH of the solution is about 0.7 to 2.0), and an alkali salt is gradually added to this to adjust the pH between 5 and 8. After adjustment,
After adding 0.001 to 5% dispersant and aluminum powder and the like and heating and stirring for 5 to 60 minutes (PH is kept below 8), 100 to 1000 ml of purified water is added, followed by filtration, washing with water,
dry.

In the method of the present invention, the colored aluminum pigment obtained as described above is optionally subjected to a water-repellent treatment with a water-repellent agent in order to further improve water repellency and adhesion to the skin.

Examples of the water repellent used in such a case include higher fatty acids such as lauric acid, myristic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, lanolin fatty acid, tall oil, isostearic acid, and dimer. Examples thereof include acids and silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane and structural analogues thereof, and they may be used alone or as a mixture of two or more.

In addition, as a specific method for water repellent treatment, a colored aluminum pigment is added to a solution in which a water repellent agent is dissolved in a volatile organic solvent such as acetone, ethyl acetate, isopropanol, and ethanol in an amount of about 0.1 to 20% by weight. 5-40% by weight is added slowly with stirring, and after stirring for 5 minutes to 2 hours, the solvent is stirred and heated to evaporate if necessary, and the surface of the colored aluminum pigment is water-repellent to about 1-10 μm. Or when the water repellent is only higher fatty acids,
Higher fatty acids 0.1 to 2 relative to the colored aluminum pigment
After uniformly mixing 0% by weight, the pressure was reduced to a vacuum state, and 60%
By stirring at ~ 120 ° C, coating with the same water repellent as described above can be performed.

The colored aluminum pigment obtained by the method of the present invention is one in which a metal oxide is uniformly and firmly adhered to the surface of aluminum powder or the like, and the aluminum powder or the like and the metal oxide behave integrally, segregation, and color. On the other hand, it does not cause unevenness or color unevenness, but on the other hand it is fragile and easily pulverized, it can be disassembled by kneading with other cosmetic ingredients, paint ingredients, etc., it has excellent dispersibility and does not require a pulverizing step. Is. Similarly, the colored aluminum pigment retains the good adhesiveness peculiar to finely powdered aluminum, suppresses the metallic luster of metallic aluminum, and maintains the infrared cut effect.
Furthermore, a wide range of color tones such as reddish, greenish, and yellowish can be obtained depending on the type of metal salt used, particularly the type of metal, and a wide range of coloring can be obtained depending on the concentration of the metal salt used.

In addition, when the colored aluminum pigment is treated with a water repellent, the water repellency is naturally improved, and the adhesion to the skin is further improved. This is especially true when applied to cosmetics. Can give favorable results.

Examples of the present invention will be shown below. Of course, the invention is not limited thereto.

Example 1. 14.4 g of ferric nitrate and 2.4 g of oxalic acid were added to purified water 50
It was dissolved in 0 ml (PH1.22), and 18.25 g of triethanolamine was injected into this solution to obtain PH5.09. Mineral spirit, 2 g of aluminum-coated titanium oxide surface-treated with oleic acid and 43.3 g of ethanol were added to this solution, and when heated at 80 to 83 ° C. for 13 minutes, PH 7.15 was obtained at this point. Purified water (500 ml) was added, filtered, washed with water and dried to obtain 2.66 g of gold-colored aluminum pigment.

Example 2. Colored aluminum pigment 1 obtained by the method of Example 1.
00 g was added to 100 g of isopropanol in which 5 g of stearic acid and 5 g of methylhydrogen polysiloxane (KF99, Shin-Etsu Chemical Co., Ltd.) were dissolved, and after stirring for 15 minutes,
After taking out and volatilizing the isopropanol, 100 ℃
And treated for 5 hours to obtain 108.5 g of a colored aluminum pigment having water repellency.

Example 3. Ferric nitrate (3.6 g), tartaric acid (0.6 g) and POE sorbitan monolaurate (1.5 g) were dissolved in purified water (150 ml) (PH1.34), and iron-EDTA chelate (6.21 g) was added thereto. After stirring, 1N sodium carbonate 3
The pH was adjusted to 7.20 by adding 1.9 ml. Next, 2 g of ethanol-treated aluminum powder was added to this solution, and the mixture was heated at 73 to 75 ° C. for 6 minutes to obtain PH 7.70 at this point. To this, 500 ml of purified water was added, followed by filtration, washing with water, When dried, 3.0 g of a colored aluminum pigment that exhibited gold was obtained.

Example 4. Colored aluminum pigment 4 obtained by the method of Example 3.
After uniformly mixing 1 g of myristic acid with 8 g, the mixture was evacuated using an evaporator, stirred at 100 ° C. for 2 hours, then returned to room temperature and taken out to obtain 48.8 g of a colored aluminum pigment having water repellency.

Example 5. 4.22 g of cobalt nitrate, 2.44 g of oxalic acid, and 3.57 g of iron-EDTA chelate were dissolved in 100 ml of purified water, and 7.86 g of triethanolamine was added to PH7.
It was set to 08. Then add 1N sodium hydroxide to add PH
After setting to 7.30, 2g of aluminum powder in this solution
And 50 ml of ethanol were added, and when heated and stirred at 85 to 87 ° C. for 10 minutes, PH7.89 was obtained at this point,
To this, 500 ml of purified water was added, filtered, washed with water, and dried to obtain 3.54 g of a colored aluminum pigment showing a green color.

Next, in order to evaluate the colored aluminum pigments obtained by the method of the present invention obtained as described above, conventional colored cosmetic powders (talc, sericite) were used as comparative products with the colored aluminum pigments obtained in Examples 1 to 5. , Kaolin, cellulose powder, titanium oxide), uncolored aluminum powder, and colored aluminum powder treated by the method of Japanese Examined Patent Publication No. 53-4004 are used to compare and color the infrared cut effect, which is a feature of the method of the present invention. A sex comparison was made.

As an evaluation method, a sample prepared by adjusting a ratio of 1 part of each test powder to 4 parts of castor oil was 100 with a Hoover Mara.
It was treated once and coated on a glass plate with a 0.5 mil doctor blade to prepare a standard product. This sample was irradiated with an infrared lamp from a height of 40 cm for 5 minutes, and the infrared cut effect was measured using an infrared integrating illuminance meter (manufactured by Suga Test Instruments Co., Ltd.). Similarly, using this standard, colorimetry was performed according to the Munsell color chart to evaluate the colorability. The results are shown in Table-1.

As shown in the results of Table-1, the colored aluminum pigment produced by the method of the present invention has a high lightness and saturation with almost no loss of the infrared ray cutting effect of the aluminum powder, and an excellent tint. It became clear that they would present. On the other hand, uncolored aluminum has remarkably low saturation, low lightness, and a gray color.
The colored aluminum powder obtained by the method shown in No. 4004 has a significantly reduced infrared ray cutting effect and has a lightness,
It was proved that the method of the present invention was excellent, since it was revealed that the color saturation was low and the color tone was dull / dirty.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kanto Hajime 648 Yayoi-cho, Shizuoka-shi, Shizuoka Prefecture, POLA CHEMICAL INDUSTRIES CO., LTD.

Claims (9)

[Claims] 1. An aluminum powder or an aluminum-coated inorganic powder is dipped in a solution containing a metal salt, an organic compound having a chelating ability, and a dispersant and having a weakly acidic to neutral PH region to obtain an aluminum powder or an aluminum coating. A method for producing a colored aluminum pigment, which comprises depositing a metal oxide layer on the surface of an inorganic powder. 2. The first claim in which the metal salt is a nitrate.
A method for producing a colored aluminum pigment according to the item. 3. The method for producing a colored aluminum pigment according to claim 1, wherein the PH region is in a range of 5 to 8 inclusive. 4. The method for producing a colored aluminum pigment according to claim 1, wherein the content of the metal oxide layer is 10 to 80% by weight based on the entire colored aluminum pigment. 5. An aluminum powder or an aluminum-coated inorganic powder is dipped in a solution containing a metal salt, an organic compound having a chelating ability, and a dispersant and having a weakly acidic to neutral PH region to obtain an aluminum powder or an aluminum-coated powder. A method for producing a colored aluminum pigment, comprising depositing a metal oxide layer on the surface of an inorganic powder, and then subjecting it to water repellent treatment with a water repellent. 6. The method according to claim 5, wherein the metal salt is nitrate.
A method for producing a colored aluminum pigment according to the item. 7. The method for producing a colored aluminum pigment according to claim 5, wherein the PH region is in the range of PH5 to PH8. 8. The method for producing a colored aluminum pigment according to claim 5, wherein the content of the metal oxide layer is 10 to 80% by weight based on the entire colored aluminum pigment. 9. The method for producing a colored aluminum pigment according to claim 5, wherein the water repellent is selected from higher fatty acids and silicone oil.