JPS62115071A - Production of black pigment - Google Patents

Abstract

PURPOSE:To obtain a black pigment which is excellent in applicability such as covering power and spread and causes neither agglomeration when incorporated in a cosmetic preparation nor color separation when applied onto the skin, by forming a thin interlayer comprised of a metal oxide or its hydrate on the surface of an inorg. and/or organic powdery material and then depositing triiron tetroxide on the interlayer. CONSTITUTION:A thin interlayer comprised of a metal oxide or its hydrate is first formed on the surface of an inorg. and/or org. powdery material. An aq. soln. contg. a ferrous (II) salt and an oxidizing agent is added in portions in the presence of a base to an aq. suspension contg. the inorg. and/or powdery material coated with the interlayer. Thus, triiron tetroxide is deposited on the surface of the inorg. and/or org. powdery material coated with the interlayer, thereby coating it with the triiron tetroxide. The percentage coating of the interlayer is about 0.01-20wt% based on the weight of the powdery material. Examples of the metal oxide or its hydrate employed as the interlayer include iron oxide, aluminum oxide, nickel oxide, chromium oxide and their hydrates.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing a black pigment, which comprises triiron tetroxide as a colorant and an inorganic and/or base material.
Or, it strongly adheres to organic powder, has excellent appearance such as feeling of use such as stretching and spreading, and color tone effect, and has good safety and stability. The object of the present invention is to provide a black pigment that does not cause color separation.

Previously, several types of black yoyo were known.
Typical examples include iron #i4 (triiron tetroxide) and carhon black. Iron black and carbon black have a high tonal effect as black and are widely used raw materials in various fields, but for example, when these pigments are used in cosmetics, they are generally blended at the same time as these pigments. Due to the difference in specific gravity from other powders such as Merck etc. and the difference in hydrophilicity and lipophilicity of the powder surface, it has poor dispersibility and, in the worst case, causes aggregation. Similarly, cosmetics containing these pigments tend to cause problems such as poor spreading and spreading, and a rough feeling when used.Furthermore, when applied to the skin, these pigments and It also had drawbacks such as separation from other powders, that is, color separation phenomenon.

On the other hand, it has been pointed out that carbon black contains carcinogenic substances such as pentupyrene, and it has been criticized as being unfavorable from a safety standpoint.

In response to this, attempts have been made to improve the above-mentioned dispersibility, elongation, spread, color separation, etc. by compounding black pigments.

For example, Japanese Patent Publication No. 39-13216 describes a method of forming a black pigment by creating a semi-transparent layer of carbon on the surface of semi-transparent mica-like flakes, and Japanese Patent Publication No. 10629-1982 r-
is a thin lead sulfide (pb) on the surface of a basic lead carbonate pearl pigment.
Furthermore, JP-A-49-128027 discloses a method of depositing triiron tetroxide on the surface of mica or titanium dioxide-coated mica to form a black pigment. Each is disclosed.

However, these methods still leave unresolved issues and cannot be said to provide sufficient satisfaction. Specifically, in Japanese Patent Publication No. 39-13216, firstly, as mentioned above, there are still safety problems with carbon fibers, and secondly, this method uses a carbon concentration of 1.5 to 3 as a point color pigment.
．． Since it reaches a maximum at 5%, the density range is narrow and the degree of blackening, in other words, the color tone effect is insufficient. In addition, the special public
Regarding No. 5-10629, lead sulfide is toxic and cannot be used in cosmetics, and there are concentration limits for lead ions (Pb) and K, making it impossible to deposit a sufficient layer of lead sulfide, resulting in blackening. In addition, lead sulfide has poor stability against oxidation, and the lead oxide and lead sulfate that are produced significantly reduce the gloss of the pigment, resulting in problems such as "clamping."

Furthermore, JP-A-49-128027 uses triiron tetroxide, which is excellent in safety and stability, and is the most useful of these prior art techniques.

However, in this method, an oxidizing agent is contained in an aqueous dispersion of mica or titanium dioxide-coated mica, and an aqueous solution of a base and iron(II) salt is added to this to deposit triiron tetroxide. Therefore, the reaction process leading to iron (If) salt → iron hydroxide → triiron tetroxide rapidly progresses due to the presence of excess oxidizing agent in the dispersion, and the residual pVc rapidly progresses, resulting in the formation of triiron tetroxide. This results in differences in the rates of formation and deposition, and that the triiron tetroxide particles are more likely than other iron oxides, such as ferric oxide! k (Fe
Since it has a large particle diameter compared to other particles such as 20s), it has problems such as difficulty in obtaining a uniform and strong coating, and as a result, it has a low degree of blackening ( If the degree of blackening is increased (low memory retention rate), the pigment will have a corresponding effect, but as the degree of blackening is increased (high retention rate), the triiron tetroxide-receiving pigment and free triiron tetroxide will coexist. Color separation occurred in the same way as when triiron tetroxide and base powder were simply mixed.

In addition, in this method, the particle size of triiron tetroxide is large,
Also, due to its weak adhesion to the base powder,
It also has the disadvantage that it is difficult to apply to base powders with different surface characteristics, such as resin powders.

Therefore, in order to solve these problems with conventional black pigments and their manufacturability, the present inventors first focused on titanium dioxide-covered mica, and conducted intensive research on making it into a black pigment. First, iron hydroxide is deposited on the surface of mica particles to increase the bonding strength between triiron tetroxide and the base powder particles, then it is deposited in triiron tetroxide, and finally oxidized. Through a reaction process in which iron hydroxide is converted to triiron tetroxide by the action of an agent, a black pearlescent pigment is obtained in which the titanium dioxide-coated and mother particle surfaces are effectively and firmly coated with triiron tetroxide. I discovered that
A patent application for this has already been filed (Japanese Patent Application No. 139415/1982).

However, even in this method, in order to strictly maintain the reaction process of deposition in the state of iron hydroxide, subsequent deposition of triiron tetroxide, and conversion of iron hydroxide to triiron tetroxide, it is necessary to Inadequacies still remain, such as the need for advanced technology in setting conditions (for example, dropping rate), and the limitation of base powders that can be applied to form black pigments.

For this reason, the inventors of the present invention have repeatedly conducted various experimental studies in order to develop an even better method for producing black pigments. After coating, when triiron tetroxide is deposited according to the method previously applied by the present inventors, the metal oxide and its hydrate layer are effective in depositing iron hydroxide at the initial stage of the reaction. A base material that plays a guiding role (adsorption effect) and makes it possible to easily deposit triiron tetroxide, and also homogenizes the surface properties of various base material powders that have different surface properties, and can be turned into a black pigment. powder a+
It was discovered that b was significantly expanded, and the present invention was completed.

That is, the present invention involves the production of an iron-containing black pigment based on an inorganic and/or organic powder and triiron tetroxide (Fes04)9. A thin interlayer of oxide or hydrate thereof is formed, and then the inorganic and/or
or iron (I) in the presence of a base in an aqueous suspension of organic powder.
f) A black pigment characterized by gradually adding an aqueous solution containing a salt and an oxidizing agent to form a precipitate of triiron tetroxide on the surface of an inorganic and/or organic powder coated with an intermediate layer. This relates to a manufacturing method.

The present invention will be explained in detail below.

The inorganic and/or organic powder to be applied to the present invention is not particularly limited as long as it is suitable for the intended use function, appearance, feel, etc. For example, inorganic powders include talc, kaolin, calcium carbonate, magnesium carbonate, silicic anhydride, bismuth oxychloride, magnesium silicate, calcium silicate, etc., while organic powders include polyethylene powder, nylon powder, etc. Examples include paratha, silk powder, cellulose powder, acrylic acid resin, and methacrylic acid resin. It is also possible to apply the present invention to pearl powders such as heat theory, fish scale foil, titanium mica, etc. In this case, a black pearl pigment with a good usability and no color separation can be obtained.

In the method of the present invention, as a first step, a small amount of a metal oxide or its hydrate is added to an inorganic and/or organic powder (hereinafter referred to as
It is important to coat the base powder (referred to as base powder) to form an intermediate layer. This intermediate layer functions as a guide (adsorption effect) and a binder (binder effect) for the uniform and strong deposition of triiron tetroxide onto the base powder, and at the same time, it acts as a binder for the uniform and strong deposition of triiron tetroxide onto the base powder. It has the function of homogenizing the surface characteristics of the material powder. Therefore, the coverage of the intermediate layer is also important. If it is too large or too small, good results will not be obtained. In the method of the present invention, the coverage of the intermediate layer is usually in the range of 0.01 to 20% by weight, preferably 0.1 to 10% by weight based on the weight of the base powder. In other words, when the amount is less than 0.01% by weight, the intermediate layer's role as a guide and binder is weak, the particle size of triiron tetroxide is large and non-uniform, and it becomes hard to solidify the base powder. The adhesion force decreases.

On the other hand, if it exceeds 20% by weight, it is better to avoid this because the inherent properties of the resin powder may be diminished, especially when the resin powder is coated with a dense metal oxide or the like.

Here, examples of the metal oxide or hydrate thereof used as the intermediate layer include iron oxide, cobalt oxide, aluminum oxide, nickel oxide, chromium oxide, and hydrates thereof.

Further, the method for forming the intermediate layer of the metal oxide or its hydrate on the surface of the base powder is as follows. That is, first, the base powder is dispersed in water (using a small amount of surfactant if necessary), rum, sodium aluminate,
Chromium chloride, chromium sulfate, nickel sulfate, etc. are added as starting materials, and the metal salts are hydrolyzed using a base and, if necessary, an oxidizing agent, to deposit metal hydroxides on the surface of the base powder. Furthermore, the metal hydroxide layer on the base powder is converted into a metal oxide layer by washing with water, sipping, drying, or burning as necessary.

The base material powder coated with the metal oxide or its hydrate in the intermediate field thus obtained may be continuously used in the second step, that is, the coating step with triiron tetroxide. Alternatively, once the first stage reaction is completed, it may be neutralized, washed with water, filtered, dried and stored, and then subjected to the second stage treatment. After the first step, the dispersion is heated to a constant temperature. This temperature range is 50 to 1
A range of 00°C is good. During this heating, it is possible to blow nitrogen gas to drive out the air in the dispersion liquid and reaction vessel.
This will prevent the formation of undesirable ferric oxide in the dispersion.

Next, an aqueous solution of a base such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, etc. is added to the dispersion,
The pH value of the system is adjusted to a range of 7-14, preferably 8-12.

Then, after adjusting the pH, if necessary, simultaneously with polybasic potassium, ferrous chloride, ferrous sulfate, ferrous phosphate, malt iron(II), etc.
An aqueous solution in which a salt and an oxidizing agent such as a nitrate such as potassium nitrate, sodium nitrate, ammonium nitrate, etc. or a chlorate such as potassium chlorate, sodium chlorate, ammonium chlorate, etc. are dissolved is gradually dropped into the dispersion. In this reaction, it is important to maintain the reaction rate, keep the reaction temperature constant within the range of 50 to 100°C, and continue stirring.

After the reaction is completed, the produced black pigment is washed with water, mixed with water,
Dry at below 0°C to obtain the desired product.

Here, the lid of triiron tetroxide can be controlled arbitrarily by changing the amount of iron (hydrokinetic salt) and oxidizing agent added.

This may be adjusted depending on the intended usability and brightness. In other words, when using only the original base powder, the base powder has a unique color tone and feel, but as the amount of triiron tetroxide increases, the feel of the base powder changes. However, the feeling of using triiron tetroxide will be slightly affected), and the brightness will also decrease. Generally, those suitable for use in cosmetics have a coating amount of 10 to 80% by weight.

Hereinafter, the method of the present invention will be described in more detail with specific production examples.

Manufacturing example 1. Talc/Fez Os/Fes 04
Field 111 Cultivated talc (60 g) was dispersed in 1200 m of pure water.

This dispersion was added with 10% sodium hydroxide solution 39- and 1
A 0% ferrous sulfate solution 67- was added and stirred.

Thereafter, air was blown into the mixture and stirring continued for 112 hours.

After completion of the reaction, filtration, water washing, and baking at 450° C. for 2 hours to obtain iron oxide (2)) coated talc. 60 g of iron oxide (0 and 1 iron oxide @) coated talc was dispersed in water again. After expelling air by blowing in nitrogen gas, the mixture was heated to 80° C. with stirring, and 10% sodium hydroxide solution was added dropwise to adjust the pH to 9. Next, stop the injection of nitrogen gas and add 10% hydroxide.) While continuing to drop the IJium solution, add 8 g of sodium nitrate, 33 g of ferrous chloride, 2.5 g of concentrated sulfuric acid, and 33 g of pure water.
60- was gradually added to the solution. During this time, PH
The amount of the 10% sodium hydroxide solution added is adjusted so that the ratio is maintained in the range of 8 to 10. During the reaction, the temperature is maintained at 80° C. and the stirring speed is kept constant. After the reaction is complete,
It was passed through the mouth, washed with water, and dried at 60°C. The composition of this pigment is Merck 70.5%, Fe! 0B4.5%, Fe
B was 0425.0%.

Production example 2. Titanium dioxide coated mica/Fed(OH)
/e304 75 g of titanium dioxide-coated mica (particle size 10 to 25 μm, titanium dioxide coverage 40%) was dispersed in 1000 μm of pure water. To this dispersion were added 58 m of a 10% sodium carbonate solution and 145 m of a 10% ferrous sulfate solution and stirred. After that, air was sucked in and stirring was continued for 2 hours.

Next, after sucking in nitrogen gas and expelling the air, it was heated to 80°C while stirring, and 20% ammonia water was added dropwise to make the P.
Adjust H to 10. Next, stop injecting nitrogen gas,
While continuing to drop 20% ammonia water, add 131 g of potassium nitrate, 540 g of ferrous sulfate, and 6 m of concentrated sulfuric acid to 1 ml of pure water.
A solution containing 000 dK was gradually added dropwise. During this time,
Adjust the dropping amount of 20% ammonia water so that the pH is maintained in the range of 9 to 11. During the reaction, the temperature is maintained at 80° C. and the stirring speed is kept constant. After the reaction was completed, the mixture was filtered through the mouth, washed with water, and dried at 60°C. The composition of this pigment is T1 (h 13.1%, hypocenter 19.6%, Fed
(OH) 2.09g, Fe3O465.3%.

Production example 3. Calcium carbonate / Al, o, / Fe3
60g of O4 calcium carbonate was dispersed in 1000ml of pure water. This dispersion [10% sodium aluminate solution 72g]
was gradually added dropwise while stirring at room temperature, the pH was adjusted to 10 using sulfuric acid, and stirring was continued for 1 hour. After completion of the reaction, the mixture was filtered, washed with water, dried at 60°C, and then calcined at 350°C for 2 hours to obtain alumina-coated calcium carbonate.

Next, 60 g of alumina-coated calcium carbonate was again dispersed in 1000-g of pure water, nitrogen gas was blown in, the temperature was heated to 80°C with stirring, and 10% sodium hydroxide solution was added dropwise to adjust the pH to 9. ! I #ffi.

Next, while stopping the injection of nitrogen gas and continuing to drop the 10% sodium hydroxide solution, 7 g of ammonium nitrate,
A solution prepared by dissolving 31 grams of ferrous phosphate and 3 grams of concentrated sulfuric acid in 360 grams of pure water was gradually added dropwise.

10 to maintain the pH in the range of 8 to 10.
% sodium hydroxide solution dropwise. During the reaction, the temperature is maintained at 80° C. and the stirring speed is kept constant. After the reaction is completed, it is filtered, washed with water, and dried at 60°C. This pigment composition is
CaCO372.0%, A1.0°3.0%, Fe3O
It was 425.0%.

Manufacturing example 4. Bismuth oxychloride/Coo/Fe5
04 Bismuth oxychloride (60 g) was dispersed in 1,000 ml of pure water. To this dispersion were added a 10% hydroxide solution (34) and a 10% cobalt chloride solution (55), and stirring was continued for 1 hour. After the reaction was completed, the mixture was filtered and dried, and then fired at 350° C. for 2 hours in a nitrogen gas atmosphere to obtain bismuth oxychloride coated with cobalt oxide.

Next, 60 g of cobalt oxide-coated bismuth oxychloride was added,
The mixture was again dispersed in 1,000 ml of pure water, blown with nitrogen gas, heated to 70° C. with stirring, and 10% potassium hydroxide solution was added dropwise to adjust the pH to 11. Subsequently, the injection of nitrogen gas was stopped, and potassium nitrate 73.2g% ferrous sulfate s O4 was added while continuing to drop the 10% potassium hydroxide solution.
A solution of 3-GS concentrated sulfuric acid dissolved in 1200-mL of pure water was gradually added dropwise. During this time, a 10% potassium hydroxide solution is added dropwise to maintain the pH in the range of 10 to 12. During the reaction, the temperature is maintained at 70° C. and the stirring speed is kept constant. After the reaction is completed, it is filtered, washed with water, and dried at 60°C. The composition of this pigment is 28.5% bismuth oxychloride, Co
o 1.5%, Fe50470.0%.

Manufacturing example 5. Nye 07 / Fed(OH) / Fe5
60g of 04 nylon powder was dispersed in 1200ml of pure water. To this dispersion were added 0.6 g of sorbitan monolaurate (polyoxyethylene (20)), 10% sodium hydroxide solution 47 and 10% ferric chloride solution 74 and stirred. Thereafter, air was blown into the mixture and stirring was continued for 2 hours. Next, after blowing nitrogen gas to drive out the air, the mixture was heated to 80° C. with stirring, and 20% aqueous ammonia was added dropwise to adjust the pH to 9. Next, stop the introduction of nitrogen gas, and while continuing to drop 20% ammonia water, add 16.6 g of sodium nitrate, 75 g of ferrous chloride, 2 g of concentrated sulfuric acid.
A solution of MIt dissolved in 360 m of pure water was slowly added dropwise. During this time, the amount of 20% ammonia water dropped is adjusted so that the pH is maintained in the range of 8 to 10. During the reaction, the temperature is maintained at 80° C. and the stirring speed is kept constant. After the reaction was completed, the mixture was filtered, washed with water, and dried at 60°C. The composition of this pigment is 55.2% nylon, FN(OH)
4.8%, Fe30440.0%.

Next, the black pigment produced by the method of the present invention was evaluated. The evaluation method was to apply each sample to the fingers and arms.
The condition was observed when the sample was rubbed strongly with the finger to spread it. As a result, the black pigments produced by the method of the present invention (Production Examples 1 to 5) had no color separation phenomenon, and the coating color was uniform. When compared with the product mixed in the same ratio as the product of the present invention, the product of the present invention had a much better feel when used with elongation and spread of 9.

Furthermore, when a cosmetic containing the black pigment obtained by the method of the present invention was evaluated, it was found that there was no color separation, the applied color was uniform, and the cosmetic was good without any dullness.

Next, examples of using the black pigment obtained by the method of the present invention will be shown. In the examples, each blending ratio indicates weight %.

Usage example 1. Eye color pigment Black pigment (manufacturing example) 50 Nylon powder 1303) Navy blue 2 Sericite 20C) Squalane 10 Silicone oil
5 (Method) After mixing and pulverizing CB), mix the powder and coat it with 0. After that, it is compression molded into a product.

Usage example 2. Eye color (4) Black pigment (Production example 5) 25 Titanium mica 25 Spherical polyethylene powder 5) Red iron
2 talc
280 Squalane 1
0 silicone oil 5
method) Usage example 1. I did it in the same way.

Usage example 3. Cheek color■ Black pigment (manufacturing example 1) 15 titanium mica 10 silica peas
6) Talc
50 Bengala 9
C) Squalane 6 silicone oil Δ (Method) Usage example 1. I did it in the same way.

Usage example 4. Eye color black pigment (manufacturing example-4-) 50 stones
50 (Method) Add 15 parts of black pearlescent pigment and 15 parts of gypsum to 1 part of water.
00 parts, dispersed with a teaser, poured into a mold, dried and solidified to form a product.

Usage example 5. foundation prisoner
25 Serisite
25 nylon powder
3 titanium mica
titanium trioxide
8 Iron oxide 0.5 Black pigment (Production example 3) 1 Preservative
0.2) Silicone oil
4 Octyldodecyl oleate 1
0 fragrance
0.3C) Burr agent 20(
Method) After mixing and pulverizing (4), mix (C) and
). After that, it is compression molded into a product.

Claims (1)

[Claims] 1) Inorganic and/or organic powder and triiron tetroxide (Fe_3
In producing an iron-containing black pigment based on O_4), first a thin intermediate layer made of a metal oxide or its hydrate is formed on the surface of an inorganic and/or organic powder,
Thereafter, an aqueous solution containing an iron(II) salt and an oxidizing agent is gradually added to the aqueous suspension of the inorganic and/or organic powder coated with the intermediate layer in the presence of a base, and the mixture is coated with the intermediate layer. 1. A method for producing a black pigment, which comprises forming a precipitate of triiron tetroxide on the surface of an inorganic and/or organic powder. 2) A thin interlayer consisting of metal oxides or their hydrates adds an aqueous solution of metal salts and optionally bases to an aqueous suspension of inorganic and/or organic powders, optionally blowing in air. a homogeneous layer of metal hydroxide obtained by depositing it on the surface of an inorganic and/or organic powder, or by further drying and/or sintering it. A method for producing a black pigment according to claim 1), wherein the black pigment is a layer comprising: 3) The method for producing a black pigment according to claim 1), wherein the coverage of the intermediate layer is 0.01 to 20% by weight based on the weight of the inorganic and/or organic powder.