JPS63159476A - Production of non-pearlescent mica/titanium pigment and make-up cosmetic prepared by blending the same - Google Patents

Abstract

PURPOSE:To obtain a pigment which does not have any pearly luster and has hiding power, good adhesion to the skin and good spreadability, by heating a mixture of mica and titanyl sulfate, hydrolyzing titanyl sulfate at a b.p. and firing the resulting solid product. CONSTITUTION:Mica or an aq. dispersion thereof (a) is mixed with titanyl sulfate (total sulfuric acid/total TiO2: 1.5-5.5) or an aq. soln. thereof (b) with stirring in such a proportion as to give a mixture wherein the concn. of titanyl sulfate is 50g/l or higher and the weight ratio of mica to titanyl sulfate is 0.01-4. The mixture is heated to a b.p. and hydrolyzed at the b.p. to deposit hydrated titanium dioxide on the surface of mica. In some cases, neutralization with an alkali is conducted and the resulting solid product is separated and fired to obtain the desired pigment. When the pigment is combined with a spherical powder, a make-up cosmetic which can be smoothly spread and has good touch can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing titanium mica pigments and make-up cosmetics containing the same. It is an object of the present invention to provide a titanium mica pigment that has good adhesion and spreadability to the skin, and a makeup cosmetic containing the same.

Traditionally, titanium mica pigments use fine flaky mica as a matrix.
A coating layer of titanium dioxide is formed on this,
Its characteristics include smoothness due to the shape of the substrate,
It has a pearlescent luster or various interference colors (burls) due to the optical properties of the substrate and the coating layer.Using this feature, it is used in many applications including paints and cosmetics. It's here.

Regarding this mica titanium pigment,
Many manufacturing methods and improved methods have already been known, including the method described in Japanese Patent No. 25644. Of course,
The purpose of the manufacturing methods and improvement methods that have been developed so far is how to obtain products with excellent pearl luster or pearl feel, and basically the surface of mica, which is the substrate, has been improved. The idea was to deposit very uniform, fine, and dense titanium dioxide on the surface of the metal to form a coating layer.

However, if these conventional mica titanium pigments are to be used in makeup cosmetics, for example, products with a pearly feel that can be used in point makeup products such as lipstick and eye color are good, but they cannot be used in foundations, powders, etc. In the case of base makeup, although it spreads better, it has the disadvantages of being too glossy, making wrinkles stand out, and creating a makeup finish that doesn't look natural and feels strange. Similarly, in the case of cosmetics that require hiding power, if you try to raise the level to a level that is satisfied with mica titanium pigments alone, the above-mentioned disadvantages will appear, so reduce the amount of mica titanium pigments and use titanium dioxide instead. It is common to use them together, but in this case, the problem of hiding power is solved, but on the other hand, it spreads hard when applied to the skin, lacks smoothness, and is difficult to apply evenly to the skin, resulting in a natural finish. I ended up not being able to get it.

On the other hand, in view of the above-mentioned drawbacks of titanium mica pigments, recently, flaky titanium pigments have been developed that have excellent adhesion and spreadability to the skin and have suppressed pearlescent luster, as disclosed in JP-A No. 60-94464. Pigments have also been announced.

However, in the case of this pigment, the pearlescent luster is not completely suppressed, and the pearlescent luster is enhanced especially when wet with oil. The problem is still far from being resolved, such as being at the same level as the previous year.

Therefore, as a result of repeated various experimental studies in view of the above-mentioned conventional problems, the inventor of the present invention conducted a reaction under certain specific conditions when coating mica as a substrate with titanium dioxide using titanyl sulfate as a starting material. If the coverage is above a certain level, the pigment will have unprecedentedly large titanium dioxide particles, will not have pearlescent luster, will have hiding power, and will have excellent adhesion and spreadability to the skin. , and that when it is blended into make-up cosmetics, the pigment properties are fully exhibited and an unprecedentedly excellent make-up cosmetic can be obtained, leading to the completion of the present invention.

That is, the present invention is a method for producing a mica titanium pigment in which the content of titanium dioxide (TiO2) in the mica titanium pigment is 40% by weight or more, comprising: (a) mica or a mica dispersion; (b) titanyl sulfate. (Total sulfuric acid/total Tio, = 1
．． 5 to 5.5) or an aqueous solution thereof, the concentration of titanyl sulfate in the mixed liquid is 501171 or more, and mica/titanyl sulfate (weight ratio) = 0.01.
The mixture was stirred under conditions such as 4 to 4, and then heated to the boiling point. At the boiling point, titanyl sulfate was hydrolyzed to form titanium dioxide on the mica surface.

/ A method for producing a non-pearl mica titanium pigment, which is characterized by depositing a hydrate, optionally neutralizing it with an alkali, separating the obtained solid product, and sintering it, as well as blending the non-pearl mica titanium pigment. The present invention relates to makeup cosmetics.

The present invention will be explained in detail below.

First, the mica used in the present invention includes natural mica such as muscovite, biotite, and sericite, and artificial mica such as fluorinated silicon mica, and is not particularly limited. In addition, the particle size of mica is 1 to 150 μm, preferably 5 μm.
~100μ.

Similarly, titanyl sulfate (TiO8O
4) may be used as it is or as an aqueous solution, or even a commercially available titanyl sulfate aqueous solution. However, in any case, when using it, total sulfuric acid/total T
Heavy equipment means that tOt is in the range of 1.5 to 5.5. If it is less than 1.5, the stability of titanyl sulfate is low and hydrolysis is too fast to obtain a titanium dioxide coating with a large particle size.On the other hand, if it is larger than 5.5, titanyl sulfate becomes too stable and hydrolyzes too quickly. It becomes difficult to be treated.

In the present invention, as a first step, mica and titanyl sulfate are mixed in an aqueous system. This can be done by adding mica to an aqueous solution of titanyl sulfate with stirring, or conversely adding titanyl sulfate to an aqueous dispersion of mica with stirring. It may be mixed with an aqueous dispersion.

There are no restrictions on the addition or mixing speed during mixing, and there is no problem as long as the temperature conditions are such that titanyl sulfate is difficult to hydrolyze, for example in the room temperature range.

However, when mica and titanyl sulfate are mixed, the concentration of titanyl sulfate in the mixed liquid is preferably 50 g/l or more, and preferably 60 g/l or more, and the mica/titanyl sulfate (weight ratio) is 0.01 to 4. It is preferably in the range of 0.1 to 1. Titanyl sulfate concentration is 50 g/l
When the size becomes smaller, the titanium dioxide obtained by hydrolysis becomes fine particles like conventional ones, and no matter how high the loss rate is, it still maintains gloss and transparency, which is the object of the present invention. will no longer be available. Also, mica/
When titanyl sulfate (weight ratio) is smaller than the above range,
The association rate between mica and titanium dioxide hydrate produced by hydrolysis of titanyl sulfate becomes low, which not only makes uniform coating difficult, but also causes free titanium dioxide hydrate to coexist, which is undesirable. If the size is larger, the coverage per cycle becomes lower, and it is necessary to increase the number of treatments to achieve the desired non-coverage, which is not economical.

Next, the mica/titanyl sulfate mixture mixed in the first step is gradually heated to the boiling point under stirring, and then further maintained at the boiling point for 30 minutes or more, preferably 2 hours or more, so that the titanyl sulfate is hydrated. It is decomposed and deposited on the mica surface as hydrated titanium dioxide.

Here, the heating conditions are not necessarily restrictive, but
Usually, preferable results are obtained if the boiling point is reached in about 30 to 90 minutes. Furthermore, the hydrolysis time is based on the economical assumption that about 60% of titanyl sulfate is usually hydrolyzed in 30 minutes, and is not a definitive factor. Therefore, when the hydrolysis rate is low (in this case, it is possible to apply two or more multilayer coatings to obtain the desired coverage).

Thereafter, the produced titanium dioxide hydrate-coated mica is filtered and washed in accordance with a conventional method to remove by-product sulfuric acid, separated, dried if necessary, and further calcined to produce the non-pearl mica titanium according to the present invention. A pigment is obtained. In addition, when removing sulfuric acid (roots), neutralization is performed using an alkaline solution such as ammonium hydroxide or sodium hydroxide, followed by washing with water, so that the sulfuric acid (roots) can be removed quickly and efficiently. However, when performing neutralization, the pH must be 7 or higher.
Instrumentation involves the following: Neutralization at a pH between 6 and 7 will reduce the hiding power of titanium dioxide after firing, so it should be avoided.Also, if you have trouble with the firing conditions, it is usually heated at 700 to 1000℃ for 30 minutes or more. It is enough.

The thus obtained non-pearl mica titanium pigment according to the present invention has a titanium dioxide-containing aroma of 4% in the mica titanium pigment.
It is important that the amount is 0% by weight or more, preferably 50% by weight or more. That is, if it is less than 40% by weight,
This is because although the pearlescent luster (burr feeling) disappears, some transparency still remains and the hiding power is insufficient.

The mica titanium pigment obtained by the method of the present invention is a unique pigment that has no pearlescent luster, has hiding power, and has excellent adhesion and spreadability to the skin. This is also clear from the comparison of electron micrographs (magnification: There is a difference in the state of adhesion of titanium dioxide particles to the surface of the mica substrate; in other words, the titanium dioxide of the comparative product, like the conventional product, is very fine particles and adheres as if it were a single plate. This difference is due to the fact that in the product of the present invention, the particle size of titanium dioxide is much larger. It is considered that this difference in adhesion state causes the product of the present invention to lose its pearlescent luster, enables adhesion and extensibility, and, in combination with the adhesion rate, imparts hiding power.

As described above, since the non-pearl mica titanium pigment according to the present invention has excellent features not found in conventional products, it can be widely applied to makeup cosmetics as it is.

In other words, when titanium dioxide, which has traditionally been used to provide concealing power, is blended in large amounts, it tends to spread hard and leave a white cast. Although it has a drawback of being easily shiny, the non-pearl mica titanium pigment according to the present invention does not have such a drawback. In addition, conventional mica titanium pigments have the above-mentioned problems and are inherently limited in their range of use, but the non-pearl mica titanium pigments of the present invention are not limited in their range of use and can be used in a wide range of applications. It can provide makeup cosmetics. Furthermore, one non-pearl according to the present invention.

By combining mica titanium pigment and spherical powder,
It is also possible to obtain a makeup cosmetic that spreads even more easily and has a smooth feeling of use.

Specifically provided makeup cosmetics include: 1. Point makeup products such as lipstick, rouge, eyeliner, eye color, eyebrow, mascara, etc., and pace makeup products such as foundation, face powder, pressed powder, powder foundation, etc. , and other dusting powders.Although the blending amount may vary depending on the dosage form and properties of the intended cosmetic, it is preferably in the range of approximately 1 to 70 parts by weight.

Next, in order to explain the present invention in more detail, examples of the present invention, comparative examples, and evaluation results are shown below.

Example 1 80 g of muscovite having an average particle size of 20 μm was added and dispersed in 1.6 μl of water with stirring. To this, at room temperature, a titanyl sulfate aqueous solution (total sulfuric acid/total TiO, = 1.7, concentration 470 g
/ll) was added and mixed for 265 minutes. Thereafter, it was heated to reach the boiling point (102°C) over about 60 minutes, and the boiling point was maintained for an additional 6 hours. After this, it is filtered and washed by the usual method,
The resulting cake was again dispersed in 1.61 liters of water, and the same aqueous titanyl sulfate solution a265d that was initially added was added thereto, and the same operation was performed under the same conditions as at the beginning. The obtained cake was again dispersed in 1.7 ml of water, and the same aqueous titanyl sulfate solution 265 ml as added initially was added thereto, and the same operation was performed under the same conditions as the first and second times.

The resulting cake was dispersed in two volumes of water, neutralized to pH 7.5 with an aqueous sodium hydroxide solution, filtered, and washed. The resulting cake was dried at 105°C for 24 hours and then further dried at 850°C.
It was baked for 4 hours. As a result of analysis of the obtained mica titanium pigment, the content of Tio was 68.6%.

0 Electron micrograph (magnification XI 0,000) Figure 1 Comparative Example 1 The initial amount of water in Example 1 was 3. ) t to 3. A mica titanium pigment was obtained by operating in the same manner as in Example 1, except that Ol was used.

As a result of analyzing the obtained pigment, TiO! The content is 69
．． It was 9chi.

Example 2 100 g of muscovite having an average particle size of 15 μm was added and dispersed in 1.7 μm of water with stirring. To this, at room temperature, titanyl sulfate aqueous solution (total sulfuric acid/total Tio, = x, 6, concentration 500,
9/)) was added and mixed. Thereafter, it took about 90 minutes to reach the boiling point by heating, and the boiling point was maintained for an additional 5 hours. After that, the resulting cake was filtered and washed in a conventional manner, and the resulting cake was again dispersed in 1.7 liters of water. To this, 3001 d of the same aqueous titanyl sulfate solution that was added initially was added, and the same operation was carried out under the same conditions as at the beginning. I did it.

The resulting cake was dispersed in water 21, neutralized to pH 7.0 with ammonium hydroxide solution, filtered and washed. The resulting cake was dried at 105°C for 5 hours.

It was baked at 900°C for 4 hours. Analysis of the obtained mica titanium pigment revealed that the TtOt content was 55.3%.

Example 3 100.9 ml of muscovite having an average particle size of 5 μm was added and dispersed in 1.71 ml of water with stirring. To this, 600 M of titanyl sulfate aqueous solution (total sulfuric acid/total T r Ox = 1.6, concentration 500 g/l) was added and mixed at room temperature. After that, it was heated and it took about 80 minutes to reach the boiling point.

The boiling point was maintained for an additional 4 hours. After this, filtration by the usual method,
After repeated washing, the resulting cake was dried at 105°C for 5 hours and further baked at 850°C for 4 hours. As a result of analyzing the obtained mica titanium pigment, the content was 48.
．． It was 5chi.

Next, the characteristic values of gloss and hiding properties of the non-pearl mica titanium pigments according to the present invention shown in Examples 1 to 3 and the comparative mica titanium pigment shown in Comparative Example 1 were measured and comparatively evaluated. .

Glossiness> Disperse 1 g of the valley sample in 9Y lacquer and apply it uniformly on whiteboards and blackboards with a 10 mil doctor blade to prepare a standard. The degree of gloss was measured using a variable angle photometer, and the results are shown in Table 1.

Hideability〉 Using each specimen used in the glossiness measurement above, measure each Y value (indicating the original brightness of the CIE standard color system) with a color difference meter, and calculate the Y value (on the blackboard) / Find the ratio of Y values (on the white board),
Concealability was evaluated. The results are shown in Table-2.

Table 1 Glossiness Table 2 Hiding property As shown in the results in Tables 1 and 2, the mica titanium pigment obtained by the method of the present invention has low glossiness and therefore produces an unnecessary pearly feel. It has become clear that the product has excellent properties not found in conventional products, with no problem and high hiding power.

Example 4 Face powder (A) Mica titanium obtained in Example 1 6.0 mel 77.
9 Aluminum stearate 0.5 Silk powder 3.0 Nylon powder
8.0 Yellow iron oxide 1.0
Bengal
0.3 group blue
0.1 Rose Ben
0.1(B) Squalane
2.0 silicone oil 1
．． 0 fragrance @o, 1 (Method) Charge (A) into a Henschel mixer, stir and mix for 5 minutes, and coarsely grind using a scoop or grinder.

Next, this was placed in a Henschel mixer, and (B) was added thereto and stirred and mixed for 5 minutes, taken out, homogenized using a pro-a-sifter, and then filled into a container.

Example 5 Powder foundation (A) Mica titanium 25.0 cm obtained in Example 2
Re-site
15.8 tal
23.0 Nylon powder 10.0 Aluminum stearate
2.5 yellow iron oxide 4.0pe
Ngara
1.0 group positive
05 para pen
0.1(B) Silicone oil
4.0 Squalane 14.0 Fragrance
Fee 0.1 (way)
Method) Charge (A) into a Henschel mixer and stir and mix for 5 minutes. Then, take it out and crush it in a crusher. next,
A Henschel mixer (B) was added to the mixture, and the mixture was stirred and mixed for 7 minutes, then taken out and pulverized using a pulverizer.The mixture was filled into a medium plate and placed in a container.

Example 6 Oil-based foundation (A) Mica titanium obtained in Example 1 32. Ota
Ruri
8.0pe/gala 1.3 yellow iron oxide 3.5 group blue
0.3(B) Solid paraffin
2.0 microcrystalline wax
1.0 Canpuri Wax 3.3 Carnauba Wax 0. Triglycerate finstearate 27.9 Idosorbitan sesquiolate 2.0 Liquid paraffin 5.0 2-Octyldodecyl oleate 8.0 Kasdol oil 5.0 (Method) After combining (A) for 5 minutes in a Henschel mixer.

Grind with a grinder. Separately, (A) was added to (B) which had been previously dissolved in a melting pot, and the mixture was heated to 80°C.

Disperse with a disperser for 5 minutes. Thereafter, it was filled into a medium plate and attached to a container.

Example 7 Cheek color (A) Mica titanium obtained in Example 3 8.0 m
Ruri 53
．． 6seli site
25. O red No. 226
1.0 Yellow Y-4 Aluminum Lake 3
．． 0 group blue
0.2 Aluminum stearate 2.0 Pa
La Pen 0.1
(B) Silicone oil 3.5 squalane 3.5 fragrance
0.1 (Method) The same procedure as in Example 5 was carried out.

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph of the mica titanium M family of Example 1, and FIG. 2 is an electron micrograph of the mica titanium pigment of Comparative Row 1. All magnifications are XIo, 6 at 000x
Ru. Patent applicant Pola Chemical Industries, Ltd. Teikoku Kako Co., Ltd.'s engraving (no change in content)

Claims (1)

[Scope of Claims] 1) A method for producing a mica titanium pigment in which the content of titanium dioxide (TiO_2) in the mica titanium pigment is 40% by weight or more, which comprises: (a) mica or a mica-dispersed water bath liquid; (b) ) Titanyl sulfate (total sulfuric acid/total TiO_2 = 1.5~
5.5) or an aqueous solution thereof under stirring under conditions such that the titanyl sulfate concentration in the mixed solution is 50 g/l or more and the mica/titanyl sulfate (weight ratio) = 0.01 to 4. After mixing and then heating to the boiling point, titanyl sulfate is hydrolyzed at the boiling point to deposit titanium dioxide hydrate on the mica surface, optionally neutralized with alkali, and the resulting solid product is separated. A method for producing a non-pearl mica titanium pigment, which comprises: 2) A make-up cosmetic comprising a non-pearl mica titanium pigment obtained by the production method according to claim 1).