JPS61257910A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide an excellent cosmetic having excellent adhesivity to the skin, resistance to water and ultraviolet-shielding effect and giving natural appearance to the skin, by coating the surface of fine titanium oxide particles with amorphous iron (III) oxyhydroxide and a hydrophobicizing agent and adding the treated particles to a cosmetic base. CONSTITUTION:Fine particles of titanium oxide having a maximum particle diameter of <=0.1mu and an average particle diameter of 0.01-0.06mu (corresponding to the diameter to give high ultraviolet-scattering effect) are coated with (A) an amorphous iron (III) oxyhydroxide produced preferably by the hydrolysis of an iron (III) salt, etc., and (B) a hydrophobicizing agent such as a higher fatty acid, etc., to obtain a hydrophobic composite pigment wherein the segregation of color, the difference between the apparent color and the applied color, and the smoking of the cosmetic are prevented by the presence of the component A, the water-resistance is improved by the component B, and the undesirable effects of the component B such as the lowering of the extensibility and spreadability of the cosmetic and the loss of uniformity of applied cosmetic are suppressed by the component A. A cosmetic having the above effects can be produced by adding the hydrophobic composite pigment to a cosmetic, especially a makeup cosmetic or an antisuntan cosmetic.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cosmetic containing a novel hydrophobized composite pigment.

More specifically, adhesion to the skin is achieved by blending amorphous iron (III) oxyhydroxide and fine particle titanium oxide whose surface is coated with a hydrophobizing agent.

Excellent water resistance, ultraviolet rays, 1-ton effect, and elongation during application.

An excellent cosmetic that has good uniformity and transparency, and provides a natural finish without causing color separation, dullness, or white cast.
In particular, it is intended to provide make-up cosmetics and sunscreen cosmetics.

Conventionally, titanium oxide has been widely used as a nine-white pigment with hiding power in cosmetics, especially make-a-tsubu cosmetics, mixed with coloring pigments such as red iron oxide, yellow iron oxide, and black iron oxide. In addition, in recent years, people have become more aware of ultraviolet rays), and in order to prevent the effects of UV rays, such as dark skin, age spots, dry skin, skin irritation, and accelerated skin aging, make-up cosmetics that also serve as sunscreen cosmetics have been developed. ), and from this point of view as well, the properties of titanium oxide, which has an ultraviolet scattering effect, have been evaluated.
It is starting to be actively used.

However, 1 normal # titanium (average particle size 0, 1~0
7μ), visible light to ultraviolet light (700nm)
Scattering in the wavelength region up to 290 nm (~290 nm) is constant, and if the amount of the compound is increased to enhance the UV-cutting effect, the spread will not penetrate when applied to the skin, and the result will be a white, floating, opaque, thick makeup. This results in a makeup effect that is far from natural. Furthermore, even in cosmetic formulations.

Titanium oxide and other coloring pigments tend to cause color separation due to differences in polarity, affinity for water and oil, specific gravity, ease of wettability, etc., resulting in mismatch between external color and coating color, It has been pointed out that it causes uneven color and dullness after application.

In light of this situation, conventionally, fine-particle titanium oxide was blended into cosmetics (Japanese Patent Publication No. 47-42502), but we have taken a step further and incorporated fine-particle titanium oxide treated with metal soap into cosmetics (Japanese Patent Publication No. 58-49307). Attempts have been made to solve the above problems by technical means such as changing the particle diameter of titanium sulfide and modifying the particle surface.

However, with the former method, although it does have a superior ultraviolet scattering effect and a slight improvement in elongation compared to ordinary titanium oxide, on the other hand, fine-particle titanium oxide is susceptible to secondary aggregation. It has drawbacks such as a bluish-white coloration due to interference light, poor stability against light, and discoloration to gray when exposed to sunlight even when blended into a single product. Furthermore, fine particle formation also causes a white cast, which is a unique characteristic of titanium oxide. Disadvantages such as lack of water resistance and lack of uniformity during coating, color separation when mixed with other coloring pigments, and mismatch between appearance color and coating color due to this.

There was no improvement in color unevenness, dullness, etc.

In addition, in the latter method, the titanium sulfide is not only made into fine particles, but also its surface is coated with metallic soap, which gives it an aqueous character, giving it transparency, ultraviolet scattering effect, and adhesion. Although it is possible to improve the elasticity and makeup durability, it has the disadvantage that the elongation and spreadability are worse compared to before treatment with metal soap, and the uniformity during application is further reduced.

Also.

Like the former method, it had no effect on white cast or color separation.

On the other hand, it has a white cast, which is a unique characteristic of titanium oxide.

It is also common to form a composite pigment of titanium oxide and other coloring pigments in order to solve all of the drawbacks such as color separation when mixed with other coloring pigments and dullness after application.

As such methods, the sintering and grinding method, the mixed grinding method (mechanochemical method), the interfacial precipitation method (deposit method), etc. are well known. Composite pigments obtained by these methods have a corresponding effect on the above-mentioned defects, although there are differences in degree; There was a problem in that the makeup lasts longer (persistence).

Therefore, in view of the problems in the conventional technology, the present inventors have conducted extensive research focusing on fine particle titanium oxide, which has a high ultraviolet scattering effect. A composite pigment obtained by coating with iron (III) oxide and a hydrophobizing agent in combination complements each other's defects and is blended into cosmetics. Sometimes.

It was discovered that an excellent make-up cosmetic, especially a sunscreen cosmetic, could be provided, and the present invention was completed.

That is, the present invention has a maximum particle size of 0.1 μm or less and an average particle size of 0.1 μm. A cosmetic product containing a hydrophobized composite pigment in which the particle surface of microtubular titanium particles of O1 to 0.06μ is coated with amorphous iron(III) oxyhydroxide and a hydrophobizing agent. It is.

The present invention will be explained in detail below.

The fine particle titanium oxide applied to the present invention includes:

The particle size is selected such that the maximum particle size is 0.1 μm or less and the average particle size is in the range of 0.01-0.06 μm. If you use something with a larger particle size than this.

This is not preferable because it introduces a decrease in the ultraviolet scattering effect.

In addition, the surface of fine titanium oxide is alumina.

Surface-modified materials such as silica may be used as long as they do not deteriorate their dispersibility in water.

Preferably, it is untreated. Furthermore, regarding the type of titanium oxide, rutile type is preferable, but
It is also possible to use the anatase type.

Next, the interfacial precipitation method (
Deposit method) is preferred, and specifically, a base such as sodium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide is added to an aqueous solution of an iron(III) salt such as ferric chloride, ferric sulfate, ferric nitrate, etc. Iron (III)
) or after hydrolyzing the iron(n) salt by adding the above salt base to an aqueous solution of iron(n) salt such as ferrous chloride, ferrous sulfate, ferrous nitrate, etc. There is a method of oxidizing by blowing in air or other gold.

Amorphous iron oxyhydroxide (I
As for the method of coating ff)', in addition to interfacial precipitation, a mixed grinding method (mechanochemical method) using amorphous iron (III) hydroxide can be considered, but the effect found in the present invention is It is not suitable for the present invention because it cannot be obtained at all. This is because, in the deposition method, iron(III) oxyhydroxide can be deposited on the surface of fine titanium oxide particles in a very microscopic state at the level of t-colloid, whereas in the mechanochemical method,
The particle size of the pigment to be deposited, such as yellow iron oxide, is too large compared to the particle size of the fine titanium oxide particles, so it is not deposited (phenomenonally, fine titanium oxide particles are deposited on the pigment surface), or even if a fine particle pigment is used. It is also presumed that this is because the deposition force on the surface of fine titanium oxide particles is weak, and M desorption occurs during processes such as mixing and pulverization.

In the present invention, as mentioned above, the purpose of surface treating fine titanium oxide particles with amorphous iron oxyhydroxide is to improve color separation in cosmetics, appearance color, and coating color. The purpose is to prevent dullness and dullness, but surprisingly, the hydrophobic treatment aimed at improving water resistance, which will be described later, causes deterioration in elongation and spreadability, and a decrease in uniformity during application. The present inventors have discovered that the fine particle titanium oxide surface-treated with the above-mentioned amorphous iron(III) oxyhydroxide has a large resistance to permanent contact.

Therefore, the composition ratio of amorphous iron(III) oxyhydroxide in the hydrophobized composite pigment according to the present invention is 1 to 50% by weight, preferably 5 to 50% by weight based on the total weight of the hydrophobized composite pigment.
A range of 30% by weight is selected.

If the amount is less than 5% by weight, the degree of improvement in elongation and spreadability decreases.

Furthermore, if the amount is less than 1% by weight, the white cast and uniformity during coating will not be sufficiently satisfactory.

On the other hand, if it exceeds 50 qbt by weight, its characteristics as a colored pigment will become stronger, and its transparency, ultraviolet scattering ability, etc. will decrease, and there will be no merit in blending it.

Next, the hydrophobic treatment of the fine particle titanium oxide/iron(III) oxyhydroxide composite pigment obtained as described above will be explained.

Examples of the hydrophobizing agent applicable to the present invention include lauric acid,
Higher fatty acids having 7 to 24 carbon atoms, such as palmitic acid, stearic acid, behenic acid, etc., or their water-soluble salts, such as alkali metal salts, ammonium salts, organic amine salts, or general products such as aluminum stearate, zinc laurate, etc. A metal soap represented by the formula (RCo)nM (where R is an aliphatic or cyclic hydrocarbon having 6 or more carbon atoms, 1M is a metal other than an alkali metal, and n indicates the valence of the metal).
, and further general formula Rr 000 Rt such as hamotyl-2-ethylhexanate and 2-octyldodecyl palmitate.
(In the formula, R1 represents a higher fatty acid residue having 7 to 23 carbon atoms, and 11 Rt represents all higher alcohol residues having 12 to 24 carbon atoms). It is appropriately selected and used depending on the purpose.

Furthermore, there are no particular restrictions on the method of hydrophobic treatment; for example, JP-A No. 53-67698, JP-A No. 54-15
Known methods such as those disclosed in No. 1137 and Japanese Unexamined Patent Publication No. 59-223231 can be applied.

However, 1. The composition ratio of the hydrophobizing agent in the hydrophobized composite pigment according to the present invention is based on the total weight of the hydrophobized composite pigment.
Although there is some variation depending on the type of hydrophobizing agent, it is required to be in the range of about 2 to 25% by weight, preferably 5 to 20% by weight. If the amount is less than 2% by weight, it will not be possible to completely improve the water resistance of particulate titanium oxide, which has deteriorated further due to iron(III) oxyhydroxide treatment, nor will it be possible to expect improvements in transparency or adhesion. On the other hand, if it exceeds 25% by weight, the elongation and
9. Poor spreadability. Uniformity during application also deteriorates.

The hydrophobized composite pigment according to the present invention obtained as described above has excellent ultraviolet scattering effects and water resistance.

Furthermore, when blended into cosmetics, it has good spreadability, adhesion, and uniformity, and there is no white cast or uneven color.

Moreover, it is ideal for imparting a transparent and natural finish. Further, this hydrophobized composite pigment can be incorporated into cosmetics in the same manner as conventional pigments. The cosmetics of the present invention provided in this way include a wide range of products such as sunscreen creams, foundations, face powders, lipsticks, rouges, eyeliners, and eyeshadows.

The amount to be blended at this time varies depending on the dosage form and purpose of the intended cosmetic, but it is approximately 1 to 70% by weight, preferably 5 to 30% by weight, based on the total weight fK of the cosmetic. selected. If the amount is less than 1 weight, the UV scattering effect will not be sufficient; on the other hand, if it exceeds 70 weight 1', the UV scattering effect will be sufficient, but the transparency will decrease and it will feel like a thickening agent. become.

Here, in order to explain the present invention in detail on all pages, a manufacturing example of a hydrophobized composite pigment according to the present invention is shown below.

Production example 1゜Ferric nitrate (Fe(NOx)s” 9HtO) 20
0 ji, 2A! After dissolving in water, fine particles of titanium oxide 160.9 with an average particle size of 0.01 to 0.04 μ
In addition to '.

Spread. To this, a 1M aqueous solution of IJ hydroxide is added little by little with sufficient stirring, and the pH of the slurry is adjusted to about 1.5. Slurry adjusted in this way
, IM hydroxide) was gradually stirred and added to an IJum aqueous solution 51, and after the addition was completed, it was allowed to stand for 1 hour, and then thoroughly washed with a large amount of water until the pH reached 7 to 8, and then suctioned and filtered. , dried.

Next, an aqueous solution 21 in which the composite pigment 200.1ili obtained above and 57.59 f sodium stearate were dissolved.
and heated to 80°C while stirring.

Slowly, 5 g of water-containing alumina was added dropwise to 1.25 J' of 0.15 N diluted hydrochloric acid. One sip after the reaction is complete.

After washing with water, it was dried at 60 to 80°C for about 48 hours, and the dried product was pulverized to obtain a hydrophobized (treated with metal soap) composite pigment.

Production example 2゜Ferrous sulfate (FeSO4'7HxO) 300gTh4
After dissolving 1 in water, the average particle size is 0.01 to 0.
Add 500 pi of titanium oxide particles of 0.04 μm and stir and disperse. Next, add 10% aqueous sodium carbonate solution aooo! to this slurry. ! '6 was gradually added, and after the addition, air was introduced at a rate of about 101/min for 20 hours under sufficient stirring to obtain a yellow sludge IJ+1z.

This is 0. After adjusting the pH to -7 to 8 with IN hydrochloric acid and thoroughly washing, the mixture was centrifugally filtered and further dried to obtain a composite pigment.

Next, the composite pigment 400. Li"t, lauric acid strength IJ 57. Dispersed in 5 parts of an aqueous solution in which S fi was dissolved, heated to 60°C, and 1.2 parts of 0.2N diluted hydrochloric acid was slowly added dropwise to this while stirring. , A neutralization reaction was carried out. After the reaction was completed, the solution was filtered one mouth and washed with water.

Drying was carried out at 60 to 80°C for about 48 hours, and the dried product was pulverized to obtain a hydrophobicized (higher fatty acid treated) composite pigment.

It should be noted that the hydrophobized composite pigment obtained as described above cannot be treated with a silicone oil agent such as dimethylpolysiloxane or methylhydrodienepolysiloxane to make it water repellent in order to make it more lipophilic. No problem. However, the point that requires attention is that the processing temperature is 200℃.
The temperature should not exceed ℃. When the temperature exceeds 200°C, the amorphous iron oxyhydroxide (I
Significant dehydration of II) occurs, resulting in a loss of transparency due to a change in crystal form and a significant loss of UV scattering effect. Furthermore, there is a great risk that the hydrophobizing agent will also deteriorate. At this time, the color itself of the hydrophobized composite pigment also changes from yellow or tan to flesh color or reddish brown.

Here, in order to evaluate the hydrophobized composite pigment according to the present invention, a sensory evaluation test was conducted by a panel specializing in sensory evaluation, and the results are shown in Table 1.

Sensory evaluation test> (a) Hydrophobized (higher fatty acid treatment) composite pigment (Production example 2
．． ), (b) Production example 2. Fine particle titanium oxide used as a raw material in (c) Production Example 2. The composite pigment obtained in the first step (reaction of ferrous sulfate and fine titanium oxide), (
d) Regarding the metal soap surface treatment fine particle titanium oxide described in JP-A-58-49307, the characteristics of (1) elongation, (3) uniformity of application to the skin, (3) transparency, and (2) whiteness. A comparison was made regarding 5 evaluation items such as lifting and adhesion. The evaluation method was conducted by 10 panelists specializing in sensory evaluation.
Judgment was made according to the following evaluation criteria. The numerical values in Table 1 are the average values of the evaluation values.

(Evaluation Criteria) (Example) Uniformity: None Transparency: None As shown in Table 1, the hydrophobized composite pigment (a) according to the present invention contains conventionally known fine particle titanium oxide (b), Iron oxyhydroxide (II
I) Compared with coated fine particle titanium oxide (C) and metal soap surface coated fine particle titanium oxide (d), they mutually complement the drawbacks of conventional powders or pigments and can be incorporated into cosmetics. It combines various characteristics that are sometimes desired. It is clear that this is a significantly superior pigment.

Next, Table 2 shows the results of evaluating the cosmetic composition of the present invention through use tests.

Usage test> Using the liquefied foundation and solid face powder of the present invention shown in Examples 2 and 4 below, tests of 23 to 57
We asked 100 women in Japan to use VC for 7 days and received their evaluations. As a comparison product.

In place of the hydrophobized composite pigment in Examples 2 and 4 described later, a combination of aluminum stearate-coated fine particle titanium oxide and yellow iron oxide as shown in JP-A-58-49307 was used, The other component compositions were the same.

As is clear from Table 2, the cosmetics of the present invention are superior to comparative products in all respects, especially in terms of elongation, white cast, and natural appearance, which were the main aims of the hydrophobic composite pigment of the present invention. The results have been shown to be effective in improving poor finish (including color separation, mismatch between external color and coating color, and dullness).

Examples of the present invention are given below. In addition, the blending ratio is based on weight.

Example 1. Sunscreen cream (A) Liquid paraffin 8.0 Vaseline 3.0 Cetanol
1.0 stearic acid
2.0 Sorbitan monostearate 2.0 Isoglobil paramethoxycinnamate 1.5 2-Hydroxy-4-methoxybenzophenone 1.5 Preservative 0.2 (B)
Hydrophobized composite pigment (Production example 2.) 10.0
(C) 1.3-butylene glycol 10.0 Potassium hydroxide 0.2 Purified water
60,6 (Method) Stir and dissolve each of (A) and (B) at 75°C and adjust the temperature. The following KCB) was added into (C) under stirring to obtain a product.

Example 2. Liquid Foundation (A) Squalane 15.0 Lanolin
3.0 stearin m
3.0 Sorbitan monooleate 2.0
Dimethylpolysiloxane 3.0POE (20
) Stearyl ether 1.0 (B) Red iron oxide 0.4 Navy blue
0.1 black iron oxide
0.1 hydrophobized composite pigment (Production example 1.
) 8.0 talc 4.
0 Serisite 2.0 (C)
Polyethylene glycol 5.0 Glycerin 3.0 Xanthan gum 0.3 Triethanolamine 0.5 Preservative
0.2 refined water 49.1 (
D) Fragrance 013 (Method) Dissolve (A) and (C) with stirring at 70 to 75°C, respectively.
Adjust the temperature to 75°C. Separately, (B) is thoroughly mixed with a mixer and then pulverized. Next, (B)t-(A) is stirred and dispersed to obtain a dispersion liquid. (C) is gradually added to this dispersion while stirring to obtain an emulsified dispersion. Next, perform cooling, and
Cooling was completely stopped at 30°C to obtain a product.

Example 3. Solid foundation (A) Sericite 40.0
Talc 1000 Hydrophobized composite pigment (Production example 1.) 30.0 Titanium mica
1.0 yellow iron oxide
0.2 red iron oxide O, S group
Blue 0.2 Calcium silicate 3.0 (B) Dimethylpolysiloxane 4.0 Liquid paraffin
10.0 Carnauba wax 0
．． 5 Preservative 0
．． 1 fragrance 0
．． 2 (Method) After thoroughly mixing (A) with a mixer, the mixture is pulverized with a pulverizer to obtain color. This was placed in a mixer, and (B)'t-, which had been previously heated and dissolved at 80° C. or above, was added thereto, and thoroughly mixed and stirred. Thereafter, the product was press-molded into a medium plate using a press machine.

Example 4. Solid face powder (A) Talc 50.0 Kaolin 5.0 Sericite
20.0 Hydrophobized composite pigment (Production example 2.) 15.0 Titanium mica
1.0 aluminum stearate 3.0 yellow iron oxide 0.1 red iron oxide
0.3 navy blue back
0.1(B) Dimethylpolysiloxane 5.0 Preservative
0.2 fragrance
O, a (Method) The same procedure as in Example 3 was carried out to obtain Yushinkin.

Example 5. Solid sunscreen (sports) (A)
Carnauba wax 3.0 Candelilla wax 6.0 Solid paraffin
5.0 Lanolin 3.
0 Castor oil 50.0 2-Ethylhexanoic acid, triglyceride 10. ON, N-dimethyl-P-aminobenzoic acid-2-ethylhexyl 4.0 (B) Hydrophobized composite pigment (Production Example 2.) 19.
0 (Method) After heating and mixing and dissolving (A) at 90°C, (B) is added and dispersed. Next, the dispersion is poured into a mold, and after cooling, the solid material is taken out and placed in a container. It was made into a product.

Claims (1)

[Claims] 1) Maximum particle size is 0.1 μ or less and average particle size is 0.01 to 0.0.
A cosmetic containing a hydrophobized composite pigment in which the particle surface of 6 μm fine particles of titanium oxide is coated with amorphous iron (III) oxyhydroxide and a hydrophobizing agent. 2) The amorphous iron(III) oxyhydroxide is iron(II)
I) obtained by hydrolysis of a salt or hydrolysis and oxidation of an iron(II) salt Claim 1
Cosmetics listed in ). 3) The cosmetic according to claim 1, wherein the hydrophobizing agent is selected from the group of higher fatty acids or water-soluble salts thereof, metal soaps, and higher fatty acid monoesters. 4) Claim No. 4, wherein the amount of amorphous iron (III) oxyhydroxide in the hydrophobized composite pigment is in the range of 1 to 50% by weight based on the total weight of the hydrophobized composite pigment. 1)
Cosmetics listed in section. 5) The cosmetic according to claim 1, wherein the amount of the hydrophobizing agent in the hydrophobized composite pigment is in the range of 2 to 25% by weight based on the total weight of the hydrophobized composite pigment. . 6) The cosmetic according to claim 1, wherein the amount of the hydrophobized composite pigment is in the range of 1 to 70% by weight based on the total weight of the cosmetic.