JPH0566923B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to cosmetics containing a novel hydrophobized composite pigment. More specifically, by blending microparticle titanium oxide whose surface is coated with amorphous iron oxyhydroxide () and a hydrophobizing agent, it has improved adhesion to the skin, water resistance, and UV blocking effect. Provides excellent cosmetics, especially makeup cosmetics and sunscreen cosmetics, that have good spreadability, uniformity, and transparency when applied, and provide a natural finish without color separation, dullness, or white cast. This is what I am trying to do. Conventionally, titanium oxide has been widely used as a white pigment with hiding power in toned cosmetics, especially make-up cosmetics, along with colored pigments such as red iron oxide, yellow iron oxide, and black iron oxide. In addition, in recent years, awareness of ultraviolet rays has increased, and as a result, dark skin,
Make-up cosmetics that also serve as sunscreen cosmetics have become mainstream for the purpose of preventing age spots, skin dryness, skin irritation, and accelerated skin aging, and from this point of view, the properties of titanium oxide, which has an ultraviolet scattering effect, have become mainstream. It is being evaluated and actively used. However, ordinary titanium oxide (average particle size
0.1 to 0.7μ), scattering in the wavelength range from visible light to ultraviolet light (700nm to 290nm) is constant, and when the amount of the compound is increased to enhance the UV blocking effect, the elongation when applied to the skin is The makeup becomes heavy, white, and opaque, resulting in a thick makeup that is far from a natural makeup effect. Furthermore, even in cosmetic formulations, titanium oxide and other coloring pigments tend to differentiate in color due to differences in their polarity, affinity for water and oil, specific gravity, ease of wettability, etc. It has been pointed out that problems include mismatch between the appearance color and the applied color, uneven color, and dullness after application. In light of this situation, conventional efforts have been to incorporate fine-particle titanium oxide into cosmetics (Japanese Patent Publication No. 47-42502), or go one step further and incorporate fine-particle titanium oxide treated with metallic 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 size of titanium oxide or modifying the particle surface. However, in the case of the former method, although it certainly has 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 prone to secondary agglomeration and interference. It had drawbacks such as a bluish-white color development when exposed to light, poor stability against light, and even when it was incorporated into products, it turned gray when exposed to sunlight. Furthermore,
Even when made into fine particles, a white cast, which is a unique characteristic of titanium oxide, is produced. There are no defects such as lack of water resistance, lack of uniformity during application, color separation when mixed with other coloring pigments, mismatch between the appearance color and the applied color, uneven color, dullness, etc. There was no improvement. In addition, in the latter method, titanium oxide is not only made into fine particles, but also its surface is coated with metal soap, which gives it water resistance, transparency, ultraviolet scattering effect, adhesion, and cosmetic properties. Although it is possible to improve durability, it has the disadvantage that it elongates and has poor spreadability compared to before treatment with metal soap, and the uniformity during application further deteriorates. Also,
Like the former method, it had no effect on white cast or color separation. On the other hand, the unique characteristics of titanium oxide, such as white cast,
It is also common to form a composite pigment of titanium oxide and other color pigments, which should solve problems such as color separation when mixed with other color 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 exhibit a corresponding effect on the above-mentioned drawbacks, although there are differences in degree, but on the contrary, water resistance deteriorates with each method, and adhesion after application deteriorates. There was a problem that makeup wear (persistence) decreased. 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. iron oxide()
The product obtained by a coating treatment using a combination of a hydrophobizing agent and a hydrophobizing agent can become a composite pigment that complements each other's defects and has no defects, and when blended into cosmetics, it has a particularly smooth and natural appearance. The present inventors have discovered that it is possible to provide make-up cosmetics, especially sunscreen cosmetics, with an excellent finish, and have completed the present invention. That is, in the present invention, the particle surface of fine titanium oxide particles having a maximum particle size of 0.1 μm or less and an average particle size of 0.01 to 0.06 μm is coated with amorphous iron oxyhydroxide () and a hydrophobizing agent. The present invention relates to a cosmetic containing a hydrophobized composite pigment. The present invention will be explained in detail below. The fine particle titanium oxide to be applied to the present invention is selected from particles having a maximum particle size of 0.1 μm or less and an average particle size of 0.01 to 0.06 μm. If a particle size larger than this is used,
This is not preferable because it introduces a decrease in the ultraviolet scattering effect.
Further, the fine particle titanium oxide may be surface-modified with alumina, silica, etc., as long as it does not deteriorate its dispersibility in water, but it is preferable to use one without any treatment. . Furthermore, as for the type of titanium oxide, rutile type is preferred, but anatase type can also be used. Next, as a method for coating the surface of the fine particles of titanium oxide with amorphous iron oxyhydroxide (2), an interfacial precipitation method (deposit method) is preferable. A base such as sodium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, etc. is added to an aqueous solution of ferric sulfate, ferric nitrate, etc. to hydrolyze iron () salts, or iron () salts such as There is a method in which the above base is added to an aqueous solution of ferrous chloride, ferrous sulfate, ferrous nitrate, etc. to hydrolyze the iron () salt, and then oxidized by blowing air or the like. In addition to the interfacial precipitation method, a mixed milling method (mechanochemical method) using amorphous iron hydroxide (2) is also considered as a method for coating the surface of fine titanium oxide particles with amorphous iron oxyhydroxide (2). However, the effect found in the present invention cannot be obtained at all, and it is not suitable for the present invention. This is because the deposit method allows iron oxyhydroxide to be deposited on the surface of fine titanium oxide particles at the colloidal level in a very microscopic state, whereas the mechanochemical method allows iron oxyhydroxide to be deposited on the surface of fine particles of titanium oxide, whereas in the mechanochemical method, the particle size of the pigment to be deposited, such as yellow iron oxide, can be reduced. is too large compared to the particle size of the fine titanium oxide particles and is not deposited (phenomenonally, fine titanium oxide particles are deposited on the surface of the pigment), or even if a fine particle pigment is used, the deposition force on the surface of the fine titanium oxide particles is insufficient. This is thought to be due to the fact that it is weak and detachment occurs during processes such as mixing and grinding. In the present invention, as mentioned above, the purpose of surface treatment of fine titanium oxide particles with amorphous iron oxyhydroxide () is to prevent color separation in cosmetics and to match appearance color and applied color. , to prevent dullness, but surprisingly, the hydrophobic treatment aimed at improving water resistance, which will be described later, causes deterioration in elongation and spreadability, as well as a decrease in uniformity during application. The present inventors have discovered that fine particle titanium oxide whose surface is treated with the above-mentioned amorphous iron oxyhydroxide (2) has great resistance to the harmful effects. Therefore, the composition ratio of amorphous iron oxyhydroxide () in the hydrophobized composite pigment according to the present invention is:
1 to 50% by weight based on the total weight of the hydrophobized composite pigment
Preferably a range of 5 to 30% by weight is selected. 5
If it is less than % by weight, the degree of improvement in elongation and spreadability decreases,
Further, if the amount is less than 1% by weight, white cast and uniformity during coating may not be sufficiently satisfactory.
On the other hand, when it exceeds 30% by weight, the transparency and ultraviolet scattering ability begin to show a decreasing tendency, and when it exceeds 50% by weight, its character as a mere colored pigment becomes stronger.
The benefits of combination are lost. Next, the hydrophobic treatment of the fine particle titanium oxide/iron oxyhydroxide () composite pigment obtained as described above will be explained. Examples of the hydrophobizing agent applicable to the present invention include higher fatty acids having 7 to 24 carbon atoms, such as lauric acid, palmitic acid, stearic acid, and behenic acid. If the number of carbon atoms is less than 7, the hydrophobicity will be insufficient, and if it exceeds 24, the adhesion to the skin and the smoothness during application will deteriorate. In addition, the above-mentioned carbon number 7
Water-soluble salts of ~24 higher fatty acids, such as alkali metal salts, ammonium salts, organic amine salts, or aluminum stearate, zinc laurate, etc. Metal soaps of the general formula (RCoo) _o M (where R
is an aliphatic or cyclic hydrocarbon having 6 or more carbon atoms, M is a metal other than an alkali metal, and n is the valence of the metal), and furthermore, cetyl-2-ethylhexanate, 2-octyldocyl palmitate, etc. general formula for
Examples include higher fatty acid monoesters represented by R ₁ COOR ₂ (in the formula, R ₁ represents a higher fatty acid residue having 7 to 23 carbon atoms, and R ₂ represents a higher alcohol residue having 12 to 24 carbon atoms). , are appropriately selected from these groups according to the purpose of use and used. Furthermore, there are no particular restrictions on the method of hydrophobic treatment; for example, JP-A-53-67698, JP-A-54
Known methods such as those disclosed in Japanese Patent Application Laid-open No. 151137 and Japanese Patent Application Laid-Open No. 59-223231 can be applied. However, the composition ratio of the hydrophobizing agent in the hydrophobizing composite pigment according to the present invention is approximately 2% of the total weight of the hydrophobizing composite pigment, although there is some variation depending on the type of hydrophobizing agent. A range of ˜25% by weight, preferably 5-20% by weight is required. If the amount is less than 2% by weight, it will not be possible to improve the water resistance of the particulate titanium oxide, which has deteriorated further due to iron 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 spreadability will deteriorate, and the uniformity during application will deteriorate, even after iron oxyhydroxide treatment. The hydrophobized composite pigment according to the present invention obtained as described above has excellent ultraviolet scattering effects and water resistance,
In addition, when blended into cosmetics, it has good spreadability, adhesion, and uniformity, and is ideal for providing a natural finish with no white cast, uneven color, and transparency. It's summery. 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, blushers, eyeliners, and eye shadows. The amount to be blended at this time varies depending on the dosage form and purpose of the cosmetic, but is preferably approximately 1 to 70% by weight based on the total weight of the cosmetic.
A range of ~30% by weight is selected. If the amount is less than 1% by weight, the UV scattering effect will not be sufficient.
On the other hand, if it exceeds 70% by weight, the ultraviolet scattering effect is sufficient, but the transparency decreases and the makeup becomes perceived as thick. Here, in order to explain the present invention in more detail, an example of manufacturing a hydrophobized composite pigment according to the present invention will be shown below. Production example 1 200g of ferric nitrate (Fe(NO ₃ ) _{3.9H 2} O), 2
After dissolving in water, this has an average particle size of 0.01 ~
Add 160g of 0.04μ fine particle titanium oxide and disperse. To this, add a 1M aqueous sodium hydroxide solution little by little with sufficient stirring to adjust the pH of the slurry to approximately 1.5. The slurry thus prepared was gradually added to a 1M aqueous sodium hydroxide solution 5 with stirring, and after the addition was finished, 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. It was filtered with suction and dried. Next, 200 g of the composite pigment obtained above was added to an aqueous solution 2 in which 57.5 g of sodium stearate was dissolved.
The solution was dispersed in the solution, heated to 80°C, and 1.25% of 0.15N diluted hydrochloric acid in which 5 g of hydrated alumina had been dissolved was slowly added dropwise while stirring. After the reaction was completed, it was filtered, washed with water, and then dried at 60 to 80°C for about 48 hours.
The dried product was pulverized to obtain a hydrophobized (treated with metal soap) composite pigment. Production example 2 After dissolving 300 g of ferrous sulfate (FeSO ₄ 7H ₂ O) in the water from step 4, the average particle size was 0.01 to 0.04 μ.
Add 500 g of fine particle titanium oxide and stir to disperse.
Next, 3000 g of a 10% aqueous sodium carbonate solution is gradually added to this slurry, and after the addition, air is blown in at a rate of about 10/min for 20 hours with sufficient stirring to obtain a yellow slurry. Adjust the pH to 7 with 0.1N hydrochloric acid.
After adjusting to ~8 and then thoroughly cleaning, centrifugal filtration was performed, and further drying was performed to obtain a composite pigment. Next, 400 g of the composite pigment obtained above was dispersed in aqueous solution 5 in which 57.6 g of potassium laurate was dissolved, heated to 60°C, and slowly poured into the solution while stirring.
1.2 ml of 0.2N diluted hydrochloric acid was added dropwise to perform a neutralization reaction.
After the reaction is completed, filter and wash with water, then heat to 60 to 80℃.
The pigment was dried for about 48 hours, and the dried product was pulverized to obtain a hydrophobicized (higher fatty acid treated) composite pigment. The hydrophobized composite pigment obtained as described above is treated with a silicone oil agent such as dimethylpolysiloxane or methylhydrodienepolysiloxane to make it water repellent, with the aim of making it more lipophilic. It doesn't matter. However, care must be taken that the processing temperature does not exceed 200°C. When the temperature exceeds 200℃, the amorphous iron oxyhydroxide () in the hydrophobized composite pigment significantly dehydrates, and as the crystal form changes, transparency is lost, and ultraviolet rays This results in a significant loss of the 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 expert panel conducted a sensory evaluation test, and the results are shown in Table 1. <Sensory evaluation test> (a) Hydrophobized (higher fatty acid treated) composite pigment (Production Example 2), (b) Fine particle titanium oxide used as a raw material in Production Example 2., (c) Production example 2. Regarding the composite pigment obtained in the first step (reaction of ferrous sulfate and fine-particle titanium oxide), (d) metal soap surface treatment fine-particle titanium oxide described in JP-A-58-49307, <A>
Stretchability, <B> Uniformity of application to the skin, <C> Transparency,
Comparisons were made on five evaluation items: (d) whiteness lifting and (e) adhesion. The evaluation method was determined by 10 panelists specializing in sensory evaluation according to the following evaluation criteria. The numerical values in Table 1 are the average values of the evaluation values.

【table】

【table】

[Table] As shown in the results in Table 1, the hydrophobized composite pigment (a) according to the present invention is made from conventionally known fine particle titanium oxide.
(b), Iron oxyhydroxide () coated fine particle titanium oxide
(c) Compared to (d) fine particle titanium oxide coated on the surface of metal soap, it complements the drawbacks of conventional powders or pigments and has various properties desired when incorporated into cosmetics. It is clear that this is an extremely superior pigment. Next, Table 2 shows the results of evaluating the cosmetics of the present invention through use tests. <Usage test> Using the liquid foundation and solid face powder of the present invention shown in Examples 2 and 4 below, 100 women aged 23 to 57 years were used for 7 days, and their evaluation was obtained. . In addition, as a comparison product, instead 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 disclosed in JP-A-58-49307 was used, and the other components were the same.

[Table] As is clear from Table 2, the cosmetics of the present invention are superior to the comparative products in all respects, especially in terms of elongation, which was the main aim of making the hydrophobic composite pigment according to the present invention.
The effects of improving white cast and natural finish (including color separation, mismatch between external color and coating color, and dullness) have been fully demonstrated. Examples of the present invention are shown below. Incidentally, the blending ratio is expressed in weight %. Example 1 Sunscreen cream (A) Liquid paraffin 8.0 Vaseline 3.0 Setanol 1.0 Stearic acid 2.0 Sorbitan monostearate 2.0 Isopropyl paramethoxycinnamate 1.5 2-Hydroxy-4-methoxybenzophenone 1.5 Preservative 0.2 (B) Hydrophobic 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 (A) and (B) at 75°C and adjust the temperature. Next, (B) is added to (C) under stirring and dispersed. This dispersion was gradually added to (A) under stirring, emulsified, and then cooled to 30°C to form a product. Example 2 Liquid foundation (A) Squalane 15.0 Lanolin 3.0 Stearic acid 3.0 Sorbitan monooleate 2.0 Dimethylpolysiloxane 3.0 POE (20) Stearyl ether 1.0 (B) Red iron oxide 0.4 Prussian blue 0.1 Black iron oxide 0.1 Hydrophobized composite Pigment (Production Example 1) 8.0 Talc 4.0 Sericite 2.0 (C) Polyethylene glycol 5.0 Glycerin 3.0 Xanthan gum 0.3 Triethanolamine 0.5 Preservative 0.2 Purified water 49.1 (D) Fragrance 0.3 (Method) (A) and (C) respectively Stir and dissolve at 70-75℃, 75℃
Adjust the temperature. Separately, (B) is thoroughly mixed with a mixer and then ground. Next, (B) is stirred and dispersed in (A) to obtain a dispersion liquid. (C) is gradually added to this dispersion while stirring to obtain an emulsified dispersion. Next, cool to 50℃.
Add flavor at 30°C, stop cooling at 30°C, and obtain a product. Example 3 Solid foundation (A) Sericite 40.0 Talc 10.0 Hydrophobized composite pigment (Production example 1.) 30.0 Titanium mica 1.0 Yellow iron oxide 0.2 Red iron oxide 0.8 Ultramarine 0.2 Calcium silicate 3.0 (B) Dimethyl poly Siloxane 4.0 Liquid paraffin 10.0 Carnauba wax 0.5 Preservative 0.1 Fragrance 0.2 (Method) After thoroughly mixing (A) with a mixer, pulverize with a pulverizer to obtain color. This is placed in a mixer, and (B), which has been previously heated and dissolved at 80° C. or above, is added thereto, and thoroughly mixed and stirred. Thereafter, the product was press-molded into a medium plate using a press machine. Example 4 Solid phase 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 Ultramarine 0.1 (B) Dimethyl Polysiloxane 5.0 Preservative 0.2 Perfume 0.3 (Method) A product was obtained in the same manner as in Example 3. Example 5 Solid sunscreen (sports) (A) Carnaupa wax 3.0 Candelilla wax 6.0 Solid paraffin 5.0 Lanolin 3.0 Castor oil 50.0 2-ethylhexanoic acid liglyceride 10.0 N,N-dimethyl-P-amino Benzoic 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 liquid was poured into a mold, and after cooling, the solid material was taken out and placed in a container to form a product.

Claims (1)

[Claims] 1. The particle surface of fine titanium oxide particles having a maximum particle size of 0.1μ or less and an average particle size of 0.01 to 0.06μ is coated with amorphous iron oxyhydroxide () and a hydrophobizing agent. A cosmetic containing a hydrophobized composite pigment. 2. Claim 1, wherein the amorphous iron oxyhydroxide () is obtained by hydrolysis of an iron () salt, or by hydrolysis and oxidation of an iron () salt. cosmetics. 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 1, wherein the amount of amorphous iron 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. Cosmetics listed. 5 The amount of the hydrophobizing agent in the hydrophobized composite pigment is 2 to 2 to the total weight of the hydrophobized composite pigment.
The cosmetic composition according to claim 1, which is in the range of 25% by weight. 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.