JPS5849307A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide a cosmetic having low opacity and excellent transparency, by using titanium oxide fine powder having specific particle diameter and surface-treated with a metallic soap, as a component. CONSTITUTION:Fine powder of titanium oxide having the maximum particle diameter of <=0.07mu and average particle diameter of 10-40mmu, is surface- treated with a metallic soap of formula (RCOO)nM (R is >=6C aliphatic or cyclic hydrocarbon group; M is metal other than alkali metal; n is valence of the metal) and having high dispersibility, lubricity, flexibility, adhesivity, and stability, e.g. aluminum stearate, calcium stearate, magnesium stearate, zinc palmitate, etc. The objective cosmetic contains the treated titanium oxide in an amount of >=1%, and preferably <=20%. The ratio of the titanium oxide fine powder to the metallic soap is preferably 95:5-75:25. The cosmetic is preferably used as an anti-suntan cosmetic.

Description

[Detailed Description of the Invention] The present invention is a cosmetic using surface-treated titanium oxide (=
related.

More specifically, the present invention relates to an anti-skinned cosmetic with less whitishness and excellent transparency, containing fine particle titanium oxide whose surface has been treated with metal soap.

Titanium oxide is widely used in cosmetics as an inert and safe powder. Titanium oxide has a large hiding power, and when applied to the skin, it remains white, resulting in a so-called thick makeup, making it difficult to obtain a natural finish.

There is also a known technique of adding fine particles of titanium oxide to improve the transparency, but fine particles of titanium oxide tend to cause secondary aggregation, and although the transparency can be improved to some extent, a natural finish cannot be obtained. In addition, there are problems such as the appearance of a bluish color due to interference light, which does not have much of an effect on brightening the skin, and the tendency to discolor. has been considered.

The purpose of the present invention is to solve the problems of the conventional methods described above, and to apply fine particle titanium oxide that has undergone a specific surface treatment to cosmetics. In other words, the present invention provides cosmetics with a maximum particle size of 0807 whose surface is coated with metal soap.
The present invention relates to a cosmetic containing 1 or more and preferably 20 or less microparticles of surface-treated titanium oxide having an average particle diameter of 10 to 40 m.mu. or less.

The metallic stone of the particle surface-treated titanium oxide applied to the present invention is a compound represented by the general formula (RCOO)nM (where R is an aliphatic or cyclic hydrocarbon group having 6 or more carbon atoms, and M is an alkali Among metals other than metals (n indicates the valence of the metal), those with excellent dispersibility, lubricity, flexibility, adhesion, and high safety are preferred, such as aluminum stearate, calcium stearate, and magnesium stearate. , zinc palmitate, zinc laurate, zinc oleate, barium stearate, and other powders and waxes.

When obtaining the particulate surface-treated titanium oxide according to the present invention, the metal soap may be surface-treated by an appropriate method (for example, a solvent method) after or during the production process of the particulate titanium oxide. , may be obtained using a metal oxide hydrate and a higher fatty acid as starting materials so that the final product forms a film of metal soap (in this case, some surplus may be produced). . When such a method is used (=, aluminum hydroxide (water alumina), magnesium hydroxide, zinc hydroxide, barium hydroxide, etc. are used as starting materials for the former. Higher fatty acids for the latter are ordinary ones. Caproic acid, capric acid, lauric acid, myristic acid, stearic acid, oleic acid,
Straight chain, branched, or saturated ones having 8 to 24 carbon atoms, preferably straight chain saturated ones having 16 to 22 carbon atoms, such as behenic acid and isostearic acid. In addition to higher fatty acids, silicone oil can also be used in combination. Commercially available products include fine particle titanium oxide 1.00-S (manufactured by Teikoku Kako Co., Ltd.) made from iris alumina and lauric acid as starting materials.

In the present invention, when the surface is treated with metal soap, for example, JP-A-54-151137 is preferably used.

Metal soap is effective in that it does not significantly increase the amount of coating during surface treatment, coats fine titanium oxide particles in an amount suitable for obtaining transparency, and is difficult to aggregate.

In the surface-treated titanium of the present invention, as mentioned above, the average particle size is 1'0:40 mμ as the specified particle size range.
Particles larger than this are disadvantageous because they not only have a coarse texture but also a strong whitish tinge. It is technically conceivable to use finer particles of titanium oxide, but it is difficult to prevent secondary agglomeration.
This is not desirable in terms of increased manufacturing costs. Regarding the type of titanium oxide, the rutile type is more preferable than the anatase type, but up to about 20 titanium oxide may be contained.

The present invention (=The content ratio of fine particle titanium oxide and metal soap in the fine particle surface-treated titanium oxide used is 99:
The ratio is 1 to 50:50, preferably 95:5 to 75:25. If there is more metal soap than this, the particle size itself becomes larger, which tends to appear whiter and reduce transparency. Also, if there is not enough metal soap, the characteristics of untreated ones will stand out,
However, there is no benefit from the coating treatment.The present inventors measured the specific surface area of the fine titanium particles of the present invention under the following conditions, and found that it was in the range of 50 to 70 m2'g.

Furthermore, it has been found that the shape of the particles can also be in the form of ordinary grains, such as curved or rod-like.

<Measurement of specific surface area> Method: Continuous flow method (ADS-GC device) Sample
: P-25,1005 untreated, 100S pre-treated: P-25,1005 untreated -+24hrs, 60°C
Drying under reduced pressure, 1005.24hrs RT Drying under reduced pressure This surface-treated titanium oxide has many possibilities as a raw material for cosmetics.

In the first place, transparency is an important element of the finish obtained when applying cosmetics, especially powdered cosmetics, to the skin.When transparency is required, traditionally highly transparent natural minerals are blended. This natural mineral has unique properties derived from its crystal structure and denseness, and it is difficult to obtain a grain with the desired grain size -:9.'. Taking the case of sericite, a typical mineral, for example, even if the same sericite is produced in different places, the ratio of grain size to grain thickness will be different, and it will not be possible to obtain the same texture.In particular,
The problem is a decrease in transparency caused by irregularities in particle thickness and particle size. For this reason, in the past, powder particles with relatively large particles were used to achieve a sense of transparency, but when such powder particles were used, they gave the skin a rough particle feel and gave a feeling of use. This results in a decrease in the quality of the cosmetics, which in turn results in coarse-textured cosmetics, leading to a decline in quality. In other words, there is a limit to the maximum transparency and particle size of conventional clay minerals, and it is difficult to expect greater transparency.

Table 1 (1) 0.2g of Shirohenben handle, 2.09g of titanium oxide, and 1.2f of castor oil
The mixture is kneaded with a Huber muller and packed in a colorimetric glass cell for spectroscopic colorimetry. From the Hunter colorimetric value, white discoloration = 100-, ρT stone = 〒5 "; Determined by i- in front of the mouth.

(2) Covering power The relative value is determined from the spectral reflectance at 5,340 nm using the same sample as for whitening.

Table 1 compares the whitening and covering power of commercially available rutile-type titanium oxide, commercially available fine particle titanium oxide, and surface-treated titanium oxide related to the present invention.

It can be seen that the surface-treated titanium oxide has excellent transparency because it has less whitening and less covering power.

FIG. 1 shows the difference in transmittance of visible light and ultraviolet rays. The surface-treated product has a lower ultraviolet shielding effect than others, but its visible light transmittance is twice that of normal rutile type and 15 times that of fine-particle titanium oxide. This proves that the transparency is truly excellent.

　　　゛The samples shown in Figure 1 are as follows.

0 Base emulsion only 1 〃 + Rutile type titanium oxide (5 Hara Sangyo R
680) 5% 2 〃 10 fine particles titanium oxide P-255chi 3p +tt rt100S1
5chi 4 # +/I II 10
0s5 Tibase emulsion composition Aluminum stearate 15 parts POE (
5) Hydrogenated castor oil derivative 80 Liquid paraffin 13.0 Olive oil
180 microcrystalline wax
50 Purified Water 54.5 Among skin cosmetics, when used as a sunscreen cosmetic, the property of surface-treated titanium oxide having a low ultraviolet cut rate is considered to be disadvantageous. However, the present invention is useful even in this case. That is, the ultraviolet cut rate can be reliably increased by increasing the amount of powder.

Increasing the amount of powder also reduces the transparency, but the first
As shown in the figure, the surface-treated titanium oxide containing 15 titanium oxide has a UV cut rate equivalent to that of 5 titanium oxide particles, but is still superior in transparency.

The amount of titanium oxide in all cosmetics varies depending on the purpose and properties of the cosmetic, but generally it is desirable to be between 1% and 20% (by weight).Adding less than 1% will have little effect, and adding a large amount will It does not meet the original purpose of cosmetics.

Furthermore, (a) commercially available regular titanium oxide (rutile type), (b)
Commercially available fine particle titanium oxide (P-25), (c) surface-treated titanium oxide of the present invention, transparency, (B) skin brightening effect, (C) whiteness of coating color, (D) ultraviolet light cutting effect A comparative test was conducted.

The results are shown in Table 2 below.

After applying the raw titanium oxide powder samples shown in (1) to (iii) below in Table 2 using a puff, 10 panelists applied
The performance was evaluated and the results are shown in Table 3.

(i): #particle titanium 1oo-5 (present invention) (ii
) : Untreated fine particle titanium oxide (III) : (
Mixture of metal scum and unroasted fine particle titanium oxide with the same composition as i) (evaluation criteria) <A> None Yes 012345
6 <Mouth> White Not white 01
23456 Table 3 As can be judged from the results in Tables 2 and 3, the cosmetics of the present invention have several characteristics compared to conventional cosmetics containing titanium oxide. That is, there is no blue-white coloration in the interference color. To provide a cosmetic having effects such as brightness in makeup finish. It also has good dispersibility, has a smooth and smooth feel, and is free from stickiness. Furthermore, there is provided a cosmetic that has an appropriate UV-blocking effect and gives a natural finish with a significantly improved sense of transparency.

Due to these characteristics, the present invention is an industrially useful invention that increases the commercial value of cosmetics.

Examples are shown below.

Example [1] Pressed powder A was placed in a planetary mixer and mixed for 10 minutes, then taken out and pulverized using a pulverizer. Next, the mixture was transferred to a Henschel mixer, B was added thereto, stirred and mixed for 8 minutes, taken out, homogenized using a blower sifter, and then filled into containers to produce a product.

The surface-treated titanium oxide used was Tie280,
Surface treated with 20% aluminum laurate (
Teikoku Kako Co., Ltd. fine particle titanium oxide 100-3), maximum particle size 0.07μ or less, average particle size (length) 32m1L,
Monoteal with a specific surface area of 6o and 7sWf/y.

Example [2] Powder eyeshadow I iron black
46 C (fragrance 0.3 A) was mixed for 3 minutes in a Henschel mixer, and then crushed in a crusher.Then, the crushed product was transferred to a Henschel mixer, and B, which was dissolved at 60°C, was added to another container. ,7
Stir and mix for 4 minutes, add C, stir and mix for 2 minutes, take out and homogenize with a blower sifter, then fill in a container to make a product.

Example [3] Foundation C (fragrance 03 A and B were dissolved and dispersed separately and kept at 80°C, and B was added to A.
Add little by little and stir thoroughly to emulsify.

When emulsification is complete, stir at 80°C for 5 minutes, cool with water, and
Cool to 0°C. Thereafter, C is added, the mixture is cooled to 30°C, and the mixture is taken out and filled into a container to form a product.

Example [4] Sunscreen powder tartar 80
5% by weight crystalline cellulose 5.0 ultramarine 10 spherical calcium silicate 4.0 squalane
5.4 Surface treatment titanium oxide
5.0 (Surface treatment agent: 10% stearic acid, 10% alumina for water use) Example [5] Sunscreen powder tartar 75.5% by weight Crystalline cellulose 5.0 Ultramarine 1
．． 0 Spherical calcium silicate 4.0 Cinnamate ester 5.0 Surface treated titanium oxide
10.0 (Surface treatment agent: 10% stearic acid, 10% water-use alumina) Example [6] (Sunscreen Compact) Tal
ri 533
6-layer fine particle titanium 100-5 13.0
Bengara 02 Ultramarine 0.04 Yellow iron oxide 04 Silk powder 2.0 Seri, Cyto 10.0 Aluminum stearate 2.0 Mica
10.0 Cinnamate ester 5.0 Silicone KF99
3.8 Fragrance 0.2

[Brief explanation of the drawing]

FIG. 1 shows the wavelength cut rates in the ultraviolet and visible light regions of cosmetics using the surface-treated titanium oxide of the present invention and conventional titanium oxide. FIG. 2 shows an electron micrograph (150,000 times magnification) of the surface-treated titanium oxide used in the present invention. O-based emulsion only 1,2 Conventional titanium oxide 3,4 Invention product (15,5%) Patent applicant Asamichi Kato, patent attorney, Pola Chemical Industries, Ltd. Figure 1 □ Wavelength (field) Procedural amendment ( (Voluntary) July 2, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1, Indication of the Case 1982 Patent Application No. 144779 (September 1981)
3. Relationship with the case of the person making the amendment Patent applicant: 4, Agent: 6, Number of inventions increased by the amendment: None 7, Subject of amendment: 1, Detailed explanation of the invention in the specification shall be corrected in the following manner. l) Delete the text from lines 1-8 of page 8 of the specification, ``Figure 1 is...'' to ``shown in Table 3'' at the end of page 11, and insert a written sentence. (Hereinafter referred to as "Continued") "Next, we will compare the cosmetics containing the surface-treated particulate titanium oxide (Titanium 1008) of the present invention with the conventional cosmetics containing commercially available particulate titanium oxide (Titanium P-25). In addition, the transparency was demonstrated by measuring the degree of change in color tone depending on the concentration of various formulations.As a method for measuring color tone, sample 9f of the various formulation examples shown in Table 2 below was measured with a diameter of 5 mm. Press and pack it into a medium plate with a thickness of approximately 3mm, using a Nippon Juishoku Co., Ltd. color difference meter (Model Z-1001DP). The results were measured using L (whiteness), a (redness), and b (
Yellowness) values are shown in Table 3. Table 2: Various Prescription Examples Weight % Table 3 Color Tone Measurement Results Hata In Table 3, △L, △a, and N represent the following meanings. ΔL = Conventional product value 1 Invented value Δa = Conventional product a value 1 Invention a value △b = Conventional product value 1 Invented value (evaluation) (1) In the comparison of 5% content, titanium P -25 (prescription example ■) tends to be whiter and has a lighter tone, whereas in the case of Titanium 100S, the color tone of the pigment appears faithfully, and the transparency is high. I can say that. (2) In the comparison of the content of 10%, it is concluded that the above (1)
) is similar to the case of 5%, but the difference is larger than that of 5%. (3) Even when formula example ■ containing 5% titanium P-25 is burnt and Titanium 100S is added at 10% (prescription example ■), titanium 100S is still less white and the pigment is less intense. Color fidelity is poor. The transparency is more than double at this density. As can be judged from the above results, the product of the present invention was proven to have a clearly more transparent feel than the conventional product. Furthermore, the cosmetics using the surface-treated titanium oxide according to the present invention are characteristically excellent in terms of ultraviolet scattering effect. The figure shows the absorbance in the ultraviolet and visible regions demonstrating this ultraviolet scattering effect. The test method consisted of sample a (invention) with the basic formulation shown in Table 4 below, and sample b in which the surface-treated titanium oxide in this recipe was replaced with commercially available fine particle titanium oxide (P-25). , using 0.32 each of sample C in which sample sample a of the same basic formulation was replaced with ordinary titanium oxide (Thai 4-ri 680), and each of them was mixed with castor oil 0.32.
Knead with 84'f and Hooper mala, of which 0.9
2 was mixed with a 7-lac alcohol solution 4112, and then coated on a quartz glass plate using a 0.5 milled data blade. After drying in the air, the absorbance of the coating film was measured. Table 4 Sample a (basic formulation) Talc 84.5 parts by weight Microcrystalline cellulose 5.0 group
Blue 0.1 Squalane 5.4 Surface-treated titanium oxide ” 5.0100.0 As is clear from Figure 1, sample a containing surface-treated titanium oxide according to the present invention is different from conventional fine particle titanium oxide and Sample b1 containing normal titanium oxide
Compared to Sample C, the absorbance in the ultraviolet region (290-31
5 nm), it shows an equivalent or significantly higher value, and has an excellent ultraviolet scattering effect. In particular, this wavelength corresponds to the UV-B region that causes sunburn, and it can be said that the surface-treated titanium oxide of the present invention is suitable for preventing sunburn. The content of surface-treated fine particle titanium oxide in all cosmetics varies depending on the purpose and properties of the cosmetic, but is generally 1 to 20%.
% (weight) is preferred. Addition of less than 1% will have little effect, and addition of a large amount will not meet the original purpose of cosmetics. If necessary, it may be used in combination with other ultraviolet absorbers or ultraviolet scattering agents. Furthermore, regarding (4) sun protection powder containing (a) commercially available regular titanium oxide (rutile type), (b) commercially available fine particle titanium oxide (P-25), and (c) surface-treated titanium oxide of the present invention, (4) ) Transparency, [F]) Skin brightening effect, whiteness of 0 coating color, and 0 UV cut effect were compared in a comparative test. The samples include the sunscreen/gourder (in the case of (C)) of Example 4 described later, and the sunscreen/growder in which the surface-treated titanium oxide of the present invention was replaced with (a) in this formulation. , (b) was replaced with a sunscreen and a powder, respectively. The results are shown in Table 5 below. After applying the raw titanium oxide powder samples shown in Table 5 below (1) to (nil) with a puff, a sensory evaluation was performed by 10 panelists, and the results are shown in Table 6.''2) Specification No. 12
On the 9th line of the page, "Table 3" is corrected to "Table 6." 3) Correct "Tables 2 and 3" in the first line of Mr. 1.3 of the specification to "Tables 5 and 6." 2. The column of the brief description of the drawings in the specification shall be amended as follows. l) On page 18, line 17 of the specification, "wavelength cut rate" is corrected to "absorbance." 2) Delete lines 1 and 2 of page 19 of the specification, and add [a
Sample a (invention product), b Sample b (conventional product),
C sample C (insert for conventional product). 3. The drawings are amended as follows. Figure 1 is deleted and replaced with attached sheet (correction) Figure 1. (That's all) Figure 1 Work section - Visible part → Freeze length/7177?) Procedural amendment (10th November 1980 LfIJ Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of the case 1983 Patent No. 1 775) (Showa 5)
(filed on September 16, 2016) 3. Relationship with the case of the person making the amendment Patent applicant 4, agent address 105 East 5;
1'll: Niji 1; 6 Kano Fuji Ainon Subi I+
11. '+,': r::story, l'', l:tIS-+
12 persons Name (8u31) No. 1 Physician Asahi Kato
Neck Ni+ -, -, , +5, Date of correction order
Spontaneous 6 Number of inventions increased by amendment None 7. Detailed explanation of the invention in the specification subject to amendment Column 8, Contents of amendment As shown in the attached sheet, the Detailed explanation of the invention column in the description is amended as follows: do. (1) On line 14 of No. 3 of the specification, "1-metal oxide" is corrected to "1-metal ion." (2) Page 3, line 18, after “1 (water-use alumina),” “aluminum sulfate, potassium aluminum sulfate, -
Insert 1〇

Claims (1)

[Claims] 1. A cosmetic comprising fine particle surface-treated titanium oxide having a surface coating of metal soap and having a maximum particle size of 0.07 μm or less and an average particle size of 10 to 40 μm.