JP5173424B2 - Cosmetics - Google Patents

Description

  The present invention relates to a cosmetic containing titanium dioxide powder. More specifically, the appearance and color change at the time of application are small, and when used, there is smoothness per skin, transparency and familiarity with the skin. The present invention relates to a cosmetic material that is excellent in lightness, has no whitening, and has excellent hiding power.

  Conventionally, titanium dioxide has been designed to have concealability, whiteness, and weather resistance suitable for industrial purposes. For this reason, when conventional titanium dioxide is blended in cosmetics, the hiding property is too high, so that there is a problem of lack of familiarity with the skin and easy whitening. In addition, since the particle size is too small, it is difficult to disperse in a multi-component system such as cosmetics, and it tends to agglomerate, so that there is a problem that appearance and color change at the time of application are likely to occur. Furthermore, conventional titanium dioxide has many irregular shapes, and cosmetics containing the titanium dioxide have a serious problem that they lack smoothness.

  In order to solve these problems, a technique for obtaining flaky titanium dioxide using a potassium compound has been reported (Patent Document 1). However, cosmetics using the flaky titanium dioxide have not been sufficiently concealed and have physical properties. Further, a technique using a titanium oxide pigment having an average particle size of 0.28 to 0.95 μm for cosmetics (Patent Document 2), a primary particle size of 0.1 μm to 14 μm, and an integrated value of a constant particle size distribution Although technology (patent document 3) using titanium oxide defined by the numerical value represented for makeup cosmetics has been reported, all cosmetics have sufficient physical properties and moderate concealing properties. I couldn't.

As described above, titanium dioxide suitable for use in cosmetics is not yet known, and even if titanium dioxide is blended, a cosmetic having an appropriate hiding property and excellent cosmetic performance cannot be obtained. Was the actual situation.
JP-A-7-155731 JP-A-6-24938 JP-A-8-277208

  Therefore, there is a need for the development of a cosmetic compounded with titanium dioxide that has a suitable hiding property and skin familiarity, has a smooth feel, has low cohesiveness, and does not easily change its appearance and color when applied. The object is to provide titanium dioxide from which such cosmetics can be obtained.

  As a result of intensive research on the physical properties of titanium dioxide to solve the above-mentioned problems, the present inventor has made use of titanium dioxide powder satisfying certain properties, thereby providing a makeup having an appropriate hiding property and excellent cosmetic performance. The present inventors have found that a charge can be obtained and have completed the present invention.

  That is, the present invention is a powder having an average particle size of 1.5 to 2.5 μm, a whiteness of 97.0 or more, and a molded product obtained by pressing the powder has a disintegration strength of 140 g or less. A cosmetic comprising titanium powder.

  Further, in the present invention, the titanium dioxide powder is coated on its surface with a hydrous oxide and / or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin, cobalt and manganese. It is the cosmetics described above.

  Moreover, this invention is the said cosmetics further containing a white pigment with an average particle diameter of 0.1-50 micrometers.

  The cosmetic of the present invention has little appearance and color change at the time of application, smoothness per skin when used, excellent transparency and skin familiarity, no whitening, and excellent hiding power is there.

  The titanium dioxide powder used in the present invention must first have an average particle size in the range of 1.5 to 2.5 μm. In the present invention, the average particle diameter is a laser diffraction type in which 0.05% by mass of titanium dioxide powder is mixed with 0.3% by mass of sodium hexametaphosphate having a pH of 10.5 and dispersed by ultrasonic waves for 3 minutes. It means the volume average particle diameter measured with a particle size distribution measuring device (HORIBA LA-910). If the average particle diameter is smaller than 1.5 μm, it is not preferable because it is inferior to the appearance and the color change at the time of application, smoothness per skin, lack of whitening and the like. On the other hand, if the average particle size is larger than 2.5 μm, the appearance and the color change during coating and the hiding power are inferior. By blending titanium dioxide with an average particle size of 1.5 to 2.5 μm, it has a smooth feel, has excellent spreadability, has an appropriate concealing property, and can form a natural cosmetic film. You can get a fee.

  If the average particle diameter is in the above range, the particle size distribution of the titanium dioxide powder is not particularly limited, but the particle size distribution is preferably in the range of 0.5 to 6.0 μm. More preferably, the volume fraction of 5 to 2.5 μm is 40% or more. If it is this range, the cosmetics which are excellent in extension spread by a smoother use feeling, have moderate hiding property, and can form a natural cosmetic film are obtained.

The titanium dioxide powder used in the present invention has a whiteness of 97.0 or more. In the present invention, the whiteness refers to 10 g of titanium dioxide filled in a circular aluminum metal pan having a diameter of 5.2 cm and a thickness of 2 mm, and is 67.5 kg / cm ² using a hydraulic foot press machine manufactured by Riken Seiki Co., Ltd. It means the lightness value (L value) obtained by measuring the color of the pressed molded product with a spectroscopic color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. When the whiteness is lower than 97.0, a color dullness occurs when mixed with an oil component, and a cosmetic with good brightness and saturation cannot be obtained. When the value of whiteness is 97.0 or more, a good cosmetic with good color development and no color dullness can be obtained.

  Further, the titanium dioxide powder used in the present invention needs to have a collapse strength of a molded product obtained by pressing of 140 g or less, and considering the strength when blended in a solid powder cosmetic, it is preferably 60 to 140 g. is there. In general, titanium dioxide powder has high surface activity and is easy to aggregate, and when it is highly cohesive, it is difficult to disperse uniformly when blended into cosmetics, and the appearance and color change during application increase. Since it exists in the form of a point or an aggregate, the problem that it is difficult to obtain a smooth feel at the time of coating arises. Therefore, the titanium dioxide powder used in the present invention needs to have low cohesiveness. Aggregation is a phenomenon in which particles are attracted to each other. Therefore, as a parameter that represents the agglomeration force, the cohesive force between the particles is used, and this force is required when collapsing the molded product obtained by pressing the particles at a constant pressure. The bond strength is expressed by the collapse strength.

Specifically, the disintegration strength in the present invention is as follows: 3.5 g of titanium dioxide is filled in a rectangular metal mold having a length of 31.5 mm and a width of 16 mm, and is 155 kg / min with a hydraulic press manufactured by Riken Seiki Co., Ltd. For a molded product pressed at cm ^2, it means a bending load value (g) measured by a rheometer manufactured by Fudo Kogyo Co., Ltd. (condition: T-shaped plunger, table ascending speed 6 cm / min).

  If it is in the above-mentioned range of disintegration strength, it is possible to obtain a natural cosmetic with a smooth use feeling, excellent elongation, and little appearance and color change upon application. When the disintegration strength is larger than 140 g, it is difficult to uniformly disperse when blended in cosmetics, resulting in a problem that the appearance and color change during application increase, and it exists in the form of an aggregate. It is difficult to obtain a smooth feel.

  Titanium dioxide that satisfies the above three conditions can be blended in cosmetics to obtain excellent concealability and cosmetic properties, but more preferably satisfies one or more of the following conditions.

  First, the shape of the titanium dioxide powder is preferably flaky or plate-like. When the shape is flaky or plate-like, it is possible to obtain a cosmetic material that has a smoother feeling of use, is excellent in stretch spread, has an appropriate concealing property, and can form a natural cosmetic film. Specifically, the flaky or plate-like titanium dioxide powder preferably has a ratio of the major axis to the thickness (aspect ratio) of 6 or more, more preferably 7.5 or more. This aspect ratio is obtained, for example, by measuring the major axis and thickness from a 20,000-fold electron micrograph of 50 titanium dioxide particles and calculating the average value of the ratios.

  The titanium dioxide powder preferably has a concealment degree of 32 to 38. In the present invention, the degree of concealment (ΔL) means that 10 parts by mass of titanium dioxide and (alkyl acrylate / dimethicone) copolymer volatile silicone solution (KP-545 manufactured by Shin-Etsu Chemical Co., Ltd.) are volatilized to a resin content of 10% by mass. 90 parts by weight of a mixed silicone (solution prepared with decamethylcyclopentasiloxane) was dispersed for 24 hours in a paint shaker and applied to a glass plate with a thickness of 6 μm. (ΔL = L value (white background) −L value (black background))}. The lower the numerical value of the concealment degree, the higher the concealment power, the lower the transparency, and the higher the tendency to white out. If the degree of hiding is in the range of 32 to 38, moderate hiding power as a cosmetic can be exhibited.

  Furthermore, the rutile ratio of the titanium dioxide powder is preferably 70% or less, particularly preferably 30 to 70%. If an attempt is made to increase the rutile ratio of titanium dioxide, it is necessary to bake at a high temperature. If the bake is carried out at a high temperature, a color dullness tends to occur, and a cosmetic with good brightness and saturation cannot be obtained. Therefore, it is preferable to keep the rutile ratio low, and if it is 70% or less, a cosmetic with good color development and no color dullness can be obtained.

In the present invention, the rutile ratio is a value determined by the following method. That is, a diffraction peak attributed to the (110) plane of rutile (R-type) titanium dioxide and a diffraction peak attributed to the (101) plane of anatase (A-type) titanium dioxide measured by an X-ray diffractometer. Each net integral intensity (NET: a value obtained by separately measuring the background in the same measurement range and excluding this influence) is calculated. By using the value X obtained from the following formula using these values and applying a calibration curve prepared in advance from the measurement result of a mixture in which the ratio of rutile titanium dioxide and anatase titanium dioxide is known, the rutile ratio Asked.
X = NET (R type) / {NET (R type) + NET (A type)} × 100

  The X-ray diffraction peak was measured by filling the titanium dioxide with an aluminum cell for X-ray diffraction so that the surface was smooth, and using a RINT-2200 manufactured by Rigaku Corporation under the conditions shown in Table 1 below.

  The titanium dioxide powder of the present invention described above can be blended in cosmetics as it is, but may be surface-treated if necessary. This surface treatment is performed, for example, by coating titanium dioxide powder with a hydrous oxide and / or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin, cobalt, and manganese. . By coating the surface of the titanium dioxide powder with the above hydrous oxide or oxide, the catalytic activity of the titanium dioxide powder itself can be reduced, and the quality of the oil component, colorant, etc. is not easily deteriorated. Cosmetics can be obtained.

  Although the coating amount with the hydrous oxide and / or oxide in the surface treatment is not particularly limited, it is 0.1 to 10% by mass (hereinafter simply referred to as “oxide conversion total amount” of each element with respect to titanium dioxide). The range is preferably abbreviated as “%”.

  The cosmetic of the present invention can be produced by blending the titanium dioxide powder into the cosmetic according to a conventional method, but if necessary, the average particle diameter is 0.1 to 50 μm in combination with the titanium dioxide powder. White pigments can be blended. Examples of the white pigment include those conventionally used, for example, titanium dioxide outside the above conditions, zinc oxide, cerium oxide, barium sulfate and the like, and these can be used singly or in combination of two or more. .

  The content of the white pigment is not particularly limited, but is preferably 1: 5 to 10: 1 in a mass ratio of the titanium dioxide powder and the white pigment having an average particle diameter of 0.1 to 50 μm. If it is this range, when mix | blending with cosmetics, a more preferable effect can be exhibited in concealment property, smooth usability, etc., without preventing the effect of the said titanium dioxide.

  The cosmetics of the present invention further include components usually used in cosmetics, for example, oily components, powder components, surfactants, aqueous components, ultraviolet absorbers, humectants, antioxidants, preservatives, perfumes and the like. Can be blended to impart each effect.

  Examples of the dosage form of the cosmetic of the present invention include a powder dosage form, an oil-in-water emulsifier type, a water-in-oil emulsifier type, an oil-based dosage form, and a solvent dosage form. Examples of the form include powder, powder solid, oily solid, cream, gel, liquid, mousse, and spray. The cosmetics of the present invention can be applied to any makeup cosmetics such as foundations, concealers, white powders, eye shadows, blushers, makeup bases, and skin care cosmetics such as emulsions, creams, and cosmetics. Among these, makeup cosmetics in powder form, powder solid form, and oily solid form are suitable.

  Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited by these.

Production Example 1
A layered titanic acid compound prepared by a known method (sample D described in Example 4 of republished patent WO99-11574) is placed in a crucible, dried in an electric furnace at a temperature of 650 ° C. for 1 hour, and then heat treated. Titanium dioxide powder was obtained by grinding using a mill (manufactured by Alpine). The electron micrograph of this titanium dioxide powder is as shown in FIG. 1, and was a plate-like particle having a thickness of about 300 nm. The particle size distribution of the obtained titanium dioxide powder is shown in FIG.

Production Example 2
An appropriate amount of water was added to the titanium dioxide powder obtained in Production Example 1 to form a slurry. The slurry was heated to 80 ° C. and neutralized with a 200 g / liter sodium hydroxide aqueous solution so that the pH became 8. Next, 300 g / liter of sodium aluminate and 20% by mass sulfuric acid were simultaneously added over 20 minutes while maintaining the pH of the slurry at 8-9, and after stirring for 10 minutes, the pH was adjusted to 5 with 20% by mass sulfuric acid. The mixture was neutralized for 30 minutes so as to be .5. Thereafter, washing, filtration, drying, and pulverization using a hammer mill were performed to obtain titanium dioxide in which aluminum hydroxide was coated with 3% by mass in terms of Al ₂ O _{3 with} respect to TiO ₂ . The particle size distribution of the obtained titanium dioxide powder is shown in FIG.

  About the titanium dioxide powder obtained by manufacture example 1 and 2, and the commercially available titanium dioxide powder (titanium dioxide powder 1-4), the physical property was measured by the above-mentioned measuring method, and sensory evaluation was performed by the following method. The results are shown in Table 2.

(Sensory evaluation method for smoothness)
Regarding the smoothness of the titanium dioxide powder, each sample was tested by 20 professional panelists, and each panel was evaluated according to the following evaluation criteria in 7 levels and given a score. The average value was calculated and judged in 4 stages according to the following criteria.
(Evaluation criteria)
(Score): (Evaluation)
6: very good 5: good 4: slightly good 3: normal 2: slightly bad 1: bad 0: very bad (judgment criteria)
(Average score): (Judgment)
5.0 or more: ◎ (very good)
3.5 or more and less than 5.0: ○ (good)
1.5 or more and less than 3.5: △ (Normal)
Less than 1.5: × (defect)

Titanium dioxide powder 1; Taipei A-100 (manufactured by Ishihara Sangyo Co., Ltd.)
Titanium dioxide powder 2; Taipei CR-50 (Ishihara Sangyo Co., Ltd.)
Titanium dioxide powder 3; MP-100 (manufactured by Teika)
Titanium dioxide powder 4; Luxeren silk D (manufactured by Sumitomo Chemical Co., Ltd.)

Example 1
Solid powdery powder foundation The foundations of the present invention products 1 to 4 and comparative products 1 to 3 having the composition shown in Table 3 were prepared by the following production method, and the appearance and color change at the time of application were smooth and smooth per skin. In addition, evaluation was made with respect to whiteness (transparency, good skin familiarity) and hiding power (cover effect). The results are also shown in Table 3.

(Note 1) Powder treated with 2% octyltriethoxysilane (Note 2) Powder treated with 3% methylhydrogenpolysiloxane (Note 3) KSG-16 [manufactured by Shin-Etsu Chemical Co., Ltd.]
(Note 4) KF-96 (10CS) [manufactured by Shin-Etsu Chemical Co., Ltd.]

(Production method)
A. Ingredients 15 to 18 are dissolved by heating at 60 ° C. and stirred uniformly.
B. Components 1 to 14 are mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.), then A is added and dispersed uniformly.
C. B is pulverized with a pulverizer.
D. C was filled in a metal pan and compression molded to obtain a foundation.

(Evaluation method 1)
The following evaluation items: (b) Appearance and little color change during application, (b) Smoothness per skin, (c) No whitening (transparency, good skin familiarity), (d) Concealment power ( With respect to the cover effect), each sample is subjected to a use test by 20 specialist panels, and each panel member evaluates it according to the following evaluation criteria in 7 grades and gives a score. It was calculated and determined in 4 stages according to the following criteria.
(Evaluation item)
(B) Appearance and little color change during application (b) Smoothness per skin (c) No whitening (transparency, good skin familiarity)
(D) Concealment power (cover effect)

(Evaluation criteria)
(Score): (Evaluation)
6: very good 5: good 4: slightly good 3: normal 2: slightly bad 1: bad 0: very bad (judgment criteria)
(Average score): (Judgment)
5.0 or more: ◎ (very good)
3.5 or more and less than 5.0: ○ (good)
1.5 or more and less than 3.5: △ (Normal)
Less than 1.5: × (defect)

  The foundations of the present invention products 1 to 4 have good hiding power, little appearance and little color change at the time of application, excellent smoothness per skin when used, excellent skin familiarity, transparency, and no whitening Things were obtained. On the other hand, Comparative Product 1 in which a large amount of titanium dioxide powder 2 was blended had problems in smoothness per skin and no whitening. Further, the comparative product 2 in which the titanium dioxide powder 3 having a slightly larger particle size is replaced with titanium oxide has a problem in appearance and color change at the time of application, and the comparative product 3 in which the titanium dioxide powder 4 having a larger particle size is further replaced. I was not satisfied with the hiding power.

Example 2
Water-in-oil emulsified liquid foundation

(Production method)
A. Components (1) to (9) are uniformly mixed and dispersed.
B. Components (10) to (13) are mixed uniformly.
C. B was added to A and emulsified to obtain a water-in-oil emulsified liquid foundation.

  The water-in-oil emulsified liquid foundation of the present invention has little change in appearance and color at the time of application, softness per skin when used, excellent transparency and skin familiarity, no whitening and hiding power Was also excellent.

Example 3
Oil-in-water emulsified liquid foundation

(Production method)
A. Ingredients (1) to (5) are heated to 75 ° C. and mixed and dissolved uniformly.
B. Ingredients (12)-(15), (17) are heated to 75 ° C. and mixed and dissolved uniformly.
C. Components (6) to (11) are added to A and dispersed with a three-roller.
D. B is added to C heated to 75 ° C. and emulsified.
E. D was cooled, component (16) was added, and an oil-in-water emulsified liquid foundation was obtained.

  The oil-in-water emulsified liquid foundation of Example 3 has little appearance and color change during application, has softness per skin when used, has excellent transparency and skin familiarity, has no whitening, and has a hiding power Also had excellent quality.

Example 4
Solid powder cake foundation (use water)

(Production method)
A. Components (1) to (8) and (11) are mixed and dispersed.
B. Components (9) to (10) and (12) are heated to 50 ° C. and mixed uniformly.
C. Add B to A and mix evenly.
D. C was pulverized and compression molded into a dish to obtain a solid powder cake foundation.

  The solid powder cake foundation of Example 4 has little appearance and color change at the time of application, has softness per skin when used, has excellent transparency and skin familiarity, has no whitening, and has a hiding power Had excellent quality.

Example 5
Solid powdery white powder

(Production method)
A. Components (1) to (6) are uniformly mixed and dispersed.
B. Add component (7) to A and mix and disperse uniformly.
C. B was pulverized and compression molded into a resin dish to obtain a solid powdery white powder.

  The solid powdery white powder of Example 5 has little appearance and color change at the time of application, has softness per skin when used, excellent transparency and familiarity with skin, no whitening and excellent hiding power Had good quality.

Example 6
Powdered cheek

(Production method)
A. Components (1) to (7) are uniformly mixed and dispersed.
B. A was pulverized and filled into a container to obtain a powdery cheek.

  The powdered cheek red of Example 6 has little appearance and color change at the time of application, has softness per skin when used, has excellent transparency and familiarity with skin, has no whitening, and has excellent hiding power Had good quality.

Example 7
Solid powder eye shadow

(Production method)
A. Components (1) to (7) are uniformly mixed and dispersed.
B. Components (8) to (10) are heated to 50 ° C. and mixed uniformly.
C. Add B to A and mix and disperse uniformly.
D. C was pulverized and compression molded into a dish to obtain a solid powder eye shadow.

  The solid powder eye shadow of Example 7 has little appearance and color change at the time of application, softness per skin when used, excellent transparency and skin familiarity, no whitening and hiding power Had excellent quality.

  The cosmetic of the present invention has little appearance and color change at the time of application, smoothness per skin when used, excellent transparency and skin familiarity, no whitening, and excellent hiding power Therefore, it can be advantageously used as a makeup cosmetic or a skin care cosmetic.

2 is an electron micrograph of titanium dioxide powder obtained in Production Example 1. 2 is a graph showing the particle size distribution of titanium dioxide powder obtained in Production Example 1. FIG. 4 is a graph showing the particle size distribution of titanium dioxide powder obtained in Production Example 2. FIG.

Claims (3)

A flaky or plate-like powder having an average particle size of 1.5 to 2.5 μm and a whiteness of 97.0 or more, and a molded product obtained by pressing the powder has a disintegration strength of 140 g or less . A cosmetic comprising titanium dioxide powder.   The titanium dioxide powder has a surface coated with a hydrous oxide and / or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin, cobalt and manganese. 1. Cosmetics according to 1.   The cosmetic according to claim 1 or 2, further comprising a white pigment having an average particle size of 0.1 to 50 µm.