JPH11158035A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic presenting nice coated color without making skin texture and wrinkles noticeable, by including highly cohesive titanium oxide with each specific primary particle size, secondary particle size and crystal form. SOLUTION: This cosmetic is obtained by including (A) highly cohesive titanium oxide with a primary particle size of 0.001-0.15 μm and a secondary particle size of 0.6-2.0 μm, having anatase crystal form, and capable of giving coating films pref. with an L-value of 35-60 and b-value of -10 to 0, and (B) as necessary, such ingredients as powder, lubricant, resin, surfactant, ultraviolet light shielding agent, antioxidant, perfume, moisturizer; wherein the component A may be coated with the (hydrous) oxide of an element selected from Al, Si, Zr, Ti and Zn, and furthermore, either simultaneously with the above treatment or singly, may be coated with an organic matter selected from silicone compound, silane, metallic soap, fluorine compound, water-soluble polymeric compound and N-acylated lysine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition which contains titanium oxide having a transparent feeling and has a beautiful application color with less noticeable skin texture and wrinkles.

[0002]

2. Description of the Related Art Conventionally, titanium oxide blended in cosmetics has a pigment-grade titanium oxide (primary particle diameter of 0.15 to 0.3 μm) for hiding as a white pigment and a titanium oxide for protection against ultraviolet rays. Ultrafine titanium oxide (primary particle size 0.01
０．０５0.05 μm).
Under these circumstances, according to Japanese Patent Application Laid-Open No. Hei 9-221411, the average primary particle diameter in the intermediate region between the pigment-grade titanium oxide and the ultrafine titanium oxide exceeds 0.10 μm and falls below 0.1 μm.
It is disclosed that titanium oxide in the range of 4 μm or less (hereinafter referred to as “intermediate particle size titanium oxide”) has an appropriate finish and a natural hiding power. When a reproduction experiment is performed by the method described in the publication, the white beauty of titanium oxide is superior to conventional pigment-grade titanium oxide in terms of white beauty, but not as high as that of ultrafine titanium oxide. However, there is a limit to how often it can be used as a hiding material. Therefore, by coloring the intermediate particle size titanium oxide yellow, the bluish color of the titanium oxide disappears and a natural flesh color can be formed.

[0003]

The ultrafine titanium oxide also has a bluish whiteness as described above, and there is a limit to its use as a concealing material. On the other hand, high-cover type foundations contain a large amount of pigment grade titanium oxide,
Pigment grade titanium oxide has a high degree of whiteness, and thus has a problem that skin texture and wrinkles are noticeable. Even with the use of titanium oxide having an intermediate particle size, there is a problem that an uncomfortable feeling of skin color due to the bluish whiteness appears. In addition, although titanium oxide having an intermediate particle diameter colored in yellow is effective, there is a problem that if the amount is increased, the yellow color becomes too strong.

[0004]

The present inventors have conducted intensive studies to solve these problems, and as a result, have found that the primary particle diameter is 0.001 to 0.15 μm and the secondary particle diameter is 0.6 to 0.6 μm.
It has been found that an anatase-type titanium oxide having a thickness of 2.0 μm gives a natural and appropriate white color without being colored, and has an ultraviolet protection ability. The present inventors have found that the cosmetics containing this titanium oxide show a beautiful coating color without noticeable skin texture and wrinkles, and completed the present invention. That is, the present invention has a primary particle diameter of 0.001 to 0.15 μm.
m and a secondary particle diameter of 0.6 to 2.0 μm, and a crystal form comprising a highly cohesive titanium oxide having an anatase.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The strongly cohesive titanium oxide used in the present invention has a primary particle diameter of 0.001 to 0.15 μm, a secondary particle diameter of 0.6 to 2.0 μm, and a crystal form of anatase. Is a strongly cohesive titanium oxide. The strongly cohesive titanium oxide is one which is not easily disintegrated into primary particles even when mechanically dispersed under the conditions usually used industrially, and most of the particles remain as secondary particles. Since the light scattering ability is determined by the state dispersed in the medium, that is, the secondary particle diameter, when the secondary particle diameter is in the above range, a sense of transparency to visible light occurs, and like the ultrafine titanium oxide. Since blue light is not scattered preferentially, a natural color tone without bluish tinge is given. Furthermore, the specific surface area is large in accordance with the primary particle diameter, even though it is strongly cohesive, so that the ultraviolet ray absorbing ability is considerably higher than when the secondary particle diameter is almost the same and the primary particle diameter is large.

In the present invention, the primary particle size is determined by the following method. First, 0.5 g of powder is pulverized for 10 minutes with an Ishikawa stirring stirrer (manufactured by Ishikawa Plant), and a transmission electron micrograph is taken. From that photo,
The primary particle diameter is measured with a Particle Analyzer (manufactured by Carl Zeiss Co., Ltd.), and the calculated weight average diameter is defined as the primary particle diameter. Next, regarding the secondary particle diameter, this is expressed as a median diameter when the powder is dispersed in water and measured with a laser diffraction / scattering type particle size distribution device LA-910 manufactured by Horiba, Ltd. Here, in order to disperse the powder in water, sodium hexametaphosphate is dissolved in ion-exchanged water to form a 1.0% aqueous solution, and 17.0 g of this aqueous solution is used.
And 17.0 g of powder together with 40 g of 0.5 mm zircon beads into a 140 cc glass mayonnaise bottle,
The measurement is performed after the paint shaker dispersion is performed for 5 minutes. In addition, even when the secondary particle diameter of the pigment titanium oxide or the ultrafine titanium oxide is obtained by this method, the secondary particle diameter is not always the same as the primary particle diameter, and the value of the agglomerated particles may be obtained. Only two or three particle diameters are agglomerated, which is 0.5 μm or less.

Although the particle size is determined by the above method, the strongly cohesive titanium oxide used in the present invention has a primary particle size of 0.00
1 to 0.15 μm, preferably 0.01 to 0.1 μm,
And a secondary particle diameter of 0.6 to 2.0 μm. When the primary particle size exceeds the above range, it is difficult to obtain a highly cohesive titanium oxide, and the ultraviolet absorbing ability is reduced.
When the primary particle diameter is less than 0.001 μm, the crystallinity of titanium oxide is deteriorated, and the original physical properties of titanium oxide are impaired.
On the other hand, if the secondary particle diameter is less than 0.6 μm, it has the same concealing property as the pigmented titanium oxide, and the appropriate transparency and natural feeling of the strongly cohesive titanium oxide cannot be obtained. Further, those having a secondary particle size of more than 2.0 μm are substantially difficult to obtain, and are liable to be broken and hardly to have strong cohesiveness.

The above is a general description of the characteristics of the strongly cohesive titanium oxide used in the present invention. An index that expresses this characteristic more specifically and simply will be described. That is, the strongly cohesive titanium oxide is characterized in that a titanium oxide-containing coating film is prepared by the following method, and the L value is 35 to 50 and the b value is -10 to 0 when measured by a color difference meter. .

[Method of Making Titanium Oxide-Containing Coating Film and Measuring Color of Coating] Ink-making adjustment method <Mill base>-Using 140 cc glass mayonnaise bottle-Titanium oxide sample 10.0 g Veccosol J-524-IM-60 (*) 12.0 g Solvent (4/1 = xylol / n-butanol) 0 g 0.5 mm zircon beads 60.0 g Paint shaker dispersed for 10 minutes <stabilization> Mill base 34.0 g Beccosol J-524-IM-60 12.0 g Paint shaker 5 minute dispersed <let down> Stabilized product 2.3 g Beccosol J -524-IM-60 16.9 g 20% NC clear lacquer 23.2 g DBP (di-n-butyl phthalate) 1.1 g Cellosolve acetate 0.8 g Paint shaker 5 minutes dispersion. (*) Alkyd varnish manufactured by Dainippon Ink and Chemicals, Inc. (**) 20% NC clear lacquer 1 / 2RSNC (75% IPA wet) 26.7% by weight Xylol 12.2% by weight n-butanol 9. 8% by weight ethyl acetate 25.6% by weight butyl acetate 6.5% by weight MIBK 19.2% by weight << paint constants >> alkyd / NC / DBP = 9/4/1 P / B = 3PHR

[0010] 2. Coating film preparation and coating color measurement method After coating (8 μm film thickness after drying) on a morest chart paper with an applicator, the color on the black background of the coating film obtained by natural drying is measured with a color difference meter (SM manufactured by Suga Test Instruments Co., Ltd.). The color is measured with a color computer SM-5).

When compared with other materials by this method, pigment titanium oxide generally has a large hiding power and high whiteness, so that the L value exceeds 50, and in the case of ultrafine titanium oxide, blue The b value becomes less than -10 due to light scattering.

The strongly cohesive titanium oxide used in the present invention has at least one kind selected from the group consisting of Al, Si, Zr, Ti and Zn on the surface of the particles for the purpose of suppressing the solid catalyst activity and photocatalytic activity. The hydrated oxide and / or oxide may be coated, and simultaneously with these treatments,
Or alone, at least one selected from the group consisting of silicone compounds, silanes, metal soaps, fluorine compounds, water-soluble polymer compounds, N-acylated lysine, polyols, acrylic resins, methacrylic resins, styrene resins, urethane resins, and the like. Organic substances may be coated. By these surface treatments, improvement of wettability, impartation of sebum resistance, and improvement of dispersibility can be appropriately performed. Among them, silicone compounds such as methylhydrogenpolysiloxane, trimethylsiloxysilicic acid, fluoroalkyl / polyoxyalkylene co-modified silicone, silanes such as octyltriethoxysilane, metal soaps such as zinc stearate, perfluoroalkylphosphoric acid Diethanolamine salts, Teflon, fluorine compounds such as perfluoroalkylsilane, deoxyribonucleic acid, water-soluble polymer compounds such as hyaluronic acid, those treated with N-acylated lysine such as N-lauroyl lysine, It is particularly preferable because of the characteristics described above.

As the method for producing the strongly cohesive titanium oxide used in the present invention, for example, the following two-stage method can be used. A step of heating and hydrolyzing the aqueous solution of titanyl sulfate in the presence of a nucleus A step of calcining the hydrolysis product at a temperature of 600 to 900 ° C. Titanyl sulfate as a starting material is usually produced by reacting ilmenite ore with sulfuric acid. be able to. This is called digestion in the titanium oxide industry, but not limited to ilmenite ore, for example, hydrous titanium oxide may be digested. After diluting this product with water and removing impurities as necessary, hydrolysis is performed by heating. At this time, nuclei, which are microcrystals of titanium oxide, are added for the purpose of accelerating the hydrolysis reaction and adjusting the particle size and crystallinity. The hydrolysis product thus obtained is filtered, washed if necessary, and then calcined at 600 to 900 ° C. If the sintering temperature is lower than this range, the primary particle diameter becomes small but does not cause strong aggregation. Conversely, if the sintering temperature is high, the primary particle diameter becomes too large and the titanium oxide of the present invention cannot be obtained. After this, if necessary, crush,
After sizing, Al, Si, Zr, Ti,
A hydrated oxide and / or oxide such as Zn may be coated.

It is considered that the fact that the titanium oxide used in the present invention is strongly cohesive is mainly derived from the above-mentioned production method. Although the details of the mechanism of the strong cohesion are not always clear, there is a state where the surface energy becomes very large at the stage of crystal growth in the hydrolysis or baking step, and it is considered that the particles are strongly aggregated at that time. .

In the cosmetic of the present invention, in addition to the above-mentioned strongly cohesive titanium oxide, powders (pigments, dyes, resins), oils, fluorine compounds, resins, surfactants and the like which are usually used in cosmetics,
UV protection agents, antioxidants, thickeners, preservatives, fragrances, humectants, biologically active ingredients, salts, solvents, chelating agents, neutralizing agents,
Components such as a pH adjuster can be simultaneously added.

Examples of the powder include dyes such as Red No. 104, Red No. 201, Yellow No. 4, Blue No. 1 and Black No. 401, lake dyes such as Yellow No. 4 Al Lake, Yellow No. 203 Ba Lake, nylon Powder, silk powder,
Urethane powder, Teflon powder, Silicone powder, Cellulose powder, Silicone elastomer,
Polymers such as chitin, chitosan, calcium alginate, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, colored pigments such as ultramarine and navy blue, white pigments such as titanium oxide and cerium oxide, talc and mica , Pearl pigments such as mica titanium, metal salts such as barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate and magnesium silicate, inorganic powders such as silica and alumina, fine particles of titanium oxide and fine particles Zinc oxide, particulate iron oxide, alumina-treated particulate titanium oxide, silica-treated particulate titanium oxide, bentonite, smectite, and the like. The shape and size of these powders are not particularly limited. Of these, the use of a combination of strongly cohesive titanium oxide and an inorganic UV protection component such as fine particle titanium oxide and fine particle zinc oxide is preferred from the viewpoint of improving the UV protection effect.

The above-mentioned powder may be subjected to various conventionally known surface treatments, for example, silicone treatment, silane treatment, fluorine compound treatment, oil treatment, metal soap treatment, wax treatment, N
-An acylated lysine treatment, a water-soluble polymer compound treatment, a resin treatment, a metal oxide treatment, a plasma treatment, a mechanochemical treatment, a tackifier treatment or the like may or may not be performed.

Examples of oils include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyl dodecanol, fatty acids such as isostearic acid, undecylenic acid and oleic acid, glycerin, sorbitol, ethylene glycol, and the like. Polyhydric alcohols such as propylene glycol and polyethylene glycol, myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyldecyl dimethyloctanoate, glyceryl monostearate, glyceryl diethyl phthalate,
Esters such as ethylene glycol monostearate and octyl oxystearate, hydrocarbons such as liquid paraffin, petrolatum, squalane, waxes such as lanolin, reduced lanolin, carnauba wax, mink oil, cocoa butter,
Fats and oils such as coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, and olive oil, and ethylene / α-olefin / co-oligomers.

Examples of other forms of oils include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, and fluoroalkyl / polyoxyalkylene co-modified organopolysiloxane. , Alkyl-modified organopolysiloxane, end-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone, amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid, silicone RTV rubber and other silicone compounds, perfluoropolyether And fluorine compounds such as pitch fluoride, fluorocarbon, fluoroalcohol and fluorinated silicone resin.

As the surfactant, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine surfactant can be used.

As the solvent, purified water, ethanol, light liquid isoparaffin, lower alcohol, ethers, L
Examples include PG, fluorocarbon, N-methylpyrrolidone, fluoroalcohol, perfluoropolyether, CFC substitute, volatile silicone, and the like.

Examples of the ultraviolet absorber which is an organic ultraviolet protective agent include, for example, paramethoxycinnamic acid 2
-Ethylhexyl, 2-ethylhexyl paradimethylaminobenzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2'-dihydroxy-4-methoxybenzophenone, p-methoxyhydro Cinnamic acid diethanolamine salt, para-aminobenzoic acid (hereinafter abbreviated as PABA), homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,
3-diphenyl acrylate, octyl dimethyl PAB
A, octyl methoxycinnamate, octyl salicylate,
2-phenyl-benzimidazole-5-sulfuric acid, triethanolamine salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ′, 4,4′-tetrahydroxybenzophenone, , 2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, 4- (3,4
-Dimethoxyphenylmethylene) -2,5-dioxo-
2-ethylhexyl 1-imidazolidinepropionate,
These polymer derivatives are exemplified. When these ultraviolet absorbers are used in combination with strongly cohesive titanium oxide or an inorganic ultraviolet protective agent, they are effective in improving the ultraviolet protective ability of the product.

In the cosmetic of the present invention, it is preferable to use an antioxidant in combination in order to prevent deterioration of other components due to photocatalytic activity such as zinc oxide powder. , For example, tocopherols, SOD,
Plants such as phenols, terpenes, butylhydroxytoluene, vitamin C, vitamin E, catechins, glucose, hyaluronic acid, β-carotene, tetrahydrocurcumin, tea extract, sesame extract, anthocyanins, glycosides, etc. Conventionally known substances such as antioxidants can be used.

Examples of the cosmetics of the present invention include makeup cosmetics such as foundation, white powder, eyeshadow, eyeliner, cheek, lipstick, nail color, emulsions, creams, lotions, calamine lotions, sunscreens, and makeup bases , Suntan, after-shave lotion, pre-shave lotion, pack, cleansing, facial cleansing, anti-acne cosmetics and other basic cosmetics, hair color, body powder, deodorant, soap, body shampoo, bath salt, perfume, etc. .

In the cosmetic of the present invention, the compounding amount of the strongly cohesive titanium oxide is 0.1 to the total amount of the cosmetic.
It is preferably from 80 to 80% by weight, more preferably from 1 to 50% by weight.

The dosage form of the cosmetic of the present invention is a two-layer
Conventionally known dosage forms such as a water-in-oil emulsion, an oil-in-water emulsion, a gel, a spray, a mousse, an oil, and a solid can be used. In particular, solids, solid emulsions, gels, water-in-oil emulsions, oil-in-water emulsions, oils, mousses, and the like are preferable as foundation applications.

[0027]

The present invention will be described below in more detail with reference to production examples and examples. In addition, the evaluation method of the manufacture example used the method described above. The cosmetics were evaluated according to the following methods and criteria.

(1) Evaluation of Sensory Characteristics The sensory characteristics of the prototype (cosmetic) were evaluated using 20 specialized panelists. Evaluation items include "whether texture and wrinkles are not noticeable", "whether there is natural natural covering power",
The evaluation was performed on three items, "Is the feeling better?""Textures and wrinkles are not noticeable", "It has natural covering power",
+5 points for "excellent feel", "texture and wrinkles are noticeable",
"Whiteness is conspicuous" and "bad feeling" were set to 0 points, and the score was evaluated in a total of 4 levels, and the total score of all members was used as the evaluation result. Therefore, the higher the score, the higher the evaluation.

(2) UV Protective Effect The UV protective effect of the prototype (cosmetic) was evaluated using six specialized panelists. Cycling was performed outdoors during the day, and evaluation was performed according to the evaluation criteria shown in Table 1 from the state of sunburn. The evaluation result was the sum of the scores of all panelists. Therefore, the higher the score, the higher the UV protection effect.

[0030]

[Table 1]

Production Example 1 (Preparation of Strongly Cohesive Titanium Oxide) A nucleus obtained by neutralizing titanium tetrachloride with caustic soda in an aqueous solution of titanyl sulfate (200 g / l as TiO ₂ ) obtained by cooking ilmenite ore. Was added, and the mixture was hydrolyzed by heating at 110 ° C. for 3 hours to obtain an aqueous suspension containing hydrous titanium oxide. This aqueous suspension was filtered and sufficiently washed. The obtained washed cake is 700
By calcining at ℃ for 3 hours, titanium oxide was obtained. (Surface treatment) The titanium oxide was made into an aqueous slurry of 200 g / l, and aluminum sulfate and sodium hydroxide were added to coat the surface of the titanium oxide with hydrous aluminum hydroxide. The surface treatment amount was 5.0% by weight based on TiO _{2 in} terms of Al ₂ O ₃ . Thereafter, the slurry was filtered and washed, and the obtained washed cake was dried at 120 ° C. for 24 hours, and pulverized to obtain an anatase-type strongly cohesive titanium oxide used in the present invention.

Highly cohesive titanium oxide of Production Example 1, commercially available ultrafine titanium oxide (rutile type) (sample A), pigment grade titanium oxide (anatase type) (sample B), pigment grade titanium oxide (rutile type) (sample A) Table 1 shows the results of evaluation of the sample C) and the titanium oxide (rutile type) having an intermediate particle size (sample D). The crystal form of each sample was measured using a powder X-ray diffraction method. The transmittance was measured by coating each sample with the above-mentioned method, applying the sample to a cellulose triacetate film, and using a spectrophotometer (Shimadzu Corporation). UV-2200A, with an integrating sphere), and the transmittance at 300 nm was measured. Also,
Sample D was used by synthesizing a sample having a specific surface area of 12.7 m ² / g.

[0033]

[Table 2]

From Table 2, it can be seen that the strongly cohesive titanium oxide used in the present invention has a lower L value of the coating film than the existing pigment-grade titanium oxide (samples B and C), that is, has a low hiding power and an ultraviolet ray. It turns out that the shielding ability is high. Further, it can be seen that the b value of the coating film is higher than that of the ultrafine titanium oxide (sample A), that is, the blueness is small. Furthermore, even when compared with titanium oxide having an intermediate particle size (sample D), it can be seen that the hiding power is low and the bluish color is small.

Example 1 (Foundation) Using the strongly cohesive titanium oxide of Production Example 1, a high-cover type foundation was prepared according to the formulation shown in Table 3. All the pigments used were heat-treated pigments of 3% by weight of methyl hydrogen polysiloxane.

[0036]

[Table 3]

The components shown in Table 3 were mixed using a Henschel mixer, and then pulverized using an atomizer. Next, the product passed through the mesh was stamped on a metal plate using a metal mold to obtain a product.

Comparative Example 1 (Foundation) A product was obtained in the same manner as in Example 1 except that the silicone-treated, pigment-grade titanium oxide of Sample C was used instead of the silicone-treated strongly cohesive titanium oxide of Example 1. Was.

Comparative Example 2 (Foundation) A product was prepared in the same manner as in Example 1 except that the silicone-treated titanium oxide having an intermediate particle diameter of Sample D was used instead of the silicone-treated strongly cohesive titanium oxide of Example 1. Obtained.

Table 4 shows the evaluation results of the examples and the comparative examples.

[0041]

[Table 4]

From Table 4, it can be seen that Example 1 of the present invention has a natural skin covering power, a natural feel without any noticeable skin texture and wrinkles, an excellent feel, and a sufficient UV protection effect. It turns out. On the other hand, in Comparative Example 1 in which the conventional pigment-grade titanium oxide was blended, problems such as noticeable texture and wrinkles and whitening occurred,
The evaluation result worsened. Further, in Comparative Example 2 using the intermediate particle size titanium oxide, the texture and wrinkles were not noticeable, the feel was excellent, and it had a sufficient ultraviolet ray protective effect. They came out and couldn't get natural coverage.

[0043]

As described above, the cosmetic of the present invention, which contains a highly cohesive titanium oxide, has a natural skin covering power and is excellent in feel, without noticeable skin texture and wrinkles. And it has a sufficient ultraviolet protection effect.

Claims (4)

[Claims] (1) a primary particle diameter of 0.001 to 0.15 μm;
m, and a secondary particle diameter of 0.6 to 2.0 μm, and a crystal form comprising strongly cohesive titanium oxide having an anatase. 2. The method according to claim 1, wherein said titanium oxide has a high cohesive titanium oxide film.
The cosmetic according to claim 1, which is a highly cohesive titanium oxide having a value of 35 to 50 and a b value of -10 to 0. 3. The method according to claim 1, wherein the surface of the strongly cohesive titanium oxide particles is coated with Al,
The cosmetic according to claim 1 or 2, wherein the cosmetic is coated with a hydrated oxide and / or oxide of at least one element selected from the group consisting of Si, Zr, Ti, and Zn. 4. The surface of strongly coagulating titanium oxide particles is coated with at least one organic substance selected from the group consisting of silicone compounds, silanes, metal soaps, fluorine compounds, water-soluble polymer compounds, and N-acylated lysine. Claim 1
4. The cosmetic according to any one of 3.