JPS61194011A - Makeup cosmetic - Google Patents

Abstract

PURPOSE:The titled cosmetic having improved removing properties of contents, and improved deterioration of coloring material, oily component, perfume, etc., without losing hiding power of titanium dioxide of its own, obtained by using spherical titanium dioxide having a specific ratio of particles with the maximum diameter to particles with the minimum diameters and a specified average particle diameter. CONSTITUTION:A makeup cosmetic is blended with preferably 5-40wt% spherical titanium dioxide comprising >=70wt%, preferably >=85wt% particles with the minimum particle diameter based on particles with the maximum particle diameter, having 0.1-30mu average particle diameter, to give the cosmetic having hiding power of titanium dioxide of its own, good spread, not causing caking even in use with time in case of a compression molded article of middle pan, having improved removing properties of contents, and improved stability of color tone and smell, etc. The conventional blending ratio of titanium dioxide is <=10wt% in the case of toilet powder, and usually <=20wt% in the case of oily compact foundation since utility, etc., are damaged, but a blending ratio up to 50wt% can be attained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to makeup cosmetics that have concealing properties, are excellent in content removal and usability, and are excellent in stability of color tone, odor, etc. More specifically, the present invention has an average particle size of 0.1 to
To provide a makeup cosmetic which utilizes the advantages of conventional titanium dioxide and eliminates its disadvantages by blending true spherical titanium dioxide with a particle size of 30μ and a minimum particle diameter of 70% or more of the maximum particle diameter.

BACKGROUND OF THE INVENTION Titanium dioxide pigments usually do not have a specific particle shape and are lumpy particles.Both anatase and rutile types absorb almost no visible light and are white in color, with the anatase type having a refractive index of 2. 55 and 2.70 for the rutile type, both of which are the highest among white pigments. In addition, the particle size of commercially available titanium dioxide for pigments is in the form of fine particles (usually 0.1 μm) that have an ultraviolet absorption effect.
Generally, the anatase type has an average value of 0.
2μ, and an average of 0.25μ for the rutile type, and these are considered to be the particle sizes of titanium dioxide that have the greatest scattering effect.

As described above, titanium dioxide has a large scattering effect and a large refractive index, so it is particularly preferably incorporated into make-up cosmetics that require coloring power and hiding power.

However, in order to further improve the hiding power of a cosmetic using titanium dioxide, it is generally necessary to increase the amount of the titanium dioxide, although it depends on the particle size of the titanium dioxide. However, in this case, the adhesion of titanium dioxide powder to the skin is strong, making the cosmetics difficult to spread, and in the case of solid powder cosmetics that are compression molded into medium plates, etc., as they are used. This tends to cause the so-called caking phenomenon in which the surface of the puff hardens, resulting in poor puff quality. Furthermore, since titanium dioxide has surface activity, there is also the problem that it degrades the coloring materials and oils that are mixed with it.

All of the above-mentioned problems are caused by the basic characteristics of titanium dioxide powder itself, that is, the optical properties and particle shape as mentioned above, and in order to solve these problems,
Reduce the amount of titanium dioxide without losing its characteristics, use it in combination with other smooth powders (e.g. mica, nylon powder, etc.), and carefully examine the coloring materials, oils, fragrances, etc. that are added. I had to choose.

Problems to be Solved by the Invention The inventors of the present invention have made intensive studies to solve the above-mentioned drawbacks of conventional titanium dioxide, and have found that the particles have a true spherical shape with a minimum diameter of 70% or more of the maximum diameter, and Average particle size is 0.1-3
It was discovered that the above-mentioned problems could be solved by blending titanium dioxide with a particle size of 0μ, and the present invention was completed.

Means for solving the problem, the present invention provides true spherical particles with a minimum diameter of 70% or more, preferably 85% or more of the maximum diameter, and an average particle diameter of 0.1
By blending titanium dioxide with a particle size of ~30μ, the product spreads well without losing its original concealing properties, and in the case of compression molded inner plates, it does not cause caking even after use over time, and the content remains good. The present invention provides a makeup cosmetic that does not cause deterioration of coloring materials, oils, fragrances, etc., which are mixed at the same time.

The configuration of the present invention will be explained in detail below.

Conventionally, the amount of titanium dioxide added to powder white powder, solid white powder, solid foundation, solid eye shadow, emulsified foundation, lipstick, blusher, etc. is usually 10% by weight or less, and it is also used in oil-based compact foundation and sticks. The amount of titanium dioxide blended into stick foundations, stick eye shadows, etc. is usually about 20% by weight or less, but according to the present invention, the amount of titanium dioxide can be up to 50% by weight, preferably 5% by weight.
It can be blended in an amount of up to 40% by weight.

True spherical titanium dioxide having a minimum diameter of particles of 70% or more, preferably 85% or more of the maximum diameter, which is blended into the makeup cosmetic of the present invention, can be prepared, for example, as follows.

That is, an aqueous solution of titanium salt, for example, an aqueous solution of titanium tetrachloride or titanyl sulfate, is hydrolyzed in the presence of an alkali or by heating, washed with aqueous ammonia, and then a dispersant such as an inorganic electrolyte or a water-soluble polymer is added. A fine titanium sol is produced, and an emulsifier such as a surfactant, for example a nonionic surfactant such as polyoxyethylene glycerin fatty acid ester, is added to this, an organic solvent such as hexane is added, and the mixture is heated using a homomixer etc. A W10 type emulsion is prepared by mechanical force. A hardening agent such as formaldehyde, acetaldehyde, or lecithin is added to this titanium sol emulsion, which is then filtered and dried. In some cases, the desired true spherical titanium dioxide can be obtained by firing at a temperature of 200 to 900°C. At this time, particles of various sizes can be obtained by changing reaction operating conditions and raw materials (hereinafter referred to as the emulsion method).

In addition, volatile liquid titanium (IV) compounds, such as titanium isopropoxide, titanium ethoxide, titanium bentoxide, etc., can be heated and evaporated and brought into contact with water vapor droplets to instantly hydrolyze the volatile liquid titanium. , becomes titanium hydroxide. This product is heated to a temperature of 200-1000
By firing at ℃, the desired true spherical titanium dioxide can be obtained. At this time, particles of various sizes can be obtained by changing the reaction operating conditions and raw materials (hereinafter referred to as the steam contact method).

An electron micrograph showing the crystal structure of the titanium dioxide used in the make-up cosmetics according to the present invention obtained in this way is shown in FIG. The properties are shown in Table 1.

Margin below *1: Measured by B, E, T method using Shimabara Micromeritex, Rapid Surface Area Analysis 2200 (units, (/g, gas used: nitrogen) *
2: To measure the coefficient of dynamic friction, stick a double-sided adhesive tape on a horizontally installed iron plate, place a sufficient amount of the sample on it, and apply a load (5 to 10
The stress was measured using a strain gauge when the sample was moved at a speed of 10 mm per second by applying 0 g/cJ). measurement).

*3: Titanium dioxide A to E in Table 1 were prepared as follows or the following commercially available products were used.

A: Manufactured by steam contact method, titanium ethoxide 5
00gr was heated to 200°C, and the generated steam was sent through a helium gas carrier at a flow rate of 200 ml/win to cause a contact reaction with water vapor. Send a helium gas carrier until the titanium ethoxide liquid runs out.
Reacted with water vapor. The resulting atomized white fine powder was collected and calcined at 500°C for 2 hours to form true spherical titanium dioxide L.
Obtained 30gr.

B: Manufactured by emulsion method, containing 1/2 mol of T
Add 1/2 mol of Na to the iCl4 aqueous solution 11 with stirring.
2 Aqueous CO3 solution was added to adjust the pH to 7, followed by hydrolysis. The generated titanium hydroxide is washed with water, and further 1/1O
A molar Na40H* solution was added and washed with water.

Add purified water to the generated titanium hydroxide to make a total amount of 300-
And so. Add to this 2% polyvinyl alcohol aqueous solution 150
- was added to produce a titanium sol. After adding 10% polyoxyethylene glycerin fatty acid ester and n-hexane 1500% to the amount of the produced titanium sol to form a W2O type emulsion in a homomixer,
In addition, 1% of the amount of titanium sol produced is added as a hardening agent for the emulsified particles.
% formaldehyde was added. 700℃ after filtration and drying
The mixture was fired for 2 hours to obtain 38 gr of perfectly spherical titanium dioxide.

C: National Lead
) Titanium dioxide #328 manufactured by Laporte Corporation D: Titanium dioxide VC manufactured by Laporte Corporation E: Titanium dioxide P-25 manufactured by Degussa Corporation As is clear from the results in Table 1, compared to conventional titanium dioxide, the carbon dioxide used in the present invention Titanium has a very small coefficient of dynamic friction and is extremely easy to use, especially in terms of slippage. This is due to the fact that the particle shape of the titanium dioxide used in the present invention is perfectly spherical. As mentioned above, when trying to produce cosmetics with concealing properties, when conventional titanium dioxide is blended, the cosmetics have sufficient concealing properties as intended but do not spread very well. It has been extremely difficult to prepare cosmetics that are easy to use and spread easily. However, when spherical titanium dioxide according to the present invention was used, the spreadability was quite good even when the amount of titanium dioxide was increased, which broke the conventional concept of blending titanium dioxide.

Since the titanium dioxide blended into the makeup cosmetic according to the present invention is perfectly spherical, when a powder product is compression molded into an inner tray, a suitable amount of voids are created in the product, and as a result, a considerable amount of titanium dioxide ( For example, even when 20 to 50% by weight was added, the cosmetic did not cause any caking when used over time. In this way, 20 to 50 titanium dioxide
The fact that it can be blended in % by weight and does not cause caking also breaks the conventional concept of titanium dioxide.

Furthermore, the titanium dioxide used in the present invention has a low surface activity, and therefore has the feature of being extremely stable even when coexisting with colorants, oils, and fragrances.

In contrast, in the case of conventional titanium dioxide, dyes and organic pigments that are blended at the same time often fade, oils and waxes with double bonds deteriorate, and odor changes occur. Ta.

Table 2 shows the titanium dioxide used in the present invention, the conventional titanium dioxide, and a trace amount of fragrance (bergamot oil 0.
1%) and Red No. 202 (0,5%) in castor oil (roll milling) at room temperature (R, 7,2
5°C), 40°C, and 90% humidity for one month.

The standard product for comparison was kneaded under the same conditions immediately before the judgment.

*1: Sensory evaluation (The odor of fragrance and castor oil was evaluated in comparison with standard products using the following criteria.) ○... Not at all △... Slightly present ×... Obviously present *2: Sample was placed in a glass cell, and the color was measured using a Hitachi Color Analyzer 607. The difference in color (color difference) from the standard product was calculated.

*3: See Table 1 (margin below) As is clear from the results in Table 2, in the case of the titanium dioxide of the present invention, there was extremely little deterioration of castor oil and perfume, and there was almost no fading of Red No. 202. On the other hand,
In the case of conventional titanium dioxide, castor oil and fragrance deteriorated, and the color of Red No. 202 also deteriorated significantly.

The makeup cosmetic according to the present invention is used for the skin,
Including all cosmetics for the purpose of protection and makeup,
Cosmetics may contain optional raw materials that are commonly added to conventional cosmetics, such as various oils, surfactants, powders, water-soluble polymers, preservatives, drugs, pigments, fragrances, humectants, and water, as necessary. can be blended. Examples of such raw materials include oils such as liquid paraffin, petrolatum, paraffin wax, squalane, beeswax, aluna wax, olive oil, lanolin, higher alcohols, fatty acids,
Oils commonly used in cosmetics such as synthetic ester oils of higher alcohols and fatty acids are used, and surfactants include polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, and glycerin. Nonionic surfactants such as fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, fatty acid soap such as sodium stearate, triethanolamine palmitate, etc. Surfactants commonly used in cosmetics such as anionic surfactants, cationic surfactants, and amphoteric surfactants are used, and water-soluble polymers include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, polyvinyl alcohol, and polyvinylpyrrolidone. , tragacanth gum, carrageenan, locust bean gum, dextrin, dextrin fatty acid ester, carboxyvinyl polymer, xanthine gum, gelatin,
Water-soluble polymers commonly used in cosmetics such as sodium alginate and gum arabic are used, and moisturizers include sorbyl, xylitol, glycerin, maltitol, propylene glycol, 1,3-butylene glycol, 1, Moisturizing agents commonly used in cosmetics such as 4-butylene glycol, sodium pyrrolidonecarboxylate, lactic acid, sodium lactate, and polyethylene glycol are used, and preservatives such as roseoxybenzoic acid alkyl ester, sodium benzoate, and potassium sorbate are used. Preservatives commonly used in cosmetics are used, and drugs commonly used in cosmetics include vitamins, herbal medicines, anti-inflammatory agents, and disinfectants.Powders include talc, kaolin, sericite, and muscovite. , synthetic mica, phlogopite, red mica, biotite, lithian mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, strontium citrate, tungstic acid Metal salts, α-iron oxide,
Inorganic powders such as hydrated iron oxide, silica, hydroxyapatite, nylon powder, polyethylene powder, benzoguanamine powder, tetrafluoroethylene powder, distyrene benzene vinyl polymer powder, microcrystalline cellulose and other organic powders, titanium oxide, oxidized Inorganic white pigments such as zinc, inorganic red pigments such as iron oxide (red iron oxide) and iron titanate, inorganic yellow pigments such as yellow iron oxide and ocher, inorganic purple pigments such as mango violet and cobalt violet, chromium oxide, Inorganic green pigments such as chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and navy blue, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, fish scale foil, colored oxidation Pearl pigments such as titanium coated mica Metal powder pigments such as aluminum powder and cumber powder are used, and the pigments include red 10
No. 4, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red No. 202, Red No. 226, Red No. 227, Red No. 230, Orange No. 206, Orange No. 207, Yellow 202
No., Green No. 201, Green No. 204, Blue No. 201, Green No. 205, tar pigments, carminic acid, laccaic acid,
Lakes of natural pigments such as calsamine, brasillin, and crocin are used.

Examples Next, the present invention will be explained in more detail with reference to examples.
It goes without saying that the scope of the present invention is not limited to these Examples. In addition, the compounding amount is weight%.

Example 1: Solid foundation ingredient wt% mica
40 Talc 15 True spherical titanium dioxide 30 (average particle size 0.
4μ) Iron oxide 3゜5 Liquid paraffin 6 Lanolin
4 Sorbitan Sesquiolate 1.5 Flavor Appropriate amount Preservative While mixing mica talcum, titanium dioxide, and iron oxide with a Henschel mixer, the remaining ingredients were gradually added. Next, it was crushed and compression molded into a predetermined medium plate to obtain a solid foundation.

The true spherical titanium dioxide used in the above formulation was produced by the steam contact method described above, using titanium methoxide.
The heating temperature was 300° C., and the other conditions were the same as those for spherical titanium dioxide A shown in Table 1.

Comparative Example 1: Solid Foundation In place of the true spherical titanium dioxide in Example 1, titanium dioxide A-110 manufactured by Ishiya Sangyo (average particle size 0° 4μ) was used.
) A solid foundation was produced in the same manner as in Example 1 except that the following was used.

Comparative Example 2: Solid Foundation A solid foundation was produced in the same manner as in Comparative Example 1 except that the amount of titanium dioxide was 15% and the amount of mica was 55%.

The various physical properties of the solid foundations produced in Example 1, Comparative Example 1, and Comparative Example 2 were as shown in Table 3.

*1: UES) Using an IIMA hardness needle and a load of 1 pound, measure at 5 locations on the press surface and average. The smaller the value, the harder it is.

*2: Removal to urethane puff ○: J amount of contents can be removed.

△: There is little looseness.

×: *3:○: Can be applied lightly and smoothly to the face.

△: Slightly slow spread.

×: Spreads slowly.

*4: Coverage When applied to the face: ○: Almost hides the color of the face, giving a finish close to the color of foundation.

×: The color of the face remains as it is, and the finish does not show the color of the foundation.

Measurements of *2, *3, and *4 were based on sensory evaluation by 10 expert panels.

Comparative Example 1, which contained 30% of conventional titanium dioxide, was hard;
What's wrong with the contents? Comparative Example 2, in which the amount of titanium dioxide was reduced in order to improve the content, resulted in insufficient coverage.

Furthermore, when conventional titanium dioxide is blended, caking occurs over time and it is difficult to apply to the puff. In Example 1, in which the titanium dioxide of the present invention was blended, no caking occurred over time, even though the blended amount was as high as 30%. Covering power is also sufficient. Furthermore, Example 1 has extremely light spreadability during application.

Example 2: Oil-based stick eyeshadow ingredients
weight% kaolin
15 Mica 10 True spherical titanium dioxide 10 (average particle size 0.
1μ) Yellow iron oxide 3 Black iron oxide 1 Ultramarine 8 Scrawane 39゜5 Isopropyl myristate 7 Sorbitan monooleate 1
．． 2 Polyethylene wax 4 Carnauba wax
1.3 Fragrance
The entire amount of oil/wax was charged into a pot and heated at 85°C to dissolve it transparently.Next, powder was added thereto and well dispersed. Note that the powder may be mixed and pulverized in advance. Finally, a fragrance was added, and the mixture was filled into a predetermined container at 80° C. and cooled to produce the desired oily stick eye shadow.

The titanium dioxide used was produced by the vapor contact method described above, and was the same as spherical titanium dioxide A on page 1 of Table 1, except that titanium ethoxide was heated and evaporated at 200°C, and the flow rate of the He carrier gas was 300 mg/win. Manufactured under the same conditions.

Comparative Example 3: Oil-based stick eyeshadow In Example 2, titanium dioxide was replaced by Degussa and K.

An oil-based stick eye shadow was produced in the same manner as in Example 2, except that titanium dioxide P-25 (average particle size: 0.03 μm) was used.

The oil-based stick eye shadow produced in Example 2 spread easily and had no odor or color change over time, but the stick eye shadow of Comparative Example 3 spread slightly poorly and did not spread well over time even when unused. A slight off-odor (rancid odor of souffle) was observed in Kezuki.

Example 3: Solid blush component Weight% talc
55 Mica 20 True spherical titanium dioxide 10 (average particle size 3μ
) Liquid paraffin 4 Lanolin 0.7 Red 202
No. 0.3 fragrance
Appropriate amount of preservative: While thoroughly mixing the powder part with a blender, an oil part heated to 80''C was added, and after mixing, it was pulverized.

These pulverized products were compression molded into a predetermined container to produce a solid blush.

The blended true spherical titanium dioxide was manufactured by the emulsion method described above, and the manufacturing conditions were exactly the same as those for the No. 1 surface-layered spherical titanium dioxide B.

Comparative Example 4: Solid blush Example 3 except that titanium dioxide in Example 3 was replaced with commercially available anatase titanium dioxide (average particle size 3μ)
A solid blush was produced in the same manner as above. The blush produced in Example 3 spread well, did not cause caking over time, and did not cause the organic pigment (Red No. 202) to discolor or fade.
The blush of Comparative Example 4 was a little difficult to spread, and caking occurred three weeks after use, and the color of Red No. 202 was noticeably faded. In addition, as a result of color measurement using a Hitachi color analyzer,
The color difference after several months was 1.2 for the blusher of Example 3 and 4.7 for the blusher of Comparative Example 4.

Example 4: Emulsified foundation ingredient Weight %■ Stage? Phosphoric acid 0.4 ■ Isostearic acid 0.3 ■ Isopropyl myristate 4 ■ Sclawane 1
2 ■POEα0) Stearyl ether 2 ■ Cetyl alcohol 033 ■ True spherical titanium dioxide 5 (average particle size 28 μ) ■ Talc 10 ■ Iron oxide pigment 3 [Phase] Preservative
0303 ■ Triethanolamine
0.420 propylene glycol
50 Oval water 57.19 ■Fragrance 0.3 After heating and dissolving the above bottom portions ■ to ■ at 85°C, components ■ to ■ were added and uniformly dispersed. A mixture of components [phase] to 0 dissolved by heating at 85° C. was gradually added thereto and emulsified. Thereafter, the mixture was stirred and cooled to 45°C.

Add ingredient (■) to this, stir and cool to 35℃, and take out.
Filled the container. The true spherical titanium dioxide was prepared by the above-mentioned emulsion method, and polyoxyethylene sorbitol fatty acid ester and benzene were used together when making the W2O type emulsion. Other conditions were the same as those for spherical titanium dioxide B on page 1 of Table 1.

The emulsified foundation thus obtained was light and spreadable.

Example 5: Lipstick ingredients Weight %■Polyethylene wax 3■Serecine wax
4■Microcrystalline wax 4
■Carnauba wax 2■Kyandelilla wax 5■Liquid paraffin
15 ■ Castor oil 25 ■
Di-2-hebutylundecane 30 acid glycerin ■ Red iron oxide 0.2 [Phase] True spherical titanium dioxide 3 (average particle size 13 μ) ■ Red No. 202 1 @ Yellow No. 4
0.80 Titanium cochoid mica 7. Antioxidant Amount [Phase] Fragrance The above components (1) to (2) were placed in a pot and melted at 90°C.

Ingredients ① to ① and ＠■ were added to this and uniformly dissolved at 80 to 85°C. Next, components ① to 0 were added and dispersed at 85°C. After degassing, the mixture was poured into a designated container and solidified in a bath. The true spherical titanium dioxide was prepared by the emulsion method described above, and was produced under the same conditions as the spherical titanium dioxide B on page 1 of Table 1, except that lecithin was used in an amount of 0.6% of the amount of titanium sol produced as a hardening agent.

The lipstick thus obtained was light and spreadable.

[Brief explanation of drawings]

Figure 1 shows true spherical titanium dioxide (
This is an electron micrograph (3000x magnification) showing the crystal structure of spherical titanium dioxide B) on page 1 of Table 1.

Claims (1)

[Claims] 1. A makeup cosmetic characterized by containing true spherical titanium dioxide having an average particle size of 0.1 to 30μ, in which the minimum particle size is 70% or more of the maximum particle size.