JPS6019282B2 - cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides cosmetics, in particular, pigments that have colored gloss or colored high gloss, and both have transparency, and also prevent precipitation, segregation, color separation, and color. It does not cause stuffiness, and when used on the skin, it gives a sense of transparency, luster, and firmness, and the pigment spreads easily on the skin, especially when the pigment contains more than 1.5% of the pigment. This relates to a fender material that can be applied evenly and uniformly.

Titanium oxide coated mica, which is conventionally available to the public,
titanium oxide coated barium sulfate, titanium oxide coated talc, titanium oxide coated mica colored by containing iron oxide, or titanium oxide coated mica based pearl pigment or iris foil pigment in which the optical thickness of the titanium oxide layer is changed; is bismuth oxychloride coated mica,
Pearl pigments or iris foil pigments such as bismuth oxychloride are
When mixed together, pearl pigments exhibit a silver color, and iris foil pigments exhibit an iridescent color, but most pigments do not have sufficient transparency and clear color tone, and most of them only have glitter.

In particular, when the concentration of these pigments exceeds 3%, the influence of titanium oxide and bismuth oxychloride appears strongly, resulting in increased adhesion and extremely reduced transparency.Especially in the case of bismuth-based luster pigments, In cosmetics, the content is limited to 20% or less due to legal regulations, and it is impossible to use higher concentrations. In addition, although pearlescent pigments have glitter, they are not inherently transparent; for example, when applied to cosmetics, they provide a transparent luster and firmness that brings out the skin tone. It is difficult to obtain an effect. Furthermore, when colored pigments and iris foil pigments are used together, there is a disadvantage that the glossy pigments appear to stand out due to differences in affinity with the oil in the sebum or oil content, as well as differences in transparency and color tone, impairing the makeup effect. Furthermore, when colored pigments, especially organic pigments, are added in an amount of 1.5% or more to cosmetics, there are drawbacks such as the pigments not spreading well and not being applied uniformly to the skin. Furthermore, conventional pigments generally differ during production, storage, etc. due to differences in crystal form, affinity, specific gravity, particle size distribution, surface activity, etc.
Not only does it cause sedimentation, polarization, color separation, and color unevenness during transportation, which causes a decline in quality, but it also has drawbacks such as being subject to change over time when applied to cosmetics. The present invention aims to solve these problems and provide a cosmetic that has transparency, colored gloss or high colored gloss, spreads well, and does not change over time. It was invented for this purpose.

That is, in order to achieve this objective, the cosmetics according to the present invention:
Gel solutions of aluminum hydroxide or aluminum salts;
Finely powdered mica that is not coated with metal oxides: Acidic dyes and one or more mixed dyes of natural dyes; are mixed and reacted to deposit and form a thin film of dye-impregnated aluminum salt on the surface of finely powdered mica. The first feature is that a pigment having a colored luster and transparency is blended into the thin film. The second feature is that it contains a colored pigment that is coated on top and has high gloss and transparency.

In the present invention, finely powdered mica that is not coated with a metal oxide is used as described above, such as muscovite, sericite, rhodochite, synthetic mica, phlogopite, biotite, and licha mica (scale mica).
, soda mica, Chinwald mica, haloid mica, or modified versions of these are applied, and their content is 3 to 4%.
Impurities such as iron are removed by heat treatment at 40 to 60 oo using an aqueous solution of sulfuric acid, hydrochloric acid, nitric acid, or an inorganic acid such as chromic acid, and then washed and dried. do.

The fine powder mica preferably has a surface as smooth as possible, an average particle size of about 3 to 50 mm, and a thickness as thin as possible. For example, 0.05~0.
If a material with a thickness of about 51 is applied, a product with excellent transparency and gloss can be obtained, and in this case, if the average particle size is about 30 mm or more, it has transparency and at the same time has glitter and a metallic feel. Becomes a pigment. In addition, there are various acid dyes that can be applied to the present invention, but when considering application to cosmetics, Red No. 2, Red No. 3, Yellow No. 4, Yellow No. 5, Green No. 3, and Blue No. 1 are considered. , Blue No. 2, Red No. 227, Red No. 203
-No. 1, red No. 203-2, red No. 232, clear color 205
No., clear color 207, yellow 202-1, yellow 202-2
No., Yellow No. 203, Green No. 201, Green No. 204, Green No. 205, Blue No. 205, Brown No. 201, Red No. 401, Red No. 405, Red No. 503, Red No. 504, Red No. 5
No. 06, clear color No. 402, yellow No. 402, yellow No. 403-1
Yellow No. 406, Yellow No. 407, Green No. 402, Purple No. 401, Black No. 401, etc. are preferred, and other edible natural pigments such as carminic acid, laccaic acid, praziline, crocin, and calsamine, which are currently commercially available, are also applicable. can.

Furthermore, any acidic dye other than those mentioned above may be used as long as it forms an aluminum salt, and one or a mixture of two or more of these dyes may be used. Here, a specific example of a method for producing a pigment having colored luster and transparency to be used in cosmetics according to the first invention will be described below.

[Method 1] 1 part by weight of dry aluminum hydroxide gel (hereinafter abbreviated as DHAG) is suspended in 3 to 100 parts by weight of deionized water,
After flooding the mixture to 40-70qC and gradually adding 1-5 parts by weight of concentrated hydrochloric acid (36%), the temperature was maintained and the mixture was heated for 15-6 minutes to obtain a solution of 0.5-3.5. Make an aluminum hydroxide gel solution.

This gel solution contains 0.0% fine powder mica that is not coated with metal oxide.
1-5. 0.001 to 0.25 parts by weight of the dye was completely dissolved in deionized water to form a dye solution, and then the dye solution was gradually added, and the dye was co-immersed. The insoluble I-type aluminum salt is precipitated on finely powdered mica to form a thin film, and if necessary, the unevenness is adjusted to 3 to 8 and the liquid temperature is further raised to 50 to 8. The precipitate is matured by keeping it warm for 3 hours, left to cool, and then separated by furnace, washed with water, dehydrated with acetone, and air-dried to obtain the desired pigment. Here, DHAG
The smaller the ratio of mica to finely powdered mica, the easier the precipitate can be separated, and the resulting pigment is also brittle and easier to crush, resulting in increased gloss. [Method 0] 0 of aluminum salts such as potassium aluminum sulfate, sodium aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, sodium aluminate, etc.
．． Add 1 part by weight of finely powdered mica not coated with a metal oxide to 0.01 to 2.5 parts by weight of a 1 molar aqueous solution, and further add deionized water appropriately so that the finely powdered mica is uniformly suspended in water. adjust.

After thoroughly lighting the mixture, an alkaline dye solution dissolved in a warm alkaline solution such as IN sodium carbonate, caustic soda, or aqueous ammonia is gradually added to 0.001 to 0.25 parts by weight of the acid dye. The amount of alkaline solution at this time is equal to or up to twice the specified amount of aluminum salt used previously. This mixture is mixed to form a gel of the aluminum salt aqueous solution, and the insoluble aluminum salt impregnated with the dye is precipitated on the finely powdered mica to form a thin film. When the reaction is completed with sufficient precipitation, the gel solution is raised to 90°C, and the precipitate is aged at 60 to 80 qC for 3 to 3 hours. After cooling, the precipitate is separated in a furnace, washed with water, dehydrated with acetone, and air-dried. The desired pigment is obtained. The properties of the pigment obtained are similar to those obtained by method 1. [Method m
] After dissolving 0.001 to 0.25 parts by weight of the dye in a 0.1N heated alkaline solution, add 1 part by weight of finely powdered mica that is not coated with metal oxides and stir to disperse uniformly. Then, gradually add 0.01 to 2.5 parts by weight of a 0.1 molar aqueous solution of an aluminum salt as shown in the method below and mix.
By adjusting the pH to 4 to 8, the aluminum salt aqueous solution is gelled, and the insoluble aluminum salt impregnated with the dye is precipitated on the finely powdered mica to form a thin film.

The amount of alkaline liquid is the same as in method n, and the subsequent treatment is the same as in method 0, and the properties of the pigment obtained are the same as in the method described above. As is clear from the above method, the pigment used in the cosmetic composition of the present invention can be obtained in substantially one coating step by simply mixing the raw materials, and can be produced very easily.

The resulting colored glossy and transparent pigment is
It is not simply a process of depositing dye-adhered aluminum salt on the surface of finely powdered mica, but an extremely thin film of dye-impregnated aluminum salt is deposited, and this thin film is almost uniform. It attaches to the surface and behaves in unison with the fine mica powder. In general, aluminum lake remains in a gel-like state even after it is formed, making it difficult to heat it in a furnace, and it becomes a hard cake after drying, requiring a great deal of effort and special equipment to make it into a fine powder. The pigment used is brittle and can be easily pulverized, so it is pulverized by kneading it with the cosmetic ingredients and does not require a particular pulverization step. In addition, this pigment is well dispersed in the medium, and a glossy colored product that takes advantage of the spreadability and transparency of powdered mica can be obtained, and it does not cause polarization, color separation, color unevenness, or pigment sedimentation. It is. Furthermore, the vivid color tone of the dye is utilized, and by selecting the color tone of the dye, it is possible to obtain any color tone such as red, clear color, green, purple, flesh color, and others. Furthermore, the pigment used in the present invention has no skin irritation or toxicity, and in a training session in which it was applied to the frontal area of 88 women with healthy skin, no abnormalities were observed after 2 hours and 7 hours. I couldn't. The cosmetic composition of the present invention containing such a pigment exhibits a clear color tone, matches the appearance color of the product with the applied color, provides gloss, and is also excellent in heat resistance. Forced vibration test, aging test For example, no pigment sedimentation, segregation, color separation, or change in gloss tone is observed even after storage for 6 months at a temperature of 40 to 11 pi. Excellent stability and light resistance. was recognized.

Next, the pigment used in the ikesha material according to the second invention, which is the second feature of the present invention, is obtained by adding the pigment obtained by the above method to a water-insoluble resin, an alcohol-soluble resin, a water-impregnable resin, etc. A coating made by treating a coating agent consisting of one or a mixture of two or more types of cellulose in the presence of a volatile organic solvent, and which is deposited on the surface or thin film of the pigment. It uses a colored pigment with high gloss and transparency whose transparency and gloss are further increased by the synergistic effect of light reflection and refraction by the thin film of the agent.

Examples of water-resistant resins used in the production of this pigment include resins such as alkyd, polyester, acrylic, polyurethane, polyamide, epoxy, and cyclohexane, and examples of alcohol-soluble resins include methacrylic acid ester polymer, polyvinylpyrrolidone, Examples of resins include vinyl acetate copolymer, polyvinyl acetal diethylaminoacetate, phenol, sucrose fatty acid ester, sucrose benzoate ester, 2-methyl-5 vinyl-pyridine methyl acrylate methacrylic acid copolymer, and water-insoluble cellulose. Examples include ethyl cellulose, propyl cellulose, butyl cellulose, and benzyl cellulose.

Volatile organic solvents include acetone, ethyl acetate, and isof. Examples include propyl alcohol, ethyl alcohol, etc., and a coating agent selected from the above is added to the volatile organic solvent at 0.1 to 20%. About 5 to 4% by weight of the pigment used in the first invention was gradually added to the dissolved solution of about 5 to 4 weight % of the pigment used in the first invention, and the mixture was heated for another 10 minutes to 4 hours. In this case, the solvent is evaporated by overflowing, and a coating agent having a thickness of about 1 to 10 mm is formed on the surface of the pigment. This coating protects the pigment according to the first invention and further increases transparency and gloss. That is, the colored, high-gloss, and transparent pigments obtained by this method are not only more brilliant and lustrous than the pigments used in the Irihoko pigment of the first invention, but also have the same brittleness as these pigments. It is easily pulverized and dispersed by mixing and coagulating it with cosmetic ingredients without requiring any particular pulverization process.

Similar to the pigment used in the first invention, this pigment has no skin irritation or toxicity, and is similar to the pigment used in the first invention.
The cosmetic according to the second invention has the same characteristics as the cosmetic containing the pigments used in the first invention. Examples of producing pigments used in the cosmetics of the present invention are shown below. Production example 1 5 kg of DHAG was suspended in 50 k9 of deionized water, 5 k9 of concentrated hydrochloric acid (36%) was gradually added, and the mixture was kept warm at 40 oo.
After stirring for a while, an aluminum hydroxide gel solution with pH 3.0 was obtained.

250-350 mesh sericite 5K9 was flooded in a 4% aqueous hydrochloric acid solution for 30 minutes, washed with deionized water, dried, added to the aluminum hydroxide gel solution, and mixed uniformly, and then red. 604 No.50 deionized water 10X9
A dye solution dissolved in the liquid was gradually added, kept at 60 to 70°C, and stirred for 1 hour to deposit an insoluble aluminum salt thin film impregnated with red No. 504 on the surface of the fine powdered sericite, and then left to stand overnight. After leaving to cool, the precipitate is separated in a furnace, further washed with deionized water, and air-dried to form a brittle red luster in which a thin film of insoluble aluminum salt impregnated with red No. 504 is deposited on the surface of the finely powdered sericite. A transparent pigment with .

Production Example 2 0.5K9 of the pigment obtained in Production Example 1 was added to 5K9 of an inpropyl alcohol solution of 2% polyvinyl acetalized diethylaminoacetate, and after stirring for 3 minutes, the mixture was thoroughly evaporated while removing the volatile alcohol. A transparent pigment with red high gloss was obtained.

Production example 250-35 treated by incubating with 33% sulfuric acid aqueous solution at 60°C for 30 minutes, washing with deionized water, and drying.
1 kg of 0-mesh muscovite was added to 1 kg of a 0.1 mol sodium aluminum sulfate aqueous solution and stirred thoroughly to form a uniform dispersion.

1.0 mol caustic soda aqueous solution perfused to 40 qo
．． An alkaline dye solution obtained by dissolving 100 g of carminic acid in 6K9 was gradually added to the dispersion and mixed with Takaazusa until the pH was 6.
After gelling this mixture and precipitating a thin film of insoluble aluminum salt impregnated with carminic acid on the surface of finely powdered muscovite, the gel solution was heated to 90°C and then heated to 70 to 80 qo. The precipitate was kept for 1 hour, and then allowed to stand overnight, after which the precipitate was separated in a furnace, washed with deionized water, and air-dried to form a thin film of amorphous aluminum impregnated with carminic acid on the surface of the fine powdered muscovite. A transparent pigment with a brittle purple luster was obtained.

Production Example 4 Muscovite lk9 of 250-350 mesh, which had been heated at 50o0 for 40 minutes in a 3% nitric acid solution, washed with deionized water, dried and treated, was added to a 0.1 mol aluminum chloride aqueous solution 2X9 and thoroughly stirred. to make a uniform dispersion.

0.5 mol aqueous sodium carbonate solution heated to 40°C
．． A dye solution obtained by dissolving Red No. 2 No. 1 Yu and Yellow No. 2021 No. 2 No. 2 in 6 kg was gradually added to the dispersion liquid and mixed with the dyestuff to adjust the pH to 8. This mixture was gelatinized and powdered into fine powder. After precipitating a thin film of insoluble aluminum salt impregnated with Red No. 2 and Yellow No. 2020 on the surface of the mother,
The gel solution was raised to 80°C, then kept at 60°C for 1 hour, and then left to cool overnight. No. 2 and yellow 20
A transparent pigment with a flesh-colored luster and a brittle pigment in which a thin film of an insoluble aluminum salt was precipitated and formed by co-immersion with No. 2'1' was obtained.

Production Example 4' 1kg of the pigment obtained in Production Example 4 was added to 10k9 of a 3% butyl cellulose solution in isopropyl alcohol, and the mixture was left in the ocean for 3 minutes, after which the volatile alcohol was completely vaporized and a transparent pigment with a flesh-colored high gloss was obtained. I got the pigment.

Production example 5 0.5 mol of 2.5 ml of laccaic acid, a natural dye, 40
Aqueous sodium carbonate solution 0.3k9 and deionized water lk at °C
250 was treated by dissolving it in 9 and flooding it with a 3% aqueous sulfuric acid solution for 30 minutes at 6°C, then washing with deionized water and drying.
~350 mesh muscovite lk9 is added and stirred thoroughly to form a uniform dispersion.

To this dispersion, 0.5k9 of a 0.1 mol potassium aluminum sulfate aqueous solution was gradually added and mixed to adjust the pH to 8.
After gelling this mixture and precipitating a thin film of insoluble aluminum salt impregnated with laccaic acid on the surface of finely powdered muscovite, the gel solution was concentrated at 80 oo for 30 minutes, and then left to cool overnight. After that, the precipitate was separated in a furnace, washed with deionized water, dehydrated with acetone, and air-dried to make it brittle, with a thin film of unmoated aluminum salt mixed with laccaic acid precipitated on the surface of the finely powdered muscovite. A transparent pigment with pink luster was obtained. Production Example 6 1kg of the pigment obtained in Production Example 5 was mixed with 5kg of an inpropyl alcohol solution of 2% polypynylacetalized diethylaminoacetate.
and 2% butyl cellulose inpropyl alcohol solution 5K9, and after stirring for 3 powders, the volatile alcohol was completely vaporized to obtain a transparent pigment with pink high gloss.

Next, the results of performance experiments on the pigment used in the present invention will be shown.

[Experiment 1] The following experiment was conducted regarding the light resistance of the pigments used in the cosmetics of the first and second inventions.

Samples include Red No. 202, Yellow No. 4 Aluminum Lake, Yellow No. 5 Aluminum Lake, and the above Production Examples 1, 2, and 3.
, 4', 5, 6 each pigment A, B, C, E
, F" and "G" were used to calculate the color difference (△B) from that obtained by irradiating for 12 hours with a xenon tester manufactured by Shimadzu Corporation at a position 4 degrees from the light source. The results are shown in the following table.

From the above table it can be seen that it is possible to obtain pigments with better lightfastness than the pigments of the same day.

[Experiment 2] Comparative product (X) in which fine powder mica was mixed with red No. 504 aluminum lake, and the above-mentioned production examples 1, 2, and 4 according to the production method disclosed in JP-A-51-17910.
, 4', 5, and 6, and each control pigment (commercially available pearl pigment Thymilon M yen 119 product manufactured by Merck & Co., Ltd., mica scales coated with 27-31% titanium dioxide) Conventional products (A', B', D
', E', F', G', ) and Production Examples 1, 2, 4, 4'
The pigments (A, B, D, B, F, G) used in the present invention, which are composed of the pigments made by , 5 and 6, were tested using pressed powder to give a glossy feeling and a glittery feeling. The following table shows the results of a sensory test of , transparency (skin feel), and changes over time.

However, the subjects to be tested are 100 women. Moreover, the inspection method is as follows. Glossiness: Use regular emulsion as a base, apply pressed powder on top and check the gloss of the applied surface.

Glitter: Use an oil-rich foundation as a base, apply pressed powder on top, and check the quality of the gloss on the applied surface. Transparency: Observe after inspecting the glossiness.

When the skin was not visible due to presto powder, it was rated as ``fair'', and when the skin looked good, it was rated as ``Ryoichi''. A new I-Q surname correction and look at the difference between the left and right.

Slight differences were defined as "normal" and marked differences were defined as "excellent."From the above results, the cosmetic products using the pigments used in the present invention were superior in gloss and transparency compared to comparative products. , and it can be seen that there is little brightness and change over time.

In addition, the cosmetic products of the present invention are inferior to conventional products containing dye-containing luster pigments in terms of glossiness, but have less glitter, and it can be seen that there is a marked difference in change over time and transparency. Next, examples of the cosmetics of the present invention will be shown.

The blending ratio is shown in parts by weight. Example 1 Face/Guda talc 340 Orin 30A Sericite 50 Crystalline cellulose 40 Red glossy transparent pigment of Production Example 1 500B Mudo Gojiwo Chemi State Tsuma 3C Fragrance 3 Production method A with a capacity of 8 and a Henschel mixer for 50 pm The mixture mixed and dispersed for 2 minutes is pulverized using a pulverizer, and the mixture is mixed and dispersed.

The obtained pulverized material and B were mixed in a Henschel mixer at 20 pm.
After heating for 5 minutes, add to C, stir for 1 minute at 30 pm, and then fill into a container to prepare a product. Example 2 Pressed Powder A'Ashitemuro; Umstairt 6th Chamber Member L Red high-gloss transparent pigment of Production Example 2 200B Squalane 70C Fragrance
5 Production Method A was mixed for 30 minutes in a V-type blender with a volume of 5, and the mixture was pulverized and mixed in a pulverizer.

The pulverized mixture and B were mixed in a shell mixer with a capacity of 8 and 1
After stirring for 10 minutes at 20 pm, C was added, and after further stirring for 1 minute, the mixture was pulverized and dispersed using a pulverizer, and the pulverized product was filled into a medium tray to form a product.

Example 3 Ishiyado liquid paraffin 400 activator
5o solid paraffin
10A Sucrose fatty acid ester
40 power lunaba wax
15 Candelilla Wax 15B
{Setana Sakaki 4 Hishi C fragrance lo Manufacturing method Capacity 2 Gradually add B to A melted at 80o0 in the melting pot, disperse and defoam under vacuum, then add C while gently stirring. After it is completely dispersed, it is poured into a medium plate and cooled to form a product.

Example 4 Con/Guct Foundation Wood Wax 8o Lanolin
50 Ethylene glycol distearate 90A Microcrystalline wax 20 Isopropyl myristate 200 Liquid paraffin
40 butyl hydroxytoluene
0.5, activator 5
-Motor paraffin 310 activator
10.5B valve handle
8o titanium oxide
80C fragrance
3 o Production method Capacity 2 A was melted at 80 qo in the melting pot, and B was processed in a vibrating ball mill for 30 minutes to form a paste. C is added and dispersed to make it completely uniform, then it is filled into a container and cooled to form a product.

Example 5 Nail enamel A Tsuruwajito et al. Rokuko Vertical coating groove Nitrocellulose 10 Vinyl acetate 9 Dibutyl phthalate
3B Toluene
23n-phthyl acetate
20 ethyl acetate 6n
-Butanol 3 Production method Add B to A, which is dispersed and crushed for 30 minutes using a horizontal agglomeration machine, and stirred for 1 hour.Then, the product is prepared by filling into containers.

Example 6 Ivensil carbon black 0.
Titanium pentoxide 12 Ultramarine blue 10 Red No. 226
5 Pink high gloss transparent pigment of Production Example 6 15 Myristic acid
10 activators
7 zinc myristate
20 liquid paraffin 1
2 Candelilla wax 12 Ceresin 6 Butyl hydroxyl toluene 0.05 Production method The above mixture was dissolved and dispersed in a melting pot at 100q0, then kneaded three times with a Tsuru kneading roll, and then redissolved and dispersed in a melting pot at 100°C. Pour into a mold, cool to 40 qo, mold with an extruder, and store in a container to make a product.

Claims (1)

[Claims] 1. Gel solution of aluminum hydroxide or aluminum salt; fine powder mica not coated with metal oxide; one or more mixed dyes of acid dyes and natural dyes; 1. A cosmetic comprising, as a cosmetic ingredient, a pigment having colored luster and transparency, which is formed by depositing a thin film of an insoluble aluminum salt impregnated with a dye on the surface. 2 Gel solution of aluminum hydroxide or aluminum salt; finely powdered mica not coated with metal oxide; one or more mixed dyes of acidic dyes and natural dyes; impregnated with dye on the surface of finely powdered mica by mixing and reacting. A colored pigment having high gloss and transparency, which is obtained by depositing a thin film of an insoluble aluminum salt, and then coating the thin film with one or a mixture of two or more of water-insoluble resins, alcohol-soluble resins, and water-insoluble cellulose. A cosmetic product characterized by containing the following as a cosmetic ingredient.