Abstract:
Method for producing powder-based solid cosmetic by mixing powdered cosmetic ingredients and organic bentonite with a volatile chlorofluorohydrocarbon-containing solvent and then shaping and drying the mixture. This method produces makeup cosmetics having no oily, sticky feeling and having excellent adhesiveness.

Description:
This application is a continuation of application Ser. No. 122,634, filed Nov. 12, 1987, which is a continuation of application Ser. No. 734,354, filed May 14, 1985, both now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to a process for producing a powder-based solid cosmetic by solidifying powder particles with a binder, and a cosmetic product prepared by this process. 
     Conventional makeup cosmetics are prepared by mixing powdered cosmetic ingredients with fat or wax and shaping the resulting mixture. These conventional cosmetics are oily and sticky, and the makeup obtained upon application wears off rapidly. They also do not feel good to the makeup wearer, and do not have satisfactory adherence to the skin. Furthermore, these cosmetics containing fat or wax are formed by pressing the ingredients, or in the alternative, by heating the ingredients, handling them while they are in molten state to shape them, then cooling the obtained product. These steps are time-consuming and costly. 
     A process for producing a powder-based solid cosmetic has been proposed which consists of solidifying powdered cosmetic ingredients with a binder which is soluble in non-aqueous solvents such as methyl cellulose, rosin, shellac, wax, polyvinyl acetate, and acrylate polymer. This process, however, has a disadvantage in that the binder migrates in the drying step to form a film on the surface of the solid, and such film prevents the complete drying of the solid. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to obtain a powder-based solid cosmetic having adequate strength in its solid form, and giving a long-lasting makeup finish which has good adhesion to the skin, does not feel oily or sticky but feels good to the makeup wearer. 
     Another object of the present invention is to provide a process for producing a powder-based solid cosmetic which is easy to dry in the course of its manufacture. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In the process for producing a powder-based solid cosmetic according to the present invention, the above-described objects are achieved by mixing a powdered cosmetic composition and organic bentonite with a volatile solvent which is a chlorofluorohydrocarbon or consists essentially of such chlorofluorohydrocarbon, then shaping the resulting mixture, and drying the shaped cosmetic item. 
     The formulation used in this process contains the following essential ingredients: a powdered cosmetic composition which consists essentially of powdered cosmetic ingredients; organic bentonite; and a volatile chlorofluoro-hydrocarbon-containing solvent. With this formulation, it is believed that, upon reaction with the solvent, organic bentonite swells to form a network structure which exhibits an effective binder function, absorbs the powdered cosmetic composition, and retains its shape even after the solvent has evaporated. Thus, the powder-based solid cosmetic of this invention has the proper strength, hardness, and breakage resistance in its solid form, and yet it feels good upon use, has good adherence to the skin, and gives good makeup durability. 
     In a conventional process for producing a powder-based solid cosmetic, a binder is used which is soluble in the non-aqueous solvent used. As a result, a film tends to form on the surface of the cosmetic product during the drying step in the course of the manufacturing process. This problem is not encountered in the process of this invention because the organic bentonite used is not soluble in the solvent used. 
     Furthermore, when a binder which is soluble in a non-aqueous solvent is mixed with powdered cosmetic ingredients which are water-repellent, there is a tendency for the inside of the cosmetic item to be difficult to fix. This problem is not encountered in the process of the present invention because the organic bentonite has good miscibility with the water-repellent powdered cosmetic ingredients. 
     The process of this invention has additional advantages in that the chlorofluorohydrocarbon-containing solvent used is safe for workers and does not present a fire hazard, thus it can be removed simply by drying. 
     The powdered cosmetic composition used in this invention consists essentially of powdered cosmetic ingredients. Examples of such powdered ingredients which are commonly used in makeup cosmetics are: white pigment such as titanium oxide, zinc oxide, zirconium oxide or the like; color pigment such as red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue, Berlin blue, chromium oxide, chromium hydroxide, carbon black, coal tar coloring material, natural coloring matter or the like; pearlescent pigment such as fish scale guanine, mica titanium, bismuth oxychloride or the like; metallic soap such as magnesium stearate, calcium stearate, aluminum stearate, zinc laurate, zinc palmitate or the like; extender pigment such as talc, kaoline, white mica powder, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, clay, starch, nylon powder, polyethylene powder or the like; metallic pigment such as aluminum powder or the like. 
     It is known that cosmetics which are improved in feeling, adherence and spreadability can be prepared with the above-mentioned powdered cosmetic ingredients if they have been surface-treated with a silicone such as methyl hydrogen polysiloxane, with metallic soap, or with salts of N-acyl amino acids, in particular salts of N-acyl-L-glutamic acid. Such treatment imparts a cosmetically desirable water repellency to the powdered cosmetic ingredients. In the process of this invention, the powdered cosmetic ingredients used may be of the treated or untreated variety, or a mixture of both. They may be properly formulated according to the type of cosmetics and their intended usage. 
     The organic bentonite used in this invention is prepared from bentonite by reacting with cationic surface active agent to form the thickening and gelation of non-aqueous solvent, and one which is conventionally used to prevent the precipitation of pigment and pearl essence in nail enamel. In this invention, however, it is used as a binder for the powdered cosmetic composition. It is believed that the organic bentonite swells, without dissolving in a solvent, to form a network which absorbs the powdered cosmetic composition and retains its shape after the solvent has been removed. 
     The powder-based solid cosmetic which contains organic bentonite as a binder has desired physical properties such as strength, hardness, and flexural resistance in its solid form. Upon use, this cosmetic has the characteristic of feeling good to the makeup wearer for a prolonged period. These effects are not observed when inorganic bentonite or a hydrophilic binder is used. 
     The organic bentonite used in this invention is not particularly limited. Commercially available organic bentonite can be used. Preferred examples of commercial products include &#34;Bentone&#34; made by National Lead Industries, Inc. (U.S.), &#34;S-ben&#34; made by Hojun Yoko Co., and &#34;Olben&#34; made by Shiraishi Kogyo Co. They are equivalent to stearalkonium hectorite (Bentone 27), quarternium-18 bentonite (Bentone 34), and quarternium-18 hectorite (Bentone 38), respectively, which are listed in the Cosmetic Ingredients Dictionary issued by CTFA (The Cosmetic, Toiletry and Fragrance Association, Inc.). 
     The proportion of organic bentonite in the formulation is generally in the range from 0.05 wt% to 40 wt% based on the quantity of powdered cosmetic composition used. The preferred range is from 0.1 wt% to 15 wt% for producing a powder-based solid cosmetic which has good strength and organoleptic properties such as touch, feel, adherence, and makeup durability. If the proportion of organic bentonite is less than 0.05 wt%, shaping is difficult and the resulting product is poor in strength even if shaping is possible. Organic bentonite in excess of 40 wt% gives a product which is poor in feel and touch. 
     Organic bentonite may be used in combination with solvent-insoluble microcrystalline cellulose or metallic soap which increases the strength and helps to maintain the shape of the product. 
     The volatile solvent used in the process of this invention is a volatile chlorofluorohydrocarbon, or consists essentially of such chlorofluorohydrocarbon. The chlorofluorohydrocarbon causes the organic bentonite to swell completely, thereby allowing the organic bentonite to act as a binder. 
     The solvent used in the process of this invention is low-boiling, has low toxicity, and is non-flammable. Therefore, its removal from the shaped cosmetic product can be done simply by drying. No specially adapted precautions or equipment are required since the solvent does present a health risk or a fire risk. 
     Suitable volatile chlorofluorohydrocarbons are 1,1,1- and 1,1,2-trichlorofluoroethane, with 1,1,2-trichlorofluoroethane being preferred. Commercially available solvents containing trichlorofluoroethane can be used. Examples of such commercially available volatile solvents include &#34;Fronshowa&#34; made by Showa Denko Co., &#34;Freon&#34; made by Mitsui Fluorochemical Co., &#34;Fronsolve&#34; made by Asahi Glass Co., and &#34;CG Trifron&#34; made by Central Glass Co., all being Japanese corporations. Table 1 shows the physical properties of some typical commercial solvents. 
     
                                           TABLE 1__________________________________________________________________________     FronshowaProduct Name     FS-3    CG Trifron A Fronsolve AE__________________________________________________________________________Molecular formula and composition     CCl.sub.2 F--CClF.sub.2              ##STR1##                           ##STR2##Molecular weight     187.38  --           --Boiling point     47.57° C.             43.9° C.                          44.7° C.Flash point *1     None    None         NoneToxicity *2     1000 ppm             ca. 1000 ppm ca. 1000 ppm__________________________________________________________________________ *1 The flashpoints (closed) of other solvents are as follows: Ethanol: 13° C., toluene: 4° C., trichloroethylene: none, and acetone: 18° C. *2 The maximum tolerance established by ACGIH. Values for other solvents are as follows: Ethanol: 1000 ppm, toluene: 100 ppm and trichloroethylene 100 ppm. *The flashpoint and toxicity of other solvents are shown to illustrate th advantages of the solvents used in this invention, with respect to the safety and health of workers. 
    
     The amount of volatile solvent in the cosmetic formulation is preferably in the rang of 0.3 to 6 times (by weight) the total amount of the powdered cosmetic composition and organic bentonite. If this ratio is less than 0.3 times, the formulation does not solidify readily. If this ratio is greater than 6 times, the formulation takes an excessively long time to solidify and the solvent is lost. 
     In addition to the above-mentioned essential ingredients, i.e., powdered materials, organic bentonite, and volatile chlorofluorohydrocarbon-containing solvent, the cosmetic formulation used in the process of this invention may be incorporated with a small amount of a polar substance such as propylene carbonate, ethanol and acid which enhances the binder effect of the organic bentonite. In addition, the formulation may be further incorporated with antiseptics, antioxidants, and ultraviolet absorbers which are commonly used to prevent degradation of the cosmetic with time. 
     EXAMPLES 
     The process of this invention is described with reference to the following examples and comparative examples, in which &#34;parts&#34; means &#34;parts by weight&#34;. It is to be understood that the invention is not limited to the described examples. 
     EXAMPLE 1 
     EYE SHADOW 
     
         ______________________________________Mica titanium          95 partsBentone 38             5 partsPerfume               quantity                 suitableFronsolve AE          400 parts______________________________________ 
    
     EXAMPLE 2 
     EYE SHADOW 
     
         ______________________________________Amino acid-treated titanium mica                     95 partsBentone 38                5 partsPerfume                  quantity                    suitableFronsolve AE             400 parts______________________________________ 
    
     EXAMPLE 3 
     ROUGE 
     
         ______________________________________Silicone-treated mica    22 partsSilicone-treated titanium mica                    22 partsSilicone-treated talc    34 partsSilicone-treated inorganic pigment                    8 partsSilicone-treated color pigment                    2.7 partsZinc stearate            10 partsS-ben                    1.3 partsPerfume                  quantity                    suitableAntiseptic               quantity                    suitableCG Trifron A             300 parts______________________________________ 
    
     EXAMPLE 4 
     FOUNDATION 
     
         ______________________________________Metallic soap-treated talc                   50 partsMetallic soap-treated sericite                   10 partsMetallic soap-treated mica                   20 partsSilicone-treated titanium oxide                   6 partsSilicone-treated red iron oxide                   2.3 partsZinc stearate           10 partsBentone 27              1.7 partsFronshowa FS-3          500 parts______________________________________ 
    
     The products in the above-mentioned four examples were produced as follows. First, the powdered materials and organic bentonite were thoroughly mixed. Then the proper amounts of perfume and antiseptic were added. Finally, the volatile chlorofluorohydrocarbon-containing solvent was added to make a uniform mixture. The mixture was shaped into a stick, 8 mm in diameter, by using a press molder, following by drying at 40° C. for solvent removal. Thus were obtained stick-shaped products. 
     COMPARATIVE EXAMPLE 1 
     COMPACT POWDER 
     
         ______________________________________Mica                   50.0 partsTalc                   2.0 partsTitanium oxide         15.0 partsRed iron oxide         20.4 partsLanolin                3.0 partsIsopropyl myristate    5.5 partsSurfactant             3.7 partsAntiseptic             0.1 partsPerfume                0.3 parts&#34;Isoper H&#34;*            20.0 parts______________________________________ *A synthetic volatile solvent derived from a petroleum hydrocarbon, boiling point 171-193° C., available from Humble Oil and Refinery Co. (USA) 
    
     COMPARATIVE EXAMPLE 2 
     EYE SHADOW 
     
         ______________________________________Mica                  59.3   partsPearl essence         15.0   partsInorganic pigment     15.0   partsLanolin               4.5    partsSqualane              4.5    partsSurfactant            1.0    partAntiseptic            0.5    partsPerfume               0.2    partsIsopropyl alcohol     30.0   parts______________________________________ 
    
     The above-mentioned two comparative examples represent known formulations wherein fat or wax is used in the place of organic bentonite, and a volatile solvent is used which is not a volatile chlorofluorohydrocarbon-containing solvent. The products in these comparative examples were prepared as follows. First, the ingredients were uniformly mixed, and the mixture was shaped into a stick, 8 mm in diameter, by using an extruder, followed by drying at 60° C. for 24 hours. Thus were obtained stick-shaped products. 
     The powder-based solid cosmetics obtained in the above examples and comparative examples were subjected to a flexural test, disintegration test, and organoleptic test. The results are shown in Table 2. 
     
                       TABLE 2______________________________________  Examples          Comp. Examples  No. 1 No. 2   No. 3   No. 4 No. 1 No. 2______________________________________Flexural test    310      433      750   980 218   52(g)Disintegra-    433     1860    &gt;2000 &gt;2000 220   70tion (g)OrganoleptictestAdherence    Fair    Good    Good  Good  Poor  PoorSlip     Fair    Good    Good  Good  Good  PoorStrength Good    Good    Good  Good  Good  Break______________________________________ Flexural test: Measured with a rheometer, Model NRM3002D, made by Fudo Kogyo K.K. (distance between the supports: 20 mm; temperature: 30° C.) Disintegration test: Measured with the same rheometer as mentioned above. The sample stick, 8 mm in diameter, was cut into a 5 mm long piece, and the force required to crush the piece in the direction of the diameter wa measured.