JPH06102606B2 - Pigment composed of polyvalent metal salt of amidosulfonic acid and cosmetics containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a pigment comprising a novel polyvalent metal salt of amidosulfonic acid and a pigment containing the pigment, and has high spreadability (spreading) to the skin, strong adhesion, Smoothness, good finish, makeup hold,
The present invention relates to an excellent cosmetic having moldability, feeling of use and the like.

[Problems to be Solved by Prior Art and Invention]

Conventionally, water- and oil-insoluble cosmetic powder pigments include inorganic pigments such as talc and mica; inorganic coloring pigments such as titanium dioxide and zinc oxide; organic coloring pigments such as organic tar dyes; titanium mica composites. Chemical pigments; resin powders such as nylon powders; and coating-treated powders whose surfaces are treated with a known coating agent such as silicon have been used.

These are blended in an appropriate amount in consideration of the spreadability, stickiness, covering power, moldability, etc. of cosmetics, but in the cosmetics using conventional powders, spreadability, smoothness, adhesiveness, finish, It was not always satisfactory in terms of makeup lasting, stability and moldability. For example, in the case of powder cosmetics based on commonly used extender pigments such as talc and mica, talc or mica with a large particle size may be used in order to increase smoothness. There is a problem in that the adhesiveness, moldability, makeup lasting, etc. are lost. Spherical resin powder such as nylon powder or polystyrene powder is also used, but it has a strong bulkiness and poor adhesion, so it has flexibility in cosmetics,
It has a drawback that it cannot give a moist feeling, the cosmetic does not adhere well to the skin, and the moldability is deteriorated.

On the other hand, metal soap may be blended in makeup for the purpose of improving adhesion, moldability, and makeup lasting, but metal soap imparts satisfactory performance in terms of smoothness, adhesion, etc. Hard to say.

Therefore, a pigment capable of imparting good spreadability, smoothness, adhesiveness, finish, makeup retention, stability, moldability, and the like to cosmetics, and a cosmetic having excellent usability in combination with the pigment are desired. It was

[Means for Solving the Problems]

As a result of intensive studies conducted by the present inventors in view of the above situation,
The present invention has been completed by finding that a cosmetic containing a pigment composed of a polyvalent metal salt of amidosulfonic acid represented by the following general formula (I) has excellent properties such as spreadability, smoothness, and feeling of use. did.

That is, the present invention has the following general formula (I) [In the formula, R ¹ represents a linear or branched alkyl, alkenyl or hydroxyalkyl group having 7 to 21 carbon atoms, R ² represents a hydrogen atom or a methyl group, X represents an ethylene group, a propylene group or Where M represents a polyvalent metal atom, m represents a valence of M, and n represents an integer of 1 to 4] and a pigment comprising an amidosulfonic acid polyvalent metal salt represented by The present invention provides a cosmetic product characterized by:

Examples of the alkyl group represented by R ¹ in the general formula (I) include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, Examples thereof include an octadecyl group, a nonadecyl group, an eicosyl group, and a henicosyl group; examples of the alkenyl group include 2-heptenyl, 2-octene-8-ynyl group and 3,4-dipropyl-
1,3-hexadiene-5-ynyl group, 5,5-dimethyl-1
-Hexyl group, 4-vinyl-1-heptene-5-ynyl group, 5- (3-pentenyl) -3,6,8-decatriene-
1-ynyl group, 6- (1,3-pentadienyl) -2,4,7-
Dodecatriene-9-ynyl group, 2-nonyl-2-butenyl group and the like can be mentioned; as the hydroxyalkyl group,
Examples thereof include a hydroxyheptyl group, a hydroxydecyl group, a hydroxytetradecyl group, and a hydroxynonadecyl group. Further, as the polyvalent metal atom represented by M, Al, C
Examples thereof include a, Zn, Mg, Fe and Ti.

Further, since the amidosulfonic acid polyvalent metal salt (I) is used as a pigment component of cosmetics, it must be water-insoluble or sparingly soluble.

The amide sulfonic acid polyvalent metal salt (I) of the present invention can be produced, for example, in the same manner as a usual metal soap synthesis method. That is, for example, amidosulfonic acid (Wherein R ¹ , R ² and X are the same as above), the soluble metal salt is dissolved in water, and an aqueous solution of the water-soluble polyvalent metal salt is added to the solution in an approximately equal amount, and after salt exchange, By sufficiently stirring, filtering, washing with water, and then drying, the amide sulfonic acid polyvalent metal salt pigment of the present invention is produced. As the water-soluble polyvalent metal salt used here, for example, aluminum sulfate, aluminum chloride, aluminum nitrate, potassium aluminum sulfate, magnesium chloride, magnesium sulfate, magnesium nitrate, potassium magnesium sulfate,
Examples thereof include calcium chloride, zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, zirconium sulfate, zirconium chloride, titanium oxysulfate and titanium tetrachloride.

The longer the addition time of this water-soluble polyvalent metal salt, the larger the particle diameter of the polyvalent metal salt of amidosulfonic acid can be obtained.

The crystal powder of the polyvalent metal salt of amide sulfonic acid obtained can be needle-shaped, pomegranate-shaped, or plate-shaped crystals depending on the reaction conditions, the type of salt, etc., but especially when the plate-shaped crystals are mixed in a cosmetic, It is preferable because it is excellent in usability.

The thus-obtained polyvalent metal salt of amidosulfonic acid (I) may be blended as it is in a cosmetic composition, or may be used as a treated powder for hydrophobizing other pigments.

The particle size of the pigment of the amidosulfonic acid polyvalent metal salt (I) used in the cosmetics of the present invention is not particularly limited, but the average particle size (measured by SK laser manufactured by Seishin Enterprise Co., Ltd.) is preferably in the range of 0.1 to 50 μm. If it is smaller than 0.1 μm, smoothness is impaired, and if it is larger than 50 μm, it is rough. The polyvalent metal salt of amidosulfonic acid (I) is preferably blended in the cosmetic composition of the present invention in an amount of 0.1 to 99% by weight (hereinafter referred to simply as "%"). If it is less than 0.1%, the above-mentioned effects are not sufficiently exhibited.

In addition to the above-mentioned amide sulfonic acid polyvalent metal salt (I) pigment, the cosmetic of the present invention includes cosmetic powder normally used in cosmetics and various oil agents, surfactants, wetting agents, water as optional components. , Alcohol, an antiseptic, an ultraviolet absorber, an antioxidant, a fragrance and the like can be appropriately blended as necessary.

As the powder for cosmetics, any known powder can be used as long as the effects of the present invention are not impaired. For example, talc, kaolin, mica, sericite, inorganic extender pigments such as synthetic mica; titanium oxide, Inorganic colorants such as zinc oxide, ultramarine blue, chromium oxide and iron oxide; organic colorants such as organic tar dyes and lakes; composite cosmetics such as titanium mica and iron oxide coated mica; nylon powder, polymethylmethacrylate (PMMA) Spherical powders such as silica beads; and coating-treated powders obtained by treating the surface of these cosmetic powders with a known coating agent such as silicon, higher fatty acid, higher alcohol, ester, wax and the like. You may use these 1 type or in mixture of 2 or more types. Among these powders for cosmetics, when used as cosmetics such as makeup cosmetics and body cosmetics, talc, kaolin, salicite, mica, titanium oxide, iron oxide, mica titanium, iron oxide coated mica Inorganic powders such as

As an optional oil agent, liquid paraffin, petrolatum,
Paraffin wax, polyethylene wax, squalane, ceresin wax, beeswax, carnauba wax, candelilla wax, hydrogenated castor oil, olive oil, lanolin, lanolin alcohol, lanolin fatty acids, higher alcohols, fatty acids, synthetic ester oils of higher alcohols and fatty acids, silicones and the like; As the surfactant, anionic surfactant such as soap, alkyl sulfate, monoalkyl phosphate, etc., and polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester glycerin fatty acid ester Nonionic surfactants such as polyoxyethylene hydrogenated castor oil and polyoxyethylene sorbitol fatty acid ester; humectants such as sorbitol, glycerin, preservative Pyrene glycol, isopropylene glycol, 1,3-butylene glycol, lactic acid, sodium lactate polyethylene glycol, etc .; as preservatives, alkyl paraoxybenzoate ester, sodium benzoate, potassium sorbate, phenoxyethanol, etc .; as antioxidants Is tocopherol, sezamol, sezamoline, lecithin and the like; examples of the ultraviolet absorber include 2,4-dihydroxybezophenone and 2,2′-dihydroxy-4-methoxybenzophenone.
It is not limited to these.

The form of the cosmetic of the present invention is not particularly limited, and is prepared by a conventional method by arbitrarily combining the above components and the like to obtain a powder-based, oil-based, emulsified, solubilized or water-dispersed cosmetic. be able to. Specifically, powder foundation, eye shadow, emulsion foundation, lipstick, makeup base,
Cosmetics such as nail enamel, eyeliner, body powder, beber powder, and blusher can be used.

〔The invention's effect〕

The polyvalent metal salt of amidosulfonic acid of the present invention has extremely good slipperiness when blended into a cosmetic composition, has no roughness, has transparency, has a water-repellent method, and has strong adhesiveness, and can be further spread on the skin. Over time, it exhibits an extremely excellent effect of having a characteristic that it is moist, does not feel thick when applied, and repels water well.

In addition, it can be used as a powder for lubricants for plastic molding, extender pigments for coating, lubricants for coating paper / recording materials, lubricants for plastic processing of metals, etc. by utilizing the effect of improving slippage. it can.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Test Examples. The present invention is not limited to the following examples and can be applied to all makeup cosmetics.

(Manufacturing Example 1) 20 g of N-lauroyltaurine Na salt and 380 g of ion-exchanged water were put into a four-mouth frothco 1 equipped with a stirrer, a dropping funnel, and a thermometer to prepare a uniform solution. While stirring this solution
The mixture was heated to 40 ° C., and 135 g of a 5% calcium chloride aqueous solution was added dropwise from the dropping funnel over 15 minutes. Crystals of N-lauroyltaurine Ca salt were precipitated as in the case of dropping. After the dropping was completed, the mixture was further stirred at 40 ° C. for 1 hour to complete the salt exchange. After completion of stirring, the mixture was allowed to cool to room temperature, then filtered and washed. The obtained crystals were dried at room temperature to give 19.4% of white crystals of the target N-lauryl taurine Ca salt.
got g. Yield 98.9%.

Thus obtained N-lauryl taurine Ca salt was a plate crystal as shown in FIG. 1, when the shape was examined by a scanning electron micrograph.

Analytical value Measured value Calculated value ・ Elemental analysis Ca (%) 6.1 6.1 N (%) 4.3 4.3 ・ IR (cm ^-1 ) CON 1655,1580 SO ₃ 1210 ・ Particle size Average particle size 7.9 μm * Average particle size is Seishin SKLASER MICRON SIZ Co., Ltd.
Particle size distribution (μm) Fixed particle size volume cumulative distribution (%) 1.0 1.2 1.5 2.5 2.0 5.9 3.0 12.2 4.0 20.4 6.0 34.5 8.0 50.5 12.0 70.6 16.0 82.2 24.0 95.0 32.0 100.0 48.0 100.0 64.0 100.0 96.0 100.0 128.0 100.0 192.0 100.0 (Production Example 2) Into a four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer, 20 g of N-palmityl taurine Na salt and 380 g of deionized water were added to obtain a uniform solution. did. This solution was heated to 40 g with stirring, and 115 g of a 5% aqueous solution of calcium chloride was added dropwise from the dropping funnel over 15 minutes. Crystals of N-palmitoiutaurin Ca salt were precipitated at the same time as the dropping.
After the dropping was completed, the mixture was further stirred at 40 ° C. for 1 hour to complete the salt exchange. After completion of stirring, the mixture was allowed to cool to room temperature, then filtered and washed. The obtained crystal room temperature is dried at room temperature,
As a result, 19.5 g of white crystals of the desired N-palmitoiutaurine Ca salt were obtained. Yield 98.3%.

This was a plate crystal having an average particle size of 2.4 μm.

Particle size distribution: Particle size (μm) Fixed particle size Volume cumulative distribution (%) 1.0 9.0 1.5 20.4 2.0 40.4 3.0 66.5 4.0 82.5 6.0 95.3 8.0 100.0 12.0 100.0 16.0 100.0 24.0 100.0 32.0 100.0 48.0 100.0 64.0 100.0 96.0 100.0 128.0 100.0 192.0 100.0 (Production Example 3) By the same method as in Production Examples 1 and 2, a 5% aqueous barium chloride solution was added dropwise to a uniform aqueous solution of N-lauroy rotaurine Na salt to obtain white crystals of the target N-lauroy rotaurine Ba salt. Obtained. Yield 98.7%.

This was a plate crystal having an average particle size of 3.9 μm.

Particle size distribution: Particle size (μm) Fixed particle size Volume cumulative distribution (%) 1.0 7.7 1.5 14.4 2.0 24.5 3.0 39.9 4.0 50.8 6.0 64.0 8.0 74.5 12.0 85.0 16.0 91.4 24.0 98.2 32.0 100.0 48.0 100.0 64.0 100.0 96.0 100.0 128.0 100.0 192.0 100.0 Test Example 1 The relative friction coefficient of the polyvalent metal salt particles of N-amidosulfonic acid prepared in Production Examples 1 to 3 and the extender pigments of mica and sericite were measured. Relative friction coefficient was measured by using Shinto Chemical's surface powder tester Haydon Model 14 and a certain amount of the sample was applied to tracing paper, and the friction coefficient of the tracing paper itself was measured. The coefficient was used.

The results are shown in Table 1.

From this result, it can be seen that the friction coefficient of the present invention is small, and that the spreadability is good when blended in the cosmetic.

Example 1 Powder foundation <Formulation> (%) N-lauroy rotaurine Ca salt of Production Example 1 20 Talc Remaining amount Sericite 10 Titanium oxide 1 Bengala 1.5 Black iron oxide 0.2 Yellow iron oxide 2 Fine powder wax (press aid) 10 Fragrance 0.1 total 100 [Production Method] Powder components were mixed and pulverized, transferred to a Henschel mixer, and an oil agent and a fragrance were added and mixed to be uniform.
This was press-molded on a gold plate to obtain a product. The foundation thus obtained was excellent in feeling of spreading and the like, was also water-repellent, and was excellent in familiarity with the skin.

Example 2 Loose type face powder <Formulation> (%) N-palmitoiutaurin Ca salt of Production Example 50 50 Talc Remaining amount Titanium oxide 0.5 Bengala 0.1 Liquid paraffin 1 Perfume 0.1 Total 100 [Production method] Powder components are mixed and ground Then, this was transferred to a Henschel mixer, an oil agent and a fragrance were added and mixed evenly, and then passed through a sieve to obtain a product.

The loose type face powder obtained in this way is
It spreads well, and it was excellent without the powderyness found in conventional loose-type face powders.

Example 3 Oily foundation <Formulation> (%) N-lauroy rotaurine Ba salt of Production Example 3 20 Talc Remaining amount Kaolin 5 Titanium oxide 5 Bengala 1 Black iron oxide 0.1 Yellow iron oxide 0.6 Squalane 25 Isopropyl palmitate 15 Ceresin 7 Fragrance 0.1 total 100 [Production Method] The powder components were mixed and pulverized, and the powder components were separately heated and added to the dissolved oil phase component with stirring, and mixed so as to be uniform. This was filled in a gold plate and cooled to obtain a product. The oily type face powder thus obtained was excellent in the feeling of spreading and the like, was also water-repellent, and was excellent in the familiarity with the skin.

Example 4 Creamy foundation <Formulation> (%) N-palmitoyl tavernrin Ca salt 5 of Production Example 2 N-lauryl taurine Ba salt of Production Example 3 10 Titanium oxide 5 Bengala 1 Black iron oxide 0.1 Yellow iron oxide 0.6 Water residue Amount Preservative 0.1 Triethanolamine 1.2 Sorbit 3 Stearic acid 5 Lipophilic type glycerin monostearate 2.5 Cetostearyl alcohol 1 Propylene glycol monolaurate 3 Squalane 25 Olive oil 8 Fragrance 0.1 Total 100 [Manufacturing method] did. Separately water phase component ~
A solution was prepared by mixing, and a crushed pigment was added to disperse the solution and then heated to 75 ° C. What melt | dissolved the oil-based component ~ 80 degreeC by heating was added to the water phase adjusted previously, stirring, and was emulsified. This was cooled with stirring, a fragrance was added at 50 ° C., and cooled with stirring.

Example 5 Finishing powder <Prescription> (%) Mica residual amount N-laurylutaurin Ca salt of Production Example 1 50 Talc 20 Titanium oxide 0.5 Bengala 0.1 Yellow iron oxide 0.1 Black iron oxide 0.11 Liquid paraffin 8 Beeswax 2 Preservative A suitable amount of fragrance Trace amount Total 100 [Manufacturing] Ingredients (~) are mixed and ground. This is transferred to a high-speed blender, and components (1) to (8) are mixed and dissolved, and the mixture is uniformly mixed. The ingredients are added to this mixture, mixed and then ground again and passed through a sieve. This is further gold compression-molded.

Example 6 Cream foundation <Formulation> (%) Stearic acid 5.5 Lipophilic lipophilic glyceryl monostearate 2.5 Cetostearyl alcohol 1 Propylene glycol monolaurate 3 Squalane 7 Olive oil 8 Water balance Preservative Suitable amount Triethanolamine 1.2 Solbit 3 Titanium oxide Acid 10 Talc 5 Coloring pigment Appropriate amount N-palmitoi taurine Ca salt of Production Example 2 8 Fragrance Total amount 100 [Production method] Components 1 to 5 are mixed and pulverized. Separately, prepare a solution in which the aqueous phase components ~ are mixed, add a crushed pigment and disperse,
Heat to 75 ° C. A mixture of the oil phase components (1) and (2) heated to 80 ° C. is added to the previously prepared aqueous phase with stirring to emulsify. This is cooled with stirring, and a fragrance is added at 50 ° C. and cooled with stirring to obtain a product.

Example 7 O / W type cream <Prescription> (%) Beeswax 5.5 Cetanol 4.5 Hydrogenated lanolin 7 Squalane 33 Fatty acid glycerin 3.5 Lipophilic type glyceryl monostearate 2 Polyoxyethylene sorbitan monolaurate (20E.O.) 2 N-Lauroyl taurine Ba salt of Production Example 3 8 Fragrance Trace amount Preservative proper amount Antioxidant proper amount Propylene glycol 5 water proper amount total 100 [Manufacturing Method] The components and the water phase part are stirred and mixed and kept at 80 ° C. Mix other ingredients and heat to melt to 80 ° C. In this oil phase part, in addition to the above-mentioned water phase part, preliminary emulsification is carried out, and the product is obtained by uniformly emulsifying with a homomixer and then cooling to 30 ° C.

Example 8 Solid type powder <Formulation> (%) Remaining amount of mica N-lauroyltaurine Ca salt of Preparation Example 50 Talc 20 Titanium oxide 0.5 Bengala 0.1 Yellow iron oxide 0.1 Black iron oxide 0.11 Liquid paraffin 8 Beeswax 2 Preservative A proper amount fragrance Total amount of ingredients 100 [Manufacturing method] Mix and grind components ~. This is transferred to a high-speed blender, and then, a mixture of the components (1) to (80 ° C.) dissolved therein is added and uniformly mixed. The ingredients are added to this mixture, mixed, and then ground again and passed through a sieve. This is further gold compression-molded.

Example 9 Blusher <Formulation> (%) Mica residual amount N-palmitoiltaurine Ca salt of Production Example 50 50 Talc 20 Titanium oxide 4 Zinc stearate 5 Rice starch 5 Coloring material 3 Liquid paraffin 3 Preservative A suitable amount of perfume Micro amount total 100 [Manufacturing method] Mix components (1) to (3) and apply color. Next, components (1) to (3) are added by spraying in a mixer, mixed evenly, passed through a sieve, and then compressed into a gold plate using a pressing machine to harden.

Example 10 Eye shadow <Formulation> (%) Mica remaining amount N-lauroy rotaurine Ba salt of Production Example 3 50 Talc 5 Mica titanium 5 Zinc stearate 5 Zinc laurate 3 Colored pigment 10 Liquid paraffin 7.5 Preservative proper amount Fragrance Trace amount Total 100 [Production method] Mix components (1) to (3) and develop. Next, components (1) to (3) are added by spraying in a mixer, mixed evenly, passed through a sieve, and then compressed into a gold plate using a pressing machine to harden.

Example 11 Lipstick <Formulation> (%) Titanium oxide 1 Red No. 201 1 Red No. 202 2 Yellow No. 4 Aluminum lake 1 Red No. 223 0.1 N-lauroyltaurine Ca salt of Production Example 1 5 Castor oil Residual octyldodecanol 15 Lanolin 5 Liquid lanolin 5 Beeswax 5 Ozokerite 4 Candelilla wax 7 Carnauba wax 1 Antioxidant Proper amount Preservative Proper amount Perfume Minor amount 100 [Manufacturing method] Heat and melt components ~ to mix uniformly. to this~
Is added, and the mixture is kneaded with a roll mill to be uniformly dispersed, then re-melted, added with, defoamed, poured into a mold, and rapidly cooled to solidify. Remove the cake from the mold and load it in a container. Next, after adjusting the appearance of the stick, let it pass through the flame,
Make the surface uniform.

Example 12 Eyeliner <Formulation> (%) Carnauba wax 5 Beeswax 1 Microcrystalline wax 10 White waricen 1 Light liquid isoparaffin Residual amount Organic Bentonite 0.5 N-Lawilly-L-taurine Ba 10 in Production Example 3 Titan oxide 3 Carbon black 2 Preservative A proper amount Add a part of 100 [Production Method] in total, and disperse and gel through a colloid mill. On the other hand, (1) and (2) are mixed, heated to dissolve, added (3), cooled, kneaded by a roll mill, and heated again to be melted, bentonite gel and the rest are added, and the mixture is cooled with stirring.

[Brief description of drawings]

FIG. 1 shows N-lauryl taurine Ca obtained in Production Example 1.
It is a scanning electron micrograph which shows the crystal structure of a salt.

Claims (2)

[Claims] 1. The following general formula (I): [In the formula, R ¹ represents a linear or branched alkyl, alkenyl or hydroxyalkyl group having 7 to 21 carbon atoms, R ² represents a hydrogen atom or a methyl group, X represents an ethylene group, a propylene group or And M is a polyvalent metal atom, m is a valence of M, and n is an integer of 1 to 4]. 2. A cosmetic containing the pigment according to claim 1.