JPH0818965B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a cosmetic, particularly a cosmetic developed with the intention of suppressing the occurrence of contact dermatitis.

(Prior Art and Problems to be Solved by the Invention) Conventionally, various kinds of cosmetics have been used, but in recent years, the occurrence of a skin disease called "contact dermatitis" called so-called cosmetic rash. It has become an important issue in the use of cosmetics.

This contact dermatitis is considered to be caused by the contact between the causative substance and the skin. For example, it is contained in certain tar pigments that are mixed in lipsticks, iron oxides and clay minerals that are mixed in foundations. It is presumed that metals as impurities, especially chromium, nickel, and cobalt are causative substances.

In particular, since the contact dermatitis is an allergic disease, the allergen in the pigment is recognized as the most important person, and the test examples thereof have been actually reported.

The present invention has been made in view of such problems, and an object thereof is to provide a cosmetic that can suppress the occurrence of the contact dermatitis as described above.

(Means for Solving the Problems) In order to solve such problems, the present invention provides a coloring agent by microcapsules in order to avoid direct contact with the skin such as coloring agents as the above-mentioned causative substances. It was made from the viewpoint of enclosing etc.

That is, means for solving the above problems of the present invention, at least one colorant is coated with an insoluble polymer, and the colorant coated with the insoluble polymer, alkaline earth metal silicate, alkali Average contained in a wall material consisting of at least one of earth metal carbonate, alkaline earth metal sulfate, alkaline earth metal phosphate, metal oxide, metal hydroxide, metal silicate, and metal carbonate Particle size is
This is because microcapsules of 0.1 to 30 μm were blended.

The microcapsules to be mixed with such cosmetics are manufactured by the method for manufacturing microcapsules of Japanese Patent Application No. 63-2825 previously filed by the present inventors.

That is, first, an adsorbent water-soluble polymer is adsorbed on the surface of the colorant in advance, and the adsorbed colorant of the water-soluble polymer is treated with an alkali metal silicate or carbonate, phosphate,
An inorganic compound such as sulfate is suspended and dispersed in water, and the dispersion is mixed with an organic solvent having a solubility in water of 5% or more to prepare a W / O emulsion, and then the selected inorganic An aqueous solution of an alkaline earth metal salt or metal salt capable of forming a water-insoluble precipitate by reaction with a compound is mixed with the emulsion to form a micro hollow wall material consisting of the water-insoluble precipitate, then By optionally filtering and washing with water, the colorant is encapsulated in the wall substance to produce microcapsules.

Then, when the wall substance is formed by the reaction of forming the water-insoluble precipitate as described above, the water-soluble polymer reacts with the inorganic compound such as a metal salt to cause the insoluble polymer to be deposited inside the wall substance. It will be formed at the same time.

As the water-soluble polymer used in such production,
Anionic water-soluble polymers such as carboxymethyl cellulose, sodium caseinate, sodium alginate and gum arabic are preferable.

Further, the amount of the water-soluble polymer varies depending on its type, but is 20 to 200% with respect to the weight of the organic pigment, and if it is less than this, the organic pigment is not suitably dispersed in the aqueous phase, while, If the amount is too large, the stability of the W / O emulsion will be poor, and the viscosity will be too high, making handling difficult. There is no particular limitation on the viscosity of the water-soluble polymer,
Since a high-viscosity one is difficult to handle, a low-viscosity one is preferable.

Further, when producing the microcapsules as described above, as the alkali metal silicate, for example JIS1
No. Sodium silicate, JIS No. 2 sodium silicate, JIS No. 3 sodium silicate, sodium metasilicate, potassium silicate (K ₂ O ・ nSiO ₂ , n = _{2 to} 3.8), etc. are also exemplified, and alkali metal carbonates Examples thereof include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and the like. Examples of alkali metal phosphates include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, and phosphoric acid 2
Examples include potassium hydrogen, dipotassium hydrogen phosphate, and potassium triphosphate, and examples of alkali metal sulfates include sodium sulfate and potassium sulfate.

Examples of the organic solvent include saturated aliphatic hydrocarbons such as n-hexane, decane and octane, aromatic hydrocarbons such as toluene, benzene and xylene, and alicyclic hydrocarbons such as cyclohexane.

Of course, these solvents may be used alone or in combination of two or more.

Further, as the emulsifier used in the production method, a nonionic surfactant having an HLB value in the range of 3.5 to 6.0 can be preferably used. As a typical example, for example,
Examples include sorbitan sesquioleate, sorbitan monooleate, and polyoxyethylene sorbitan trioleate.

Further, as an aqueous solution mixed with the emulsion, magnesium chloride, calcium chloride, barium chloride, magnesium nitrate, calcium nitrate, barium nitrate, zinc sulfate,
Examples thereof include alkaline earth metal salts or metal salt aqueous solutions of zinc chloride, aluminum sulfate, aluminum chloride, aluminum nitrate and the like.

However, the types of aqueous solutions of the above-mentioned alkali metal silicates, organic solvents, emulsifiers, alkaline earth metal salts, etc. are not limited to the above.

(Function) In the cosmetic of the present invention, since the colorant contained in the cosmetic is included in the wall substance of the microcapsules as described above, the colorant is removed by the wall substance. Will be prevented from coming into direct contact with.

More importantly, since the above-mentioned wall substance is generally a porous substance, it is possible to prevent contact between the colorant and the skin as described above, but the allergen in the colorant causes pores of the wall substance. It cannot prevent leaching from the. However, in the cosmetic of the present invention, since the colorant is further coated with the insoluble polymer inside the wall substance, the insoluble polymer also prevents the allergen from falling off.

This makes it possible to prevent not only the contact of the coloring agent, which is considered to be a factor of contact dermatitis, with the skin, but also the contact of the allergen itself with the skin.

(Example) Hereinafter, the Example of this invention is described.

Preparation Example 1 First, as an example (Example 1 described later), a preparation example of a silica wall microcapsule of Red No. 219 (hereinafter abbreviated as R-219) to be blended in a cosmetic will be described.

R-219 (Brilliant Lake Red R) 7.0 g was moistened with 4 ml of methanol to give 2.5% as an example of water-soluble polymer.
% Carboxymethylcellulose (CMC Daicel 1110, Daicel Chemical) and 1.0% sodium alginate (Duck Algin NSPLL, Kibun Food Chemifa) mixed solution 150ml
Is added and stirred to prepare a dispersion liquid of R-219.

Then mixed with the dispersion 150ml and 2.4 mol / 1 sodium silicate No. of _{(Na 2 O · 2SiO 2 ·} xH 2 O) aqueous solution of 150ml,
After sufficiently dispersing the pigment, pour it into 400 ml of a 2% n-hexane solution of a sorbitan sesquioleate and polyoxyethylene (20) sorbitan trioleate (4: 1) mixture as an emulsifier and emulsify for 30 seconds with a homomixer. , W / O emulsion is prepared.

Next, this emulsion is poured into 1500 ml of a 1.5 mol / calcium chloride aqueous solution, stirred for 30 minutes, and allowed to stand for 1 hour.

After that, solid-liquid separation is performed by centrifugal dispersion, followed by filtration, washing with water, washing with alcohol and drying.

As a result, 9.2 wt% of R-219 (wt% relative to the weight of the sphere) is enclosed in the hollow portion of the micro hollow wall material containing calcium silicate as the main component, and the average particle diameter is 4.0. 75.2 g of μm microcapsules were obtained.

In addition, the microcapsules are suspended in water again, diluted hydrochloric acid is added to the mixture while stirring, and acid treatment is carried out, and if necessary, washing and drying are carried out to obtain fine hollow particles containing silica as a main component. In the hollow part of the wall material, the upper part R-21
As a result, 57.2 g of microcapsules having an average particle diameter of 4.0 μm, which were spherical bodies constituted by encapsulating 12.0% by weight of 9 (% by weight based on the weight of the sphere), were obtained.

Example 1 This example is an example of a cosmetic composition in which the microcapsules prepared as in Preparation Example 1 above were mixed with lipstick.

 Its composition is as follows.

Ingredients% by weight Microcapsules of Preparation Example 20.0 Carnauba wax 1.6 Ceresin 12.8 Salami beeswax 3.2 Octyldodecanol 14.0 Glycerin tri-2-ethylhexanoate 14.0 Diisostearylmalate 16.2 Neopentyl glycol dioctanoate 18.0 Perfume Preservatives, antioxidants When producing the cosmetics of this example, the above
In addition to a part of the mixed liquid of (3), it is treated with three rollers to form a pigment part. Next, the other components are mixed, heated and melted, and then the above-mentioned pigment portion is added and uniformly dispersed with a homomixer. Then, after dispersion, the mixture is poured into a mold to be rapidly cooled, and a stick-shaped product is inserted into a container for framing.

When the cosmetic (lipstick) of this Example was used on 10 female panelists who had been sensitized to R-219, no one showed an allergic reaction such as erythema or edema.

Preparation Example 2 Next, the red 226 compounded in the cosmetic of Example 2 of the postoperative technique.
No. (hereinafter abbreviated as R-226), Red No. 202 (hereinafter R-20
(Abbreviated as 2), carbon black, and a preparation example of titanium oxide-encapsulating silica wall microcapsules will be described.

R-226 (6.53 g), R-202 (1.63 g) and carbon black (0.16 g) were mixed and wetted with methanol (4 ml) to prepare 2.0% carboxymethyl cellulose (CMC Daicel 1110, Daicel). Chemistry) and 1.5%
200 ml of a mixed aqueous solution of sodium alginate (Duck Algin NSPLL, Kibun Food Chemifa) is added and stirred to prepare a mixed dispersion of R-226, R-202 and carbon black.

Then mixed with the dispersion 200ml and 2.4 mol / 1 sodium silicate No. of _{(Na 2 O · 2SiO 2 ·} xH 2 O) aqueous solution of 200ml,
Further, 8.16 g of titanium oxide was added and mixed to sufficiently disperse the pigment, and then poured into 600 ml of a 5% triene solution of a mixture of sorbitan sesquioleate as an emulsifier and polyoxyethylene (20) sorbitan trioleate (3: 1). , Emulsify with a homomixer for 20 seconds to prepare a W / O type emulsion.

Next, this emulsion is poured into 2000 ml of a 1.7 mol / calcium chloride aqueous solution, stirred for 30 minutes, and allowed to stand for 2 hours.

Thereafter, the same operation as in the above Preparation 1 is carried out, and 6.0% by weight of R-226, 1.5% by weight of R-202, and carbon black are contained in the hollow portion of the fine hollow wall material containing calcium silicate as a main component. Is 0.15% by weight and titanium oxide is 7.5% by weight, respectively, and is a spherical body with an average particle size of 2.5μ.
108.0 g of m microcapsules were obtained.

Further, by performing the same acid treatment as in Preparation Example 1, 8.0% by weight of R-226, 2.0% by weight of R-202, carbon black were added to the hollow portion of the fine hollow wall material containing silica as a main component. Was obtained, and 81.0 g of microcapsules having an average particle diameter of 2.5 μm, which were spherical bodies constituted by encapsulating 0.2% by weight and 10.0% by weight of titanium oxide, respectively, were obtained.

Example 2 This example is an example of a cosmetic in which the microcapsules prepared as in the above Preparation Example 2 were blended in lipstick.

 Its composition is as follows.

Ingredients% by weight Microcapsules of Preparation Example 20.0 Candelilla wax 2.0 Ceresin 13.0 Salami beeswax 2.4 Octyldodecanol 7.0 Glycerin tri-2-ethylhexanoate 25.0 Diisostearylmalate 25.0 Neopentyl glycol dioctanoate 5.4 Perfume Suitable preservative, oxidation Inhibitor Trace amount Since the method for producing this cosmetic material is the same as that in Example 1 above, its explanation is omitted.

Preparation Example 3 Next, a description will be given of a preparation example of silica wall microcapsules containing titanium oxide, red iron oxide, yellow iron oxide, and black iron oxide, which are mixed in the cosmetic material of Example 3 described later.

Titanium oxide (52.3 g), red iron oxide (1.6 g), yellow iron oxide (8.2 g) and black iron oxide (0.9 g) were mixed, and this was mixed with 2.0% carboxymethyl cellulose (CMC Daicel 11
07, Daicel Chemistry) and 1.0% sodium alginate (Duck Algin NSPLL, Kibun Food Chemifa) mixed solution
Add 200 ml and stir to prepare a mixed dispersion of the above titanium oxide, red iron oxide, yellow iron oxide, and black iron oxide.

Then mixed with the dispersion 200ml and 2.4 mol / 1 sodium silicate No. of _{(Na 2 O · 2SiO 2 ·} xH 2 O) aqueous solution of 200ml,
4% benzene solution 700 of sorbitan sesquioleate and polyoxyethylene (20) sorbitan monooleate (6: 1) mixture as emulsifier after well dispersed pigment
Pour the mixture into ml and emulsify for 3 minutes with a homomixer to prepare a W / O type emulsion.

Next, this emulsion is poured into 1800 ml of 1.6 mol / magnesium chloride aqueous solution, stirred for 30 minutes, and then subjected to solid-liquid separation by centrifugation. Then, filtration, water washing, alcohol washing and drying are performed.

The powder thus obtained is suspended again in water, diluted hydrochloric acid is added with stirring to adjust the pH to 4, and then filtered, washed with water, and dried to remove the fine hollow wall material containing silica as a main component. 41.5% by weight of titanium oxide, 1.3% by weight of red iron oxide, 6.5% by weight of yellow iron oxide, and 0.
Average particle size of 2.2, which is a spherical body composed of 7% by weight
119.7 g of microcapsules of μm were obtained.

Example 3 This example is an example of a cosmetic in which the microcapsules prepared in Preparation Example 3 above were mixed in an emulsion foundation.

Ingredients wt% Microcapsules of Preparation Example 3 23.0 Cetanol 1.75 Salix beeswax 0.35 Vaseline 2.60 Octyldodecyl myristate 8.00 Lipophilic glyceryl monostearate 0.75 N-acyl-L-glutamate sodium 0.40 1,3-Butylene glycol 5.40 Glycerin 5.30 Xanthan gum 0.17 Purified water Remaining amount Perfume Appropriate amount Preservative, antioxidant Trace amount When manufacturing the cosmetics of this example,
Add a part of the mixture and knead thoroughly (pigment part). Is added to a part of and dissolved (xanthan gum part). ,
,,, and the rest of the pigment, the pigment portion and the xanthan gum portion are mixed, heated and kept at 70 ° C. (aqueous phase). Also,
Are mixed, heated and melted, and kept at 70 ° C (oil phase). After evenly dispersing in the aqueous phase with a homomixer, the oil phase is added to the aqueous phase, the mixture is uniformly emulsified with a homomixer, and the cosmetic is produced by stirring while cooling after the emulsification. Become.

When the cosmetics of this example were used on 5 patients with metal allergies such as cobalt and nickel, none of them showed any allergic reaction.

Test Example Next, a test example of the skin contact allergenicity test of the microcapsules in the cosmetic as described above will be described.

(1) Introduction Using the R-219 (Brilliant Lake Red R), which is generally considered to have a high skin sensitizing property, as a sample, an allergic test using guinea pigs was performed to find out that the cosmetic of the present invention The effect on contact dermatitis was examined.

 The results are shown below.

(2) Test method (a) Sample (a) Microcapsules encapsulating R-219 (TOT Pigment LOT.NO.5152) (microcapsules of Preparation Example 1) Encapsulation rate of R-219: 12% by weight Average particle size Diameter: 4 μm (b) Untreated R-219 (LOT.NO.5152, manufactured by Tohoku Pigment Co., Ltd.) which is not microencapsulated was used as a ratio control.

(B) Sensitization concentration (a) R-219: 25% (base) (b) DNCB (2,4-dinitrochlorobenzene): 1%
(99.5% alcohol) (c) Control group: Base (12% PEG6000 + 88% PEG400).

(D) Control group: alcohol (99.5%) (c) Sensitization operation (a) Hartley white guinea pig (female) Weight 430-5
90g of healthy one was used.

(B) The head hair of a guinea pig was shaved with an electric hair clipper and an electric razor.

(C) The FCA (Freu
nd's complete adjuvant): Distilled water (1: 1) emulsion
0.1 ml each was injected intradermally.

(D) Stripping the epidermis in the compartment with cellophane tape
Then, light erythema was caused to occur, each test sample was applied to the site, and the operation was repeated 5 times in every day.

(D) Induced concentration (a) The following samples were applied to guinea pigs that had been sensitized with 25% of R-219.

R-219-encapsulated microcapsules ... Base, 1%, 5% (10 guinea pigs) Untreated R-219 ... Base, 1%, 5% (guinea pigs 10)
R) 219-encapsulated microcapsules ... Base, 0.05%, 0.2%
(9 guinea pigs) Untreated R-219 ... base, 0.05%, 0.2% (9 guinea pigs) For the above, in order to facilitate comparison with ,
Prepared at the concentration as R-219.

(B) Guinea pigs (5%) sensitized with 1% DNCB
DNCB (alcohol, 0.1%, 1%) was applied to each mouse).

(C) As a control group, the base, 5% R-219-encapsulated microcapsules, and 5% untreated R-219 were applied to guinea pigs (5 animals) sensitized with the base, respectively.

(D) As a control group, guinea pigs (4 animals) sensitized with alcohol were treated with alcohol and 5% R-219.
Encapsulated microcapsules, 5% untreated R-219, and 1% DNCB were applied respectively.

(E) Inducing operation (a) Three weeks after the sensitizing operation, the back hair of the guinea pig was shaved with an electric clipper and an electric razor, and the inducing concentration, base, and alcohol of each relevant test sample were applied at the midline. did.

(B) The determination was performed three times at 24 hours, 48 hours and 72 hours, and erythema and edema were observed.

(3) Results The results of the guinea pig skin contact allergy test are shown below.

As is clear from Tables 1 and 2 above, R-219MC
Regarding (microcapsules containing R-219),
None of the evoked concentrations and bases were allergic.

On the other hand, as for untreated R-219 (R-219 which is not microencapsulated), as shown in Tables 1 and 2 above, the reaction rate and the average reaction strength increase with the increase of the evoked concentration. 90% reaction rate at −219 concentration of 5%
Met.

Further, as is clear from Table 3, it was used as a positive control.
DNCB showed almost the same allergic reaction as before, thus showing that there was no abnormal experimental condition.

Further, as shown in Table 4, a control group, which was sensitized with a base and alcohol, was evoked with each sample, the base and alcohol, but no reaction was observed and it was negative. It was

In each of the above tables, the reaction rate and average reaction intensity are represented by the following formula.

In the above examples, calcium silicate or silica was used as the micro hollow wall material, but the material of this wall material is not limited to the above examples, and the point is that the alkaline earth metal silicate is used. , At least one of alkaline earth metal carbonates, alkaline earth metal sulfates, alkaline earth metal phosphates, metal oxides, metal hydroxides, metal silicates, and metal carbonates are used as wall materials Just do it.

Further, the type of colorant is not limited to R-219, R-226 and the like in the examples, and colorants such as various dyes can be used.

Further, an extender pigment may be included in the wall substance together with the colorant.

The point is that at least one colorant is included in the wall substance.

Furthermore, the types and composition ratios of the components of the base material of the cosmetic are not limited to those in the above examples, and can be arbitrarily changed according to the type of cosmetic.

(Effects of the Invention) As described above, in the present invention, since the colorant contained in the cosmetic is included in the wall substance of the microcapsule, the colorant directly contacts the skin by the wall substance. Will be prevented.

Furthermore, since the colorant is further coated with an insoluble polymer inside the wall substance, even if the wall substance is a porous substance, the insoluble polymer prevents the leaching of allergen in the colorant. Will be done.

Therefore, it is possible to prevent not only the contact of the coloring agent, which is recognized as a factor of contact dermatitis, with the skin, but also the contact of the allergen itself, which has been recognized as an important factor, with the skin. Can be solved
The present invention has a particularly remarkable effect of being able to provide a cosmetic material having an excellent effect of suppressing contact dermatitis.

And, as mentioned above, coloring agents (allergens) to the skin
As a result of the prevention of contact with the skin, even if the user has already been sensitized to the colorant in the cosmetic before using the cosmetic, as long as the cosmetic of the present invention is used thereafter, it causes allergies. Is significantly lower than before, and
If the user has not yet been sensitized to the coloring agent, the sensitizing property of the coloring agent itself can be reduced as long as the cosmetic of the present invention is used thereafter, and therefore, before the use of the cosmetic agent, The use of the cosmetic of the present invention suppresses the occurrence of contact dermatitis regardless of whether or not sensitization is present, that is, whether or not an antibody is produced by the coloring agent in the body of the user.

[Brief description of drawings]

1 to 4 are diagrams showing the results of the skin contact allergenicity test of R-219-encapsulated microcapsules and untreated R-219 in guinea pigs, and FIG. 1 shows the reaction rate and R after 48 hours from application. Fig. 2 is a graph showing the relationship between the -219 concentration, Fig. 2 is a graph showing the relationship between the average reaction intensity 48 hours after the application and R-219 concentration, and Fig. 3 is the reaction rate 72 hours after the application and the R-219 concentration. Fig. 4 is a graph showing the relationship, and Fig. 4 is a graph showing the relationship between the average reaction intensity 72 hours after application and the R-219 concentration.

 ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-63-54310 (JP, A) JP-A-1-180243 (JP, A)

Claims (2)

[Claims] 1. At least one colorant coated with an insoluble polymer, and the colorant coated with the insoluble polymer is an alkaline earth metal silicate, an alkaline earth metal carbonate, or an alkaline earth metal. Microcapsules with an average particle size of 0.1 to 30 μm encapsulated in a wall substance composed of at least one of sulfate, alkaline earth metal phosphate, metal oxide, metal hydroxide, metal silicate, and metal carbonate. Cosmetics characterized by being blended. 2. The cosmetic according to claim 1, wherein the insoluble polymer is a polymer produced by a reaction between an anionic water-soluble polymer and a metal salt.