JPH111411A - Silica / zinc oxide composite, method for producing the same and cosmetics incorporating the same - Google Patents

Abstract

(57) Abstract: An object of the present invention is to provide a substance having sebum solidification absorption effect, transparency and soft focus. A silica / zinc oxide composite characterized in that fine zinc oxide particles adhere to the silica surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silica / zinc oxide composite, a method for producing the same, and a cosmetic containing the same, and more particularly to an improvement in the mechanism of zinc oxide adhesion.

[0002]

2. Description of the Related Art Sebum secreted from the skin has a function of protecting the skin from the outside world and, at the same time, is mixed with an oil component such as a foundation, an activator, etc., and causes the makeup to collapse over time. In addition, when a large amount of sebum is secreted, the sebum floats on the face of the face, causing so-called “sebum shine”. For this reason, attempts have been made to improve the longevity of the makeup and to suppress the shine of sebum by blending a powder such as zinc white that solidifies the sebum or a powder that absorbs the sebum such as porous silica into the foundation. .

[0003]

However, porous silica, which is generally used as a sebum absorbent, has a limited amount of oil absorption and has an excellent ability to suppress sebum immediately after application, but has a long-lasting cosmetic durability. Is not enough. Zinhua, such as fine zinc white, has the ability to solidify sebum and prevent makeup collapse.However, it takes a long time to completely solidify sebum, so makeup collapse may occur before sebum solidifies. Can be considered. Also, if it is added in a large amount to cosmetics or the like, it becomes whitish when applied on the skin, and the finish may be unnatural. The present invention has been made in view of the problems of the prior art,
The purpose is to provide a substance having sebum solidification absorption effect, transparency and soft focus.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and found that a silica / zinc oxide composite (silica / zinc oxide) obtained by complexing silica sol and zinc oxide. Silica such as basic zinc carbonate complex /
Concept containing a weak acid zinc salt complex) has excellent sebum solidification absorption effect, transparency and soft focus effect when formulated in cosmetics, etc., and gives a natural matte feeling when applied to the skin And completed the present invention. That is, the silica / zinc oxide composite according to the present invention is characterized in that fine zinc oxide particles adhere to the silica surface.

In the composite according to the present invention, it is preferable that fine zinc oxide particles are observed in spots on an electron microscope photograph under the following condition A. Condition A: That is, FIG. 1 shows an electron micrograph of the silica / basic zinc carbonate composite, and FIG.
An M image, and FIG. 7B is an 8OKα observation image. The instruments used to obtain each were a scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.) and an energy dispersive X-ray analyzer (EMAX-5770W, manufactured by Horiba, Ltd.).

[0006] As is clear from the figure, it was confirmed by 8OKα that extremely fine basic zinc carbonate particles were present on the silica powder, and the contact area was increased by the fine zinc particles. It is considered that even if a relatively small amount of the compound is blended, it can exert excellent sebum solidifying ability and the like, and also exhibit properties such as oil absorption of silica itself. FIG. 2 shows an electron micrograph of the silica / zinc oxide composite. FIG. 2A is an SEM image, and FIG. 2B is an 8OKα observation image. As in FIG. 1, very fine zinc oxide particles are present on the silica powder. Further, the method for producing a silica / weak acid zinc salt composite according to the present invention comprises adding a zinc salt to a silica sol dispersion, adding a weak acid strong base salt to the obtained gel composition, and adding a basic zinc salt / silica sol composite. It is characterized in that a dispersion is obtained and this is dried.

In the present invention, the zinc salt added to the silica sol dispersion is preferably zinc chloride, and the weak acid strong base salt is preferably sodium carbonate. In the method for producing a silica / zinc oxide composite according to the present invention,
It is preferable that the silica / weak acid zinc salt composite is heated and dehydrated. Further, in the present invention, it is preferable that a strong base is added to the silica / weak acid zinc salt complex to adjust the pH to 8 or more, and the obtained gel composition is dried to obtain a silica / zinc oxide complex. Further, the cosmetic according to the present invention is characterized by blending the silica / zinc oxide composite.

[0008]

Embodiments of the present invention will be described below. The zinc oxide composite according to one embodiment of the present invention can be manufactured as follows. In this embodiment, zinc oxide was carried in the composite in an amount corresponding to 20% by weight of silica sol in terms of zinc chloride.

A silica / basic zinc carbonate composite 2 L beaker was charged with 250 g of a 30% silica sol dispersion (Snowtex XS: manufactured by Nissan Chemical) and diluted with the same amount of ion-exchanged water. A 1M aqueous solution of zinc chloride 11
0 ml was gradually added while stirring with a homomixer. 200 ml of 0.8 M aqueous sodium carbonate solution was added to the obtained gel composition.
Was added and mixed again with a homomixer. The obtained aqueous solution of basic zinc carbonate / silica sol complex was subjected to 10,000
The precipitate was collected by centrifugation at rpm for 20 minutes, and washing with water was repeated three times. The obtained product was freeze-dried to obtain a silica / basic zinc carbonate composite.

Synthesis of Silica / Zinc Oxide Complex The silica / basic zinc carbonate complex aqueous solution prepared in the same manner as described above was heated and dehydrated at 90 ° C. The obtained solid was finely pulverized using a pulverizer, and the obtained powder was washed three times with water.
The powder was dried to obtain a silica / zinc oxide composite.
Among the silica / zinc chloride composites to be blended in the cosmetic composition according to the present invention, the silica / basic zinc carbonate composite is different from the method of dehydrating basic zinc carbonate in the above-described embodiment in that zinc ion A hydroxide such as sodium hydroxide, potassium hydroxide, and calcium hydroxide is added to the gelled product of silica and silica so that the pH of the solution becomes 8 or more, and a gel composition in which zinc oxide is precipitated is added. The gel composition can also be obtained by drying and then washing with water. other,
It can also be obtained by heating silica / basic zinc carbonate powder at 120 ° C. or higher.

In the present invention, when the amount of zinc oxide or basic zinc carbonate supported on the silica sol increases, the sebum solidification rate tends to increase.
At the same time, the transparency of the powder is lost. In particular, when the loading exceeds 100% by weight of the silica sol, the transparency of the powder is remarkably reduced, and the sebum solidification rate reaches a peak. Therefore, in consideration of the transparency and the sebum solidification rate, zinc oxide or basic zinc carbonate is considered. Is preferably 100% by weight or less, particularly preferably 10 to 50% by weight, based on the silica sol. Further, the zinc salt added to the silica sol dispersion is not limited to zinc chloride, and for example, an organic zinc compound such as zinc acetate can be used.

The amount of the silica / zinc compound in the cosmetic of the present invention varies depending on the kind of the cosmetic, but is usually 0.1 to 98% by weight, preferably 0.5 to 80% by weight. Used. If it is less than 0.1% by weight, various expected effects may be insufficient, and even if 98% or more is added, no further increase in the effect is observed. The cosmetic of the present invention can be in the form of powder, cake, pencil, stick, ointment, liquid, etc., for example, lotion, emulsion, facial cosmetics such as cream,
It includes makeup cosmetics such as foundation, lipstick, eye shadow, blusher, eyeliner, nail enamel and mascara, and hair cosmetics such as hair treatment, hair liquid, set lotion and the like.

The cosmetic of the present invention may contain, in addition to the above-mentioned essential components, components commonly used in cosmetics as long as the effects of the present invention are not impaired. For example, petrolatum, lanolin, ceresin, carnauba wax, candelilla wax, solids such as higher alcohols, semi-solid oils, squalane, liquid paraffin, liquid oils such as ester oils, oils such as silicone oils, oils such as silicone oils, humectants such as sodium hyaluronate and glycerin Surfactants such as cationic surfactants and nonionic surfactants, pigments, preservatives, fragrances, activators and the like can be appropriately compounded. Since the silica / zinc compound composite obtained in the present invention has a function of solidifying a higher fatty acid having fluidity, in order to further enhance the effect of the composite, the use of a liquid fatty acid such as oleic acid should be avoided. Is preferred.

Next, the present invention will be described with reference to more specific test examples of the present invention. First, the test method will be described. Sebum solidification rate The solidification rate of liquid fatty acid, one of the sebum constituents, was measured. The measuring method is as follows. 2 g of the cosmetic is placed in a 50 ml vial, 5 g of oleic acid is added thereto, and the mixture is stirred so that the powder and oleic acid are uniformly mixed. This was allowed to stand, and the time (minutes) at which the mixture hardened and did not flow even when the vial was tilted was measured. The sebum solidification rate was evaluated based on this time. Oil absorption amount Take 5 g of the cosmetic on the ointment plate, drop squalane as an oil similar to sebum, and knead it evenly with a spatula. The amount was defined as the oil absorption of the cosmetic (ml / 100 g).

[0015] Sensory evaluation of the finish when the cosmetic was applied was performed using panels of six finishes each. Rating Evaluation 1: Very whitish and unnatural 2: Whitish and unnatural 3: Unavailable 4: Somewhat natural 5: Natural without feeling whitish

Transparency 2 g of a cosmetic was dispersed in 10 g of cellulose lacquer to form a coating film on black paper using an applicator having a thickness of 100 μm. This is dried and lightness (L
Value). The lower the lightness, the more noticeable the black color of the base was. Therefore, the transparency was evaluated based on the lightness. Soft-focus cosmetic material manufactured by the Murakami Color Research Laboratory those thin and uniformly applied on the pressure-sensitive adhesive tape goniometer spectrophotometer GS
It was attached to a P-1 variable-angle gloss meter, and the L value of reflected light from -25 to 45 degrees was measured for incident light at 45 degrees. As an index of the magnitude of the soft focus property, a ratio of (L value at a reflection angle of 45 degrees) / (L value at a reflection angle of −25 degrees) is taken. As this value is larger, the gloss is higher and the soft focus property is smaller. It was defined that the closer this value was to 1, that is, the more the L value of the reflected light did not change in the regular reflection direction or the diffuse reflection direction, the more matte the touch was and the greater the soft focus property.

[0017]

[Table 1] {Test Example 1 2 3 4} ────────────────────── Silica / zinc oxide composite 75.0---Silica-75.0-60.0 Zinc white--75.0 15.0 Kaolin 5.0 5.0 5.0 5.0 Titanium dioxide 3.0 3.0 3.0 3.0 Zinc myristate 5.0 3.0 3.0 3.0 Magnesium carbonate 5.0 3.0 3.0 3.0 Sericite 7.0 7.0 7.0 7.0 Colored pigment Suitable amount Suitable amount Suitable amount Fragrance Suitable amount Suitable amount Suitable amount 量─────────────── Sebum solidification rate 24 No solidification 58 About half a day Oil absorption 144 121 47 92 Finish 4 4 1 3 Transparency 28.1 23.9 38.6 29.8 Soft focus property 1.12 1.06 1.46 1.15 ─ ──────────────────────────────

<Production Method> The silica / zinc oxide composite is mixed with a blender. The remaining ingredients are added to the mixture, mixed well, and after toning, the fragrance is sprayed and uniformly mixed. This was pulverized with a pulverizer and passed through a sieve to prepare a white powder. <Results> As is clear from Table 1, in the case of silica alone (Test Example 2), almost no sebum solidification action was observed. On the other hand, in the case of zinc white alone (Test Example 3), the sebum solidification effect was recognized, but the speed was not satisfactory, and both the finish and the transparency were poor. In the case of using a mixture of silica and zinc white at a ratio of 8: 2 (Test Example 4), although sebum solidification ability is produced, the speed is extremely slow, which may be insufficient for practical use. It can be understood. In contrast, Test Example 1, which is an embodiment of the present invention, exhibited extremely excellent characteristics as compared with any of the above Test Examples.

[0019]

EXAMPLES Specific examples of the composition of the present invention will be described below. Formulation Example 1 Powdery Foundation Talc 15.0 2. Mica 30.0 3. Silica / zinc oxide composite 15.0 4. Titanium dioxide 15.0 5. 5. Mica titanium 3.0 Zinc stearate 1.0 7. Nylon powder 5.0 8. Iron oxide red 1.09. Iron oxide yellow 3.0 10. Iron oxide black 0.2 11. Squalane 6.0 12. Lanolin acetate 1.0 13. Octyldodecyl myristate 2.0 14. Neopentyl glycol diisooctanoate 2.0 15. Sorbitan monooleate 0.5 16. Preservative appropriate amount 17. Antioxidant appropriate amount 18. Appropriate amount of fragrance

<Preparation method> Components 1 and 8 to 10 are mixed with a Henschel mixer, components 2 to 7 are added to the mixture, mixed well, and components 12 to 18 obtained by heating and melting at 70 ° C. are added. Mixed. Thereafter, the mixture was pulverized with a 5HP pulperizer (Hosokawa Micron) and formed into a middle plate to obtain a desired powdery foundation. Similarly,
Comparative formulation example 1 was a cosmetic formulation containing kaolin instead of the silica / zinc oxide composite. <Evaluation> Formulation Example 1 Comparative Formulation Example 1 Oil absorption (ml / 100 g cosmetic) 46.8 38.8 Based on the above results, the cosmetic of this formulation has a high oil absorption of squalane and an excellent sebum absorption ability. The result was shown.

Formulation Example 2 Emulsion foundation Ion exchange water 60.9 2. Dispersant 0.1 3. Dipropylene glycol 5.0 4. Preservative appropriate amount 5. 5. Polyoxyethylene-modified dimethylpolysiloxane 4.0 Decamethylcyclopentasiloxane 12.0 7. Liquid paraffin 5.0 8. Silica / zinc oxide composite 10.0 9. Sericite 0.36 10. Titanium dioxide 8.32 11. Iron oxide yellow 0.80 12. Iron oxide red 0.36 13. Iron oxide black 0.16 14. Appropriate amount of fragrance

<Production method> After components 1-4 were heated and stirred at 70 ° C, components 9-13 were added and dispersed. This was previously heated to 70 ° C., added to components 5 to 7, and emulsified and dispersed. After cooling to room temperature, 14 was added to obtain the desired emulsified foundation. Similarly, a cosmetic formulation containing zinc white instead of the silica / zinc oxide composite was designated as Comparative Formulation Example 2. <Evaluation> Formulation Example 2 Comparative Formulation Example 2 Finish 3.8 2.8 From these results, it was confirmed that the cosmetics of this Formulation Example did not feel whitish and had a natural finish.

Formulation Example 3 Powder Spray 1. Aluminum chlorohydrate (fine powder) 30.0 2. Silica / basic zinc carbonate composite (fine powder) 20.0 Silicon treated talc 15.0 4. Triclosan 0.15. 5. Isopropyl myristate 21.9 Dimethyl polysiloxane 10.0 7. 7. Sorbitan fatty acid ester 3.0 Appropriate amount of fragrance

<Production Method> A mixture of components 1 to 8 is placed in an aerosol container, a valve is attached, and a propellant is filled. Similarly, a cosmetic formulation containing zinc white instead of the silica / zinc oxide composite was used as Comparative Formulation Example 3. <Evaluation> Formulation Example 3 Comparative Formulation Example 3 Transparency 51.8 62.4 From these results, it is understood that the cosmetic of this Formulation Example has a high degree of transparency and a black underlayer clearly appears. Thus, it was confirmed that the cosmetic of this formulation example had a high transparency and a beautiful finish.

Formulation Example 4 Amphibian Foundation 1. Silicone treated talc 19.0 2. 2. Siliconized mica 40.0 Silicone treated titanium dioxide 5.0 4. 4. silica / zinc oxide composite 15.0 Silicone treated bengala 1.06. 6. Siliconized iron oxide yellow 3.0 7. Siliconized black iron oxide 0.2 8. Zinc stearate 0.1 Nylon powder 2.0 10. Squalane 4.0 11. Solid paraffin 0.5 12. Dimethyl polysiloxane 4.0 13. Glycerin triisooctanoate 5.0 14. Octyl methoxycinnamate 1.0 15. Preservative appropriate amount 16. Appropriate amount of antioxidant 17. Spice

<Preparation method> Components 1 to 9 were mixed with a Henschel mixer, and components 10 to 17 which were dissolved by heating at 70 ° C were added and mixed. Thereafter, the mixture was pulverized with a 5HP pulperizer (Hosokawa Micron) and molded into a middle plate to obtain a target dual-use foundation. Similarly, a cosmetic formulation containing zinc white instead of the silica / zinc oxide composite was designated as Comparative Formulation Example 4. <Evaluation> Formulation Example 4 Comparative Formulation Example 4 L value at a reflection angle of 45 degrees 104.11 131.72 L value at a reflection angle of −25 degrees 91.68 95.63 Soft focus property (/) 1.14 1.38 The results show that the cosmetic of Formulation Example 4 had a soft focus property close to 1 and had a natural matte feeling.

Formulation Example 5 Oily stick foundation Silica / basic zinc carbonate composite 13.0 2. Titanium oxide 7.0 3. Kaolin 20.0 4. Talc 2.05. Mica 3.3 6. Iron oxide red 1.0 7. 7. Iron oxide yellow 3.0 Iron oxide black 0.29. Solid paraffin 3.0 10. Microcrystalline wax 7.0 11. Vaseline 15.0 12. Dimethyl polysiloxane 3.0 13. Squalane 5.0 14. Isopropyl palmitate 17.0 15. Antioxidant appropriate amount 16. Appropriate amount of fragrance <Production method> Components 9 to 15 were dissolved at 85 ° C, and component 1 was added thereto.
After mixing with a disper, the mixture was dispersed with a colloid mill. 16 was added, and after deaeration, it was poured into a container at 70 ° C. and cooled.

Formulation Example 6 Sunscreen Agent Silica / basic zinc carbonate composite 5.0 2. Ion-exchanged water 54.95 3.1,3-butylene glycol 7.0 4. 4. Disodium edetate 0.05 Triethanolamine 1.0 6. Oxybenzone 2.0 7. 7. Octyl paramethoxycinnamate 5.0 Squalane 10.0 9. Vaseline 5.0 10. Stearyl alcohol 3.0 11. Stearic acid 3.0 12. Glyceryl monostearate 3.0 13. Ethyl polyacrylate 1.0 14. Antioxidant appropriate amount 15. Preservative appropriate amount 16. Appropriate amount of fragrance <Production method> Components 2 to 5 are heated to 70 ° C and dissolved. Add 1 to this and disperse enough. A solution obtained by heating and dissolving 6 to 16 was added thereto, and the mixture was emulsified and dispersed using a homogenizer. Thereafter, the mixture was stirred and cooled to room temperature to obtain a desired sunscreen.

Formulation Example 7 W / O type sunscreen agent Deionized water 38.3 2.1,3-butylene glycol 5.0 3. 3. silica / zinc oxide composite 3.0 Octyl paramethoxycinnamate 5.0 5.0. Oxybenzone 3.0 6.4-tert-4'-methoxydibenzoylmethane 1.0 7. Squalane 40.0 8. Glycerin diisostearate 3.0 9. Organically modified montmorillonite 1.5 10. Preservatives qs. Appropriate amount of fragrance <Production method> Components 4 to 11 are heated and dissolved at 70 ° C. Add 3 to this and disperse enough. A solution obtained by heating and dissolving 1 and 2 was added thereto, and the mixture was emulsified and dispersed using a homogenizer. Thereafter, the mixture was stirred and cooled to room temperature to obtain a desired W / O type sunscreen.

Formulation Example 8 Blush 1. Kaolin 19.0 2. 2. silica / basic zinc carbonate composite 5.0 Bengala 0.34. Red No. 202 0.55. Ceresin 15.0 6. Vaseline 20.0 7. Liquid paraffin 25.0 8. 8. Isopropyl myristate 15.0 Antioxidant appropriate amount 10. Appropriate amount of fragrance <Production method> Components 1 to 4 are added to a part of 7, and treated with a roller (pigment part). On the other hand, 4 is dissolved in a part of 10 (dye part). 5 to 10 are heated and dissolved at 90 ° C., and a pigment portion is added thereto and uniformly dispersed by a homomixer. After the dispersion, the mixture was filled in a predetermined container to obtain a target blusher.

Formulation Example 9 Deodorant powder Aluminum chlorohydrate 5.0 2. 2. silica / basic zinc carbonate composite 10.0 Talc 82.0 4. Liquid paraffin 3.0 5. Appropriate perfume <Production method> After the powder components are sufficiently mixed, the perfume dissolved in liquid paraffin is uniformly sprayed and mixed. After pulverizing this powder, compression molding is performed.

Formulation Example 10 Mud-washing wash pack Dipropylene glycol 5.0 2. 2. polyethylene glycol 400 8.0 Glycerin 10.0 4. Montmorillonite 2.05. Ethanol 8.0 6. Titanium oxide 5.0 7. 7. silica / zinc oxide composite 15.0 Appropriate amount of flavor 9. Preservative appropriate amount 10. Surfactant appropriate amount 11. Ion-exchanged water 47.0 <Production method> Add 1, 2, 3, and 11 to component 4 and disperse them sufficiently. 8, 9, and 10 are added and dissolved in 5, and added to the above-mentioned dispersed phase. Next, 6 and 7 are added and sufficiently dispersed, deaerated and filtered.

[0033]

As described above, according to the silica / zinc oxide composite according to the present invention, by forming extremely fine zinc oxide particles on the silica surface, the contact area of the zinc oxide can be increased, and the silica can be used. A composite can be obtained without impairing the properties. Further, according to the cosmetic according to the present invention, the use of the above-mentioned complex makes it possible to greatly improve oil absorbency, sebum solidifying ability, transparency and soft focus.

[Brief description of the drawings]

FIG. 1 is an electron micrograph showing a particle surface state of a silica / basic zinc carbonate composite according to one example of the present invention.

FIG. 2 is an electron micrograph showing a particle surface state of a silica / zinc oxide composite according to one example of the present invention.

Claims (8)

[Claims] 1. A silica / zinc oxide composite, characterized in that fine zinc oxide particles adhere to the silica surface. 2. The silica / zinc oxide composite according to claim 1, wherein the fine zinc oxide particles are observed as spots on an electron microscope photograph under the following condition A. Condition A: 3. A zinc salt is added to the silica sol dispersion, a weak acid strong base salt is added to the obtained gel composition to obtain a basic zinc salt / silica sol composite dispersion, and this is dried. For producing a silica / weak acid zinc salt composite. 4. The method of claim 3, wherein the zinc salt added to the silica sol dispersion is zinc chloride, and the weak acid strong base salt is sodium carbonate. Method. 5. The silica / weak acid zinc salt composite obtained in claim 3 which is dehydrated by heating.
A method for producing a zinc oxide composite. 6. A silica / zinc oxide composite, characterized in that a strong base is added to the silica / weak acid zinc salt composite obtained in claim 3 to adjust the pH to 8 or more, and the obtained gel composition is dried. Production method. 7. A cosmetic comprising the silica / zinc oxide composite according to claim 1 or 2. 8. The cosmetic according to claim 7, which is substantially free of liquid fatty acids.