WO2002047640A1

WO2002047640A1 - Cosmetic comprising fine zinc oxide powder having electrically conductivity

Info

Publication number: WO2002047640A1
Application number: PCT/JP2000/008783
Authority: WO
Inventors: Tatsuhiko Ikeda; Hisahiko Mine; Takao Tanaka
Original assignee: Hakusui Tech Co., Ltd.
Priority date: 1999-06-16
Filing date: 2000-12-13
Publication date: 2002-06-20
Also published as: JP2001002529A

Abstract

A cosmetic characterized as comprising a fine zinc oxide powder having electrically conductivity which has a specific surface area of 2 to 100 m2/g and a volume resistivity of 105 Ω • cm or less. The cosmetic is excellent in long hour durability of the effect of protecting a skin against ultraviolet rays.

Description

Description Cosmetics containing conductive zinc oxide fine powder

TECHNICAL FIELD The present invention relates to a cosmetic which is excellent in ultraviolet absorbing ability and makeup, which is blended with conductive zinc oxide fine powder.

Background branch art

Makeup cosmetics such as foundations, lotions, emulsions, and creams and basic cosmetics have the aesthetic role of hiding the skin's skin, giving them the desired color, giving them an attractive appearance and making them look beautiful. It also has a protective role.

In particular, in recent years, the environmental problem of ozone layer destruction has become a major issue, and recent dermatological research has shown that exposure to ultraviolet light causes spots, freckles, and aging of the skin. It has been clarified that ultraviolet rays have a more adverse effect on skin than expected, such as damaging the genes of skin cells, and there has been much interest in protecting skin from harmful ultraviolet rays. For this reason, cosmetics are also required to have an ultraviolet shielding effect that protects the skin from ultraviolet rays. In order to respond to this, cosmetics such as makeup cosmetics and basic cosmetics that contain an ultraviolet absorber such as zinc oxide are required. Cosmetics have been developed.

Above all, zinc oxide particles basically have excellent ultraviolet absorption ability, and some cosmetics or zinc oxyzinc compounds suitable for cosmetics in which this is blended as an ultraviolet absorber have been proposed. (Japanese Unexamined Patent Publication Nos. Hei 5-171, No. 29, No. Hei 5-2,468, No. 23, Japanese Unexamined Patent Publication No. Hei 5-212, No. 18, No. Hei 7-118, No. 33, No. No. 7-105358, Japanese Patent Application Laid-Open No. Hei 8-53358). As a result, when the makeup is applied with a cosmetic in which zinc oxide is combined as an ultraviolet absorber, the role of protecting the skin from ultraviolet rays has been almost satisfied.

However, if the makeup is actually applied to the skin, the cosmetics peel off due to sweating, etc. over time, so that the effect cannot be maintained for a long time. It was not always easy. The long-lasting effect, that is, good makeup lasting, is one of the most important factors in achieving the full potential of zinc oxide and protecting the skin. In addition, cosmetics that have good make-up often do not need to be redressed, and from this point of view, the need for cosmetics with good make-up is extremely high.

In addition, in order to maintain the effect of protecting skin from ultraviolet rays over a long period of time in cosmetics containing zinc oxide, for example, Japanese Patent Application Laid-Open No. It has been proposed to use zinc oxide having a small element content to increase the reactivity with free fatty acids present in sebum and to gel the sebum. However, this method can certainly increase the reactivity with free fatty acids present in sebum to some extent, but it is difficult to significantly improve the makeup stickiness by itself. Some improvement is required.

Nikko

The present invention has been made in view of the above, and an object of the present invention is to provide a cosmetic composition that protects the skin from ultraviolet rays over a long period of time and has good makeup.

That is, according to the present invention, the specific surface area is 2~1 0 O m ² Zg, of which characterized by being obtained by blending a conductive zinc oxide fine powder is less than a volume resistivity of 1 0 ⁵ Ω · cm粧Fees are provided.

Sun »Violent 开

Hereinafter, the present invention will be described in detail.

As the conductive zinc oxide used in the present invention, the specific surface area is 2~1 0 O m ² / g, more preferably ^{1 0~: L 0 O m 2} gs more preferably ^{2 0 - 1 0 O m 2} / g of fine powder is desirable. If the specific surface area is much smaller than 2, although the performance such as the ultraviolet absorbing ability is not changed, the added cosmetic does not have transparency and is not suitable for the original purpose of the cosmetic, which is not preferable. Further, those having a specific surface area of more than 10 O m ² / g are difficult to manufacture with the current technology, the manufacturing cost is high, and practical use is practically difficult.

The specific surface area in the present invention is a value measured by a known BET method. Incidentally, when these specific surface areas are converted into particle diameters, they are 0.01 to 0.5 zm, preferably It is about 0.01 to 0.1 m.

Further, as the conductivity of a conductive zinc oxide used in the present invention, less or less body volume resistivity 10 ⁵ Ω · cm, preferably 500 Omega · cm or less, rather more preferably it is below 100 Omega · cm is there. On the other hand, the lower limit of the volume resistivity is preferably lower, but the range in which the production is actually easy is about 10 to 500 Ω · cm. When the volume resistivity exceeds 10 ⁵ Ω · cm, the ability to prevent infrared transmission, which is the object of the present invention, decreases, and the effect of suppressing perspiration of the skin decreases. In the present invention, the volume resistivity of the conductive zinc oxide is a value measured by a tester by placing 10 g of a sample in a cylinder having an inner diameter of 25 mm and having an inner surface treated with a fluororesin, applying a pressure of l O Okg / cm ² , and using a tester. cm).

The conductive zinc oxide used in the present invention contains A ¹³⁺ , B ³⁺ ,

1 n ³⁺ s ^Ti ⁴ Sn ⁴⁺ or the like is doped to impart conductivity. Among them, aluminum is most preferable as the dopant (conductivity-imparting component) in terms of doping performance and cost.

As a method for producing electroconductive zinc oxide used in the present invention, even the Not specific surface area is particularly limited 2 to 100 m ² / g, a volume resistivity of 10 ⁵ Ω ■ cm or less, preferably 500 Omega · cm Basically, any method can be used as long as the following conductive zinc oxide fine powder can be obtained, but the following method is most preferable from the viewpoint of easy implementation.

The zinc oxide used as a starting material is the France method, in which zinc is melted and evaporated and oxidized in the gas phase, the zinc ore is calcined, coke reduced, and oxidized, and the zinc oxide is dissolved in zinc salt solution. Any of a wet method of precipitating zinc carbonate, drying and calcining may be used, but the specific surface area is preferably in the above range.

The zinc oxide fine particles produced by these general production methods are used in an aqueous solution containing an ammonium salt such as ammonium carbonate and a water-soluble salt of aluminum or titanium, as disclosed in, for example, Japanese Patent Publication No. 62-41171. The resulting cake is washed with water and dried, and then reduced and fired in a reducing atmosphere such as hydrogen at a temperature of about 400 to 1,000 ° C for about 0.2 to 3 hours. Thus, the zinc oxide crystal lattice is sufficiently doped with Al ³⁺ , B ^{3 In} ³⁺ or Ti ⁴⁺ , Surface area 2~1 0 0 m ^2, g, a volume resistivity of 1 0 ⁵ Ω · cm or less, preferably 5 0 0 Ω cm electroconductive zinc oxide powder or less is obtained.

The particle shape of the conductive zinc oxide fine powder to be used may be any of spherical, scale-like, flake-like, plate-like, crushed, irregular, plate-like, and needle-like.

The cosmetic of the present invention is not particularly limited, and any cosmetic may be used for the purpose of protecting the skin from ultraviolet rays. However, basic cosmetics for conditioning the skin, base makeup and point makeup Makeup cosmetics used in cosmetics are particularly preferred. Specific examples include white powder, foundation, prest powder, lipstick, lipstick, eyeshadow, sun oil, sunburn cream, loose powder, milky lotion, and lotion.

The components of the cosmetic in which the conductive zinc oxide fine powder of the present invention is blended include the components blended in ordinary cosmetics, for example, a base component generally used in cosmetics, and a general drug effect imparting component ( For example, humectants, anti-inflammatory agents, blood circulation promoters, etc.), oils, pigments, fragrances and the like are used.

These include, for example, silica, talc, red iron oxide, clay, My power, bentonite, titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, CI pigment yellow, yellow iron oxide, black iron oxide, etc. Iron oxide, silk powder

-Organic and inorganic fillers and pigments such as polyamide powder; lanolin, dicerin, paraffin, wax, carnauba wax, candelilla wax, ceresin, 1,3-butylene glycol, lauryl alcohol, stearic acid, lauric acid, cetyl Solid or semi-solid oils such as alcohol; orip oil, jojoba oil, oleic acid, oleyl alcohol, isohexadecyl alcohol, dimethylpolysiloxane, liquid paraffin, squalene, octyldodecyl myristate, neopentyl glycol diisoxate Liquid oils such as styrene and squalane; water-soluble polymers such as methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, xanthan gum, dextrin, gelatin, and sodium alginate; Phosphoric acid esters, polyoxyethylene monostearate sorbitan tail, triethanolamine § Min, Monoorein sorbitan, Monoorein acid polyoxyethylene sorbitan, glycerin and glycerin monostearate, etc. Surfactants such as fatty acid esters and benzyltrimethylammonium chloride; humectants such as sorbitol, mannitol, glycerin, lactic acid, beevine, sodium hyaluronate and propylene glycol, other preservatives, and fragrances , PH regulators, various amino acids, bactericides, antioxidants and the like.

In addition, the proportion of conductive zinc oxide in cosmetics cannot be determined unconditionally because it differs depending on the type and properties of the cosmetic used, but it cannot be applied to the skin except for volatile components such as water and alcohol. It is desirable to contain at least 3% (% by mass, the same applies hereinafter) of the residual component mass. The mixing ratio is more preferably 10% to 80%, further preferably 15 to 65%, and most preferably 15 to 50%. If the blending ratio is less than 3%, the combined use of other ultraviolet absorbers (ultraviolet ray shielding agents), even if the ultraviolet absorption ability can be maintained, basically the infrared absorption prevention ability is insufficient. is there. On the other hand, if used in a cosmetic in an excessive amount, the feeling of use becomes worse.

When blending the conductive zinc oxide particles of the present invention into cosmetics, in order to improve the compatibility between the particles and the ingredients, unless the properties of zinc oxide are impaired, for example, silane coupling The surface treatment of the zinc oxide particles with an agent, silicone oil, titanate coupling agent, alcohol, surfactant, other known surface treatment agent or surface modifying agent can also be performed.

In the case of a cosmetic, the conductive zinc oxide of the present invention does not cause any problem when used in combination with another ultraviolet absorber as described above. Examples of such other ultraviolet absorbers include inorganic compounds such as titanium oxide, cerium oxide, and iron oxide; organic compounds such as benzophenone-based ultraviolet absorbers, benzimidazole-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers. Compounds.

Example

Hereinafter, the present invention will be described with reference to examples. However, these are merely examples of the embodiments, and the technical scope of the present invention is not limited by them (parts indicate parts by mass and% indicates mass% unless otherwise specified).

(T) Sample preparation

(Making of Pau, Leifa Division) (Example 1)

As the conductive zinc oxide, one having a specific surface area of 10 m ² , g and a volume resistivity of 90 Ω · cm (manufactured by Huxitech: conductive zinc oxide 23-K) was used.

The powder components of 50 parts of conductive zinc oxide, 10 parts of talc, 10 parts of my strength, 1 part of red iron oxide, 3 parts of iron yellow oxide, 0.2 parts of black iron oxide and 10 parts of polyamide powder are mixed by a mixer. A mixed powder was obtained.

Add 5 parts of liquid paraffin, 6 parts of squalane, 2 parts of octyl dodecyl myristate, 2 parts of neopentylglycol diisooctanoate, 0.8 parts of sorbitan monooleate and an appropriate amount of perfume to this mixed powder, and mix thoroughly. The powdery foundation was manufactured. The amount of conductive zinc oxide in the foundation was 50% by mass as a residual component on the skin excluding volatile components.

(Comparative Example 1)

A powdery foundation was used in the same manner as in Example 1 except that zinc oxide used had a specific surface area of 1 Om ² / g and a volume resistivity of 100 M · Ωcm (manufactured by Huxitech Co., Ltd .: zinc oxide super 10). Was manufactured. The content of zinc oxide in the foundation was 50% by mass as a residual component on the skin excluding volatile components.

(Making a cake foundation)

(Example 2)

As the conductive zinc oxide, one having a specific surface area of 1 Om ² / g and a volume resistivity of 90 Ω · cm (manufactured by Huxitech: conductive zinc oxide 23-K) was used.

Powder component of 32 parts of conductive zinc oxide, 15 parts of talc, 16 parts of my strength, 1 part of bengara, 2.8 parts of iron yellow oxide, 0.2 parts of black iron oxide and 15 parts of polyamide powder in a mixer The mixture was mixed to obtain a mixed powder.

To this mixed powder were added 4 parts of polyoxyethylene sorbine monooleate (20E.II.), 8 parts of squalane, 6 parts of silicone oil, and an appropriate amount of perfume, and the mixture was thoroughly stirred and mixed to produce a cake foundation. The content of conductive zinc oxide in the cake foundation was 32% by mass as a residual component on the skin excluding volatile components. (Comparative Example 2)

The same procedure as in Example 2 was carried out except that the specific surface area was 1 Om ² / g, and the volume resistivity was 10 ΟΜΩ'cm (manufactured by Huxitech Co., Ltd .: zinc oxide super 10 (SUPER-10)). To make a cake foundation. The content of zinc oxide in the cake foundation was 32% by mass as a residual component on the skin excluding volatile components.

(〇ZW¾, fabrication of chemical foundation)

(Example 3)

Conductive zinc oxide 10 parts, Bengala 0.5 parts, yellow iron oxide 1.4 parts, black iron oxide 0.1 parts, bentonite 0.5 parts, purified water 55 parts, triethanolamine 1 part, propylene glycol Using 10 parts, polyoxyethylene sorbine monostearate 1 part, glycerin monostearate 2 parts, liquid paraffin 7.5 parts, lanolin 2 parts, stearic acid 2 parts and isohexadecyl alcohol 7 parts A 0 ZW emulsified foundation was produced by the following procedure.

That is, propylene glycol in which bentonite was dispersed was first added to purified water, followed by stirring and mixing, and then triethanolamine and polyoxyethylene sorbitan monostearate were further added and mixed. To this, mixed powder obtained by mixing conductive zinc oxide, red iron oxide, yellow iron oxide, and black iron oxide with a mixer was added, and the mixture was treated by a homomixer.

Further, glycerin monostearate, liquid paraffin, lanolin, stearic acid, and isohexadecyl alcohol were added, and the mixture was treated with a homogenizer. Finally, an appropriate amount of flavor was added, and the mixture was sufficiently stirred and mixed to produce a 0 / W emulsified foundation. The amount of the conductive zinc oxide in the 0 / W emulsified foundation was 22% by mass as a residual component on the skin excluding volatile components.

(Comparative Example 3)

Except using zinc oxide having a specific surface area of 1 Om ² Zg and a volume resistivity of 10 ΟΜΩcm (manufactured by Haku Sittech Co., Ltd .: zinc oxide super 10-10). In the same manner as in Example 3, a 0 / W emulsion type foundation was produced. The amount of zinc oxide in the 0 / W emulsion-type foundation was 22% by mass as a residual component on the skin excluding volatile components.

(Preparation of 7k) '' [Example 4]

(Production of conductive zinc oxide)

Conductive zinc oxide (specific surface area: 25 m ² / g, volume resistivity: 40 Ωcm) was used as zinc oxide.

This conductive zinc oxide was produced as follows. That is, 30 g of reagent primary ammonium carbonate was dissolved in 500 cc of water, and another solution of 5 g of aluminum sulfate dissolved in 50 cc of water was put into the above ammonium carbonate solution. This solution was separately placed in a dispersion prepared by dispersing 100 g of Zinc flower in the French method in 200 cc of water, heated to 60 ° C and stirred, and after 1 hour, filtered and washed with water, and the cake was dried. Thereafter, firing was performed at 760 ° C. for 120 minutes in a hydrogen atmosphere to obtain conductive zinc oxide. It was confirmed that the obtained conductive zinc oxide had a specific surface area of 25 m ² / g and a volume resistivity of 40 Ω · cm.

1.6 parts of the above conductive zinc oxide, 0.1 parts of red iron oxide, 0.1 parts of yellow iron oxide, 2 parts of glycerin, 2 parts of 1,3-butylene glycol, 1 part of propylene glycol, 0.2 parts of camphor Part, ethanol 15 parts, purified water 78 parts, and appropriate amount of fragrance, and the following procedure was used to produce lotion.

First, the organic components consisting of ethanol, glycerin, 1,3-butylene glycol, propylene glycol and fragrance are mixed. Next, purified water, camphor, conductive zinc oxide, red iron oxide and yellow iron oxide were stirred and dispersed, and the organic mixture previously mixed was added to this dispersion, followed by stirring to prepare a lotion. The content of conductive zinc oxide in the lotion was 22% by mass as a residual component on the skin excluding volatile components. (Comparative Example 4)

Makeup is performed in the same manner as in Example 4 except that zinc oxide has a specific surface area of 3 Om ² / g and a volume resistivity of 100ΜΩ · cm (manufactured by Haxis Tech Co., Ltd .: zinc oxide super 30). Water was produced. The amount of zinc oxide in the lotion is It was 22% by mass as a residual component on the skin excluding volatile components.

(¾, Preparation of liquid)

(Example 5)

(Production of conductive zinc oxide)

As zinc oxide, conductive zinc oxide (having a specific surface area of 18 m ² / g and a volume resistivity of 120 Ω ■ cm) was used.

This conductive zinc oxide was manufactured as follows. That is, 30 g of reagent primary ammonium carbonate was dissolved in 500 cc of water, and a solution of 5 g of aluminum sulfate dissolved in 50 cc of water was added to the above ammonium carbonate solution. This solution was separately placed in a dispersion prepared by dispersing 100 g of French Zinc Flower in 200 cc of water, heated to 60 ° C and stirred, filtered for 1 hour, washed with water, dried, and dried. Calcination was performed at 780 ° C for 60 minutes in a hydrogen atmosphere to obtain conductive zinc oxide. It was confirmed that the obtained conductive zinc oxide had a specific surface area of 18 m ² / g and a volume resistivity of 120 Ω · cm.

10 parts of conductive zinc oxide obtained above, 50 parts of purified water, 7 parts of propylene glycol, 4 parts of sorbitan sesquioleate, 1 part of polyoxyethylene sorbine monooleate (20E.0.), 1 part of liquid paraffin Using 2 parts of lanolin, 8 parts of squalane, 1 part of silicone oil, and 2 parts of beeswax, an emulsion was prepared by the following procedure.

First, propylene glycol and conductive zinc oxide are added to purified water, and mixed at 70 ° C with heat. After heating and dissolving liquid paraffin, lanolin, squalane, silicone oil and bead wax, add sorbic acid sesquioleate and monooleic acid polyoxyethylene sorbic acid (20E.0.) And adjust to 70 ° C. Purified water containing ethanol and conductive zinc oxide was gradually added and emulsified to produce an emulsion. The content of conductive zinc oxide in the emulsion was 20% by mass as a residual component on the skin excluding volatile components.

(Comparative Example 5)

The specific surface area was 3 Om ² / g and the volume resistivity was 10 10Ω · cm (Zinc Oxide: Zinc Oxide Super 30). Except for this, an emulsion was prepared in the same manner as in Example 4. The content of zinc oxide in the emulsion was 20% by mass as a residual component on the skin excluding volatile components.

(Making cream)

(Example 6)

Conductive zinc oxide 10 parts, purified water 45 parts, ceanol 2 parts, glycerin 8 parts, propylene glycol monostearate 2 parts, stearic acid 2 parts, silicone oil 5 parts, lanolin 2 parts, squalane 15 parts, octane Using 8 parts of cetyl acid and 1 part of microcrystalline wax, a cream was produced by the following procedure.

The oil consisting of propylene glycol monostearate, ceanol, lanolin, silicone oil, cetyl octanoate, stearic acid, squalane, and microcrisine linux was heated and stirred at 70 ° C.

After glycerin was dissolved in purified water, the conductive zinc oxide was stirred and mixed, the temperature was adjusted to 70 ° C., and the heated and mixed oil was added and emulsified with a homomixer to produce a cream. The content of the conductive zinc oxide in the cream was 18% by mass as a residual component on the skin excluding volatile components.

(Comparative Example 6)

The same procedure as in Example 6 was carried out except that the specific surface area was 1 Om ² / g and the volume resistivity was 10 10Ω · cm (Haztec: zinc oxide super 10 (SUPER-10)). An emulsion was made. The content of zinc oxide in the cream was 18% by mass as a residual component on the skin excluding volatile components.

(U) Sample evaluation

Using the various cosmetics of Example and Comparative Example produced in (I), the ultraviolet impermeability and infrared impermeability as well as the makeup stickiness and hot flash were measured.

① UV opacity, infrared opacity:

Of the prepared cosmetics, powdery foundation and cake foundation are applied using puffs on PET films, and emulsified foundations, lotions, emulsions and creams are applied on PET films. Spectrometer (day This spectrometer V_570 type).

The measurement results are summarized in [Table 1] as transmittance at each wavelength in the ultraviolet, visible, and infrared regions. ^j Table 1

② Makeup, hot flash:

i) With regard to makeup stickiness, 10 female panelists were subjected to a sensory test using the cosmetics of Examples and Comparative Examples. As a result, ◎ indicates that 8 to 10 persons preferred the embodiment, Δ indicates that 5 to 7 persons preferred, and X indicates the others. ii) Regarding the hot flashes, 10 female panelists also used the cosmetics of Examples and Comparative Examples to go out outdoors under the fine weather, and listened to the heat generated by the sensory test. As a result, ◎ indicates that 8 to 10 persons were less in the Example, Δ indicates that 5 to 7 persons were smaller, and X indicates the others.

The results of the above sensory tests are shown in [Table 2]. Table 2

As can be seen from the transmittance at each wavelength in Table 1, there is almost no difference in the transmittance in the visible region between the example and the comparative example in all the examples, but the examples in the ultraviolet and infrared regions are different. In each case, the transmittance is lower than that of the comparative example, and it can be seen that the ultraviolet ray preventing effect and the infrared ray preventing effect are larger than those of the comparative example.

In addition, from the results of the sensory tests in Table 2, the conductive zinc oxide of the present invention, which has good cosmetic durability and little hot flash, is used for cosmetics in all examples, although the degree varies. The effect of blending was confirmed.

Function for Kake no Kamo II

ADVANTAGE OF THE INVENTION According to this invention, while providing ultraviolet-ray absorption ability which mix | blend conductive zinc oxide fine powder, the cosmetics excellent in makeup stickiness are provided. The fact that this makeup collapse is small is, of course, not only an effect of preventing ultraviolet rays, but also the aesthetic role of cosmetics, which is the original purpose of makeup, can be maintained for a long time, which is very convenient.

Claims

The scope of the claims

1. ratios cosmetic surface area characterized by being obtained by blending 2~10 Om ² / g, the conductive Seisani匕zinc fine powder is less than a volume resistivity of 1 Ο δ Ω · ^cm.

2. The cosmetic according to claim 1, wherein the volume resistivity of the conductive zinc oxide fine powder is 500 Ω · cm or less.

3. The cosmetic according to claim 1, wherein the amount of the conductive zinc oxide fine powder is at least 3% by mass as a residual component on the skin excluding volatile components.

4. The cosmetic according to claim 1, wherein the conductive zinc oxide fine powder is a zinc oxide fine powder using aluminum as a conductivity-imparting component.