JPH08104606A - Cosmetic - Google Patents

Abstract

PURPOSE: To obtain a cosmetic by compounding finely particled inorganic powder easily dispersible by weak dispersion force, free from the exposure of untreated surface even applied with strong dispersion force and excellent in ultraviolet screening effect. CONSTITUTION: This cosmetic is obtained by compounding one or more kinds of finely particled inorganic powder, preferably titanium oxide, silica, alumina, zinc oxide, ferric oxide, cerium oxide or zirconium oxide having an particle diameter of 0. l-0.01μm and coated with an organosilicon compound by applying wet grinding or wet dissociation with a medium stirring mill. The organosilicon compound is preferably a methylhydrogenpolysiloxane, a dimethylpolysiloxane having viscosity of 2-100cs or an alkylsilane having a carbon number of <=10 in the alkyl group. The wet grinding or wet dissociation is usually performed in a mixture of 0.1-50 pts.wt. of the organosilicon compound and 50-5000 pts.wt. of a solvent based on 100 pts.wt. of a fine particled inorganic powder base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic containing a surface-treated fine particle inorganic powder.

[0002]

2. Description of the Related Art Inorganic fine particles such as fine particles of titanium oxide and fine particles of zinc oxide have an ultraviolet shielding effect, and are therefore used as sunscreen cosmetics by being blended with cosmetics (Japanese Patent Publication No. 47-42502). JP-A-49-45
No. 0, JP-A-64-7941 and the like).

In order to fully exert the ultraviolet ray shielding effect of the fine particle inorganic powder blended in the above cosmetics, it is necessary to use it in a state of being sufficiently dispersed in the blending system. A method of surface-coating an inorganic powder with an organic compound, an organometallic compound or the like and then blending it into a cosmetic has been studied (Japanese Patent Laid-Open Nos. 58-49307 and 59-172415, 59-172415, Japanese Patent Laid-Open No. 59-172415). 62-1450
11 and JP-A-62-67015).

[0004]

However, even if the powder is surface-coated with an organic compound or an organometallic compound, the surface-treated powder provided by a general treatment has a difference in the cohesive force of the base material. Even though the size of the particles is different, the surface treatment is usually performed on tens to hundreds of single particles.

For this reason, if a strong dispersion is applied to the cosmetic composition, the agglomerated particles of the surface-treated powder may be broken, or the paste may be formed by three rolls, or may be formed by pressing. However, as a result, the force of the re-grinding step functions, and the agglomerated particles are also broken by such a step, and as a result, the surface that has not been surface-treated is exposed and the characteristics deteriorate, which is a problem. Was there.

When the above surface-treated powder is used in cosmetics, a homogenizer or a Henschel mixer or other disperser or crusher having only a weak dispersing force does not expose the untreated surface, but the powder is not exposed. It could not be blended in a sufficiently dispersed state.

Moreover, in the actual production of cosmetics,
In addition to inorganic UV-screening agents such as particulate titanium oxide, plate-like mineral powders such as sericite, mica, and talc are often compounded, so using a disperser or crusher with strong dispersive power Even the powdery powder will be crushed, which will impair the properties of the finished cosmetic material such as a slippery feeling.

Further, it is not impossible to add only the surface-treated fine-particle inorganic powder to the cosmetic composition after predispersing, but in this case, the number of steps is increased, and especially in the case of a solid cosmetic composition. It also disturbs the dispersion state of the ingredients.

For the above reasons, there has been a demand for a cosmetic composition which can be sufficiently dispersed even if it is compounded with a weak dispersive power and has a high ultraviolet shielding effect.

[0010]

According to the present invention, a finely divided inorganic powder is included which can be easily dispersed even with a weak dispersing force and which does not expose an untreated surface even when subjected to a strong dispersion. And a cosmetic having an excellent ultraviolet shielding effect.

That is, the present invention has an average particle size of 0.1 to 0.1.
One or more fine particle inorganic powders having a size of 0.01 μm are selected from the group of organosilicon compounds consisting of methylhydrogenated polysiloxane, dimethylpolysiloxane having a viscosity of 2 to 100 cs, and alkylsilane having an alkyl group moiety having 10 or less carbon atoms. When the surface coating treatment is performed with one or more of the above-mentioned ones, it is a cosmetic in which a powder obtained by treating by using a process of wet crushing or wet pulverizing using a medium stirring mill is blended.

The cosmetic of the present invention contains a fine inorganic powder which is finely and uniformly surface-coated with the above-mentioned organic silicon compound by a method including a step of crushing or crushing. Even if you use a disperser that only has
The powder can be in a sufficiently dispersed state.

Hereinafter, the present invention will be described in detail. As the fine particle inorganic fine powder used in the present invention, fine particle titanium oxide, silica, alumina, zinc oxide, especially for the following reasons.
Cerium oxide, zirconium oxide, iron oxide and the like are effective and preferable.

Fine particle titanium oxide: Unlike ordinary titanium oxide for white pigments, since it has an average particle diameter of 0.1 to 0.01 μm, it has a light-transmitting property in the visible light portion and has an ultraviolet ray, particularly UV-B. Since it has an excellent ultraviolet ray shielding effect in the region, it is used in cosmetics and the like as described above.
For the cosmetics of the present invention, rutile type, anatase type,
Any crystal type such as amorphous can be used.

Silica and alumina: Finer powders than fine particle titanium oxide are commercially available. By mixing these, fine particle titanium oxide can be prevented from agglomerating and the distance between individual fine particle titanium oxide particles can be lengthened. . As a result, the silica and alumina particles themselves have almost no ultraviolet shielding effect, but the ultraviolet shielding effect as a composite is improved.

Zinc oxide, cerium oxide, zirconium oxide: These particles themselves are fine particles having strong agglomeration, and it is necessary to disintegrate the agglomerates and perform surface treatment. However, it should be mixed with fine particle titanium oxide to form a composite. Thus, it is possible to supplement the ultraviolet ray shielding effect in the UV-A region, which is one of the drawbacks of the particulate titanium oxide itself.

Iron oxide: Fine particles In addition to complementing the characteristics of fine particles having an ultraviolet shielding effect such as titanium oxide, a beige-colored composite powder can be obtained. Such a composite powder is, for example, obtained by subjecting uniformly mixed fine particles of titanium oxide and iron oxide to the surface treatment with the above-mentioned organosilicon compound, and therefore, when the titanium oxide and iron oxide are doped or deposited. Similarly, a powder that does not cause color separation can be finished.

The surface treatment agent used in the present invention includes methyl hydrogenated polysiloxane, dimethyl polysiloxane,
Various silicone oils such as methylphenylpolysiloxane, methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane,
Various alkylsilanes such as octyltriethoxysilane, n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, various fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane , Various organosilicon compounds such as silane coupling agents such as vinyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and metal-based coupling agents such as titanium-based, aluminum-based and alumina-zirconia-based, isostearic acid , Fatty acids such as stearic acid and their metal salts, and further surfactants were investigated. In particular, methyl hydrogenated polysiloxane, viscosity 2-10
Preferable results were obtained when one or more selected from the organosilicon compound group consisting of 0 cs dimethylpolysiloxane and an alkylsilane having an alkyl group moiety having 10 or less carbon atoms.

Here, the above-mentioned organosilicon compound which can be preferably used as the surface treating agent in the present invention will be described in more detail.

The methyl hydrogenated polysiloxane specifically refers to methyl hydrogenated polysiloxane, methyl hydrogenated cyclopolysiloxane and the like.

The dimethylpolysiloxane specifically refers to dimethylpolysiloxane, cyclodimethylpolysiloxane, and the like, among which the viscosity at room temperature is 2 to
It is preferably 1000 cs (centistokes), more preferably 2 to 100 cs. Viscosity 10
If it is 00 cs or more, the dispersibility is not sufficient.

The alkylsilane referred to in the present invention refers to a compound represented by the following structural formula. R ^a _n -Si (OR ^b )
_{^{4-n, R a n -SiR}} c x (OR b) 4-nx, R a n -SiC
_{^{l 4-n, R a n}} -SiR c x Cl 4-nx. Of these, silanes having an alkyl group having 10 or less carbon atoms that can be preferably used in the present invention include (R ^a : an alkyl group having 1 to 10 carbon atoms) (R ^b : an alkyl group having 1 to 4 carbon atoms) ) (R ^c : hydrogen atom, or methyl, ethyl group), specifically, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane. , Hexyltrimethoxysilane, octyltriethoxysilane and the like. In the case of a compound in which the alkyl group has 11 or more carbon atoms, the dispersibility becomes insufficient, probably because the carbon chain is too long.

As the treatment of the powder to be blended in the cosmetic of the present invention, it is essential to use the step of wet crushing or wet crushing using a medium stirring mill, but a specific example of the treatment is required. First, a fine particle inorganic powder base material, an organic silicon compound, a solvent, etc. are premixed and supplied to a medium stirring mill such as a sand grinder mill for treatment, and then the solvent is removed to form a powder. It is usually done.

As the medium agitating mill used in the present invention, a sand grinder mill, a tower mill, an attritor or the like can be used to obtain suitable results even if any device can be forcibly agitated. A sand grinder mill will be described as an example of these.

The sand grinder mill is a container in which beads are filled as a medium, and a stirring disk mounted perpendicularly to the rotating shaft is rotated at high speed to crush and disperse the agglomerated particles of the base material powder. The apparatus has a step of performing, and there are various modes such as vertical type / horizontal type, continuous type / batch type, and the like. When blended in the cosmetic of the present invention, there is no problem as long as it is a type in which the organic silicon compound can be surface-coated while wet-grinding or wet-crushing the fine-particle inorganic powder as the base powder.

As the beads used in the sand grinder mill, balls made of glass, alumina, zircon, zirconia, steel, flint stone, etc. as raw materials can be used, but those having high hardness and true specific gravity to avoid contamination. And preferably made of zirconia or zircon. As the size of the beads, those having a diameter of about 1 to 2 mm are usually used, but since the base material powder used in the present invention is fine particles, it is 0.3 to 1.0.
It is preferable to use one having a size of about mm.

As the stirring disk used in the sand grinder mill, various materials such as stainless steel, nylon and ceramics can be usually used, but the base powder used in the present invention is an inorganic powder. It is preferably made of wear-resistant ceramics, and in particular, when using beads made of zirconia or zircon as described above, it is preferable to use a zirconia disk.

The solvent for wet pulverization or wet pulverization is not particularly limited, and water, various alcohols such as methanol, ethanol and isopropyl alcohol,
Various organic solvents such as benzene, toluene, and paraffin may be used alone or in combination of two or more depending on the degree of dispersion of the fine particle inorganic powder base material and the characteristics of the organic silicon compound used.

The mixing ratio of each component such as the fine particle inorganic powder base material, the organic silicon compound, and the solvent during the wet crushing or the wet crushing is actually the target quality of the final product and the selection of efficient wet process conditions. Therefore, it is necessary to select an appropriate ratio depending on the type and combination of the medium to be used, but usually, the organosilicon compound is 0.1 to 50, preferably 1 to 30 with respect to 100 parts by weight of the fine particle inorganic powder base material. Parts by weight, solvent 50-5
000 It is preferably used in the range of 100 to 2000 parts by weight.

The fine particles of the organic silicon compound surface-coated inorganic powder obtained by utilizing the above steps are used as a raw material for cosmetics, as a powder or dispersed in a solvent such as alcohol or water, or as an oil or resin. It can be used by kneading.

By using the cosmetic raw material obtained above, white powder, foundation, pressed powder,
Water use foundation, oil foundation, emulsion foundation, lipstick, blusher, eye shadow, eyebrow,
It is possible to manufacture cosmetics such as eyeliner, mascara, nail color, cheek color, base foundation, sunscreen agent, emulsion and lotion.

In the cosmetic of the present invention, within the range to achieve the object of the present invention, oils, powders, solvents, surfactants, ultraviolet absorbers, preservatives and sterilizers which are usually used in cosmetics. Agents, preservatives, antioxidants, hormones, vitamins, moisturizers, fragrances and the like can be optionally mixed.

[0033]

The cosmetic material of the present invention is surface-treated at the same time while the powder base material to be blended is crushed into fine particles,
Since the surface of the particles close to the primary particles has been surface-treated, crushing during compounding does not cause agglomerated particles to break up and leave an untreated surface. As compared with the cosmetics, the dispersibility is greatly improved, and as a result, it is effective as a cosmetic having excellent properties such as ultraviolet ray shielding properties.

[0034]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.

A. Production of Surface-treated Fine Particle Inorganic Powder Sample 1-12 Inorganic Powder Base Material Containing Fine Particle Titanium Oxide Total 1,000
The surface treatment agent and the solvent of the types and amounts shown in Table 1 and Table 2 were mixed with g, and mixed by a stirrer to prepare a slurry, and then wet-processed using a horizontal continuous sand grinder mill. It was crushed. The residence time of the slurry in the mill was 5 minutes. The treated slurry is
It was put into a kneader and the solvent was removed by heating under reduced pressure to obtain a surface-treated powder. For Samples 2 to 5, fine particles of titanium oxide were mixed with the types and amounts of sub-base materials shown in Table 1 to make a total of 1,000 g, which was used as the inorganic powder base material. In addition, for Samples 1 to 5, 9, 10, and 12, further 1 is added to the surface-treated powder obtained in the above step.
Curing was performed at a temperature of 20 to 150 ° C. In addition,
Samples 1, 2, 4, 5,
No. 13 had a mean particle size of 35 nm (nanometer), and Samples 3 and 6 to 12 had a mean particle size of 15 nm.

Sample 13 The same type of substrate, surface treatment agent and solvent as in Sample 1 were used, blended in the same ratio as in Sample 1, and mixed with a blade stirrer to prepare a slurry, which was then wet crushed. Instead, the mixture was directly put into a kneader and heated under reduced pressure to remove the solvent to obtain a surface-treated powder, which was further cured at a temperature of 120 to 150 ° C.

Sample 14-16 Inorganic powder base material containing fine particle zinc oxide Total 1,000 g
On the other hand, the surface treatment agent and the solvent of the types and amounts shown in Table 3 were blended and mixed with a stirrer to prepare a slurry, and then wet crushing treatment was performed using a horizontal continuous sand grinder mill. The residence time of the slurry in the mill was 5 minutes. The treated slurry was put into a kneader, the solvent was removed by heating under reduced pressure to obtain a surface-treated powder, and further cured at a temperature of 120 to 150 ° C. Samples 15 and 16 were prepared by mixing the particulate zinc oxide with the sub-base materials in the types and amounts shown in Table 3 to obtain a total of 1.
What was made into 000g was used as an inorganic powder base material.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

* 1 Shin-Etsu Chemical Co., Ltd. KF99 * 2 Shin-Etsu Chemical Co., Ltd. KBM3103 * 3 Shin-Etsu Chemical Co., Ltd. LS-8600 * 4 Shin-Etsu Chemical Co., Ltd. KF96 20CS * 5 Shin-Etsu Chemical Co., Ltd. KF994 * 6 Shin-Etsu Chemical Kogyo Co., Ltd. KBM22 * 7 Shin-Etsu Chemical Co., Ltd. KF96 1000CS * 8 Shin-Etsu Chemical Co., Ltd. LS-6970 Note that the cosmetics containing the powders of Sample 1-10 and Sample 14-16 are within the scope of the present invention. It is a cosmetic.

B. Comparison of Dispersibility For each surface-treated powder of Sample 1-16 produced above, in order to evaluate the dispersibility, the light transmittance was measured in a liquid paraffin dispersion system using a paint conditioner. 1.35 g of each sample powder is put into a glass bottle with a lid of 140 ml and liquid paraffin #
52.0 g of 70 and 5.2 g of a dispersant were added to obtain 1.5
60 g of mm glass beads were added and dispersed for 5 minutes with a paint conditioner (red devil). The obtained paste was applied onto a polyester film by using a bar coater # 8, and a spectrophotometer (UV-31 manufactured by Shimadzu Corporation).
00), the light transmittance in the ultraviolet region (300 nm) was measured.

The results obtained are shown in Table 4. Since the fine particle titanium oxide has a function of scattering ultraviolet rays, if the surface-treated powder is sufficiently dispersed, as a result, the ultraviolet transmittance of the paste becomes small. Therefore, it is indicated that the smaller the ultraviolet transmittance, the better the dispersibility.

[0044]

[Table 4]

As shown in Table 4 above, as is clear from the difference in light transmittance between Sample 1 and Sample 13 when dispersed in liquid paraffin, which is one of the oils often used in cosmetics, the medium The product of the present invention (sample 1 compounded product) in which the powder in which the organosilicon compound is surface-coated by using the process of wet pulverization or wet crushing using a stirring mill is blended is compared even under the same dispersion conditions. Since the ultraviolet ray transmittance is lower than that of the product (sample 13 blended product), it can be seen that the dispersibility is more excellent. Further, as is clear by comparing the light transmittances of Samples 1 to 10 and Samples 11 and 12, even when the surface treatment is performed through the same wet disintegration step, the dispersibility varies depending on the type of treatment agent, It can be seen that the samples within the scope of the present invention have excellent dispersibility.

Example 1 A foundation was prepared according to the following formulation. The blending amount is% by weight. (1) Fine particle titanium oxide of sample 1 10.0 (2) Titanium oxide 10.0 (3) Talc 28.0 (4) Sericite 32.0 (5) Iron oxide 5.0 (6) Liquid paraffin 10. 0 (7) Methylpolysiloxane 4.0 (8) Sorbitan monooleate 1.0 (9) Antioxidant proper amount (10) Perfume proper amount Mixing (1) to (5) with a Henschel mixer and mixing and dissolving in advance uniformly (6) to (10) were added and mixed well. Then, this was crushed and compression molded.

Comparative Example 1 In place of the fine titanium oxide powder obtained in Sample 1, the fine titanium oxide powder of Sample 13 was used to prepare a foundation with the same formulation as in Example 1.

Using the foundations prepared in Example 1 and Comparative Example 1, the transmittance of ultraviolet rays at 300 nm was measured by the same method as in the above "B. Comparison of dispersibility". Table 5 shows the obtained results.

Example 2 A sunscreen agent was prepared according to the following formulation. The blending amount is% by weight. (1) Ultraviolet absorber (phenyl salicylate) 2.0 (2) Fine particle titanium oxide of Sample 10 10.0 (3) Kaolin 2.5 (4) Cetyl alcohol 4.0 (5) Vaseline 5.0 (6) Liquid paraffin 10.0 (7) Silicon oil 2.0 (8) Gluceryl monostearate 2.5 (9) Polyoxyethylene cetyl alcohol ether 3.0 (10) Propylene glycol 5.0 (11) Ethanol 54 0.0 (12) Perfume proper amount (13) Preservative proper amount Components other than (2) and (3) were uniformly mixed and dissolved, and (2) and (3) were gradually added to the mixture and homogenized with a homomixer. It was mixed and dispersed to obtain a product.

Comparative Example 2 Instead of the fine titanium oxide powder obtained in Sample 10,
Example 2 using the fine particle titanium oxide powder of Sample 12
A sunscreen agent was prepared with the same formulation as.

The sunscreen agents prepared in Example 2 and Comparative Example 2 were applied as they were on a quartz plate using a film applicator (gap 34 μm), and the thickness was 300 nm.
The transmittance of ultraviolet rays in the above was measured. Table 5 shows the obtained results.

[0052]

[Table 5] As is clear from Table 5, each example is 30 more than the comparative example.
The ultraviolet ray transmittance at 0 nm was low, and the ultraviolet ray shielding effect was excellent.

Claims (3)

[Claims] 1. An organic silicon compound is surface-coated by using a process of wet pulverization or wet pulverization using a medium stirring mill, and the average particle diameter is 0.1 to 0.01 μm.
Cosmetics characterized by blending one or more types of fine particle inorganic powders. 2. The cosmetic according to claim 1, wherein the fine inorganic powder is one or more selected from titanium oxide, silica, alumina, zinc oxide, iron oxide, cerium oxide and zirconium oxide. 3. The organosilicon compound is one or more selected from methylhydrogenated polysiloxane, dimethylpolysiloxane having a viscosity of 2 to 100 cs, and alkylsilane having an alkyl group moiety having 10 or less carbon atoms. Cosmetics described in.