JPH07330361A - Iron oxide fine particle-dispersed flaky glass and cosmetic formulated therewith - Google Patents

Abstract

PURPOSE:To obtain the subject glass having high ultraviolet-screening ability and uniform colorability and also having high transparency for visible light, and to obtain a high-quality cosmetic formulated with this glass. CONSTITUTION:The objective smooth-surfaced flaky glass contains, so as to stand at 0.1-85wt.% in a dispersed state in the form of virtually isolated particles, iron oxide fine particles 1-300nm in diameter derived from hydroxyl- bearing colloid particles. The flaky glass has >=80% transmittance for the visible light with wavelengths of 700-800nm and also ultraviolet-screening ability. Iron oxide fine particles 1-20nm in diameter may also be used, which is obtained by coating a base material with a solution containing a hydrolyzable organometallic compound capable of polycondensation and an iron compound followed by drying, peeling the resultant film which is then sintered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to iron oxide fine particle-dispersed flake-shaped glass, particularly flake-shaped glass and cosmetics suitable for a UV-screening agent or coloring agent having a high UV-screening ability and high transparency to visible light. Regarding fees.

[0002]

2. Description of the Related Art Iron oxide is added to and blended with paints, plastic films, base materials for cosmetics, etc., and is used as an ultraviolet shielding agent or a coloring agent. In general, iron oxide fine particles used for this purpose are powdery and difficult to uniformly disperse in a medium, and even once dispersed, there is a problem in that they agglomerate with time and become fooled or uneven. there were. In particular, when a large amount of cosmetics is blended, the above-mentioned problem becomes remarkable, and further, there is a problem that slippage is deteriorated and spreadability (spreading) on the skin is deteriorated.

In order to solve the above problems, a solution containing an organometallic compound and having fine particles dispersed therein is applied onto a substrate, preferably a substrate having a smooth surface, and dried to be peeled from the substrate. After that, a method for producing flaky glass characterized by heat treatment is disclosed (Japanese Patent Laid-Open No. 63-12).
6818, JP-A-1-143821, and JP-A-4-928.
32). The flake glass in which iron oxide fine particles are dispersed according to this method does not aggregate with time and spreads well, but if the fine particles are not sufficiently dispersed, the visible light transparency and the ultraviolet shielding efficiency are low. , Etc.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned prior art, the present invention has a high UV-shielding ability and a uniform coloring property, which have been difficult to manufacture conventionally, and has a high transparency to visible light.
It is intended to provide glass flakes in which iron oxide fine particles are dispersed and high-quality cosmetics containing the same.

[0005]

[Means for Solving the Problems] In order to solve this problem,
The present inventors added an iron-containing colloid or an iron compound to a solution containing an organic metal compound capable of hydrolysis and polycondensation and water, and applied this on a substrate, preferably a substrate having a smooth surface. Then, it was found that an iron oxide fine particle-dispersed glass flake having excellent visible light transparency can be easily and efficiently produced by heat-treating after drying, peeling from the substrate, and the present invention.

That is, according to the first aspect of the present invention, iron oxide fine particles derived from colloidal particles having a hydroxyl group and having a particle size of 1 to 300 nm are agglomerated to 0.1 to 85% by weight without agglomeration. In the glass flakes substantially dispersed and contained in the form of single particles, the transmittance for visible light having a wavelength of 700 to 800 nm is 80% or more over the entire area,
In addition, the present invention is a glass flakes in which iron oxide fine particles are dispersed and which has an ultraviolet shielding ability and has a smooth surface. The second aspect of the present invention is to apply a solution containing a hydrolyzable and polycondensable organometallic compound and an iron compound to a substrate. Iron oxide fine particles having a particle diameter of 1 to 20 nm obtained by drying, peeling, and sintering,
A flake-like silica glass, which is substantially dispersed in the form of a single particle without agglomeration so as to have a content of 0.1 to 85% by weight, and has a transmittance of visible light having a wavelength of 700 to 800 nm over the entire region. It is a flake-shaped silica glass in which iron oxide fine particles are dispersed and which has a smooth surface and has a UV shielding ability of 80% or more.

The diameter of the iron oxide fine particles in the glass flakes dispersed with iron oxide fine particles of the present invention is 1 nm or more and 300 nm or less. If it is less than 1 nm, the light scattering effect by the fine particles is reduced, the ultraviolet shielding effect is reduced, and the color tone of coloring is not good, which is not preferable. If it is larger than 300 nm, the transparency to visible light is impaired, which is also not preferable.

The iron oxide content in the iron oxide fine particle-dispersed glass flake is preferably 0.1% by weight or more and 85% by weight or less. When the content is less than 0.1% by weight, the ultraviolet ray shielding effect is insufficient and the color is light, which is not preferable. If the content is more than 85% by weight, the glass phase becomes discontinuous, the flake glass tends to be brittle, and the transparency to visible light also becomes low, which is not preferable. More preferable content is 1
It is 40% by weight.

The transmittance of the glass flakes is the refractive index.
Wavelength 700-800 when dispersed in any medium 1.3-1.6
The transmittance for visible light of nm is 80% or more over the entire area. However, the transmittance here is a value measured by a spectrophotometer in accordance with the method of JIS K0115, with the transmittance of only the medium being 100%.

The iron oxide fine particles in the present invention are derived from colloidal particles having a hydroxyl group or are iron oxide fine particles deposited in glass by heating.

The method for producing the glass flakes in which iron oxide particles are dispersed is not particularly limited, but first, 1) adding an iron-containing colloid to a solution containing an organic metal compound capable of hydrolysis and polycondensation and water, This is a method in which a base material, preferably a substrate having a smooth surface, is applied, dried and peeled from the base material, and then heat-treated to produce, and the iron oxide fine particles generated here are colloids having a hydroxyl group. It comes from particles. The next method is 2) adding iron compounds such as iron alkoxides, acetylacetone salts, acetates, nitrates, chlorides, etc. to a solution containing hydrolyzable and polycondensable organometallic compound and water, It is a method in which a material, preferably a substrate having a smooth surface, is applied, dried and peeled from a substrate, and then iron oxide fine particles are precipitated in a glass matrix by heat treatment. These methods are preferable because it is possible to obtain flake glass in which iron oxide fine particles are dispersed, which have particularly excellent characteristics.

Among the above methods, in the method 1) above in which an iron-containing colloid is added, since the colloid is uniformly dispersed in a solution containing the organometallic compound and water, the flake-like glass finally obtained. Those having extremely high dispersibility in iron oxide fine particles and having excellent characteristics can be easily produced. The iron-containing colloid is not particularly limited as long as it contains iron, but iron oxide colloids, hydrous iron oxide colloids, iron hydroxide colloids and the like are particularly preferable because they have high dispersibility in the above solution, and are 1 to 300 nm. Iron oxide fine particles having a particle size of, particularly, a particle size of 30 to 300 nm are dispersed in glass.

In addition, in the above method 2) of adding an iron compound among the above methods, iron oxide fine particles are precipitated in the glass matrix by heat treatment. A uniform dispersion of 1 to 20 nm iron oxide fine particles is obtained, and the transparency is particularly excellent.

The hydrolyzable and polycondensable organometallic compound used in the present invention may be basically any compound as long as it can be hydrolyzed and dehydrated and condensed, but a metal alkoxide having an alkoxyl group is preferable. Specifically, methoxides such as Si, Ti, Al and Zr, ethoxides, propoxides, butoxides and the like are used as a single substance or a mixture.

The solvent of the solution containing the above organometallic compound is
Basically, any substance may be used as long as it substantially dissolves the organometallic compound, but alcohols such as methanol, ethanol, propanol and butanol are most preferable.

Water is required for the hydrolysis of the organometallic compound. This may be acidic, neutral or basic, but in order to promote hydrolysis, it is preferable to use water acidified with hydrochloric acid, nitric acid, sulfuric acid or the like. The addition amount of the acid is not particularly limited, but is 0.
001-2 is good. If the amount of added acid is less than 0.001 in terms of molar ratio, the hydrolysis of the organometallic compound is not promoted sufficiently,
Also, if the molar ratio is more than 2, the effect of promoting hydrolysis is no longer improved and the acid is excessive, which is not preferable.

The water added is also necessary for stabilizing the dispersion of the iron-containing colloid. The amount of water added is preferably 10% by weight or more and 80% by weight or less of the solution. However, the amount of water referred to here is the total amount of water contained in the colloid and water newly added. If the amount of water added is less than 10% by weight of the solution, the above colloid tends to be unable to exist stably, which is not preferable. If the amount of water added is more than 80% by weight of the solution, the concentration of the solid content in the solution becomes too low and the yield of flakes becomes low, which is not preferable.

In addition, an organic thickener or the like may be added in order to change the characteristics of the solution. However, if the amount added is large, carbonization may occur in the final stage of heating, so the amount added should be kept below 10% by weight.

The substrate used in the present invention is made of metal, glass, plastic or the like and has a smooth surface. A liquid containing the above organometallic compound is applied to such a substrate to form a thin film of 0.06 to 50 microns. When this film dries, it contracts, but the substrate does not contract, so cracks occur in the film, and the film becomes flakes. In order for the substrate and the film to be separated from each other, it is preferable that there is little interaction such as strong bonding between the substrate and the film.

As a technique for forming a film on the surface of the substrate, a known technique may be used. For example, a method of immersing the substrate in a liquid containing the above-mentioned organometallic compound and then pulling it up, or dropping the liquid on the substrate. Then, a method of rotating the substrate at a high speed, a method of spraying the liquid on the substrate, or the like is used.

The thickness of the glass flakes produced by the present invention varies depending on the solution or film forming conditions, but is generally between 5 and 0.05 microns. If it is thicker than 5 μm, the difference in drying rate between the free surface after film formation and the vicinity of the substrate becomes too large, and peeling between films occurs in a direction parallel to the substrate. On the other hand, if the thickness is less than 0.05 μm, the adhesive force between the substrate and the film becomes too large, and the film does not peel from the substrate.

Regarding the heat treatment, the method is not particularly limited. Sintering temperature and time, it is preferable to heat above the conditions that ensure the transition from the gel of the matrix to the glass and the conditions in which iron oxide fine particles are stably present, or to precipitate, usually 300 to Heat at 1200 ° C for 10 minutes to 5 hours. Depending on the purpose of use, heat treatment after drying may not be necessary.

The cosmetic composition of the present invention containing the flaky glass having iron oxide fine particles dispersed therein has a high visible light transparency of the flake glass having iron oxide fine particles dispersed therein and does not change with time. It is a stable product with good color development. Further, since the iron oxide fine particles are uniformly dispersed, the ultraviolet ray shielding efficiency is good, and a small amount of high ultraviolet ray shielding is possible. Further, the flaky glass in which fine particles of iron oxide are dispersed do not aggregate with each other, and the surface is smooth and exhibits good slipperiness.
The product has a good feel and feel.

In the cosmetics used in the present invention, in addition to the iron oxide fine particle-dispersed flake-shaped glass, pigments ordinarily used may be used in combination, if necessary. For example, titanium oxide, zinc oxide, zirconium oxide, yellow iron oxide, black iron oxide, red iron oxide, ultramarine blue, dark blue, chromium oxide, inorganic pigments such as chromium hydroxide, mica titanium, pearlescent pigments such as bismuth oxychloride, tar. Pigments, natural pigments, powders of silica beads, plastic beads such as nylon and acrylic, talc, kaolin, mica, sericite, other mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, clays, etc. It is illustrated.

The amount of the glass flakes in which iron oxide particles are dispersed varies depending on the kind of the intended cosmetic, but it is used in the range of 1 to 80% by weight based on the solid components such as pigments, and especially 2 A range of up to 50% by weight is preferred. If the content is less than this, there is a problem that the ultraviolet ray shielding effect is not significantly exhibited, the coloring is not good, etc., on the contrary, even if more flaky glass is added than the upper limit, the ultraviolet ray shielding effect does not increase, and others. The amount of the pigment component is decreased, and it becomes difficult to adjust the color tone and improve the adhesion to the skin.

Further, the dispersibility of the glass flakes dispersed with iron oxide fine particles used in the present invention in cosmetics is improved,
In order to improve the feel, the surface treatment of the glass flakes can be modified without any problem. For example, methyl hydrogen polysiloxane, reactive alkyl polysiloxane, metal soap, hydrogenated lecithin, acyl amino acid, acylated collagen metal salt selected from aluminum, magnesium, calcium, titanium, zinc, zirconium, iron, etc. When surface treatment is performed with a so-called hydrophobizing agent, the surface of the flake-shaped glass changes from hydrophilic to hydrophobic, so that it becomes more familiar with the oil agent added when formulating the cosmetic composition, resulting in a cosmetic product with a good feel. .

[0027]

EXAMPLES Examples will be shown below. Example-1 5000 ml of 0.35 mol / l iron nitrate aqueous solution was heated to boil, 2
A specified aqueous potassium hydroxide solution was added dropwise to adjust the pH to 7. After returning to room temperature, the resulting red precipitate was separated, washed with water, and aged in an autoclave at 150 ° C for 10 hours. This is washed with water having a pH of 9 and ion-exchanged water to give a pH of 2
It was diluted with water containing nitric acid to obtain a hematite (α-Fe2O3) colloid of about 20% by weight. When the particle size of the colloid was measured by the dynamic light scattering method, the average particle size was about 110 nm.

2000 ml of this hematite colloid, 2200 ml of silicon tetramethoxide, 1000 ml of ethanol and 1000 ml of 2-propanol were mixed and aged at 40 ° C. for about 60 hours to obtain a coating solution. The surface of this solution was polished to a smooth thickness of 0.5.
A millimeter stainless plate was dipped and pulled up at a speed of 30 cm / min to apply the liquid to the surface. This was dried at 150 ° C., the applied gel film was peeled off, and sintered at 950 ° C. for 1 hour. After sintering, when examined by an X-ray diffraction method, only a sharp peak of hematite was detected, and the matrix was in a glass state. As a result of chemical analysis of the flakes after sintering, the content of hematite was about 30% by weight.
When observing the flakes with a transmission electron microscope, about 80 ~
It was observed that the 140 nm-sized hematite particles were monodispersed in the silica glass matrix. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 micron.

The sintered flakes were crushed with a jet mill,
Classify to an average particle size of about 10 microns, disperse about 5% by weight in vinyl resin (refractive index after curing is about 1.5),
As a film with a thickness of 0.15 mm, the transmittance was measured with a spectrophotometer.The visible light transmittance at wavelengths 700 to 800 nm was 85% or more over the entire area, and the ultraviolet light transmittance at wavelengths 350 nm or less was 5% or less. It was confirmed that the glass is reddish brown flake glass that has high transparency to visible light and effectively blocks ultraviolet rays.

Comparative Example-1 Commercially available fine particle iron oxide (trade name: Nanotite, Showa Denko
Co., Ltd., primary particle diameter 40 ~ 60 nm, hematite), using a commercially available paint shaker, so as to be 20% by weight.
It was dispersed in a 2N nitric acid aqueous solution. This suspension 2000m
l, silicon tetramethoxide 2200ml, ethanol 1000
ml and 2-propanol 1000 ml were mixed and cured at 40 ° C. for about 60 hours to obtain a coating liquid. The iron oxide concentration in this coating liquid is almost the same as the iron oxide concentration in the coating liquid of Example-1.

Using this coating solution, sintered flakes were obtained in the same manner as in Example-1. As a result of chemical analysis, the content of iron oxide was about 24% by weight. This is considered to be because iron oxide fine particles settled in the coating liquid. When the flakes were observed with a transmission electron microscope, it was observed that the fine particles monodispersed in the silica glass matrix were few and aggregates of several microns were formed. When the flakes were observed with a scanning electron microscope, iron oxide aggregates were projected from the flake surface to the outside. As a result, irregularities due to the iron oxide aggregates were observed on the flake surface, and the smoothness was poor. The thickness was about 0.6 micron.

Sintered flakes were crushed by a jet mill and classified to have an average particle size of about 10 microns, dispersed in a vinyl resin (having a refractive index of about 1.5 after curing) of about 10% by weight to give about 0.15 m.
As a film with a thickness of m, the transmittance was measured with a spectrophotometer, and the visible light transmittance at a wavelength of 700 to 800 nm was 50 to 60%.
And the ultraviolet transmittance at a wavelength of 350 nm or less was 2% or less. That is, it was confirmed that the glass was flake-shaped glass having high ultraviolet shielding performance but not high transparency to visible light.

Example-2 and Comparative Example-2 A powder foundation was prepared with the following composition. Ingredient-1 content (wt%) ------------------------------------- Prepared in Example-1 Flake glass of the present invention 1.7 Talc 78.5 Mica 9.1 Titanium oxide 3.8 Fine particle titanium oxide 1.9 Magnesium stearate 2.9 Yellow iron oxide 0.8 Black iron oxide 0.1 Silk powder 0.5

Ingredient-2 Component Content (% by weight) ------------------ Squalane 0.5 sesquilan Sorbitan oleate 0.1

Ingredient -3 content (% by weight) ---------------------------------------- Perfume 0.1-- Component 1 was stirred for 5 minutes using a Henschel mixer. While stirring and mixing component-2, which was uniformly melted at 70 ° C., was added thereto. Furthermore, after adding component-3,
Stir and mix for 1 minute, crush with atomizer to product-1
(Example-2) was obtained.

Component-4 blending amount (% by weight) ------------------------------------------------- Talc 79.5 Mica 9.3 Titanium oxide 3.8 Fine-grained titanium oxide 1.9 Magnesium stearate 2.9 Yellow iron oxide 0.8 Black iron oxide 0.1 Silk powder 0.5 ---------------------------- −−−−−−−−−−−

Component-4 was added to 5 using a Henschel mixer.
Stir for minutes. In addition to this, the components uniformly melted at 70 ℃-
While adding 2 dropwise, stirring and mixing were performed. In addition, ingredient-3
Was added, and the mixture was stirred and mixed for 1 minute and pulverized with an atomizer to obtain a product-2 (Comparative Example-2).

[0038] These were used by 20 (female) panelists for 10 days, and a 5-step method with a minimum score of 1 and a maximum score of 5 was used.
The results of the sensory tests evaluated are shown in Table 1.

[0039]

[Table 1] Table-1 ==================================== Item Powder of the present invention (product -1) Comparative Powder (Product-2) (Example-2) (Comparative Example-2) --------------------------------------- --------------- 4.8 1.5 ----------------------------------------------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Transparency 4.7 3.0 −−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−− Gloss 4.5 2.3 −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−− 4.43.1 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −− Performance sustainability 4.8 3.8 ========== =========================

As described above, it was confirmed that the cosmetic of the present invention has good spreadability (adhesion), good transparency and glossiness, excellent color development, and is resistant to fading.

Example 3 Silicon tetramethoxide 2200 ml, ethanol 1000 ml,
2-Propanol 1000 ml, 0.05N hydrochloric acid 4400 ml, and iron acetylacetone salt 22 g were mixed and cured at 35 ° C. for about 70 hours to obtain a coating solution. Using this coating solution, a flaky gel was obtained in the same manner as in Example-1. Run this gel at 1100 ° C for 3
Heat treated for hours. When the flakes were examined by an X-ray diffraction method, only the peak of hematite was detected,
The matrix was glassy. As a result of chemical analysis,
The content of hematite was about 2.5% by weight. When the flakes were observed with a transmission electron microscope, it was observed that the 1-8 nm-sized hematite particles were monodispersed in the silica glass matrix. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 micron.

Sintered flakes were crushed by a jet mill and classified to have an average particle size of about 10 microns, dispersed in a vinyl resin (having a refractive index of about 1.5 after curing) of about 10% by weight to give about 0.15 m.
As a film with a thickness of m, the transmittance was measured with a spectrophotometer and the visible light transmittance at a wavelength of 700 to 800 nm was 90% or more over the entire area, and the ultraviolet light transmittance at a wavelength of 350 nm or less was 5% or less. , Highly transparent to visible light,
It was confirmed that the glass was a reddish brown flake that effectively shielded ultraviolet rays.

Example-4 Silicon tetramethoxide 2200 ml, ethanol 1000 ml,
2-Propanol 1000 ml, 0.05N nitric acid 4400 ml and iron acetylacetone salt 3 g were mixed and cured at 35 ° C. for about 70 hours to obtain a coating solution. Using this coating solution, a flaky gel was obtained in the same manner as in Example-1. This gel at 1200 ℃
Heat treated for 5 hours. When the obtained flakes were examined by an X-ray diffraction method, only a hematite peak was detected, and the matrix was in a glass state. As a result of chemical analysis, the content of hematite was about 0.3% by weight. When the flakes were observed with a transmission electron microscope, it was observed that the 1-8 nm-sized hematite particles were monodispersed in the silica glass matrix. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 micron.

Sintered flakes were crushed and classified with a jet mill to an average particle size of about 10 microns, and dispersed in a vinyl resin (having a refractive index of about 1.5 after curing) of about 20% by weight to obtain about 0.3 mm.
As a thick film, when the transmittance was measured with a spectrophotometer, the visible light transmittance at a wavelength of 700 to 800 nm was 90% or more over the entire region, and the ultraviolet transmittance at a wavelength of 350 nm or less was 5% or less, It was confirmed that it is a reddish brown flake-like glass that has high transparency to visible light and effectively blocks ultraviolet rays.

Comparative Example-3 Commercially available fine particle iron oxide (trade name: Nanotite, Showa Denko
Co., Ltd., primary particle size 40-60nm, hematite), using a commercially available paint shaker, about 0.25% by weight dispersed in vinyl resin (refractive index after curing is about 1.5), about 0.15mm
As a thick film, the transmittance was measured with a spectrophotometer, and the visible light transmittance at a wavelength of 700 to 800 nm was 60 to 70%, and the ultraviolet transmittance at a wavelength of 350 nm or less was about 20 to 25%. . With a film of the same thickness in which about 2.5% by weight is dispersed in vinyl resin, the visible light transmittance at a wavelength of 700 to 800 nm is 45%.
~ 55% and 5% UV transmittance for wavelengths below 350 nm
It was below.

That is, it is difficult to uniformly disperse the fine iron oxide particles, and addition of a small amount thereof does not provide sufficient ultraviolet shielding. When a large amount is added, the ultraviolet ray blocking ability is improved, but the hiding property appears due to particle aggregation, and the visible light transparency is lowered.

[0047]

The above detailed description and embodiments of the present invention,
As is apparent from Comparative Examples, according to the present invention, an ultraviolet shielding agent having a high ultraviolet shielding ability and a high transparency to visible light can be obtained.

Further, in the cosmetic composition containing the flake glass in which iron oxide fine particles are dispersed according to the present invention, the flake glass in which iron oxide fine particles are dispersed has a high visible light transparency and does not change with time. A stable product with no color unevenness and good color development. Further, the glass flakes in which iron oxide fine particles are dispersed do not agglomerate with each other and exhibit good slipperiness, so that the extensibility (spreading) is good and the product is excellent in touch feeling.

Claims (3)

[Claims] 1. Iron oxide fine particles having a particle diameter of 1 to 300 nm, which are derived from colloidal particles having a hydroxyl group,
Flake glass containing 0.1 to 85% by weight of particles dispersed substantially in the form of single particles without agglomeration and having a transmittance of visible light with a wavelength of 700 to 800 nm of 80% or more over the entire area. And flake glass having a smooth surface and fine particles of iron oxide dispersed therein and having an ultraviolet shielding ability. 2. A particle diameter of 1 to 20 nm, which is obtained by applying a solution containing a hydrolyzable and polycondensable organometallic compound and an iron compound to a substrate, drying, peeling, and sintering.
Iron oxide fine particles of 0.1 to 85% by weight,
A flake-shaped silica glass which is substantially dispersed and contained in the form of single particles without agglomeration, and has a transmittance of 80% or more for visible light having a wavelength of 700 to 800 nm over the entire area, and has an ultraviolet shielding ability. , Flake-shaped silica glass with finely dispersed iron oxide particles with a smooth surface. 3. A cosmetic comprising the iron oxide fine particle-dispersed flake glass according to any one of claims 1 and 2.