JP2002038051A - Glass flake and cosmetic material brended with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass flake blended into a cosmetic material or the like that prevents the elution of boron, heavy metals and other components and that does not impair the characteristics as a pigment such as clarity of color, glittering brilliance and pearlescent appearance and the characteristics as a cosmetic raw material such as smooth feeling on the skin and good adhesion to the skin upon application. SOLUTION: The glass flake has on its surface a covering layer formed by covering the surface with one or more metal oxides selected from silica, alumina, zirconia, zinc oxide and cerium oxide in order to prevent the elution of a glass component from the glass flake.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to glass flakes and cosmetics containing the same.

[0002]

2. Description of the Related Art Glass flakes are very fine glass materials having a thickness on the order of microns.

[0003] When the surface is coated with titania, for example, the glass flake exhibits a pearl-like color tone. By blending the pearl-like glass flakes with cosmetics and resins, pearl-like products are provided.

[0004] For example, Japanese Patent Application Laid-Open No. 62-187770 describes an ultraviolet shielding pigment obtained by coating glass flakes with fine titanium oxide particles. However, titanium oxide is coated in such an amount that the pearl luster is not practically exhibited. It is described that this glass flake is useful as a raw material for cosmetics.

Japanese Patent Application Laid-Open No. H11-130978 discloses that
Rutile type T with a thickness of 50 to 250 angstroms on the surface
glass flakes are disclosed having iO ₂ layers. It is described that this glass flake is used as a pearl-like resin composition or as a pearl-like pigment used in a paint.

[0006] JP-A-5-306134 and JP-A-5-306143 disclose metal-coated flake glass. In these publications, as the metal-coated flake glass, specifically, not only metal-coated flake glass, but also
It is also applicable to a metal-coated flake glass coated with a material such as O ₂ or TiO ₂ .

[0007]

Since glass flakes, which are materials on the order of microns, have a very large specific surface area (surface area per unit mass), the external circumstance of the glass components and components added or imparted during processing is high. Elution occurs. For this reason, there are problems in safety and properties, and elution components affect other materials that come into contact with the glass flakes, making it impossible to use the glass flakes.

In recent years, the demand for safety of cosmetics has been increasing, and when a cosmetic containing glass flakes coated with titania is applied to the skin, the constituents of the glass flakes of the base material are reduced. There is a concern that boron oxide is eluted.

The types of glass flakes include C glass flakes and E glass flakes manufactured by Nippon Sheet Glass Co., Ltd.
%, And E glass contains 5 to 13% (according to a catalog of Microglass, Nippon Sheet Glass Co., Ltd.).

[0010] In addition, the “Combination component specification by cosmetic variety” supervised by the Examination Division of the Pharmaceutical Affairs Bureau, Ministry of Health and Welfare (Yakuji Nippo Co.,
Issued on April 18, 2008), the item of "boron nitride" specifies that the amount of eluted boron is 20 ppm or less.

[0011] Regarding the glass which is the base material of the pearl-like glass flakes, there is no regulation on the amount of dissolved boron in the "glass powder" of the same standard. However, from the viewpoint of safety, the elution amount is still small.

Titanium oxide includes anatase type and rutile type crystal systems. When coating the base material surface with rutile-type titanium oxide having a high refractive index and a stronger pearl tone, tin may be used as a catalyst. Tin is a heavy metal and has safety issues.

In such glass flakes, it is important to prevent the elution of other components such as boron oxide contained in the glass component and heavy metals used for imparting various functions.

However, as a result of taking measures to prevent elution, the pigment properties (color, brightness, pearliness),
The properties of cosmetic ingredients (slip feeling on skin, fit) must not be impaired.

[0015] In Japanese Patent Laid-Open No. 11-130978 described above, although the glass flakes having a TiO ₂ layer are disclosed, it is impossible to prevent elution of the glass component in the TiO ₂ layer.

Further, in the metal-coated flake glass coated with the protective coating layer disclosed in JP-A-5-306134 and JP-A-5-306143, the protective coating layer changes its color tone due to oxidation of the metal coating. It is provided in order to prevent such a situation.

Accordingly, an object of the present invention is to provide a glass flake capable of preventing the elution of glass components and the elution of components used for imparting various functions.

[0018]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the safety, properties and pigment properties of the above-mentioned cosmetic raw materials.
It has been found that by coating with one or more metal oxides selected from alumina, zirconia, zinc oxide and cerium oxide, elution of components such as boron in the glass and tin as a catalyst can be prevented.

Further, even if the glass flakes are coated with the above-mentioned metal oxide, the characteristics such as the color and brightness of the pearl-like pigment, and the slip and fit are not impaired. Therefore, the glass flake according to the present invention can be used as a raw material for cosmetics and is excellent in safety.

That is, according to the present invention, as a first aspect of the present invention, a glass component elution preventing coating of one or more metal oxides selected from silica, alumina, zirconia, zinc oxide and cerium oxide is provided on the surface. Glass flakes characterized by being formed.

According to a second aspect of the present invention, there is provided the glass flake according to the first aspect, wherein the coating is coated by 0.1 to 30% by mass% with respect to the glass flake before coating. It is.

According to a third aspect of the present invention, in the glass flake according to the first aspect, the coating is coated at 0.5 to 25% by mass with respect to the glass flake before coating. It is.

According to a fourth aspect of the present invention, in the glass flake according to the first aspect, the coating is a glass flake coated with 1 to 20% by mass% based on the glass flake before coating. .

According to a fifth aspect of the present invention, in the glass flake according to the first aspect, the coating is a glass flake formed by a metal salt method.

According to a sixth aspect of the present invention, in the glass flake according to the first aspect, the glass flake is provided with a functional film of an inorganic material in advance, and the metal flake is coated thereon. Glass flakes.

According to a seventh aspect of the present invention, in the glass flake according to the sixth aspect, the functional film is made of titania and has a pearl color tone.

According to an eighth aspect of the present invention, in the glass flake according to the first aspect, the glass flake has an average thickness of 0.1 to 2.5 μm and an average particle size of 1 to 300 μm.
m, glass flakes having an aspect ratio of 10 to 500. However, the aspect ratio is defined as average particle diameter / average thickness.

According to a ninth aspect of the present invention, there is provided a cosmetic comprising the glass flake according to any one of the first to eighth aspects.

The field of application of the glass flakes according to the present invention is not limited to cosmetics but is applied to the following fields. That is, it can be used as a filler or a pigment applied to applications requiring safety such as resins, films, paints, and inks for packaging of foods, cosmetics, and pharmaceuticals, and containers.

In addition, resins, films, paints, and the like in the electronic, electric, and semiconductor fields which dislike elution of alkali and trace components.
It can also be used as a filler or pigment for ink and the like.

In addition, the present invention can be used in fields where the dissolution of glass flakes themselves or trace amounts of added components during processing thereof has been a problem.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The glass flake applied to the present invention before forming a glass component elution preventing coating is not particularly limited. In consideration of use as a cosmetic raw material, glass flakes having the following composition and shape are preferably used. That is, the base material is silica (SiO ₂ )
Of 45 to 75% by mass, and the average thickness is 0.1 to 2.5.
μm, average particle size is 1 to 300 μm, aspect ratio is 10
-500 glass flakes. Here, the aspect ratio is defined as “average particle size / average thickness”.

The surface of the glass flake may be coated with titania in advance to obtain a glass flake having a pearl color tone.

By forming a coating of one or more metal oxides selected from silica, alumina, zirconia, zinc oxide and cerium oxide on the surface of the glass flakes, it becomes clear from the examples described later. Thus, elution of the glass component could be prevented. Also, even when blended in cosmetics, by forming a coating of metal oxide,
Glass flakes that do not impair color, brightness, smoothness or fit.

As is clear from the examples described later, not only the glass component but also the elution of tin used as a catalyst when coating rutile-type titanium oxide,
Could be prevented.

The amount of the metal oxide to be coated is 0.1 to 30 by mass with respect to the glass flake before coating.
% Is preferably applied. When the amount is 0.1% by mass or less, the effect of preventing elution is small.

On the other hand, if the coating amount of silica exceeds 30% by mass, cracks enter the coating and the coating tends to peel off. Also,
Raw materials used for forming the coating are bulky and costly. Further, for example, in the case of a pearl-like glass flake coated with titania, if the coating amount exceeds 30% by mass, the brilliant feeling as the pearl-like glass flake is reduced, and the effect as a brilliant pigment is weakened.

The coating amount of silica is more preferably 0.5 to 25% by mass, most preferably 1 to 20% by mass.

As a method of forming the coating layer, a method of depositing an oxide on the powder surface from a metal salt, a sol-gel method, a CVD method
A general method such as the LPD method or the LPD method can be used.

As a method for forming a silica film, for example, the following method can be exemplified. That is, as shown in JP-B-46-9555, a method of adding sodium silicate (water glass) to a powder slurry under alkali to precipitate silica on the powder surface (metal salt method).

As shown in JP-B-48-32415, a mixture of a powder and a tetraalkoxysilane is poured into a basic solution, and a silica coating is formed on the powder surface by hydrolysis of the tetraalkoxysilane. (Sol-gel method).

Further, as shown in JP-A-3-066676, the powder was suspended in a hydrosilicic acid solution,
A method of forming silica on powder by adding boric acid or aluminum or raising the temperature to shift the equilibrium (LPD
Law).

With respect to coating with other metal oxides such as alumina, zirconia, zinc oxide and cerium oxide, the coating can be formed by a similar method only by changing the raw materials.

The coating may be a single layer or a multilayer structure. Further, the coating may be a mixture of raw materials to form a composite of two or more metal oxides. In this case, an appropriate combination of metal oxides may be selected for the purpose of improving the compatibility with other materials when the glass flakes are mixed with other materials and for the purpose of adjusting the refractive index.

When the pearlescent glass flakes coated with the metal oxide are blended into cosmetics, the glass components are not eluted. In addition, it is a cosmetic that shows clear color without dullness, has no roughness, and has excellent spreadability and adhesion to the skin.

The blending amount of the pearl-like glass flake in the cosmetic is 1 to 100% by mass based on the total amount of the cosmetic. The blending amount of 100% refers to a case where the pearl-like glass flake is used as it is as a cosmetic, for example, a use in which the pearl-like glass flake is sprinkled on a foundation.

The cosmetics to which the glass flakes of the present invention are applied include a wide range of cosmetics such as facial cosmetics, makeup cosmetics, and hair cosmetics. For example, foundation, powdered white powder, eye shadow, brusher, makeup base, nail enamel, eyeliner,
It is preferably applied to makeup cosmetics such as mascara, lipstick and fancy powder.

The pearlescent glass flakes may be appropriately subjected to a hydrophobic treatment according to the purpose of the cosmetic. Examples of the method of the hydrophobic treatment include treatment with a silicone compound such as methyl hydrogen polysiloxane, high-viscosity silicone oil, and silicone resin, treatment with a surfactant such as an anionic surfactant and a cationic surfactant, nylon, polymethyl methacrylate, and polyethylene. , Fluororesin, treatment with a high molecular compound such as polyamino acid, perfluoro group-containing compound, lecithin, collagen, metal soap, lipophilic wax, polyhydric alcohol partial ester or complete ester, etc. Combined processing is mentioned. However, any method can be generally used as long as it can be applied to the hydrophobization treatment of the powder, and the method is not limited to these methods.

In the cosmetic of the present invention, in addition to the above-mentioned pearl-like glass flakes, other components usually used in cosmetics can be appropriately compounded as required. Other components include inorganic powder, organic powder, pigment, dye, oil component,
Examples include an organic solvent, a resin, and a plasticizer.

For example, examples of the inorganic powder include talc, kaolin, sericite, muscovite, phlogopite, phlogopite, biotite,
Lithium mica, vermiculite, magnesium carbonate, calcium carbonate, sodium silicate, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride,
Ceramic powder and the like can be mentioned.

Examples of the organic powder include nylon powder, polyethylene powder, polystyrene powder, benzoguanamine powder, polytetrafluoroethylene powder, distyrenebenzene polymer powder, epoxy powder, and acrylic powder.

Examples of the pigment include inorganic white pigments such as titanium oxide and zinc oxide such as microcrystalline cellulose; inorganic red pigments such as iron oxide (iron oxide) and iron titanate; and inorganic brown pigments such as γ iron oxide. Pigments, yellow iron oxide, inorganic yellow pigments such as loess, black iron oxide, inorganic black pigments such as carbon black, mango violet, inorganic violet pigments such as cobalt violet, chromium oxide, chromium hydroxide, Inorganic green pigments such as cobalt titanate, inorganic blue pigments such as ultramarine and navy blue, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, fish scale foil, colored titanium oxide coated Examples include pearl pigments such as mica, and metal powder pigments such as aluminum powder and copper powder.

The dyes include Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228
No. 4, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, etc., organic pigments such as Red No. 3, Red No. 104
No., Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202,
Organic pigments such as yellow No. 203, green No. 3 and blue No. 1 zirconium, barium, and aluminum lakes, and natural pigments such as chlorophyll and β-carotene.

Further, squalane, liquid paraffin, petrolatum, microcrystalline wax, okezolite, ceresin, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid,
Cetyl alcohol, hexadecyl alcohol, oleyl alcohol, cetyl 2-ethylhexanoate, palmitic acid
2-ethylhexyl, 2-octyldodecyl myristate,
Neopentyl glycol di-2-ethylhexanoate, tri-
Glycerol 2-ethylhexanoate, 2-octyldodecyl oleate, isopropyl myristate, glycerol triisostearate, glycerol tricoconut oil, olive oil, avocado oil, beeswax, myristyl myristate, mink oil, lanolin and other hydrocarbons, Examples include silicone oils, higher fatty acids, esters of fats and oils, higher alcohols, and waxes.

Further, acetone, toluene, butyl acetate,
Organic solvents such as acetate esters, resins such as alkyd resins and urea resins, plasticizers such as camphor and acetyltributyl citrate, ultraviolet absorbers, antioxidants, preservatives, surfactants, humectants, fragrances, water, alcohol And thickeners.

The cosmetic according to the present invention may be in the form of powder, cake, pencil, stick, ointment, liquid, emulsion, cream or the like.

[0057]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

(Examples 1 to 8) First, pearl-like glass flakes were produced. That is, C glass is
It was melted at 00 ° C., blown into a cylindrical shape, stretched into a thin film, and solidified by cooling, thereby thinning to a predetermined thickness. This was pulverized and classified to produce glass flakes having predetermined thickness, particle size and aspect ratio. The glass flakes were suspended in a titanyl sulfate solution, and the suspension was heated and boiled for 1 hour to coat the glass flakes with titania of various thicknesses. This was filtered, washed with water, dried, and further heat-treated at 600 ° C. for 30 minutes to obtain a pearl-like glass flake.

The color development varies depending on the thickness of the titania to be coated. Further, the specific surface area varies depending on the thickness and particle size of the base material, and as a result, the coating thickness also varies. For this reason, titania-coated glass flakes were appropriately sampled from the suspension, and the amount of titanyl sulfate added was adjusted while observing the color to obtain pearl-like glass flakes having an arbitrary color tone.

The obtained pearl-like glass flake was coated with silica by the following method. That is, 50 g of pearl-like glass flakes are suspended in 0.5 liter of purified water, kept at 75 ° C. in a water bath, and a sodium silicate solution (silica content: 37.1%, manufactured by Wako Pure Chemical Industries) is used as silica content. The pearl-based glass flakes were weighed so as to have a predetermined mass%, and a 10-fold dilution with purified water was slowly added. At this time, the suspension was advanced with 3.5% hydrochloric acid while maintaining the pH of the suspension at 9.2 to 9.4. After the addition, stirring was continued at 75 ° C. for 30 minutes.

Thereafter, the suspension was filtered through filter paper to remove the powdery solid, washed with water to neutralize the pH, and further washed with water for 10 minutes.
After drying at 0 ° C. for 2 hours, a pearl-like glass flake coated with silica was obtained.

The pearl-like glass flakes having various thicknesses, particle diameters and aspect ratios coated with the various mass ratios of silica thus produced were evaluated by the following methods.

<Amount of Boron Eluted> Purity test of “Bonium Nitride”, a compound component standard for each cosmetic variety (4) A test solution was prepared according to the method of the amount of boron eluted, and the solution was quantitatively analyzed by an atomic absorption method.

The preparation method of the test solution is as follows. (1) Take 2.5 g of the test sample in a fluororesin beaker, add 10 ml of ethanol, stir well, further add 40 ml of water, stir well, place a fluororesin watch glass, and heat on a hot plate for 1 hour. . (2) After standing to cool, the mixture is filtered, the residue is washed with a small amount of water, and the washing is combined with the filtrate. (3) This solution was further added to a membrane filter (0.22
μm). (4) Take the whole amount of the filtrate into a fluororesin beaker and add sulfuric acid 1
Add ml and boil for 10 minutes on a hot plate. (5) After standing to cool, put this solution in a polyethylene volumetric flask, wash the fluorocarbon resin beaker with a small amount of water, adjust the volume to the polyethylene volumetric flask, and add water to make exactly 50 ml. And

<Measurement of color difference and brightness> 5 g of a sample was mixed with 45 g (solid content mass) of an acrylic resin (Acrylic Auto Clear Spar, manufactured by Nippon Paint Co., Ltd.), and the mixture was sufficiently stirred and mixed with a paint shaker. Then, this mixed solution was applied on a opaque measurement paper to form a coating film.

The hue (a value, b value) and lightness (L value) of this coating film were measured using a CR300 colorimeter manufactured by Minolta Co., Ltd., and pearl-like glass flakes (a ₀ , b ₀ , L) not coated with silica were measured. ₀ ) was determined by the following equation.

Embedded image Color difference ΔE = {{(a−a ₀ ) ² + (b−b ₀ ) ² + (L−L ₀ ) ² }

The coating film was visually observed, and the brilliancy was represented by the following criteria. ◎: There is a very brilliant brilliant ：: There is a brilliant brilliant. Δ: There is some glitter. X: The feeling of glitter is not so much felt.

Table 1 shows the measurement results of the boron elution amount of the silica-coated pearlescent glass flakes prepared as described above and the pearlescent glass flakes not coated with silica. Furthermore, color difference Δ in silica-coated pearlescent glass flakes
Table 1 also shows the measurement results of E.

(Comparative Examples 1 to 3) As comparative examples, pearlescent glass flakes (Comparative Examples 1 and 2) which were not coated with silica as in Examples 2 and 8 described above, and pearlescent glass flakes as in Example 8 Boron elution amount and color difference ΔE in pearlescent glass flakes (Comparative Example 3) in which glass flakes were coated with 50% by mass of silica by the method of the above-described example.
Table 1 also shows the measurement results.

From Table 1, it was found that all of the silica-coated pearlescent glass flakes had an elution amount of boron of nd (the lower limit of quantification of 0.25 ppm or less), and no elution was observed. On the other hand, in Comparative Examples 1 and 2 not coated with silica, the elution amount of boron was 2
Exceeds 0 ppm, and the purity test of “Boron Nitride”, a compounding component standard by cosmetic varieties (4) Standard of 20 ppm of dissolved boron
Is over.

When the coating amount of silica is 1 to 30% by mass, the color difference ΔE is 3 or less as compared with the case where no silica is coated, there is no large change in hue, and the same as the original pearlescent glass flake. Can be used as a pigment. On the other hand, in Comparative Example 3 in which silica was coated at 50% by mass, ΔE was 4.5, and it can be recognized that there was a color difference in appearance. Also, a slight decrease in glitter is observed. If used in the same composition as the original pearlescent glass flakes, the color will be different.

[0072]

[Table 1] Various properties of pearl-like glass flakes coated with silica Example 1 2 3 4 5 6 ─────────────────────────────────── Average thickness (μm) 2.3 2.3 2.3 1.3 0.4 0.6 Average particle size (μm) 450 80 40 25 40 80 Aspect ratio 196 35 17 19 100 113 Reflection color Silver Silver Silver Yellow Green Green Silica mass% 1 3 3 3 6 15 Boron elution amount ppm ndndndndndnd Color difference ΔE 0.5 1.3 1.0 1.5 2.0 2.5 Brightness ◎ ◎ ◎ ◎ ◎ ◎ ─────────────────────────────────── Example 7 8 Comparative example 1 2 3 ─────────────────────────────────── Average thickness (μm) 2.3 1.3 2.3 1.3 1.3 Average particle size (μm) 450 80 80 80 80 Aspect ratio 196 62 35 62 62 Reflection color Blue Red Silver Red Red Silica mass% 3 20 0 0 50 Boron elution amount ppm ndnd 36 26 nd Color difference ΔE 1.2 2.8--4.5 Brightness ◎ ◎ ◎ ◎ ○ ───────────── ────────────────────── Note) nd: Lower limit of quantification (0.25ppm) or less

(Examples 9 to 14) The glass flakes produced by the methods of the above-described examples were treated in the following manner to produce tin-containing pearlescent glass flakes.
That is, C having an average thickness of 1.3 μm and an average particle size of 80 μm.
100 g of glass flake was added to 1 liter of a 200 ppm solution of stannous chloride dihydrate adjusted to pH 2 with diluted hydrochloric acid, stirred for 10 minutes, and filtered. Next, the glass flakes were added to 1 liter of a 15 ppm solution of hexachloroplatinic acid hexahydrate, stirred for 10 minutes, and filtered.

Subsequently, an aqueous solution 1 having a pH of about 1 with hydrochloric acid
To 1 liter, add the treated glass flakes,
The solution temperature was raised to 75 ° C. A titanium tetrachloride (TiCl ₄ ) solution was slowly added thereto to cover the titanium oxide. At this time, sodium hydroxide was appropriately added so that the pH did not change. Then, filter water washing,
It was dried and further heat-treated at 600 ° C. for 30 minutes to obtain a pearl-like glass flake. In this method, rutile type titania was precipitated.

For the same reason as described in the above embodiment, titania-coated glass flakes are appropriately sampled from the suspension, and the amount of titanium tetrachloride is adjusted while watching the color of the flakes, and the pearl of any color tone is adjusted. A tempered glass flake was obtained.

When the obtained pearl-like glass flakes are coated with silica in the same manner as in Example 1 described above, the amount of boron eluted, the amount of tin eluted (measurement methods are as follows), and the case where silica is not coated Was measured for the color difference from the pearl-like glass flakes, and the glitter was observed. Table 2 shows the results.

<Tin Elution Amount> A test solution was prepared in accordance with the method of lead (3) lead test for the formulation of “glass powder” according to the standard of the composition of each cosmetic variety, and quantitatively analyzed by ICP. That is,
Take a 1.0 g sample, add 30 ml of water and 3 ml of hydrochloric acid, boil for 20 minutes, and filter. Wash the residue with a small amount of water, combine the washings with the filtrate, and use this as the test solution.
Quantitative analysis was performed by ICP.

(Comparative Examples 4 to 6) As comparative examples, pearlescent glass flakes which are not coated with silica as in Examples 10 and 13 described above (Comparative Examples 4 and 5)
In the same manner as in Example 13 described above, the amount of boron eluted, the amount of tin eluted, and the color difference ΔE in the pearlescent glass flakes (Comparative Example 6) coated with 50% by mass of silica by the method of Example described above. Table 2 also shows the measurement results of glitter.
It was shown to.

From the table, it can be seen that all of the pearl-like glass flakes coated with silica have a boron elution amount of n. d. (The lower limit of quantification was 0.25 ppm or less), indicating that no recognized elution had occurred. On the other hand, in Comparative Examples 4 and 5, which were not coated with silica, the boron elution amount exceeded 20 ppm.
m.

Regarding the elution amount of tin, the pearl-like glass flake coated with silica was 8 to 15 ppm, and Comparative Examples 4 and 5, which did not compare silica, had 20 ppm.
However, it was found that the amount of elution was considerably prevented.

When the coating amount of silica is 1 to 30% by mass, the color difference ΔE
Is 3 or less, there is no significant change in hue, and it can be used as a pigment in the same manner as the original pearlescent glass flake. On the other hand, in Comparative Example 3 in which silica was coated at 50% by mass, ΔE was 4.1, and it can be recognized that there was a difference in color in appearance. If used in the same composition as the original pearlescent glass flakes, the color will be different.

[0082]

[Table 2] Various properties of tin-containing titania-coated glass flakes of various shapes ────────────────────────────────── ─ Example 9 10 11 12 13 14 ─────────────────────────────────── Average thickness (μm) 2.3 2.3 2.3 1.3 1.3 0.6 Average particle size (μm) 450 80 40 25 80 80 Aspect ratio 196 35 17 19 62 113 Reflection color Silver Silver Silver Yellow Red Green Silica mass% 1 3 3 3 6 15 Boron elution amount ppm ndndndndndnd Tin elution amount ppm 8 6 6 15 12 18 Color difference ΔE 0.4 1.0 1.0 1.3 1.8 2.6 Brightness ◎ ◎ ◎ ◎ ◎ ◎ ─────────────────────────── ──────── Comparative example 4 5 6 ─────────────────────────────────── Average thickness (μm) 2.3 1.3 1.3 Average particle size (μm) 80 80 80 Aspect 35 62 62 Reflection color Silver Red Red Silica mass% 0 0 50 Boron elution amount ppm 33 28 nd Tin elution amount ppm 22 26 11 Color difference ΔE-− 4.1 Brightness ◎ ◎ ○ ──────────── ─────────────────────── Note) nd: Lower limit of quantification (0.25ppm) or less

Example 15 50 g of red colored pearlescent glass flakes having an average thickness of 1.3 μm and an average particle size of 80 μm
Was suspended in 0.5 liter of purified water and kept at 75 ° C. in a water bath.
4 g (7.1%, manufactured by Wako Pure Chemical Industries, Ltd., 3% by mass based on the pearl-like glass flakes as a silica content) diluted 10-fold with purified water was slowly added. At this time, the suspension was advanced while maintaining the pH of the suspension at 9.2 to 9.4 with 3.5% hydrochloric acid.
After the addition, stirring was continued at 75 ° C. for 30 minutes to coat the silica.

Thereafter, aluminum chloride hexahydrate 1.8 was obtained.
g (2% by mass based on the pearl-like glass flakes as alumina) was diluted 20 times with purified water, and a solution was slowly added dropwise. At this time, pH is adjusted with 5% aqueous sodium hydroxide solution.
Was maintained at 5.3 to 5.7. 75 ° C after addition
For 30 minutes to coat the alumina. Thereafter, the suspension was filtered through filter paper to remove the powder solid, washed with water, and p
After neutralizing H, it was dried at 100 ° C. for 2 hours. In this way, a pearl-like glass flake having a two-layer coating of silica coating and alumina coating was obtained.

The amount of boron eluted from the pearl-like glass flakes is n. d. (The lower limit of quantification was 0.25 ppm or less). The color difference ΔE from the uncoated pearlescent glass flake was 1.8, and there was no visible color difference.

Example 16 2 mol of zirconium hydrofluoric acid was mixed with 100 ml of purified water and kept at 35 ° C., and 10 g of red-colored pearl-like glass flakes having an average thickness of 1.3 μm and an average particle size of 80 μm were added thereto. And stirred for 2 hours. Thereafter, the suspension was filtered with filter paper to take out a powder solid, washed with water to neutralize the pH, and dried at 100 ° C. for 2 hours to produce a pearl-like glass flake coated with zirconia.

According to the LPD method, not all of the reactants of the added zirconium hydrofluoric acid coat the powder surface. Therefore, the powder was observed with an electron microscope to check the coating amount. As a result, the coating thickness of zirconia was about 50 nm. When the coating amount was calculated from this, it was about 17% by mass.

The leaching amount of boron of the pearl-like glass flakes coated with zirconia was n. d. (Quantitative lower limit 0.
25 ppm or less). The color difference ΔE from the pearl-like glass flakes not coated with zirconium was 1.5, and there was no visible color difference.

Next, a cosmetic in which glass flakes (pearl-like glass flakes) coated with a metal oxide are blended as a pearlescent pigment will be described below. For the evaluation of the cosmetics, 10 panelists performed a sensory evaluation of 5 levels from 1 to 5 for the items in Table 3.

[0090]

[Table 3] ─────────────────────────────────── ＼ Evaluation items Smoothness Smoothness Brightness Color ＼ ＼ 1 bad no no no dirty 2 somewhat bad No Slightly Not Slightly Slightly dull 3 Normal Normal Normal Somewhat normal 4 Somewhat good Somewhat some good Clean 5 Good Very good Very good Very high Very clean ───────────── ──────────────────────

The results are shown below as the average values of the five-level evaluations of ten persons. ◎: 4.5 to 5.0 ○: 3.5 to less than 4.5 ●: 2.5 to less than 3.5 △: 1.5 to less than 2.5 ×: 1.0 to less than 1.5

(Example 17: Powder foundation) A powder foundation comprising the following components was prepared. (1) Titanium oxide 7 (2) Talc 20 (3) Muscovite 3 (4) Pearl-like glass flake of Example 2 55 (5) Nylon powder 2 (6) Red iron oxide 0.5 (7) Yellow iron oxide 1 (8) Black iron oxide 0.1 (9) Silicon oil 1 (10) 2-Ethylhexyl barmitate 9 (11) Sorbitan sesquioleate 1 (12) Preservative 0.3 (13) Fragrance 0.1 (mass) %)

The components (1) to (8) were mixed with a Henschel mixer, and the mixture obtained by heating and dissolving the components (9) to (13) was added and mixed, and then pulverized with a pulverizer. 0.1568P on the middle plate of 5.3mm diameter
a (= 160 kg / cm ² ) to obtain a powder foundation.

(Comparative Example 7) In the formulation of Example 17, the pearl-like glass flake of the component (4) was replaced with the pearl-like glass flake of Comparative Example 1 as Comparative Example 7.
It was produced in the same manner as in Example 17. Table 3 shows the results of the sensory tests of Example 17 and Comparative Example 7.

From Table 3, it can be seen that the powder foundation according to the present invention has no difference in all aspects from the powder foundation blended with pearl-like glass flakes not coated with silica, and has a good spread, close contact, smoothness, brilliant feeling, etc. It turned out to be excellent in color cleanliness.

[0096]

[Table 4] び Noby Adhesion Smoothness Brightness Beautiful color Example 17 ○ ○ ○ ◎ ◎ Comparative Example 7 ○ ○ ○ ◎ ◎ ────────────────────────────────── ─

Example 18: Brusher A brusher comprising the following components was prepared. (1) Talc 12.6 (2) Sericite 8.1 (3) Mica 25.4 (4) Pearl-like glass flake of Example 2 45.0 (5) Red No. 226 0.4 (6) Squalane 3 0.0 (7) 2-ethylhexyl palmitate 5.0 (8) Preservative 0.3 (9) Fragrance 0.2 (% by mass)

The components (1) to (5) were mixed with a Henschel mixer, and the mixture obtained by heating and dissolving the components (6) to (9) was sprayed and further mixed. 0.11cm on a 6cm middle plate
Molding was performed at a pressure of 76 Pa (= 120 kg / cm ² ) to obtain a brusher according to the present invention.

(Comparative Example 8) In the formulation of Example 18, the pearl-like glass flake of the component (4) was replaced with the pearl-like glass flake of Comparative Example 1 to obtain Comparative Example 8.
It was produced in the same manner as in Example 18. Table 5 shows the results of the sensory tests of Example 18 and Comparative Example 8.

According to Table 5, the brusher according to the present invention is:
On all sides, it was found that there was no difference from the brushers containing pearl-like glass flakes not coated with silica, and that they were excellent in stretchability, adhesion, smoothness, glitter, and beautiful color.

[0101]

[Table 5] び Noby Adhesion Smoothness Brightness Beautiful color ─────────────────────────────────── Example 18 ○ ○ ○ ◎ ◎ Comparative Example 8 ○ ○ ○ ◎ ◎ ───────────────────────────────────

(Example 19: Nail enamel) A nail enamel consisting of the following components was prepared. (1) Nitrocellulose 12 (2) Modified alkyd resin 12 (3) Acetyl tributyl citrate 5 (4) n-butyl acetate 36.4 (5) Ethyl acetate 6 (6) n-butyl alcohol 2 (7) Toluene 21 (8) Iron oxide pigment 0.5 (9) Titanium dioxide 0.1 (10) Pearl-like glass flake of Example 8 3 (11) Mica 1 (12) Organically modified montmorillonite 1 (% by mass)

The components (1) to (7) (but a part of the component (4)) were dissolved, and the solution was mixed with the component (12) and the remainder of the component (4) to form a gel. After mixing, components (8) to (11) were added and mixed, and the mixture was filled in a container to obtain a nail enamel according to the present invention.

(Comparative Example 9) In the same manner as in Example 19, except that the pearl-like glass flake of the component (10) was replaced with the pearl-like glass flake of Comparative Example 5 in the formulation of Example 19, It was produced. Table 5 shows the results of the sensory tests of Example 19 and Comparative Example 9.

From Table 6, it can be seen that the nail enamel according to the present invention has no difference in all aspects from the nail enamel blended with pearl-like glass flakes not coated with silica. It turned out to be excellent in color cleanliness.

[0106]

[Table 6] び Noby Adhesion Smoothness Brightness Beautiful color ─────────────────────────────────── Example 19 ○ ○ ◎ ◎ ◎ Comparative Example 9 ○ ○ ◎ ◎ ◎ ───────────────────────────────────

[0107]

As is apparent from the above description, the prevention of glass component elution by one or more metal oxides selected from silica, alumina, zirconia, zinc oxide and cerium oxide on the surface of glass flakes. By forming the coating, elution of the glass component of the glass flakes could be prevented. In addition, the elution of tin used in forming the titania coating could be prevented.

Therefore, the glass flake according to the present invention can be used as a safe material. Moreover, even when this glass flake is used as a raw material for cosmetics, it is possible to obtain a cosmetic which has no dullness, shows a clear coloration comparable to that of conventional glass flakes, has no rough feeling, spreads to the skin, and is excellent in adhesion.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Juichi Ino 3-5-1, Doshumachi, Chuo-ku, Osaka-shi, Osaka F-term in Nippon Sheet Glass Co., Ltd. 4C083 AB171 AB172 AB211 AB212 AB221 AB222 AB232 AB241 AB242 AB432 AB442 AC022 AC032 AC102 AC352 AC372 AC442 AC862 AD072 AD092 AD152 AD262 CC01 CC12 CC28 DD23 EE06 4J037 CA08 CA12 CA24 DD05 DD09 DD10 EE03 FF03 FF26

Claims (9)

[Claims] Claims: 1. A surface comprising one or two selected from silica, alumina, zirconia, zinc oxide and cerium oxide
A glass flake characterized in that a glass component elution prevention coating is formed by at least one kind of metal oxide. 2. The glass flake according to claim 1, wherein the coating is based on the glass flakes before coating.
And glass flakes coated with 0.1 to 30%. 3. The glass flake according to claim 1, wherein the coating has a mass% of the glass flake before coating.
And glass flakes coated with 0.5 to 25%. 4. The glass flake according to claim 1, wherein the coating is based on the glass flakes before coating.
And glass flakes coated with 1-20%. 5. The glass flake according to claim 1, wherein the coating is formed by a metal salt method. 6. The glass flake according to claim 1, wherein the glass flake is provided with a functional film of an inorganic material in advance, and the metal flake is coated thereon. 7. The glass flake according to claim 6, wherein the functional film is made of titania and has a pearl color tone. 8. The glass flake according to claim 1, wherein the glass flake has an average thickness of 0.1 to 2.5.
μm, average particle size is 1 to 300 μm, aspect ratio is 10
Glass flakes that are ~ 500. However, the aspect ratio is defined as average particle size / average thickness. 9. A cosmetic comprising the glass flake according to claim 1.