JPH069210A - Red synthetic mica, its production and ultraviolet screening agent containing the same mica - Google Patents

Abstract

PURPOSE:To obtain red synthetic mica coloring in red close to flesh color, having light resistance, effectively screening ultraviolet light and to provide an ultraviolet light scrrening agent containing the synthetic mica. CONSTITUTION:The synthetic mica is of the formula (I): X1/3-1Y2-3(Z4O10) F2x0.75-2x0.99 (I) (in the formula, X is one or more ions selected from the group consisting of Na, K, Li, Ca, Rb and Sr; Y is Mg, Fe, Ni, Mn, Al, Li, Co, Ti and Zn; Z is one or more ions selected from Al, Si, Ge, Fe, B, Co and Ti and at least one of Y and Z is iron ion). The number of mols of iron contained in the synthetic mica is 0.01-3mols and the color of the synthetic mica measured by powder cell method is L*=55-75, a*=5-20 and b*=5-20 by L*a*b* color display system.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel red synthetic mica used as a base for cosmetics, paints, inks, coating agents, plastics, films, fibers, glass and glazes.
The present invention relates to a method for producing the same and an ultraviolet blocking agent containing the mica.

[0002]

2. Description of the Related Art Mica powder is used for paint additives, plastic additives, cosmetics, etc. by utilizing its properties such as excellent insulating property, leafing property and lubricating property. Known examples of naturally occurring mica include muscovite, phlogopite and biotite, which are grayish white and blackish brown. Also,
Mica can be synthesized by various methods. It is also known that mica with high whiteness can be obtained from these synthetic products and that a colored synthetic mica can be produced by coordinating a coloring element in the crystal structure. . On the other hand, mica is often used for cosmetics because it has advantages such as excellent transparency, gloss, and extensibility in use. Recently, not only natural mica but also synthetic mica has been developed as an additive for cosmetics. For example,
Japanese Unexamined Patent Publication No. 63-241072 discloses a synthetic mica powder in which elution of fluorine ions is small, surface activity is small, and oil content is good.

[0004]

As described above, since mica has excellent properties, it has no coloring property.
Only the properties due to the scale shape, such as insulating properties and leafing properties, could be used. In the fields of paints, plastics, cosmetics, etc., there is a strong demand for materials that are reddish and have an ultraviolet blocking effect that improves the durability of organic substances. A colorant such as iron was needed. However, the organic red dye has a drawback that it is poor in light resistance, and since iron oxide is a fine particle having a high refractive index, it tends to cause unevenness and has a drawback that the transparency as a cosmetic is impaired. On the other hand, in cosmetics, an ultraviolet scattering agent such as titanium oxide or an organic ultraviolet absorber is used for protection against ultraviolet rays. However, UV scatterers
Although it has an excellent effect of blocking ultraviolet rays, it also scatters visible light at the same time, thus impairing the transparency, choking,
There is a defect that causes whitening of cosmetics, and although an organic ultraviolet absorber has a remarkable ultraviolet absorbing ability in a specific wavelength range, it has a defect of poor weather resistance. The present invention is intended to solve such a conventional problem, and an object thereof is to provide a synthetic mica that has a red coloration close to the skin color and that effectively blocks ultraviolet rays.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted extensive studies and as a result, heat treated synthetic mica in which the iron-containing mole number in the synthetic mica was 0.01 to 3 moles at a specific temperature. It has been found that a novel synthetic mica that exhibits a bright red appearance with light resistance, which has never been found in conventional synthetic mica, and has an extremely excellent ultraviolet blocking ability can be obtained, and has reached the present invention. did. That is, the present invention provides the following formula (I): X _{1/3 to 1} Y _{2 to 3} (Z ₄ O ₁₀ ) F _{2x0.75 to 2x0.99} (I) (wherein X is Na, K or Li). Represents one or more ions selected from the group consisting of Ca, Rb and Sr, and Y represents Mg, Fe, Ni, Mn, Al, Li,
Co, Ti and Zn represent one or more ions selected from the group consisting of Z, Z represents Al, Si, Ge, Fe, B, one or more ions selected from the group consisting of Co and Ti, Y and At least one of Z contains iron ions. ), The iron-containing mole number in the synthetic mica is 0.01 to 3 moles, and the color of the synthetic mica measured by the powder cell method is L
* a * b * Red color synthetic mica characterized by L * = 55 ■ 75, a * = 5 ■ 20, b * = 5 ■ 20 in color system, method for producing the mica and containing the mica It is a UV blocking agent.

The red mica of the present invention must contain Fe without fail, and synthetic mica containing no Fe does not turn red. The Fe-containing mole number in the synthetic mica of the present invention is 0.01 3 mole, preferably 0.1 2 mole, and more preferably 0.2 1 mole. If it is less than 0.01 mol, the red color is too weak, and if it exceeds 3 mol, the mica crystal becomes defective. Fe is coordinated at the octahedral position represented by Y and the tetrahedral position represented by Z in the general formula (1). As the number of moles of Fe coordinated to the octahedral position increases, the redness of mica can be increased. As described above, in the present invention, iron must always be included in the crystal structure, and the effect of the present invention cannot be exhibited if it is simply attached to the surface of mica. The red mica of the present invention, as represented by the general formula (1),
The mole number of fluorine in the synthetic mica needs to be 75% to 99% of the stoichiometric composition of the synthetic mica, preferably 80% to 97.5%, more preferably 90% to 95%. If it is less than 75%, it will not be a synthetic mica, and if it exceeds 99%, it will not be red.

The novel red mica of the present invention has the following formula (II): X _{1/3 to 1} Y _{2 to 3} (Z ₄ O ₁₀ ) F ₂ (II) (wherein X is Na, K, Li, Represents one or more ions selected from the group consisting of Ca, Rb and Sr, Y is Mg, Fe, Ni, Mn, Al, Li,
Co, Ti and Zn represent one or more ions selected from the group consisting of Z, Z represents Al, Si, Ge, Fe, B, one or more ions selected from the group consisting of Co and Ti, Y and At least one of Z represents an iron ion. ), The synthetic mica having an iron-containing mole number of 0.01 to 3 mol can be heat-treated at 600 to 1200 ° C.

The raw material synthetic mica represented by the above formula (II) is
It can be synthesized by a known hydrothermal method, solid phase reaction method, melt synthesis method, or the like. The mica thus synthesized is pulverized by a wet or dry method to give a powder of about 0.1 to 100 μm,
The red mica of the present invention can be produced by treating the mica powder with an aqueous solution of one or more of an acid or a chelating agent and then heat-treating at 600 to 1200 ° C. Inorganic and organic acids can be used as the acid for treating the mica powder. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, chloric acid, perchloric acid, periodic acid, bromic acid, phosphoric acid, boric acid and carbonic acid, and examples of the organic acid include formic acid, acetic acid,
Acrylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, carboxylic acids such as adipic acid, pimelic acid and phthalic acid, oxycarboxylic acids such as lactic acid, malic acid, tartaric acid and citric acid, glycine, alanine, Examples include amino acids such as valine, leucine, tyrosine, threonine, serine, proline, tryptophan, methionine, cystine, thyroxine, asparagine, glutamic acid, lysine and arginine. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexane-tetraacetic acid, N-oxyethylethylenediamine-triacetic acid, ethyleneglycolbis-tetraacetic acid, ethylenediaminetetrapropionic acid and the like.

The treatment time and treatment temperature of the mica powder with an acid or a chelating agent may be appropriately selected depending on the type and concentration of the acid or the chelating agent. Generally, a treatment time of several minutes to several days is sufficient, a treatment temperature of 0 to 100 ° C. is sufficient, and a concentration of the treatment aqueous solution is preferably about 0.05 to 10 mol / liter. For example, when 0.1N hydrochloric acid is used and the treatment is performed at 20 ° C., the treatment time is preferably about 30 minutes and 5 hours. As a treatment method, any known method such as a method using a stirrer, aeration and immersion can be applied. The heat treatment temperature is 600-1200 ° C, preferably 900-1100 ° C. If it is less than 600 ° C, the mica does not turn red and is 1200 ° C.
When it exceeds, it does not turn red, and the mica decomposes. The heat treatment time is generally several seconds to several days, and may be appropriately selected depending on the heat treatment temperature. For example, F at the octahedron position
When fluorine phlogopite containing 0.2 mol of e is used as a raw material, it is preferably treated at 1000 ° C. for 0.5 to 10 hours. The heat treatment atmosphere may be any of an oxidizing atmosphere, a reducing atmosphere, an argon gas atmosphere, a N ₂ atmosphere, an ammonia gas atmosphere, a vacuum, etc., and may be a combination thereof, depending on the intended use and function of the synthetic mica. It may be selected appropriately. As the heat treatment apparatus, any known furnace such as a gas furnace, an electric furnace, a rotary kiln and a batch furnace can be used.

The red mica represented by the formula (I) of the present invention can be used alone or in combination with an extender pigment, a coloring pigment, an ultraviolet scattering agent, an ultraviolet absorbing agent and the like to prepare an ultraviolet blocking agent. Examples of extender pigments that can be used in the present invention include talc, kaolin, mica, calcium carbonate, magnesium carbonate,
Examples thereof include magnesium silicate, anhydrous silicic acid, barium sulfate, nylon powder, polyethylene powder, polystyrene powder, and the like.Examples of color pigments include iron oxide, ultramarine blue,
Examples thereof include chromium oxide, navy blue, and carbon black.Examples of the ultraviolet scattering agent include titanium oxide, ultrafine particle titanium oxide and zinc oxide, and examples of the ultraviolet absorbing agent include:
Examples thereof include benzophenone-based and benzotriazole-based ultraviolet absorbers. The content of the red mica represented by the formula (I) is preferably about 1% to 100%, and may be appropriately selected depending on the intended use, properties and the like.

[0011]

The function of the present invention is disclosed in JP-A-2-2
89417 discloses that the Fe content is 2 18% by weight in terms of Fe ₂ O ₃ ,
Value Fe content is 0.8 wt% or less in terms of FeO, and above
An ultraviolet absorbing synthetic mica in which the weight ratio of the FeO converted value to the sum of the FeO converted value and the Fe ₂ O ₃ converted value is FeO / FeO + Fe ₂ O ₃ ≦ 0.1 is described. However, the synthetic mica described in this publication is a synthetic mica having a high degree of whiteness, and the synthetic mica colored red like the present invention is not disclosed at all. In addition, Daimon Nobutoshi's Industrial Chemistry Magazine Volume 55, No. 11, Ni-containing mica is greenish yellow, Mn-containing mica is brown, Co-containing mica is pink or blue, Fe-containing mica. Is described as exhibiting a greenish black color or brown (blackish brown), and Fe mica exhibiting a red color is not disclosed at all. In fact, when color measurement is performed on brown mica containing Fe, the numerical value of a *, which is a scale of redness, is about -1 ■ 1, and a * = 5 ■ 20 red scale-like mica of the present invention. Is completely different from. However, the present invention has been found to be a bright red color with a sense of transparency by setting a specific element at a specific position, and by setting the number of moles of fluorine and the number of moles of Fe ions within a particular range. However, such an effect is completely unpredictable from the above-mentioned conventional techniques.

[0012]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Example 1 Potassium silicofluoride 24.4 g, magnesium oxide 22.3 g, aluminum oxide 11.3 g, silicon dioxide 33.2 g and iron oxide 8.8 g
Mix for 30 minutes in a mold mixer. Next, this mixture was put into an alumina crucible, melted in an electric furnace at 1450 ° C. for 30 minutes, and then cooled in the furnace. Thus, 95 g of iron-containing synthetic mica was obtained. This was crushed for 48 hours in a ball mill, and 90 g of the powdered iron-containing mica was treated in 1 liter of a 0.05N hydrochloric acid aqueous solution at room temperature for 48 hours with stirring, followed by dehydration, washing and drying. 80g of this dry powder was put in an alumina crucible and heated at 1000 ℃ in an electric furnace.
After heat treatment for 10 hours, 75 g of the synthetic mica of the present invention was obtained. The color of the obtained synthetic mica powder was red, and as a result of measurement with an X-ray diffractometer RAD-B manufactured by Rigaku Denki Co., Ltd., the X-ray diffraction pattern was in agreement with the synthetic mica, as shown in FIG. Analysis of iron by ESCA confirmed that iron was contained in the crystal structure. With respect to the synthetic mica obtained as described above, L * a * b *, ultraviolet transmittance, and the number of moles of iron and fluorine contained were measured by the following methods. The results are shown in Table-1. (Measurement method) (1) Measurement of L * a * b *: 1 g of a sample was sampled and placed in a powder cell of a color difference meter (CR-200) manufactured by Minolta for measurement. (2) UV transmittance measurement: 20% caster oil sample
Add it in a concentration and knead it with a three-roll mill, then add 10 on a quartz plate.
The coating was applied in a thickness of μm, and the ultraviolet transmittance at 300 nm was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation). (3) Measurement of the number of moles of iron and fluorine contained in the synthetic mica powder:
Iron was measured by atomic absorption spectrometry, and fluorine was measured by absorptiometry.

Example 2 24.7 g of potassium silicofluoride, 27.1 g of magnesium oxide, 5.7 g of aluminum oxide, 33.6 g of silicon dioxide and 8.9 g of iron oxide were mixed with V
The amount of the red synthetic mica of the present invention shown in Table 1 was obtained in the same manner as in Example 1 except that the mixing was performed for 30 minutes using a mold mixer. The X-ray diffraction pattern measured in the same manner as in Example 1 was consistent with that of synthetic mica. It was confirmed that iron was contained in the crystal structure in the same manner as in Example 1. For the obtained mica, L * a * b *, the ultraviolet transmittance and the number of moles of iron and fluorine contained were measured in the same manner as in Example 1. The results are shown in Table-1. Example 3 The same procedure as in Example 1 was carried out except that the heat treatment temperature was changed to 700 ° C. to obtain the red synthetic mica of the present invention in the amounts shown in Table 1. The X-ray diffraction pattern measured in the same manner as in Example 1 was consistent with that of synthetic mica. It was confirmed that iron was contained in the crystal structure in the same manner as in Example 1. For the obtained mica, L * a * b *, the ultraviolet transmittance and the number of moles of iron and fluorine contained were measured in the same manner as in Example 1. The results are shown in Table-1.

Example 4 The same procedure as in Example 1 was carried out except that the heat treatment temperature was 1200 ° C. and the heat treatment time was 5 minutes, and the red synthetic mica of the present invention is shown in Table 1. I got the amount. The X-ray diffraction pattern measured in the same manner as in Example 1 was consistent with that of synthetic mica. It was confirmed that iron was contained in the crystal structure in the same manner as in Example 1.
For the obtained mica, L * a * b *, the ultraviolet transmittance and the number of moles of iron and fluorine contained were measured in the same manner as in Example 1. The results are shown in Table-1. Example 5 The same procedure as in Example 1 was carried out except that a 10% aqueous citric acid solution was used in place of 0.05N hydrochloric acid, and the red synthetic mica of the present invention was obtained in the amounts shown in Table 1. It was The X-ray diffraction pattern measured in the same manner as in Example 1 was consistent with that of synthetic mica.
It was confirmed that iron was contained in the crystal structure in the same manner as in Example 1. For the obtained mica, L * was obtained as in Example 1.
The a * b *, ultraviolet transmittance, and the number of moles of iron and fluorine contained were measured. The results are shown in Table-1.

Comparative Example 1 25.5 g of potassium silicofluoride, 28.0 g of magnesium oxide, 11.8 g of aluminum oxide and 34.8 g of silicon dioxide were mixed in a V-type mixer 3 times.
The mixture was mixed for 0 minutes and treated in the same manner as in Example 1 to obtain an iron-free synthetic mica. For the obtained mica, L * a * b *, the ultraviolet transmittance and the number of moles of iron and fluorine contained were measured in the same manner as in Example 1. The results are shown in Table-1. Comparative Example 2 A synthetic mica was produced in the same manner as in Example 1 except that the heat treatment was not performed. For the obtained mica, L * a * b *, the ultraviolet transmittance and the number of moles of iron and fluorine contained were measured in the same manner as in Example 1. The results are shown in Table-1. Comparative Example 3 A synthetic mica was obtained in the same manner as in Example 1 except that the heat treatment temperature was 600 ° C. For the obtained mica, as in Example 1, L * a * b *, ultraviolet transmittance and iron,
The number of moles of fluorine contained was measured. The results are shown in Table-1. Comparative Example 4 A synthetic mica was obtained in the same manner as in Example 1 except that the heat treatment temperature was changed to 1300 ° C. For the obtained mica, as in Example 1, L * a * b *, ultraviolet transmittance and iron,
The number of moles of fluorine contained was measured. The results are shown in Table-1.

[0016]

[Table-1]

Next, examples in which the red synthetic mica of the present invention is applied to cosmetics will be shown, but the present invention is not limited to these examples. In the examples, the compounding ratio is “wt%”. Example 6: Oily stick foundation (1) Titanium dioxide 11.0 (2) Kaolin 13.0 (3) The red synthetic mica of the present invention obtained in Example 1 16.5 (4) Squalane 35.0 (5) ) Cetyl 2-ethylhexanoate 16.5 (6) Sorbitan sesquioleate 1.5 (7) Aristo wax 4.5 (8) Carnauba wax 1.8 (9) Perfume 0.2

The above components (4), (5) and (6) are added to 8 parts.
Mix at 0 ° C., add the components (1), (2) and (3) to the mixture, mix with a disper, and then subject to TK mill treatment. Then, the components (7) and (8) are dissolved by heating, added to and mixed with the TK mill treated product, and degassed.
Then, the above component (9) was gradually mixed and then charged into a container at 80 ° C. and cooled to obtain an oily stick foundation of the present invention.

Example 7: Solid foundation (1) Titanium dioxide 5.0 (2) Fine particle titanium dioxide 10.0 (3) Talc 8.0 (4) Muscovite 22.0 (5) In Example 2 The obtained red synthetic mica of the present invention 30.0 (6) Nylon powder 10.0 (7) Yellow iron oxide 1.0 (8) Black iron oxide 0.2 (9) Silicone oil 1.8 (10) 2- Ethylhexyl palmitate 10.1 (11) Sorbitan sesquioleate 1.5 (12) Preservative 0.3 (13) Perfume 0.1

The components (1) to (8) are mixed with a Henschel mixer, and the mixture is heated and dissolved in the mixture (9) to (8).
After the component (13) was added and mixed, it was pulverized with a pulverizer and molded into an inner dish to obtain a solid foundation of the present invention.

Example 8: Emulsion foundation (1) Stearic acid 0.4 (2) Isostearic acid 0.3 (3) Cetyl 2-ethylhexanoate 4.0 (4) Liquid paraffin 11.0 (5) POE (10) Stearyl ether 2.5 (6) Talc 10.0 (7) Muscovite 5.0 (8) Red synthetic mica of the present invention obtained in Example 3 6.0 (9) Yellow iron oxide 9 (10) Black iron oxide 0.1 (11) Cetyl alcohol 0.3 (12) Preservative 0.07 (13) Triethanolamine 0.42 (14) Propylene glycol 5.0 (15) Preservative 0. 02 (16) Ion-exchanged water 53.69 (17) Perfume 0.3

The components (1) to (12) are heated to 85 ° C., dissolved and mixed, and then uniformly dispersed by a disper. The above (13)-
The mixture of components (16) is gradually added and emulsified with a homomixer. The temperature at the time of emulsification is maintained at 85 ° C for 10 minutes and stirred, and then cooled by stirring to 45 ° C. The component (17) above was added thereto, and the mixture was continuously stirred and cooled to 35 ° C. and then filled in a container to obtain an emulsion foundation of the present invention.

[0023]

[Effect] As described above, according to the present invention, a specific element is provided at a specific position, and moreover, the number of moles of fluorine and the number of moles of iron ions are set within a certain range, so that the conventional seed mica can be obtained It is possible to obtain a novel synthetic mica having a light-resistant red color with transparency that is not seen at all. Since the synthetic mica of the present invention is extremely excellent in UV blocking ability, it can be mixed and used as a UV blocking agent in cosmetics, plastics, paints and the like without a coloring agent, and further, red coloring is deteriorated by light. There is no problem. Further, the red scale-like mica of the present invention is close to the color of the skin and has a transparent and bright red color, and is therefore particularly useful for cosmetics, especially foundations and the like.

[0024]

[Brief description of drawings]

FIG. 1 is an X-ray diffraction chart of the composite mica powder of the present invention obtained in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akitsugu Ando, Toyo Kogyo Co., Ltd., 1 Akemi-cho, Toyohashi-shi, Aichi Prefecture (72) Inventor Fukuji Suzuki, Fukuji, Kanagawa-ku, Yokohama, Kanagawa-ku, 1050, Shinba-cho Shiseido Research Institute (72) Inventor Kazuhisa Ohno 1050 Shinba-cho, Kohoku-ku, Yokohama, Kanagawa Shiseido Research Institute (72) Inventor Katsuki Ogawa 1050 Shinba-cho, Kohoku-ku, Yokohama, Kanagawa Shiseido Research Institute

Claims (5)

[Claims] 1. The following formula (I): X _{1/3 to 1} Y _{2 to 3} (Z ₄ O ₁₀ ) F _{2x0.75 to 2x0.99} (I) (wherein X is Na, K, Li, Represents one or more ions selected from the group consisting of Ca, Rb and Sr, Y is Mg, Fe, Ni, Mn, Al, Li,
Co, Ti and Zn represent one or more ions selected from the group consisting of Z, Z represents Al, Si, Ge, Fe, B, one or more ions selected from the group consisting of Co and Ti, Y and At least one of Z represents an iron ion. ), The iron-containing mole number in the synthetic mica is 0.01 to 3 moles, and the color of the synthetic mica measured by the powder cell method is L *.
Red synthetic mica characterized by L * = 55 * 75, a * = 5 * 20, b * = 5 * 20 in the a * b * color system. 2. The following formula (II): X _{1/3 to 1} Y _{2 to 3} (Z ₄ O ₁₀ ) F ₂ (II) (wherein X represents Na, K, Li, Ca, Rb and Sr). Represents one or more ions selected from the group consisting of Y, Mg, Fe, Ni, Mn, Al, Li,
Co, Ti and Zn represent one or more ions selected from the group consisting of Z, Z represents Al, Si, Ge, Fe, B, one or more ions selected from the group consisting of Co and Ti, Y and At least one of Z represents an iron ion. The synthetic mica represented by the formula (1), wherein the iron-containing mole number in the synthetic mica is 0.01 to 3 moles, the synthetic mica is heat-treated at 600 to 1200 ° C. Manufacturing method of red synthetic mica. 3. A synthetic mica having an iron-containing mole number of 0.01 to 3 moles is treated with an aqueous solution of one or more acids or chelating agents, and then heat treated at 600 to 1200 ° C. A method for producing the described red synthetic mica. 4. The following formula (I): X _{1/3 to 1} Y _{2 to 3} (Z ₄ O ₁₀ ) F _{2x0.75 to 2x0.99} (I) (wherein X is Na, K, Li, Represents one or more ions selected from the group consisting of Ca, Rb and Sr, Y is Mg, Fe, Ni, Mn, Al, Li,
Co, Ti and Zn represent one or more ions selected from the group consisting of Z, Z represents Al, Si, Ge, Fe, B, one or more ions selected from the group consisting of Co and Ti, Y and At least one of Z represents an iron ion. ), The iron-containing mole number in the synthetic mica is 0.01 to 3 moles, and the color of the synthetic mica measured by the powder cell method is L *.
An ultraviolet blocker containing a red synthetic mica having L * = 55 * 75, a * = 5 * 20, b * = 5 * 20 in the a * b * color system. 5. The ultraviolet blocking agent according to claim 4, wherein the ultraviolet blocking agent is a cosmetic ultraviolet blocking agent to be blended with cosmetics.