JP7163070B2 - Cosmetic additives and cosmetics containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to alumina-silica particles suitably used as additives blended in cosmetics to impart soft focus and/or anti-wrinkle effect. That is, the present invention relates to the use of alumina-silica particles having soft-focus and/or wrinkle-hiding effects as cosmetic additives.

Cosmetics such as foundations, base makers, and lipsticks are required to have a property called soft focus. For example, when a cosmetic is applied to the skin to form a cosmetic film, the soft focus property refers to the property that the surface of the skin becomes blurred, making it difficult to see spots, freckles, pores, or fine wrinkles on the skin. It means that a large proportion of the light that hits the surface (total irradiation light) does not go straight through the decorative coating film and is diffused.

Inorganic powders such as silica have been conventionally used to impart such soft-focus properties to decorative coating films formed from cosmetics. For example, Patent Document 1 reports that spherical silica or the like is effective in imparting soft focus properties. Further, Patent Documents 2 and 3 disclose spherical silica particles produced by using polyacrylamide or carboxymethylcellulose as an aggregation growth agent and neutralizing alkali silicate with an acid in the presence of this aggregation growth agent. It is described to be used as a filler for cosmetics. Furthermore, in Patent Document 4, when producing silica by reacting alkali silicate with acid in the presence of an aggregation growth agent, silica particles are produced by partial neutralization, and then remain in the reaction system. By gradually neutralizing unneutralized alkali silicate, silica is precipitated on the generated silica granules. It is described that silica particles of 0.7 to 0.85 can be obtained, and that the silica particles impart excellent soft-focus properties to cosmetics and that the soft-focus properties are also excellent in persistence.

Japanese Patent Application Laid-Open No. 2001-199839 JP-A-05-193927 JP-A-07-232911 JP 2010-184856 A

With the spherical silica particles described in Patent Documents 1 to 3, even if the soft-focus property is exhibited by blending it in cosmetics, there is a problem in the sustainability of the soft-focus property. Specifically, when applied to the skin to form a cosmetic film, its optical properties change over time, or it falls off from the skin due to perspiration, etc., resulting in a short-term decrease in soft focus or a loss of soft focus. There is the problem of damage. The silica particles described in Patent Literature 4 improve the sustainability problem. Specifically, since the silica particles described in Patent Document 4 have a high oil absorption, they have the property of quickly absorbing sweat and the like, and have a circularity of 0.7 to 0.85, which is slightly deformed from a spherical shape. It is difficult to fall off from the surface of the skin. Therefore, it can be stably present in the decorative coating film and can provide a sustained and excellent soft focus property.

Since the silica particles described in these Patent Documents 1 to 4 are all spherical or spherical with a high degree of circularity, they can impart high lubricity when blended in cosmetics. However, high slipperiness spreads easily when applied to the skin, but on the other hand, it also causes slippage on the skin, resulting in a decrease in skin familiarity and skin adhesion, and in turn, a decrease in covering power. In order to make blemishes, freckles, and fine wrinkles less visible, it is necessary to spread evenly over the surface of the skin while maintaining its covering power, and to adhere to the skin so that it is integrated with the skin. It is required to have flexibility and staying power.

The present invention has particle properties different from those of conventionally known silica particles, and is an alumina-silica system capable of imparting excellent soft-focus properties, fine wrinkle concealing effect, and/or good feeling in use to cosmetics. An object of the present invention is to provide a new use of particles as a cosmetic additive.

The present inventors have found that alumina-silica-based cubic particles having specific properties and physical properties prepared by reacting zeolite produced from sodium silicate and sodium aluminate with acid can be blended into cosmetics. Thus, the inventors have found that the cosmetic can be imparted with an excellent soft-focus property and exhibit an effect of making fine wrinkles and pores inconspicuous. In addition, the particles have moderate slip properties, and when applied to the skin, the cosmetic containing the particles smoothly spreads and spreads, and when it is in close contact with the skin, it stays moderately stretched, resulting in good spreadability and familiarity with the skin. It was confirmed that it has good (skin adhesion) and, by extension, good usability.

Further research revealed that surface treatment of the alumina-silica particles with a room temperature curable silicone composition to make them hydrophobic can improve slipping between the particles, and as a result, when applied to the skin. It has been found that the slipperiness can be further improved while maintaining an appropriate staying power, and the wrinkle-hiding effect can also be improved.

The present invention has been completed based on such findings, and includes the following embodiments.
(I) cosmetic additive
(I-1) A cosmetic additive having alumina-silica particles,
A cosmetic additive characterized in that the alumina-silica particles have the following characteristics:
(1) cubic primary particles with a side length of 0.3 to 20 μm as observed by scanning electron microscopy;
(2) a refractive index of 1.48 to 1.52 by the liquid immersion method;
(3) a volume-based average particle size of 1 to 20 μm by the Coulter Counter method;
(4) Oil absorption according to JIS K5101-13-2 is 10 ml/100 g or more and less than 50 ml/100 g.
(5) The specific surface area by the BET method is 20 m ² /g or less.
(I-2) The cosmetic additive according to (I-1), wherein the alumina-silica particles have a water adsorption amount of 0 to 5% by a gas adsorption method.
(I-3) The alumina-silica-based particles have a composition in which the molar ratio of SiO ₂ /Al ₂ O ₃ is in the range of 1.8 to 5, and are substantially amorphous in X-ray diffraction. The cosmetic additive according to (I-1) or (I-2), which is
(I-4) A cosmetic additive comprising hydrophobized alumina-silica particles obtained by hydrophobizing the surface of the alumina-silica particles according to any one of (I-1) to (I-3).
(I-5) The surfaces of the alumina-silica particles, wherein the hydrophobized alumina-silica particles are described in any one of (I-1) to (I-3), are coated with a cured room-temperature-curable silicone composition. The cosmetic additive according to (I-4), which comprises:
Here, the room temperature curing silicone composition is
a first oligomer containing a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group;
a second oligomer containing no dialkylsiloxane unit and containing an alkoxy group-containing siloxane unit containing an alkoxy group;
silicone oil;
a catalyst;
A room temperature curing silicone composition containing an organic solvent,
The ratio of the total amount of the first oligomer and the second oligomer in the room temperature curable silicone composition is 20% by mass or more and 50% by mass or less,
The ratio of the first oligomer to 1 part by mass of the second oligomer is 0.15 parts by mass or more and 10 parts by mass or less,
The silicone oil has a kinematic viscosity at 25° C. of 100 mm ² /s or more,
the catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates;
The vapor pressure of the organic solvent at 20° C. is lkPa or higher.
(I-6) In the hydrophobized alumina-silica particles, the proportion by mass of the alumina-silica particles is 90 parts by mass or less with respect to 10 parts by mass of the cured product of the room-temperature curing silicone composition coated on the surface. , the cosmetic additive according to (I-5).
(I-7) The hydrophobized alumina-silica particles are the alumina-silica particles according to any one of (I-1) to (I-3), the surface of which is coated with methyl hydrogen silicone oil, and heated. The cosmetic additive according to (I-4), which is surface-treated.
(I-8) Any one of (I-1) to (I-7) wherein the alumina-silica particles or hydrophobized alumina-silica particles have any one of the following properties (a) to (d) Cosmetic additives described in:
(a) Average coefficient of friction (MIU): 0.3 to 0.7
(b) Concealability index: 6 or less (c) Wrinkle blurring index: 32 or less (d) Haze: 30-80.
(I-9) of (I-1) to (I-8), wherein the cosmetic additive is a soft focus imparting agent, a wrinkle concealing effect imparting agent (irregularity correcting agent), and/or an extensibility imparting agent; A cosmetic additive according to any one of the above.

(II) Method for producing hydrophobized alumina-silica particles (II-1) The alumina-silica particles described in any one of (I-1) to (I-3) are coated with methyl hydrogen silicone oil, A method for producing surface-hydrophobicized alumina-silica particles, comprising a heat treatment step.
(II-2) A method for producing surface-hydrophobicized alumina-silica particles, comprising the following steps (A) and (B):
(A) A step of coating the surface of the alumina-silica particles according to any one of (I-1) to (I-3) with a room temperature curable silicone composition:
Here, the room temperature curing silicone composition is
a first oligomer containing a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group;
a second oligomer containing no dialkylsiloxane unit and containing an alkoxy group-containing siloxane unit containing an alkoxy group;
silicone oil;
a catalyst;
containing an organic solvent,
The ratio of the total amount of the first oligomer and the second oligomer in the room temperature curable silicone composition is 20% by mass or more and 50% by mass or less,
The ratio of the first oligomer to 1 part by mass of the second oligomer is 0.15 parts by mass or more and 10 parts by mass or less,
The silicone oil has a kinematic viscosity at 25° C. of 100 mm ² /s or more,
the catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates;
The organic solvent has a vapor pressure of 1 kPa or more at 20° C.; and (B) a step of curing the room-temperature-curable silicone composition coated on the surface of the alumina-silica particles.
(II-3) Alumina-silica particles having a hydrophobized surface have any one of the following characteristics (a) to (d): (II-1) or (II-2) Production method:
(a) Average coefficient of friction (MIU): 0.3 to 0.6
(b) Concealability index: 5 or less (c) Wrinkle blurring index: 28 or less (d) Haze: 34-80.
(II-4) In the hydrophobized alumina-silica particles, the proportion of the alumina-silica particles is 90 parts by mass or less per 10 parts by mass of the cured product of the room-temperature curing silicone composition coated on the surface. The production method described in (II-2) or (II-3), which is a method.
(II-5) The production method according to any one of (II-2) to (II-4), wherein the organic solvent is an alcohol solvent.
(II-6) The ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer and the silicone oil is 40 to 300 parts by mass, (II-2) The production method according to any one of (II-5).
(II-7) (II-2) to (II-6), wherein the ratio of the catalyst to the total amount of 100 parts by mass of the first oligomer and the second oligomer is 2 to 55 parts by mass. ).

(III) Cosmetics (III-1) Cosmetics characterized by containing the cosmetic additive described in any one of (I-1) to (I-9).
(III-2) The cosmetic according to (III-1), containing the cosmetic additive in a proportion of 1 to 50% by mass.
(III-3) The cosmetic according to (III-1) or (III-2), wherein the cosmetic is a make-up cosmetic.

The alumina-silica-based particles used in the present invention, when blended in cosmetics, are highly sensitive to light, based on their properties such as particle shape, particle diameter, refractive index, specific surface area and/or water adsorption amount. Scattering properties can be imparted. In other words, in a cosmetic containing the particles of the present invention, light is transmitted through the cosmetic film while undergoing multiple scattering. can do.

In addition, when the alumina-silica particles used in the present invention are blended in cosmetics, especially based on the particle shape and particle size, they do not fall into skin grooves such as fine wrinkles and cover them well. A wrinkle hiding effect can be exhibited. Similarly, the effect of covering the pores of the skin and adjusting the texture of the skin after makeup (irregularity correction effect) can be exhibited.

Furthermore, since the alumina-silica particles used in the present invention have a cubic shape, they have a large planar fixing area, and when blended in cosmetics and applied to the skin, they are physically difficult to remove from the skin, exhibiting a long-lasting effect. can do.

In addition, by treating the surface of the alumina-silica particles with a hydrophobizing agent such as methylhydrogensilicone oil or a room temperature curable silicone composition to make the surface hydrophobic, it is possible to improve the lubricity between the particles. can. As a result, when it is applied to the skin, it is possible to further improve slipperiness while maintaining appropriate staying power, and also to improve wrinkle-hiding effect.

1 shows a photographic image of alumina-silica-based cubic particles 1 (Example 1) of the present invention produced in Production Example 1, observed and photographed with a scanning electron microscope. 1 shows a photographic image of alumina-silica-based cubic particles 2 (Example 2) of the present invention produced in Production Example 2, which was observed and photographed with a scanning electron microscope. 1 shows a photographic image of alumina-silica-based cubic particles 3 (Example 3) of the present invention produced in Production Example 3, observed and photographed with a scanning electron microscope. 1 shows an X-ray diffraction profile of alumina-silica-based cubic particles 1 (Example 1) of the present invention produced in Production Example 1. FIG.

(I) Alumina-silica-based cubic particles The alumina-silica-based cubic particles (hereinafter also simply referred to as "the particles of the present invention") constituting the cosmetic additive of the present invention have the following properties and characteristics. Characterized by
(1) Consists of cubic primary particles with a side length of 0.3 to 20 μm as observed by a scanning electron microscope.
(2) It has a refractive index of 1.48 to 1.52 by the liquid immersion method.
(3) The volume-based average particle diameter measured by the Coulter Counter method is 1 to 20 μm.
(4) The oil absorption according to JIS K5101-13-2 is 10ml/100g or more and less than 50ml/100g.
(5) The specific surface area by the BET method is 20 m ² /g or less.

Each of these characteristics of the particles of the present invention will be described below.

In the present invention, the term "soft focus" means that when a cosmetic such as a foundation containing the particles of the present invention is applied to the skin, spots, freckles, pores, fine wrinkles, etc. are blurred and inconspicuous due to the light scattering effect. , refers to the action of adjusting the appearance of the skin so that it looks smooth. The "soft focus property" can be evaluated using a Haze meter as shown in Experimental Example 1 described later.

(1) Shape and Particle Diameter The particles of the present invention are characterized in that the primary particles are cubic in shape and have a side length of 0.3 to 20 μm when observed with a scanning electron microscope. It is preferably 0.5 to 20 μm, more preferably 1.5 to 12 μm. As an example, FIGS. 1 to 3 show images obtained by observing the primary particles of the particles of the present invention (Examples 1 to 3) produced in Production Examples 1 to 3 with a scanning electron microscope. As shown in these figures, the particles of the present invention are primary particles (fine particles) having a substantially cubic shape consisting of 6 faces and 8 corners, and having almost regular shapes and sizes. The particles of the present invention having such a shape have high light scattering performance (light diffusing power) and can exhibit good soft focus properties. In addition, the texture and slipperiness are also good. Here, good skin slipperiness does not simply mean having high skin slipperiness, but that when applied to the skin, it adheres appropriately to the skin and stays on the skin and spreads uniformly on the skin surface, that is, moderate slipperiness. It means that it has a staying property.

In general, spherical (including true spherical) fine particles are said to have the effect of hiding fine wrinkles by falling into and filling the skin sulcus such as fine wrinkles. There is a problem that lines stand out and fine wrinkles are conspicuous. On the other hand, since the particles of the present invention have a cubic shape, a plurality of particles are entangled on the skin surface, and the skin can be covered so as to cover the skin grooves such as fine wrinkles, so the effect of hiding fine wrinkles is excellent. ing. For the same reason, it is also excellent in the effect of hiding pores, and can contribute to the effect of smoothing the unevenness of the skin and adjusting the texture of the skin after makeup. Furthermore, since the particles of the present invention have a cubic shape, they have a large planar fixing area, and when blended in cosmetics and applied to the skin, they are physically difficult to remove from the skin, and can exhibit a long-lasting effect.

(2) Refractive Index The particles of the present invention are characterized by having a refractive index of 1.48 to 1.52.

Here, the refractive index can be determined by an immersion method. Specifically, as described in the examples below, two solvents having different refractive indices (α-bromnaphthalene and kerosene) were used to prepare solvents having various refractive indices, and the solvents were prepared according to Larsen's oil immersion method. can be determined by observing the movement of Becke lines with an optical microscope after immersing the particles of the present invention taken on a slide glass in the solvent.

The refractive index affects the soft focus property. When blended in a cosmetic, if there is an appropriate difference in refractive index between the liquid component in the cosmetic and the water content of sweat, light is scattered at the interface, thereby exhibiting soft-focus properties. In general, silica-based particles having a small difference in refractive index become transparent when wet with water such as perspiration, resulting in a marked decrease in the hiding effect. For this reason, the soft focus property is maintained even when sweating, and appropriate concealing property can be exhibited. Therefore, the particles of the present invention preferably have a refractive index of 1.48 to 1.52, more preferably 1.49 to 1.51.

(3) Volume-Based Average Particle Size The particles of the present invention are characterized by having a volume-based average particle size of 1 to 20 μm.

Here, the volume-based average particle diameter can be obtained by the Coulter counter method. Specifically, as described in the examples below, a dispersion obtained by dispersing 0.5 g of the particles of the present invention in 150 ml of deionized water was subjected to a Coulter counter to measure the volume-based particle size distribution. By obtaining the median diameter (D ₅₀ ), the volume-based average particle diameter of the particles can be obtained.

If the particle diameter is larger than the wavelength of light, a light scattering effect occurs, so the volume-based average diameter is preferably 1 μm or more. As shown in Experimental Example 1 (Table 1), in the case of the particles of the present invention, the smaller the volume-based average particle diameter, the higher the haze value (haze) and the better the soft focus property. Although not bound by theory, this is because when the amount added to the cosmetic on a weight basis is the same, more particles with a smaller volume-based average particle size can be blended, resulting in a higher light scattering effect. This is thought to be due to From the viewpoint of soft focus, the volume-based average particle diameter is preferably 12 μm or less. On the other hand, in the case of the particles of the present invention, the wrinkle-hiding effect improves as the volume-based average particle diameter increases. Although this is also not bound by theory, it is believed that the larger the volume-based average particle diameter is, the higher the effect of covering the sulcus cutis is. From the viewpoint of both soft focus property and wrinkle hiding effect (irregularity correction effect), the volume-based average particle diameter of the particles of the present invention is preferably 1 to 10 μm, and more preferably 1.5 from the viewpoint of high soft focus property. ~4 μm.

(4) Oil Absorption The particles of the present invention are characterized by having an oil absorption in the range of 10 ml/100 g or more and less than 50 ml/100 g.

Here, the oil absorption is according to JIS. K. 5101-13-1: 2004 (refined linseed oil method). Specifically, it can be determined from the amount of refined linseed oil (ml/100 g) at the time when refined linseed oil is gradually added to the particles of the present invention and mixed to form a paste of appropriate hardness.

In general, porous particles having pores on their surfaces have a large oil absorption. However, similar to the specific surface area and the amount of water absorption, when it is blended in cosmetics or applied to the skin, the liquid components and sweat in the cosmetics permeate the pores on the surface of the fine particles, and the surface of the particles becomes wet. There is a problem that the refractive index is lowered and the soft focus property is lowered. On the other hand, since the particles of the present invention have a small oil absorption as described above, regardless of the environmental conditions in which the particles of the present invention exist, the original refractive index of the particles is less likely to be impaired, and the original refractive index, etc. It is possible to exhibit a high soft focus property. From this point of view, the oil absorption of the particles of the present invention is preferably 10-45 ml/100 g, more preferably 10-35 ml/100 g.

The oil absorption also affects the sebum-absorbing ability of the cosmetic when the particles of the present invention are blended in the cosmetic. If the oil absorption is too high, the ability to remove sebum from the skin increases, which may burden the skin, such as dryness and itchiness. Since the particles of the present invention have an oil absorption amount within the above range, they are characterized by moderate suppression of degreasing from the skin and less burden on the skin.

(5) Specific Surface Area The particles of the present invention are characterized by having a specific surface area of 20 m ² /g or less as determined by the BET method in connection with having the aforementioned particle shape and particle size characteristics. It is preferably 1 to 10 m ² /g, more preferably 1 to 5 m ² /g.

In general, porous particles having pores on their surfaces have a large specific surface area. However, in this case, when blended in a cosmetic, the liquid component in the cosmetic penetrates into the pores on the surface of the microparticles, and sweat penetrates into the pores on the surface of the microparticles after applying to the skin. There is a problem that the particles become wet with a liquid, and the original refractive index of the particles is lowered, resulting in a decrease in the soft focus property. In contrast, the particles of the present invention have a small specific surface area, as described above. It has a feature that it can exhibit high soft focus property.

In addition to the chemical and physical properties mentioned above, the particles of the present invention have several further chemical and physical properties.

(6) Water adsorption amount The particles of the present invention are characterized by having a water adsorption amount of 0 to 5%.

Here, the moisture adsorption amount can be determined by a gas adsorption method. Specifically, as described in the examples below, the particles of the present invention are pretreated by leaving them under vacuum conditions at 150° C. for 2 hours, and then the particles are subjected to a water vapor partial pressure P _T (P/P ₀ ) to obtain a moisture adsorption isotherm in the range of 0.001 to 0.9 (equilibrium determination time: 300 seconds), and the measured value at water vapor partial pressure P _T (P/P ₀ ) of 0.75 is calculated as the unit mass of the particles of the present invention. It can be obtained by converting to the amount of water adsorbed (% by mass) per unit.

The water absorption amount affects the moisturizing properties of the skin when the particles of the present invention are blended in cosmetics. If the moisture absorption amount is too high, the ability to deprive the sebum of moisture that gives moisture to the skin increases, which may burden the skin such as dryness and itchiness. Since the particles of the present invention have a water adsorption amount within the above range, they have a feature that the skin retains an appropriate amount of moisture. From this point of view, the water adsorption amount of the particles of the present invention is preferably 0 to 3%, more preferably 0 to 1%.

(7) Molar ratio of SiO ₂ /Al ₂ O ₃ The particles of the present invention are characterized by having a composition in which the molar ratio of SiO ₂ /Al ₂ O ₃ is in the range of 1.8-5. It is preferably 1.85 to 2.5, more preferably 1.9 to 2.1.

The SiO ₂ /Al ₂ O ₃ molar ratio of the particles of the present invention is within the above range, so that the particles can have a cubic shape with a certain particle size as described above. In other words, the molar ratio is a useful requirement for configuring the shape of the particles of the present invention.

(8) Amorphousness The particles of the present invention are characterized by being substantially amorphous. The term "substantially amorphous" as used herein means that the material is amorphous and no crystallization is observed when measured by X-ray diffractometry. The method for measuring the degree of crystallinity by X-ray diffraction is as described in Examples below.

(9) Apparent Specific Gravity The particles of the present invention are characterized by having an apparent specific gravity in the range of 0.5 to 1.1 g/cm ³ .

Here, the apparent specific gravity is JIS. K. 6220-1:2001 7.7. Specifically, as shown in Examples described later, it can be determined by applying a constant load to the particles of the present invention and measuring the specific gravity at that time.

The apparent specific gravity is a parameter linked with the oil absorption amount. Therefore, when the apparent specific gravity is low, the oil absorption tends to be high, and the ability to remove oil from the sebum tends to be high. Since the particles of the present invention have an apparent specific gravity within the above range, degreasing from the skin is appropriately suppressed, and the particles are characterized by less burden on the skin. From this point of view, the apparent specific gravity of the particles of the present invention is preferably 0.5 to 1.1 g/cm ³ , more preferably 0.65 to 1.1 g/cm ³ .

(10) Ignition loss The particles of the present invention are characterized by having an ignition loss in the range of 0 to 6%.

Here, the ignition loss is determined according to JIS. K. 0067: 1992, 4.2. Specifically, as shown in Examples described later, a predetermined amount of the particles of the present invention is placed in an evaporating dish and ignited at 860° C. for 20 minutes in an electric furnace, and the mass of the test sample that has decreased after ignition is measured. can be obtained by

Since the ignition loss is a parameter linked to the water adsorption amount, it affects the moisturizing properties of the skin when blended in cosmetics. If the ignition loss is too high, the ability to take away the moisture that moisturizes the skin increases. Since the particles of the present invention have an ignition loss within the above range, they have a feature that the skin's moisturizing properties are appropriately maintained. From this point of view, the ignition loss of the particles of the present invention is preferably 0 to 5%, more preferably 0 to 3%.

(11) Hunter Whiteness The particles of the present invention are characterized by having a whiteness in the range of 80 to 100%. The whiteness can be measured based on the Hunter whiteness test method. Specifically, it can be measured using a Hunter reflectometer having a blue filter (effective wavelength: 457 nm), as shown in Examples described later.

The whiteness of the particles of the present invention is as described above, and has a sufficient whiteness to be incorporated in cosmetics. If the whiteness is lower than 80%, the skin looks dull when blended in cosmetics, which is undesirable. From this point of view, the whiteness of the particles of the present invention is preferably 85 to 100%, more preferably 90 to 100%.

(12) Haze value (soft focus)
As described above, the particles of the present invention can impart a soft focus property to a cosmetic by blending it in the cosmetic. Such soft focus property can be evaluated as a Haze value. The haze value is a numerical value indicating the degree of fogging (blurring), and the higher the numerical value, the higher the soft focus property and the higher the hiding property (covering power). The haze value can be determined by "diffuse transmittance/total light transmittance×100" and can be usually measured with a haze meter.

Specifically, the Haze value is obtained by mixing the particles of the present invention and silicone oil at a ratio of 1:9 (mass ratio) and forming a coating film having a thickness of 20 μm on a PET sheet, as described in the examples below. can be made and measured with a Haze meter according to ASTM D1003. The haze value of the particles of the present invention for visible light is 35% or more. It is preferably 40% or more, more preferably 50% or more, and particularly preferably 55% or more. As shown in Table 1, the particles of the present invention have a higher haze value and are superior in soft-focus property as compared with spherical silica particles. Therefore, by blending it as a cosmetic additive in cosmetics, it is possible to impart a blurring effect to the cosmetics.

(13) Average friction coefficient (slipperiness)
The particles of the present invention may preferably have an average friction coefficient of 0.7 or less, more preferably 0.6 or less. The lower the average coefficient of friction, the better the extensibility, which is preferable. From this point of view, the lower limit can be, for example, 0.3 or more.

The average friction coefficient is a physical property value that serves as an index for evaluating the slipperiness of the particles of the present invention, and the smaller the value, the higher the slipperiness. The coefficient of friction of the particles of the present invention can be measured using a friction tester (Friction Tester KSE-SE: manufactured by Kato Tech Co., Ltd.). In the measurement, the particles of the present invention, which are test samples, are directly applied to the artificial skin. According to the particles of the present invention having the desired average coefficient of friction, it has moderate slipperiness on the artificial skin and between the particles, and when applied to the skin, it spreads evenly on the skin and moderately stays on the skin. Effective.

(14) Optical evaluation of wrinkle hiding property: (a) hiding property index, (b) wrinkle blurring property index Wrinkle hiding property is the ability to hide the substrate when applied to the skin. The greater the effect of blurring pores and fine wrinkles (wrinkle blurring effect), the better the evaluation. The hiding index and the wrinkle-blurring index are physical property values that serve as indices for evaluating the hiding effect and wrinkle-blurring effect of the particles of the present invention, respectively. It shows that the hiding property is exhibited satisfactorily. The particles of the present invention may preferably have a hiding index of 6 or less, more preferably 5 or less. Although the lower limit is not limited, 1 or more can be exemplified. The particles of the present invention may preferably have a wrinkle blurring index of 32 or less, more preferably 28 or less. Although the lower limit is not limited, 20 or more, preferably 25 or more can be exemplified.

The opacity index and the wrinkle blurring index of the particles of the present invention can be measured by the method described in Examples below.

(II) Method for Producing Alumina-Silica Based Cubic Particles The particles of the present invention used in the present invention are crystalline zeolite having a cubic particle form, although the crystal structure is substantially destroyed, the particle form is substantially It is prepared by removing the alkali metal content in the zeolite by acid neutralization under non-damaging conditions.

The crystalline zeolite used as a raw material includes zeolite A, zeolite X, zeolite Y, etc., but zeolite A is preferable because of its ease of synthesis and availability and the properties of alumina-silica particles after production. be able to. Although not limited, the raw material zeolite preferably has a primary particle size (the length of one side of a cubic particle measured by a scanning electron microscope) in the range of 0.3 to 20 μm. According to the crystalline zeolite in this particle size range, the alumina-silica particles with a primary particle size of 0.3 to 20 μm used in the present invention are treated with a relatively mild acid to remove the alkali content in a short time. It can be removed and amorphized.

The acid used for neutralizing the crystalline zeolite may be either an inorganic acid or an organic acid, but from an economical point of view inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid are preferably used. Sulfuric acid is preferred. Usually, these acids are diluted with water to about 5 to 30% by weight, preferably about 10 to 20% by weight, and used in the form of an aqueous solution for the neutralization reaction with the crystalline zeolite.

When an acid is added to an aqueous slurry of crystalline zeolite, the pH of the slurry shifts to the acidic side as the acid is added, but after the addition of the acid, the pH of the liquid shifts to the alkaline side again and remains at a constant pH value. Tend. In order to remove the alkali metal content in the crystalline zeolite and form a stable amorphous product, an acid is added so that the stable pH is 3 to 7, preferably 4 to 6.5. It is desirable to

Amorphous alumina-silica-based cubic particles obtained by acid-treating crystalline zeolite to remove alkali by elution are filtered, washed with water if necessary, dried, and then calcined. Firing is not limited, but is carried out at a temperature of 300 to 300 using an electric furnace, for example, so that the amount of water absorbed by the gas adsorption method of the prepared amorphous alumina-silica-based cubic particles is 0 to 5% as described above. It is preferable to carry out at 800° C. for about 0.5 to 24 hours.

(III) Hydrophobized alumina-silica cubic particles and method for producing the same The hydrophobized alumina-silica cubic particles of the present invention are prepared by subjecting the surface of the alumina-silica cubic particles (particles of the present invention) to hydrophobic treatment (repellent treatment). water treatment). Such hydrophobization treatment is not particularly limited, and conventionally known methods such as water-repellent surface treatment with silicone can be used. Examples of such silicone treatment include a method of coating the particle surface with silicone oil (Japanese Patent Application Laid-Open No. 2007-176738, etc.), and a method of coating the particle surface with methylhydrogensilicone (quasi-drug name methylhydrogenpolysiloxane). A method of heat treatment at ~180 ° C. (Japanese Patent Laid-Open No. 2005-350588), a method of reacting with hydrogensilane using a fluorine-containing boron-based catalyst to silylate the surface (WO2015/136913), etc. are exemplified without limitation. can do. A preferable method is to coat the surface of the aforementioned alumina-silica-based cubic particles (particles of the present invention) with methylhydrogensilicone, followed by heat treatment. Although the heating temperature is not limited, 100 to 180° C. can be exemplified as described above.

Alternatively, the surface of the aforementioned alumina-silica-based cubic particles (particles of the present invention) can be coated with a room-temperature-curable silicone composition. That is, the hydrophobized alumina-silica-based cubic particles are obtained by coating the surface of the particles of the present invention described above with a cured product of the room-temperature-curable silicone composition.

(1) Room-temperature-curable silicone composition The room-temperature-curable silicone composition used for coating the cubic alumina-silica particles is a composition that forms a film and cures at room temperature. Here, normal temperature is a temperature at which heating (specifically, heating to 50° C. or higher) is not performed, for example, less than 50° C., preferably 40° C. or lower, and for example, 0° C. or higher, preferably 10° C. or higher. . The term normal temperature is used synonymously with room temperature.

A room-temperature-curable silicone composition (hereinafter also simply referred to as "silicone composition") contains a first oligomer, a second oligomer, silicone oil, a catalyst, and an organic solvent.

The first oligomer forms a siloxane matrix together with the second oligomer in the coating, and is a non-adhesive aid that assists the non-adhesiveness and water repellency of the silicone oil in the coating even when the coating is rubbed. As a result, the coating can effectively suppress deterioration in non-adhesiveness after a long period of time.

The first oligomer contains a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group. Specifically, the first oligomer is a siloxane oligomer represented by the following formula (1).

(Wherein, R ¹ to R ⁹ may be the same or different, and at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group. represents a hydrogen group, X is a siloxane unit, a and e may be the same or different and are 1 or 2, b is an integer of 2 to 20, C is an integer of 2 to 10 is an integer and d is an integer from 2 to 20.)

Examples of l-valent saturated hydrocarbon groups represented by R ¹ to R ⁹ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n- Examples include alkyl groups having 1 to 6 carbon atoms such as pentyl and n-hexyl. A methyl group is preferred.

Examples of l-valent aromatic hydrocarbon groups represented by R ¹ to R ⁹ include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl. A phenyl group is preferred.

R ¹ to R ⁹ preferably include a methyl group and/or a phenyl group, more preferably a methyl group.

In the first oligomer, unit I is an alkoxy group-containing siloxane unit. That is, unit ^I contains an alkoxy group represented by R2O.

a represents the number of alkoxy groups represented by R ² O— bonded to silicon atoms in unit I, preferably 2; In that case, in unit I, the number (3-a) of monovalent hydrocarbon groups represented by R ¹ bonded to silicon atoms is preferably 1 (=3-2).

In unit I, the oxygen atom in Si—O— is bonded to one of the silicon atoms in units II to IV described below. Thereby, the Si—O— of this unit I forms a siloxane bond in the first oligomer.

Unit I is a molecular terminal unit in the first oligomer.

Unit II is an alkoxy group-containing siloxane unit. That is, unit II contains an alkoxy group represented by ^R4O .

b means the number of units II. b is an integer of preferably 3 or more and preferably 13 or less.

Unit III is a siloxane unit having two oxygen atoms bonded to the silicon atom. Unit III may also contain an alkoxy group.

Examples of the siloxane unit represented by X include, for example, Unit VI represented by the following formula (2) alone, Unit II and Unit I in combination (when having Unit I at the end via Unit II), Unit II and Unit V (when having unit V at the terminal via unit II), and combinations of unit II and unit VI (when having unit VI at the terminal via unit II).

Unit VI includes a cyclic siloxane unit represented by the following formula (2).

(Wherein, m is an integer of 2 or more. Z ¹ is the l-valent hydrocarbon group or alkoxy group described above.)

The monovalent hydrocarbon group represented by Z ¹ is preferably a methyl group, and the monovalent alkoxy group represented by Z ¹ is preferably a methoxy group.

c means the number of units III. c is preferably an integer of 6 or less.

Unit IV is a dialkylsiloxane unit. That is, unit IV contains an alkyl group represented by ^R6 and ^R7 . d means the number of units IV. d is preferably an integer of 6 or less.

Unit V is an alkoxy group-containing siloxane unit. That is, unit V contains an alkoxy group represented by ^R9O . The silicon atom in unit V bonds to any oxygen atom in units II to IV. The silicon atom in unit V thereby constitutes a siloxane bond in the first oligomer. Unit V is a molecular terminal unit in the first oligomer.

e is the number of alkoxy groups represented by R ⁹ O— bonded to silicon atoms in unit V, preferably 2; In that case, the number (3-e) of l-valent hydrocarbon groups represented by R ⁸ bonded to silicon atoms in unit V is preferably 1 (=3-2).

Each unit and its number described above are specified by ¹ H-NMR and ²⁹ Si-NMR.

The first oligomer can also be represented by the following average compositional formula (A).

Average compositional formula (A):
R ^P _α Si(OR ^q ) _β O _(4-α-β) (A)
(In the formula, R ^P and R ^q may be the same or different and represent a monovalent hydrocarbon group. α has an average value within the range of 0.40 to 1.70. β indicates the value at which the ratio of OR ^q bonded to silicon atoms in the average composition formula (A) is 5% by mass or more and less than 40% by mass.)

The monovalent hydrocarbon group is the same as the monovalent hydrocarbon group described above.

In the average composition formula (A), R ^p is a monovalent hydrocarbon group similar to R ¹ , R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above general formula (1). R ^q includes the same monovalent hydrocarbon groups as R ² , R ⁴ and R ⁹ in general formula (1) above.

In addition, β in the average composition formula (A) is such that the ratio of OR ^q bonded to silicon atoms in the average composition formula (A) is, for example, 10% by mass or more, preferably 20% by mass or more, or, for example, 35% by mass. % or less, preferably 30 mass % or less.

Specifically, the first oligomer is, for example, a methyl-based silicone alkoxy oligomer containing a dimethylsiloxane unit and a methoxy group-containing siloxane unit, a methylphenylsiloxane unit, and a siloxane unit containing a methoxy group and a phenoxy group. Examples include methylphenyl-based silicone alkoxy oligomers contained therein, preferably methyl-based silicone alkoxy oligomers.

The methyl-based silicone alkoxy oligomer is
For example, it is represented by the following formula (3).

(Wherein, b to d and X are the same as b to d and X in formula (1).)

Such methyl-based silicone alkoxy oligomers are produced, for example, from methyltrimethoxysilane and dimethyldimethoxysilane.

The molecular weight of the first oligomer is, for example, 500 or more, preferably 1,000 or more, and is, for example, 3,000 or less, preferably 2,000 or less.

A commercially available product is used as the first oligomer. For example, X-40-9250 (methyl-based silicone alkoxy oligomer in which b is 8, c is 4, and d is 4 in formula (3), manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified.

The ratio of the first oligomer in the silicone composition is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 6% by mass or more, Also, for example, it is less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 10% by mass or less.

The second oligomer forms a siloxane matrix with the first oligomer in the coating. The second oligomer does not contain a dialkylsiloxane unit but contains an alkoxy group-containing siloxane unit. Specifically, the second oligomer is a siloxane oligomer represented by the following formula (4).

( ^Wherein , R 11 to R ¹⁷ may be the same or different, and at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group. represents a hydrogen group, Y is a siloxane unit, f and i may be the same or different and are 1 or 2, g is an integer of 2 to 20, h is an integer of 2 to 18 is an integer.)

^Monovalent saturated hydrocarbon groups represented by R 11 to R ¹⁷ include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl , n-hexyl and other alkyl groups having 1 to 6 carbon atoms. A methyl group is preferred.

Examples of monovalent aromatic hydrocarbon groups represented by R ¹¹ to R ¹⁷ include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl. A phenyl group is preferred.

R ^ll to R ¹⁷ are preferably a methyl group and/or a phenyl group, more preferably a methyl group.

In the second oligomer, unit XI is an alkoxy group-containing siloxane unit. That is, unit XI contains an alkoxy group represented by R ¹² O.

f means the number of alkoxy groups represented by R ¹² O— bonded to silicon atoms in unit XI, preferably 2; In that case, the number (3-f) of ^monovalent hydrocarbon groups represented by R 11 bonded to silicon atoms in unit XI is preferably 1 (=3-2).

The oxygen atom in unit XI is bonded to the silicon atom in unit XII or unit XIII described below. Thereby, the Si—O— of this unit XI forms a siloxane bond in the second oligomer.

Unit XI is a molecular terminal unit in the second oligomer.

Unit XII is an alkoxy group-containing siloxane unit. That is, unit XII contains an alkoxy group represented by ^R14O . g means the number of units XII. g is an integer of preferably 3 or more and preferably 17 or less.

Unit XIII is a siloxane unit having two oxygen atoms bonded to a silicon atom. Unit XIII may also contain an alkoxy group.

As the siloxane unit represented by Y, for example, unit XV represented by the following formula (5) alone, a combination of unit XII and unit XI (when having unit XI at the terminal via unit XII), unit XII and unit XIV A combination (when having unit XIV at the terminal via unit XII), and a combination of unit XII and unit XV (when having unit XV at the terminal via unit XII) are exemplified.

Unit XV includes a cyclic siloxane unit represented by the following formula (5).

(In the formula, j is an integer of 2 or more. Z ² is the monovalent hydrocarbon group or alkoxy group described above.)

^The monovalent hydrocarbon group represented by ^Z2 is preferably a methyl group, and the monovalent alkoxy group represented by Z2 is preferably a methoxy group.

h means the number of units XIII. h is preferably an integer of 3 or more and preferably 15 or less.

The silicon atom in unit XIV is bonded to the oxygen atom in unit XII or unit XIII. The silicon atom in unit XIV thereby forms a siloxane bond in the second oligomer. Unit XIV is a molecular terminal unit in the second oligomer.

i means the number of R ¹⁷ O-alkoxy groups bonded to the silicon atom in unit XIV, preferably 2; In that case, in unit XIV, the number (3-i) of monovalent hydrocarbon groups represented by R ¹⁶ bonded to silicon atoms is preferably 1 (=3-2).

Each unit and its number described above are specified by ¹ H-NMR and ²⁹ Si-NMR.

The second oligomer can also be represented by the following average compositional formula (B).

Average compositional formula (B):
R ^t γSi(OR ^s ) _δO ( _4-γ-δ) (B)
(In the formula, R ^t and R ^s may be the same or different and represent a monovalent hydrocarbon group. γ has an average value within the range of 0.40 to 1.70. δ indicates the value at which the ratio of OR ^s bonded to silicon atoms in the average composition formula (B) is 5% by mass or more and less than 40% by mass.)

In the average composition formula (B), R ^t includes the same monovalent hydrocarbon groups as R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁶ in the general formula (4), and R ^s Examples include the same monovalent hydrocarbon groups as R ¹² , R ¹⁴ and R ¹⁷ in general formula (4) above.

In addition, δ in the average composition formula (B) is such that the ratio of ^ORS bonded to silicon atoms in the average composition formula (B) is, for example, 10% by mass or more, preferably 20% by mass or more, or, for example, 35% by mass. The values are as follows.

Specifically, the second oligomer includes, for example, a methyl-based silicone alkoxy oligomer and a methylphenyl-based silicone alkoxy oligomer, preferably a methyl-based silicone alkoxy oligomer.

Examples of methyl-based silicone alkoxy oligomers include methyl-based silicone methoxy oligomers produced from methyltrimethoxysilane.

A methyl-based silicone methoxy oligomer is represented, for example, by the following formula (6).

(Wherein, g, h and Y are the same as g, h and Y in formula (5).)

Such methyl-based silicone alkoxy oligomers are produced, for example, from methyltrimethoxysilane.

The molecular weight of the second oligomer is, for example, 500 or more, preferably 1,000 or more, and is, for example, 4,000 or less, preferably 3,000 or less.

A commercial product is used as the second oligomer. For example, KC-89 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-515 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-500 (in formula (6), g is 10 and h is 4 methyl silicone alkoxy oligomer, Shin-Etsu Kagaku Kogyo Co., Ltd.), X-40-9225 (methyl-based silicone alkoxy oligomer in which g is 12 and h is 10 in formula (6), Shin-Etsu Chemical Co., Ltd.), US-SG2403 (Dow Corning Toray Co., Ltd.) ) can be exemplified.

The ratio of the second oligomer in the silicone composition is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, and is, for example, less than 50% by mass, It is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

The ratio of the first oligomer to the second oligomer (first oligomer/second oligomer: mass ratio) is 0.15 or more, preferably 0.16 or more, more preferably 0.18 or more, further preferably 0.20 or more, More preferably, it is 0.22 or more. In addition, the ratio of the first oligomer to the second oligomer is 10 or less, preferably 9 or less, more preferably 7 or less, still more preferably 5 or less, particularly preferably 2 or less, furthermore preferably 1.0 or less, furthermore 0.5 It is below.

If the ratio of the first oligomer to the second oligomer is below the above lower limit or above the above upper limit, the coating will have reduced lubricity and water repellency. In other words, when the above ratio is at least the above lower limit and below the above upper limit, the coating can exhibit high lubricity and water repellency.

The ratio of the total amount of the first oligomer and the second oligomer (curing component) in the silicone composition is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass or more. . If the ratio is less than the above lower limit, the ratios of the first oligomer and the second oligomer (curing component) are too small, so that a film cannot be reliably formed when the curing component is cured at room temperature. In other words, if the ratio of the above total amount is equal to or higher than the above lower limit, the ratio of the curing component does not become excessively small, so that the curing component can be cured at room temperature to reliably form a coating.

The ratio of the total amount of the first oligomer and the second oligomer (curing component) in the silicone composition is 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less. If the proportion of the above total amount exceeds the above upper limit, the viscosity of the surface treatment using the silicone composition will be high, and therefore the uniformity of the coating will be reduced. In other words, if the proportion of the above total amount is equal to or less than the above upper limit, the viscosity will be sufficiently low for coating, and uniform surface treatment will be possible.

Silicone oil is a component that imparts slipperiness and water repellency to the film. Silicone oil has a linear main chain, for example, a repeating polysiloxane structure (--(SiO)n--). Examples of silicone oils include straight silicone oils (unmodified silicone oils) such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. In addition to straight silicone oils, silicone oils include modified silicone oils in which the ends and/or side chains of the main chain are modified with alkyl groups, alkenyl groups (including vinyl groups), alkynyl groups, phenyl groups, ionic groups, etc. Also included are silicone oils. The ionic group includes, for example, an anionic group such as a mercapto group, and a cationic group such as an amino group. These silicone oils can be used alone or in combination of two or more.

The silicone oil preferably includes straight silicone oil, more preferably polydimethylsiloxane.

A commercially available product is used as the silicone oil. For example, KF-96 series (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 series (manufactured by Shin-Etsu Chemical Co., Ltd.), SH200 series (manufactured by Dow Corning Toray), TSF451 series (manufactured by Momentive Performance Materials Japan) , and YF-33 series (manufactured by Momentive Performance Materials Japan).

The kinematic viscosity of the silicone oil at 25° C. is 100 mm ² /s or higher, preferably 200 mm ² /s or higher, more preferably 500 mm ² /s or higher, most preferably 1000 mm ² /s or higher. In addition, the kinematic viscosity of silicone oil at 25° C. is, for example, 1,000,000 mm ² /s or less, preferably 500,000 mm ² /s or less, more preferably 100,000 mm ² /s or less, and still more preferably 10,000 mm ² /s. s or less.

If the kinematic viscosity of the silicone oil is less than the lower limit described above, the film cannot stably exhibit slipperiness and water repellency. In other words, if the kinematic viscosity of the silicone oil is equal to or higher than the lower limit described above, it is possible to stably impart lubricity and water repellency to the coating. On the other hand, if the kinematic viscosity of the silicone oil is equal to or less than the upper limit described above, the silicone oil can be easily handled and the silicone composition can be easily prepared.

The proportion of silicone oil in the silicone composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass or more, and , for example, 10% by mass or less, preferably 5% by mass or less, more preferably 2.5% by mass or less.

The ratio of the silicone oil to the total amount of 100 parts by mass of the first oligomer and the second oligomer is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and, for example, 20 parts by mass or less. , preferably 10 parts by mass or less, more preferably 7 parts by mass or less.

The ratio of the total amount of the first oligomer, the second oligomer, and the silicone oil in the silicone composition is, for example, 21% by mass or more, preferably 26% by mass or more, more preferably 31% by mass or more, and still more preferably 36% by mass or more. be. If the ratio of the total amount is at least the above lower limit, the ratio of the curing component is prevented from becoming excessively small, and the curing component can be cured at room temperature to reliably form a coating.

The ratio of the total amount of the first oligomer, the second oligomer and the silicone oil in the silicone composition is, for example, 51% by mass or less, preferably 46% by mass or less, more preferably 41% by mass. If the proportion of the above total amount is equal to or less than the above upper limit, a uniform surface treatment can be achieved, and therefore a uniform coating can be formed.

When the silicone composition is cured at room temperature, the catalyst reacts with moisture in the air and hydrolyzes to generate active [metal atom-OH], [metal atom-OH], the first oligomer and the first It is a curing catalyst for condensation reaction with 2 oligomers.

The catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates.

Examples of metal alkoxides include titanium alkoxide, aluminum alkoxide, zirconium alkoxide (e.g., zirconium tetra-n-butoxide, zirconium tetra-n-propoxide), germanium alkoxide (e.g., germanium tetraethoxide), tin alkoxide (e.g., tin tetra-n-propoxide). -butoxide, tin tetra tert-butoxide), hafnium alkoxides (e.g. hafnium tetra-2-propoxide, hafnium tetra tert-butoxide), niobium alkoxides (e.g. niobium pentaethoxide), tantalum alkoxides (e.g. tantalum penta-n-butoxide, tantalum pentaethoxide) and the like. Preferred are titanium alkoxide and aluminum alkoxide.

Examples of titanium alkoxide include titanium trialkoxide, titanium tetraalkoxide and the like, preferably titanium tetraalkoxide. Titanium tetraalkoxides include, for example, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide (e.g., titanium tetraisopropoxide, titanium tetra-n-propoxide, etc.), titanium tetrabutoxide (e.g., titanium tetraisobutoxide , titanium tetra n-butoxide, etc.), titanium tetrapentoxide, titanium tetrahexoxide, titanium tetra(2-ethylhexoxide) and the like.

Examples of aluminum alkoxide include aluminum trialkoxide. Aluminum trialkoxides include, for example, aluminum triethoxide, aluminum tripropoxide (e.g., aluminum triisopropoxide, aluminum tri-n-propoxide), aluminum tributoxide (e.g., aluminum trisec-butoxide, aluminum tri-n- butoxide) and the like.

The three or four alkoxy groups in the metal alkoxide differ in reactivity depending on the number of carbon atoms and the presence or absence of branching. On the other hand, if the hydrolysis proceeds too quickly, the handleability (stability) may deteriorate. Therefore, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, and titanium tetra-n-butoxide are preferred among titanium alkoxides in consideration of reactivity and stability. Among aluminum alkoxides, aluminum triethoxide, aluminum triisopropoxide and aluminum trisec-butoxide are preferred.

A commercial product such as D-25 (titanium tetra n-butoxide, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the metal alkoxide.

Examples of metal chelate compounds include metal chelate compounds having β-diketones, phosphate esters, alkanolamines, etc. as ligands.

β-diketones include, for example, 2,4-pentanedione, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, 1,3-diphenyl-1,3-propanedione, 2,4-hexanedione, 3,5 -heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 5,5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, 1,3-cyclohexanedione and the like. 2,4-Pentanedione is preferred.

Octylene glycol includes, for example, 2-ethyl-3-hydroxyhexoxide.

Phosphate esters include, for example, 2-ethylhexyl phosphate.

Examples of alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like.

As ligands, β-diketones are preferred.

The central metal (metal atom) forming the metal chelate compound is not particularly limited, and examples thereof include aluminum, titanium, zirconium, niobium, magnesium, calcium, chromium, manganese, iron, cobalt, nickel, steel, zinc, gallium, Examples include palladium, indium, and tin. Aluminum, titanium and zirconium are preferred.

Specifically, examples of metal chelate compounds include aluminum chelate compounds, titanium chelate compounds, zirconium chelate compounds, magnesium chelate compounds (e.g., diaquabis(2,4-pentanedionato)magnesium), calcium chelate compounds (e.g., , diaquabis(2,4-pentanedionato) calcium, etc.), chromium chelate compounds (e.g., tris(2,4-pentanedionato)chromium, etc.), manganese chelate compounds (e.g., diaquabis(2,4-pentanedionato) ) manganese), iron chelate compounds (e.g., tris(2,4-pentanedionato)iron, etc.), cobalt chelate compounds (e.g., tris(2,4-pentanedionato)cobalt, etc.), nickel chelate compounds (e.g., , bis(2,4-pentanedionato)nickel, etc.), copper chelates (e.g., bis(2,4-pentanedionato)copper, etc.), zinc chelates (e.g., bis(2,4-pentanedionato) ) zinc, etc.), tris(2,4-pentanedionato)gallium, etc.), niobium chelate compounds (e.g., tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionatoniobium (IV), etc. ), palladium chelate compounds (e.g., bis(2,4-pentanedionato)palladium, etc.), indium chelate compounds (e.g., tris(2,4-pentanedionato)indium, etc.), suzuki rate compounds (e.g., bis( 2,4-pentanedionato) tin, etc.).

As metal chelate compounds, aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds are preferred. More preferably, the metal chelate compound includes an aluminum chelate compound and a titanium chelate compound from the viewpoint of maintaining excellent toughness (strength) in the coating.

Examples of aluminum chelate compounds include tris(2,4-pentanedionato)aluminum, tris(ethylacetoacetate)aluminum, and bis(ethylacetoacetate)(2,4-pentanedionato)aluminum. Tris(2,4-pentanedionato)aluminum is preferred.

Examples of titanium chelate compounds include tetrakis(2,4-pentanedionato)titanium and tetrakis(ethylacetoacetate)titanium. Tetrakis(2,4-pentanedionato)titanium is preferred.

Zirconium chelate compounds include, for example, tetrakis(2,4-pentanedionato)zirconium and tetrakis(ethylacetoacetate)zirconium. Tetrakis(2,4-pentanedionato)zirconium is preferred.

Moreover, the metal chelate compound includes an alkoxy group-containing metal chelate compound that further contains an alkoxy group in addition to the ligands described above. Alkoxy groups include, for example, methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, and the like. Alkoxy groups preferably include 2-propoxy. Specifically, the alkoxy group-containing metal chelate compounds include, for example, alkoxy group-containing aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, bis(2,4-pentanedionato)bis(2-propanolato)titanium alkoxy group-containing titanium chelate compounds such as

A metal carboxylate is a metal salt of a carboxylic acid. Examples of carboxylic acids include linear carboxylic acids such as ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, and tetradecanoic acid. branched carboxylic acids such as -methylbutanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, 3,5,5-trimethylhexanoic acid, such as naphthenic acid, etc. and the like. Branched carboxylic acids are preferred, and 2-ethylhexanoic acid is more preferred.

The metal that forms the metal salt is not particularly limited, and includes, for example, the same metals as the above-described central metal (the central metal that forms the metal chelate compound), preferably zinc, iron, cobalt, and manganese. be done.

Examples of metal carboxylates include aluminum carboxylate, titanium carboxylate, zirconium carboxylate, niobium carboxylate, magnesium carboxylate, calcium carboxylate, chromium carboxylate, manganese carboxylate, iron carboxylate, acid salts, cobalt carboxylates, nickel carboxylates, copper carboxylates, zinc carboxylates, gallium carboxylates, palladium carboxylates, indium carboxylates, tin carboxylates, tantalum carboxylates, and the like. . Metal carboxylates preferably include zinc carboxylate, iron carboxylate, cobalt carboxylate, and manganese carboxylate.

Examples of zinc carboxylates include zinc bis(2-ethylhexanoate), zinc acetate, and zinc naphthenate. Bis(2-ethylhexanoate)zinc is preferred.

Examples of iron carboxylates include iron bis(2-ethylhexanoate), iron acetate, and iron naphthenate. Preferably, iron bis(2-ethylhexanoate) is used.

Cobalt carboxylates include, for example, cobalt bis(2-ethylhexanoate), cobalt acetate, and cobalt naphthenate. Bis(2-ethylhexanoic acid) cobalt is preferred.

Manganese carboxylates include, for example, manganese bis(2-ethylhexanoate), manganese acetate, and manganese naphthenate. Bis(2-ethylhexanoic acid) manganese is preferred.

As a catalyst, acids such as phosphoric acid and acetic acid do not generate metal atoms —OH, and therefore cannot cause dehydration condensation of the OH groups based on the alkoxy groups of the first oligomer and the second oligomer. As a result, the curing reaction of the first oligomer and the second oligomer cannot proceed rapidly at room temperature, and the acid described above is unsuitable as a catalyst.

Catalysts may be used singly or in combination. As catalysts, metal alkoxides, metal chelate compounds and metal carboxylates are preferably used alone.
The catalyst may be prepared as a catalyst solution dissolved in an organic solvent, which will be described later.

The proportion of the catalyst in the silicone composition is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, and is, for example, 25% by mass or less, preferably 15% by mass or less. .

The ratio of the catalyst to the total amount of 100 parts by mass of the first oligomer and the second oligomer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and particularly preferably. is 20 parts by mass or more, and is, for example, 55 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

When the proportion of the catalyst is at least the above lower limit and below the above upper limit, the first oligomer and the second oligomer can be rapidly cured at room temperature to form a coating at room temperature.

The organic solvent is a high vapor pressure solvent having a vapor pressure higher than the lower limit value described later. Specifically, high vapor pressure solvents include, for example, alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol (2-propanol); Glycol ether solvents (high vapor pressure glycol ether solvents) such as ethylene glycol dimethyl ether; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and acetylacetone; Paraffinic solvents (high vapor pressure paraffinic solvents) such as n-heptane, n-octane and isooctane; naphthenic solvents such as cyclopentane and cyclohexane; aromatic solvents such as benzene, toluene, xylene and trimethylbenzene; For example, it is selected from aromatic solvents such as benzene, toluene and xylene. These organic solvents are used singly or in combination of two or more. As the organic solvent, an alcoholic solvent is preferably selected.

The vapor pressure of the organic solvent at 20° C. is 1 kPa (7.5 mmHg) or more, preferably 2 kPa (15 mmHg) or more, more preferably 3 kPa (22.5 mmHg) or more. In addition, the vapor pressure of the organic solvent at 20° C. is 100 kPa (750 mmHg) or less, preferably 25 kPa (187 mmHg) or less, more preferably 10 kPa (75 mmHg) or less, still more preferably 7 kPa (52 mmHg) or less, and particularly preferably , 5 kPa (38 mmHg) or less.

If the vapor pressure of the organic solvent is less than the above lower limit, the organic solvent cannot be rapidly removed (distilled off) when the silicone composition is cured at room temperature, and therefore a film cannot be formed. In other words, if the vapor pressure of the organic solvent is equal to or higher than the above lower limit, the organic solvent can be rapidly removed (distilled off) when the silicone composition is cured at room temperature, so that a coating can be formed. On the other hand, if the vapor pressure of the organic solvent is equal to or less than the upper limit described above, the rapid removal (distillation) of the organic solvent is suppressed when coating with the silicone composition, resulting in uneven thickness of the coating. can be suppressed.

On the other hand, the organic solvent is a solvent with a high vapor pressure, but a small amount of solvent with a low vapor pressure below the above-mentioned lower limit of vapor pressure can be allowed to be mixed so as not to impair the effects of the present invention. For example, inclusion of a low vapor pressure solvent contained in the catalyst solution described above is acceptable.

The vapor pressure of the low vapor pressure solvent at 20° C. is, for example, less than 1 kPa. Examples of low vapor pressure solvents include low vapor pressure glycol ether solvents such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, low vapor pressure paraffin solvents such as mineral turpentine, and petroleum solvents such as mineral spirits. be done.

The mixing ratio of the vapor pressure solvent is, for example, 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 100 parts by mass of the high vapor pressure solvent. is 1 part by mass or less. In addition, the mixing ratio of the low vapor pressure solvent in the silicone composition is, for example, less than 10% by mass, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1.0% by mass or less, and particularly preferably 0% by mass. 0.5% by mass or less, particularly preferably 0.1% by mass or less.

Although water is not an organic solvent, it is an unsuitable aqueous solvent for the silicone composition because the curing reaction of the first oligomer and the second oligomer is too fast.

The proportion of the organic solvent (high vapor pressure solvent) in the silicone composition is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass. % or more, and is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less.

The ratio of the organic solvent to 100 parts by mass of the total amount of the first oligomer, the second oligomer and the silicone oil is, for example, 40 parts by mass or more, preferably 80 parts by mass or more, more preferably 120 parts by mass or more, and still more preferably 140 parts by mass. In addition, it is, for example, 300 parts by mass or less, preferably 200 parts by mass or less, and more preferably 160 parts by mass or less.

If the proportion of the organic solvent is at least the lower limit described above, the silicone composition will be excellent in handleability, and it will be possible to suppress the occurrence of unevenness in the thickness of the coating due to excessively rapid drying after coating. can. On the other hand, when the proportion of the organic solvent is equal to or less than the above upper limit, it is possible to suppress an excessive decrease in yield.

Next, preparation of the silicone composition will be described.

To prepare the silicone composition, first, the first oligomer, the second oligomer, the silicone oil, the organic solvent, and, if necessary, additives are blended in the proportions described above and mixed to form the silicone composition. to prepare. On the other hand, a catalyst is separately prepared. This prepares the silicone composition and the catalyst as a two-component curable composition.

Subsequently, the silicone composition and the catalyst are blended in the above proportions and mixed to prepare the silicone composition. In the preparation of this silicone composition, the catalyst produces metal-OH groups by its hydrolysis.

In summary, the room-temperature-curable silicone composition used in the present invention contains a first oligomer, a second oligomer, a catalyst and an organic solvent, and the ratio of the total amount of the first oligomer to the second oligomer is 20 mass. % or more, the catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates, and the organic solvent has a vapor pressure of 1 kPa or more at 20°C. Therefore, the silicone composition can be cured at room temperature. As a result, this silicone composition is suitable for surface treatment that does not require heat treatment.

Moreover, the silicone composition contains silicone oil, and the kinematic viscosity of the silicone oil at 25° C. is 100 mm ² /s or more. Therefore, the film, which is a cured product of the silicone composition, has excellent lubricity and water repellency.

Furthermore, a silicone composition in which the ratio of the first oligomer to the second oligomer is 0.15 or more and 10 or less is excellent in coating lubricity and water repellency.

Moreover, a silicone composition in which the total amount of the first oligomer and the second oligomer is 50% by mass or less of the total is excellent in uniform coating properties.

Moreover, if the organic solvent is an alcohol-based solvent, it is possible to suppress the condensation reaction of the first oligomer and the second oligomer to produce alcohol. In other words, the reaction between the first oligomer and the second oligomer during storage of the silicone composition (especially the silicone composition in the two-part curable composition) can be suppressed. Therefore, this silicone composition has excellent storage stability.

Further, if the ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer and the silicone oil is 40 parts by mass or more and 300 parts by mass or less, the handling of the silicone composition is improved. In addition to being excellent, it is possible to suppress the occurrence of unevenness in the thickness of the coating due to excessively rapid drying after coating, and it is possible to suppress an excessive decrease in yield.

Further, if the ratio of the catalyst to the total amount of 100 parts by mass of the first oligomer and the second oligomer is 2 parts by mass or more and 55 parts by mass or less, the first oligomer and the second oligomer are It cures quickly and can form a coating at room temperature.

The silicone composition thus prepared can form a coating film (cured product) having a hardness equivalent to a pencil hardness of 2H or more, preferably 4H or more. The pencil hardness can be measured, for example, according to JIS K 5600-5-4 (1999), on an aluminum plate for paint test conforming to JIS H 4000, which is coated with the silicone composition and cured at room temperature. Such a coating film can be formed, for example, by applying the silicone composition to the surface of a coating test plate such as a test aluminum plate conforming to JIS H 4000 and allowing it to stand at room temperature. The time for standing is not limited as long as the organic solvent in the silicone composition is distilled off (removed) and the first oligomer and the second oligomer are cured in the presence of the catalyst. Time or less can be exemplified. By doing so, OH groups are generated from the alkoxy groups in the first oligomer and the second oligomer, and the dehydration reactions with [metal atom--OH] based on the catalyst proceed with the curing reaction. Subsequently, alcohol, which is a by-product of the above reaction, is distilled off (removed) together with the organic solvent. The silicone composition thus cures to form a coating.

[Modification]
The following variants can also be used as the silicone composition.

In the above description, the silicone composition is prepared as a two-component curable composition, but for example, the silicone composition can also be prepared as a one-component curable composition.

Specifically, the first oligomer, the second oligomer, the silicone oil, the catalyst and the organic solvent are blended in the absence of moisture (humidity) in the air. Specifically, the components described above are blended and mixed in an atmosphere of an inert gas such as nitrogen, and the mixture is sealed in a container. Immediately before use, the container is unsealed and the silicone composition is applied to the object. This one-component curable composition can also exhibit the same effect as the two-component curable composition.

In addition, although this silicone composition is a room temperature curing type, if necessary, it can be cured at room temperature and then heated (further heat curing), or it can be heat cured instead of room temperature curing. As for the heating temperature, a known temperature condition such as heating at 50° C. or higher is adopted.

(2) Hydrophobized alumina-silica-based cubic particles The hydrophobized alumina-silica-based cubic particles of the present invention (hereinafter also referred to as "hydrophobized particles of the present invention") are prepared by using the silicone composition prepared by the above method. It can be prepared by surface-treating alumina-silica-based cubic particles (particles of the present invention). The surface treatment can be carried out by mixing the particles of the present invention with the silicone composition and then leaving the mixture at room temperature.

The silicone composition and the particles of the present invention are preferably mixed with stirring so that the silicone composition uniformly adheres to the surfaces of the particles of the present invention and uniformly covers the entire surfaces of the particles of the present invention. At this time, if an excessive amount of the silicone composition is mixed with the particles of the present invention, the particles of the present invention tend to agglomerate and form clumps. Therefore, although the ratio of the silicone composition to 100 parts by mass of the particles of the present invention is not limited, it is usually 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and usually 30 parts by mass or less. , preferably 25 parts by mass or less, more preferably 20 parts by mass or less (wet mass ratio).

If the ratio of the silicone composition to 100 parts by mass of the particles of the present invention is significantly less than 1 part by mass, the surfaces of the particles of the present invention cannot be sufficiently coated. On the other hand, if the proportion of the silicone composition exceeds 30 parts by mass and is significantly increased, the silicone composition on the surface tends to adhere to each other and the hydrophobized particles of the present invention tend to aggregate or clump together. The ratio of the cured silicone composition to 100 parts by mass of the particles of the present invention is not limited, but is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and more preferably 0.5 parts by mass or more. and usually 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less (dry mass ratio).

The stirring and mixing of the silicone composition and the particles of the present invention can be carried out at room temperature. Thus, the surface of the particles of the present invention is coated with the silicone composition. Next, by leaving the particles of the present invention coated with the silicone composition on the surface at room temperature, the silicone composition hardens on the surface of the particles of the present invention to produce alumina-silica cubic particles having a hydrophobized surface. do.

Here, the time for standing at room temperature is not particularly limited as long as the organic solvent can be distilled off (removed) and the first oligomer and the second oligomer can be cured in the presence of the catalyst. Specifically, it is, for example, 30 minutes or longer, preferably 1 hour or longer, more preferably 10 hours or longer, still more preferably 20 hours or longer, and 50 hours or shorter. As a result, OH groups are generated from the alkoxy groups in the first oligomer and the second oligomer, which undergo a dehydration reaction with [metal atom--OH] based on the catalyst to proceed with the curing reaction. Subsequently, alcohol, which is a by-product when OH groups are generated from the alkoxy groups of the first oligomer and the second oligomer, is removed (distilled off) together with the organic solvent.

This makes it possible to prepare hydrophobized alumina-silica cubic particles whose surfaces are coated with a coating of a cured product of the room-temperature-curable silicone composition. The thickness of the coating can be appropriately adjusted and is not limited, but is, for example, 0.01 μm or more, preferably 0.05 μm or more, and is, for example, 0.5 μm or less, preferably 0.2 μm or less. be able to.

The hydrophobized particles of the present invention may have at least one property selected from the group consisting of (a) to (d) below.
(a) Average coefficient of friction (MIU): 0.3 to 0.6
(b) Concealability index: 5 or less (c) Wrinkle blurring index: 28 or less (d) Haze: 34-80.

(a) Average friction coefficient (slipperiness)
The hydrophobized particles of the present invention may preferably have an average coefficient of friction of 0.6 or less, more preferably 0.5 or less. The lower the average coefficient of friction, the better the extensibility, which is preferable. From that point of view, the lower limit is, for example, 0.3 or more.

The method for measuring the average coefficient of friction is as described above, and the measurement can be performed by directly applying the hydrophobized particles, which are the test sample, to the artificial skin. According to the hydrophobized particles of the present invention having the desired average coefficient of friction, compared to the non-hydrophobized particles of the present invention, it has a higher moderate slipperiness on artificial skin and between particles, When applied to the skin, it spreads evenly on the skin and has the effect of moderately staying stretched.

Optical evaluation of wrinkle hiding property: (b) Hiding index, (c) Wrinkle blurring index The hiding index and wrinkle blurring index are indices for evaluating the hiding effect and wrinkle blurring effect of the hydrophobized particles of the present invention, respectively. In any case, the smaller the numerical value, the lower the concealing effect and the higher the wrinkle-shading effect, indicating that the wrinkle-hiding property is exhibited satisfactorily. The hydrophobic particles of the present invention may preferably have a hiding index of 6 or less, more preferably 5 or less. As a lower limit, although it is not limited, 1 or more can be exemplified. The hydrophobized particles of the present invention may preferably have a wrinkle blurring index of 32 or less, more preferably 28 or less. As the lower limit, although not limited, 25 or more, preferably 20 or more can be exemplified.

The hiding index and wrinkle blurring index of the hydrophobized particles of the present invention can be measured by the method described in the examples below, and are said to be superior in wrinkle hiding effect compared to the particles of the present invention that have not been hydrophobized. have an effect.

(d) Haze value (soft focus property)
The hydrophobized particles of the present invention may preferably have a haze value of 34% or more, more preferably 40% or more, in visible light. The upper limit can be, for example, 90% or less, preferably 80% or less. The hydrophobized particles of the present invention have a high haze value and excellent soft focus properties as compared with untreated particles (particles of the present invention). Therefore, by blending it into cosmetics as a cosmetic additive, it is possible to impart a higher blurring effect to the cosmetics.

(IV) Use as Cosmetic Additive and Cosmetics Containing It The alumina-silica-based cubic particles (particles of the present invention) described above have a cubic shape with six flat faces. In addition, since it has a specific refractive index, particle size, oil absorbency, and specific surface area, it can be blended into various cosmetics as a soft focus imparting agent to improve the soft focus of the cosmetics. That is, when blended in cosmetics, as a result of the presence of a large number of particles within a predetermined area, light is transmitted through the cosmetic film while undergoing multiple scattering. Excellent soft focus property can be imparted.

Such soft focus properties of the particles of the present invention can be evaluated by a Haze meter in accordance with ASTM D1003, as shown in Experimental Examples described later. Specifically, as described above, a coating film formed by coating a PET sheet with a solution in which the particles of the present invention are mixed in a ratio of 1:9 (mass ratio) in silicone oil to a thickness of about 20 μm. Haze (cloudiness) is as high as 34% or more, preferably 40% or more, more preferably 50% or more, and still more preferably as high as 55% or more, which is useful for the particles to enhance the soft focus property. It is shown that.

In addition, since the particles of the present invention have a cubic shape, they can impart appropriate smoothness to the skin when blended in cosmetics. Specifically, since the particles of the present invention are in the form of particles, they have higher slipperiness than plate-like bodies and exhibit good extensibility (spreadability). On the other hand, since it has a cubic shape with a flat surface, it has the advantage of being moderately applied and adhered to the skin, resulting in excellent covering power.

Furthermore, the particles of the present invention, unlike spherical particles (including true spherical particles), have flat surfaces and thus have a large planar fixing area. It also has the advantage of being excellent in hiding pores and fine wrinkles (covering power, unevenness correction effect) by covering the skin with a flat surface that adheres well to the skin without falling into the grooves. That is, when the particles of the present invention are blended into a cosmetic, they can spread smoothly over the skin, cover pores and fine wrinkles, smoothen the skin surface after makeup, and integrate with the skin. It can be adhered to provide coverage.

When the particles of the present invention are blended into a cosmetic as a soft focus imparting agent and/or wrinkle-masking effect agent (or unevenness correcting agent), it varies depending on the type of the cosmetic to be blended, but at least 1 to 50 mass in the cosmetic. %, the desired soft focus property can be imparted. From the viewpoint of soft focus, spreadability on the skin, and covering power, the content is preferably 5 to 30% by mass.

Cosmetics prepared by blending the particles of the present invention are used in the form of liquids, milky lotions, creams, powders, foams, solids, and the like. As a soft focus imparting agent for cosmetics requiring It is blended as an effect imparting agent or unevenness correcting agent. Cosmetics that require soft focus and/or cosmetics that are required to improve the texture of the skin after makeup include, but are not limited to, foundation, concealer, blush, white powder (white powder, loose powder, pressed powder ), control color, foundation, BB cream, eye color, and lipstick; These cosmetics generally contain water-repellent oil components such as film-forming polymers, surfactants, thickeners, water, moisturizing agents, fragrances, pigments or dyes, and silicone oil, depending on their intended use or mode of use. , UV absorbers, astringents, cooling agents, anti-inflammatory agents, whitening agents, various extracts, plant and seaweed extracts, etc. By doing so, the soft focus property, wrinkle hiding effect and/or unevenness correcting effect can be enhanced.

The present invention will be described below based on Production Examples and Experimental Examples. However, the production examples and experimental examples are merely examples for facilitating understanding of the present invention, and the present invention is not limited to these. Moreover, in the following Production Examples and Experimental Examples, "%" means "% by mass" unless otherwise specified. In addition, unless otherwise specified, the following experiments were carried out at room temperature (25±5° C.) and atmospheric pressure.

Various measurement methods and conditions used in the following production examples and experimental examples are as follows.

[Measuring method]
(1) Fluorescent X-rays (SiO ₂ /Al ₂ O ₃ molar ratio)
For the elemental analysis necessary for calculating the alkali metal content in terms of oxide and the molar ratio of SiO ₂ /Al ₂ O ₃ , Rigaku ZSX primus II manufactured by Rigaku Co., Ltd. was used, the target was Rh, and the analytical line was Kα. Others were measured under the following conditions.
<Si> Tube voltage: 30 kV, tube current: 100 mA, detector: PC, analyzing crystal: PET
<Al> Tube voltage: 30 kV, tube current: 100 mA, detector: PC, analyzing crystal: PET
The standard sample was dried at 110° C. for 2 hours.

(2) Evaluation of crystallinity by X-ray diffractometry The crystallinity analysis of the sample powder by X-ray diffractometry was carried out using a “specimen horizontal multi-purpose X-ray diffractometer Ultima IV” manufactured by Rigaku Co., Ltd. under the following conditions. did.
X-ray source: Cu Kα ray target: Cu
Filter: Curved crystal graphite monochromator Detector: Scintillation detector Voltage: 40 kV
Current: 40mA
Step size: 0.02°
Counting time: 0.6 sec/step
Slit: Divergence slit 2/3° Receiving slit 0.3 mm SS2/3°.

(3) Measurement of shape and particle size by scanning electron microscope observation A two-dimensional photographic image obtained by taking a photograph of the sample (dry powder) with a scanning electron microscope (JSM-6510LA manufactured by JEOL JEOL Ltd.) , the particle shape and particle size (length of one side) of the sample powder were measured.

(4) Refractive index (immersion method)
A plurality of solvents having different refractive indices were prepared by mixing two solvents (α-bromnaphthalene and kerosene), and the refractive index of each prepared solvent was measured in advance with an Abbe refractometer. Next, according to Larsen's oil immersion method, a few mg of sample powder was placed on a slide glass, a drop of solvent (with a known refractive index) was added, a cover glass was placed on the slide, and the solvent was immersed. The movement was observed and the refractive index was obtained from the movement.

(5) Volume-based average particle size (Coulter counter method)
0.5 g of the sample powder was weighed into a 200 ml beaker, 150 ml of deionized water was added thereto, and dispersed for 3 minutes with stirring. This dispersion was subjected to a Coulter counter (Precise particle size distribution measuring device Multiizer 3 manufactured by Beckman Coulter, Inc.) to measure the volume-based particle size distribution, and the volume-based median diameter (D ₅₀ ) was obtained. The aperture tubes used for the measurement had an inner diameter of 50 μm for the samples produced in Production Examples 1 and 2 (Examples 1 and 2), and an inner diameter of 100 μm for the samples produced in Production Example 3 (Example 3). I used the one from In addition, the comparative example measured by the laser diffraction method using MastersizerS by Malvern.

(6) Oil absorption (JIS K5101-13-2)
JIS. K. 5101-13-1: 2004 (refined linseed oil method).

Specifically, the sample to be tested is placed on a measurement plate, and 4 to 5 drops of refined linseed oil are gradually added to the test sample at a time, and the refined linseed oil is kneaded into the sample each time using a palette knife. This process is repeated until lumps are formed, and the drop is stopped when the paste becomes a smooth consistency. It should be noted that this paste can be spread without cracking or crumbling, and should adhere lightly to the measuring plate. The oil absorption (ml/100 g) can be obtained from the final use amount (ml) of the refined linseed oil according to the following formula.

[Number 1]
Oil absorption (ml/100g) = (100 x V)/m
V: Volume of linseed oil consumed (ml)
m: mass of test sample (g)

(7) Specific surface area (BET method)
Nitrogen adsorption isotherms were measured using a Micromeritics TriStar 3000. It was obtained by the BET method from the nitrogen adsorption isotherm at a specific pressure of 0.2 or less.

(8) Moisture adsorption amount (gas adsorption method)
Using Belsorp Max manufactured by Bel Japan Co., Ltd., the moisture adsorption isotherm was determined in the range of water vapor partial pressure P _T (P/P ₀ ) from 0.001 to 0.9. The pretreatment was performed under vacuum conditions at 150° C. for 2 hours. The equilibrium determination time was 300 seconds. The measured value when the water vapor partial pressure P _T (P/P ₀ ) was 0.75 was converted into the amount of adsorption per unit mass of the base material, and the amount of water adsorption (% by mass) was obtained.

(9) Apparent specific gravity (JIS K-6220-1 7.7)
JIS. K. 6220-1 7.7:2001, it was measured according to the following method.
1) Insert the piston (outer diameter 21.80 ± 0.05 mm, length 115 mm, mass 190 g) into the cylinder (inner diameter 22.00 ± 0.05 mm, inner depth 100 mm) and let it drop naturally is measured to the nearest 0.01 mm.
2) Pull out the piston, weigh 1 to 5 g of the sample to be tested accurately to 0.01 g, and pour it into the cylinder.
3) Gently drop the piston from the upper part of the cylinder, and when it reaches the surface of the sample, lightly rotate the piston once to make the piston fit well.
4) Calculate the apparent specific gravity (g/cm ³ ) according to the following formula.

[Number 2]
Apparent specific gravity (g/cm ³ )=[m ₀ ]/(0.7854×d ² ×[h ₂ −h ₁ ])
m ₀ : mass of test sample (g)
d: Diameter of cylinder (cm)
h ₂ : Height difference (cm) between piston and cylinder when test sample is present
h ₁ : Difference in height between piston and cylinder (cm) when no test sample is present

(10) Ignition loss (Ig-loss) (JIS K-0067 4.2) (860°C x 20min)
JIS. K. 0067 4.2: 1992, it was measured according to the following method. However, the ignition conditions of 860° C.×20 minutes were adopted.
1) Place the test sample in an evaporating dish and measure its mass to the order of 0.1 mg.
2) Place the evaporating dish containing the sample in an electric furnace, and gradually raise the temperature to 860° C. and ignite.
3) After igniting at 860°C for 20 minutes, quickly transfer the evaporating dish to a desiccator and allow to cool. After allowing to cool, measure the mass to the order of 0.1 mg.
4) Repeat the above 3 until the mass becomes constant (constant weight), and calculate the apparent specific gravity (g/cm ³ ) from the final mass according to the following formula.

[Number 3]
Ignition loss (%) = ([W ₁ -W ₂ ]/[W ₁ -W ₃ ]) x 100
W ₁ : Mass (g) of test sample and evaporating dish before ignition
W ₂ : Mass (g) of test sample and evaporating dish after ignition
W ₃ : mass of evaporating dish (g)

(11) Hunter whiteness (JIS P-8123)
It was measured using a Hunter automatic reflectometer TR-600 OPTICAL UNIT manufactured by Tokyo Denshoku.

Production Example 1 Method for producing alumina-silica-based cubic particles 1 (Example 1) As liquid A, 358.6 g of No. 3 sodium silicate (SiO ₂ =23% by weight, Na ₂ O=7.4% by weight) and 504 g of water. 338.1 g of sodium aluminate (Al ₂ O ₃ =23% by weight, Na ₂ O=19.2% by weight), 117.7 g of a 49% by weight aqueous solution of caustic soda, and 480.9 g of water as solution B. was prepared by mixing. 781 L each of liquid A and liquid B were mixed so as to have the following molar ratio, to prepare a total amount of 1800 g.

[Blending conditions (molar ratio)]
_Na2O / _SiO2 = 1.6
_SiO2 / _Al2O3 = _1.8
H2O / _Na2O =38

Specifically, the prepared A solution was placed in a 2 L stainless steel container, stirred while being heated to 60 ° C., and B solution was slowly added and mixed under stirring conditions to obtain a uniform aluminosilicate as a whole. An acid-alkali gel was obtained. After aging for 3 hours under stirring conditions of 60° C., the temperature was further raised to 90° C. while stirring, and reaction was carried out under the same conditions for 2 hours to effect crystallization. The resulting crystals were collected by filtration using a Nutsche and washed with water to obtain a cake of A-type zeolite (crystalline zeolite) having a volume-based average particle size of 2.3 μm and weighing 195 g in absolute dry weight at 860°C.

Next, 150 g of this A-type zeolite cake was taken out at 860° C. absolute dry weight, and dispersed in water to prepare a slurry containing 25% A-type zeolite. A 14% aqueous solution of sulfuric acid was slowly added to this solution at room temperature over 15 hours with stirring in such an amount that the molar ratio of H ₂ SO ₄ to Na ₂ O in the A-type zeolite was 0.85. A pH of 4 was obtained. By such acid treatment, the alkali content is eluted and removed from the crystalline zeolite to form an amorphous material. Although the addition of sulfuric acid causes the pH of the slurry to shift to the acidic side, it is preferable to adjust the pH of the slurry to be in the range of 4 to 7 in order to efficiently amorphize the slurry.

One hour after the addition of the aqueous sulfuric acid solution, the resulting amorphous material was collected by filtration using a Nutsche (Buchner funnel), washed with water, dried, placed in a crucible, and placed in a small electric furnace at 450°C for 1 hour. Baked for hours. Then, after cooling to room temperature, it was pulverized using a jet mill. FIG. 1 shows an image of the pulverized product observed with a scanning electron microscope. As can be seen from FIG. 1, it was confirmed that the pulverized material had a cubic shape in which the constituent primary particles were almost uniform in size and were well dispersed. This was designated as "alumina-silica-based cubic particles 1" (hereinafter also simply referred to as "cubic particles 1") (Example 1), and its properties and physical properties were measured according to the various measurement methods described above.

The properties and physical properties of the prepared alumina-silica-based cubic particles 1 are shown below.

・molar ratio of SiO ₂ /Al ₂ O ₃ =2
・ Crystallinity by X-ray diffraction method: Amorphous (amorphous) (see Fig. 4)
・Shape and particle diameter observed by scanning electron microscope: cubic with a side of about 0.5 to 3 μm (see Fig. 1)
・Refractive index by immersion method: 1.50
・ Volume-based average particle size by the call counter method: 1.8 μm
・Oil absorption according to JIS K5101-13-2: 31ml/100g
・Specific surface area by BET method: 4 m ² /g
・Moisture adsorption amount by gas adsorption method: 0.6%
・Apparent specific gravity: 0.63g/ml
・ Ignition loss (Ig-loss): 2.7%
・Hunter whiteness: 95%

Production Example 2 Method for producing alumina-silica-based cubic particles 2 (Example 2) Using the raw materials having the same composition as in Production Example 1, 316.8 g of No. 3 sodium silicate and 550.7 g of water were mixed and prepared as liquid A. As liquid B, 298.7 g of sodium aluminate, 104.0 g of 49% aqueous sodium hydroxide solution and 529.8 g of water were mixed and prepared. 795 L each of liquid A and liquid B were mixed so as to have the following molar ratio, and a total amount of 1800 g was prepared.

[Blending conditions (molar ratio)]
_Na2O / _SiO2 = 1.6
_SiO2 / _Al2O3 = _1.8
H2O / _Na2O =44

Specifically, the prepared A solution was placed in a 2 L stainless steel container, stirred while being heated to 70 ° C., and B solution was slowly added and mixed under stirring conditions to obtain a uniform aluminosilicate throughout. An acid-alkali gel was obtained. After aging this under stirring conditions of 70° C. for 2 hours, the temperature of this aluminosilicate alkali gel was raised to 90° C. while stirring, and the reaction was carried out under the same conditions for 2 hours to effect crystallization. Then, the resulting crystals were collected by filtration using a Nutsche and washed with water to obtain a cake of A-type zeolite (crystalline zeolite) having a volume-based average particle size of 2.9 μm and weighing 172 g in absolute dry weight at 860°C.

Then, 150 g of absolute dry weight was taken from the above cake, and a 25% slurry was prepared in the same manner as in Production Example 1. A 14% sulfuric acid aqueous solution was added to the A-type zeolite so that the molar ratio of H ₂ SO ₄ to Na ₂ O in the A-type zeolite was 0.82, and acid treatment was performed to make it amorphous. , and dried. Further, in the same manner as in Production Example 1, this was placed in a crucible and fired in a small electric furnace at 450° C. for 1 hour, cooled to room temperature, and pulverized using a jet mill. FIG. 2 shows an image of the pulverized product observed with a scanning electron microscope. As can be seen from FIG. 2, it was confirmed that the pulverized material had a cubic shape in which the constituent primary particles were almost uniform in size and were well dispersed. These were designated as "alumina-silica-based cubic particles 2" (hereinafter also simply referred to as "cubic particles 2") (Example 2), and their properties and physical properties were measured according to the various measurement methods described above.

The properties and physical properties of the prepared alumina-silica-based cubic particles 2 are shown below.

・molar ratio of SiO ₂ /Al ₂ O ₃ =2
・Crystallinity by X-ray diffraction method: Amorphous (amorphous)
・Shape and particle diameter observed by scanning electron microscope: cubic with a side of about 1 to 3.5 μm (see Figure 2)
・Refractive index by immersion method: 1.50
・ Volume-based average particle size by the call counter method: 2.5 μm
・Oil absorption according to JIS K5101-13-2: 33ml/100g
・Specific surface area by BET method: 3 m ² /g
・Moisture adsorption amount by gas adsorption method: 0.4%
・Apparent specific gravity: 0.73g/ml
・ Ignition loss (Ig-loss): 3.2%
・Hunter whiteness: 93%

Production Example 3 Method for producing alumina-silica-based cubic particles 3 (Example 3) Using the same raw materials as in Production Example 1, 128.0 g of No. 3 sodium silicate and 758.9 g of water were mixed and prepared as liquid A. As liquid B, 120.6 g of sodium aluminate, 42.0 g of 49% aqueous sodium hydroxide solution and 750.5 g of water were mixed and prepared. 857 L each of liquid A and liquid B were mixed so as to have the following molar ratio, to prepare a total amount of 1800 g.

[Blending conditions (molar ratio)]
_Na2O / _SiO2 = 1.6
_SiO2 / _Al2O3 = _1.8
H2O / _Na2O =120

Specifically, the prepared A solution was placed in a 2 L stainless steel container, stirred while being heated to 70 ° C., and B solution was slowly added and mixed under stirring conditions to obtain a uniform aluminosilicate throughout. An acid-alkali gel was obtained. After aging at 70° C. for 1 hour with stirring, the temperature of the aluminosilicate alkali gel was raised to 95° C. with stirring, and the reaction was carried out under the same conditions for 24 hours to effect crystallization. The resulting crystals were collected by filtration and washed with water to obtain a cake of A-type zeolite (crystalline zeolite) having a volume-based average particle diameter of 11.6 μm and weighing 70 g in terms of absolute dry weight.

Next, 65 g of absolute dry weight was taken from the above cake, and a 25% slurry was prepared in the same manner as in Production Example 1. A 14% aqueous solution of sulfuric acid was added to the A-type zeolite so that the molar ratio of H ₂ SO ₄ to Na ₂ O in the A-type zeolite was 0.95. , and dried. Further, in the same manner as in Production Example 1, this was placed in a crucible and fired in a small electric furnace at 450° C. for 1 hour, cooled to room temperature, and pulverized using a jet mill. FIG. 3 shows an image of the pulverized product observed with a scanning electron microscope. As can be seen from FIG. 3, it was confirmed that the pulverized material had a cubic shape in which the constituent primary particles were almost uniform in size and were well dispersed. This was designated as "alumina-silica-based cubic particles 3" (hereinafter also simply referred to as "cubic particles 3") (Example 3), and its properties and physical properties were measured according to the various measurement methods described above.

The properties and physical properties of the prepared alumina-silica cubic particles 3 are shown below.

・molar ratio of SiO ₂ /Al ₂ O ₃ =2
・Crystallinity by X-ray diffraction method: Amorphous (amorphous)
・Shape and particle diameter observed by scanning electron microscope: cubic with a side of about 3 to 12 μm (see FIG. 3) ・Refractive index by immersion method: 1.50
・ Volume-based average particle size by the call counter method: 10.3 μm
・Oil absorption according to JIS K5101-13-2: 30ml/100g
・Specific surface area by BET method: 4 m ² /g
・Moisture adsorption amount by gas adsorption method: 0.7%
・Apparent specific gravity: 1.01g/ml
・ Ignition loss (Ig-loss): 2.6%
• Hunter whiteness: 85%.

Production Example 4 Method for producing hydrophobized alumina-silica cubic particles 1-1 to 3-1 (Examples 4 to 6) Hydrophobized alumina-silica cubic particles 1-1 to 3-1 (Examples 4 to 6) Each component used in the production of is described below.
・X-40-9250: In the above formula (3), b is 8, c is 4, and d is 4 methyl-based silicone alkoxy oligomer (first oligomer), manufactured by Shin-Etsu Chemical Co., Ltd. ・KR-500 : In the above formula (6), g is 10, h is 4 methyl-based silicone methoxy oligomer (second oligomer), manufactured by Shin-Etsu Chemical Co., Ltd. KF-96-1000cs: oily polydimethylsiloxane, Kinematic viscosity (25°C): 1,000 mm ² /s, Shin-Etsu Chemical Co., Ltd. D-25: Titanium (IV) tetra-n-butoxide, Shin-Etsu Chemical Co., Ltd. 2-propanol: at 20°C Steam pressure 4kPa
・ Water: vapor pressure 2.3 kPa at 20 ° C
· Alumina - silica-based cubic particles 1 to 3 (Examples 1 to 3)

(1) Preparation of room temperature curable silicone composition In a 500 ml glass container, add 6.8 parts of X-40-9250, 27.4 parts of KR-500, 1.8 parts of KF-96-1000cs, and 2-propanol. 54.0 parts of D-25 at a ratio of 10.0 parts, using a magnetic stirrer, stirred at room temperature for 20 minutes to give a silicone composition (one-liquid curable silicone composition) (density : 0.90 g/cm ³ ) was prepared. The weight reduction rate of the silicone composition upon curing is 69.5% (the weight after curing is 30.5% of the liquid weight before curing). The silicone composition is applied to the surface of a test aluminum plate conforming to JIS H 4000, and the pencil hardness of the coating film after standing at room temperature for 18 hours is 5H, and the pencil hardness of the coating film after standing for 24 hours is also 5H. Met .

The cubic particles 1 to 3 prepared in Examples 1 to 3 were surface-treated (hydrophobicized) using the room-temperature-curable silicone composition thus prepared as a surface treatment agent.

(2) Surface treatment of cubic particles 1-3 (Examples 4-6)
200 g of each of the cubic particles 1 to 3 (Examples 1 to 3) and 40 g of the surface treatment agent (room temperature curable silicone composition) prepared in (1) above were mixed to make the surface of each of the cubic particles 1 to 3 hydrophobic. treated. The treatment was performed at room temperature.

Specifically, each of the cubic particles 1 to 3 was placed in a stirrer (Super Mixer Piccolo manufactured by Kawata Co., Ltd.), and while stirring at 1000 rpm, the surface treatment agent (normal temperature curing silicone composition) was added dropwise over 2 minutes. The mixture was mixed until uniform with continued stirring for 5 minutes. After standing at room temperature for 1 day, crushed with a jet mill (AO jet mill manufactured by Seishin Enterprise Co., Ltd.), hydrophobized alumina-silica-based cubic particles 1-1 to 3-1 (hereinafter simply “hydrophobicized cubic particles 1-1 to 3-1” or “cubic particles 1-1 to 3-1”) (Examples 4 to 6) were obtained.

Table 1 shows the hydrophobized alumina-silica cubic particles 1-1 to 3-1 (Examples 4 to 6), the amount of the cubic particles 1 to 3, the amount of the room temperature curing silicone composition, and the amount after surface treatment. % of the cured silicone composition relative to the cubic particles of .

Production Example 5 Method for producing hydrophobized alumina-silica cubic particles 1-2 to 3-2 (Examples 7 to 9) Hydrophobized alumina-silica cubic particles 1-2 to 3-2 (Examples 7 to 9) Each component used in the production of is described below.
・ KF-9901: Methyl hydrogen polysiloxane solution (manufactured by Shin-Etsu Chemical Co., Ltd.)
· Alumina - silica-based cubic particles 1 to 3 (Examples 1 to 3)

(1) Surface treatment of cubic particles 1-3 (Examples 7-9)
30 parts of KF-9901 and 70 parts of 2-propanol were mixed in a 500 ml glass container and stirred at room temperature for 20 minutes using a magnetic stirrer to prepare 300 g of KF-9901 diluted solution. The weight reduction rate of the diluent after surface treatment is 70% (the weight after surface treatment is 30% of the weight of the diluent). 200 g of each of the cubic particles 1 to 3 (Examples 1 to 3) and 40 g of the surface treatment agent (KF-9901 diluted solution) prepared in (1) above are mixed to make the surface of each of the cubic particles 1 to 3 hydrophobic. processed. The treatment was performed at room temperature.

Specifically, each cubic particle 1 to 3 was charged in a stirrer (Super Mixer Piccolo manufactured by Kawata Co., Ltd.), and while stirring at 1000 rpm, a surface treatment agent (KF-9901 diluted solution) was added dropwise over 2 minutes, Stirring was continued for 5 minutes to mix until uniform. The obtained powder was dried at 50° C. for 2 hours and then heat-treated at 180° C. for 3 hours. Furthermore, it is pulverized with a jet mill (AO jet mill manufactured by Seishin Enterprise Co., Ltd.), and hydrophobized alumina-silica-based cubic particles 1-2, 2-2, 3-2 (hereinafter simply “hydrophobicized cubic particles 1- 2 to 3-2” or “cubic particles 1-2 to 3-2”) (Examples 7 to 9) were obtained.

Table 1 shows the blending amount of cubic particles 1-3 and the blending amount of KF-9901 diluted solution (silicone composition) for hydrophobized alumina-silica-based cubic particles 1-2 to 3-2 (Examples 7 to 9). , mass % of the silicone composition after curing to the cubic particles after surface treatment.

Production Example 6 Method for producing hydrophobized alumina-silica cubic particles (Examples 10 to 24) Surface-treated alumina-silica cubic particles 1 to 3 (Examples 1 to 3) in Production Example 4 above: 100 parts by mass Other than adjusting the blending amount so that the proportion of room temperature curing silicone composition after curing is 1 part by mass or 2 parts by mass (dry mass % of room temperature curing silicone composition: 1 mass % or 2 mass %) In the same manner as in Production Example 4, hydrophobized alumina-silica-based cubic particles 1-3 to 3-3 (dry mass%: 1 mass%) (Examples 10-12), and hydrophobized alumina-silica-based Cubic particles 1-4 to 3-4 (dry mass %: 2 mass %) (Examples 13 to 15) were prepared. In Production Example 5, the ratio of the cured silicone composition (methylhydrogenpolysiloxane) to 100 parts by mass of the surface-treated alumina-silica-based cubic particles 1 to 3 (Examples 1 to 3) was 1 part by mass. Or 2 parts by mass (dry mass% of the silicone composition: 1% by mass or 2% by mass) except that the blending amount is adjusted in the same manner as in Production Example 5, hydrophobized alumina-silica-based cubic particles 1-5 to 3-5 (dry mass%: 1 mass%) (Examples 16 to 18), and hydrophobized alumina-silica-based cubic particles 1-6 to 3-6 (dry mass%: 2 mass%) ( Examples 19-21) were prepared. These hydrophobized alumina-silica-based cubic particles are hereinafter simply referred to as "hydrophobicized cubic particles" or "cubic particles".

Experimental Example 1 Evaluation of soft focus performance Cubic particles 1 to 3 produced in Production Examples 1 to 3 (Examples 1 to 3), cubic particles 1-1 to 3-1 hydrophobized in Production Example 4 (implementation Examples 4 to 6), cubic particles 1-2 to 3-2 hydrophobized in Production Example 5 (Examples 7 to 9), cubic particles 1-3 to 3-3 hydrophobized in Production Example 6 (Examples 10-12), cubic particles 1-4-3-4 (Examples 13-15), cubic particles 1-5-3-5 (Examples 16-18), and cubic particles 1-6-3 -6 (Examples 19 to 21) and commercially available spherical silica particles 1 to 4 (hereinafter simply referred to as "spherical particles 1 to 4") (Comparative Examples 1 to 4), respectively, silicone oil (Shin-Etsu Chemical KF -96-1000CS, refractive index 1.40) at a mass ratio of 1:9, and a coating film having a thickness of about 20 µm was formed on a PET sheet using a bar coater (No. 9). In preparing the coating film, the cubic particles of Examples 1 to 3 were mixed with 0.001% nonionic surfactant Emulgen A-500 (manufactured by Kao Corporation) before mixing with silicone oil for the data shown in Table 1. After dispersing in water containing and applying ultrasonic waves, the sedimented particles were removed and the dried product was used (water elutriation classification). On the other hand, the data in Table 3 for the cubic particles of Examples 1 to 3 were used without being subjected to elutriation and classification, but directly mixed with silicone oil.

The soft focus property was evaluated by measuring the haze (cloudiness) of the coating film with a haze meter (BYK Gardner Haze-gard plus (Toyo Seiki Seisakusho)) in accordance with ASTM D1003. Table 1 shows the haze of the coating films prepared using the cubic particles of Examples 1 to 9 and the spherical silica particles of Comparative Examples 1 to 4 as the particles, and the cubic particles of Examples 10 to 21 were used. Table 2 shows the haze of the coating film. Table 2 also shows the haze of coating films prepared by mixing the cubic particles of Examples 1 to 3 with silicone oil without elutriation classification (Examples (1) to (3)). .

As shown in Tables 1 and 2, the alumina-silica-based cubic particles 1 to 3 (Examples 1 to 3) of the present invention having a cubic shape are higher than the silica particles having a true spherical shape (Comparative Examples 1 to 4). It can be seen that the haze value is high and the soft focus property is excellent. Further, it was confirmed that the alumina-silica-based cubic particles 1 to 3 (Examples 1 to 3) of the present invention were further subjected to a hydrophobizing treatment to further increase the Haze value and improve the soft focus property ( Examples 4-21).

For reference, physical property values (refractive index, volume-based average particle diameter, oil absorption, specific surface area, moisture Table 3 shows a comparison of adsorption amounts).

Experimental Example 2 Evaluation of Wrinkle-Hiding Effect For each of the cubic particles 1 to 3 (Examples 1 to 3) produced in Production Examples 1 to 3 and the commercially available spherical particles 1 to 4 (Comparative Examples 1 to 4), The wrinkle-hiding effect was evaluated by the following method.

(1) Evaluation method i. A 3.0 cm x 3.0 cm piece of dried pigskin for handicrafts is cut, and one half is protected with sellotape (registered trademark).
ii. 0.01 g of various particles (Examples 1 to 3, Comparative Examples 1 to 4) are applied to one half that is not protected by Sellotape (registered trademark), and the finger is reciprocated up and down 30 times to make it fit.
iii. Affix the pork skin to the center of the glass slide (2.45 cm from each end) with double-sided tape to secure it.
iv. While irradiating with a ring light in a darkroom, the camera lens position was fixed on a tripod at a height of 13.5 cm, the white balance was set to 4000K, and the surface of pigskin was photographed.

Camera: OLYMPUS PEN E-PL8
Lens: M. ZUIKO DIGITAL ED 30mm f3.5 Marco Aperture F4.0
Shutter speed 1/125 sec.
v. The photographs taken are visually observed, and the wrinkle-hiding effect is evaluated based on the following criteria.

◎ (remarkably effective): the unevenness of the pigskin epidermis is not conspicuous ○ (effective): the unevenness of the pigskin epidermis is not noticeable △ (slightly effective): compared to the pigskin surface on which particles are not applied Unevenness of the epidermis is blurred.
× (no effect): Blurring of unevenness of the pigskin epidermis is insufficient compared to the surface to which the particles are not applied.

(2) Evaluation results The results are collectively shown in Table 3 described above.

From the results in Tables 1 and 2, the cubic particles of the present invention (Examples 1 to 3 and 4 to 21) have a higher refractive index and Although the weight-based average particle diameters were almost the same, it was confirmed that the haze value was significantly high in both cases, and the soft focus property was high. The reasons for this include the high refractive index and the cubic shape of the particles of the present invention. In general, porous particles are said to have high light dispersion and soft focus properties, but the particles of the present invention cannot be said to be porous due to their specific surface area, water adsorption and oil absorption. Further, the particles of the present invention and spherical particles 3 (Comparative Example 3) are similar in weight-based average particle size, specific surface area, water adsorption amount, and oil absorption amount. However, since the particles of the present invention have a significantly higher Haze value, the difference can be attributed to the higher refractive index of the particles of the present invention and their cubic rather than spherical shape. Although not the results of the particles of the present invention, comparison between true spherical particles 1 (Comparative Example 1) and true spherical particles 3 (Comparative Example 3), true spherical particles 2 (Comparative Example 2) and true spherical particles 4 (Comparative From the comparison with Example 4), the haze value (soft focus property) is higher for particles with low oil absorption, specific surface area, and water adsorption amount, that is, particles that cannot be said to be porous (including non-porous). A trend was observed. From this fact, the porous particles are wetted by the solvent oil penetrating into their pores, and the refractive index difference between oil and silica becomes smaller than the refractive index difference between air and silica, so the light scattering effect at the interface is small. It is thought that the haze value (soft focus property) became low. From the results in Tables 1 and 2, it was confirmed that even the cubic particles of the present invention can have a higher haze value and an improved soft focus property by subjecting the surface to hydrophobic treatment. The effect was well recognized by normal-temperature curing silicone treatment. It was also observed that the haze value tended to increase as the amount of surface treatment for hydrophobization increased.

Further, from the results in Table 3, the alumina-silica-based cubic particles of the present invention (Examples 1 to 3, 4 to 21) are compared with silica true spherical particles 1 to 4 (Comparative Examples 1 to 4), Although the weight-based average particle diameters were almost the same, all had significantly high wrinkle-hiding effects. This is because the spherical particles 1 to 4 are spherical fine particles, so they easily fall into the skin grooves of the skin such as wrinkles and are filled. On the other hand, the cubic particles of the present invention have a large planar fixing area, so that multiple particles are entangled, and when spread on the skin surface, they do not fall into skin grooves such as pores and fine wrinkles. It is considered that the unevenness can be covered well by covering the skin so as to adhere to the skin and cover the skin without falling into the cutaneous groove. It was found that the wrinkle-hiding effect (skin-covering effect, irregularity-correcting effect) of the particles of the present invention tends to increase as the weight-based average particle size increases.

All of the particles (Examples 1 to 21 and Comparative Examples 1 to 4) had a good texture and a good slip property on dry pigskin. In particular, the alumina-silica-based cubic particles of the present invention (Examples 1 to 3) and their hydrophobized particles (Examples 4 to 21) have both moderate slipperiness and staying power, and are smooth on the skin. It is expected to have excellent adhesion to the skin by being able to spread evenly and staying moderately.

Experimental Example 3 Evaluation of slipperiness (coefficient of friction)
Cubic particles 1 to 3 produced in Production Examples 1 to 3 (Examples 1 to 3), cubic particles 1-1 to 3-1 hydrophobized in Production Example 4 (Examples 4 to 6), Production Examples Each of the cubic particles 1-2 to 3-2 (Examples 7 to 9) hydrophobized in 5 was evaluated for slipperiness by the following method. Specifically, the slipperiness of each test sample was evaluated by the coefficient of friction obtained using a friction tester (friction tester KSE-SE: manufactured by Kato Tech Co., Ltd.).

In addition, test samples were prepared by the following method for use in the friction tester.
(i) Weigh out 5 mg of the test sample.
(ii) Artificial skin with a width of 3 cm on a friction tester (Suprale (registered trademark) manufactured by Idemitsu Techno Fine Co., Ltd.: Top: 100% polyurethane (containing protein powder), base fabric: 80% rayon, 20% nylon) put the
(iii) The weighed sample to be tested is dispersed on the artificial skin, and is evenly applied to an area of 3×8 cm with a rubber glove.
(iv) Under the conditions of a load of 25 g and a speed of 1 mm/sec, automatic measurement is performed using a friction tester to obtain an average friction coefficient (MIU).
(v) Perform this operation three times and take the average value as the average coefficient of friction.

Table 3 shows the measurement results.

Experimental Example 4 Evaluation of concealing effect and wrinkle-blurring effect (optical evaluation)
The cubic particles 1 to 3 (Examples 1 to 3), hydrophobized cubic particles 1-1 to 3-1 (Examples 4 to 6), and cubic particles 1-2 to 3-2 (Examples 7 to 9). ), cubic particles 1-3 to 3-3 (Examples 10 to 12), cubic particles 1-4 to 3-4 (Examples 13 to 15), cubic particles 1-5 to 3-5 (Examples 16 to 18) and cubic particles 1-6 to 3-6 (Examples 19 to 21) were evaluated for wrinkle-hiding action by the following method. Specifically, each test sample was applied to dried pigskin, and the concealing effect and wrinkle blurring effect on the substrate were optically evaluated. Dried pigskin is formed of 50 to 100 micron elliptical protrusions and 5 to 20 μm width and 5 to 20 μm depth recesses (grooves) with several microns of unevenness on the surface, and has fine wrinkles. It is a skin model similar to human skin (skin). In addition, it can be said that the smaller the values of both the hiding property index and the wrinkle blurring property index, the better the cosmetic raw material.

[Evaluation procedure for concealability index and wrinkle blurring index]
(1) Apply 0.1 g of the test sample to half of a 3 cm x 3 cm dry pigskin for handicrafts.
(2) Affix the pigskin to a slide glass (7.9 cm wide) in an area 2.45 cm away from both ends. (3) In a dark room where light was blocked, while illuminating with a ring light (Arm System LED ring light LED-R72 for stereoscopic microscopes, intensity 2.0), a lens (Olympus M.ZUIKO DIGTAL ED 30 mm) A camera (OLYMPUS PEN E-PL8 manufactured by Olympus Corporation) equipped with an f3.5 Macro is adjusted and fixed so that the distance between the lens and the slide glass (test sample) is 13.3 cm. : Manual mode, white balance 4000K, aperture value F5.6, shutter speed 1/125 sec, ISO sensitivity 1250).
(4) Calculation of brightness by image editing:
Images captured on a PC installed with processing software (ex. free software Gimp) are captured, and the dry pig skin area to which the test sample is not applied (applied area) and the dry pig skin area to which the test sample is applied (non-applied area). For each of , 50 pixels of unevenness are randomly selected.
(5) Each pixel is subjected to SUV conversion, the brightness (V value) is measured for each concave portion and convex portion of each region (applied region, non-applied region), and the average value is calculated.
(6) Apply the obtained average value to the following formula to evaluate the hiding property and wrinkle blurring property. According to the following formula, the closer to 0 both the opacity index and the wrinkle blurring index, the better the tendency.

[Number 4]
Concealability index = V' convex - V convex Wrinkle blurring index = V' convex - V' concave
V-convex: average brightness of convex portions of dry pigskin not coated with test sample
V'convex: average value of brightness of the convex part of the dry pig skin coated with the test sample
V′ concave: average brightness value of concave of dried pigskin coated with test sample Table 4 also shows the measurement results.

From the results in Table 4, it was observed that the average coefficient of friction of the particles made hydrophobic by room-temperature curing silicone tends to decrease as the surface treatment amount (hydrophobic coating amount) increases. However, in the case of particles having a large particle diameter of 10 μm, the average coefficient of friction tended to increase when the coating amount of room temperature curing silicone was 6 wt %. In the case of particles made hydrophobic by methylhydrogenpolysiloxane (KF-9901), as in the above case, the average friction coefficient tended to decrease as the surface treatment amount (hydrophobic coating amount) increased. was less than room temperature cure silicone. In particular, when the particle size is 10 μm, the coefficient of friction becomes large because KF-9901 remains in excess in the treatment of 6 wt %. From this, it was confirmed that the hydrophobizing surface treatment with a silicone composition can obtain a large effect even when a small amount of the silicone composition is used. On the other hand, if the amount of the silicone composition is more than necessary, not only will the effect be reduced, but also the mixing workability will be deteriorated. There was also a tendency for the sex to decline.

Formulation example 1
Using the particles of the present invention (Examples 1 to 3) or the hydrophobized particles of the present invention (Examples 4 to 21) as test particles, a powder foundation is prepared according to the following formulation.

(powder foundation)
Ingredient Amount (% by mass)
(1) Siliconized talc 10.00
(2) Siliconized sericite 33.80
(3) Silicone treated synthetic phlogopite 10.00
(4) Siliconized titanium oxide 10.00
(5) Siliconized iron oxide 3.00
(6) Siliconized zinc oxide 2.00
(7) Polymethyl methacrylate 7.00
(8) Boron nitride 3.00
(9) Methylparaben 0.20
(10) Test particles (Example) 10.00
(11) Methylpolysiloxane 4.90
(12) Dioctyl succinate 4.00
(13) Squalane 2.00
(14) Perfume 0.10
Total 100.00

Specifically, the above components (1) to (10) are uniformly mixed in a Henschel mixer, the remaining binder components (11) to (14) are added, mixed, and then pulverized again. and passed through a sieve. This is compression-molded on a metal plate to obtain a powder foundation.

Formulation example 2
Using the particles of the present invention (Examples 1 to 3) or the hydrophobized particles of the present invention (Examples 4 to 21) as the particles to be tested, a makeup base is prepared according to the following formulation.

(Makeup base)
Ingredient Amount (% by mass)
(1) methyl sesquistearate glucoside 1.00
(2) sodium stearoyl lactylate 0.20
(3) Hardened rapeseed oil alcohol 3.50
(4) Squalane 6.00
(5) Octyldodecyl myristate 6.00
(6) Methylphenylpolysiloxane 6.00
(7) macadamia nut oil fatty acid phytosteryl 2.00
(8) Polyglyceryl triisostearate 1.00
(9) butyl paraben 0.10
(10) Purified water 51.94
(11) Synthetic sodium/magnesium silicate 1.00
(12) hydroxyethanediphosphonic acid 0.06
(13) xanthan gum 0.20
(14) 1,3-butylene glycol 10.00
(15) Methylparaben 0.20
(16) diglycerin 5.00
(17) Test particles (Example) 5.00
(18) methylpolysiloxane 0.50
Total 100.00

Specifically, in the above formulation, the water phase components (10) to (13) are stirred and mixed, heated and maintained at 85°C. Oil phase components (1) to (9) are mixed and heated to dissolve at 80°C. After that, the water phase component described above is added to the oil phase component and pre-emulsified, and after uniformly emulsifying with a homomixer, the homomixer is stopped and stirring is continued, and the component (14) to (15) is dissolved. Add the mixture up to 17). Subsequently, cooling is started, component (18) is added at about 70°C, and the mixture is further cooled to 35°C to obtain a makeup base.

Formulation example 3
Using the particles of the present invention (Examples 1 to 3) or the hydrophobized particles of the present invention (Examples 4 to 21) as the particles to be tested, an oily foundation is prepared according to the following formulation.

(oil foundation)
Ingredient Amount (% by mass)
(1) Liquid paraffin 18.00
(2) Isopropyl palmitate 15.00
(3) Liquid Lanolin 4.50
(4) Microcrystalline wax 4.50
(5) Seresin 10.00
(6) Carnauba wax 2.00
(7) Sorbitan sesquioleate 1.00
(8) Paraben 0.20
(9) Titanium oxide 14.00
(10) Kaolin 7.50
(11) Talc 11.00
(12) iron oxide 4.00
(13) Test particles (Example) 8.00
(14) Perfume 0.30
Total 100.00

Specifically, in the above formulation, components (1) to (8) are heated and melted at 80° C., and a mixture of (9) to (12) is added. The mixture is kneaded with a roll mill, heated and melted again, and (13) is added thereto and mixed uniformly. After defoaming, (14) is added, poured into a medium plate and cooled to obtain an oily foundation.

Formulation example 4
Using the particles of the present invention (Examples 1 to 3) or the hydrophobized particles of the present invention (Examples 4 to 21) as the particles to be tested, lipsticks are prepared according to the following formulation.

(lipstick prescription)
Ingredient Amount (% by mass)
(1) Seresin 10.00
(2) Microcrystalline wax 2.00
(3) Carnauba wax 1.00
(4) Synthetic hydrocarbon wax 2.00
(5) Isopropyl dimerate 15.00
(6) Tri(caprylic-capric)glycerin 34.35
(7) Dipentaerythritol fatty acid ester 3.50
(8) Vitamin E 0.10
(9) Polyglyceryl triisostearate 12.00
(10) Colorant 7.00
(11) Synthetic phlogopite 10.00
(12) Test particles (Example) 3.00
(13) Perfume 0.05
Total 100.00

Specifically, components (9) to (12) of the above formulation are dispersed by a roller mill. After that, components (1) to (8) are heated and melted, and the mixture of components (9) to (12) and component (13) are added and mixed well. The mixture is filtered, poured into a mold at a high temperature, cooled, and the molded product is filled in a container to obtain a lipstick. The obtained lipstick is excellent in soft focus even when the powder is blended in an oily state, and makes vertical wrinkles on the lips less visible.

Claims (13)

A cosmetic additive comprising hydrophobized alumina-silica particles obtained by hydrophobizing the surface of alumina-silica particles,
The surface of the hydrophobized alumina-silica particles is coated with a cured product of a room temperature curing silicone composition,
A cosmetic additive characterized in that the alumina-silica particles have the following properties:
(1) cubic primary particles with a side length of 0.3 to 20 μm as observed by scanning electron microscopy;
(2) a refractive index of 1.48 to 1.52 by the liquid immersion method;
(3) a volume-based average particle size of 1 to 20 μm by the Coulter Counter method;
(4) Oil absorption according to JIS K5101-13-2 is 10 ml/100 g or more and less than 50 ml/100 g.
(5) The specific surface area by the BET method is 20 m ² /g or less.
Here, the room temperature curing silicone composition is
a first oligomer containing a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group;
a second oligomer containing no dialkylsiloxane unit and containing an alkoxy group-containing siloxane unit containing an alkoxy group;
silicone oil;
a catalyst;
A room temperature curing silicone composition containing an organic solvent,
The ratio of the total amount of the first oligomer and the second oligomer in the room temperature curable silicone composition is 20% by mass or more and 50% by mass or less,
The ratio of the first oligomer to 1 part by mass of the second oligomer is 0.15 parts by mass or more and 10 parts by mass or less,
The silicone oil has a kinematic viscosity at 25° C. of 100 mm ² /s or more,
the catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates;
The vapor pressure of the organic solvent at 20° C. is 1 kPa or higher. A cosmetic additive comprising alumina-silica particles,
A cosmetic additive characterized in that the alumina-silica particles have the following characteristics:
(1) cubic primary particles with a side length of 0.3 to 20 μm as observed by scanning electron microscopy;
(2) a refractive index of 1.48 to 1.52 by the liquid immersion method;
(3) a volume-based average particle size of 1 to 20 μm by the Coulter Counter method;
(4) Oil absorption according to JIS K5101-13-2 is 10 ml/100 g or more and less than 50 ml/100 g.
(5) the specific surface area by the BET method is 20 m ² /g or less ,
However, the above cosmetic additives exclude the following amorphous silica-alumina antibacterial agents:
Moisture adsorption at a relative humidity of 75%, comprising cubic to spherical particles containing an antibacterial metal component, at least a portion of which is a silver component, and having a particle size in the range of 0.2 to 30 µm as measured by electron microscopy. An amorphous silica-alumina antibacterial agent having excellent discoloration resistance, characterized by having an amount of 5% or less and a specific surface area of 30 m ² /g or less according to the BET method. A cosmetic additive comprising alumina-silica particles,
The alumina-silica particles have an apparent specific gravity of 0.65 to 1.1 g/cm ³ ,
A cosmetic additive characterized in that the alumina-silica particles have the following characteristics:
(1) cubic primary particles with a side length of 0.3 to 20 μm as observed by scanning electron microscopy;
(2) a refractive index of 1.48 to 1.52 by the liquid immersion method;
(3) a volume-based average particle size of 1 to 20 μm by the Coulter Counter method;
(4) Oil absorption according to JIS K5101-13-2 is 10 ml/100 g or more and less than 50 ml/100 g.
(5) The specific surface area by the BET method is 20 m ² /g or less. The cosmetic additive according to any one of claims 1 to 3, wherein the alumina-silica particles further have the following properties:
(6) The water adsorption amount by the gas adsorption method is 0 to 5%. The alumina-silica-based particles have a composition in which the molar ratio of SiO ₂ /Al ₂ O ₃ is in the range of 1.8 to 5, and are substantially amorphous in terms of X-ray diffraction. The cosmetic additive according to any one of claims 1 to 4 . 4. A cosmetic additive comprising hydrophobized alumina-silica particles according to claim 2 or 3 , which are obtained by hydrophobizing the surface of the alumina-silica particles. According to claim 6 , the hydrophobized alumina-silica particles are obtained by coating the surface of the alumina-silica particles according to claim 2 or 3 with a cured product of a room temperature curing silicone composition. Cosmetic additives:
Here, the room temperature curing silicone composition is
a first oligomer containing a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group;
a second oligomer containing no dialkylsiloxane unit and containing an alkoxy group-containing siloxane unit containing an alkoxy group;
silicone oil;
a catalyst;
A room temperature curing silicone composition containing an organic solvent,
The ratio of the total amount of the first oligomer and the second oligomer in the room temperature curable silicone composition is 20% by mass or more and 50% by mass or less,
The ratio of the first oligomer to 1 part by mass of the second oligomer is 0.15 parts by mass or more and 10 parts by mass or less,
The silicone oil has a kinematic viscosity at 25° C. of 100 mm ² /s or more,
the catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates;
The vapor pressure of the organic solvent at 20° C. is lkPa or higher. The hydrophobized alumina-silica particles according to claim 6 are obtained by coating the surface of the alumina-silica particles according to claim 2 or 3 with methylhydrogensilicone oil and subjecting the particles to heat treatment. cosmetic additive. The cosmetic additive according to any one of claims 1 to 8 , wherein the cosmetic additive is an agent for imparting soft focus, an agent for imparting wrinkles (irregularity correction agent), and/or an agent for imparting extensibility. A method for producing alumina-silica particles having a hydrophobized surface,
The alumina-silica particles have the following characteristics
(1) cubic primary particles with a side length of 0.3 to 20 μm as observed by scanning electron microscopy;
(2) a refractive index of 1.48 to 1.52 by the liquid immersion method;
(3) a volume-based average particle size of 1 to 20 μm by the Coulter Counter method;
(4) Oil absorption according to JIS K5101-13-2 is 10 ml/100 g or more and less than 50 ml/100 g.
(5) The specific surface area by the BET method is 20 m ² /g or less.
has
A method for producing surface-hydrophobicized alumina-silica particles, comprising the following steps (A) and (B) or (C):
(A) Coating the surface of the alumina-silica particles with a room temperature curing silicone composition:
Here, the room temperature curing silicone composition is
a first oligomer containing a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group;
a second oligomer containing no dialkylsiloxane unit and containing an alkoxy group-containing siloxane unit containing an alkoxy group;
silicone oil;
a catalyst;
containing an organic solvent,
The ratio of the total amount of the first oligomer and the second oligomer in the room temperature curable silicone composition is 20% by mass or more and 50% by mass or less,
The ratio of the first oligomer to 1 part by mass of the second oligomer is 0.15 parts by mass or more and 10 parts by mass or less,
The silicone oil has a kinematic viscosity at 25° C. of 100 mm ² /s or more,
the catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates;
The organic solvent has a vapor pressure of 1 kPa or more at 20° C., and (B) curing the room-temperature-curable silicone composition coated on the surface of the alumina-silica particles; or (C) the alumina-silica. After coating the surface of the system particles with methyl hydrogen silicone oil, a step of heat-treating. A cosmetic comprising the cosmetic additive according to any one of claims 1 to 9 . 12. The cosmetic according to claim 11 , containing the cosmetic additive in a proportion of 1 to 50% by mass. 13. The cosmetic according to claim 12 , wherein the cosmetic is a make-up cosmetic.

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