WO2019187254A1

WO2019187254A1 - Cosmetic additive and cosmetic

Info

Publication number: WO2019187254A1
Application number: PCT/JP2018/037554
Authority: WO
Inventors: 大島　純治; 皆川　円; 紘一島野
Original assignee: 大阪ガスケミカル株式会社; 水澤化学工業株式会社
Priority date: 2018-03-29
Filing date: 2018-10-09
Publication date: 2019-10-03

Abstract

Provided is a cosmetic additive containing alumina-silica particles, characterized in that the alumina-silica particles have the following characteristics: (1) the particles comprise cuboid primary particles having a length of one side when measured by scanning electron microscope observation of 0.3 to 20 µm; (2) the refractive index according to the immersion method falls within the range of 1.48-1.52, inclusive; (3) the volume-standard average particle size using the Coulter counter method falls within the range of 1-20 µm, inclusive; (4) oil absorption according to JIS K5101-13-2 is from 10 ml/100g to less than 50 ml/100g; and (5) the specific surface area according to the BET theory does not exceed 20 m2/g.

Description

Cosmetic additives and cosmetics

The present invention relates to an alumina-silica-based particle that is suitably used as an additive blended in cosmetics in order to impart a soft focus property and / or a hiding effect. That is, the present invention relates to the use of alumina-silica particles having a soft focus property and / or a hiding effect as a cosmetic additive.

Cosmetics such as foundations, base makers, and lipsticks require a property called soft focus. This soft focus property means that, for example, when a cosmetic film is formed by applying cosmetics to the skin, the surface of the skin becomes blurred, so that it is difficult to see skin spots, freckles, pores or wrinkles, etc. This means that the ratio of diffused light without traveling straight through the decorative coating film is large in the light (total irradiated light) hitting the light.

Conventionally, inorganic powders such as silica have been used in order to impart such soft focus to a cosmetic coating film formed from cosmetics. For example, Patent Document 1 reports that spherical silica or the like is effective for imparting soft focus properties. In Patent Documents 2 and 3, spherical silica particles produced by using polyacrylamide or carboxymethyl cellulose as an aggregating growth agent and neutralizing an alkali silicate with an acid in the presence of the aggregating growth agent are disclosed. It is described that it is used as a filler for cosmetics. Furthermore, in Patent Document 4, when silica is produced by reacting an alkali silicate with an acid in the presence of an aggregating growth agent, silica particles are produced by partial neutralization, and then remain in the reaction system. By gradually neutralizing the unneutralized alkali silicate, the silica is precipitated on the generated silica particles, thereby providing a circularity of 0, which has a larger primary particle size than conventional spherical silica. It is described that silica particles of .7 to 0.85 can be obtained, and that the silica particles impart excellent soft focus properties to cosmetics and have excellent durability.

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

The spherical silica particles described in Patent Documents 1 to 3 have a problem in their sustainability even if they exhibit soft focus properties when blended in cosmetics. Specifically, when it is applied to the skin to form a decorative film, its optical properties change over time, or it drops off from the skin due to sweat, etc. There is a problem of being damaged. The silica particles described in Patent Document 4 are obtained by improving the sustainability problem. Specifically, since the silica particles described in Patent Document 4 have a high oil absorption, they have the property of absorbing sweat and the like, and the degree of circularity is 0.7 to 0.85, which is slightly deformed from a spherical shape. Therefore, it is hard to come off from the surface of the skin. For this reason, it exists stably in a cosmetic coating film, and can provide the outstanding soft focus property continuously.

Since the silica particles described in Patent Documents 1 to 4 are all spherical or have a high circularity, they can impart high slipperiness when blended in cosmetics. However, while high slipperiness tends to stretch when applied to the skin, it also causes upward slipping, resulting in a decrease in familiarity with the skin and a feeling of close contact with the skin, and a decrease in covering power. In order to make it difficult to see stains, freckles, wrinkles, etc., it is also necessary to stretch evenly on the skin surface while maintaining the covering power on the skin, and to adhere to the skin so that it can be integrated properly. It is required to have the property and retention.

The present invention has an alumina-silica system that has particle characteristics different from those of conventionally known silica particles, and can impart an excellent soft focus property, a small hiding effect, and / or a good feeling of use to cosmetics. The purpose of the particles is to provide a new use as a cosmetic additive.

The inventors of the present invention have formulated alumina-silica-based cubic particles having specific properties and physical properties prepared by reacting a zeolite produced from sodium silicate and sodium aluminate with an acid into cosmetics. Thus, the present inventors have found that the cosmetic has excellent soft focus properties and exhibits an effect of making small wrinkles and pores inconspicuous. In addition, the particles have appropriate slipping properties, and cosmetics formulated with the particles will spread and spread smoothly when applied to the skin. It was confirmed that the (skin adhesiveness) was good, and that it had good usability.

As a result of further research, it was possible to improve the slipping property between the particles by subjecting the alumina-silica particles to surface treatment with a room temperature curable silicone composition to make them hydrophobic, and as a result, when applied to the skin. In addition, the present inventors have found that the slipperiness can be further improved while maintaining a moderate retention property, and the hiding effect is also 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, wherein the alumina-silica-based particles have the following characteristics:
(1) It consists of cubic primary particles having a side length of 0.3 to 20 μm as observed with a scanning electron microscope.
(2) The refractive index by the immersion method is 1.48 to 1.52.
(3) The volume-based average particle size by Coulter counter method is 1 to 20 μm.
(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 BET method is 20 m < ² > / g or less.
(I-2) The cosmetic additive according to (I-1), wherein the moisture adsorption amount of the alumina-silica particles by gas adsorption method is 0 to 5%.
(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 terms of X-ray diffraction. A cosmetic additive according to (I-1) or (I-2).
(I-4) A cosmetic additive having 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 surface of the alumina-silica particles according to any one of (I-1) to (I-3) is coated with a cured product of a room temperature-curable silicone composition, wherein the hydrophobized alumina-silica particles are The cosmetic additive as described in (I-4):
Here, the room temperature curable 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 an alkoxy group-containing siloxane unit that does not contain a dialkylsiloxane unit and contains an alkoxy group;
With silicone oil,
A catalyst,
A room temperature curable 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 kinematic viscosity at 25 ° C. of the silicone oil is 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 more.
(I-6) In the hydrophobized alumina-silica particles, the ratio of the alumina-silica particles to 90 parts by mass with respect to 10 parts by mass of the cured product of the room temperature curing silicone composition coated on the surface is 90 parts by mass or less. Cosmetic additives according to (I-5).
(I-7) The surface of the alumina-silica particles described in any one of (I-1) to (I-3) 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-based particle or the hydrophobized alumina-silica-based particle has any one of the following characteristics (a) to (d): Cosmetic additives described in:
(A) Average friction coefficient (MIU): 0.3 to 0.7
(B) Hiding power index: 6 or less (c) Haze blurring index: 32 or less (d) Haze: 30-80.
(I-9) (I-1) to (I-8), wherein the cosmetic additive is a soft focus property imparting agent, a hiding effect imparting agent (unevenness correcting agent), and / or an extensibility imparting agent. Cosmetic additive described in any one.
(II) Production Method of 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 alumina-silica-based particles having a hydrophobic surface, the method comprising a heat treatment step.
(II-2) A method for producing alumina-silica particles having a hydrophobic surface, which comprises the following steps (A) and (B):
(A) A step of coating the surface of the alumina-silica-based particles described in any one of (I-1) to (I-3) with a room temperature-curable silicone composition:
Here, the room temperature curable 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 an alkoxy group-containing siloxane unit that does not contain a dialkylsiloxane unit and contains an alkoxy group;
With 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 kinematic viscosity at 25 ° C. of the silicone oil is 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 at 20 ° C. of 1 kPa or more: 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 hydrophobic surface are those having any one of the following characteristics (a) to (d): (II-1) or (II-2) Manufacturing method: (a) Average friction coefficient (MIU): 0.3 to 0.6
(B) Hiding property index: 5 or less (c) Haze blurring index: 28 or less (d) Haze: 34-80.
(II-4) The hydrophobized alumina-silica-based particles are produced so that the ratio of the alumina-silica-based particles to 90 parts by mass or less with respect to 10 parts by mass of the cured product of the room temperature-curable silicone composition coated on the surface. The production method according to (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 to (II-5).
(II-7) 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, (II-2) to (II-6) The manufacturing method in any one of).
(III) Cosmetic (III-1) A cosmetic comprising the cosmetic additive according to any one of (I-1) to (I-9).
(III-2) The cosmetic according to (III-1), which contains the cosmetic additive in an amount of 1 to 50% by mass.
(III-3) The cosmetic according to (III-1) or (III-2), wherein the cosmetic is a makeup cosmetic.

When the alumina-silica-based particles used in the present invention are blended in cosmetics, the cosmetics have high light properties based on properties such as particle shape, particle size, refractive index, specific surface area and / or moisture adsorption amount. Scatterability can be imparted. In other words, the cosmetic containing the particles of the present invention transmits light through the decorative film while multiple scattering of light, and as a result, the proportion of diffused light in the transmitted light increases and gives excellent soft focus properties. can do.

The alumina-silica-based particles used in the present invention, when blended in cosmetics, can be covered with a lid that does not fall into the skin crevice such as small wrinkles, especially based on the particle shape and particle size. It is possible to exert a concealment effect. Similarly, the effect (unevenness correction effect) of covering and covering skin pores well and adjusting the texture of the skin after makeup can be exhibited.

Furthermore, the alumina-silica-based particles used in the present invention have a cubical shape due to their cubic shape, and are difficult to physically remove from the skin when blended in cosmetics and applied to the skin, and exhibit a long lasting effect. can do.

In addition, the surface of the alumina-silica-based particles can be treated with a hydrophobizing agent such as methyl hydrogen silicone oil or a room-temperature curable silicone composition to improve hydrophobicity between the particles. it can. As a result, when applied to the skin, the slipperiness can be further improved while maintaining an appropriate retention, and the hiding effect can be improved.

The photographic image which observed and image | photographed the alumina-silica-type cubic particle 1 (Example 1) of this invention manufactured by the manufacture example 1 with the scanning electron microscope is shown. The photographic image which observed and image | photographed the alumina-silica-type cubic particle 2 (Example 2) of this invention manufactured by the manufacture example 2 with the scanning electron microscope is shown. The photographic image which observed and image | photographed the alumina-silica-type cubic particle 3 (Example 3) of this invention manufactured by the manufacture example 3 with the scanning electron microscope is shown. The X-ray diffraction profile of the alumina-silica-based cubic particles 1 of the present invention produced in Production Example 1 (Example 1) is shown.

(I) Alumina-silica cubic particles The alumina-silica cubic particles constituting the cosmetic additive of the present invention (hereinafter also simply referred to as “the present particles”) have the following properties and characteristics: Features.
(1) It consists of cubic primary particles having a side length of 0.3 to 20 μm as observed with a scanning electron microscope.
(2) The refractive index by the immersion method is 1.48 to 1.52.
(3) The volume-based average particle diameter by the Coulter counter method is 1 to 20 μm.
(4) The 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 BET method is 20 m < ² > / g or less.

Hereinafter, each of these characteristics of the particles of the present invention will be described.

In the present invention, “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, wrinkles, etc. are blurred by the light scattering effect so as to be inconspicuous. It means the effect of adjusting the appearance of the skin so that it looks smooth. The “soft focus” can be evaluated using a Haze meter as shown in Experimental Example 1 described later.

(1) Shape and Particle Size The particles of the present invention are characterized in that the shape of the primary particles is cubic and the length of one side by observation with a scanning electron microscope is 0.3 to 20 μm. The thickness is preferably 0.5 to 20 μm, more preferably 1.5 to 12 μm. As an example, images obtained by observing primary particles of the present invention particles (Examples 1 to 3) produced in Production Examples 1 to 3 with a scanning electron microscope are shown in FIGS. As shown in these figures, the particles of the present invention are primary particles (fine particles) having a cubic shape composed of approximately six faces and eight corners, and the shape and size are almost arranged. The particles of the present invention having such a shape have high light scattering performance (light diffusibility) and can exhibit good soft focus properties. Moreover, the touch and skin slipperiness are also good. Here, “smooth skin smoothness” does not simply mean that the skin is highly slippery, but when it is applied to the skin, it stays in close contact with the skin and stays on the skin evenly, that is, it is moderately slippery. It means that it has retention.

In general, spherical (including true spherical) fine particles are said to have the effect of hiding the wrinkles by falling into the skin crevice such as a small wrinkle and filling it, but in fact, the light along the crevice by light rays There is a problem that the line is raised and the gavel stands out. In contrast, the particles of the present invention have a cubic shape, so that a plurality of particles are entangled on the surface of the skin, and the skin can be covered so as to cover the skin groove such as a small wrinkle. ing. For the same reason, it is excellent in the effect of concealing 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, the planar fixed area is large, and when blended in cosmetics and applied to the skin, the particles of the present invention are difficult to physically remove from the skin and can exhibit a long lasting effect.

(2) Refractive index The particles of the present invention have a refractive index of 1.48 to 1.52.

Here, the refractive index can be obtained by an immersion method. Specifically, as described in the examples described later, solvents having various refractive indexes are prepared using two solvents (α-bromonaphthalene and kerosene) having different refractive indexes, and according to Larsen's oil immersion method. It can be determined by immersing the solvent in the particles of the present invention taken on a slide glass and then observing the movement of the Becke line with an optical microscope.

) The curvature ratio affects the soft focus. When blended in a cosmetic, if the difference in refractive index between the liquid component in the cosmetic and the moisture of sweat is moderate, light is scattered at the interface to exhibit soft focus properties. In general, silica-based particles having a small refractive index difference become transparent when wetted with water such as sweat, and the concealing effect is remarkably reduced. However, the particles of the present invention that are alumina-silica-based particles are difficult to become transparent even when wetted with water. For this reason, even if it sweats, soft focus property is maintained and moderate concealment property can be exhibited. Therefore, it is desirable that the particles of the present invention have a refractive index of preferably 1.48 to 1.52, more preferably 1.49 to 1.51.

(3) Volume-based average particle diameter The particles of the present invention have a volume-based average particle diameter of 1 to 20 μm.

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

When the particle diameter is larger than the wavelength of light, a light scattering effect is produced, so that the volume standard 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 haze value (cloudiness) increases and the soft focus property improves as the volume reference average particle size decreases. Although not bound by theory, this means that if the amount added to the cosmetic on a weight basis is the same, particles with a smaller volume-based average particle size can contain more particles, so the light scattering effect is higher. This is probably due to this. From the viewpoint of soft focus properties, the volume-based average particle size is preferably 12 μm or less. On the other hand, in the case of the particles of the present invention, the hiding effect improves as the volume-based average particle size increases. Although this is not bound by theory, it is considered that the larger the volume-based average particle diameter is, the higher the covering effect on the skin groove is. From both aspects of soft focus and hiding effect (unevenness 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. ~ 4 μm.

(4) Oil absorption amount The particles of the present invention have an oil absorption amount in the range of 10 ml / 100 g or more and less than 50 ml / 100 g.

(The oil absorption is JIS. K. 5101-13-1: 2004 (refined linseed oil method). Specifically, oil can be gradually added to the refined sesame to the particles of the present invention and mixed to obtain a refined sesame oil amount (ml / 100 g) when the paste has an appropriate hardness.

Generally, porous particles having pores on the surface have a large oil absorption. However, as with the specific surface area and moisture absorption, when blended into cosmetics or applied to the skin, the liquid surface or sweat in the cosmetics penetrates into the pores of the fine particle surface, resulting in wet particle surfaces. There is a problem that the refractive index is lowered and the soft focus property is lowered. In contrast, the particles of the present invention, as described above, have a small oil absorption, so that the original refractive index of the particles of the present invention is not easily impaired regardless of the presence environment of the particles of the present invention. High soft focus. From this viewpoint, the oil absorption amount of the particles of the present invention is preferably 10 to 45 ml / 100 g, more preferably 10 to 35 ml / 100 g.

Also, the oil absorption amount affects the sebum absorption capacity of the cosmetic when the particles of the present invention are blended in the cosmetic. If the amount of oil absorption is too high, the ability to degrease the sebum from the skin will increase, and there may be a burden on the skin, such as crispiness and itching. Since the oil absorption of the present invention particles is in the above range, degreasing from the skin is moderately suppressed, and the burden on the skin is small.

(5) Specific surface area The particles of the present invention are characterized in that the specific surface area by the BET method is 20 m ² / g or less in relation to having the above-described particle shape and particle size characteristics. Preferably 1 ~ ^10m 2 / g, more preferably 1 ~ ^5m 2 / g.

Generally, porous particles having pores on the surface 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 fine particles, or sweat permeates into the pores on the surface of the fine particles after application to the skin, thereby There is a problem that the liquid becomes wet and the original refractive index of the particles is lowered, so that the soft focus property is lowered. In contrast, the particles of the present invention, as described above, have a small specific surface area, so that the original refractive index of the particles is unlikely to be impaired regardless of the presence environment state of the particles of the present invention. It has the feature that it can exhibit high soft focus.

The particles of the present invention have some chemical and physical properties in addition to the chemical and physical properties described above.

(6) Moisture adsorption amount The particles of the present invention are characterized in that the moisture adsorption amount is 0 to 5%.

Here, the moisture adsorption amount can be determined by a gas adsorption method. Specifically, as described in the examples described later, the particles of the present invention are preliminarily left to stand for 2 hours under a vacuum condition of 150 ° C., and then the water vapor partial pressure P _T (P / P ₀ ) obtains a moisture adsorption isotherm at a range of from 0.001 to 0.9 (equilibration determination time: 300 seconds), the measured value in the water vapor partial pressure _{_{P T (P / P 0)}} 0.75, the present invention particles unit mass It can be calculated in terms of the amount of moisture adsorbed (percent by mass).

The moisture adsorption amount affects the moisture retention of the skin when the particles of the present invention are blended in cosmetics. If the amount of moisture adsorption is too high, the ability to remove moisture that moisturizes the skin from the sebum increases, which may put a burden on the skin, for example, it may become thick and itchy. The particles of the present invention have a feature that the moisture retention of the skin is appropriately maintained because the moisture adsorption amount is in the above range. From this viewpoint, 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 have a composition having a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 1.8 to 5. Preferably it is 1.85 to 2.5, more preferably 1.9 to 2.1.

The particles of the present invention can have a cubic shape having a certain particle size as described above when the SiO ₂ / Al ₂ O ₃ molar ratio is in the above range. That is, the molar ratio is a useful requirement for configuring the shape of the particles of the present invention.

(8) Amorphous The particles of the present invention are substantially amorphous. Here, “substantially amorphous” means amorphous when measured by X-ray diffraction and no crystallization is observed. In addition, the measuring method of the crystallinity degree by X-ray diffraction method is as the description in the Example mentioned later.

(9) Apparent specific gravity The particles of the present invention have an apparent specific gravity in the range of 0.5 to 1.1 g / cm ³ .

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

The apparent specific gravity is a parameter linked to the oil absorption amount. For this reason, when the apparent specific gravity is small, the oil absorption amount increases and the ability to degrease from sebum tends to increase. Since the apparent specific gravity is in the above range, the particles of the present invention are characterized in that degreasing from the skin is moderately suppressed and the burden on the skin is small. From this viewpoint, 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) Loss on ignition The particles of the present invention are characterized in that their loss on ignition is in the range of 0 to 6%.

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

Since the loss on ignition is a parameter linked to the amount of moisture adsorbed, it affects the moisture retention of the skin when blended into cosmetics. If the loss on ignition is too high, the ability to take away moisture that moisturizes the skin will increase. Since the ignition loss is in the above range, the particles of the present invention have a feature that the moisture retaining property of the skin is appropriately maintained. From this viewpoint, 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 in that the whiteness is 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 the examples described later.

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

(12) Haze value (soft focus property)
As described above, the particles of the present invention can impart soft focus properties to the 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 cloudiness (blurring). The higher the numerical value, the higher the soft focus property and the higher the concealing property (covering power). The haze value can be determined by “diffuse transmittance / total light transmittance × 100”, and can usually be measured with a haze meter.

Specifically, as described in the examples described later, the haze value is obtained by mixing the particles of the present invention and silicone oil in a ratio of 1: 9 (mass ratio) and coating a PET sheet with a thickness of 20 μm. Can be measured with a Haze meter in accordance with ASTM D1003. The Haze value of the particles of the present invention with visible light is 35% or more. Preferably it is 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 high Haze value and an excellent soft focus property as compared with the spherical silica particles. For this reason, the blurring effect can be provided to cosmetics by mix | blending this with cosmetics as a cosmetics additive.

(13) Average friction coefficient (sliding property)
The particles of the present invention may have an average coefficient of friction of preferably 0.7 or less, more preferably 0.6 or less. The lower the average friction coefficient, the better the extensibility and the better, but it is also useful that the average friction coefficient stays moderately from the viewpoint of adhesion to the skin and covering power. From that viewpoint, the lower limit value may be 0.3 or more, for example.

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 friction coefficient of the particles of the present invention can be measured using a friction feeling tester (friction feeling tester KSE-SE: manufactured by Kato Tech Co., Ltd.). In the measurement, the particles of the present invention, which is a test sample, are directly applied to artificial skin. According to the particles of the present invention having the desired average friction coefficient, it has an appropriate slip property on the artificial skin and between the particles, and when applied to the skin, it stretches uniformly on the skin and stays moderately stretched. There is an effect.

(14) Optical evaluation of hiding property: (a) Hiding property index, (b) Haze blurring property index Hiding property is the smaller the hiding effect, which is the ability to hide the substrate when applied to the skin, and The greater the effect of blurring pores and small wrinkles (the wrinkle blurring effect), the better the evaluation. The opacity index and the obscuration index are physical property values that serve as indices for evaluating the obscuration effect and obscuration effect of the particles of the present invention, respectively. It shows that the concealability is exhibited well. The particles of the present invention may have a concealment index of preferably 6 or less, more preferably 5 or less. Although it does not restrict | limit as a lower limit, 1 or more can be illustrated. In addition, the particles of the present invention may have a blurring property index of preferably 32 or less, more preferably 28 or less. Although it does not restrict | limit as a lower limit, 20 or more, Preferably 25 or more can be illustrated.

The hiding property index and the blurring property index of the particles of the present invention can be measured by the methods described in Examples described later.

(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 morphology, although the crystal structure is substantially destroyed, the particle morphology is substantially It is produced by neutralizing with an acid under conditions that are not impaired, and removing the alkali metal content in the zeolite.

Examples of the crystalline zeolite used as a raw material include zeolite A, zeolite X, zeolite Y and the like. Zeolite A is preferred because of the ease of synthesis and availability and the characteristics of the alumina-silica particles after production. be able to. Further, although the raw material zeolite is not limited, it is preferable to use a material having a primary particle size (the length of one side of cubic particles 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 alkali content in the alumina-silica particles having a primary particle size of 0.3 to 20 μm used in the present invention can be reduced within a short time by a relatively mild acid treatment. It can be removed to make it amorphous.

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

When an acid is added to an aqueous slurry of crystalline zeolite, the pH of the slurry shifts to the acidic side with the addition of the acid, 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 do.

Amorphous alumina-silica-based cubic particles obtained by acid treatment of crystalline zeolite and elution and removal of alkali are filtered, washed with water if necessary, dried, and then fired. The firing is not limited, but the amorphous alumina-silica-based cubic particles to be prepared have a water adsorption amount of 0 to 5% by the gas adsorption method as described above. It is preferably carried 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 above-mentioned alumina-silica cubic particles (invention particles) to a hydrophobic treatment (repellency). It can be prepared by water treatment). Such a hydrophobizing treatment is not particularly limited, and a conventionally known method such as a water repellent surface treatment with silicone can be used. As such a silicone treatment, a method in which the particle surface is coated with silicone oil (Japanese Patent Application Laid-Open No. 2007-176738, etc.), methyl hydrogen silicone (quasi-drug name methyl hydrogen polysiloxane) is coated on the particle surface, and 100 Examples of the heat treatment at ˜180 ° C. (Japanese Patent Laid-Open No. 2005-350588), the method of reacting with hydrogensilane using a fluorine-containing boron catalyst to silylate the surface (WO2015 / 136913), and the like are exemplified without any limitation. can do. Preferably, the above-mentioned alumina-silica cubic particles (the particles of the present invention) are coated with methyl hydrogen silicone and heat-treated. Although the heating temperature is not limited, 100 to 180 ° C. can be exemplified as described above.

As another method, it can also be prepared by coating the surface of the aforementioned alumina-silica-based cubic particles (particles of the present invention) with a room temperature curable silicone composition. That is, the hydrophobized alumina-silica-based cubic particles are obtained by coating the surface of the above-described particles of the present invention with a cured product of a room temperature curable silicone composition.
(1) Room temperature curable silicone composition The room temperature curable silicone composition used for coating alumina-silica cubic particles is a composition that can be cured by forming a film at room temperature. Here, normal temperature is a temperature at which heating (specifically heating at 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 room temperature is used synonymously with room temperature.

The 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 is a non-sticking auxiliary agent that forms a siloxane matrix together with the second oligomer in the coating and assists the non-stickiness and water repellency of the silicone oil in the coating even when the coating is rubbed. As a result, the coating can effectively suppress a decrease 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 from each other, and at least one monovalent carbon selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group) X represents a siloxane unit, a and e may be the same or different from each other, and are 1 or 2. b is an integer of 2 to 20, and C is 2 to 10. (It is an integer, and d is an integer of 2 to 20.)
Examples of the l-valent saturated hydrocarbon group represented by R ¹ to R ⁹ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n- Examples thereof include alkyl groups having 1 to 6 carbon atoms such as pentyl and n-hexyl. A methyl group is preferred.

Examples of the l-valent aromatic hydrocarbon group 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 are preferably a methyl group and / or a phenyl group, and more preferably a methyl group.

In the first oligomer, unit I is an alkoxy group-containing siloxane unit. That is, the unit I contains an alkoxy group represented by R ² O.

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

In unit I, an oxygen atom in Si—O— is bonded to any silicon atom in units II to IV described below. Thereby, the Si—O— of the 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, the unit II contains an alkoxy group represented by R ⁴ O.

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

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

Examples of the siloxane unit represented by X include, for example, unit VI alone represented by the following formula (2), a combination of unit II and unit I (when unit I is terminated at unit II), unit II and unit V And a combination of unit II and unit VI (when unit VI is located at the end via unit II).

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

(In the formula, m is an integer of 2 or more. Z ¹ is the above-described l-valent hydrocarbon group or alkoxy group.)
Examples of the monovalent hydrocarbon group represented by Z ^1, preferably include a methyl group, the monovalent alkoxy groups represented by Z ^1, with preference given to methoxy.

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 R ⁶ and R ⁷ . 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, the unit V contains an alkoxy group represented by R ⁹ O. The silicon atom in the unit V is bonded to any oxygen atom in the units II to IV. Thereby, the silicon atom in the unit V forms a siloxane bond in the first oligomer. Unit V is a molecular terminal unit in the first oligomer.

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

Each of the above units and their number is specified by ¹ H-NMR and ²⁹ Si-NMR.

Also, the first oligomer can be represented by the following average composition formula (A).

Average composition 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 from each other, and represent a monovalent hydrocarbon group. Α has an average value in the range of 0.40 to 1.70. Β represents a value at which the ratio of OR ^q bonded to the silicon atom 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 above-described monovalent hydrocarbon group.

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

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

Specifically, the first oligomer includes, for example, a methyl 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 thereof include a methylphenyl silicone alkoxy oligomer, preferably a methyl silicone alkoxy oligomer.

Methyl silicone alkoxy oligomer
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 silicone alkoxy oligomers are produced from, for example, methyltrimethoxysilane and dimethyldimethoxysilane.

The molecular weight of the first oligomer is, for example, 500 or more, preferably 1000 or more, and for example, 3000 or less, preferably 2000 or less.

A commercially available product is used as the first oligomer. For example, X-40-9250 (methyl 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.) is exemplified.

The proportion 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, further preferably 5% by mass or more, and particularly preferably 6% by mass or more. For example, it is less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less, further 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 ^{ll ~} R ^17, which may be different Do or phase to each other, a monovalent saturated hydrocarbon group and a monovalent least one monovalent hydrocarbon selected from the group consisting of an aromatic hydrocarbon group Y represents a siloxane unit, and f and i may be the same or different from each other, and are 1 or 2. g is an integer of 2 to 20, and h is 2 to 18. (It is an integer.)
The monovalent saturated hydrocarbon group represented by R ^ll ~ ^{R 17,} for example, methyl, ethyl, n- propyl, iso- propyl, n- butyl, sec- butyl, iso- butyl, tert- butyl, n- pentyl And alkyl groups having 1 to 6 carbon atoms such as n-hexyl. A methyl group is preferred.

Examples of the monovalent aromatic hydrocarbon group 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.

As R ^{ll ~} R ^17, preferably include methyl and / or phenyl group, more preferably a methyl group.

In the second oligomer, the unit XI is an alkoxy group-containing siloxane unit. That is, the 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 the silicon atom in the unit XI, and is preferably 2. In that case, the number (3-f) of monovalent hydrocarbon groups represented by R ^ll bonded to a silicon atom in the unit XI is preferably 1 (= 3-2).

The oxygen atom in the unit XI is bonded to the silicon atom of the unit XII or unit XIII described below. Thereby, the Si—O— of the 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, the unit XII contains an alkoxy group represented by R ¹⁴ O. g means the number of units XII. g is preferably an integer of 3 or more, preferably 17 or less.

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

Examples of the siloxane unit represented by Y include unit XV represented by the following formula (5) alone, a combination of unit XII and unit XI (when unit XI is terminated via unit XII), unit XII and unit XIV Combinations (when unit XIV is terminated via unit XII), units XII and units XV (when unit XV is terminated via unit XII) are included.

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 above-described monovalent hydrocarbon group or alkoxy group.)
Examples of the monovalent hydrocarbon group represented by Z ^2, preferably include a methyl group, the monovalent alkoxy groups represented by Z ^2, with preference given to methoxy.

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

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

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

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

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

Average composition formula (B):
R ^t γSi (OR ^s ) _δ O _(4-γ-δ) (B)
(In the formula, R ^t and R ^s may be the same or different from each other, and represent a monovalent hydrocarbon group. Γ has an average value in the range of 0.40 to 1.70. Δ represents a 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), as the ^{^{^{^{R t, R 11, R 13}}}} , R 15 1 monovalent hydrocarbon ^group, the same as ^{R 16} in the general formula (4). Examples of ^{R s} is Examples thereof include the same monovalent hydrocarbon groups as R ¹² , R ¹⁴ , and R ¹⁷ in the general formula (4).

The ratio of the OR ^S is δ in average compositional formula (B) bonded to silicon atoms in the average composition formula (B) is, for example, 10 mass% or more, preferably 20 mass% or more, and is, for example 35 wt% The value is as follows.

Specifically, examples of the second oligomer include a methyl silicone alkoxy oligomer and a methyl phenyl silicone alkoxy oligomer, and a methyl silicone alkoxy oligomer is preferable.

Examples of the methyl silicone alkoxy oligomer include a methyl silicone methoxy oligomer produced from methyl trimethoxysilane.

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

(In the formula, g, h and Y are the same as g, h and Y in formula (5).)
Such a methyl silicone alkoxy oligomer is produced from, for example, methyltrimethoxysilane.

The molecular weight of the second oligomer is, for example, 500 or more, preferably 1000 or more, and for example, 4000 or less, preferably 3000 or less.

A commercially available product is used for 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), methyl-based silicone alkoxy oligomers in which g is 10 and h is 4, Shin-Etsu Chemical Industry Co., Ltd.), X-40-9225 (Methyl silicone alkoxy oligomer having g of 12 and h of 10 in formula (6), manufactured by Shin-Etsu Chemical Co., Ltd.), US-SG2403 (Toray Dow Corning) Manufactured) and the like.

The proportion 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, further preferably 25% by mass or more, and for example, less than 50% by mass, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 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. The ratio of the first oligomer to the second oligomer is 10 or less, preferably 9 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 2 or less, further 1.0 or less, and further 0.5. It is as follows.

When the ratio of the first oligomer to the second oligomer is less than the above lower limit or exceeds the above upper limit, the slipperiness and water repellency of the coating are lowered. In other words, if the above ratio is not less than the above lower limit and not more than the above upper limit, the coating film can exhibit high slipperiness 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 further preferably 35% by mass or more. . If the ratio does not satisfy the above lower limit, the ratio of the first oligomer and the second oligomer (curing component) is excessively small, so that the coating cannot be reliably formed when the curing component is cured at room temperature. In other words, if the ratio of the total amount is equal to or more than the lower limit described above, the ratio of the curing component is not excessively reduced, so that the curing component can be cured at room temperature to reliably form a coating film.

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. When the ratio of the total amount described above exceeds the upper limit described above, the viscosity when the surface treatment is performed using the silicone composition is increased, and therefore the uniformity of the coating is decreased. In other words, if the ratio of the total amount is equal to or less than the above upper limit, the viscosity becomes low enough to coat and uniform surface treatment is possible.

Silicone oil is a component that imparts slipperiness and water repellency to the coating. Silicone oil has a linear main chain and has, for example, a polysiloxane repeating structure (-(SiO) n-). Examples of the silicone oil include straight silicone oil (unmodified silicone oil) such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. As silicone oil, in addition to straight silicone oil, the main chain ends and / or side chains are modified with alkyl groups, alkenyl groups (including vinyl groups), alkynyl groups, phenyl groups, ionic groups, etc. A silicone oil is also mentioned. Examples of the ionic group include 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.

As the silicone oil, straight silicone oil is preferable, and polydimethylsiloxane is more preferable.

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 Toray Dow Corning), TSF451 series (manufactured by Momentive Performance Material Japan) YF-33 series (made by Momentive Performance Material Japan) and the like.

Kinematic viscosity at 25 ° C. of the silicone oil 100 mm ² / s or more, preferably 200 mm ² / s or more, more preferably 500 mm ² / s or more, most preferably 1000 mm ² / s or more. The kinematic viscosity at 25 ° C. of the silicone oil 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 below the lower limit described above, the coating 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, the coating film can be stably provided with slipperiness and water repellency. On the other hand, if the kinematic viscosity of the silicone oil is less than or equal to the above upper limit, the silicone oil can be easily handled and the silicone composition can be easily prepared.

The ratio of the 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 further preferably 1.5% by mass or more. For example, it is 10 mass% or less, Preferably it is 5 mass% or less, More preferably, it is 2.5 mass% or less.

The ratio of the silicone oil to the total amount of the first oligomer and the second oligomer of 100 parts by mass 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 further preferably 36% by mass or more. is there. If the ratio of the total amount is equal to or more than the above lower limit, the ratio of the curing component is prevented from being excessively reduced, and the curing component can be cured at room temperature to reliably form a coating film.

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, and more preferably 41% by mass. If the ratio of the total amount is equal to or less than the above upper limit, uniform surface treatment can be performed, and therefore a uniform film can be formed.

When the silicone composition is cured at room temperature, the catalyst reacts with moisture in the air to hydrolyze to produce active [metal atom-OH], [metal atom-OH], the first oligomer and the first oligomer. It is a curing catalyst that causes a condensation reaction between two oligomers.

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

Examples of the metal alkoxide include titanium alkoxide, aluminum alkoxide, zirconium alkoxide (eg, zirconium tetra n-butoxide, zirconium tetra n-propoxide), germanium alkoxide (eg, germanium tetraethoxide), tin alkoxide (eg, tin tetra n). -Butoxide, tin tetra-tert-butoxide), hafnium alkoxide (eg, hafnium tetra-2-propoxide, hafnium tetra-tert-butoxide), niobium alkoxide (eg, niobium pentaethoxide), tantalum alkoxide (eg, tantalum penta n-butoxide, Tantalum pentaethoxide). Preferably, titanium alkoxide and aluminum alkoxide are used.

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

Examples of the aluminum alkoxide include aluminum trialkoxide. Examples of the aluminum trialkoxide include aluminum triethoxide, aluminum tripropoxide (eg, aluminum triisopropoxide, aluminum tri-n-propoxide), aluminum tributoxide (eg, aluminum tri-sec-butoxide, aluminum tri-n-oxide). Butoxide) and the like.

Note that the reactivity of each of the three or four alkoxy groups in the metal alkoxide differs 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 decrease. Therefore, considering reactivity and stability, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, and titanium tetra n-butoxide are preferable among titanium alkoxides. Of the aluminum alkoxides, aluminum triethoxide, aluminum triisopropoxide, and aluminum trisec-butoxide are preferable.

As the metal alkoxide, a commercially available product is used, for example, D-25 (titanium tetra n-butoxide, manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the metal chelate compound include a metal chelate compound having β-diketone, phosphate ester, alkanolamine or the like as a ligand.

Examples of β-diketone include 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, Examples include 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, and the like. Preferably, 2,4-pentanedione is used.

Examples of octylene glycol include 2-ethyl-3-hydroxyhexoxide.

Examples of the phosphate ester include 2-ethylhexyl phosphate.

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

Preferred examples of the ligand include β-diketone.

The central metal (metal atom) forming the metal chelate compound is not particularly limited. For example, aluminum, titanium, zirconium, niobium, magnesium, calcium, chromium, manganese, iron, cobalt, nickel, steel, zinc, gallium, Palladium, indium, tin, etc. are mentioned. Preferably, aluminum, titanium, and zirconium are used.

Specifically, examples of the metal chelate compound include an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound, a magnesium chelate compound (eg, diaquabis (2,4-pentanedionato) magnesium), a calcium chelate compound (eg, Diaquabis (2,4-pentanedionato) calcium), chromium chelate compounds (for example, tris (2,4-pentanedionato) chromium), manganese chelate compounds (for example, diaquabis (2,4-pentanedionato) ) Manganese), iron chelate compounds (eg, tris (2,4-pentanedionato) iron), cobalt chelate compounds (eg, tris (2,4-pentandionato) cobalt), nickel chelate compounds (eg, , (2,4-pentanedionato) nickel), copper chelate (eg, bis (2,4-pentandionato) copper), zinc chelate (eg, bis (2,4-pentanedionato) Zinc, etc.), tris (2,4-pentanedionato) gallium, etc.), niobium chelate compounds (eg, tetrakis (2,2,6,6-tetramethyl-3,5-heptaneedionatoniobium (IV), etc.) Palladium chelate compounds (eg, bis (2,4-pentanedionato) palladium), indium chelate compounds (eg, tris (2,4-pentanedionato) indium), tin chelate compounds (eg, bis (2 , 4-pentandionato) tin, etc.).

Preferred examples of the metal chelate compound include an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound. More preferred examples of the metal chelate compound include an aluminum chelate compound and a titanium chelate compound from the viewpoint of maintaining excellent fastness (strength) in the coating.

Examples of the aluminum chelate compound include tris (2,4-pentanedionato) aluminum, tris (ethylacetoacetate) aluminum, bis (ethylacetoacetate) (2,4-pentanedionato) aluminum, and the like. Preferably, tris (2,4-pentanedionato) aluminum is used.

Examples of the titanium chelate compound include tetrakis (2,4-pentanedionato) titanium, tetrakis (ethyl acetoacetate) titanium, and the like. Preferably, tetrakis (2,4-pentanedionato) titanium is used.

Examples of the zirconium chelate compound include tetrakis (2,4-pentanedionato) zirconium and tetrakis (ethylacetoacetate) zirconium. Preferably, tetrakis (2,4-pentanedionato) zirconium is used.

Further, the metal chelate compound includes an alkoxy group-containing metal chelate compound further containing an alkoxy group in addition to the above-described ligand. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy and the like. As the alkoxy group, 2-propoxy is preferable. Specifically, the alkoxy group-containing metal chelate compound includes, for example, an alkoxy group-containing aluminum chelate compound such as aluminum ethyl acetoacetate diisopropylate, such as bis (2,4-pentanedionato) bis (2-propanolate) titanium. And alkoxy group-containing titanium chelate compounds.

The metal carboxylate is a metal salt of carboxylic acid. Examples of the carboxylic acid 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 2-methylbutanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, 3,5,5-trimethylhexanoic acid, such as naphthenic acid And cyclic carboxylic acids. Preferably, branched carboxylic acid is mentioned, More preferably, 2-ethylhexanoic acid is mentioned.

The metal that forms the metal salt is not particularly limited, and examples thereof include the same metals as the above-described center metal (center metal that forms the metal chelate compound), preferably zinc, iron, cobalt, and manganese. It is 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, etc. . Preferred examples of the metal carboxylate include zinc carboxylate, iron carboxylate, cobalt carboxylate and manganese carboxylate.

Examples of the zinc carboxylate include bis (2-ethylhexanoic acid) zinc, zinc acetate, and zinc naphthenate. Preferably, bis (2-ethylhexanoic acid) zinc is used.

Examples of the iron carboxylate include bis (2-ethylhexanoic acid) iron, iron acetate, and iron naphthenate. Preferably, bis (2-ethylhexanoic acid) iron is used.

Examples of the cobalt carboxylate include bis (2-ethylhexanoic acid) cobalt, cobalt acetate, and cobalt naphthenate. Preferably, bis (2-ethylhexanoic acid) cobalt is used.

Examples of manganese carboxylate include bis (2-ethylhexanoic acid) manganese, manganese acetate, manganese naphthenate, and the like. Preferably, bis (2-ethylhexanoic acid) manganese is used.

Note that, as a catalyst, acids such as phosphoric acid and acetic acid do not generate a metal atom —OH, and therefore OH groups based on the alkoxy groups of the first oligomer and the second oligomer cannot be dehydrated and condensed. As a result, the curing reaction of the first oligomer and the second oligomer cannot proceed rapidly at room temperature, and the above-described acid is unsuitable as a catalyst.

The catalyst can be used alone or in combination. As the catalyst, preferably, each of metal alkoxide, metal chelate compound and metal carboxylate is used alone.
The catalyst may be prepared as a catalyst solution dissolved in an organic solvent described later.

The ratio 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 for example, 25% by mass or less, preferably 15% by mass or less. .

As a ratio of the catalyst with respect to 100 parts by mass of the total amount of the first oligomer and the second oligomer, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, particularly preferably. Is 20 parts by mass or more, and for example 55 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

If the ratio of the catalyst is not less than the above-described lower limit and not more than the above-described upper limit, the first oligomer and the second oligomer are rapidly cured at room temperature, and a film can be formed at room temperature.

Organic solvent is a high vapor pressure solvent that is equal to or higher than the lower limit of the vapor pressure described later. Specifically, the high vapor pressure solvent is, for example, an alcohol solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol); for example, ethyl acetate, butyl acetate, methoxybutyl acetate, ethyl glycol acetate, amyl acetate, etc. For example, glycol ether solvents such as ethylene glycol dimethyl ether (high vapor pressure glycol ether solvents); for example, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and acetyl acetone; Paraffinic solvents (high vapor pressure paraffinic solvents) such as n-hebutane, n-octane and isooctane; for example, naphthenic solvents such as cyclopentane and cyclohexane, benzene, toluene, xyle , Aromatic solvents such as trimethylbenzene; for example, benzene, toluene, is selected from an aromatic solvent such as xylene. These organic solvents are used alone or in combination of two or more. As the organic solvent, an alcohol 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. 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, more preferably 7 kPa (52 mmHg) or less, particularly preferably. 5 kPa (38 mmHg) or less.

If the vapor pressure of the organic solvent does not satisfy the above lower limit, when the silicone composition is cured at room temperature, the organic solvent cannot be rapidly removed (evaporated), and thus a film cannot be formed. In other words, when the vapor pressure of the organic solvent is equal to or higher than the lower limit described above, the organic solvent can be quickly removed (evaporated) when the silicone composition is cured at room temperature, and thus a coating film can be formed. On the other hand, if the vapor pressure of the organic solvent is not more than the above upper limit, the organic solvent is prevented from being rapidly removed (distilled off) when coating with the silicone composition, and thus uneven thickness is generated in the coating. Can be suppressed.

On the other hand, the organic solvent is a high vapor pressure solvent, but the low vapor pressure solvent lower than the lower limit value of the vapor pressure described above can allow a very small amount of contamination that does not impair the effects of the present invention. For example, mixing of the low vapor pressure solvent contained in the catalyst solution described above is allowed.

The vapor pressure at 20 ° C. of the low vapor pressure solvent is, for example, less than 1 kPa. Examples of the low vapor pressure solvent 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 terpenes, and petroleum solvents such as mineral spirits. It is 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, further preferably 3 parts by mass or less, particularly preferably 100 parts by mass of the high vapor pressure solvent. Is 1 part by mass or less. 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, still more preferably 1.0% by mass or less, and particularly preferably 0. 0.5% by mass or less, particularly preferably 0.1% by mass or less.

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

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, further preferably 40% by mass or more, and particularly preferably 50% by mass. % Or more, 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 the total amount of 100 parts by mass 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 further preferably 140 parts by mass. In addition, for example, it is 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 160 parts by mass or less.

If the ratio of the organic solvent is equal to or more than the lower limit described above, the handling of the silicone composition is excellent, and it is possible to suppress the generation of uneven thickness of the coating resulting from excessively rapid drying after coating. it can. On the other hand, if the ratio of the organic solvent is equal to or less than the above upper limit, an excessive decrease in yield can be suppressed.

Next, preparation of the silicone composition will be described.

In order to prepare the silicone composition, first, the first oligomer, the second oligomer, the silicone oil, the organic solvent, and, if necessary, the additive are blended and mixed in the above-described ratio, and the silicone composition is mixed. To prepare. Meanwhile, a catalyst is prepared separately. Thereby, a silicone composition and a catalyst are prepared as a two-component curable composition.

Subsequently, the silicone composition and the catalyst are blended in the above-described proportions and mixed to prepare a silicone composition. In the preparation of the silicone composition, the catalyst generates a metal-OH group by hydrolysis.

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

The silicone composition contains a silicone oil, and the kinematic viscosity at 25 ° C. of the silicone oil is 100 mm ² / s or more. Therefore, the coating film that is a cured product of the silicone composition is excellent in slipperiness and water repellency.

Furthermore, the 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 the slipperiness and water repellency of the film.

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

Further, when the organic solvent is an alcohol solvent, it is possible to suppress the first oligomer and the second oligomer from undergoing a condensation reaction to produce an alcohol. That is, the reaction of the first oligomer and the second oligomer during storage of the silicone composition (in particular, the silicone composition in the two-component curable composition) can be suppressed. Therefore, this silicone composition is excellent in storage stability.

Moreover, 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 property of the silicone composition is improved. In addition to being excellent, it is possible to suppress the occurrence of uneven coating thickness due to excessively rapid drying after coating, and to suppress an excessive decrease in yield.

Moreover, 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 at room temperature. It hardens quickly and can form a film at room temperature.

According to the silicone composition thus prepared, a coating film (cured product) having a hardness corresponding to a pencil hardness of 2H or higher, preferably 4H or higher can be formed. The pencil hardness can be measured, for example, according to the description of JIS K 5600-5-4 (1999) on a JIS H 4000-compliant aluminum plate applied with the silicone composition and cured at room temperature. Such a coating film can be formed by applying the silicone composition to the surface of a test plate for coating such as a test aluminum plate conforming to JIS H 4000 and leaving it at room temperature. The time for leaving 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. The following can be exemplified. By doing so, an OH group is generated from the alkoxy group in the first oligomer and the second oligomer, and the OH group is dehydrated with [metal atom-OH] based on the catalyst, and the curing reaction proceeds. Subsequently, alcohol as a by-product of the above reaction is distilled off (removed) together with the organic solvent. Thus, the silicone composition cures to form a coating film.
[Modification]
The following modifications 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 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 above-described components are blended and mixed in an inert gas atmosphere such as nitrogen and sealed in a container. And just before use, the container is opened and the silicone composition is coated on the object. Even with this one-component curable composition, the same effects as the two-component curable composition can be obtained.

Moreover, although this silicone composition is a normal temperature curing type, if necessary, it can be heated after room temperature curing (further thermal curing), or can be thermally cured instead of room temperature curing. As the heating temperature, for example, 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 “the hydrophobized particles of the present invention”) are described above using the silicone composition prepared by the above method. It can be prepared by subjecting the alumina-silica-based cubic particles (the particles of the present invention) to surface treatment. The surface treatment can be carried out by mixing the particles of the present invention and the silicone composition and then leaving them at room temperature.

The mixing of the silicone composition and the particles of the present invention is preferably performed with stirring so that the silicone composition uniformly adheres to the surfaces of the particles of the present invention and uniformly coats the entire surface 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 are agglomerated with each other and are likely to become lumps. Accordingly, the ratio of the silicone composition to 100 parts by mass of the particles of the present invention is not limited, but 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).

When the ratio of the silicone composition is significantly less than 1 part by mass with respect to 100 parts by mass of the present particles, the surface of the present particles cannot be sufficiently covered. On the other hand, when the ratio of the silicone composition is significantly increased beyond 30 parts by mass, the silicone compositions on the surface tend to adhere to each other and the hydrophobized particles of the present invention tend to be aggregated or lumped. In addition, although it does not restrict | limit as a ratio of the silicone composition after hardening with respect to 100 mass parts of this invention particle | grains, For example, 0.1 mass part or more, Preferably it is 0.2 mass part or more, More preferably, it is 0.5 mass part or more. Moreover, it is 10 mass parts or less normally, Preferably it is 8 mass parts or less, More preferably, 6 mass parts or less can be mentioned (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 (coated) with the silicone composition. Next, the particles of the present invention whose surfaces are coated with the silicone composition are allowed to stand at room temperature, whereby the silicone composition is cured on the surfaces of the particles of the present invention, and alumina-silica-based cubic particles having a hydrophobic surface are generated. To do.

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

Thereby, hydrophobized alumina-silica-based cubic particles whose surface is coated with a film made of a cured product of a room temperature curable silicone composition can be prepared. 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 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 characteristic selected from the group consisting of the following (a) to (d).
(A) Average friction coefficient (MIU): 0.3 to 0.6
(B) Hiding property index: 5 or less (c) Haze blurring index: 28 or less (d) Haze: 34-80.

(A) Average friction coefficient (sliding property)
The hydrophobic particles of the present invention may have an average friction coefficient of preferably 0.6 or less, more preferably 0.5 or less. The lower the average friction coefficient, the better the extensibility and the better, but it is also useful that the average friction coefficient stays moderately from the viewpoint of adhesion to the skin and covering power. From that viewpoint, the lower limit is, for example, 0.3 or more.

The measurement method of the average friction coefficient is as described above, and can be measured by applying the hydrophobized particles as the test sample to the artificial skin as they are. According to the hydrophobized particles of the present invention having the desired average friction coefficient, compared with the hydrophobized untreated particles of the present invention, it has a higher moderate slip on the artificial skin and between the particles, When applied to the skin, it stretches uniformly on the skin and has the effect of staying moderately stretched.

Optical evaluation of hiding property: (b) Hiding property index, (c) Haze blurring index Hiding property index and haze blurring property index are indexes for evaluating the hiding effect and haze blurring effect of the hydrophobized particles of the present invention, respectively. Each of the physical property values is such that as the numerical value is smaller, the hiding effect is lower and the haze blurring effect is higher, and the hiding effect is better exhibited. The hydrophobized particles of the present invention may preferably have a concealment index of 6 or less, more preferably 5 or less. As a lower limit, although not limited, one or more can be exemplified. The hydrophobized particles of the present invention may have a wrinkle blurring index of preferably 32 or less, more preferably 28 or less. As a lower limit, although not limited, 25 or more, preferably 20 or more can be exemplified.

The hiding property index and the blurring property index of the hydrophobized particles of the present invention can be measured by the method described in the examples described later, and are superior in the hiding effect compared to the hydrophobized untreated particles of the present invention. Has an effect.

(D) Haze value (soft focus property)
The hydrophobized particles of the present invention may preferably have a Haze value of visible light of 34% or more, more preferably 40% or more. As an upper limit, 90% or less can be mentioned, for example, Preferably it is 80% or less. The hydrophobized particles of the present invention have a high Haze value and excellent soft focusability compared to untreated particles (present particles). For this reason, a high blurring effect can be given to cosmetics by mix | blending this with cosmetics as a cosmetics additive.

(IV) Use as a cosmetic additive and cosmetics containing the same The above-mentioned alumina-silica-based cubic particles (invention particles) have a cubic shape having six flat surfaces. Moreover, since it has a specific refractive index, a particle size, oil absorption, and a specific surface area, the soft focus property of cosmetics can be improved by mix | blending with various cosmetics as a soft focus provision agent. That is, when blended in cosmetics, as a result of the presence of a large number of particles within a predetermined area, light will be transmitted through the cosmetic film while being scattered multiple times, and therefore the proportion of diffused light in the transmitted light is increased, Excellent soft focus can be imparted.

Such soft focusability of the particles of the present invention can be evaluated by a Haze meter in accordance with ASTM D1003 as shown in the experimental examples described later. Specifically, as described above, a coating film formed by applying a solution in which the particles of the present invention are mixed with silicone oil at a ratio of 1: 9 (mass ratio) to a thickness of about 20 μm on a PET sheet. The haze (cloudiness) is 34% or higher, preferably 40% or higher, more preferably 50% or higher, and even more preferably 55% or higher. This is useful for increasing the soft focus of the particles. It is shown that.

Further, since the particles of the present invention have a cubic shape, it is possible to impart an appropriate skin slipping property to the cosmetic by blending it with the cosmetic. Specifically, since the particles of the present invention are in the form of particles, they have high slipperiness compared to a plate-like body and exhibit good extensibility (elongation spreadability). On the other hand, since it is a cubic shape having a flat surface, there is an advantage that it is excellently covered and can be applied to the skin appropriately and has excellent covering power.

Furthermore, unlike the spherical particles (including true spherical particles), the particles of the present invention have a flat surface and a large flat surface fixing area, or the particles are entangled with each other, and when spread on the skin surface, skin such as pores and small wrinkles There is also an advantage that it is excellent in the effect of covering pores and small wrinkles (covering power, unevenness correction effect) by covering the flat surface so as to close the skin well without falling into the groove. That is, when the particles of the present invention are blended into cosmetics, they can be spread smoothly on the skin, covered with pores and small wrinkles and smoothed, and the skin surface after makeup is smoothed and integrated with the skin. The cover force can be applied by close contact.

When the particles of the present invention are blended in cosmetics as a soft focus imparting agent or / and a hiding effect agent (or an unevenness correcting agent), depending on the type of cosmetics to be blended, at least 1 to 50 mass in the cosmetics. By blending in an amount of%, the desired soft focus property can be imparted. From the viewpoint of soft focus properties, skin extensibility, 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, emulsions, creams, powders, foams, solids, etc. Among such cosmetics, particularly soft focus properties As a soft focus imparting agent for cosmetics that require skin care, and / or for masking cosmetics that require skin irregularities such as pores and wrinkles to correct the skin texture after makeup. It is blended as an effect imparting agent or an unevenness correcting agent. The cosmetics requiring soft focus and / or the cosmetics required to prepare the skin texture after makeup are not particularly limited, but foundation, concealer, blusher, white powder (funny, loose powder, pressed powder) ), Makeup cosmetics such as control color, base material, BB cream, eye color, lipstick, etc .; skin care cosmetics such as milky lotion, cream, beauty liquid, day cream, sunscreen, and the like. These cosmetics generally have a water-repellent oil component such as a film-forming polymer, a surfactant, a thickener, water, a moisturizer, a fragrance, a pigment or a dye, or a silicone oil, depending on the application or use form. , UV absorbers, astringents, refreshing agents, flame retardants, whitening agents, various extracts, plant and seaweed extract and other cosmetic ingredients in appropriate amounts By doing so, the soft focus property, the concealment effect, and / or the unevenness correction effect can be enhanced.

Hereinafter, the present invention will be described based on manufacturing examples and experimental examples. However, the said manufacture example and experiment example are the illustrations for making an understanding of this invention easy, and this invention is not limited to these at all. In the following production examples and experimental examples, “%” means “% by mass” unless otherwise specified. In addition, unless otherwise specified, the following experiments were performed under normal temperature (25 ± 5 ° C.) and atmospheric pressure conditions.

Various measurement methods and conditions used in the following production examples and experimental examples are as follows.
[Measuring method]
(1) Fluorescent X-ray (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 Corporation was used, the target was Rh, and the analytical line was Kα The others were measured under the following conditions.
<Si> Tube voltage: 30 kV, tube current: 100 mA, detector: PC, spectral crystal: PET
<Al> Tube voltage: 30 kV, tube current: 100 mA, detector: PC, spectral crystal: PET
The sample was based on a product dried at 110 ° C. for 2 hours.

(2) Evaluation of crystallinity by X-ray diffraction method The crystallinity analysis of the sample powder by X-ray diffraction method was carried out using “Sample horizontal multi-purpose X-ray diffractometer Ultima IV” manufactured by Rigaku Corporation 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: 40 mA
Step size: 0.02 °
Counting time: 0.6 sec / step
Slit: Divergent slit 2/3 ° Light receiving slit 0.3 mm SS2 / 3 °.

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

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

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

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

Specifically, a test sample is placed on a measuring plate, and 4 to 5 drops of oil are gradually added to the refined sesame at a time, and each time, the oil is kneaded into the sample with a pallet knife. This is repeated until dripping is continued until the paste has a smooth hardness. In addition, this paste can be spread without cracking or becoming crumbly, and it should be a thing which only adheres to a measurement board lightly. The amount of oil absorption (ml / 100 g) can be obtained from the final amount (ml) of refined linseed oil according to the following equation.
[Equation 1]
Oil absorption (ml / 100g) = (100 × V) / m
V: Volume of oil consumed (ml)
m: Mass of the test sample (g)
(7) Specific surface area (BET method)
Using a TriStar 3000 manufactured by Micromeritics, nitrogen adsorption isotherms were measured. It was determined by the BET method from a nitrogen adsorption isotherm with a specific pressure of 0.2 or less.

(8) Moisture adsorption (gas adsorption method)
Using a Belsorb Max manufactured by Nippon Bell Co., Ltd., a water adsorption isotherm in the range of the water vapor partial pressure P _T (P / P ₀ ) in the range of 0.001 to 0.9 was determined. The pretreatment was performed under vacuum conditions at 150 ° C. for 2 hours. The equilibrium judgment time was 300 seconds. A measured value at a water vapor partial pressure P _T (P / P ₀ ) of 0.75 was converted to an adsorption amount per unit mass of the substrate, and was defined as a moisture adsorption amount (% by mass).

(9) Apparent specific gravity (JIS K-6220-1 7.7)
JIS. K. Measurement was performed according to the following method according to 6220-1 7.7: 2001.
1) Put the piston (outer diameter 21.80 ± 0.05mm, length 115mm, mass 190g) into the cylinder (inner diameter 22.00 ± 0.05mm, inner depth 100mm) and let it drop naturally, then the upper protrusion dimension Is measured to 0.01 mm.
2) Pull out the piston, weigh and pour the test sample 1-5g into the cylinder correctly to 0.01g, drop the sample adhering to the side of the cylinder and make the upper surface of the contents flat.
3) Gently drop the piston from the top of the cylinder, and when it reaches the sample surface, lightly rotate the piston once to familiarize it well.
4) The apparent specific gravity (g / cm ³ ) is calculated according to the following formula.
[Equation 2]
Apparent specific gravity (g / cm ³ ) = [m ₀ ] / (0.7854 × d ² × [h ₂ −h ₁ ])
m ₀ : Mass of the test sample (g)
d: Diameter of the cylinder (cm)
h ₂ : height difference (cm) between piston and cylinder when test sample is present
h ₁ : height difference (cm) between piston and cylinder when no test sample is present

(10) Loss on ignition (Ig-loss) (JIS K-0067 4.2) (860 ° C. × 20 min) JIS. K. Measured according to the following method in accordance with 4.2: 1992. However, ignited conditions of 860 ° C. × 20 minutes were adopted.
1) Put a test sample in an evaporating dish and measure its mass to the order of 0.1 mg.
2) Put the evaporating dish containing the sample in an electric furnace, gradually raise the temperature and ignite at 860 ° C. 3) After igniting at 860 ° C. for 20 minutes, the evaporating dish is quickly transferred to a desiccator and allowed to cool, and after standing to cool, its mass is measured to the order of 0.1 mg.
4) The above 3 is repeated until the mass becomes constant (constant weight), and the apparent specific gravity (g / cm ³ ) is calculated from the final mass according to the following formula.
[Equation 3]
Loss on ignition (%) = ([W ₁ −W ₂ ] / [W ₁ −W ₃ ]) × 100
W ₁ : Mass of test sample and evaporating dish before ignition (g)
W ₂ : Mass of test sample and evaporating dish after ignition (g)
W ₃ : Mass of evaporating dish (g)

(11) Hunter whiteness (JIS P-8123)
Measurements were made using a Tokyo Denshoku Hunter automatic reflectometer TR-600 OPTICAL UNIT.

Production Example 1 Production Method of Alumina-Silica-Based Cubic Particles 1 (Example 1) 358.6 g of No. 3 sodium silicate (SiO ₂ = 23 wt%, Na ₂ O = 7.4 wt%) as a liquid A and water 504 7 g was mixed and prepared as liquid B, sodium aluminate (Al ₂ O ₃ = 23 wt%, Na ₂ O = 19.2 wt%) 338.1 g, 49 wt% caustic soda aqueous solution 117.7 g, water 480.9 g Were mixed and prepared. Liquid A and Liquid B were mixed by 781 L each so that the following molar ratio was obtained, to prepare a total amount of 1800 g.
[Mixing conditions (molar ratio)]
Na ₂ O / SiO ₂ = 1.6
SiO ₂ / Al ₂ O ₃ = 1.8
H ₂ O / Na ₂ O = 38
Specifically, the prepared liquid A is put into a 2 L stainless steel container, and this is stirred while being heated to 60 ° C., and liquid B is slowly added to and mixed with the mixture under the stirring conditions. An acid-alkali gel was used. This was aged for 3 hours under stirring at 60 ° C., then heated to 90 ° C. with further stirring, and allowed to react for 2 hours under the same conditions for 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 195 g in terms of absolute dry weight at 860 ° C.

Next, 150 g of an 860 ° C. absolute dry weight equivalent was separated from this A-type zeolite cake and dispersed in water to prepare a slurry containing 25% A-type zeolite. A 14% sulfuric acid aqueous solution in which the molar ratio of H ₂ SO ₄ to Na ₂ O in the A-type zeolite was 0.85 was slowly added under stirring at room temperature over 15 hours. The pH was 4. By such acid treatment, the alkali component is eluted and removed from the crystalline zeolite to become an amorphous product. Although the pH of the slurry shifts to the acidic side by the addition of sulfuric acid, it is preferable to adjust the pH of the slurry to be in the range of 4 to 7 in order to make it amorphous efficiently.

After 1 hour from the end of the addition of the aqueous sulfuric acid solution, the obtained amorphous substance was collected by filtration using a Nutsche (Buchner funnel), washed with water, dried, put in a crucible, and placed in a small electric furnace at 450 ° C. Baked for hours. Then, after cooling to room temperature, it was pulverized using a jet mill. The image which observed the obtained ground material with the scanning electron microscope is shown in FIG. As can be seen from FIG. 1, it was confirmed that the pulverized product had a cubic shape in which the sizes of the constituent primary particles were substantially uniform and were well dispersed. This was designated as “alumina-silica cubic particles 1” (hereinafter also simply referred to as “cubic particles 1”) (Example 1), and 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 1 are shown below.

SiO ₂ / Al ₂ O ₃ molar ratio = 2
-Crystallinity by X-ray diffraction method: amorphous (amorphous) (see Fig. 4)
・ Shape and particle size observed with a scanning electron microscope: a cube with sides of about 0.5-3μm (see Fig. 1)
-Refractive index by immersion method: 1.50
-Volume-based average particle diameter by the Cole 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 by gas adsorption method: 0.6%
-Apparent specific gravity: 0.63 g / ml
・ Ignition loss (Ig-loss): 2.7%
・ Hunter whiteness: 95%

Production Example 2 Production Method of Alumina-Silica Cubic Particles 2 (Example 2) Using 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 B solution, 298.7 g of sodium aluminate, 104.0 g of 49% sodium hydroxide aqueous solution, and 529.8 g of water were mixed and prepared. In order to obtain the following molar ratio, 795 L of liquid A and liquid B were mixed to prepare a total amount of 1800 g.
[Mixing conditions (molar ratio)]
Na ₂ O / SiO ₂ = 1.6
SiO ₂ / Al ₂ O ₃ = 1.8
H ₂ O / Na ₂ O = 44
Specifically, the prepared solution A is placed in a 2 L stainless steel container and stirred while heating to 70 ° C., and solution B is slowly added to and mixed with the solution under stirring conditions. An acid-alkali gel was used. This was aged under stirring at 70 ° C. for 2 hours, and then the alkali aluminosilicate gel was heated to 90 ° C. with stirring and reacted for 2 hours under the same conditions for crystallization. Next, 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 172 g in terms of 860 ° C. absolute dry weight.

Next, 150 g of an absolute dry weight equivalent was fractionated from the cake, and a 25% slurry was prepared in the same manner as in Production Example 1. A 14% sulfuric acid aqueous solution having an amount of 0.82 to the molar ratio of H ₂ SO ₄ to Na ₂ O in the A-type zeolite was added to this to make it amorphous, which was filtered and washed with water. And dried. Further, in the same manner as in Production Example 1, this was put in a crucible and fired at 450 ° C. for 1 hour in a small electric furnace, cooled to room temperature, and then pulverized using a jet mill. The image which observed the obtained ground material with the scanning electron microscope is shown in FIG. As can be seen from FIG. 2, the pulverized product has a cubic shape in which the sizes of the constituent primary particles are substantially uniform, and it was confirmed that the pulverized product was well dispersed. This was designated as “alumina-silica cubic particles 2” (hereinafter also simply referred to as “cubic particles 2”) (Example 2), and 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 2 are shown below.

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

Production Example 3 Production Method of Alumina-Silica Cubic Particles 3 (Example 3) Using raw materials having the same composition 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 B solution, 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. The liquid A and the liquid B were mixed by 857 L each so that the following molar ratio was obtained, and the total amount was adjusted to 1800 g.
[Mixing conditions (molar ratio)]
Na ₂ O _/ SiO ₂ = 1.6
SiO ₂ / Al ₂ O ₃ = 1.8
H ₂ O / Na ₂ O = 120
Specifically, the prepared solution A is placed in a 2 L stainless steel container and stirred while heating to 70 ° C., and solution B is slowly added to and mixed with the solution under stirring conditions. An acid-alkali gel was used. After aging for 1 hour with stirring at 70 ° C., this aluminosilicate alkali gel was heated to 95 ° C. with stirring and reacted for 24 hours under the same conditions for crystallization. Next, 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 an absolute dry weight conversion of 70 g.

Next, 65 g of an absolute dry weight equivalent was separated from the cake, and a 25% slurry was prepared in the same manner as in Production Example 1. A 14% sulfuric acid aqueous solution in such an amount that the molar ratio of H ₂ SO ₄ to Na ₂ O in the A-type zeolite was 0.95 was poured into the solution to make it amorphous, which was filtered and washed with water. And dried. Further, in the same manner as in Production Example 1, this was put in a crucible and fired at 450 ° C. for 1 hour in a small electric furnace, cooled to room temperature, and then pulverized using a jet mill. The image which observed the obtained ground material with the scanning electron microscope is shown in FIG. As can be seen from FIG. 3, it was confirmed that the pulverized product had a cubic shape in which the sizes of the constituent primary particles were substantially uniform and were well dispersed. This was designated as “alumina-silica cubic particles 3” (hereinafter, also simply referred to as “cubic particles 3”) (Example 3), and 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.

SiO ₂ / Al ₂ O ₃ molar ratio = 2
-Crystallinity by X-ray diffraction method: Amorphous (amorphous)
・ Shape and particle size observed with a scanning electron microscope: a cube with a side of about 3 to 12 μm (see FIG. 3) ・ Refractive index by immersion method: 1.50
・ Volume-based average particle diameter by the Cole 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 by gas adsorption method: 0.7%
-Apparent specific gravity: 1.01 g / ml
・ Ignition loss (Ig-loss): 2.6%
Hunter whiteness: 85%.

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

(1) Preparation of room temperature curable silicone composition In a 500 ml glass container, 6.8 parts of X-40-9250, 27.4 parts of KR-500, 1.8 parts of KF-96-1000cs, 2-propanol 54.0 parts, D-25 in a proportion of 10.0 parts, and stirred for 20 minutes at room temperature using a magnetic stirrer, silicone composition (one-part curable silicone composition) (density) : 0.90 g / cm ³ ) was prepared in an amount of 300 g. The mass reduction rate of the silicone composition upon curing is 69.5% (the mass after curing is 30.5% of the liquid mass before curing). The silicone composition is applied to the surface of a test aluminum plate in accordance with JIS H 4000, 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 .

Each of the cubic particles 1 to 3 prepared in Examples 1 to 3 was surface-treated (hydrophobized) using the room temperature curable silicone composition thus prepared as a surface treatment agent.

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

Specifically, each of the cubic particles 1 to 3 is charged into a stirrer (Kawata Supermixer Piccolo), and the surface treatment agent (room temperature curable silicone composition) is dropped over 2 minutes while stirring at 1000 rpm. Stirring was continued for 5 minutes and mixed until uniform. After standing at room temperature for 1 day, it was pulverized with a jet mill (AO jet mill manufactured by Seishin Enterprise Co., Ltd.) and hydrophobized alumina-silica cubic particles 1-1 to 3-1 (hereinafter simply referred to as “hydrophobized cubic particles”). 1-1 to 3-1 ”or“ cubic particles 1-1 to 3-1 ”) (Examples 4 to 6).

Table 1 shows the amount of the cubic particles 1 to 3, the amount of the room temperature curable silicone composition, and the surface treatment for the hydrophobized alumina-silica cubic particles 1-1 to 3-1 (Examples 4 to 6). The mass% of the silicone composition after curing with respect to the cubic particles is also described.

Production Example 5 Production Method of 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 for manufacture of is described below.
KF-9901: Methyl hydrogen polysiloxane solution (manufactured by Shin-Etsu Chemical Co., Ltd.) Alumina-silica cubic particles 1 to 3 (Examples 1 to 3)

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

Specifically, each of the cubic particles 1 to 3 was charged into a stirrer (Kawata Supermixer Piccolo), and the surface treatment agent (KF-9901 diluted solution) was added dropwise over 2 minutes while stirring at 1000 rpm. Stirring was continued for 5 minutes and mixed until uniform. The obtained powder was dried at 50 ° C. for 2 hours and then heat-treated at 180 ° C. for 3 hours. Further, it was pulverized by a jet mill (AO jet mill manufactured by Seishin Enterprise Co., Ltd.), and hydrophobized alumina-silica cubic particles 1-2, 2-2, 3-2 (hereinafter simply referred to as “hydrophobized cube particles 1- 2 to 3-2 ”or“ cubic particles 1-2 to 3-2 ”) (Examples 7 to 9).

Table 1 shows the amount of the cubic particles 1 to 3 and the amount of the KF-9901 diluent (silicone composition) for the hydrophobized alumina-silica cubic particles 1-2 to 3-2 (Examples 7 to 9). The mass% of the silicone composition after curing with respect to the cubic particles after the surface treatment is described together.

Production Example 6 Production Method of Hydrophobized Alumina-Silica Cubic Particles (Examples 10 to 24) In Production Example 4, 100 parts by mass of alumina-silica cubic particles 1 to 3 (Examples 1 to 3) after surface treatment Other than adjusting the blending amount so that the ratio of the normal temperature curable silicone composition after curing to 1 mass part or 2 mass parts (dry mass% of the normal temperature curable silicone composition: 1 mass% or 2 mass%) Were the same methods as in Production Example 4, but hydrophobized alumina-silica cubic particles 1-3 to 3-3 (dry mass%: 1 mass%) (Examples 10 to 12), and hydrophobized alumina-silica system. Cubic particles 1-4 to 3-4 (dry mass%: 2 mass%) (Examples 13 to 15) were prepared. In addition, in Production Example 5, the ratio of the cured silicone composition (methyl hydrogen polysiloxane) to 100 parts by mass of the alumina-silica cubic particles 1 to 3 (Examples 1 to 3) after the surface treatment was 1 part by mass. Alternatively, the hydrophobized alumina-silica-based cubic particles are prepared in the same manner as in Production Example 5 except that the blending amount is adjusted to 2 parts by mass (dry mass% of the silicone composition: 1 mass% or 2 mass%). 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. Hereinafter, these hydrophobized alumina-silica-based cubic particles are also simply referred to as “hydrophobized cubic particles” or “cubic particles”.

Experimental Example 1 Evaluation of Soft Focus Performance Cube 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 (Execution Example) Examples 4 to 6), cubic particles 1-2 to 3-2 hydrophobized in Production Example 5 (Examples 7 to 9), and cubic particles 1-3 to 3-3 hydrophobized in Production Example 6 (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) and commercially available true spherical silica particles 1 to 4 (hereinafter, simply referred to as “true spherical particles 1 to 4”) (Comparative Examples 1 to 4) were each made of silicone oil (KF manufactured by Shin-Etsu Chemical). -96-1000CS, with a refractive index of 1.40) and a mass ratio of 1: 9. To prepare a coating film having a thickness of about 20μm by using a coater (No.9). In preparing the coating film, the cubic particles of Examples 1 to 3 were obtained from 0.001% of the nonionic surfactant Emulgen A-500 (manufactured by Kao) before mixing with silicone oil. After being dispersed in water containing water and subjected to ultrasonic waves, the dried particles were used after removing the precipitated particles (waterpox classification). On the other hand, the data shown in Table 3 for the cubic particles of Examples 1 to 3 were used as they were mixed with silicone oil without being subjected to elutriation classification.

Soft focus property was evaluated by measuring the haze (cloudiness) of the coating film with a Haze meter (Haze-gard plus (Toyo Seiki Seisakusho) manufactured by BYK Gardner) in accordance with ASTM D1003. Table 1 shows the haze of the coatings prepared using the cubic particles of Examples 1 to 9 and the true spherical silica particles of Comparative Examples 1 to 4 as 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 the coatings prepared by mixing the cubic particles of Examples 1 to 3 with silicone oil without classifying them (Examples (1) to (3)). .

As shown in Tables 1 and 2, the alumina-silica-based cubic particles 1 to 3 of the present invention having a cubic shape (Examples 1 to 3) are more 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 by further hydrophobizing the alumina-silica-based cubic particles 1 to 3 (Examples 1 to 3) of the present invention, the Haze value can be further increased and the soft focus property can be improved ( Examples 4 to 21).

For reference, the physical properties (refractive index, volume-based average particle diameter, oil absorption, specific surface area, moisture content) of the cubic particles 1 to 3 (Examples 1 to 3) and the spherical particles 1 to 4 (Comparative Examples 1 to 4) A table comparing the amount of adsorption) is shown in Table 3.

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

(1) Evaluation method i. Cut dry pork skin for handicraft into 3.0 cm x 3.0 cm, and protect one half with cello tape (registered trademark).
ii. 0.01 g of various particles (Examples 1 to 3 and Comparative Examples 1 to 4) are applied to one half of one side that is not protected with Cellotape (registered trademark), and are conditioned by reciprocating up and down 30 times with a finger.
iii. Attach the pig skin to the center of the slide glass (2.45 cm from each end) with double-sided tape and fix it.
iv. While irradiating with a ring light in the dark room, the camera lens position was fixed at a height of 13.5 cm, the white balance was set to 4000K, and the pig skin surface was photographed.

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

◎ (Remarkably effective): The unevenness of the pig skin epidermis is not noticeable ○ (Effective): The unevenness of the pig skin epidermis is not conspicuous △ (Slightly effective): Pig skin compared to the surface where the particles are not applied The unevenness of the epidermis is blurred.
X (no effect): The unevenness of the surface of the pig skin is insufficient as compared with the surface on which no particles are applied.

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

From the results of Tables 1 and 2, the particles of the present invention having a cubic shape (Examples 1 to 3, 4 to 21) are compared with the spherical particles 1 to 4 (Comparative Examples 1 to 4). Although the weight-based average particle diameter is almost the same, it was confirmed that all have significantly high Haze values and high soft focus properties. The reason is that the refractive index is high and the particles of the present invention are in a cubic shape. In general, porous particles are said to have high light dispersibility and high soft focus, but the particles of the present invention are hardly porous due to their specific surface area, moisture adsorption amount and oil absorption amount. In addition, the present invention particles and the true spherical particles 3 (Comparative Example 3) are similar in weight-based average particle diameter, specific surface area, moisture adsorption amount, and oil absorption amount. However, since the Haze value of the particles of the present invention is significantly higher, the difference can be attributed to the fact that the particles of the present invention have a high refractive index and are not spherical but cubic. In addition, although it is not a result of this invention particle | grains, the comparison of the spherical particle 1 (comparative example 1) and the spherical particle 3 (comparative example 3), the spherical particle 2 (comparative example 2), and the spherical particle 4 (comparison) From the comparison with Example 4), the Haze value (soft focus property) is higher for particles with low oil absorption, specific surface area, and moisture adsorption, that is, particles that are difficult to say porous (including non-porous). A trend was observed. This also indicates that the porous particle has less oil scattering effect at the interface because the solvent oil penetrates into the pores and gets wet, so the difference in refractive index between the oil and silica is smaller than the difference in refractive index between air and silica. It seems that the haze value (soft focus property) has become low. From the results in Tables 1 and 2, it was confirmed that even in the present invention particles having a cubic shape, the Haze value is increased and the soft focus property is improved by hydrophobizing the surface. The effect was well recognized by room temperature curing silicone treatment. Further, it was recognized that as the surface treatment amount for hydrophobization increases, the Haze value tends to increase.

Further, from the results in Table 3, the particles of the present invention (Examples 1 to 3, 4 to 21) having an alumina-silica cubic shape are compared with the silica spherical particles 1 to 4 (Comparative Examples 1 to 4). Although the weight-based average particle size was almost the same, all had a significantly high concealment effect. Since the spherical particles 1 to 4 are spherical particles, they are easily filled into the skin crevice such as wrinkles. As a result, the distribution density of wrinkles increases, and the wrinkles are conspicuous. On the other hand, the particles of the present invention that are in the shape of a cube have a large flat surface fixing area, or a plurality of particles are entangled, and when spread on the skin surface, the particles do not fall into the skin grooves such as pores and small wrinkles. It is considered that the unevenness can be satisfactorily covered by covering the skin so as to close the skin and cover the skin without falling into the skin groove. It was recognized that the hiding effect (skin covering effect, unevenness correcting effect) of the particles of the present invention tended to increase as the weight-based average particle size increased.

Each particle (Examples 1 to 21 and Comparative Examples 1 to 4) had a good touch and also had good sliding properties on dried pork skin. In particular, the particles of the present invention (Examples 1 to 3) and the hydrophobized particles (Examples 4 to 21) having an alumina-silica cubic shape have both appropriate slip properties and retention properties, and are smooth on the skin. It is expected to have excellent adhesion to the skin by being able to spread on the skin and staying moderately.

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

In addition, in order to use for a friction tester, the test sample was prepared by the following method.
(I) Weigh 5 mg of the test sample.
(Ii) Artificial skin with a width of 3 cm on a friction tester (Supplare (registered trademark) manufactured by Idemitsu Techno Fine: Top: 100% polyurethane (containing protein powder), base fabric: 80% rayon, 20% nylon) Put.
(Iii) The weighed test sample is dispersed and placed on the artificial skin, and is uniformly applied in a 3 × 8 cm range with rubber gloves.
(Iv) Under the conditions of a load of 25 g and a speed of 1 mm / second, automatic measurement by a friction tester is performed to obtain an average friction coefficient (MIU).
(V) This operation is performed three times, and the average value is defined as the average friction coefficient.

Table 3 shows the measurement results.

Experimental Example 4 Evaluation of hiding effect and blurring effect (optical evaluation)
Cubic particles 1 to 3 (Examples 1 to 3), hydrophobized cubic particles 1-1 to 3-1 (Examples 4 to 6), 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 the hiding effect by the following method. Specifically, each test sample was applied to dried pork skin, and the concealing effect and the blurring effect on the substrate were optically evaluated. Dried pork skin is composed of an elliptical convex part of 50 to 100 microns with concaves and convexes of several microns on the surface, a concave part (groove) having a width of 5 to 20 μm and a depth of 5 to 20 μm, and has a small wrinkle. It is a skin model similar to human skin (skin). In addition, it can be said that it is an outstanding cosmetic raw material, so that a numerical value is small in both the concealment index and the wrinkle blurring index.

[Evaluation procedure for concealment index and blurring index]
(1) Apply 0.1 g of the test sample to half of 3 cm × 3 cm dry pork skin for handicrafts.
(2) The pig skin is pasted in an area 2.45 cm away from both ends of a slide glass (width 7.9 cm). (3) A lens (M.ZUIKO DIGTAL manufactured by Olympus Co., Ltd.) is irradiated with a ring light (LED ring illumination LED-R72 for stereo microscopes manufactured by Arm Systems Co., Ltd., intensity 2.0) in a dark room where light is blocked. ED 30mm f3.5 Macro) (OLYMPUS PEN E-PL8 manufactured by Olympus Co., Ltd.) is adjusted and fixed so that the distance between the lens and the slide glass (test sample) is 13.3 cm. (Shooting conditions: white balance 4000K, aperture value F5.6, shutter speed 1/125 sec, ISO sensitivity 1250 in manual mode).
(4) Calculation of brightness by image editing:
Captured images are taken on a PC installed with processing software (ex. Free software Gimp), and a dry pig skin area where the test sample is not applied (application area) and a dry pig skin area where the test sample is applied (non-application area) For each of the above, randomly select 50 pixels on the uneven part.
(5) Each pixel is subjected to SUV conversion, the brightness (V value) is measured for each of the concave and convex portions in each region (coating region, non-coating region), and the average value is calculated.
(6) The average value obtained is applied to the following equation to evaluate the hiding property and blurring property. According to the following formula, both the concealment index and the blurring characteristic index show better tendencies as the values are closer to zero.

[Equation 4]
Concealment index = V'convex-V convex 皺 Blurability index = V'convex-V 'concave V convex: Average brightness value of the convex part of the dried pig skin not coated with the test sample V' convex: Test sample applied Brightness average value of convex part of dried pork skin V ′ concave: Brightness average value of concave part of dry pig skin coated with test sample Table 4 also shows the measurement results.

From the results shown in Table 4, it was recognized that the average friction coefficient of the hydrophobic particles made from room temperature-curing silicone tended to decrease as the surface treatment amount (hydrophobic coating amount) increased. However, in the case of 10 μm particles having a large particle size, the average friction coefficient tended to increase conversely when the coating amount of the room temperature curing silicone was 6 wt%. In the same way as above, hydrophobized particles with methyl hydrogen polysiloxane (KF-9901) showed a tendency that the average friction coefficient decreased as the surface treatment amount (hydrophobic coating amount) increased. Was less than room temperature cured silicone. In particular, when the particle diameter is 10 μm, KF-9901 remains excessively in the 6 wt% treatment, so that the friction coefficient increases. From this, it was confirmed that the hydrophobized surface treatment with the silicone composition can achieve a great effect even when a small amount of the silicone composition is used. On the other hand, if the amount of the silicone composition is larger than necessary, not only the effect is reduced, but also the mixing workability is deteriorated, and the presence of the excess silicone composition makes the particle surface wet and crushing work. There was 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 the following test particles, a powder foundation is prepared according to the following formulation.
(Powder foundation)
Component Blending amount (% by mass)
(1) Silicone-treated talc 10.00
(2) Silicone-treated sericite 33.80
(3) Silicone-treated synthetic phlogopite 10.00
(4) Silicone-treated titanium oxide 10.00
(5) Silicone-treated iron oxide 3.00
(6) Silicone-treated zinc oxide 2.00
(7) Polymethyl methacrylate 7.00
(8) Boron nitride 3.00
(9) Methylparaben 0.20
(10) Test particle (Example) 10.00
(11) Methyl polysiloxane 4.90
(12) Dioctyl succinate 4.00
(13) Squalane 2.00
(14) Fragrance 0.10
Total 100.00

Specifically, the above components (1) to (10) are uniformly mixed with a Henschel mixer, the remaining binder components (11) to (14) are added, mixed, and then pulverized again. And passed through the sieve. This is compression molded into a metal pan 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 following test particles, a makeup base is prepared according to the following formulation.
(Makeup base)
Component Blending amount (% by mass)
(1) Methyl glucoside sesquistearate 1.00
(2) Sodium stearoyl lactate 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) Butylparaben 0.10
(10) Purified water 51.94
(11) Synthetic sodium silicate / magnesium 1.00
(12) Hydroxyethane diphosphonic 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 particle (Example) 5.00
(18) Methyl polysiloxane 0.50
Total 100.00

Specifically, in the above formulation, the water phase components (10) to (13) are stirred and mixed and heated to 85 ° C. Oil phase components (1) to (9) are mixed and dissolved by heating to 80 ° C. Thereafter, the above-mentioned aqueous phase component is added to this oil phase component and preliminarily emulsified, and uniformly emulsified with a homomixer. Then, the homomixer is stopped and stirring is continued, while the components (14) to (14) to (14) are dissolved. Add the mixture up to 17). Subsequently, cooling is started and component (18) is added at about 70 ° C., and 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 following test particles, an oily foundation is prepared according to the following formulation.
(Oil foundation)
Component Blending amount (% by mass)
(1) Liquid paraffin 18.00
(2) Isopropyl palmitate 15.00
(3) Liquid lanolin 4.50
(4) Microcrystalline wax 4.50
(5) Ceresin 10.00
(6) Carnavalou 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 particle (Example) 8.00
(14) Fragrance 0.30
Total 100.00

Specifically, in the above formulation, the components (1) to (8) are melted by heating at 80 ° C., and the mixture of (9) to (12) is added thereto. The mixture is kneaded with a roll mill, heated and melted again, and (13) is added thereto and mixed uniformly. After defoaming this, (14) is added, poured into an inner pan 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 test particles below, lipstick is prepared according to the following formulation.
(Lipstick prescription)
Component Blending amount (% by mass)
(1) Ceresin 10.00
(2) Microcrystalline wax 2.00
(3) Carnauba 1.00
(4) Synthetic hydrocarbon wax 2.00
(5) Isopropyl dimer acid 15.00
(6) Tri (capryl / capric acid) glycerin 34.35
(7) Dipentaerythritol fatty acid ester 3.50
(8) Vitamin E 0.10
(9) Polyglyceryl triisostearate 12.00
(10) Coloring 7.00
(11) Synthetic phlogopite 10.00
(12) Test particle (Example) 3.00
(13) Fragrance 0.05
Total 100.00

Specifically, the components (9) to (12) of the above prescription are dispersed with a roller mill. Thereafter, components (1) to (8) are heated and melted, and the mixture of components (9) to (12) and component (13) are added and mixed well. Filter, pour into a mold at high temperature, cool and mold into a container to obtain a lipstick. The obtained lipstick is excellent in soft focus property even if the powder is blended in a state where it is wet with oil, and makes it difficult to see the vertical lines of the lips.

Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Modifications of the present invention apparent to those skilled in the art are intended to be included within the scope of the following claims.

The cosmetic additive of the present invention is added to cosmetics.

Claims

Having alumina-silica particles,
A cosmetic additive, wherein the alumina-silica-based particles have the following characteristics:
(1) It consists of cubic primary particles having a side length of 0.3 to 20 μm as observed with a scanning electron microscope.
(2) The refractive index by the immersion method is 1.48 to 1.52.
(3) The volume-based average particle size by Coulter counter method is 1 to 20 μm.
(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 BET method is 20 m < 2 > / g or less.
The cosmetic additive according to claim 1, wherein the alumina-silica-based particles further have the following characteristics:
(6) The moisture adsorption amount by the gas adsorption method is 0 to 5%.
The alumina - silica based particles, and wherein the molar ratio of SiO 2 / Al 2 O 3 has a composition in the range of 1.8 to 5, X-ray diffraction studies to substantially amorphous The cosmetic additive according to claim 1.
A cosmetic additive comprising hydrophobized alumina-silica particles obtained by hydrophobizing the surface of the alumina-silica particles according to claim 1.
The cosmetic additive according to claim 4, wherein the hydrophobized alumina-silica-based particles are obtained by coating the surface of the alumina-silica-based particles with a cured product of the following normal temperature curable silicone composition.
The room temperature curable 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 an alkoxy group-containing siloxane unit that does not contain a dialkylsiloxane unit and contains an alkoxy group;
With 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 kinematic viscosity at 25 ° C. of the silicone oil is 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 more.
The cosmetic additive according to claim 4, wherein the hydrophobized alumina-silica particles are obtained by coating the surfaces of the alumina-silica particles with methyl hydrogen silicone oil and subjecting them to a heating surface treatment.
The cosmetic additive according to claim 1, wherein the cosmetic additive is a soft focus property imparting agent, a hiding effect imparting agent (concave / convex correction agent), and / or an extensibility imparting agent.
A method for producing alumina-silica-based particles having a hydrophobic surface, comprising the following steps (A) and (B) or (C):
(A) Step of coating the surface of the alumina-silica-based particles with a room temperature curable silicone composition:
Here, the room temperature curable 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 an alkoxy group-containing siloxane unit that does not contain a dialkylsiloxane unit and contains an alkoxy group;
With 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 kinematic viscosity at 25 ° C. of the silicone oil is 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;
A vapor pressure of the organic solvent at 20 ° C. of 1 kPa or more, and (B) a step of curing the room temperature curable silicone composition coated on the surface of the alumina-silica particles; or (C) the alumina-silica A process in which the surfaces of the system particles are coated with methyl hydrogen silicone oil and then heat-treated.
A cosmetic comprising the cosmetic additive according to claim 1.
10. The cosmetic according to claim 9, containing the cosmetic additive in a proportion of 1 to 50% by mass.
The cosmetic according to claim 10, which is a makeup cosmetic.