JP2011256098A - Method for producing silica-based particle, silica-based particle and application of the silica-based particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing silica-based particles, having substantially no cavity in the interior portion of the particle, wherein the interior portion is porous or nonporous (not porous), or silica-based particles having an outer shell and having a cavity inside the outer shell, wherein the outer shell is porous or nonporous, and silica-based fine particles having an outer shell and having a cavity inside the outer shell, wherein the outer shell is porous or nonporous and the interior portion is kept under negative pressure.SOLUTION: The method comprises: (a) a step of preparing silica-based particle precursor particles by spray-drying an alkali silicate aqueous solution in a hot air flow; (b) a step of immersing the silica-based particle precursor particles in an acid aqueous solution to remove the alkali; and (c) a step of drying and heat-treating the resulting particles.

Description

  The present invention relates to a method for producing silica-based fine particles, the silica-based fine particles, and a cosmetic, a resin composition, and a heat insulating material containing the silica-based fine particles.

Silica-based particles are known in various shapes and sizes, and their uses are diverse.
Silica fine particles and silica colloidal fine particles having an average particle size of nano-order are used as various fillers. Further, the applicant of the present application suitably uses silica-based fine particles having cavities inside as low-refractive index fillers. It is disclosed. (Japanese Patent Laid-Open No. 2001-233611: Patent Document 1)

Further, an inorganic oxide fine particle aggregate having an average particle diameter of 1 to 100 μm in which inorganic oxide fine particles having an average particle diameter of 2 to 250 nm are aggregated, and spherical porous particles in which this is coated with a silica-based coating layer, It is disclosed that when porous particles are used as a filler for cosmetics, a light effect is obtained by using particles that are very light, soft and have good elongation, and have a low refractive index. (Japanese Unexamined Patent Application Publication No. 2002-160907: Patent Document 2, WO2004 / 006873 International Publication: Patent Document 3)
However, the refractive index of the spherical porous particles and non-porous particles is not necessarily high, and when the refractive index is lowered, the strength of the particles is lowered, and there is a limitation in use. In addition, for these particles, first, a silica sol having a particle size of the order of nm is prepared, and this is spray-dried to prepare an inorganic oxide fine particle aggregate having an average particle size of 1 to 100 μm, and then a silica coating layer Therefore, there is a limitation in cosmetics and other uses.

JP-A-2005-206436 (Patent Document 4) discloses an amorphous spherical silica hollow having an average particle diameter of 0.5 to 8 μm, a sphericity of 0.85 or more, and an average hollowness of 20 to 70% by volume. A powder and a production method thereof are disclosed, and it is disclosed that the powder is excellent in strength, lightness, heat insulation, low dielectric properties, and the like.
However, the amorphous spherical silica hollow powder is obtained by supplying a silica raw material powder having a specific surface area of 40 m ² / g or more and an average particle diameter of 10 μm or less into a high-temperature flame to make it spherical and hollow. In addition, there are particles having a particle size about 5 times the average particle size, the particle size distribution is non-uniform, the application is limited, and in order to make the particle size more uniform, the particle size distribution of the silica raw material powder is more It is necessary to make it uniform, and it is easy to select particles in which fine particles are fused on the particle surface, which is unsuitable for applications requiring smooth surface.

JP-A-4-2607 (Patent Document 5) discloses that a water glass aqueous solution is sprayed in a low-temperature combustion region of 200 to 500 ° C. in a combustion gas flow flowing in a sealed cylindrical furnace, and dealkalized. A method is disclosed in which the produced glass fine particle intermediate is retained in a high-temperature furnace at 1300 ° C. or higher for a certain period of time, foamed by rapid dehydration, and converted into a silica balloon.
However, as a result of testing this method, the present applicant has found that dealkalization is difficult, and even if it is not possible, it is not reproducible. Then, when the particles are fused when exposed to a high temperature of 1300 ° C. or higher without adding hydrocarbons. There was a problem.

Furthermore, in Japanese Patent Application Laid-Open No. 4-104907 (Patent Document 6), an alkali metal silicate aqueous solution is atomized and introduced into an air stream at 100 to 500 ° C. to form a glass balloon to adjust the removal amount of alkali metal. Thus, a method for producing a silica balloon in which the pore diameter of the silica balloon is controlled is disclosed. At this time, spray drying and ultrasonic vibration are employed as the atomizing method.
However, as a result of a test conducted by the applicant of the present invention in accordance with the spray drying method, it was difficult to efficiently obtain a desired silica balloon because a part of the glass balloon was dissolved in the alkali metal removal step.
Moreover, the silica balloon obtained was only a porous silica balloon having pores, and non-porous particles having cavities inside could not be obtained.

  As a result of intensive studies on the above problems, the present inventors have spray-dried an alkali silicate aqueous solution having a predetermined concentration, and immersed in an aqueous solution containing an amount of acid sufficient to remove alkali in the particles obtained by spraying. Thus, the present invention was completed by finding that silica particles having voids inside can be obtained by removing the alkali and silicifying the particles.

JP 2001-233611 A JP 2002-160907 A WO2004 / 006873 International Publication JP 2005-206436 A JP-A-4-2607 JP-A-4-104907

  The present invention includes a silica-based particle having a spherical particle shape, substantially no void inside the particle, and porous or non-porous (non-porous) inside, or an outer shell. Silica-based particles having a void in the outer shell and a porous or non-porous outer shell, and further having an outer shell, a void inside the outer shell, the outer shell being non-porous, and a negative inside It is an object of the present invention to provide a method for producing silica-based particles that is a pressure, a silica-based fine particle, and a cosmetic, a resin composition, and a heat insulating material containing the same.

The method for producing silica-based particles of the present invention is characterized by comprising the following steps (a) to (c).
(A) A step of preparing silica-based particle precursor particles by spray drying an alkali silicate aqueous solution in a hot air stream (b) A step of immersing the silica-based particle precursor particles in an acid aqueous solution to remove alkali (c) Drying・ Process to heat treatment

The SiO ₂ / M ₂ O molar ratio (wherein M represents an alkali metal) of the alkali silicate aqueous solution is in the range of 1 to 5, and the SiO ₂ concentration is preferably in the range of 1 to 30% by weight. .
It is preferable that the inlet temperature of hot air in the spray drying is in the range of 150 to 600 ° C and the outlet temperature is in the range of 40 to 300 ° C.
In the step (b), the molar ratio (Ma) / (Msp) between the number of moles of M ₂ O (Msp) and the number of moles of acid (Ma) in the silica particle precursor particles is 0.6 to 4.7. in the range, the concentration of the silica-based particles precursor particles is preferably in the range of 1 to 30 wt% as SiO _2.
The drying / heat treatment temperature in the step (c) is preferably in the range of 30 to 1200 ° C.

The method for producing silica-based particles of the present invention preferably produces silica-based particles having an average particle diameter in the range of 0.1 to 200 μm.
It is preferable that the inlet temperature in the spray drying is in the range of 150 to 300 ° C, the outlet temperature is in the range of 40 to 120 ° C, and the porosity of the silica-based particles obtained is less than 20% by volume.
It is preferable that the drying / heat treatment temperature in the step (c) is in the range of 30 to 120 ° C., and the silica-based particles obtained are porous.
It is preferable that the drying / heat treatment temperature in the step (c) is in the range of 90 to 1200 ° C., and the resulting silica-based particles are non-porous.

The inlet temperature in the spray drying is in the range of 300 to 600 ° C., the outlet temperature is in the range of 120 to 300 ° C., the resulting silica-based particles have an outer silica layer, and the porosity inside the outer shell is 20 It is preferable to be in the range of ~ 95% by volume.
It is preferable that the drying / heat treatment temperature in the step (c) is in the range of 30 to 120 ° C., and the outer silica layer of the obtained silica-based particles is porous.
It is preferable that the drying / heating temperature in the step (c) is in the range of 90 to 1200 ° C., and the outer silica layer of the obtained silica-based particles is nonporous.

It is preferable that the drying / heating treatment in the step (c) is performed under reduced pressure, and the inside of the outer shell layer of the obtained silica-based particles has a negative pressure.
The silica-based fine particles of the present invention have an average particle diameter in the range of 0.1 to 200 μm, have a cavity inside the outer shell silica layer, and the void ratio in the range of 20 to 95% by weight, The outer shell silica layer is nonporous, and the inside of the cavity is negative pressure.
The negative pressure inside the cavity is preferably 133 hPa or less.

The cosmetic of the present invention is characterized in that the silica-based particles described above are blended in the range of 0.1 to 30% by weight.
The resin composition of the present invention is characterized in that the silica-based particles described above are blended in an amount of 1 to 90% by weight.
The heat insulating material of the present invention is characterized by having silica shell particles having the outer shell silica layer described above and having a void ratio in the range of 20 to 95% by volume inside the outer shell.

According to the present invention, the particle shape is spherical, the inside of the particle is substantially free of cavities, the inside is porous or non-porous (non-porous) silica-based particle, or the outer shell, Silica-based particles having a void inside the shell and the outer shell being porous or non-porous, and further having an outer shell having a void inside the shell and the outer shell being porous or non-porous In addition, silica-based fine particles having a negative pressure inside can be easily and economically produced.
Moreover, according to this invention, the cosmetics, heat insulating material, and resin composition using the said silica type particle can be provided.

[Method for producing silica-based particles]
Below, the manufacturing method of the silica type particle which concerns on this invention is demonstrated first.
The method for producing silica-based particles according to the present invention is characterized by comprising the following steps (a) to (c).
(A) A step of preparing silica-based particle precursor particles by spray drying an alkali silicate aqueous solution in a hot air stream (b) A step of immersing the silica-based particle precursor particles in an acid aqueous solution to remove alkali (c) Drying・ Process to heat treatment

Step (a)
An aqueous silica silicate solution is spray-dried in a hot air stream to prepare silica-based particle precursor particles.
As the alkali silicate used in the present invention, sodium silicate and potassium silicate soluble in water are usually used.
The SiO ₂ / M ₂ O molar ratio of alkali silicate (where M represents an alkali metal) is preferably in the range of 1 to 5, more preferably 2 to 4.
When the SiO ₂ / M ₂ O molar ratio of the alkali silicate is less than 1, the alkali amount is too large, so that not only acid cleaning in the step (b) described later becomes difficult, but also the deliquescence of the spray-dried product is remarkable. Therefore, silica-based fine particles may not be obtained.
When the SiO ₂ / M ₂ O molar ratio of the alkali silicate exceeds 5, the solubility of the alkali silicate is reduced, and it is difficult to prepare an aqueous solution. Even if it is possible, silica fine particles of several nm or less are generated in the aqueous solution. In some cases, silica-based particle precursor particles that can be used in the present invention may not be obtained even by spray drying.

The concentration of the alkali silicate aqueous solution as SiO ₂ is preferably in the range of 1 to 30% by weight, more preferably 5 to 28% by weight.
When the concentration of the alkali silicate aqueous solution as SiO ₂ is less than 1% by weight, it may be inefficient when productivity is taken into consideration.
If the concentration of the alkali silicate aqueous solution as SiO ₂ exceeds 30% by weight, the stability as the alkali silicate aqueous solution is remarkably lowered and the viscosity may become high and spray drying may be difficult. In some cases, the diameter distribution, the thickness of the outer shell, and the like are extremely nonuniform, and the application may be limited.

  The alkali silicate aqueous solution is spray-dried in a hot air stream, and the spray-drying method is not particularly limited as long as silica-based fine particles to be described later can be obtained. This method can be adopted. In the present invention, the two-fluid nozzle method is suitable for obtaining particles having cavities inside.

It is preferable that the inlet temperature of hot air in spray drying is in the range of 150 to 600 ° C and the outlet temperature is in the range of 40 to 300 ° C.
When the inlet temperature of hot air is less than 150 ° C., drying may be insufficient, and silica-based particle precursor particles having cavities in the interior cannot be obtained, and silica-based particle precursor particles having no internal cavities are obtained. Even if obtained, the drying is insufficient, the adhesion to the wall of the spray drying chamber is severe, and the yield may be significantly reduced.
When the hot air inlet temperature exceeds 600 ° C., silica-based particle precursor particles having no internal cavities cannot be obtained. Furthermore, even when silica-based particle precursor particles having cavities inside are obtained, the drying is too fast, so that the particle diameter increases and the outer shell thickness decreases, and the silica-based particle precursor particles are easily broken. This is not preferable. In addition, it is not economical because high-temperature equipment is required.

When the outlet temperature of the hot air was less than 40 ° C., drying was insufficient, and not only silica-based particle precursor particles having cavities inside but also silica-based particle precursor particles having no internal cavities were obtained. However, the adhesion to the spray drying chamber wall surface and the like is severe, and the yield may be significantly reduced.
When the outlet temperature of hot air exceeds 300 ° C., silica-based particle precursor particles having no internal cavities cannot be obtained. Furthermore, even when silica-based particle precursor particles having cavities inside are obtained, the drying is too fast, so that the particle diameter increases and the outer shell thickness decreases, and the silica-based particle precursor particles are easily broken. This is not preferable.

  The precursor particles here are alkali silicate particles obtained by spray-drying an alkali silicate aqueous solution, and are silica-based by removing the alkali by an acid aqueous solution dipping step in a later step (b) described later. It is the thing of the previous stage which becomes a particle.

In the present invention, when producing solid silica-based particles (first aspect), the inlet temperature in the spray drying is in the range of 150 to 300 ° C, more preferably 160 to 250 ° C, and the outlet temperature is 40 to 120. It is preferable that it exists in the range of 50 degreeC and also 50-100 degreeC.
At this time, when the inlet temperature in spray drying is less than 150 ° C., even if silica-based particle precursor particles without internal cavities are obtained, the drying is insufficient and the adhesion to the spray drying chamber wall surface is severe and The rate may decrease significantly.
When the inlet temperature in spray drying exceeds 300 ° C., it may be difficult to obtain particles without cavities inside, although it varies depending on the outlet temperature.

When the outlet temperature of the hot air is less than 40 ° C., the drying becomes insufficient, the adhesion to the spray drying chamber wall surface and the like is severe, and the yield may be significantly reduced.
If the outlet temperature of the hot air exceeds 120 ° C., it may be difficult to obtain particles having no cavities inside, depending on the inlet temperature.

In the present invention, when producing hollow silica-based particles (second embodiment), the inlet temperature in the spray drying is in the range of 300 to 600 ° C, more preferably 350 to 550 ° C, and the outlet temperature is 120 to 300 ° C. Furthermore, it is preferable that it exists in the range of 130-250 degreeC.
At this time, when the inlet temperature in spray drying is less than 300 ° C., it may vary depending on the outlet temperature, but silica-based particles having cavities inside may not be obtained.
When the inlet temperature in spray drying exceeds 600 ° C., ruptured silica-based particle precursor particles are formed, and it may be difficult to obtain silica-based particles having cavities therein. However, the thickness of the outer shell may be reduced, and the strength of the resulting silica-based particles may be insufficient.

When the outlet temperature of hot air is less than 120 ° C., silica-based particles having cavities inside may not be obtained.
When the outlet temperature of the hot air exceeds 300 ° C., the silica-based particle precursor particles in a bursting state are formed, and it may be difficult to obtain silica-based particles having cavities inside. However, the thickness of the outer shell may be reduced, and the strength of the silica-based particles obtained may be insufficient.

Step (b)
Silica-based particle precursor particles are immersed in an acid aqueous solution to remove alkali.
Examples of the acid include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as acetic acid, tartaric acid, and malic acid. Usually, such an acid is used, but a cation exchange resin or the like can also be used. In the present invention, mineral acids such as hydrochloric acid, nitric acid and sulfuric acid are preferably used.

When the silica-based particle precursor particles are immersed in the acid aqueous solution, the molar ratio (Ma) / (Msp) between the number of moles of M ₂ O (Msp) and the number of moles of acid (Ma) in the silica particle precursor particles is 0. It is preferable to immerse so that it may become the range of 1.6-4.7, and also 1-4.
When the molar ratio (Ma) / (Msp) is less than 0.6, the amount of acid relative to M ₂ O is too small, so that condensation of silicic acid, which is considered to occur along with the removal of alkali, silica of silicic acid In some cases, the skeletonization does not proceed and the silica-based particle precursor particles are partially dissolved, or the dissolved alkali silicate is gelled.
Even if the molar ratio (Ma) / (Msp) exceeds 4.7, the above-described condensation and skeletonization of silicic acid does not proceed, and the acid is excessive and not economical.

The concentration of the silica-based particle precursor particles when immersed in an aqueous acid solution is 1 to 30 wt% as SiO _2, and more preferably in the range of 5 to 25 wt%.
The concentration of the silica-based particle precursor particles when immersed in aqueous acid solution in the case of less than 1% by weight SiO _2, alkali removal, there is no problem in cleanability production efficiency decreases. Further, depending on the molar ratio of the acid and silica described above and the silica and alkali molar ratio of the alkali silicate, the concentration of the acid may be lowered, and the silica-based particle precursor particles may be partially dissolved or dissolved silicic acid. The alkali may gel.
If the concentration of the silica-based particle precursor particles when immersed in an acid aqueous solution exceeds 30% by weight as SiO ₂ , the concentration may be too high and alkali removal and cleaning efficiency may be reduced. When the particle diameter of the particles is small, the viscosity of the dispersion is particularly high, and alkali removal and cleaning efficiency may be reduced.

The conditions for removing the alkali are not particularly limited as long as the alkali can be removed, but the temperature is generally in the range of 5 to 70 ° C. and the time is in the range of 0.5 to 24 hours.
Subsequently, it wash | cleans by a conventionally well-known method. For example, it may be filtered and washed with pure water.
In the present invention, the alkali removal and washing can be repeated as necessary.

The remaining amount of alkali after washing varies depending on the use, but it is preferably 0.5% by weight or less, more preferably 0.1% by weight or less as M ₂ O.
According to the method of the present invention, when the silica-based particle precursor is immersed in an acid aqueous solution under the above-described conditions, the residual amount of alkali does not exceed 0.5 wt% as M ₂ O, but 0.5 wt% If it exceeds, when used as a cosmetic, for example, when dispersed in water, the pH of the dispersion becomes extremely high, so that the stability in the cosmetic formulation may be significantly inhibited, and the efficacy of the cosmetic may be inhibited.

Step (c)
Next, it is dried and heated.
The drying / heat treatment temperature is preferably in the range of 30 to 1200 ° C.
When producing solid silica-based particles according to the present invention (first embodiment) that are porous and hollow silica-based particles (second embodiment) that have a porous outer shell The drying / heat treatment temperature is preferably 30 to 120 ° C, more preferably 40 to 100 ° C.

When the drying / heat treatment temperature is less than 30 ° C., a large amount of adhering water remains, and there is a problem that productivity is reduced because the drying treatment takes a long time in addition to the limitation of use.
If the drying / heat treatment temperature exceeds 120 ° C., the pores formed when the alkali is removed may disappear and porous silica-based particles and porous silica-based particles may not be obtained.
Note that, for example, the drying / heating treatment is performed at 120 ° C., and the porous silica-based particles and the outer shell are porous without disappearing even if the second drying / heating treatment is performed at a higher temperature. Quality silica-based particles may be obtained.

Solid silica-based particles according to the present invention (first embodiment) that are nonporous and hollow silica-based particles (second embodiment) that have non-porous outer shells are produced. In this case, the drying / heat treatment temperature is preferably in the range of 90 to 1200 ° C, more preferably 110 to 1150 ° C.
When the drying / heat treatment temperature is less than 90 ° C., pores may not disappear, and non-porous silica-based particles or silica-based particles having a non-porous outer shell may not be obtained.
Even if the drying / heating temperature exceeds 1200 ° C, it does not become non-porous, and the particle strength does not improve, resulting in aggregate particles that are difficult to disperse depending on the temperature and particle size. There is.

[Silica particles]
The solid silica-based particles (first aspect) according to the present invention are preferably substantially free of voids inside and preferably have a porosity of less than 20% by volume.
Here, the porosity is determined by measuring a TEM photograph of particles, measuring the particle size of 50 particles, measuring the average particle size as the average value, and then breaking the particles by half. The diameter of the cavity is measured for each piece of fracture, the average diameter of the cavity is determined, and the average cavity volume ratio of the cavity is determined by calculation. Note that the hollow portion is spherical. Furthermore, the porosity does not include the pore volume of the porous portion.
When the porosity exceeds 20% by volume, the outer shell portion is reduced, and when the outer shell portion is used for useful applications such as an adsorbent and an oil absorbent, the adsorbed amount and the oil absorbed amount may be insufficient. .

The hollow silica-based particles (second aspect) according to the present invention preferably have cavities in the interior and have a particle porosity of 20 to 95% by volume, more preferably 25 to 90% by volume.
When the porosity is less than 20% by volume, the refractive index is not sufficiently low, and a sufficient heat insulating effect may not be obtained even when used as a heat insulating material.
It is difficult to obtain a silica-based particle having a porosity of more than 95% by volume. Even if it is obtained, the shell may become thin depending on the particle diameter, and the particle strength may be insufficient.

  The silica-based particles of the present invention have an average particle diameter in the range of 0.1 to 200 μm in any aspect. Those having an average particle diameter of less than 0.1 μm and those having an average particle diameter exceeding 200 μm are difficult to produce using the spray drying method in view of productivity using the spray drying method.

When the hollow silica-based particles (second aspect) are produced, when the drying / heating treatment is performed under reduced pressure, silica particles having a negative pressure inside the outer shell layer of the obtained silica-based particles can be obtained. .
The spherical silica-based particles obtained at this time have a low refractive index, and when used in cosmetics, the effects of silica-based particles such as lubricity, the effect of blurring skin defects and transparency can be obtained. Moreover, when it uses as a heat insulating material, it is excellent in the heat insulation effect.

Therefore, the silica-based particles obtained by drying and heat treatment under reduced pressure have an average particle diameter in the range of 0.1 to 200 μm and have cavities inside the outer shell silica layer, and the porosity of the cavities. Is in the range of 20 to 95% by weight, the outer silica layer is non-porous, and the inside of the cavity is negative pressure.
The negative pressure inside the cavity is preferably 133 hPa or less.
Silica-based particles having a negative pressure inside the cavity have a low refractive index and excellent heat insulating properties.

[Cosmetics]
The cosmetic according to the present invention is characterized by blending silica-based particles obtained by any one of the production methods described above.
In the cosmetic according to the present invention, the amount of the silica-based particles is preferably in the range of 0.1 to 30% by weight, and particularly preferably in the range of 1 to 20% by weight. If the blending amount of the silica particles is less than 0.1% by weight, the blending effect of the silica particles such as lubricity, the effect of blurring the skin, and the transparency cannot be obtained. The required colorability, oiliness, etc. may be impaired.

In addition, when blending the silica-based particles of the present invention into cosmetics, the surface thereof is conventionally known surface treatment agents such as silicone compounds, fluorine compounds, metal soaps, silane coupling agents, titanate coupling agents, amino acids. Or lecithin may be used.
The cosmetic composition of the present invention is composed of the silica-based particles and components that are usually blended in the cosmetic composition, for example, oils such as olive oil, rapeseed oil, and beef tallow, jojoba oil, carnauba wax, candelilla wax, beeswax and the like. Waxes, paraffin, squalane, synthetic and vegetable squalane, α-olefin oligomers, microcrystalline wax, hydrocarbons such as pentane, hexane, fatty acids such as stearic acid, myristic acid, oleic acid, α-hydroxy acid, Isostearyl alcohol, octyldodecanol, lauryl alcohol, ethanol, isopropanol, butyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, behenyl alcohol, and other alcohols, alkyl glyceryl ethers, isopropyl myristate, palmimi Esters such as isopropyl acetate, ethyl stearate, ethyl oleate, cetyl laurate, decyl oleate, polyhydric alcohols such as ethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, glycerin, diglycerin, sorbitol, Sugars such as glucose, sucrose and trehalose, methylpolysiloxane, methylhydrogenpolysiloxane, methylphenyl silicone oil, various modified silicone oils, silicone oils such as cyclic dimethylsilicone oil, fluorine oils such as perfluoropolyether, gum arabic Carrageenan, agar, xanthan gum, gelatin, alginic acid, guar gum, albumin, pullulan, carboxyvinyl polymer, cellulose and its derivatives, polyacrylamide, poly Various polymers such as sodium chlorate, polyvinyl alcohol, anions, cations, various nonionic surfactants, animal and plant extracts, amino acids and peptides, vitamins, cinnamic acid such as octyl paramethoxycinnamate, salicylic acid , Benzoic acid ester, urocanic acid, benzophenone and other UV protection agents, bactericides / preservatives, antioxidants, modified or unmodified clay minerals, solvents such as butyl acetate, acetone, toluene, various particles Titanium oxide, zinc oxide, aluminum oxide, aluminum hydroxide, bengara, yellow iron oxide, black iron oxide, cerium oxide, zirconium oxide, silica, mica, talc, sericite, boron nitride, sulfuric acid with diameter, particle size distribution and shape Barium, titanium mica with pearl luster, and their composites Pigment or dye, water, contains at least one such perfume. Here, inorganic compounds such as titanium oxide and zinc oxide may be used after being subjected to surface treatment such as silicon treatment, fluorine treatment, and metal soap treatment.

In addition, resin particles such as polymethyl acrylate, nylon, silicone resin, silicone rubber, polyethylene, polyester, and polyurethane may be included.
Further, as an active ingredient having a whitening effect, arbutin, kojic acid, vitamin C, sodium ascorbate, magnesium ascorbate phosphate, ascorbyl di-palmitate, ascorbyl glucoside, other ascorbic acid derivatives, placenta extract, sulfur, oil Plant extracts such as soluble licorice extract and mulberry extract, linoleic acid, linolenic acid, lactic acid, tranexamic acid and the like can be included.
Effective ingredients with anti-aging effects such as vitamin C, carotenoids, flavonoids, tannins, cafe derivatives, lignans, saponins, retinoic acid and retinoic acid structural analogs, N-acetylglucosamine, α-hydroxy acids, etc. Ingredients, polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol, mixed isomerized sugars, sugars such as trehalose, pullulan, sodium hyaluronate, collagen, elastin, chitin / chitosan, sodium chondroitin sulfate, etc. Polymers, amino acids, betaines, ceramides, sphingolipids, cholesterol and derivatives thereof, ε-aminocaproic acid, glycyrrhizic acid, various vitamins, and the like can be included.

The cosmetics of the present invention include quasi-drug raw material standards 2006 (issued by Yakuji Nippo Co., Ltd., June 16, 2006) and International Cosmetic Ingredient Dictionary and Handbook (issued by The Cosmetic, Toiletry, and Fragrance). Cosmetic ingredients listed in Association, 13th Edition 2010) etc. can be used without particular limitation.
The cosmetic according to the present invention can be produced by a conventionally known general method.

  The cosmetics produced by such a method are used in various forms such as powder, cake, pencil, stick, cream, gel, mousse, liquid, cream, and more specifically described. Washing cosmetics such as soap, cleansing foam, makeup remover, moisturizing / rough skin prevention, acne, keratin care, massage, wrinkle / sagging, dullness / bearing, UV care, whitening, antioxidant care, etc. Skincare cosmetics, powder foundation, liquid foundation, cream foundation, mousse foundation, pressed powder, base makeup cosmetics such as makeup base, eye shadow, eyebrow, eyeliner, mascara, lipstick, etc. point makeup cosmetics, For hair growth, anti-dandruff, itching, cleaning, co Hair care cosmetics such as conditioning, hair styling, permanent wave, hair color, hair bleach, etc., for washing, sun protection, hand roughening, slimming, blood circulation improvement, itching suppression, body odor prevention, antiperspirant, body hair care, For repellant, body care cosmetics such as body powder, perfume, eau de parfum, eau de toilette, eau de cologne, shower colon, fragrance cosmetics such as perfume, body lotion, bath oil, oral care products such as toothpaste, mouthwash, etc. Can be mentioned.

[Insulation]
Silica-based particles obtained by the production method of the present invention can be suitably used as a heat insulating material.
As the silica-based particles used for the heat insulating material, hollow silica-based particles (second embodiment), preferably silica-based particles having a non-porous outer shell, and further, silica-based particles having a negative pressure inside the cavity In particular, silica-based particles having a negative pressure of 133 hPa (100 mmHg) or less are preferable.
As usage for the heat insulating material, it can be used in accordance with a conventionally known method, for example,
It can be used by filling a partition wall for heat insulation, and has been proposed for various uses such as being blended with a housing building material (wall material, window material, etc.) or used as a sheet containing as a heat insulation filler.

[Resin composition]
Silica-based particles obtained by the production method of the present invention can be blended in the resin composition. The blending amount varies depending on the use, but is preferably in the range of 1 to 90% by weight.
If the resin composition is a film, it can be used as the sheet-like heat insulating material, and particles having a large porosity, particularly silica-based particles having a non-porous shell and a negative pressure inside the void are not hygroscopic and have a low The dielectric constant can be maintained over a long period of time, and it can be suitably used as a low dielectric constant film.
Moreover, it can be used suitably also as a multilayer printed circuit board or a semiconductor sealing material.

As the resin, a conventionally known resin can be used, for example, an epoxy resin, a silicone resin, a phenol resin, a melamine resin, a urea resin, an unsaturated polyester, a fluorine resin exemplified in JP-A-2005-206436. , BT resin, polyimide, polyamideimide, polyetherimide and other polyamides, polybutylene terephthalate, polyethylene terephthalate, etc. polyester, polyphenylene sulfide, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS Resins such as resin, AAS resin, and AES resin are used.
Furthermore, when a curing agent is necessary to cure the resin, a curing agent and a curing accelerator can be used, and various additives can be used as necessary.

[Example 1]
Preparation of silica-based particles (1) Using 3000 g of water glass aqueous solution (SiO ₂ / Na ₂ O molar ratio: 3.2, SiO ₂ concentration: 24 wt%) at a flow rate of 0.62 kg / hr in one of two fluid nozzles, The other nozzle was sprayed with hot air having an inlet temperature of 250 ° C. at a flow rate of 31800 L / hr (air / liquid volume ratio 63600) to obtain silica-based particle precursor particles (1). At this time, the outlet temperature was 50 ° C.
Next, 500 g of silica-based particle precursor particles (1) were immersed in 3200 g of a 10 wt% sulfuric acid aqueous solution and stirred for 1.5 hours. At this time, the solid content (SiO ₂ ) concentration was 10.2 wt%, the temperature of the dispersion was 35 ° C., and the pH was 3.0. The molar ratio (Ma) / (Msp) with the number of moles of acid (Ma) was 1.2.
Next, the silica-based particles (1) were prepared by drying and heat treatment at 80 ° C. for 60 hours in a dryer.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, oil absorption and feel characteristics of the obtained silica particles (1) were measured, and the results are shown in the table.
The oil absorption was measured by the following method, and the results are shown in the table.

Oil absorption pigment test method Measured according to JIS-K5101. The outline is obtained by measuring the amount of oil that is absorbed into the silica-based particles (1) under certain conditions and dividing the oil absorption by the weight of the silica-based particles (1). In the present invention, the oil absorption is indicated in ml / 100 g.

Sensory characteristics The powder of silica particles (1) is subjected to a sensory test by 20 expert panelists. (1) Smooth feeling, (2) Moist feeling, (3) Rolling feeling, (4) Uniform spreading Interviews were conducted on seven evaluation items: (5) Adhesion to the skin, (6) Persistence of rolling feeling, and (7) Low sharpness of silica-based particles (1). The result is evaluated based on the following evaluation point criteria (a). Subsequently, the evaluation points given by each person are summed up, and the evaluation relating to the feel of the porous silica-based particles is performed based on the following evaluation criteria (b).

Evaluation point criteria (a )
5 points: Excellent.
4 points: Excellent.
3 points: Normal.
2 points: Inferior.
1 point: Very inferior.
Evaluation criteria (b)
◎: Total score is 80 or more ○: Total score is 60 or more and less than 80 △: Total score is 40 or more and less than 60 ▲: Total score is 20 or more and less than 40 ×: Total score is less than 20

[Example 2]
Preparation of silica-based particles (2) Silica-based particles (2) were prepared in the same manner as in Example 1 except that drying and heat treatment were performed at 120 ° C for 24 hours.
The resulting silica-based particles (2) were measured for average particle size, specific surface area, particle density, porosity, residual amount of alkali, oil absorption and feel characteristics, and the results are shown in the table.

[Example 3]
Preparation of silica-based particles (3) Silica-based particles (3) were prepared in the same manner as in Example 1 except that spray drying was performed at an inlet temperature of 400 ° C and an outlet temperature of 150 ° C.
The resulting silica-based particles (3) were measured for average particle size, specific surface area, particle density, porosity, residual amount of alkali, oil absorption and feel characteristics, and the results are shown in the table.

[Example 4]
Preparation of silica-based particles (4) Silica-based particles (4) were prepared in the same manner as in Example 3 except that drying and heat treatment were performed at 120 ° C for 24 hours.
The resulting silica-based particles (4) were measured for average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption and feel characteristics, and the results are shown in the table.

[Example 5]
Preparation of silica-based particles (5) In Example 4, silica-based particles (5) were prepared in the same manner except that drying and heat treatment were performed at 120 ° C. for 24 hours while evacuating with a vacuum pump at a reduced pressure of 1 hPa. Prepared.
The resulting silica-based particles (5) were measured for average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption and feel characteristics, and the results are shown in the table. The void internal pressure is shown in the table as the degree of pressure reduction during the drying / heating treatment.

Further, the void internal pressure was measured by the following method and evaluated according to the following criteria.
A 100 cc glass bottle connected to one of the U-tube manometers was charged with a weight equivalent to 40 cc of silica-based particles (5) in terms of particle density, and then 50 cc of a sodium hydroxide aqueous solution with a concentration of 48% by weight was added immediately. The vent valve was closed and sealed. The space of the air layer inside the glass bottle at this time was 10 cc. Next, while stirring with a magnetic stirrer, the silica-based particles (5) were dissolved by heating in an oil bath at 80 ° C. for 15 hours, and then cooled to room temperature. The space of the air layer at this time was 25 cc (the volume of the air layer inside the glass bottle: 10 cc and the internal void volume of the silica-based particles: approximately 16 cc). Thereby, it turned out that the internal space | gap of the silica type particle | grains was open | released by melt | dissolution of the silica. Next, the other U-tube manometer was connected to a 100 cc glass bottle filled with 90 cc of a 48% aqueous sodium hydroxide solution, and the vapor pressures inside both glass bottles were made equal. Thus, the internal pressure of the silica-based particles can be calculated from Boyle's law based on the differential pressure measured with a manometer. The pressure inside the U-tube manometer at this time was read to calculate the internal pressure of the air gap.
As a result, the void internal pressure of the silica-based particles (5) was ◎.

Evaluation standard differential pressure is 133 hPa or less: ◎
Differential pressure is over 133 hPa to 500 hPa: ○
Differential pressure is over 500 hPa and less than 1013 hPa: Δ
Differential pressure is 1013 hPa: ×

[Example 6]
Preparation of silica-based particles (6) Using 3000 g of a water glass aqueous solution (SiO ₂ / Na ₂ O molar ratio: 3.2, SiO ₂ concentration: 24% by weight), air was supplied to the other nozzle at a flow rate of 0.12 kg / hr. Silica-based particle precursor particles (2) were obtained by spraying with hot air having an inlet temperature of 250 ° C. at a flow rate of 31800 L / hr (air / liquid volume ratio 318000). At this time, the outlet temperature was 50 ° C.
Subsequently, 500 g of silica-based particle precursor particles (2) were immersed in 3200 g of a 10 wt% sulfuric acid aqueous solution and stirred for 1.5 hours. At this time, the solid content (SiO ₂ ) concentration was 10.2 wt%, the temperature of the dispersion was 35 ° C., and the pH was 3.0. The molar ratio (Ma) / (Msp) with the number of moles of acid (Ma) was 1.2.
Subsequently, it dried and heat-processed at 80 degreeC for 60 hours with the dryer, and prepared the silica type particle (6).
The resulting silica-based particles (6) were measured for average particle diameter, specific surface area, particle density, porosity, residual alkali amount, oil absorption and feel characteristics, and the results are shown in the table.

[Example 7]
Preparation of silica-based particles (7) Silica-based particles (7) were prepared in the same manner as in Example 6 except that they were dried and heated at 120 ° C for 24 hours.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, oil absorption and feel characteristics of the obtained silica particles (7) were measured, and the results are shown in the table.

[Example 8]
Preparation of silica-based particles (8) In Example 6, sprayed with hot air having an inlet temperature of 400 ° C. (the outlet temperature was 150 ° C. at this time), dried and heat-treated while evacuating with a vacuum pump at a reduced pressure of 1 hPa. A silica-based particle (8) was prepared in the same manner except that was carried out at 120 ° C. for 24 hours.
The average particle diameter, specific surface area, particle density, porosity, void internal pressure, residual amount of alkali, oil absorption and feel characteristics of the obtained silica particles (8) were measured, and the results are shown in the table. The void internal pressure of the silica-based particles (8) was ◎.

[Example 9]
Preparation of silica-based particles (9) Using 3000 g of water glass aqueous solution (SiO ₂ / Na ₂ O molar ratio 3.2, SiO ₂ concentration 24 wt%) at a flow rate of 0.62 kg / hr in one of two fluid nozzles, The other nozzle was sprayed with hot air at an inlet temperature of 250 ° C. at a flow rate of 15900 L / hr (air / liquid volume ratio 31800) to obtain silica-based particle precursor particles (9). At this time, the outlet temperature was 50 ° C.
Subsequently, 500 g of silica-based particle precursor particles (3) were immersed in 3200 g of a 10 wt% sulfuric acid aqueous solution and stirred for 1.5 hours. At this time, the solid content (SiO ₂ ) concentration was 10.2 wt%, the temperature of the dispersion was 35 ° C., and the pH was 3.0. The molar ratio (Ma) / (Msp) with the number of moles of acid (Ma) was 1.2.
Subsequently, it dried and heat-processed for 60 hours at 80 degreeC with the dryer, and prepared the silica particle (9).
The resulting silica-based particles (9) were measured for average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption and feel characteristics, and the results are shown in the table.

[Example 10]
Preparation of silica-based particles (10) In Example 9, spraying is performed on hot air having an inlet temperature of 400 ° C. (at this time, the outlet temperature is 150 ° C.), and the drying / heating treatment is performed at 120 ° C. for 24 hours. Silica-based particles (10) were prepared.
The resulting silica-based particles (10) were measured for average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption and feel characteristics, and the results are shown in the table.

[Example 11]
Preparation of silica-based particles (11) In Example 10, silica-based particles (11) were prepared in the same manner except that drying and heat treatment were performed at 120 ° C. for 24 hours while evacuating with a vacuum pump at a reduced pressure of 1 hPa. Prepared.
The average particle diameter, specific surface area, particle density, void ratio, void internal pressure, residual alkali amount, oil absorption and feel characteristics of the obtained silica particles (11) were measured, and the results are shown in the table. The void internal pressure of the silica-based particles (11) was ◎.

[Comparative Example 1]
Preparation of silica-based particles (R1) Using 3000 g of a water glass aqueous solution (SiO ₂ / Na ₂ O molar ratio 3.2, SiO ₂ concentration 24 wt%) at a flow rate of 0.62 kg / hr in one of two fluid nozzles, An attempt was made to obtain silica-based particle precursor particles by spraying hot air having an inlet temperature of 140 ° C. at a flow rate of 31800 L / hr (air / liquid volume ratio 63600) to the other nozzle, but drying was insufficient. Furthermore, it was impossible to obtain a dry powder by adhering to the inner wall of the drying chamber and the inner wall of the pipe. At this time, the outlet temperature was 30 ° C. Therefore, subsequent steps (b) and (c) were not performed.

[Comparative Example 2]
Preparation of silica-based particles (R2) Silica-based particle precursor particles (R2) were obtained in the same manner as in Comparative Example 1 except that the particles were sprayed with hot air having an inlet temperature of 700 ° C. At this time, the outlet temperature was 350 ° C. The silica-based particle precursor particle (R2) had a thin shell and contained bowl-like and crushed particles therein, so the subsequent steps (b) and (c) were not performed.

[Comparative Example 3]
Preparation of silica-based particles (R3) It was prepared in the same manner as in Example 1. 500 g of silica-based particle precursor particles (1) were immersed in 3200 g of a 1% by weight sulfuric acid aqueous solution and stirred. At this time, the molar ratio (Ma) / (Msp) to the number of moles (Ma) of the acid was 0.12, the solid content (SiO ₂ ) concentration was 10.2 wt%, the temperature was 30 ° C., and 1.5 hours. PH = 9.5, but in the acid washing step, the amount of acid was too small, so that the dissolution of particles was noticeable and the yield after the completion of the step was remarkably low. For this reason, the subsequent step (c) was not carried out.

[Comparative Example 4]
Preparation of silica-based particles (R4) Silica-based particle precursor particles (R4) were prepared in the same manner as in Example 3 except that a water glass aqueous solution having a SiO ₂ concentration of 24% by weight was concentrated to a SiO ₂ concentration of 42% by weight. Got. At this time, the outlet temperature was 170 ° C. However, many non-uniform non-spherical particles were observed in the spray-dried product. For this reason, steps (b) and (c) were not performed.
In addition, it is thought that the density | concentration of water glass aqueous solution became too high and became highly viscous, and it was dried before the droplet of the sprayed water glass aqueous solution spheroidized.

[Comparative Example 5]
Preparation of silica-based particles (R5) 7,500 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: S-20L, average particle size 19 nm, SiO ₂ concentration 20% by weight) was used with a rotary disk method spray dryer. The carrier powder (R5) was obtained by spraying in a hot air stream having an inlet temperature of 170 ° C. at a flow rate of 8 kg / hr. At this time, the outlet temperature was 100 ° C.
The average particle diameter, specific surface area, particle density, porosity, residual alkali amount, oil absorption and feel characteristics of the obtained silica particles (R5) were measured, and the results are shown in the table.

[Examples 12 to 22] and [Comparative Example 6]
Preparation of the powder foundation The silica-based particle components (1) and (2) to (9) obtained in Examples 1 to 11 and Comparative Example 5 were respectively mixed so that the blending ratios (% by weight) shown in the following table were obtained. The mixture was stirred and mixed uniformly. Next, the following cosmetic ingredients (10) to (12) were put in this mixer and stirred, and further uniformly mixed. Next, after crushing the obtained cake-like substance, about 12 g was taken out from it, put into a square metal pan of 46 mm × 54 mm × 4 mm, and press molded.
Thus, Example cosmetics P1 to P11 and Comparative cosmetic PR5 containing silica-based particles were obtained.

  Next, the feeling of use of the example cosmetics P1 to P11 and the comparative example cosmetic PR5 obtained in this way were evaluated with respect to the feeling during application and the finished feeling (feel after application) by the following test methods. The results are shown in the table.

Test method A powder foundation containing silica-based particle powder is subjected to a sensory test by 20 expert panelists. (1) Uniform stretch during application to the skin, (2) Moist feeling, (3) Smoothness , And (4) Interview survey on 6 evaluation items: uniformity of cosmetic film after application to skin, (5) moist feeling, and (6) softness. The result is evaluated based on the following evaluation point criteria (a). Subsequently, the evaluation points given by each person are summed up, and an evaluation relating to the feeling of use of the foundation is performed based on the following evaluation criteria (b).

Evaluation point criteria (a )
5 points: Excellent.
4 points: Excellent.
3 points: Normal.
2 points: Inferior.
1 point: Very inferior.

Evaluation criteria (b )
◎: Total score is 80 or more ○: Total score is 60 or more and less than 80 △: Total score is 40 or more and less than 60 ▲: Total score is 20 or more and less than 40 ×: Total score is less than 20 As a result, it was found that the cosmetics of the examples were very excellent in use feeling during and after application.

[Examples 23 to 34] and [Comparative Example 7]
Preparation of lotion Example in which components (1) to (3) were heated to 80 ° C. and uniformly mixed so as to have the blending ratio (% by weight) shown in the following table, and heated to 80 ° C. and uniformly mixed The silica-based particle components (4) and (5) to (8) obtained in 1 to 11 and Comparative Example 5 were added and stirred to mix uniformly. Next, it cooled to 50 degreeC, and added and stirred component (9)-(11), and also mixed uniformly. Subsequently, it cooled to room temperature and obtained Example cosmetics L1-L11 and Comparative Example cosmetics LR5 which mix | blended the silica type particle | grains.

  Next, the feeling of use (redispersibility of silica-based particles before use and feel during application) and the finish (feel after application) of Example cosmetics L1 to L11 and Comparative Example cosmetic LR5 thus obtained. ) Was evaluated by the following test method. The results are shown in the table.

Test method A lotion containing silica-based particle powder was subjected to a sensory test by 20 expert panelists. 1) Redispersibility of silica-based particles before use, 2) Uniform elongation during application to the skin, And 3) Conduct interviews on three evaluation items for the soft focus property of the cosmetic film after application to the skin. The result is evaluated based on the following evaluation point criteria (a). Subsequently, the evaluation points given by each person are summed up, and an evaluation relating to the feeling of use of the foundation is performed based on the following evaluation criteria (b).

Evaluation point criteria (a )
5 points: Excellent.
4 points: Excellent.
3 points: Normal.
2 points: Inferior.
1 point: Very inferior.

Evaluation criteria (b )
◎: Total score is 80 or more ○: Total score is 60 or more and less than 80 △: Total score is 40 or more and less than 60 ▲: Total score is 20 or more and less than 40 ×: Total score is less than 20 As a result, it was found that the cosmetics of the examples were very excellent in use feeling during and after application.

[Examples 35 to 39] and [Comparative Examples 8 to 10]
Preparation of thermal insulation material Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd., light acrylate DPE-6A) 4.4 g, and 1,6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd., light acrylate 1,6HX-A) 4.4 g was mixed and 0.7 g of photoinitiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Ciba Japan, DAROCUR TPO) was mixed therewith. This was dissolved in 2.3 g of polyethylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd., MFG) to prepare a mixed resin solution.

  Next, each silica-based particle obtained in Examples 4, 5, 8, 10, and 11 was added to 11.8 g of the mixed resin solution (resin specific gravity: 1.1 g / cc, resin volume: 8.0 cc). After adding 5.1 g, 5.1 g, 5.9 g, 4.5 g, and 4.5 g to 33% by volume (3.9 cc) in terms of conversion, respectively, a horn type ultrasonic device (manufactured by Maritime Radio Co., Ltd.) And 5 points of resin solutions for forming a heat insulating material were prepared. The reason for converting the particle density is to make the number of particles equal and make comparisons.

Each heat insulating material forming resin solution was applied to a PET substrate using a bar coater (bar No. 18), dried at 80 ° C. for 2 minutes, and further cured by UV irradiation (300 mJ / cm ² ). Substrates H1 to H5 with heat insulating thin films were obtained.
In addition, the resin solution prepared in the same manner except that the silica-based particles were not blended, and the silica-based particles obtained in Example 1 and Comparative Example 5 were each 33% by volume in terms of particle density. In addition, 3 points of resin solutions prepared in the same manner except that 8.6 g was blended were similarly applied, dried and cured to obtain bases RH1 to RH3 with comparative heat insulating thin films.
About each obtained base material with a heat insulation thin film, heat insulation is evaluated as follows, and a result is shown in a table | surface.

Thermal insulation evaluation A base material with a thin film is placed on a dedicated jig, irradiated with an infrared lamp (185W) for 30 minutes from directly above the surface of the thin film (base material), and from the base material on the opposite side of the thin film. A temperature sensor was installed directly below 8 cm to measure the temperature. At that time, the temperature before infrared irradiation was in the range of 24.0 to 24.5 ° C. The results are shown in Table 8.

Claims (18)

A method for producing silica-based particles comprising the following steps (a) to (c).
(A) A step of preparing silica-based particle precursor particles by spray drying an alkali silicate aqueous solution in a hot air stream (b) A step of immersing the silica-based particle precursor particles in an acid aqueous solution to remove alkali (c) Drying・ Process to heat treatment The SiO ₂ / M ₂ O molar ratio (where M represents an alkali metal) of the alkali silicate aqueous solution is in the range of 1 to 5, and the SiO ₂ concentration is in the range of 1 to 30% by weight. The method for producing silica-based particles according to claim 1.   The method for producing silica-based particles according to claim 1 or 2, wherein an inlet temperature of hot air in the spray drying is in a range of 150 to 600 ° C and an outlet temperature is in a range of 40 to 300 ° C. In the step (b), the molar ratio (Ma) / (Msp) between the number of moles of M ₂ O (Msp) and the number of moles of acid (Ma) in the silica particle precursor particles is 0.6 to 4.7. in the range, method for producing a silica-based particles according to claim 1 in which the concentration of the silica-based particle precursor particles, characterized in that in the range of 1 to 30 wt% as SiO _2.   The method for producing silica-based particles according to any one of claims 1 to 4, wherein the drying / heating treatment temperature in the step (c) is in the range of 30 to 1200 ° C.   6. The method for producing silica-based particles according to claim 1, wherein the average particle diameter is in the range of 0.1 to 200 [mu] m.   The inlet temperature in the spray drying is in the range of 150 to 300 ° C, the outlet temperature is in the range of 40 to 120 ° C, and the resulting silica-based particles have a porosity of less than 20% by volume. The manufacturing method of the silica-type particle in any one of 1-6.   The method for producing silica-based particles according to claim 7, wherein the drying / heating treatment temperature in the step (c) is in the range of 30 to 120 ° C, and the obtained silica-based particles are porous.   The method for producing silica-based particles according to claim 7, wherein the drying / heating treatment temperature in the step (c) is in the range of 90 to 1200 ° C, and the obtained silica-based particles are non-porous.   The inlet temperature in the spray drying is in the range of 300 to 600 ° C., the outlet temperature is in the range of 120 to 300 ° C., the resulting silica-based particles have an outer silica layer, and the porosity inside the outer shell is 20 It is in the range of -95 volume%, The manufacturing method of the silica type particle | grains in any one of Claims 1-6 characterized by the above-mentioned.   11. The silica-based particles according to claim 10, wherein the drying / heating treatment temperature in the step (c) is in the range of 30 to 120 ° C., and the resulting outer silica layer of the silica-based particles is porous. Manufacturing method.   11. The silica-based silica according to claim 10, wherein the drying / heating treatment temperature in the step (c) is in the range of 90 to 1200 ° C., and the outer silica layer of the obtained silica-based particles is nonporous. Particle production method. The method for producing silica-based particles according to claim 12, wherein the drying / heating treatment in the step (c) is performed under reduced pressure, and the inside of the outer shell layer of the silica-based particles obtained is at a negative pressure.
  The average particle size is in the range of 0.1 to 200 μm, the outer silica layer has cavities, the porosity of the cavities is in the range of 20 to 95% by weight, and the outer silica layer is non-porous. Silica-based particles characterized in that the inside of the cavity has a negative pressure. The silica-based particles according to claim 14, wherein the negative pressure inside the cavity is 133 hPa or less.
Cosmetics comprising the silica-based particles obtained by the production method according to claim 1 or the silica-based particles according to claim 14 or 15 in a range of 0.1 to 30% by weight. Fee.
  A resin composition comprising the silica-based particles obtained by the production method according to claim 1 or the silica-based particles according to claim 14 or 15 in an amount of 1 to 90% by weight. .   The heat insulating material formed by mix | blending the silica type particle obtained by the manufacturing method in any one of Claims 10-13, or the silica type particle of Claim 14 or 15.