JP5850705B2 - Method for producing dye-encapsulated silica-based particles, dye-encapsulated silica-based particles, and cosmetics containing the same - Google Patents

Description

  The present invention relates to a method for producing dye-encapsulated silica-based particles, dye-encapsulated silica-based particles, and uses of the particles.

Conventionally, dyes and pigments are used in various applications such as inks, paints, and cosmetics.
For example, cosmetics are used in make-up cosmetics and skin care cosmetics. However, when dyes and pigments are added to cosmetics as they are, it is difficult to adjust the hue, and depending on the pigments used, It is known that the feel is not necessarily good.
In addition, when the dye is blended, if it is directly applied to the skin or the like, bleeding may occur, and there is a disadvantage that it is difficult to remove from the skin once dried. In addition, it is known that acid dyes are easily discolored by chlorine and light contained in tap water.
In recent years, for the purpose of solving such problems, colored particles using a dye as a colorant and cosmetics containing the same have been developed.

As such colored particles, (1) an acid dye laminate in which the surface of powder particles as a base is coated with an acid dye-containing clay material in which a polybasic group and an acid dye are confined between water-swellable clay mineral layers Pigment (Patent Document 1), (2) Composite pigment in which the surface of inorganic compound particles is coated with a dye or a mixture of dye and inorganic compound (Patent Document 2), (3) The surface of silicon dioxide sphere is made of iron oxide or the like Inorganic spherical absorbing pigment formed by coating a metal oxide or a coloring material such as the metal oxide and an organic dye (Patent Document 3), (4) Polymer matrix material in which a dye is microencapsulated (Patent Document 4), (5 ) Pigment in which solvating dye is incorporated in resin (Patent Document 5), (6) Polymer layer obtained by graft polymerization of monomer having functional group modified with functional organic compound such as dye on particle surface Forming Modified inorganic fine particles for cosmetics (Patent Document 6), (7) colored spherical silicone in which a reactive dye is adsorbed on the surface of fine particles surface-treated with an organosilicon compound having an amino group There are fine particles (Patent Document 7).
The applicant of the present application discloses colored alumina / silica particles in which a dye is fixed to an alumina component present on the outer surface of the porous alumina / silica particles and the inner surface of the pores (Patent Document 8).

However, in order to manufacture these colored particulate substances, since any process requires a complicated process, the manufacturing cost is increased.
Further, the color of the dye or pigment itself does not appear as it is, and in some cases, the dye may be eluted or faded. Furthermore, for example, when blended in cosmetics, although it has been improved, it still causes bleeding, and once dried, it may be difficult to remove from the skin, and these improvements have been desired.

JP 2004-331878 A JP-A-1-157908 Japanese Patent Laid-Open No. 2001-49142 JP-T-2006-519211 JP-A-3-258712 JP 2003-63932 A JP 2003-335632 A JP 2009-120653 A

The inventors of the present invention spray dried an alkali silicate aqueous solution having a predetermined concentration, immersed in an aqueous solution containing a sufficient amount of acid to remove the alkali in the particles obtained by spraying, and removed the alkali to remove the silica particles. It has been found that spherical silica particles having a solid or hollow interior can be obtained.
At this time, when the dye was dispersed in an aqueous alkali silicate solution, it was found that dye-containing silica-based particles colored in the same color as the dye used were obtained, and the present invention was completed.

An object of the present invention is to provide a method for producing a dye-encapsulated silica-based particle, a dye-encapsulated silica-based particle, and a use of the particle.
More specifically, (1) spherical pigment-encapsulated silica-based particles whose inside is a porous or nonporous (nonporous) silica phase, or (2) an outer shell and a cavity inside the outer shell In addition, in the pigment-encapsulated silica-based particles whose outer shell is a porous or non-porous silica phase, and (3) in the pigment-encapsulated silica-based particles in which the cavity has a negative pressure, the pigment is sealed in the silica phase and / or the cavity The pigments are not easily eluted or discolored (discolored) because they are incorporated into the cosmetics. It is an object of the present invention to provide a method for producing dye-encapsulated silica-based particles having excellent properties, dye-encapsulated silica-based particles, and uses of the particles.

The method for producing dye-encapsulated silica-based particles according to the present invention is characterized by comprising the following steps (a) to (c).
(A) Step of preparing a dye-containing silica-based particle precursor particle by spray-drying a dye-containing alkali silicate aqueous solution in a hot air stream (b) Dipping the dye-containing silica-based particle precursor particle in an acid aqueous solution to remove the alkali Step (c) to dry and heat-treat

The pigment-containing alkali silicate aqueous solution has a SiO ₂ / M ₂ O molar ratio (where M represents an alkali metal) in the range of 1 to 5, and a SiO ₂ concentration (C _S ) of 1 to 30% by weight. It is preferable that the concentration ratio (C _D ) / (C _S ) between the pigment concentration (C _D ) and the SiO ₂ concentration (C _S ) is in the range of 0.0002 to 1.
The pigment is preferably a water-soluble dye.

It is preferable that the inlet temperature of the hot air in the spray drying in the step (a) is in the range of 100 to 600 ° C and the outlet temperature is in the range of 40 to 300 ° C.
In the step (b), the molar ratio (Ma) / (Ms) between the number of moles of M ₂ O (Ms) and the number of moles of acid (Ma) in the dye-containing silica-based particle precursor particles is 0.6-4. It is preferable that the concentration of the dye-containing silica-based particle precursor particles is in the range of 1 to 30% by weight as the solid content.
The drying / heat treatment temperature in the step (c) is preferably in the range of 30 to 300 ° C.
In the method for producing a dye-encapsulated silica-based particle of the present invention, the average particle diameter is preferably in the range of 0.1 to 200 μm, and the content of the dye is preferably in the range of 0.5 to 50% by weight as the solid content.

In the spray drying in the step (a), the inlet temperature is in the range of 100 to 300 ° C., the outlet temperature is in the range of 40 to 120 ° C., and the porosity of the resulting dye-containing silica-based particles is less than 5% by volume. It is preferable.
At this time, it is preferable that the drying / heat treatment temperature in the step (c) is in the range of 30 to 120 ° C., and the obtained dye-containing silica-based particles are porous.
At this time, it is preferable that the drying / heating treatment temperature in the step (c) is in the range of 90 to 300 ° C., and the resulting dye-containing silica-based particles are non-porous.

In the spray drying of the step (a), the inlet temperature is in the range of 300 to 600 ° C., the outlet temperature is in the range of 120 to 300 ° C., and the resulting dye-encapsulated silica-based particles have an outer shell silica layer, The porosity inside the shell is preferably in the range of 5 to 95% by volume.
At this time, 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 resulting dye-encapsulated silica-based particles is porous.
At this time, it is preferable that the drying / heat treatment temperature in the step (c) is in the range of 90 to 300 ° C., and the outer silica layer of the obtained dye-encapsulated silica-based particles is nonporous.
At this time, it is further 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 resulting dye-encapsulated silica-based particles has a negative pressure.

The pigment-encapsulated silica-based particles according to the present invention are characterized in that the average particle diameter is in the range of 0.1 to 200 μm, and the pigment content is in the range of 0.5 to 50% by weight as the solid content.
The pigment is preferably a natural dye and / or a synthetic dye.

The pigment-encapsulated silica-based particles of the first aspect according to the present invention preferably have a porosity of less than 5% by volume.
The dye-containing silica-based particles may be porous or non-porous.
The dye-encapsulated silica-based particles of the second aspect according to the present invention preferably have an outer silica layer and a porosity inside the outer shell is preferably in the range of 5 to 95% by volume.
The outer shell silica layer may be porous, but is preferably nonporous, and more preferably has a negative pressure inside the outer shell layer.

The cosmetic according to the present invention is characterized by blending the dye-encapsulated silica-based particles obtained by any one of the production methods described above or the dye-encapsulated silica-based particles described above.
The compounding amount of the dye-containing silica-based particles is preferably in the range of 0.1 to 30% by weight.

  The heat insulating material according to the present invention is characterized in that the dye-containing silica-based particles obtained by any one of the production methods described above or the dye-containing silica-based particles described above are blended.

According to the present invention, (1) spherical silica-based particles whose inside is a porous or non-porous (non-porous) silica phase, or (2) having an outer shell and having a cavity inside the outer shell In addition, spherical silica-based particles whose outer shell is a porous or non-porous silica phase, and (3) spherical silica-based particles whose cavity is negative pressure, the silica phase and / or cavities, a dye on the inner wall of the cavity Since it is contained, the dye does not easily elute and does not fade. For this reason, when the pigment-encapsulated silica-based particles of the present invention are used in cosmetics, they do not cause bleeding or discoloration, and are excellent in lubricity because the particles are spherical.

[Method for producing dye-encapsulated silica-based particles]
Below, the manufacturing method of the dye inclusion | inner_cover silica particle which concerns on this invention is demonstrated first.
The method for producing dye-encapsulated silica-based particles according to the present invention is characterized by comprising the following steps (a) to (c).
(A) Step of preparing a dye-containing silica-based particle precursor particle by spray-drying a dye-containing alkali silicate aqueous solution in a hot air stream (b) Dipping the dye-containing silica-based particle precursor particle in an acid aqueous solution to remove the alkali Step (c) to dry and heat-treat

Step (a)
The dye-containing alkali silicate aqueous solution is spray-dried in a hot air stream to prepare dye-containing silica-based particle precursor particles.
First, a dye-containing alkali silicate aqueous solution is prepared.
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 it becomes difficult to remove the alkali by the acid in the step (b) described later, and the deliquescence of the spray-dried product May become difficult to obtain dye-encapsulated silica-based particles.
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, dye-encapsulated silica-based particle precursor particles that can be used in the present invention cannot be obtained even by spray drying.

The concentration of the alkali silicate aqueous solution is not particularly limited as long as the concentration of the dye-containing alkali silicate aqueous solution described later is in the range described later, but the concentration as SiO ₂ is generally in the range of 1 to 30% by weight, more preferably in the range of 5 to 28% by weight. Preferably there is.

Dye As the dye used in the present invention, a dye is preferably used, and a water-soluble dye is particularly preferable.
As the dye, a water-soluble natural dye or synthetic dye can be used.
Examples of natural dyes include plant-derived dyes such as Akane, Ai, Turmeric, safflower, Mussaki (purple root), and animal dyes such as shellfish purple obtained from Ibonishi and cochineal obtained from Enjimushi.
Examples of synthetic dyes include direct dyes, acid dyes, basic dyes, reactive dyes, vat dyes, naphthol dyes, mordant dyes, metal complex salt dyes, disperse dyes, and fluorescent whitening dyes.

  In addition to the above dyes, ultraviolet absorbing dyes, near infrared absorbing dyes, dichroic dyes for liquid crystal displays, dyes for color filters, dyes for polarizing films, electrochromic dyes, electroluminescent dyes, ink jet dyes, heat sensitive dyes, Pressure dyes, dyes for sublimation transfer, dyes for melt transfer, diazo photosensitive materials, dyes for electrophotography, charge control agents for toners, dyes for laser recording, color development color photographs, silver dye bleaching color photosensitive materials, sensitizing dyes , Photochromic dyes, thermochromic dyes, dyes for chemiluminescence, dyes for dry films, dyes for stationery, dyes for plastic glasses lenses, dyes for colored smoke, dyes for organic nonlinear optics, invisible dyes, dyes for energy conversion (organic photoelectric conversion Water-soluble functional dyes such as dyes for use can also be used.

  In addition, when the pigment-encapsulated silica-based particles of the present invention are blended in cosmetics, the quasi-drug raw material standard 2006 (issued by Yakuji Nippo Inc., June 16, 2006), International Cosmetic Ingredient Dictionary and Handbook (published by The Cosmetic, Toiletry, and Fragrance Association, 13th Edition 2010) are preferably used.

A dye-containing alkali silicate aqueous solution is prepared by dissolving or dispersing the dye in the alkali silicate aqueous solution.
The concentration of the SiO ₂ of the dye-containing alkali silicate aqueous solution _{(C S)} 1 to 30 wt%, more preferably in the range of 5 to 28 wt%.
If the concentration of the SiO ₂ of the dye-containing alkali silicate aqueous solution (C _S) is less than 1 wt%, it may become inefficient when considering productivity.
When the concentration (C _S ) of the dye-containing alkali silicate aqueous solution as SiO ₂ exceeds 30% by weight, the stability as the dye-containing alkali silicate aqueous solution is remarkably lowered and may become highly viscous, making spray drying difficult. Even if spray drying is possible, the particle size distribution, the thickness of the outer shell, etc. may be extremely nonuniform, and the application may be limited.

Further, the concentration ratio (C _D ) / (C _S ) between the dye concentration (C _D ) and the SiO ₂ concentration (C _S ) is in the range of 0.0002 to 1, more preferably 0.002 to 0.9. Is preferred.
If the dye concentration _{(C D)} and a SiO ₂ concentration _{(C S)} and the concentration ratio of _{(C D) / (C S} ) is less than 0.0002, varies depending on the kind of the dye, the resulting dye encapsulated silica Since the pigment content in the particles is small, there are cases where sufficient coloring effects cannot be obtained when used in cosmetics and other applications.
If the concentration ratio of the dye concentration _{(C D)} and a SiO ₂ concentration _{(C S) (C D)} / (C S) exceeds 1, the dye is too large, the internal part of the dye silica phase or shell Since it is difficult to be contained in the cavity, it may be easily eluted or fading easily.

The above dye-containing alkali silicate aqueous solution is spray-dried in a hot air stream to prepare dye-containing silica-based particle precursor particles.
The spray drying method is not particularly limited as long as the dye-encapsulated silica-based particles to be described later are obtained, but conventionally known methods such as a rotating disk method, a pressurized nozzle method, and a two-fluid nozzle method can be employed.
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 100 to 600 ° C and the outlet temperature is in the range of 40 to 300 ° C.
When the inlet temperature of the hot air is less than 100 ° C., drying may be insufficient, and the dye-encapsulated silica-based particle precursor particles having cavities in the interior cannot be obtained, and the dye-encapsulated silica having no cavities in the interior Even if the system particle precursor particles are obtained, the drying may be insufficient, the adhesion to the spray drying chamber wall surface and the like may be severe, and the yield may be significantly reduced.
If the inlet temperature of the hot air exceeds 600 ° C., dye-containing silica-based particle precursor particles having no cavities inside cannot be obtained. Furthermore, even if the dye-containing silica-based particle precursor particles having cavities inside are obtained, since the drying is too fast, the particle diameter increases and the outer shell thickness decreases, and the dye-encapsulated silica-based silica Since it becomes a particle precursor particle, it is not preferred.

When the outlet temperature of the hot air is less than 40 ° C., the drying becomes insufficient, and the dye-containing silica-based particle precursor particles having cavities therein cannot be obtained, and the dye-containing silica-based particle precursor particles having no internal cavities are obtained. Even if obtained, the adhesion to the spray drying chamber wall surface etc. is intense, and the yield may be significantly reduced.
When the outlet temperature of the hot air exceeds 300 ° C., dye-containing silica-based particle precursor particles having no cavities inside cannot be obtained. Furthermore, even if the dye-encapsulated silica-based particle precursor particles having cavities therein are obtained, the drying is too fast, so that the particle diameter increases and the outer shell thickness decreases, and the dye-encapsulated silica-based Since it becomes a particle precursor particle, it is not preferred.

  The term “precursor particles” as used herein refers to pigment-containing alkali silicate particles obtained by spray-drying a pigment-containing alkali silicate aqueous solution, and the alkali is removed by an acid aqueous solution immersion step in a later step (b) described later. This is a particle in the previous stage to become a dye-containing silica-based particle.

In the present invention, when producing solid dye-encapsulated silica-based particles (first embodiment) substantially free of cavities inside, the inlet temperature in the spray drying is 100 to 300 ° C., more preferably 150 to 250 ° C. The outlet temperature is preferably in the range of 40 to 120 ° C, more preferably 50 to 100 ° C.
At this time, when the inlet temperature in spray drying is less than 100 ° C., even if the dye-encapsulated silica-based particle precursor particles substantially free of cavities are obtained, the drying is insufficient and the surface of the spray drying chamber is In some cases, the yield is significantly reduced.
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 pigment-encapsulated silica-based particles having a cavity inside (second aspect), the inlet temperature in the spray drying is in the range of 300 to 600 ° C., further 350 to 550 ° C., The outlet temperature is preferably in the range of 120 to 300 ° C, more preferably 130 to 250 ° C.
At this time, when the inlet temperature in spray drying is less than 300 ° C., the dye-containing silica-based particles having cavities therein may not be obtained, although it varies depending on the outlet temperature.
When the inlet temperature in spray drying exceeds 600 ° C., a ruptured dye-containing silica-based particle precursor particle is formed, and it may be difficult to obtain a dye-containing silica-containing particle having a cavity inside. Even if it is obtained, the thickness of the outer shell is reduced, and the strength of the resulting dye-encapsulated silica-based particles may be insufficient.

When the outlet temperature of hot air is less than 120 ° C., dye-containing silica particles having cavities inside may not be obtained.
When the outlet temperature of the hot air exceeds 300 ° C., a ruptured dye-containing silica-based particle precursor particle is formed, and it may be difficult to obtain a dye-containing silica-containing particle having a cavity inside, Even if it is obtained, the thickness of the outer shell becomes thin, and the strength of the resulting dye-containing silica-based particles may be insufficient.

  In addition, when manufacturing the dye inclusion | inner_cover silica particle (2nd aspect), when the inlet_port | entrance temperature and outlet temperature in spray-drying are in the said range, the particle | grains which have a cavity inside are formed, In that case, a pigment | dye is Dye-containing silica-based particles that tend to exist inside the cavity (hollow wall surface) and are difficult to elute the dye are finally obtained. Although the reason for this is not necessarily clear, the droplets of the dye-containing alkali silicate aqueous solution formed by spraying first form a silica layer (coating) by drying the surface of the droplets, and the silica layer ( It is presumed that the pigment is pushed inside as the coating becomes thicker.

Step (b)
The dye-containing 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 dye-encapsulated silica-based particle precursor particles are immersed in the acid aqueous solution, the molar ratio (Ma) / (M ₂ O mole number (Ms) and acid mole number (Ma) in the dye-encapsulated silica particle precursor particles. It is preferable to immerse so that Ms) is in the range of 0.6 to 4.7, more preferably 1 to 4.5.
When the molar ratio (Ma) / (Ms) is less than 0.6, the amount of acid is too small with respect to M ₂ O, 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 dye-containing silica-based particle precursor particles are partially dissolved, or the dissolved alkali silicate is gelled.
Even when the molar ratio (Ma) / (Ms) exceeds 4.7, the above-described condensation and skeletonization of silicic acid does not proceed, and the drying conditions, the type of dye, the type of acid, the amount of use thereof, etc. Depending on the case, a part of the dye may be eluted.

The concentration of the dye contained silica-based particles 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 dye contained silica-based particles 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. In addition, depending on the molar ratio of the acid and silica described above and the molar ratio of silica and alkali of the alkali silicate, the concentration of the acid may be lowered, and the dye-containing silica-based particle precursor particles may be partially dissolved or dissolved. The silicate alkali silicate may gel.
When the concentration of the dye-encapsulated 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, resulting in reduced alkali removal and cleaning efficiency. When the particle diameter of the system particle precursor 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 immersion is generally performed in a temperature range of 5 to 70 ° C. and a time 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.
When the dye-encapsulated silica-based particle precursor is immersed in an acid aqueous solution under the above-described conditions by the method of the present invention, the residual amount of alkali does not exceed 0.5% by weight as M ₂ O, but 0.5% by weight If it exceeds 50%, 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 is significantly inhibited, and the efficacy of the cosmetic may be inhibited. is there.

Step (c)
Next, it is dried and heated.
The drying / heat treatment temperature is preferably in the range of 30 to 300 ° C, more preferably 50 to 250 ° C.
Solid dye-encapsulated silica-based particles (first embodiment) according to the present invention, which are porous and hollow dye-encapsulated silica-based particles (second embodiment) having cavities therein, the outer shell being When manufacturing a porous thing, it is preferable that drying and heat processing temperature exist in the range of 30-120 degreeC, Furthermore, 40-100 degreeC.

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.
When the drying / heat treatment temperature exceeds 120 ° C, the pores formed when the alkali is removed disappear and porous dye-encapsulated silica-based particles and porous dye-encapsulated silica-based particles cannot be obtained. There is.
Note that, for example, the drying / heating treatment is performed at 120 ° C. or less, and the pores are not lost even if the second drying / heating treatment is performed at a higher temperature, and the porous dye-encapsulated silica-based particles and the outer particles are removed. In some cases, dye-containing silica-based particles having a porous shell are obtained.

Solid dye-encapsulated silica-based particles according to the present invention (first embodiment) that are non-porous and hollow dye-encapsulated silica-based particles (second embodiment) that have a non-porous outer shell When manufacturing a thing, it is preferable that drying and heat processing temperature exist in the range of 90-300 degreeC, Furthermore, 110-250 degreeC.
When the drying / heat treatment temperature is less than 90 ° C., the pores may not disappear, and the non-porous dye-encapsulated silica-based particles or the non-porous dye-encapsulated silica-based particles may not be obtained. is there.
When the drying / heat treatment temperature exceeds 300 ° C., the color may change depending on the dye used.

  The dye-containing silica-based particles obtained in the present invention are solid dye-containing silica-based particles (first embodiment) and porous and hollow dye-containing silica-based particles (second embodiment). In the case of a porous outer shell, a part of the dye may be eluted depending on the kind of the dye or the usage of the dye-containing silica-based particles. On the other hand, solid dye-containing silica-based particles (first embodiment) that are nonporous and hollow dye-containing silica-based particles (second embodiment) that have a non-porous outer shell There is no fear of elution and it can be suitably used for various applications.

In the present invention, the nonporous dye-encapsulated silica-based particle refers to a particle having a specific surface area (SA) of approximately 27 m ² / g or less.
When the specific surface area is approximately 27 m ² / g or less, although depending on the average particle diameter and the pigment content, the pigment-encapsulated silica-based particles have substantially no micropores contributing to SA, that is, non-porous Quality.
On the other hand, the porous pigment-encapsulated silica-based particles in the present invention refer to particles having a specific surface area (SA) of more than 27 m ² / g, although it varies depending on the average particle size and pigment content.

[Dye-containing silica-based particles]
Next, the dye-containing silica-based particles according to the present invention will be described.
The pigment-encapsulated silica-based particles according to the present invention are characterized in that the average particle diameter is in the range of 0.1 to 200 μm, and the pigment content is in the range of 0.5 to 50% by weight as the solid content.
As the dye, the aforementioned dye is used.

The dye-encapsulated silica-based particles of the first aspect according to the present invention preferably have substantially no voids inside and preferably have a porosity of less than 5% by volume.
When the porosity is less than 5% by volume, dye-encapsulated silica-based particles having excellent particle strength can be obtained.
In this case, the dye-encapsulated silica-based particles may be porous or non-porous, but depending on the application and usage, there is no elution of the dye (sometimes referred to as bleed out), so that the non-porous Dye-containing silica-based particles are preferably used.

The pigment-encapsulated silica-based particle of the second aspect according to the present invention has an outer silica layer, and the porosity inside the outer shell is in the range of 5 to 95% by volume, more preferably 20 to 90% by volume. preferable.
When the porosity is less than 5% by volume, the refractive index is not sufficiently low, and even if used by blending in cosmetics, a sufficient blurring effect may not be obtained.
It is difficult to obtain a product having a porosity exceeding 95% by volume. Even if it is obtained, the shell may be thin depending on the particle diameter, and the particle strength may be insufficient.
The outer shell silica layer may be porous or non-porous. However, depending on the application and usage, there is no elution of dye (sometimes referred to as bleed-out), so non-porous dye encapsulation is possible. Silica-based particles are preferably used.

  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 generally spherical. The porosity does not include the pore volume of the porous portion.

  The dye-encapsulated silica-based particles of the present invention have a spherical particle shape and 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 a spray drying method in consideration of productivity.

In addition, the dye-containing silica-based particles of the present invention have a dye content in the dye-encapsulated silica-based particles of 0.5 to 50% by weight, preferably 1 to 45% by weight.
When the pigment content is less than 0.5% by weight, it may differ depending on the pigment type, but when used in cosmetics and other applications, a sufficient coloring effect may not be obtained.
When the dye content exceeds 50% by weight, there are too many dyes, and it is difficult for some dyes to be encapsulated in the silica phase or in the cavity inside the outer shell. There is.

  The content of the dye in the present invention was calculated from the use amount of the dye and water glass when the dye-containing silica-based particles were prepared.

When the hollow dye-encapsulated silica-based particles (second aspect) are produced, when the drying / heating treatment is performed under reduced pressure, the inside of the outer shell layer of the resulting dye-encapsulated silica-based particles has a negative pressure. Particles can be obtained.
The spherical dye-encapsulated silica-based particles obtained at this time have a low oxygen concentration in the internal voids, so that, for example, when containing a dye that is easily decomposed by ultraviolet rays, the decomposition by ultraviolet rays can be suppressed, and discoloration or fading can be prevented. In some cases, it can be suppressed.

Accordingly, the dye-encapsulated 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. It is characterized in that the porosity is in the range of 5 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 the dye-encapsulated silica-based particles obtained by any of the production methods described above.
In the cosmetic according to the present invention, the compounding amount of the dye-containing silica-based particles is 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 pigment-encapsulated silica-based particles is less than 0.1% by weight, the blending effect of the pigment-encapsulated silica-based particles such as the coloring effect by the pigment, the lubricity, the effect of blurring the skin defects, and the transparency cannot be obtained. If it exceeds wt%, the oily sensation originally required for cosmetics may be impaired.

In addition, when the pigment-encapsulated silica-based particles of the present invention are blended in cosmetics, the surface thereof is conventionally known surface treatment agents such as silicone compounds, fluorine compounds, metal soaps, silane coupling agents, titanate coupling agents. Further, it may be treated with amino acids, lecithin and the like.
Cosmetics of the present invention, the pigment-encapsulated silica-based particles, and components that may be usually blended in cosmetics, for example, oils such as olive oil, rapeseed oil, beef tallow, jojoba oil, carnauba wax, candelilla wax, Waxes such as beeswax, paraffin, squalane, synthetic and vegetable squalane, α-olefin oligomers, hydrocarbons such as microcrystalline wax, 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, Esters such as isopropyl palmitate, 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, polyacrylic acid , Various polymers such as sodium polyacrylate, polyvinyl alcohol, anion, cation, nonionic surfactants, animal and plant extracts, amino acids and peptides, vitamins, cinnamic acid such as octyl paramethoxycinnamate , Salicylic acid-based, benzoic acid ester-based, urocanic acid-based, benzophenone-based and other UV protection agents, bactericides / preservatives, antioxidants, modified or unmodified clay minerals, solvents such as butyl acetate, acetone, toluene, 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 with various particle sizes, particle size distributions and shapes , Barium sulfate, titanium mica having a pearly luster, and composites thereof Various organic pigments, organic dyes, 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 and 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 and mouthwash Can be mentioned.

[Insulation]
The dye-encapsulated silica-based particles obtained by the production method of the present invention can be suitably used as a heat insulating material.
The dye-encapsulated silica-based particles used for the heat insulating material are preferably hollow silica-based particles (second embodiment) having cavities therein and non-porous pigment-encapsulated silica-based particles.
As a method of use 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 further to a housing building material (wall material, window material, etc.). Various uses have been proposed, such as blending, using as a heat insulating filler, or a heat insulating paint including a heat insulating filler.

[Example 1]
Preparation of dye-encapsulated silica-based particles (1) To 3000 g of water glass aqueous solution (SiO ₂ / Na ₂ O molar ratio: 3.2, SiO ₂ concentration: 24% by weight), blue acidic dye (manufactured by Sakai Kasei Co., Ltd .: Blue No. 1) 14.4 g of the dissolved dye-containing alkali silicate aqueous solution at a flow rate of 0.62 kg / hr in one of the two-fluid nozzles and air at a flow rate of 31800 L / hr (air / liquid volume ratio 63600) at the other nozzle Spraying with hot air at 400 ° C. yielded dye-encapsulated silica-based particle precursor particles (1). At this time, the outlet temperature was 150 ° C. At this time, it was (C _D ) / (C _S ) = 0.02.
Next, 500 g of the dye-encapsulated silica-based particle precursor particles (1) were immersed in 3200 g of an aqueous sulfuric acid solution having a concentration of 10% by weight and stirred for 1.5 hours. At this time, the SiO ₂ concentration was 10.2% by weight, the temperature of the dispersion was 35 ° C., and the pH was 3.0. The molar ratio (Ma) / (Ms) with the number of moles of acid (Ma) was 1.2.
Subsequently, it was dried and heat-treated at 120 ° C. for 24 hours in a dryer to prepare dye-encapsulated silica-based particles (1) colored in blue.

The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation may be referred to) of the obtained dye-containing silica-based particles (1) ) And feel characteristics were measured by the following methods, and the results are shown in the table.
It was found that the dye-encapsulated silica-based particles (1) were non-porous hollow particles having a porosity of 40%, and because the transmittance was sufficiently high, there was no elution of the dye and the degree of coloring was sufficient. . Furthermore, it has been found that the touch characteristics have a sufficient function as a cosmetic material.

The average particle diameter of pigment containing silica-based particles (1) laser diffraction scattering a 3cc particle size distribution measuring apparatus (Seishin Enterprise Co., Ltd.: LMS-30) by measuring the particle size distribution, the calculated median diameter was defined as the average particle diameter.
About 30 ml of the specific surface area dye-encapsulated silica-based particles (1) are collected in a magnetic crucible (B-2 type), dried at 300 ° C. for 2 hours, put in a desiccator and cooled to room temperature. Next, 1 g of a sample was collected, and the specific surface area (m ² / g) was measured using a BET method specific surface area measuring device (manufactured by Mountec: Model M-1220).

About 30 ml of particle-density pigment-encapsulated silica-based particles (1) are collected in a magnetic crucible (type B-2), dried at 300 ° C. for 2 hours, placed in a desiccator and cooled to room temperature. Next, 15 ml of a sample was collected, and the true specific gravity was measured using a fully automatic pycnometer (manufactured by QUANTACHROME: Ultrapyc 1200e) to obtain the particle density.
A TEM photograph of the void- containing dye-encapsulated silica-based particles (1) was measured, the particle diameters of 50 particles were measured, the average particle diameter was measured as the average value, and then the particles were broken into halves. The diameter of the cavity was measured for 50 fractured sections to determine the average diameter of the cavity, and the average cavity volume ratio of the cavity was determined by calculation.

Residual alkali amount Dye-encapsulated silica-based particles (1) were measured for Na content using an atomic absorption method (manufactured by Hitachi, Ltd., atomic absorption photometer Z-2310 type), converted to Na ₂ O, and remaining alkali amount It was.
Dye content The value calculated from the amount of dye used during preparation of the dye-encapsulated silica-based particles (1) is shown.

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 pigment-encapsulated silica-based particles (1) under certain conditions and dividing the oil absorption by the weight of the pigment-encapsulated silica-based particles (1). In the present invention, the oil absorption is expressed in ml / 100 g.

Dye elution amount 0.5 g of dye-encapsulated silica-based particles (1) is collected and transferred to a 100 ml beaker. Next, 49.5 g of pH 9.0 NaOH aqueous solution prepared using distilled water and 48 wt% NaOH aqueous solution is added and suspended, and stirred for 1 hour. Furthermore, it is dispersed for 10 minutes with an ultrasonic generator (manufactured by Iuch: US-2 type) and left to stand for 1 day. Next, the dye-encapsulated silica-based particles (1) are separated with a centrifuge, and the remaining aqueous solution is filtered through a microfilter having an opening of 0.2 μm to obtain a quartz cell (length: 10 mm, width: 10 mm). Then, the transmittance at a wavelength of 400 to 800 nm was measured using a spectrophotometer (manufactured by HITACHI: U-2000), and the lowest value in this range was defined as the transmittance. . It shows that there is so much pigment | dye elution amount that this transmittance | permeability is low.

Coloration degree (saturation)
The dye-encapsulated silica-based particles (1) are collected in a full color measuring stainless steel cup, and the surface of the sample is smoothed using a flat glass plate. Next, a cover glass (Minolta: CM-A40) is set on a spectrophotometer (Minolta: CM2002), and a light source D-60, a field of view of 10 degrees, and an SCI method, L ^* a ^* b ^* table Color measurement was performed using a color system, and saturation was calculated from the following equation.
Saturation = [(a ^* ) ² + (b ^* ) ² ] ^1/2

Sensory characteristics Dye-encapsulated silica-based particles (1) are subjected to a sensory test by 20 expert panelists. (1) Smooth feeling, (2) Moist feeling, (3) Rolling feeling, (4) Uniform elongation Interviews are conducted on seven evaluation items: spreadability, (5) adhesion to the skin, (6) persistence of rolling feeling, and (7) low pigment-encapsulated 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 of the feel of the dye-containing 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 Dye-Incorporated Silica-Based Particles (2) In Example 1, 8.8 g of blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dissolved and carried out at (C _D ) / (C _S ) = 0.012. Except that, dye-encapsulated silica-based particles (2) colored in blue were prepared in the same manner.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (2) The results are shown in the table.

[Example 3]
Preparation of dye-encapsulated silica-based particles (3) In Example 1, except that 576 g of a blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dissolved and (C _D ) / (C _S ) = 0.8 Similarly, dye-encapsulated silica-based particles (3) colored in blue were prepared.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (3) The results are shown in the table.

[Example 4]
Preparation of Dye-Incorporated Silica-Based Particles (4) In Example 1, the dye-encapsulated silica-based particle precursor particles (4) were obtained by spraying with hot air having an inlet temperature of 320 ° C. At this time, the outlet temperature was 130 ° C.
Thereafter, dye-encapsulated silica-based particles (4) colored in blue were prepared in the same manner as in Example 1.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (4) The results are shown in the table.

[Example 5]
Preparation of Dye-Incorporated Silica-Based Particles (5) In Example 1, the dye-encapsulated silica-based particle precursor particles (5) were obtained by spraying with hot air having an inlet temperature of 450 ° C. At this time, the outlet temperature was 175 ° C.
Thereafter, dye-encapsulated silica-based particles (5) colored in blue were prepared in the same manner as in Example 1.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (5) The results are shown in the table.

[Example 6]
Preparation of dye-encapsulated silica-based particles (6) Dye-encapsulated silica-based particles (6) colored in blue were prepared in the same manner as in Example 1 except that they were dried and heated at 80 ° C. for 60 hours.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (6) The results are shown in the table.

[ Reference Example 7]
Preparation of dye-encapsulated silica-based particles (7) Dye-encapsulated silica-based particle precursor particles (7) were obtained in the same manner as in Example 1, except that spray drying was performed at an inlet temperature of 250 ° C and an outlet temperature of 50 ° C.
Subsequently, dye-encapsulated silica-based particles (7) colored in blue were prepared in the same manner 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, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (7) The results are shown in the table.

[ Reference Example 8]
Preparation of dye-encapsulated silica-based particles (8) Dye-encapsulated silica-based particle precursor particles (8) were obtained in the same manner as in Example 1, except that spray drying was performed at an inlet temperature of 250 ° C and an outlet temperature of 50 ° C.
Subsequently, dye-encapsulated silica-based particles (8) colored in blue were prepared in the same manner except that they were dried and heated at 80 ° C. for 60 hours.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (8) The results are shown in the table.

[Example 9]
Preparation of dye-encapsulated silica-based particles (9) In Example 1, a dye colored in blue in the same manner as in Example 1, except that 500 g of dye-encapsulated silica-based particle precursor particles (1) were immersed in 2670 g of a 10% strength by weight sulfuric acid aqueous solution. Encapsulated silica-based particles (9) were prepared. At this time, the temperature of the dispersion was 35 ° C. and the pH was 3.5. The molar ratio (Ma) / (Ms) to the number of moles of acid (Ma) was 1.0.
The average particle size, specific surface area, particle density, porosity, residual amount of alkali, pigment content, oil absorption, pigment elution amount, coloring degree (saturation) and feel characteristics of the resulting pigment-encapsulated silica-based particles (9) The results are shown in the table.

[Example 10]
Preparation of dye-containing silica-based particles (10) In Example 1, a dye colored in blue in the same manner as in Example 1, except that 500 g of dye-encapsulated silica-based particle precursor particles (1) were immersed in 8000 g of an aqueous sulfuric acid solution having a concentration of 10% by weight. Containing silica-based particles (10) were prepared. At this time, the temperature of the dispersion was 35 ° C. and the pH was 2.0. The molar ratio (Ma) / (Ms) to the number of moles of acid (Ma) was 3.0.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (10) The results are shown in the table.

[Example 11]
Preparation of dye-encapsulated silica-based particles (11) In Example 1, pigment-encapsulated silica-based particles colored in red in the same manner as in Example 1 except that 14.4 g of red acidic dye (manufactured by Kasei Chemical Co., Ltd .: Red No. 3) was dissolved. 11) was prepared.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (11) The results are shown in the table.

[Example 12]
Preparation of Dye-Incorporated Silica-Based Particles (12) A dye-containing alkali silicate aqueous solution prepared in the same manner as in Example 1 was supplied at a flow rate of 0.62 kg / hr to one of the two-fluid nozzles and 63600 L / hr of air to the other nozzle. The dye-encapsulated silica-based particle precursor particles (12) were obtained by spraying with hot air having an inlet temperature of 420 ° C. at a flow rate of (empty / liquid volume ratio 127200). At this time, the outlet temperature was 150 ° C.
Next, 500 g of the dye-encapsulated silica-based particle precursor particles (12) was immersed in 3200 g of a 10 wt% sulfuric acid aqueous solution and stirred for 1.5 hours. At this time, the SiO ₂ concentration was 10.2% by weight, the temperature of the dispersion was 35 ° C., and the pH was 3.0. The molar ratio (Ma) / (Ms) with the number of moles of acid (Ma) was 1.2.
Subsequently, it was dried and heat-treated at 120 ° C. for 24 hours in a dryer to prepare dye-encapsulated silica-based particles (12) colored in blue.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (12) The results are shown in the table.

[Example 13]
Preparation of dye-containing silica-based particles (13) A dye-containing alkali silicate aqueous solution prepared in the same manner as in Example 1 was supplied at a flow rate of 0.62 kg / hr to one of the two-fluid nozzles and air to the other nozzle at 15900 L / hr. It was sprayed on hot air with an inlet temperature of 380 ° C. at a flow rate of (empty / liquid volume ratio 31800) to obtain dye-encapsulated silica-based particle precursor particles (13). At this time, the outlet temperature was 150 ° C.
Next, 500 g of the dye-encapsulated silica-based particle precursor particle (13) was 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) / (Ms) with the number of moles of acid (Ma) was 1.2.
Subsequently, it was dried and heat-treated at 120 ° C. for 24 hours in a dryer to prepare dye-encapsulated silica-based particles (13) colored in blue.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (13) The results are shown in the table.

[Example 14]
Preparation of dye-encapsulated silica-based particles (14) The dye-encapsulated silica-based particle precursor particles (1) prepared in the same manner as in Example 1 were acid-treated and then dried while being evacuated by a vacuum pump at a reduced pressure of 1 hPa. A dye-encapsulated silica-based particle (14) having a negative pressure inside was prepared in the same manner except that the heat treatment was performed at 120 ° C. for 24 hours.
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (14) The results are shown in the table.

[Comparative Example 1]
Preparation of dye-encapsulated silica-based particles (R1) In Example 1, 0.06 g of blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dissolved and carried out at (C _D ) / (C _S ) = 0.00008 Except that, dye-encapsulated silica-based particles (R1) colored in blue were prepared in the same manner.
The average particle size, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (R1) The results are shown in the table.
The dye-encapsulated silica-based particle (R1) is a non-porous hollow particle having a porosity of 41% and has a sufficiently high transmittance, so that it has been found that the dye does not elute. It was poor in function as a material.

[Comparative Example 2]
Preparation of dye-encapsulating silica-based particles (R2) In Example 1, except that 1200 g of a blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dissolved and (C _D ) / (C _S ) = 1.67 Similarly, dye-containing silica-based particles (R2) colored in blue were prepared.
The average particle size, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and feel characteristics of the resulting dye-containing silica-based particles (R2) The results are shown in the table.
The dye-encapsulated silica-based particles (R2) are non-porous hollow particles having a porosity of 40%, and although the degree of coloring is high, the transmittance is low and the elution of the dye is remarkable.

[Comparative Example 3]
Preparation of dye-encapsulated silica-based particles (R3) In Example 1, 500 g of dye-encapsulated silica-based particle precursor particles (1) were immersed in 3200 g of an aqueous sulfuric acid solution having a concentration of 2% by weight. At this time, the temperature of the dispersion was 35 ° C. and the pH was 9.5. The molar ratio (Ma) / (Msp) with the number of moles of acid (Ma) was 0.24.
However, since the amount of acid was too small, the dissolution of the particles was noticeable during the immersion, and the particles could not be obtained. For this reason, particle evaluation was not performed.

[Comparative Example 4]
Preparation of Dye-Containing Porous Alumina-Silica Particles (R4 ) 90 g of δ-alumina particles (Degussa, AEROXIDE Alu C) having a specific surface area of 100 m ² / g and an average particle size of 0.2 μm are added to 850 g of pure water for 30 minutes. By stirring, a suspension of the alumina particles was obtained. Next, this is subjected to a disper mill (D-type, manufactured by Hosokawa Micron Corporation) to crush the aggregates of the alumina particles contained in the suspension to obtain an aqueous dispersion in which the alumina particles are dispersed. It was.

Next, 60 g of an aqueous dispersion sol containing 16.5 wt% of silica-based particles having an average particle diameter of 0.007 μm based on SiO ₂ (JGC Catalysts & Chemicals, Cataloid SN-350) is added to this aqueous dispersion for 15 minutes. By stirring, 1000 g of a mixed slurry A in which the alumina particles and the silica particles were uniformly or almost uniformly dispersed was prepared.
The solid content concentration contained in the mixed slurry A thus obtained is 10% by weight, and when the alumina particles are represented by Al ₂ O ₃ and the silica particles are represented by SiO ₂ , its weight The ratio (Al ₂ O ₃ / SiO ₂ ) was 90/10.

  Next, the mixed slurry A is heated to hot air having an inlet temperature of 250 ° C. at a flow rate of 0.62 kg / hr to one of the two fluid nozzles and air to the other nozzle at a flow rate of 31800 L / hr (air / liquid volume ratio 63600). Spraying gave alumina / silica particle powder. Further, the obtained powder of alumina / silica particles was dried at a temperature of 110 ° C. for 18 hours to obtain 650 g of porous alumina / silica particles having an almost spherical shape and an average particle diameter of 5 μm.

Next, an aqueous solution in which 1.4 g of a blue acidic dye (Blue No. 2 manufactured by Kasei Chemical Co., Ltd.) was added to 1398.6 g of pure water with stirring was dissolved. Next, 100 g of the porous alumina / silica particles A were added to this aqueous solution, stirred for 30 minutes, and then allowed to stand for 1 hour. As a result, 2600 g of a mixed slurry B containing porous alumina / silica particles B in which the acidic dye was adsorbed on the alumina component present on the outer surface of the porous alumina / silica particles A and the inner surface of the pores was obtained.
The solid content concentration contained in the mixed slurry B thus obtained is 3.85% by weight, the acidic dye is represented by Dx, and the porous alumina-silica particles are further transformed into Al ₂ O ₃ .SiO _2. When represented by ₂ , the weight ratio (Dx / Al ₂ O ₃ · SiO ₂ ) was 0.02.

Next, the washed cake obtained by dehydrating the mixed slurry B with Nutsche was dried at a temperature of 110 ° C. for 18 hours. The color of the filtrate obtained in the dehydration was colorless and transparent. Thereby, the pigment-containing porous alumina-silica particles colored in blue (R4) in which the acidic dye is immobilized on the alumina component present on the outer surface of the porous alumina-silica particles B and the inner surface of the pores. ) 102 g was obtained.

The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, dye content, oil absorption, dye elution amount, coloring degree (saturation) and color of the obtained dye-containing porous alumina / silica particles (R4) The feel characteristics were measured and the results are shown in the table.
The dye-containing porous alumina / silica particles (R4) were porous particles, and although the degree of coloring was high, the transmittance was low and the elution of the dye was remarkable.
In the neutral region (pH = 7), the dye was not eluted, but it was observed that the dye was eluted in the weak alkali region (pH = 9).

[Comparative Example 5]
Preparation of silica-based particles (R5) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: S-20L, average particle diameter 19 nm, SiO ₂ concentration 20% by weight) 3600 g, blue acidic dye (manufactured by Sakai Kasei Co., Ltd .: Blue No. 1) The pigment-containing silica sol having 7.2 g dissolved therein is supplied at a flow rate of 0.62 kg / hr to one of the two-fluid nozzles, the air is supplied to the other nozzle at a flow rate of 31800 L / hr (air / liquid volume ratio 63600), and the inlet temperature 250 The carrier powder (R5) was obtained by spraying with hot air at 0 ° C. At this time, the outlet temperature was 50 ° C. At this time, it was (C _D ) / (C _S ) = 0.02.
Measure the average particle size, specific surface area, particle density, porosity, residual amount of alkali, pigment content, oil absorption, pigment elution amount, coloring degree (saturation) and feel characteristics of the resulting silica particles (R5). The results are shown in the table.
Silica-based particles (R5) are porous particles, and although the degree of coloring is high, the transmittance is low and the elution of the dye is remarkable. That is, it was found that the silica-based particles (R5) cannot sufficiently contain the pigment.

[Examples 15 to 28] and [Comparative Example 6]
Preparation of powder foundation The silica-based particle components (1) and (2) to (9) obtained in Examples 1 to 14 and Comparative Example 5 were mixed in mixers 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 P14 and Comparative cosmetic PR5 containing silica-based particles were obtained.

  Next, the feeling of use of the cosmetics P1 to P14 and Comparative cosmetic PR5 obtained in this way was 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 totaled, and an evaluation regarding 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 29 to 42] 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 14 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-L14 and Comparative Example cosmetics LR5 which compounded silica-based particles.

  Next, the feeling of use (redispersibility of silica-based particles before use and feel during application) and the feeling of finish (feel after application) of Example cosmetics L1 to L14 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 totaled, and an evaluation regarding 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 43 to 46] and [Comparative Examples 8 and 9]
Preparation of heat 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 1, 4, 5 and 14 was added to 11.8 g of the mixed resin solution (resin specific gravity: 1.1 g / cc, resin volume: 8.0 cc) in terms of particle density. After adding 5.2 g, 6.9 g, 3.5 g, and 5.2 g to 33% by volume (3.9 cc), respectively, dispersion treatment was performed for 1 minute with a horn type ultrasonic device (manufactured by Marine Radio Service). Thus, 4 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 H4 with heat insulating thin films were obtained.
Moreover, about the resin solution prepared similarly except not mix | blending a silica type particle, and the silica type particle obtained in the comparative example 5, 8.6g was mix | blended so that it might become 33 volume% by particle density conversion. Except for the above, two resin solutions prepared in the same manner were applied in the same manner, dried and cured to obtain base materials RH1 to RH2 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 (8)

A method for producing pigment-encapsulated silica-based particles having an outer shell silica layer and having a void ratio of 5 to 95% by volume inside the outer shell ,
(A) an inlet temperature of 300 to 600 ° C. The alkali silicate aqueous solution in a hot air flow containing a dye, was spray-dried at an outlet temperature of 120 to 300 ° C., preparing a precursor particles of the dye containing silica-based particles ,
(B) the precursor particles were immersed in an acid aqueous solution, and removing the alkali,
(C) The process of drying and heat-processing , The manufacturing method of the dye inclusion | inner_cover silica particle characterized by the above-mentioned. In the step (a), the alkali silicate aqueous solution has a SiO ₂ / M ₂ O molar ratio (where M represents an alkali metal) in the range of 1 to 5, and the SiO ₂ concentration (C _S ) is 1 to 5. in the range of 30 wt%, that the concentration _{(C D)} and the SiO ₂ concentration of the dye _{(C S)} and the concentration ratio of _{(C D) / (C S} ) is in the range of 0.0002 to 1 The method for producing a dye-containing silica-based particle according to claim 1, wherein Wherein in the step (b), the range of the molar ratio of the precursor _{M 2} O mole number in the particles and (Ms) the number of moles of acid and (Ma) (Ma) / ( Ms) is from 0.6 to 4.7 The method for producing dye-encapsulated silica-based particles according to claim 1 or 2 , wherein the concentration of the precursor particles is in the range of 1 to 30% by weight as a solid content. The drying / heat treatment temperature in the step (c) is in the range of 90 to 300 ° C, and the outer silica layer of the resulting dye-containing silica-based particles is nonporous . The manufacturing method of the dye inclusion | inner_cover silica particle as described in any one . And dried and heat treatment in the step (c) under reduced pressure, according to any one of claims 1 to 4 inner shell layer is characterized by a negative pressure of the resulting dye containing silica-based particles The manufacturing method of the dye inclusion | inner_cover silica particle. A dye-encapsulated silica-based particle having an outer shell silica layer and a porosity of 5 to 95% by volume inside the outer shell, wherein the dye-encapsulated silica-based particle has an average particle diameter in the range of 0.1 to 200 μm. A pigment-encapsulated silica-based particle , wherein the pigment content is in the range of 0.5 to 50% by weight as a solid content, and the outer silica layer is nonporous . 7. The dye-encapsulated silica-based particle according to claim 6 , wherein the inside of the outer shell has a negative pressure. A cosmetic comprising pigment-containing silica-based particles having the structure according to claim 6 .