JP2013133410A - Method for producing dyestuff and/or pigment-including metal oxide particle, the dyestuff and/or pigment-including metal oxide particle, and use of the particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide dyestuff and/or pigment-including metal oxide particles, neither easily falling off and eluting the dyestuff and/or pigment nor discoloring (color-changing).SOLUTION: The dyestuff and/or pigment-including metal oxide particles are produced by: (a) preparing metal oxide particle precursor particles by spray drying in hot air flow, a predetermined hydrolyzed polycondensate dispersion of the dyestuff and/or pigment, obtained by dispersing the dyestuff and/or pigment in a specific hydrolyzed polycondensate, in which the average molecular weight of the hydrolyzed polycondensate is in a range of 500 to 100,000, the total solid concentration is in a range of 5 to 100 wt.% and the ratio (C)/(C) of the concentration (C) of the dyestuff and/or pigment as a solid part to the concentration (C) of the hydrolyzed polycondensate as a solid part is in a range of 0.0002 to 2.3; and (b) dry/heat-treating the precursor particles.

Description

  The present invention relates to a method for producing dye- and / or pigment-encapsulated metal oxide particles, a dye and / or pigment-encapsulated metal oxide particle, and a cosmetic and a heat insulating material containing the dye and / or pigment-encapsulated metal oxide particles. is there.

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.
In addition, the color of the dye or pigment itself may not appear as it is, and it may be faded. Furthermore, for example, when blended in cosmetics, it may be difficult to remove from the skin once dried, 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

  As a result of intensive studies on the above problems, the present inventors have found that when a hydrolyzed polycondensate having a predetermined degree of polymerization is hydrolyzed by a hydrolyzable organosilicon compound, It was found to have a cavity. Similarly, when a hydrolyzate of a hydrolyzable organotitanium compound having a predetermined polymerization degree is spray-dried, it has been found that the resulting particles have cavities. At this time, when the hydrolyzed polycondensate dispersion liquid contains a dye and / or pigment, the dye used, the dye colored in the same color as the pigment, the silica particles containing the pigment, and the titanium oxide particles are obtained. As a result, the present invention has been completed.

An object of this invention is to provide the manufacturing method of the metal oxide particle which included the dye and / or the pigment, the pigment inclusion | inner_cover silica particle, and the use of this particle | grain.
More specifically, (1) a spherical dye and / or pigment encapsulating metal oxide particle whose inside is a porous or nonporous (nonporous) metal oxide phase, or (2) an outer shell, Dye and / or pigment-encapsulated metal oxide particles having a cavity inside the outer shell, the outer shell being a porous or non-porous metal oxide phase, and (3) a dye having a negative pressure in the cavity and In the pigment-encapsulated metal oxide particles, since the dye and / or pigment is contained in the metal oxide phase and / or the cavity, the dye and / or pigment can be easily removed or eluted, or can be discolored (discolored). And a method for producing dye- and / or pigment-encapsulated metal oxide particles having excellent lubricity because the particles are spherical, and use of the dye- and / or pigment-encapsulated metal oxide particles and uses of the particles It is an object.

The method for producing dye- and / or pigment-encapsulated metal oxide particles according to the present invention is characterized by comprising the following steps (a) and (b).
(A) A hydrolyzed polycondensate dispersion of a hydrolyzable metal compound represented by the following formula (1) obtained by dispersing a dye and / or a pigment, wherein the hydrolyzed polycondensate has an average molecular weight of 500. In the range of ~ 100,000, the total solid content is in the range of 5 to 100% by weight, the concentration (C _D ) as the solid content of the dye and / or pigment and the solid content of the hydrolyzed polycondensate concentration _{(C H)} ratio of _{(C D) / (C H} ) is spray dried dyes and / or pigments hydrolysis condensation polymerization product dispersion in the range of 0.0002 to 2.3 in a hot air stream Step of preparing dye- and / or pigment-encapsulated metal oxide particle precursor particles R _n -MX _m-n (1)
(Wherein, M is at least one element selected from Si, Ti, Zr, and Al, and R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen, hydrogen, m: valence of element M, 3 or 4, n: integer of 0 to 2, and mn is 2 or 3)
(B) Process of drying and heat treatment

It is preferable that the dye is a natural dye or a synthetic dye, and the pigment is an organic pigment or an inorganic pigment.
It is preferable that the inlet temperature of the hot air in the spray drying is in the range of 100 to 600 ° C and the outlet temperature is in the range of 40 to 300 ° C.
The drying / heat treatment temperature in the step (b) is preferably in the range of 30 to 1200 ° C.
The average particle diameter of the dye- and / or pigment-encapsulated metal oxide particles is preferably in the range of 0.1 to 200 μm.

In the spray drying, 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 and / or pigment-encapsulated metal oxide particles is less than 5% by volume. It is preferable.
It is preferable that the drying / heat treatment temperature in the step (b) is in the range of 30 to 120 ° C., and the obtained dye and / or pigment-encapsulated metal oxide particles are porous.
It is preferable that the drying / heat treatment temperature in the step (b) is in the range of 90 to 1200 ° C., and the resulting dye and / or pigment-encapsulated metal oxide particles are nonporous.

In the spray drying, 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 and / or pigment-encapsulated metal oxide particles are placed inside the outer shell metal oxide layer. It is preferable to have a cavity, and the porosity of the cavity is in the range of 5 to 95% by volume.
It is preferable that the drying / heat treatment temperature in the step (b) is in the range of 30 to 120 ° C., and the resulting outer metal oxide layer of the dye- and / or pigment-encapsulated metal oxide particles is porous.
It is preferable that the drying / heat treatment temperature in the step (b) is in the range of 90 to 1200 ° C., and the outer metal oxide layer of the resulting dye and / or pigment-encapsulating metal oxide particles is nonporous.
It is preferable that the drying and heating treatment in the step (b) is performed under reduced pressure, and the inside of the outer shell layer of the resulting dye and / or pigment-encapsulating metal oxide particles has a negative pressure.

The dye and / or pigment-containing metal oxide particles according to the present invention include the dye and / or pigment, the average particle diameter is in the range of 0.1 to 200 μm, and the metal oxide is Si, Ti, Zr, Al. It is characterized by being an oxide of at least one element obtained from
The content of the dye and / or pigment is preferably in the range of 0.5 to 70% by weight as a solid content.
It is preferable that the dye is a natural dye or a synthetic dye, and the pigment is an organic pigment or an inorganic pigment.

The dye and / or pigment-containing metal oxide particles according to the first aspect of the present invention preferably have a porosity of less than 5% by volume.
The dye- and / or pigment-encapsulated silica-based particles may be porous or non-porous.

The dye and / or pigment-encapsulating metal oxide particles according to the second aspect of the present invention have an outer shell metal oxide layer, and have a cavity inside the outer shell metal oxide layer, and the porosity of the cavity. Is preferably in the range of 5 to 95% by volume.
The outer shell metal oxide layer may be porous, but is preferably nonporous, and more preferably has a negative pressure inside the outer shell layer.

  The dye and / or pigment-encapsulated metal oxide particles are preferably dyes and / or pigment-encapsulated metal oxide particles produced by any one of the dye and / or pigment-encapsulated metal oxide particles.

The cosmetic according to the present invention comprises the dye and / or pigment-encapsulated metal oxide particles obtained by any one of the above-described production methods, or the above-described dye and / or pigment-encapsulated metal oxide particles. It is characterized by that.
The blending amount of the dye and / or pigment-encapsulating metal oxide particles is preferably in the range of 0.1 to 30% by weight.

  The heat insulating material according to the present invention is formed by blending the dye and / or pigment-containing metal oxide particles obtained by any one of the above production methods, or any one of the dye and / or pigment-containing metal oxide particles. It is characterized by that.

According to the present invention, the particle shape is spherical, and (1) a dye and / or pigment encapsulating metal oxide particle having a porous or non-porous metal oxide phase, or (2) having an outer shell. Dye and / or pigment-encapsulated metal oxide particles having a cavity inside the outer shell, the outer shell being a porous or non-porous metal oxide phase, and (3) the cavity has a negative pressure In the dye- and / or pigment-encapsulated metal oxide particles, the dye and / or pigment is easily removed or eluted due to the inclusion of the dye and / or pigment in the metal oxide phase and / or cavity. And a method for producing dye- and / or pigment-encapsulated metal oxide particles having excellent lubricity due to the spherical shape of the particles and the use of the dye- and / or pigment-encapsulated metal oxide particles and uses of the particles You It is possible.
Moreover, according to this invention, the cosmetics and heat insulating material using the said dye and / or pigment inclusion metal oxide particle can be provided.

[Method for Producing Dye and / or Pigment-Encapsulated Metal Oxide Particles]
Below, the manufacturing method of the dye and / or pigment inclusion metal oxide particle concerning this invention is demonstrated first.
The method for producing dye- and / or pigment-encapsulated metal oxide particles according to the present invention is characterized by comprising the following steps (a) and (b).
(A) A hydrolyzed polycondensate dispersion of a hydrolyzable metal compound represented by the following formula (1) obtained by dispersing a dye and / or a pigment, wherein the hydrolyzed polycondensate has an average molecular weight of 500. In the range of ~ 100,000, the total solid content is in the range of 5 to 100% by weight, the concentration (C _D ) as the solid content of the dye and / or pigment and the solid content of the hydrolyzed polycondensate concentration _{(C H)} ratio of _{(C D) / (C H} ) is spray dried dyes and / or pigments hydrolysis condensation polymerization product dispersion in the range of 0.0002 to 2.3 in a hot air stream Step of preparing dye- and / or pigment-encapsulated metal oxide particle precursor particles R _n -MX _m-n (1)
(Wherein, M is at least one element selected from Si, Ti, Zr, and Al, and R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen, hydrogen, m: valence of element M, 3 or 4, n: integer of 0 to 2, and mn is 2 or 3)
(B) A step of drying and heat-treating the dye and / or pigment-encapsulating metal oxide particle precursor particles

Step (a)
A metal oxide particle precursor particle is prepared by spray-drying a hydrolyzed polycondensate dispersion of the hydrolyzable metal compound represented by the formula (1) obtained by dispersing a dye and / or pigment in a hot air stream. To do.

  As the hydrolyzable metal compound represented by the formula (1) used in the present invention, when the metal is specifically silicon, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxy Silane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Sisilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- ( (Meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ -(Meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxy Cypropyltrimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane , Decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluoro Octylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-amino Nopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, etc. Can be mentioned. Further, silicon tetrachloride, silane trichloride, disilicon hexachloride, and the like can also be suitably used.

  When the metal element is titanium, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra-2-ethylhexoside, titanium diisopropoxybisacetylacetonate, titanium tetraacetylacetonate, titanium dioctyloxybisoctylene glycolate, Examples include titanium diisopropoxybisethyl acetoacetate, polyhydroxytitanium stearate, titanium isopropoxyoctylene glycolate, tetrakis 2-ethylhexyloxytitanium, diisopropoxybisacetylacetonatotitanium, and the like. Moreover, titanium tetrachloride, titanyl sulfate, etc. can be used suitably.

  In addition, when the metal element is zirconium, zirconium tetraisopropoxide, zirconium tetranormal butoxide, zirconium tetra-2-ethylhexoside, and the like can be given. Moreover, tetrasalt zirconium, a zirconyl chloride, etc. can be used suitably.

When the metal element is aluminum, examples include aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-2-ethylhexoside, and the like.
Moreover, aluminum chloride, aluminum sulfate, aluminum nitrate, etc. can be used suitably.

The average molecular weight of the hydrolyzed polycondensation product of the hydrolyzable metal compound described above is preferably in the range of 500 to 100,000, more preferably 700 to 50,000.
When the average molecular weight of the hydrolyzed polycondensate is less than 500, depending on the type of hydrolyzable metal compound, when the hydrolyzable metal compound volatilizes during spray drying, metal oxide particle precursor particles cannot be obtained. Even if obtained, particles having cavities inside may not be obtained.
When the average molecular weight of the hydrolysis-condensation polymer exceeds 100,000, metal oxide particle precursor particles may be obtained, but metal oxide particles having cavities inside may not be obtained.

The average molecular weight of the hydrolyzed polycondensation product is measured by a GPC (Gel Phase Chromatography) method using a molecular weight measuring device (manufactured by Tosoh Corporation: GPC8020).
That is, 1 mL of the coating solution as a sample is placed on the eluent and passed through a gel column (manufactured by Tosoh Corp .: TSKgel, Tosoh Corp .: G5000Hxl, TSKgel G3000Hxl connected), thereby hydrodynamic volume of the molecular components in the sample. The molecular weight distribution is measured by the difference in refractive index from the reference for each hour. Next, the weight average molecular weight in terms of polystyrene is calculated by converting the measured molecular weight distribution in comparison with the distribution of polystyrene having a known molecular weight measured in advance.

Dye As the dye used in the present invention, a natural dye or a synthetic dye can be used.
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.

Pigment As the pigment used in the present invention, inorganic pigments and organic pigments are used.
Examples of inorganic pigments include white pigments such as titanium oxide, zinc oxide, zinc sulfide, and barium sulfate, yellow lead, chromium vermilion, cadmium pigments, nickel titanium, chromium titanium, yellow iron oxide, bengara, zinc chromate, and red lead. Chromatic pigments such as ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, black pigments such as carbon black, titanium black, graphite, and fluorescent pigments such as zinc sulfide, strontium sulfide, strontium aluminate It is done.

  Organic pigments include azo pigments classified as soluble azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments classified as metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinones. , Isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex, DPP, etc. Such acid dyes having acidic groups are raked with metal salts such as aluminum, calcium and barium to make them insoluble as pigments, and basic dyes having amino groups or derivatives thereof in the molecule are tannic acid or phosphoric acid. Called tungstic acid, phosphomolybdic acid, complex acid Are dye lake pigments such as to be classified into a basic dye lake was insoluble as a pigment laked the like by the complex acid.

These can also be mixed and used as needed.
Furthermore, pigments such as natural dyes and synthetic dyes can be blended with the above pigments as necessary. 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 and pigments, 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, dyes for ink jets, and heat sensitive dyes , Pressure sensitive dye, dye for sublimation transfer, dye for melt transfer, diazo photosensitive material, dye for electrophotography, charge adjusting agent for toner, dye for laser recording, color photograph for color development method, color photosensitive material for silver dye bleaching method, increase Sensitive dyes, photochromic dyes, thermochromic dyes, chemiluminescent dyes, dry film dyes, stationery dyes, plastic eyeglass lens dyes, colored smoke dyes, organic nonlinear optical dyes, invisible dyes, energy conversion dyes (organic Water-soluble functional dyes such as photoelectric conversion dyes can also be used.

  In addition, when the dye and / or pigment-encapsulated metal oxide particles of the present invention are blended in cosmetics, quasi-drug raw material standards 2006 (issued by Yakuji Nippo Co., Ltd., June 16, 2006) It is preferable to use dyes listed in the International Cosmetic Ingredient Dictionary and Handbook (issued by The Cosmetic, Toiletry, and Fragrance Association, 13th Edition 2010).

As the dispersion medium of the dispersion medium hydrolysis-condensation polymer dispersion, usually alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. Modified alcohols are used, and a mixture thereof can also be suitably used.
Furthermore, if necessary, esters, glycols, ethers, esters, and ketones may be mixed and used.

The method for preparing the hydrolyzed polycondensate dispersion varies depending on the type of hydrolyzable metal compound, and is not particularly limited as long as the hydrolyzed polycondensate having the aforementioned degree of polymerization is obtained. For example, the hydrolyzable metal described above When the compound is a hydrolyzable organometallic compound, it can be prepared by adding a necessary amount of water to an alcohol solution of the hydrolyzable organometallic compound. At this time, an acid or an alkali can be added as a hydrolysis catalyst if necessary.
In addition, when the hydrolyzable metal compound is a metal salt, it can be prepared by adding an alkali such as an alkali metal hydroxide or ammonia to the aqueous metal salt solution, although it varies depending on the type of the metal salt.

In the above, the molecular weight can be adjusted by adjusting the concentration, temperature, pH, etc. during hydrolysis or neutralization. For example, by increasing the concentration and temperature, the molecular weight and the degree of polymerization can be increased. A decomposition condensation polymer can be prepared. Furthermore, it can be prepared by aging after hydrolysis or neutralization.
In addition, the prepared hydrolyzed polycondensate dispersion can be used after removing narrow ions with an ion exchange resin or the like, if necessary, further concentrated with an ultrafiltration membrane or the like, or added with water. The density can be adjusted within the range.

Ratio (C _D ) / (Concentration (C _D ) as solid content of dye and / or pigment in the dispersion of hydrolyzed polycondensation product and concentration (C _H ) as solid content of hydrolyzed polycondensation product C _H ) is preferably in the range of 0.0002 to 2.3, more preferably 0.01 to 2.0.
When the ratio (C _D ) / (C _H ) is less than 0.0002, the content of the dye and / or pigment in the obtained dye and / or pigment-encapsulated metal oxide particles is small, so that cosmetics and other uses When used in the above, a sufficient coloring effect may not be obtained.
When the ratio (C _D ) / (C _S ) exceeds 2.3, there are too many dyes and / or pigments, and the desired dyes and / or pigment-containing metal oxide particles, in particular, dyes having cavities inside and / or Or, it may be difficult to obtain pigment-encapsulated metal oxide particles.

The total solid content of the hydrolyzed polycondensate dispersion is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.
When the concentration of the hydrolyzed polycondensate in the dispersion is less than 5% by weight as the solid content, metal oxide particles having cavities therein may not be obtained.
The concentration of the hydrolyzed polycondensate in the dispersion of 100% by weight of solid content means that there is substantially no dispersion medium and only the hydrolyzed polycondensate and the dye and / or pigment. However, depending on the type of hydrolysis-condensation polymer, it can be suitably used for the production of dye- and / or pigment-encapsulated metal oxide particles having cavities inside.

  The hydrolyzed polycondensate dispersion in which a dye and / or pigment is dispersed is spray-dried in a hot air stream, and the spray-drying method is not particularly limited as long as the dye and / or pigment-encapsulated metal oxide particles described below are obtained. Although there is no method, a conventionally known method such as a rotating disk method, a pressure nozzle method, or 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 not only a dye- and / or pigment-encapsulated metal oxide particle precursor particle having cavities inside but also cavities inside may be obtained. Even if a dye- and / or pigment-encapsulated metal oxide particle precursor particle having no pigment is obtained, drying may be insufficient, adhesion to the spray drying chamber wall surface or the like may be severe, and the yield may be significantly reduced.
When the inlet temperature of the hot air exceeds 600 ° C., dye and / or pigment-encapsulated metal oxide particle precursor particles having no voids inside cannot be obtained. Furthermore, even if a dye and / or pigment-encapsulated metal oxide particle precursor particle having a cavity inside is obtained, the drying is too fast, resulting in an increase in particle diameter and a decrease in the thickness of the outer shell. This is not preferable because it tends to be a dye- and / or pigment-encapsulated metal oxide particle precursor particle.

When the outlet temperature of the hot air is less than 40 ° C., drying is insufficient, and a dye and / or pigment-encapsulating metal oxide particle precursor particle having voids inside cannot be obtained, and a dye and / Alternatively, even if the pigment-encapsulated silica-based particle precursor particles are obtained, the adhesion to the spray-drying chamber wall surface or the like is intense, and the yield may be significantly reduced.
When the outlet temperature of the hot air exceeds 300 ° C., pigment-encapsulated silica-based particle precursor particles having no voids inside cannot be obtained. Furthermore, even if a dye and / or pigment-encapsulated metal oxide particle precursor particle having a cavity inside is obtained, the drying is too fast, resulting in an increase in particle diameter and a decrease in the thickness of the outer shell. This is not preferable because it tends to be a dye- and / or pigment-encapsulated metal oxide particle precursor particle.

  The term “precursor particles” as used herein refers to dye and / or pigment-containing metal oxide particles obtained by spray-drying a hydrolyzed polycondensate dispersion in which a dye and / or pigment is dispersed. In the step (b), it is a particle in the previous stage that becomes a dye and / or pigment-containing metal oxide particle by drying and heat treatment.

In the present invention, when producing solid dye and / or pigment-encapsulated metal oxide particles (first embodiment) substantially free of cavities inside, the inlet temperature in the spray drying is 100 to 300 ° C., It is preferably in the range of 150 to 250 ° C, and the outlet temperature is preferably in the range of 40 to 120 ° C, and more preferably in the range of 50 to 100 ° C.
At this time, when the inlet temperature in spray drying is less than 100 ° C., even if dye and / or pigment-encapsulated metal oxide particle precursor particles having substantially no voids are obtained, drying is insufficient and spraying is performed. There are cases where the adhesion to the drying chamber wall surface is severe and 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 dye and / or pigment-containing metal oxide particles (second embodiment) having cavities therein, the inlet temperature in the spray drying is 300 to 600 ° C., more preferably 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 and / or pigment-encapsulating metal oxide particles having cavities in the interior may not be obtained depending on the outlet temperature.
When the inlet temperature in spray drying exceeds 600 ° C., a ruptured dye and / or pigment-encapsulated metal oxide particle precursor particle is formed, and a dye- and / or pigment-encapsulated silica-based particle having a cavity inside is formed. In some cases, it may be difficult to obtain, and even if obtained, the thickness of the outer shell becomes thin, and the strength of the resulting dye- and / or pigment-encapsulated silica-based particles may be insufficient.

When the hot air outlet temperature is lower than 120 ° C., dye- and / or pigment-encapsulated metal oxide particles having cavities inside may not be obtained.
When the outlet temperature of hot air exceeds 300 ° C., a ruptured dye and / or pigment-encapsulated metal oxide particle precursor particle is formed, and a dye and / or pigment-encapsulated metal oxide particle having a cavity inside is formed. In some cases, it may be difficult to obtain, and even if obtained, the thickness of the outer shell becomes thin, and the strength of the resulting dye and / or pigment-encapsulated metal oxide particles may be insufficient.

  In addition, when producing dye and / or pigment-encapsulated metal oxide particles (second embodiment), if the inlet temperature and outlet temperature in spray drying are in the above ranges, particles having cavities inside are formed. At that time, dyes and / or pigments tend to be present inside the cavities (cavity wall surfaces), and finally, dyes and / or pigment-encapsulated metal oxide particles in which the dyes and / or pigments are hardly detached or eluted are obtained. . The reason for this is not necessarily clear, but the droplets of the hydrolyzable polycondensate dispersion of the hydrolyzable metal compound in which the dyes and / or pigments formed by spraying are dispersed are first dried on the surface of the droplets. Thus, it is presumed that the metal oxide layer (coating film) is formed, and the metal oxide layer (coating film) becomes thick as the drying progresses, and the dye and / or pigment is pushed inside.

Step (b)
Subsequently, the dye and / or pigment-containing metal oxide particle precursor particles are dried and heat-treated.
The drying / heat treatment temperature is preferably in the range of 30 to 1200 ° C.
Solid dye and / or pigment-encapsulated metal oxide particles according to the present invention (first embodiment) that are porous and hollow dye and / or pigment-encapsulated metal oxide particles (second embodiment) In the case of producing 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.
When the drying / heat treatment temperature exceeds 120 ° C., the pores disappear and porous dye and / or pigment encapsulated metal oxide particles, and the outer shell is porous dye and / or pigment encapsulated metal oxide particles are obtained. It may not be possible.
In addition, for example, the porous dye and / or the pigment-encapsulating metal is obtained by carrying out the drying / heating treatment at 120 ° C. and then performing the second drying / heating treatment at a higher temperature without losing the pores. Oxide particles and dye- and / or pigment-encapsulated metal oxide particles having a porous outer shell may be obtained.

Solid dye and / or pigment-encapsulated metal oxide particles according to the present invention (first embodiment), non-porous and hollow dye and / or pigment-encapsulated metal oxide particles (second embodiment) However, when producing a non-porous outer shell, the drying / heating 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., the pores may not disappear, and the non-porous dye and / or pigment-encapsulated metal oxide particles or the outer shell of the non-porous dye and / or pigment-encapsulated Metal oxide particles 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.
The heat treatment temperature is preferably selected as appropriate according to the type of dye or pigment. For example, in the case of dyes and organic pigments, it is necessary to select a low temperature within a range where the heat resistance is low and discoloration is not caused. Furthermore, it is necessary to select a low temperature within a range that does not change color depending on the type of inorganic pigment.

In the present invention, the non-porous dye and / or pigment-encapsulated metal oxide particles refer to particles having a specific surface area (SA) of about 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, the content of the dye, and the pigment, the pigment-encapsulated silica-based particles have substantially no micropores that contribute to SA, Non-porous.
On the other hand, the specific surface area (SA) of the particles exceeds about 27 m ² / g, although it differs depending on the average particle diameter, the content of the dye and the pigment, and the porous dye and / or pigment-encapsulated metal oxide particles in the present invention. Refers to particles.
When the specific surface area exceeds approximately 27 m ² / g, the dye and / or the pigment-encapsulated metal oxide particles substantially have micropores that contribute to SA, although depending on the average particle diameter, the content of the dye and the pigment. That is, it is porous.

[Dye and / or pigment encapsulated metal oxide particles]
The solid dye and / or pigment-encapsulated metal oxide particles according to the present invention (first aspect) preferably have substantially no voids inside and have a porosity of less than 5% 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 5% by volume, the outer shell portion is reduced, and when the outer shell portion is used for useful applications such as adsorbents and oil absorbents, the amount of adsorption and oil absorption may be insufficient. .

The hollow dye and / or pigment-encapsulated metal oxide particles according to the present invention (second embodiment) have cavities therein, and the porosity of the particles is from 5 to 95% by volume, more preferably from 20 to 90% by volume. It is preferable to be in the range.
When the porosity is less than 5% by volume, the effect of reducing the particle density is insufficient, the refractive index is not sufficiently low, and even if used as a heat insulating material, a sufficient heat insulating effect may not be obtained. .
It is difficult to obtain a dye- and / or pigment-encapsulated metal oxide particle having a porosity exceeding 95% by volume. Even if it is obtained, the shell becomes thin depending on the particle diameter, and the particle strength becomes insufficient. There is a case.

  The average particle size of the dye- and / or pigment-encapsulated metal oxide particles of the present invention is in the range of 0.1 to 200 μm. 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 dye and / or pigment-encapsulated metal oxide particles (second embodiment) are produced, the outer shell of the resulting dye and / or pigment-encapsulated metal oxide particles is obtained by drying and heating under reduced pressure. Dye and / or pigment-containing metal oxide particles having a negative pressure inside the layer can be obtained.
The spherical dye and / or pigment-encapsulated metal oxide particles obtained at this time have a low refractive index, and when used in cosmetics, for example, when the dye and / or pigment-encapsulated silica particles are used, lubricity In addition, it is possible to obtain the effect of blending the silica particles encapsulating dyes and / or pigments, such as an effect of ameliorating skin defects and a feeling of transparency. Moreover, when it uses as a heat insulating material, it is excellent in the heat insulation effect.

Therefore, the dye and / or pigment-encapsulated metal oxide 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 silica layer. The void ratio is in the range of 5 to 95% by weight, the outer 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.
Metal oxide particles having a negative pressure inside the cavity have a low particle density and refractive index, and are excellent in heat insulating properties.
The dye and / or pigment-encapsulated metal oxide particles according to the present invention described above are dyes and / or pigment-encapsulated metal oxide particles produced by any one of the above-described dye and / or pigment-encapsulated metal oxide particles. Preferably there is.

[Cosmetics]
The cosmetic according to the present invention is characterized in that the dye and / or pigment-encapsulated metal oxide particles obtained by any one of the production methods described above are blended.
In the cosmetic according to the present invention, the blending amount of the dye- and / or pigment-encapsulated metal oxide particles is in the range of 0.1 to 30% by weight, and particularly preferably in the range of 1 to 20% by weight. When the compounding amount of the dye and / or pigment-encapsulating metal oxide particles is less than 0.1% by weight, the dye and / or pigment-encapsulating metal such as coloring effect by the dye, pigment, lubricity, effect of blurring the skin defects, and transparency The compounding effect of the oxide particles cannot be obtained, and if it exceeds 30% by weight, the oily sensation originally required for cosmetics may be impaired.

  In addition, when the dye and / or pigment-encapsulating metal oxide 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, You may process with a titanate coupling agent, amino acids, lecithin, etc.

  The cosmetic of the present invention comprises the above-mentioned dye- and / or pigment-encapsulated metal oxide particles and components that are usually blended in the cosmetic, for example, oils such as olive oil, rapeseed oil, beef tallow, jojoba oil, carnauba wax , Waxes such as candelilla wax and beeswax, paraffin, squalane, synthetic and plant squalane, α-olefin oligomer, hydrocarbons such as microcrystalline wax, pentane, hexane, stearic acid, myristic acid, oleic acid, α- Fatty acids such as hydroxy acids, isostearyl alcohol, octyldodecanol, lauryl alcohol, ethanol, isopropanol, butyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, behenyl alcohol, alkyl glyceryl ethers, myris Esters such as isopropyl titanate, isopropyl palmitate, ethyl stearate, ethyl oleate, cetyl laurate, decyl oleate, polyhydric alcohols such as ethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, glycerin, diglycerin Saccharides such as sorbitol, glucose, sucrose, trehalose, methylpolysiloxane, methylhydrogenpolysiloxane, methylphenyl silicone oil, various modified silicone oils, silicone oils such as cyclic dimethylsilicone oil, fluorine such as perfluoropolyether Oil, gum arabic, carrageenan, agar, xanthan gum, gelatin, alginic acid, guar gum, albumin, pullulan, carboxyvinyl polymer, cellulose and its derivatives Various polymers such as polyacrylic acid amide, sodium polyacrylate, polyvinyl alcohol, anions, cations, various nonionic surfactants, animal and plant extracts, amino acids and peptides, vitamins, octyl paramethoxycinnamate, etc. Cinnamic acid, salicylic acid, benzoic acid ester, urocanic acid, benzophenone and other UV protection agents, bactericides / preservatives, antioxidants, modified or unmodified clay minerals, butyl acetate, acetone, toluene Solvents such as, various particle sizes, particle size distributions and shapes of titanium oxide, zinc oxide, aluminum oxide, aluminum hydroxide, bengara, yellow iron oxide, black iron oxide, cerium oxide, zirconium oxide, silica, mica, talc, seri Site, boron nitride, barium sulfate, titanium mica with pearl luster And composites thereof, various organic 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]
Among the dye and / or pigment-encapsulated metal oxide particles obtained by the production method of the present invention, hollow silica-based particles (second embodiment) and a non-porous dye and / or pigment-encapsulated metal in the outer shell Oxide particles are preferred as a heat insulating material. Furthermore, dye and / or pigment-encapsulated metal oxide particles having a negative pressure inside the cavity are preferred as the heat insulating material, and dye and / or pigment-encapsulated metal oxide particles having a negative pressure of 133 hPa (100 mmHg) or less are particularly preferred.
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]
The dye and / or pigment-encapsulated metal oxide particles according to the present invention, and the dye and / or pigment-encapsulated metal oxide particles obtained by the method for producing the dye and / or pigment-encapsulated metal oxide particles according to the present invention are resin compositions. Can be blended. 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 high porosity, in particular, dye- and / or pigment-containing metal oxide particles having a non-porous shell and negative pressure inside the void. Has no hygroscopicity, can maintain a low dielectric constant for a long time, and 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 required to cure the resin, a curing agent and a curing accelerator can be used, and various additives can be used as necessary.

[Dyes and pigments]
The dye-encapsulated metal oxide particles and pigment-encapsulated metal oxide particles obtained by the production method of the present invention can be used as a dye or a pigment instead of or in combination with the used dye or pigment.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the scope described in these examples.

[Example 1]
Preparation of dye-encapsulated metal oxide particles (1) Methyl silicate (manufactured by Tama Chemical Co., Ltd.) which is a hydrolyzed polycondensation product of tetramethoxysilane to 58.8 kg of modified alcohol (Nippon Alcohol Sales Co., Ltd .: Echinen F1) 17.6 kg of methyl silicate 51, SiO ₂ concentration 51 wt%, molecular weight: 400) was dissolved to prepare a hydrolyzed polycondensation alcohol solution of tetramethoxysilane having a solid concentration of 23 wt%.
Separately, 0.045 kg of 36 wt% hydrochloric acid was added to 13.5 kg of ultrapure water to prepare a 0.1 wt% hydrochloric acid aqueous solution.

Next, while stirring the hydrolyzed polycondensation alcohol solution of tetramethoxysilane, an aqueous hydrochloric acid solution was added to the solution over 5 minutes, then heated to 100 ° C. and aged for 75 minutes, and then cooled.
The solid content at this time was 10% by weight. Subsequently, using a rotary evaporator, it was concentrated to a solid content concentration of 30% by weight to obtain a hydrolyzed polycondensation product (1) (water / modified alcohol) dispersion. The molecular weight of the hydrolyzed polycondensation product (1) at this time was measured, and the results are shown in the table.
Next, it is concentrated to a solid content concentration of 30% by weight, and hydrolyzed polycondensation product (1) 3 g of a blue acidic dye (manufactured by Kasei Kasei Co., Ltd .: Blue No. 1) is dispersed in 500 g of the dispersion to obtain a hydrolyzed polycondensation product for spray drying. (1) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.

  Subsequently, the hydrolyzed polycondensate (1) dispersion liquid is flown at 0.62 kg / hr to one of the two-fluid nozzles, and air is flown to the other nozzle at a flow rate of 31800 L / hr (air / liquid volume ratio 63600). The mixture was sprayed with hot air having an inlet temperature of 400 ° C. to obtain dye-containing metal oxide particle precursor particles (1). At this time, the outlet temperature was 180 ° C. (Process (a))

Next, the dye-encapsulated metal oxide particle precursor particles (1) were heat-treated at 120 ° C. for 3 hours to prepare dye-encapsulated metal oxide particles (1). (Process (b))
The average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (1) are as follows. The results were shown in the table.

The average particle diameter of dye encapsulated metal oxide particles (1) laser diffraction scattering 3cc particle size distribution analyzer (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 metal oxide 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, 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 dye-encapsulated metal oxide 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.
Measure the TEM photograph of the void oxide-encapsulated metal oxide particles (1), measure the particle diameter of 50 particles, measure the average particle diameter as the average value, and then break the particles into 1/2 And the diameter of the cavity part was measured about 50 fracture | rupture pieces, the average diameter of the cavity part was calculated | required, and the average cavity volume ratio of the cavity part was calculated | required by calculation.

Residual alkali amount Dye-encapsulated metal oxide particles (1) were measured for Na content by atomic absorption method (manufactured by Hitachi, Ltd., atomic absorption photometer Z-2310 type), converted to Na ₂ O, and remaining alkali The amount.
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 metal oxide particles (1) under certain conditions and dividing the oil absorption amount by the weight of the dye-containing metal oxide particles (1). In the present invention, the oil absorption is indicated in ml / 100 g.

Dye elution amount 0.5 g of dye-encapsulated metal oxide particles (1) are 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 metal oxide particles (1) are separated by a centrifugal separator, and the remaining aqueous solution is filtered through a microfilter having a 0.2 μm mesh, and a quartz cell (length: 10 mm, width: 10 mm, height: 45 mm), the transmittance at a wavelength of 400 to 800 nm is measured using a spectrophotometer (HITACHI: U-2000), and the lowest value in this range is defined as the transmittance. did. It shows that there is so much pigment | dye elution amount that this transmittance | permeability is low.

Hue (saturation)
The pigment-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

Sensitive properties Dye-encapsulated metal oxide particles (1) powders are subjected to a sensory test by 20 expert panelists. (1) Smooth feeling, (2) Moist feeling, (3) Rolling feeling, (4) Uniform Interviews were conducted on seven evaluation items: stretchability, (5) adhesion to the skin, (6) persistence of rolling feeling, and (7) low crispness of dye-encapsulated metal oxide particles (1). Do. The result is evaluated based on the following evaluation point criteria (a). Next, the evaluation points given by each person are summed up, and the evaluation on the feel of the dye-containing metal oxide particles (1) 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-encapsulated metal oxide particles (2) In the same manner as in Example 1, while stirring a hydrolyzed polycondensation alcohol solution of tetramethoxysilane, an aqueous hydrochloric acid solution was added thereto for 5 minutes, and then at room temperature. After aging for 75 minutes, it was cooled.
The solid content at this time was 10% by weight. Subsequently, it was concentrated to a solid content concentration of 30% by weight using a rotary evaporator to obtain a hydrolyzed polycondensation product (2) dispersion.
The molecular weight of the hydrolyzed polycondensation product (2) at this time was measured, and the results are shown in the table.
Subsequently, it is concentrated to a solid content concentration of 30% by weight, and then hydrolyzed polycondensation product (2) 3 g of a blue acidic dye (manufactured by Kasei Kasei Co., Ltd .: Blue No. 1) is dispersed in 500 g of the dispersion to obtain a hydrolyzed polycondensation product for spray drying. (2) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.

Thereafter, the dye-containing metal oxide particles (2) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle diameter, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (2) The results are shown in the table.

[Example 3]
Preparation of dye-encapsulated metal oxide particles (3) In the same manner as in Example 1, while stirring the tetramethoxysilane hydrolyzed polycondensate alcohol solution, an aqueous hydrochloric acid solution was added to the solution over 5 minutes, and the temperature was raised to 100 ° C. Warmed and aged for 24 hours, then cooled.
The solid content at this time was 10% by weight. Subsequently, it was concentrated to a solid content concentration of 30% by weight using a rotary evaporator to obtain a hydrolyzed polycondensation product (3) dispersion.
The molecular weight of the hydrolyzed polycondensation product (3) at this time was measured, and the results are shown in the table.
Next, it is concentrated to a solid content concentration of 30% by weight, and hydrolyzed polycondensation product (3) 3 g of a blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) is dispersed in 500 g of the dispersion to obtain a hydrolyzed polycondensation product for spray drying. (3) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.

Thereafter, the dye-containing metal oxide particles (3) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (3) The results are shown in the table.

[Example 4]
Preparation of dye-encapsulated metal oxide particles (4) In Example 1, except that 0.75 g of a blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dispersed, a hydrolytic condensation polymer for spray drying ( 4) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.005.
Thereafter, the dye-containing metal oxide particles (4) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (4) The results are shown in the table.

[Example 5]
Preparation of dye-encapsulated metal oxide particles (5) Hydrolysis polycondensation polymer for spray drying (5) in the same manner as in Example 1, except that 75 g of blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dispersed. A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.5.
Thereafter, the dye-containing metal oxide particles (5) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (5) The results are shown in the table.

[Example 6]
Preparation of dye-encapsulated metal oxide particles (6) In Example 1, the dye-encapsulated metal oxide particle precursor particles (6) were obtained by spraying with hot air having an inlet temperature of 180 ° C. At this time, the outlet temperature was 50 ° C.
Thereafter, heat treatment was carried out in the same manner as in Example 1 to prepare dye-encapsulated metal oxide particles (6).
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (6) The results are shown in the table.

[Example 7]
Preparation of dye-encapsulated metal oxide particles (7) In Example 1, the dye-encapsulated metal oxide particle precursor particles (7) were obtained by spraying with hot air having an inlet temperature of 500 ° C. At this time, the outlet temperature was 230 ° C.
Thereafter, heat treatment was performed in the same manner as in Example 1 to prepare dye-containing metal oxide particles (7).
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (7) The results are shown in the table.

[Example 8]
Preparation of dye-encapsulated metal oxide particles (8) In Example 1, hydrolyzed polycondensation product (1) (water / modified alcohol) dispersion having a solid content of 10% by weight before being concentrated by a rotary evaporator was hydrolyzed and polycondensed. The product (8) was used as a dispersion. The molecular weight of the hydrolyzed polycondensation product (8) at this time was measured, and the results are shown in the table.
Subsequently, 1 g of blue acidic dye (manufactured by Kasei Kasei Co., Ltd .: Blue No. 1) is dispersed in 500 g of a dispersion of hydrolyzed polycondensate (8) having a solid content of 10% by weight, and then hydrolyzed polycondensate for spray drying (8). A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.

Thereafter, the dye-containing metal oxide particles (8) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (8) The results are shown in the table.

[Example 9]
Preparation of dye-encapsulated metal oxide particles (9) In Example 1, using a rotary evaporator, a hydrolyzed polycondensation product (9) dispersion having a solid content concentration of 35% by weight was obtained.
The degree of polymerization of the hydrolyzed polycondensation product (9) at this time was measured, and the results are shown in the table.
Next, 3.5 g of a blue acid dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) was dispersed in 500 g of a hydrolyzed polycondensation product (9) having a solid content of 35% by weight. 9) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.

Thereafter, the dye-containing metal oxide particles (9) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (9) The results are shown in the table.

[Example 10]
Preparation of pigment-encapsulated metal oxide particles (10) Concentrated to a solid concentration of 30% by weight prepared in the same manner as in Example 1, and then hydrolyzed polycondensation product (1) to 500 g of the dispersion, Bengala (Toda Kogyo Co., Ltd .: 100ED 49.5 g was dispersed to prepare a hydrolyzed polycondensation polymer (10) dispersion for spray drying. At this time, (C _D ) / (C _H ) = 0.33.

  Next, the hydrolyzed polycondensate (10) dispersion is flowed at a flow rate of 0.62 kg / hr to one of the two-fluid nozzles, and air is flowed to the other nozzle at a flow rate of 31800 L / hr (air / liquid volume ratio 63600). By spraying with hot air having an inlet temperature of 400 ° C., pigment-encapsulated metal oxide particle precursor particles (10) were obtained. At this time, the outlet temperature was 180 ° C. (Process (a))

Subsequently, the pigment-encapsulated metal oxide particle precursor particles (10) were heat-treated at 600 ° C. for 3 hours to prepare pigment-encapsulated metal oxide particles (10). (Process (b))
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual amount of alkali, oil absorption, dye elution, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (10) The results are shown in the table.

[Example 11]
Preparation of pigment-encapsulated metal oxide particles (11) In Example 10, pigment-encapsulated metal oxide particles (11) were the same except that the pigment-encapsulated metal oxide particle precursor particles (10) were dried at 80 ° C for 3 hours. Was prepared. (Process (b))
Measure and evaluate the average particle diameter, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (11) The results are shown in the table.

[Example 12]
Preparation of pigment-encapsulated metal oxide particles (12) In Example 10, pigment-encapsulated metal oxide particles (12) were similarly treated except that the pigment-encapsulated metal oxide particle precursor particles (10) were heat-treated at 1100 ° C for 3 hours. ) Was prepared. (Process (b))
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (12) The results are shown in the table.

[Example 13]
Preparation of pigment-encapsulated metal oxide particles (13) Concentrated to a solid concentration of 30% by weight prepared in the same manner as in Example 1, and then hydrolyzed polycondensation product (1) to a dispersion of 500 g of titanium oxide white pigment (Ishihara Sangyo Co., Ltd.) (Product: CR-50) 49.5 g was dispersed to prepare a hydrolyzed polycondensation polymer (13) dispersion for spray drying. At this time, (C _D ) / (C _H ) = 0.33.
Thereafter, the pigment-encapsulated metal oxide particles (13) were prepared by spray drying and heat treatment in the same manner as in Example 10.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (13) The results are shown in the table.

[Example 14]
Preparation of pigment-encapsulated metal oxide particles (14) In the same manner as in Example 10, pigment-encapsulated metal oxide particle precursor particles (10) were obtained. Next, a pigment-encapsulated metal oxide particle (14) having a negative pressure inside was prepared in the same manner except that the temperature was gradually raised while evacuating with a vacuum pump at 1 hPa and heat-treated at 600 ° C. for 3 hours. did.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (14) The results are shown in the table.

The void internal pressure of the pigment-encapsulated metal oxide particles (14) was measured by the following method and found to be 1 hPa.
A 100 cc glass bottle connected to one of the U-tube manometers is charged with a weight equivalent to 40 cc of pigment-encapsulated metal oxide particles (14) in terms of particle density, and then 50 cc of a 48 wt% sodium hydroxide aqueous solution is added. Immediately, the pressure relief valve was closed and sealed. The space of the air layer inside the glass bottle at this time was 10 cc. Next, with stirring using a magnetic stirrer, the pigment-encapsulated metal oxide particles (14) were dissolved by heating in an oil bath at 80 ° C. for 15 hours, and then cooled to room temperature. At this time, the space of the air layer was 25 cc (approximately equal to the sum of the air layer volume inside the glass bottle: 10 cc and the internal void volume of the pigment-encapsulated metal oxide particles (14): 16 cc). As a result, it was found that the internal voids of the pigment-encapsulated metal oxide particles (14) were opened by dissolution of 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. Thereby, the internal pressure of the pigment-encapsulated metal oxide particles (14) can be calculated from Boyle's law based on the differential pressure measured with a manometer. The differential pressure of the U-tube manometer at this time was read and used as the void internal pressure.

[Example 15]
Preparation of pigment-encapsulated metal oxide particles (15) 58.8 kg of modified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Echinen F1) methyltrimethyl silicate as a hydrolyzable metal compound (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) A methyltrimethylsilicate alcohol solution having a solid content of 10% by weight was prepared by dissolving 20.4 kg.
Separately, 0.045 kg of 36 wt% hydrochloric acid was added to 13.5 kg of ultrapure water to prepare a 0.1 wt% hydrochloric acid aqueous solution.
Next, while stirring the methyltrimethylsilicate alcohol solution, an aqueous hydrochloric acid solution was added to the solution over 5 minutes, and then the temperature was raised to 100 ° C. and aged for 75 minutes, followed by cooling.
The solid content at this time was 10% by weight. Subsequently, it was concentrated to a solid content concentration of 30% by weight using a rotary evaporator to obtain a hydrolyzed polycondensation product (15) dispersion. The molecular weight of the hydrolyzed polycondensation product (15) at this time was measured, and the results are shown in the table.

Subsequently, 49.5 g of Bengala (manufactured by Toda Kogyo Co., Ltd .: 100ED) is dispersed in 500 g of the dispersion obtained by concentrating the solid content to 30% by weight and then hydrolyzing and condensing polymer (15). ) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.33.

  Next, the hydrolyzed polycondensate (15) dispersion was flowed at a flow rate of 0.62 kg / hr to one of the two-fluid nozzles, and air was flowed to the other nozzle at a flow rate of 31800 L / hr (air / liquid volume ratio 63600). By spraying with hot air having an inlet temperature of 400 ° C., pigment-encapsulated metal oxide particle precursor particles (15) were obtained. At this time, the outlet temperature was 180 ° C. (Process (a))

Subsequently, the pigment-encapsulated metal oxide particle precursor particles (15) were heat-treated at 600 ° C. for 3 hours to prepare pigment-encapsulated metal oxide particles (15). (Process (b))
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (15) The results are shown in the table.

[Example 16]
Preparation of Pigment-Encapsulated Metal Oxide Particles (16) A butyl titanate polymer (manufactured by Nippon Soda Co., Ltd .: B-10, TiO ₂ concentration 35% by weight) was used as a hydrolyzed polycondensate (16) dispersion. The molecular weight of the hydrolytic condensation polymer (16) was measured, and the results are shown in the table.
Subsequently, 57.8 g of Bengala (Toda Kogyo Co., Ltd .: 100ED) was dispersed in 500 g of the hydrolyzed polycondensate (16) dispersion having a solid content of 35% by weight, and the hydrolyzed polycondensate for spray drying (16) dispersion was dispersed. Was prepared. At this time, (C _D ) / (C _H ) = 0.33.
Thereafter, the pigment-encapsulated metal oxide particles (16) were prepared by spray drying and heat treatment in the same manner as in Example 10.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (16) The results are shown in the table.

[Example 17]
Preparation of pigment-encapsulated metal oxide particles (17) Polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: PAC, Al ₂ O ₃ concentration 23% by weight, dispersion medium: water) hydrolyzed polycondensation product (17) dispersion Used as. The molecular weight of the hydrolyzed polycondensation product (17) was measured, and the results are shown in the table.
Subsequently, 38 g of Bengala (Toda Kogyo Co., Ltd .: 100ED) was dispersed in 500 g of the hydrolyzed polycondensate (17) dispersion having a solid content of 23% by weight to prepare a hydrolyzed polycondensate (17) for spray drying. did. At this time, (C _D ) / (C _H ) = 0.33.
Thereafter, the pigment-encapsulated metal oxide particles (17) were prepared by spray drying and heat treatment in the same manner as in Example 10.
Measure and evaluate the average particle diameter, specific surface area, particle density, porosity, residual amount of alkali, oil absorption, dye elution, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (17) The results are shown in the table.

[Comparative Example 1]
Preparation of dye-encapsulated metal oxide particles (R1) In the same manner as in Example 1, it was concentrated to a solid content concentration of 30% by weight to obtain a hydrolyzed polycondensation product (1) dispersion.
Next, 0.3 g of a blue acidic dye (manufactured by Kasei Kasei Co., Ltd .: Blue No. 1) is dispersed in 500 g of a hydrolyzed polycondensation product (1) having a solid content of 30% by weight. R1) A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.002.
Thereafter, the dye-containing metal oxide particles (R1) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (R1) The results are shown in the table.

[Comparative Example 2]
Preparation of dye-encapsulated metal oxide particles (R2) A hydrolyzed polycondensate (8) dispersion having a solid content of 10% by weight was obtained in the same manner as in Example 8.
Next, a hydrolyzed polycondensation product (R2) for spray-drying was prepared by dispersing 150 g of a blue acidic dye (manufactured by Kasei Kasei Co., Ltd .: Blue No. 1) in 500 g of a dispersion of hydrolyzed polycondensate (8) having a solid content of 10% by weight. A dispersion was prepared. At this time, (C _D ) / (C _H ) = 3.
Thereafter, the dye-containing metal oxide particles (R2) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (R2) The results are shown in the table.

[Comparative Example 3]
Preparation of dye-encapsulated metal oxide particles (R3) Methyl silicate (manufactured by Tama Chemical Co., Ltd.) which is a hydrolyzed polycondensation product of tetramethoxysilane to 58.8 kg of modified alcohol (Nippon Alcohol Sales Co., Ltd .: Echinen F1) 17.6 kg of methyl silicate 51, SiO ₂ concentration 51 wt%, molecular weight: 400) was dissolved to prepare a hydrolytic condensation polymer (R3) alcohol solution of tetramethoxysilane having a solid concentration of 23 wt%.
Next, 3 g of a blue acidic dye (manufactured by Kasei Chemical Co., Ltd .: Blue No. 1) is dispersed in 500 g of an alcohol solution having a solid content concentration of 23% by weight, and the hydrolyzed polycondensation product (R3) for spray drying. A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.
Subsequently, spray drying was performed in the same manner as in Example 1, but metal oxide particle precursor particles could not be obtained. This is presumably because the hydrolyzed polycondensation product transpired without forming metal oxide particle precursor particles when sprayed because the molecular weight (polymerization degree) of methyl silicate was too low.

[Comparative Example 4]
Preparation of dye-encapsulated metal oxide particles (R4) Methyl silicate (manufactured by Tama Chemical Co., Ltd.) which is a hydrolyzed polycondensation product of tetramethoxysilane to 58.8 kg of modified alcohol (Nippon Alcohol Sales Co., Ltd .: Echinen F1) 17.6 kg of methyl silicate 51, SiO ₂ concentration 51 wt%, molecular weight: 400) was dissolved to prepare a hydrolyzed polycondensation alcohol solution of tetramethoxysilane having a solid concentration of 23 wt%.
Separately, 0.45 kg of 36 wt% hydrochloric acid was added to 13.5 kg of ultrapure water to prepare a 3 wt% hydrochloric acid aqueous solution.
Next, while stirring the hydrolyzed polycondensation alcohol solution of tetramethoxysilane having a solid content concentration of 23% by weight, an aqueous hydrochloric acid solution was added thereto over 5 minutes, and then the mixture was heated to 100 ° C. and aged for 75 minutes. , Cooled.
The solid content at this time was 10% by weight. Subsequently, it was concentrated to a solid content concentration of 30% by weight using a rotary evaporator to obtain a hydrolyzed polycondensate (R4) dispersion. The molecular weight of the hydrolysis-condensation polymer (R4) at this time was measured, and the results are shown in the table.

Next, 3 g of a blue acidic dye (manufactured by Kasei Kasei Co., Ltd .: Blue No. 1) is dispersed in 500 g of a hydrolyzed polycondensate (R4) dispersion having a solid content of 30% by weight, and the hydrolyzed polycondensate for spray drying (R3). A dispersion was prepared. At this time, (C _D ) / (C _H ) = 0.02.
Thereafter, the dye-containing metal oxide particles (R4) were prepared by spray drying and heat treatment in the same manner as in Example 1.
Measure and evaluate the average particle size, specific surface area, particle density, porosity, residual alkali amount, oil absorption, dye elution amount, hue (saturation), and feel characteristics of the resulting dye-encapsulated metal oxide particles (R4) The results are shown in the table.

[Example 18]
Preparation of powder foundation Dye and / or pigment-encapsulated metal oxides obtained in Examples 1, 6, 7, 10, 13 to 17 and Comparative Example 4 so as to have a blending ratio (% by weight) shown in Table 4 below The particle components (1) and (2) to (9) were each put in a mixer and stirred to mix 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.
As a result, Example cosmetics P1, P6, P7, P10, P13 to P17, and Comparative cosmetic PR4, in which the dye and / or pigment-encapsulating metal oxide particles were blended, were obtained.

  Next, the feeling of use of the example cosmetics and comparative cosmetics obtained in this way were evaluated for the feel during application and the finished feeling (feel after application) by the following test methods. The results are shown in Table 5.

Test method Sensory test by 20 expert panelists on powder foundation containing powder of dye and / or pigment-encapsulated metal oxide particles, (1) uniform extension during application to skin, (2) moist Interviews are conducted on six evaluation items: feeling, (3) smoothness, (4) uniformity of the cosmetic film after application to the 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.

[Example 19]
Preparation of lotion The components (1) to (3) heated to 80 ° C. and uniformly mixed so as to have the blending ratio (% by weight) shown in Table 6 below were heated to 80 ° C. and uniformly mixed. Add the dye and / or pigment-encapsulated metal oxide particle components (4) and (5) to (8) obtained in Examples 1, 6, 7, 10, 13 to 17 and Comparative Example 4 and stir to mix uniformly. did. 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, L6, L7, L10, L13 to L17 and Comparative cosmetics LR4 containing dye and / or pigment-encapsulated metal oxide particle components.

  Next, the feeling of use (redispersibility of the dye and / or pigment-encapsulated metal oxide particles before use and the feeling during application) and the feeling of finish (application) of the example cosmetics and the comparative cosmetics obtained in this way The following feeling was evaluated for the following feeling. The results are shown in Table 7.

Test method Sensory test by 20 expert panelists on lotion containing powder of dye and / or pigment-encapsulated metal oxide particles 1) Re-dispersion of dye and / or pigment-encapsulated metal oxide particles before use Interviews are conducted on three evaluation items: properties, 2) uniform elongation during application to the skin, and 3) soft focus properties 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 regarding the feeling of use of the lotion 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.

[Example 20]
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.

  Subsequently, each dye obtained in Examples 1, 3, 10, 14, 16, and Comparative Example 4 was added to 11.8 g of the mixed resin solution (resin specific gravity: 1.1 g / cc, resin volume: 8.0 cc). / Or 5.1 g, 2.0 g, 7.4 g, 7.4 g, 6.2 g, and 8.6 g of the pigment-encapsulated metal oxide particles so as to be 33% by volume (3.9 cc) in terms of particle density, respectively. After the addition, 6 points of a resin solution for forming a heat insulating material were prepared by performing a dispersion treatment for 1 minute using a horn type ultrasonic device (manufactured by Maritime Radio). 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 and RH1 with heat insulating thin films were obtained.
Moreover, the resin solution prepared similarly except not mix | blending dye and / or a pigment inclusion metal oxide particle was apply | coated similarly, dried and hardened | cured, and base material RH2 with a comparative example heat insulation thin film was obtained.
About each obtained base material with a heat insulating thin film, heat insulating property was evaluated as follows, and a result is shown in Table 8.

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.

Claims (26)

A method for producing dye- and / or pigment-encapsulated metal oxide particles comprising the following steps (a) and (b):
(A) A hydrolyzed polycondensate dispersion of a hydrolyzable metal compound represented by the following formula (1) obtained by dispersing a dye and / or a pigment, wherein the hydrolyzed polycondensate has an average molecular weight of 500. In the range of ~ 100,000, the total solid content is in the range of 5 to 100% by weight, the concentration (C _D ) as the solid content of the dye and / or pigment and the solid content of the hydrolyzed polycondensate concentration _{(C H)} ratio of _{(C D) / (C H} ) is spray dried dyes and / or pigments hydrolysis condensation polymerization product dispersion in the range of 0.0002 to 2.3 in a hot air stream Step of preparing dye- and / or pigment-encapsulated metal oxide particle precursor particles R _n -MX _m-n (1)
(Wherein, M is at least one element selected from Si, Ti, Zr, and Al, and R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen, hydrogen, m: valence of element M, 3 or 4, n: integer of 0 to 2, and mn is 2 or 3)
(B) A step of drying and heat-treating the dye and / or pigment-encapsulating metal oxide particle precursor particles   2. The method for producing dye and / or pigment-containing metal oxide particles according to claim 1, wherein the dye is a natural dye or a synthetic dye, and the pigment is an organic pigment or an inorganic pigment.   The dye and / or pigment-encapsulated metal oxidation according to claim 1 or 2, wherein an inlet temperature of hot air in the spray drying is in a range of 100 to 600 ° C and an outlet temperature is in a range of 40 to 300 ° C. Method for producing product particles.   The method for producing dye- and / or pigment-encapsulated metal oxide particles according to any one of claims 1 to 3, wherein the drying and heat treatment temperature in the step (b) is in the range of 30 to 1200 ° C.   5. The method for producing dye- and / or pigment-encapsulated metal oxide particles according to claim 1, wherein the average particle diameter is in the range of 0.1 to 200 μm.   In the spray drying, 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 and / or pigment-encapsulated metal oxide particles is less than 5% by volume. The method for producing dye- and / or pigment-encapsulated metal oxide particles according to any one of claims 1 to 5.   The drying / heating treatment temperature in the step (b) is in the range of 30 to 120 ° C, and the resulting dye and / or pigment-containing metal oxide particles are porous. And / or a method for producing pigment-encapsulated metal oxide particles.   The drying / heat treatment temperature in the step (b) is in the range of 90 to 1200 ° C, and the obtained dye and / or pigment-encapsulated metal oxide particles are non-porous. A method for producing dye- and / or pigment-encapsulated metal oxide particles.   In the spray drying, 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 and / or pigment-encapsulated metal oxide particles are placed inside the outer shell metal oxide layer. The method for producing dye- and / or pigment-encapsulated metal oxide particles according to any one of claims 1 to 5, wherein the method has voids and the void ratio is in the range of 5 to 95% by volume.   The drying / heat treatment temperature in the step (b) is in the range of 30 to 120 ° C., and the resulting outer metal oxide layer of the dye- and / or pigment-encapsulated metal oxide particles is porous. The manufacturing method of the dye and / or pigment inclusion metal oxide particle of Claim 9.   The drying and heat treatment temperature in the step (b) is in the range of 90 to 1200 ° C., and the outer metal oxide layer of the resulting dye and / or pigment-encapsulating metal oxide particles is nonporous. The manufacturing method of the dye and / or pigment inclusion metal oxide particle of Claim 9. The dye according to claim 11, wherein the drying and heat treatment in the step (b) is performed under reduced pressure, and the inside of the outer shell layer of the obtained dye and / or pigment-encapsulating metal oxide particles has a negative pressure. And / or a method for producing pigment-encapsulated metal oxide particles.
  A dye and / or pigment is included, the average particle diameter is in the range of 0.1 to 200 μm, and the metal oxide is an oxide of at least one element selected from Si, Ti, Zr, and Al. Dye and / or pigment-encapsulated metal oxide particles.   14. The dye and / or pigment-encapsulated metal oxide particles according to claim 13, wherein the content of the dye and / or pigment is in the range of 0.5 to 70% by weight as a solid content.   The dye and / or pigment-containing metal oxide particles according to claim 13 or 14, wherein the dye is a natural dye or a synthetic dye, and the pigment is an organic pigment or an inorganic pigment.   The dye and / or pigment-encapsulated metal oxide particles according to any one of claims 13 to 15, wherein the porosity is less than 5% by volume.   The dye- and / or pigment-encapsulated metal oxide particles according to claim 16, which are porous.   The dye- and / or pigment-encapsulated metal oxide particles according to claim 16, which are non-porous.   The outer shell metal oxide layer is provided, the outer shell metal oxide layer has a cavity, and the void ratio is in the range of 5 to 95% by volume. The dye and / or pigment inclusion metal oxide particles according to any one of the above.   20. The dye- and / or pigment-encapsulated metal oxide particles according to claim 19, wherein the outer metal oxide layer is porous.   20. The dye- and / or pigment-encapsulated metal oxide particles according to claim 19, wherein the outer metal oxide layer is nonporous.   The dye and / or pigment-encapsulating metal oxide particles according to claim 21, wherein the inside of the outer shell layer has a negative pressure. The dye and / or pigment-encapsulated metal oxide particles are produced by the method for producing a dye and / or pigment-encapsulated metal oxide particle according to any one of claims 1 to 12. 23. The dye- and / or pigment-encapsulated metal oxide particles according to any one of 22 above.
  The dye and / or pigment-containing metal oxide particles obtained by the production method according to any one of claims 1 to 12, or the dye and / or pigment-containing metal oxide particles according to any one of claims 13 to 22 Cosmetics formulated with   25. The cosmetic according to claim 24, wherein the amount of the dye- and / or pigment-encapsulated metal oxide particles is in the range of 0.1 to 30% by weight.   The dye and / or pigment-containing metal oxide particles obtained by the production method according to any one of claims 1 to 12, or the dye and / or pigment-containing metal oxide particles according to any one of claims 13 to 22 Insulation material made by blending.