Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
  • C01B33/157—After-treatment of gels
  • C01B33/158—Purification; Drying; Dehydrating
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
  • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
  • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
  • A61K8/025—Explicitly spheroidal or spherical shape
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/25—Silicon; Compounds thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
  • C09C1/3027—Drying, calcination
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3045—Treatment with inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/62—Metallic pigments or fillers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/10—General cosmetic use
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/41—Particular ingredients further characterized by their size
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/30—Particle morphology extending in three dimensions
  • C01P2004/32—Spheres
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/19—Oil-absorption capacity, e.g. DBP values
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
  • C01P2006/82—Compositional purity water content

Definitions

• the present invention relates to porous spherical silica particles having a large specific surface area and suppressed oil absorption, and a method for producing the same.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2018-177620
• high oil absorption characteristics are obtained by increasing the porosity of silica airgel by pore control technology, and silica is made porous by shape control technology.
• a silica airgel powder that has excellent rolling properties on the skin and can obtain a smooth touch by sphericizing the silica airgel while increasing the strength of the airgel.
• the silica airgel powder described in Patent Document 1 has a high oil absorption amount, when it is blended with cosmetics, it adsorbs the oil phase component of the cosmetics so that the cosmetics can obtain a predetermined component. There was a problem that it became difficult to prescribe. Therefore, in order to solve the above problem, for example, the oil absorption amount of the silica particles is reduced by controlling the pores, or the silica particles are imparted with hydrophobicity by surface treatment to improve the dispersibility in the oil phase. Measures have been taken.
• a method of reducing the oil absorption of silica particles for example, a method of reducing the pore volume and reducing the oil absorption by controlling the firing temperature in the step of drying and firing the particles is known.
• the oil absorption of the silica particles is reduced by this method, the surface area of the silica particles is reduced due to sintering of the particles and a decrease in the number of pores, and conversely, the proportion of the area in contact with the skin is increased.
• the slipperiness of the particles became poor and a smooth tactile sensation could not be obtained.
• dehydration condensation proceeds in the particle structure, so that the silica particles can be felt harder, and there is a problem that the usability is deteriorated.
• silica particles As another method for reducing the oil absorption of silica particles, a method of making silica particles hydrophobic by surface-treating a reactive silane coupling agent such as silicone or alkylsilane is known.
• a reactive silane coupling agent such as silicone or alkylsilane
• an object of the present invention is to provide spherical silica particles having a large specific surface area, suppressed in oil absorption, and excellent in adhesion to the skin and feel, and a method for producing the same.
• the specific surface area by the BET method is 300 m 2 / g or more, and the total pore volume is 0.3 ml. It is desired that the oil absorption is suppressed to 50 ml / 100 g or less and the oil absorption amount is suppressed to 50 ml / 100 g or less.
• the ratio of the area where the silica particles come into contact with the skin can be sufficiently reduced, and it becomes difficult to feel the hardness of the silica particles when applied to the skin. Because.
• the specific surface area by the BET method is 300 m 2 / g or more and the total pore volume to 0.3 ml / g or less (that is, reducing the pore volume while increasing the specific surface area). This is because the oil absorption amount can be suppressed to a low level of 50 ml / 100 g or less, and adverse effects (aggregation of silica particles, dryness of the skin) due to excessive absorption of oil content are less likely to occur.
• At least the specific surface area by the BET method is 300 m 2 / g or more, the total pore volume is 0.3 ml / g or less, and the oil absorption amount is 50 ml / 100 g or less.
• Spherical silica particles are provided. Further, the above-mentioned spherical silica particles have a feature that they have not been calcined at a temperature of 1000 ° C. or higher in the manufacturing process.
• the water retained in the silica gel is divided into adhering water and structural water. Normally, the adhering water can be easily removed by heating at a temperature of around 100 ° C, but the structural water is completely removed even at a temperature of 400 ° C or higher. It is difficult to remove. Therefore, in the spherical silica particles of the present invention in which the firing treatment is omitted, the decrease in the specific surface area and the pore volume caused by the progress of densification is suppressed, and the water content thereof is also 1 in the structural water content. It is characterized by having a value of 6.6% or more, more preferably 2.0% or more. By having such characteristics, the spherical silica particles of the present invention have a moist and good feel.
• the silica particles of the present invention are spherical and porous, and have a large specific surface area while suppressing their oil absorption. Further, since the silica particles of the present invention are not easily broken even when used for cosmetic purposes, they can exhibit an excellent feeling of use and adhesion to the skin.
• the spherical silica particles of the present invention may be compounded with one or more metal oxides selected from the group consisting of titanium oxide, zinc oxide, iron oxide and aluminum oxide, in which case the metal oxides may be compounded.
• metal oxides selected from the group consisting of titanium oxide, zinc oxide, iron oxide and aluminum oxide, in which case the metal oxides may be compounded.
• ultraviolet shielding effect, coloring effect, etc. can be imparted to the silica particles.
• the content ratio of the metal oxide is preferably 0.5 to 30 wt%, more preferably 5 to 20 wt% with respect to the entire silica particles.
• the spherical silica particles of the present invention may be made hydrophobic by surface-treating with a reactive silane coupling agent such as silicone or alkylsilane, in which case the dispersibility in the oil agent is improved.
• a reactive silane coupling agent such as silicone or alkylsilane
• a step of removing the O phase by heating the reaction solution containing the generated spherical silica gel to separate it into two layers, an O phase and a W phase.
• a method for producing spherical silica particles comprises (4) washing the W phase containing the spherical silica gel from which the O phase has been removed, and (5) drying the washed spherical silica gel. .. Further, the dried silica particles may be crushed or further classified in order to obtain spherical silica particles having a desired average primary particle diameter.
• the specific surface area by the BET method is as large as 300 m 2 / g or more, but the oil absorption amount is suppressed to 50 ml / 100 g or less.
• Spherical silica particles can be obtained, and it is particularly effective not to perform the firing treatment after the step (5) above.
• ⁇ Preparation of emulsion> The alkaline silicate aqueous solution, a liquid immiscible with the alkaline silicate aqueous solution such as a non-polar solvent, and an emulsifier are mixed and mixed using various emulsifiers such as a stirring type, a high pressure type, an ultrasonic type, and a membrane emulsification type.
• emulsifiers such as a stirring type, a high pressure type, an ultrasonic type, and a membrane emulsification type.
• the particle size of the dispersed phase can be controlled by changing the output of the emulsifier during emulsification. For example, in the case of a stirring type emulsifier using a rotating stirring blade, the particle size becomes smaller as the rotation speed of the stirring blade is increased, and the particle size becomes larger as the rotation speed is decreased.
• the particle size of the dispersed phase can also be controlled by changing the concentration of the aqueous alkali silicate solution. For example, by reducing the concentration of the alkaline silicate aqueous solution, the particle size can be made finer, and conversely, by increasing the concentration, the viscosity can be increased and the particle size can be increased.
• alkaline silicate used in the present invention examples include sodium silicate, potassium silicate, lithium silicate and the like, and sodium silicate is particularly preferably used.
• the alkaline silicate aqueous solution can be prepared by dissolving natural silica stone or synthetic silica in an alkaline aqueous solution such as sodium hydroxide aqueous solution.
• one or more metal oxides selected from the group consisting of titanium oxide, zinc oxide, iron oxide and aluminum oxide or precursor compounds thereof may be added to the alkaline silicate aqueous solution.
• the precursor compound of the metal oxide include hydroxides, salts, and alkoxides.
• the amount of the metal oxide or precursor compound added (in terms of oxide) may be adjusted based on the calculated content ratio with respect to the entire particles.
• the liquid that is immiscible with the alkaline silicate aqueous solution used in the present invention is not particularly limited as long as it does not react with the mineral acid aqueous solution described later, and aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and tetralin are not particularly limited. , N-octane, gasoline, kerosene, aliphatic hydrocarbons such as isoparaffinic hydrocarbon oil, alicyclic hydrocarbons such as cyclononane and cyclodecane, etc., from the viewpoint of obtaining uniform and stable dispersibility. It is preferable to use aromatic hydrocarbons such as xylene.
• the emulsifier used in the present invention is not particularly limited as long as it has a stabilizing function of a W / O type emulsion, and is a highly lipophilic interface such as a polyvalent metal salt of fatty acid or a sparingly water-soluble cellulose ether. Activators can be used.
• a nonionic surfactant it is preferable to use a nonionic surfactant, and specific examples thereof include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, and sorbitan mono.
• Sorbitane fatty acid esters such as oleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.
• Polyoxyethylene fatty acid esters such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene monolaurates, polyoxyethylene monopalmitates, polyoxyethylene monostearates, and polyoxyethylene monooleates, stearic acid monoglycerides, and oleic acid monoglycerides.
• Glycerin fatty acid esters such as and the like can be mentioned.
• Examples of the mineral acid used in the present invention include sulfuric acid, nitric acid, hydrochloric acid and the like, but in general, it is preferable to use sulfuric acid, which has a strong dehydrating action and is advantageous in terms of cost.
• the W / O type emulsion containing the alkaline silicate aqueous solution is preferably mixed with a sulfuric acid aqueous solution having a concentration of 15 wt% or more, more preferably 30 wt% or more, and the upper limit is 50 wt% or less. Is preferable. If the concentration of the aqueous mineral acid solution is less than 15 wt%, coarse granular silica gel is likely to be produced, and if the concentration of the aqueous sulfuric acid solution is higher than 50 wt%, the sphericity of the produced silica gel particles may decrease. ..
• the mineral acid aqueous solution is preferably mixed with a W / O type emulsion containing an alkaline silicate aqueous solution in an amount that produces free mineral acid that does not contribute to salt formation.
• the neutralization reaction between the W / O type emulsion containing the alkaline silicate aqueous solution and the mineral acid aqueous solution is usually completed in about 5 to 120 minutes depending on the mixing conditions, etc., and the neutralization reaction is completed at the temperature of the reaction solution. It can be confirmed by starting to decline.
• the reaction solution of the W / O type emulsion containing the alkaline silicate aqueous solution and the mineral acid aqueous solution is heated as it is with stirring without separating the produced spherical silica gel after the completion of the neutralization reaction.
• the emulsion-like reaction solution is separated into an oil phase and an aqueous phase containing spherical silica gel (mineral acid aqueous solution phase). Therefore, the oil phase is removed from the reaction solution, and the mineral acid aqueous solution phase containing spherical silica gel is removed.
• High-purity spherical silica gel can be obtained by washing with pure water or the like.
• the reaction solution needs to be heated to a temperature of 50 ° C. or higher, and in consideration of the treatment time, it should be held at a temperature of preferably 50 to 120 ° C., more preferably 80 to 100 ° C. for 30 minutes to 1 hour. Is preferable.
• ratio ratio
• the numerical value (ratio) range indicated by using “-" in the present specification includes the numerical values (ratio) described before and after “-” as the minimum value (ratio) and the maximum value (ratio), respectively. Shows the range.
• the obtained silica gel particles are not calcined at a temperature of 1000 ° C. or higher, preferably at a temperature of 50 to 500 ° C., more preferably 100 to 400 ° C. It is preferable to carry out only the drying treatment of the spherical silica gel by holding the silica gel for 1 minute to 40 hours, more preferably 10 to 30 hours.
• the spherical silica of the present invention suppresses the decrease in specific surface area and pore volume caused by the progress of densification, and achieves a spherical shape and hardness suitable for obtaining a smooth touch to the skin.
• its water content is also characterized by having a structural water content of 1.6% or more.
• the porous spherical silica particles obtained by drying have an average primary particle diameter of preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m in order to exhibit a smooth feel on the skin. It is preferable to do.
• the average primary particle diameter of the silica particles becomes larger than 20 ⁇ m, the particles applied or adhered to the skin are likely to fall from the skin due to their own weight, which causes uneven makeup.
• the average primary particle diameter is smaller than 0.1 ⁇ m, the particles enter the recesses such as pores and wrinkles of the skin, which causes a problem that it is difficult to completely remove the makeup.
• the particles are crushed while being dried, so that crushing is not necessary in the post-drying step. In some cases. Further, when the particles are dried in a stationary state or when a more precise average primary particle diameter is to be controlled, the particles may be crushed or further classified in the post-drying step.
• the spherical silica particles of the present invention are characterized in that the specific surface area by the BET method is 300 m 2 / g or more, the total pore volume is 0.3 ml / g or less, and the oil absorption amount is 50 ml / 100 g or less. is doing. That is, the spherical silica particles of the present invention are porous and have a large specific surface area, but their oil absorption is suppressed, and the particles are not easily broken even when used for cosmetics. It is possible to develop a feeling of use that is excellent in feel. Further, in order to obtain such spherical silica particles, it is effective to perform only the drying treatment of the generated silica gel and omit the firing treatment.
• the method for producing silica gel particles to be dried is not limited to the above-mentioned method of emulsifying and coagulating an alkali silicate, and other production methods such as a sol-gel method can also be used.
• a sol-gel method In the production method using the sol-gel method, if the raw materials such as silicon alkoxide, alkali silicate, and silica gel sol are in the form of a solution or sol, a method of growing seed particles, a method of suspending or emulsifying and coagulating them, etc. are used. Thereby, silica gel particles to be dried can be obtained from these raw materials.
• the specific surface area according to the BET method is 300 m 2 / g or more, the total pore volume is 0.3 ml / g or less, and the oil absorption amount is 50 ml / 100 g or less. Quality spherical silica particles can be obtained.
• the spherical silica particles of the present invention are porous and have a large specific surface area, but the amount of oil absorption thereof is suppressed, and the particles are not easily broken even when used for cosmetics, so that they adhere to the skin. It is possible to develop a feeling of use that is excellent in terms of texture and feel. Therefore, the spherical silica particles of the present invention can be suitably used as a feel-improving agent for cosmetics.
• Step 1 Preparation of emulsion> 100 g of non-polar solvent (xylene), 4 g of emulsifier (sorbitan monostearate ), 400 g of No. 1 sodium silicate aqueous solution (SiO 2 conversion concentration 10 wt%), and rotation speed using an emulsifier (TK Robomix manufactured by PRIMIX).
• the emulsion was prepared by stirring at 4500 rpm for 5 minutes.
• ⁇ Step 2 Silica gel formation / removal of impurities> Add 500 g of the emulsion obtained in step 1 while stirring 500 g of a sulfuric acid aqueous solution having a concentration of 40 wt% in a container, stir at room temperature for 30 minutes, then heat to 90 ° C. under stirring and hold for 30 minutes.
• the emulsion-like reaction solution was separated into an oil phase and an aqueous phase containing spherical silica gel.
• the oil phase was removed from the separated reaction solution, and the aqueous phase containing silica gel was washed with pure water until the electrical conductivity in the aqueous phase became 80 ⁇ S / cm or less, and then dehydrated to obtain silica gel.
• ⁇ Step 3 Drying of silica gel> The silica gel obtained in Step 2 was dried at a temperature of 120 ° C. for 24 hours to prepare spherical silica particles of Example 1.
• Example 2 Spherical silica particles of Example 2 were prepared by performing the same operation under the same conditions as in Example 1 except that the type of the aqueous solution of sodium silicate used was No. 2.
• Example 3 Spherical silica particles of Example 3 were prepared by performing the same operation under the same conditions as in Example 1 except that the type of the aqueous solution of sodium silicate used was No. 3.
• Example 4 The same operation was performed under the same conditions as in Example 2 except that the heating temperature in Step 2 was set to 70 ° C. to prepare spherical silica particles of Example 4.
• Example 5 The same operation was performed under the same conditions as in Example 2 except that the heating temperature in Step 2 was set to 50 ° C. to prepare spherical silica particles of Example 5.
• Example 6 Spherical silica particles of Example 6 were produced by performing the same operation under the same conditions as in Example 2 except that the SiO 2 equivalent concentration of the aqueous sodium silicate solution used was set to 5 wt%.
• Example 7 Spherical silica particles of Example 7 were produced by performing the same operation under the same conditions as in Example 2 except that the SiO 2 equivalent concentration of the aqueous sodium silicate solution used was set to 20 wt%.
• Example 8 Spherical silica particles of Example 8 were produced by performing the same operation under the same conditions as in Example 2 except that the concentration of the aqueous sulfuric acid solution used was 30 wt%.
• Example 9 Spherical silica particles of Example 9 were produced by performing the same operation under the same conditions as in Example 2 except that the concentration of the aqueous sulfuric acid solution used was 50 wt%.
• Example 10 The same operation was carried out under the same conditions as in Example 2 except that the emulsifier used was sorbitan monopalmitate, to prepare spherical silica particles of Example 10.
• Example 11 The same operation was carried out under the same conditions as in Example 2 except that the emulsifier used was sorbitan monolaurate, to prepare spherical silica particles of Example 11.
• Example 12 Spherical silica particles of Example 12 were prepared by performing the same operation under the same conditions as in Example 2 except that the emulsifier used was sorbitan distearate.
• Example 13 Spherical silica particles of Example 13 were prepared by performing the same operation under the same conditions as in Example 2 except that the emulsifier used was sorbitan tristearate.
• Example 14 The same operation was carried out under the same conditions as in Example 2 except that the emulsifier used was sorbitan monooleate, to prepare spherical silica particles of Example 14.
• Example 15 The same operation was carried out under the same conditions as in Example 14 except that the amount of the emulsifier used was 4.8 g, to prepare spherical silica particles of Example 15.
• Example 16 The same operation was carried out under the same conditions as in Example 14 except that the amount of the emulsifier used was 3.2 g, to prepare spherical silica particles of Example 16.
• Example 17 Spherical silica particles of Example 17 were prepared by performing the same operation under the same conditions as in Example 2 except that the emulsifier used was sorbitan sesquioleate.
• Example 18 The same operation was carried out under the same conditions as in Example 2 except that the emulsifier used was sorbitan trioleate, to prepare spherical silica particles of Example 18.
• Example 19 The silica particles obtained in Step 3 were further dried at a temperature of 350 ° C. for 3 hours, and the same operation was carried out under the same conditions as in Example 2 to prepare spherical silica particles of Example 19.
• Example 20 The same operation as in Example 2 except that 0.20 g of titanium oxide (manufactured by TAYCA Corporation: brand MT-150AW) was added to the aqueous solution of sodium silicate and the operation of step 1 was performed after sufficiently mixing. To prepare the silica particles of Example 20.
• Example 21 The silica particles of Example 21 were prepared by performing the same operation under the same conditions as in Example 20 except that the amount of titanium oxide (manufactured by TAYCA Corporation: brand MT-150AW) was 4.44 g.
• Example 22 The silica particles of Example 22 were prepared by performing the same operation under the same conditions as in Example 20 except that the amount of titanium oxide (manufactured by TAYCA Corporation: brand MT-150AW) was 17.14 g.
• Comparative Example 1 The silica particles of Comparative Example 1 were produced by performing the same operation under the same conditions as in Example 2 except that the silica particles obtained in Step 3 were calcined at a temperature of 1100 ° C. for 3 hours.
• Comparative Example 2 The silica particles of Comparative Example 2 were produced by performing the same operation under the same conditions as in Example 2 except that the silica particles obtained in Step 3 were calcined at a temperature of 650 ° C. for 3 hours.
• Comparative Example 3 In order to compare silica gel with that obtained by wet water-based synthesis, commercially available silica particles (manufactured by Tosoh Silica Co., Ltd .: Nipponsil E-743) were used as the silica particles of Comparative Example 3.
• Comparative Example 4 In order to compare with the silica particles having the same average primary particle diameter and specific surface area as in Example 1, commercially available silica particles (manufactured by AGC SI-Tech Co., Ltd .: H-52) were used as the silica particles of Comparative Example 4.
• ⁇ Physical characteristic evaluation method> (Average primary particle size) The average primary particle size of the silica particles of each example and each comparative example was measured using a scanning electron microscope. Specifically, images of about 1000 silica particles taken with a scanning electron microscope (Hitachi High-Technologies Corporation: S-4800) are image-analyzed particle size distribution software (Mount-VIEW Co., Ltd .: Mac-VIEW). It was performed by analysis using.
• the specific surface area of the silica particles of each Example and each Comparative Example was measured using a specific surface area measuring device (Mt. Specifically, as a pretreatment before measurement, the silica particles are dried for 12 hours at a temperature of 105 ° C. in a desiccator in order to remove water and the like physically adsorbed on the surface of the silica particles and in the pores. It was allowed to cool. The cooled sample was degassed with nitrogen gas for 20 minutes at a temperature of 150 ° C., and the specific surface area was measured. The specific surface area was determined by applying the formula of the BET 1-point method.
• the structural water content of the silica particles of each Example and Comparative Example was measured using a thermogravimetric / differential thermal (TG-DTA) analyzer TG / DTA 6300 (manufactured by Seiko Instruments Inc.). Specifically, as a pretreatment before measurement, the silica particles are dried for 12 hours at a temperature of 105 ° C. in a desiccator in order to remove water and the like physically adsorbed on the surface of the silica particles and in the pores. It was allowed to cool. The weight loss rate (%) from room temperature to 500 ° C. when the cooled silica particles are heated from room temperature to 1200 ° C. in the air (flow rate: 200 ml / min) at a heating rate of 10 ° C./min. The difference in weight loss rate (%) from room temperature to 1100 ° C. was defined as the structural water content rate (%).
• TG-DTA thermogravimetric / differential thermal
• Table 1 shows the preparation conditions for each of the powders of Examples and Comparative Examples, and Table 2 shows the evaluation results of each.
• the spherical silica particles of Examples 1 to 19 have a specific surface area of 300 m 2 / g or more (for example, Examples 3 and 11), more preferably 400 m 2 / g, in order to obtain a high tactile evaluation.
• the above (for example, Examples 4, 6, 9, 12, 17), and the pore volume is 0.3 ml / g or less (for example, Examples 14 and 16), more preferably 0.25 ml / g or less (for example, Example). 2,7,8,18), more preferably 0.2 ml / g or less (for example, Examples 4, 6, 9, 12, 17), but particularly in comparison with Comparative Examples 3 and 4, which will be described later. It was found that the oil absorption amount was suppressed to 50 ml / 100 g or less, more preferably 30 ml / 100 g or less, and further preferably 20 ml / 100 g or less.
• the ratio of the area of the silica particles in contact with the skin can be sufficiently reduced, and when applied to the skin, it can be sufficiently reduced. It is considered that a good feel was obtained by making it difficult to feel the hardness of the silica particles.
• the specific surface area by the BET method is 300 m 2 / g or more, more preferably 400 m 2 / g or more, and the total pore volume is 0.3 ml / g or less, more preferably 0.25 ml / g or less, still more preferably.
• the oil absorption amount is 50 ml / 100 g or less, more preferably 30 ml / 100 g or less, still more preferably 20 ml / g.
• the spherical silica particles of Examples 1 to 19 are porous and have a large specific surface area, but the amount of oil absorption thereof is suppressed, and excellent adhesion to the skin and feel can be exhibited. ..
• the temperature is preferably 50 to 500 ° C, more preferably 100 to 400 ° C, preferably 1 minute to 40 hours, and more preferably 10 to 30 hours.
• the silica particles have a large specific surface area, the amount of oil absorbed thereof is suppressed, and the spherical silica particles of the present invention exhibiting excellent adhesion to the skin and a feel can be obtained. understood.
• the silica particles of Comparative Example 1 are fired at a temperature of 1100 ° C., the specific surface area and the pore volume are greatly reduced due to the progress of densification of the particles and the sintering of the particles, and further, the particles It is presumed that the hardness is increased and the particles are fused together. Therefore, it was found that the silica particles of Comparative Example 1 could not exhibit excellent adhesion to the skin and feel, resulting in poor usability.
• the silica particles of Comparative Example 3 have a specific surface area of 55 m 2 / g and a pore volume of 0.33 ml / g, which are both small values, but on the contrary, the oil absorption amount is 130.0 ml. Since it is as high as / 100 g, it was found that as a result of excessive oil absorption of the skin oil, the absorbed silica particles agglomerate and the skin surface becomes dry, and excellent adhesion and feel to the skin cannot be obtained. ..
• the silica particles of Comparative Example 4 have a specific surface area equivalent to that of the spherical silica particles of Examples 1 to 19 like the silica particles of Comparative Example 1, but the pore volume is as large as 1.60 ml / g. It was found that the oil absorption amount was as high as 247.0 ml / 100 g. Therefore, even in the silica particles of Comparative Example 4, as a result of excessive oil absorption of the oil content of the skin, aggregation of the absorbed silica particles and dryness of the skin surface occur, and the adhesion and feel to the skin are exhibited in Example 1. The result was inferior to that of the spherical silica particles of ⁇ 19.
• general silica particles are porous and have a large specific surface area and large oil absorption in order to improve the feeling of use such as rolling property, adhesion, and tactile sensation to the skin when blended in cosmetics and the like. It has a large amount (Comparative Example 4), or has a small specific surface area and a small pore volume due to pore control, but has a large oil absorption amount (Comparative Example 3), as in Examples 1 to 19. It was found that there are no spherical silica particles having excellent usability such as adhesiveness and tactile sensation because the oil absorption amount is suppressed while having a large specific surface area.
• silica gel obtained by a sol-gel method such as emulsifying and coagulating an alkali silicate. It has been found that it is effective to dry the particles only at a low temperature without firing at a high temperature.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Public Health (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Inorganic Chemistry (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Dispersion Chemistry (AREA)
• Dermatology (AREA)
• Silicon Compounds (AREA)
• Cosmetics (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=78846096

Family Applications (1)

Country Status (6)

Citations (6)

Family Cites Families (12)

• 2021
  • 2021-06-09 WO PCT/JP2021/021986 patent/WO2021251440A1/ja not_active Ceased
  • 2021-06-09 US US18/009,215 patent/US20230257273A1/en active Pending
  • 2021-06-09 JP JP2022530611A patent/JPWO2021251440A1/ja active Pending
  • 2021-06-09 CN CN202180041891.3A patent/CN115702117A/zh active Pending
  • 2021-06-09 EP EP21822711.4A patent/EP4166500A4/en active Pending
  • 2021-06-09 KR KR1020227044228A patent/KR20230023660A/ko active Pending

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events