WO2009133895A1 - チタニア微粒子複合体及び該チタニア微粒子複合体を含有する組成物 - Google Patents
チタニア微粒子複合体及び該チタニア微粒子複合体を含有する組成物 Download PDFInfo
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- WO2009133895A1 WO2009133895A1 PCT/JP2009/058368 JP2009058368W WO2009133895A1 WO 2009133895 A1 WO2009133895 A1 WO 2009133895A1 JP 2009058368 W JP2009058368 W JP 2009058368W WO 2009133895 A1 WO2009133895 A1 WO 2009133895A1
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- 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
- A61K8/29—Titanium; Compounds thereof
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- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
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- 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
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- 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
- A61K8/11—Encapsulated compositions
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- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
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- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/362—Polycarboxylic acids
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- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
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- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
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- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic 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
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- 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
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- 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
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Definitions
- the present invention relates to a titania fine particle composite useful as an ultraviolet protection agent, a method for producing the same, and a composition containing the titania fine particle composite.
- UVA Long wavelength ultraviolet rays
- UVB medium wavelength ultraviolet rays
- Zinc oxide and titanium oxide are known to have a high UV protection effect.
- titanium oxide has a high UVB shielding performance
- zinc oxide has a high UVA shielding performance.
- titanium oxide and zinc oxide tend to be hindered from uniform dispersion in an aqueous solution due to the surface activity of the fine particles. Therefore, when titanium oxide or zinc oxide is added to the cosmetic base, non-uniform dispersion occurs.
- a neutral titania sol is prepared by blending a water-soluble polymer compound (polyvinyl alcohol or the like) as a dispersion stabilizer in an acidic aqueous solution of titania fine particles, and further blending an alkaline solution as a neutralizing agent.
- a water-soluble polymer compound polyvinyl alcohol or the like
- an alkaline solution as a neutralizing agent.
- Patent Document 5 it has been difficult to maintain the stability of the neutral titania sol when a cosmetic additive is added.
- the inventors of the present invention dissolved a specific lower fatty acid or a polymer and a metal salt in a water-soluble organic solvent or a mixture of water and a water-soluble organic solvent, and neutralized the metal salt or the metal salt.
- a metal oxide fine particle composite was prepared by reducing the metal (Patent Document 8).
- the zinc oxide fine particle composite can achieve uniform dispersion in an aqueous solution, and can achieve both transparency and ultraviolet absorption.
- the fine particle composite of titanium oxide since the uniform dispersion in the aqueous solution is inferior, both the transparency and the ultraviolet absorptivity could not be sufficiently satisfied.
- the composite state is unstable, there is a problem that once the particles are aggregated, they cannot be redispersed or the viscosity is high.
- titania fine particle composites that are excellent in transparency, have an excellent ultraviolet absorption effect, and are in a stable composite state have high versatility, and therefore, their development is desired.
- JP 2001-207060 A JP 2006-160651 A Japanese Patent Laid-Open No. 2004-203768 Japanese Patent Laid-Open No. 2003-096437 Japanese Patent Publication No. 63-123815 JP 2007-291094 A Japanese Patent Laid-Open No. 2005-232069 International Publication No. 2007/057997 Pamphlet
- the present invention has been made under such circumstances, and it is an object to provide a novel titania fine particle composite that is uniformly dispersed in a dispersion medium, thereby ensuring high transparency, stability, and ultraviolet absorption ability. And Another object of the present invention is to provide a titania fine particle composite that maintains a uniform dispersion state even when added to a cosmetic together with other compositions and has high practicality as a cosmetic composition.
- a titania fine particle composite in which one or two or more kinds (hereinafter referred to as “carboxylic acid monomer or polymer”) selected from polymers having the carboxylic acid and / or carboxylic acid derivative as a constituent monomer are combined.
- the titania fine particle composite in which the half-value width of the peak of the maximum diffraction intensity derived from titania in the X-ray powder diffraction analysis is 2.0 ° or less is uniformly dispersed in the dispersion medium. And it discovered that this titania microparticle composite was obtained by neutralizing after adding the said carboxylic acid monomer or a polymer etc. to the acidic water dispersion liquid of a titania microparticle, and came to complete this invention. That is, the present invention is as follows.
- One or more selected from titania fine particles, a carboxylic acid and a carboxylic acid derivative represented by the general formula (1), and a polymer having the carboxylic acid and / or the carboxylic acid derivative as a constituent monomer Is a titania fine particle composite in which the half-width of the peak of the maximum diffraction intensity derived from the titania crystal in X-ray powder diffraction analysis is 2.0 ° or less.
- R represents a hydrogen atom, or an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a carboxyl group or a hydroxy group
- X represents a hydrogen atom
- the carboxylic acid derivative represented by the general formula (1) is selected from the group consisting of an alkali metal salt of a mono-, di- or tricarboxylic acid having 10 or less carbon atoms and a polyoxyalkylene adduct of the carboxylic acid.
- a polymer containing the carboxylic acid and / or derivative thereof represented by the general formula (1) as a constituent monomer is polyacrylic acid or polymethacrylic acid, polyacrylic acid or polymethacrylic acid alkali metal salt, and poly The titania fine particle composite according to any one of (1) to (5), which is one or more selected from the group consisting of polyoxyethylene adducts of acrylic acid or polymethacrylic acid.
- the titania fine particle composite body prepared by adding an alkali until it reaches a neutral range, after adding 2 or more types.
- General formula (1) (In the formula, R represents a hydrogen atom, or an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a carboxyl group or a hydroxy group, X represents a hydrogen atom, Represents an alkali metal or a polyoxyalkylene group having 1 to 12 moles added)
- a composition comprising the titania fine particle composite according to any one of (1) to (7).
- the composition according to (8) which is an external preparation for skin.
- a method for producing a titania fine particle composite wherein the carboxylic acid and carboxylic acid derivative represented by the general formula (1) and the carboxylic acid and / or carboxylic acid derivative are added to an acidic aqueous dispersion of titania fine particles. Including a step of adding one or two or more selected from a polymer as a constituent monomer to form a mixed solution, and a step of adding an alkali to the mixed solution until reaching a neutral range to form a neutral solution.
- a method for producing a titania fine particle composite is
- R represents a hydrogen atom, or an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a carboxyl group or a hydroxy group
- X represents a hydrogen atom
- (12) A method for producing a neutral dispersion of a titania fine particle composite, wherein the carboxylic acid and the carboxylic acid derivative represented by the general formula (1), and the carboxylic acid and / Alternatively, a step of adding one or two or more selected from a polymer having a carboxylic acid derivative as a constituent monomer to make a mixed solution, and adding a alkali to the mixed solution until reaching a neutral range, to make a neutral solution
- a method for producing a neutral dispersion of a titania fine particle composite comprising: a step of filtering the neutral liquid and washing the filtr
- R represents a hydrogen atom, or an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a carboxyl group or a hydroxy group
- X represents a hydrogen atom
- the titania fine particle composite of the present invention hardly aggregates between the titania fine particle composites and can be uniformly dispersed in a dispersion medium. Therefore, the composition containing the titania fine particle composite of the present invention has high transparency, stability, and ultraviolet absorption ability. In addition, the titania fine particle composite of the present invention can be uniformly dispersed in the dispersion medium again even if it is once filtered from the dispersion medium. Moreover, since the neutral dispersion of the titania fine particle composite of the present invention has a lower viscosity than the neutral dispersion of the conventional titania fine particle composite, it can be easily processed into a cosmetic or the like.
- the neutral dispersion of the titania fine particle composite of the present invention can be blended in a cosmetic at a high concentration. Furthermore, even if other components are added during the preparation of the cosmetic, a uniform dispersed state can be maintained. Thus, the titania fine particle composite of the present invention is excellent in practicality and versatility.
- the titania fine particle composite of the present invention is selected from titania fine particles, a carboxylic acid and a carboxylic acid derivative represented by the general formula (1), and a polymer containing the carboxylic acid and / or the carboxylic acid derivative as a constituent monomer. It is a titania fine particle composite in which one or more are combined, and the half-value width of the peak of the maximum diffraction intensity derived from the titania crystal in the X-ray powder diffraction analysis is 2.0 ° or less.
- the full width at half maximum of the peak of the maximum diffraction intensity derived from the titania crystal in the analysis chart becomes 2.0 ° or less.
- the “half width” is defined as a value obtained by conducting powder X-ray diffraction analysis under the following conditions.
- a dry sample of the titania fine particle composite is pulverized into a powder for measurement.
- X-ray diffraction (XRD) measurement of the powder for measurement is performed using an X-ray diffractometer (PANallytical X'Pert PROMPD; manufactured by Spectris Co., Ltd.).
- the half-value width is the difference (peak width) between the values on the two horizontal axes where the value of the vertical axis of the peak which is a mountain shape is half of the maximum value of the peak.
- the half width of the peak of maximum diffraction intensity represents the crystallinity of the powder.
- the half width of the peak corresponding to the (101) plane is small, that is, when the peak is sharp, it indicates that the degree of crystallinity on the (101) plane is high.
- the full width at half maximum of the peak corresponding to the (101) plane is large, that is, when the peak is gentle, crystallization on the (101) plane does not proceed, indicating that it is close to an amorphous state.
- the crystallinity of the titania fine particles which are the core of the titania fine particle composite is improved.
- the titania fine particle composite is uniformly dispersed in the dispersion medium, and can achieve transparency and ultraviolet absorption.
- a dispersion containing such a titania fine particle composite at a high concentration is a dispersion containing a conventional titania fine particle composite at the same concentration.
- the viscosity is significantly lower than that. This is presumably because the interaction between the titania fine particles and the carboxylic acid monomer or polymer is increased.
- the titania fine particle composite having a half-value width of 2.0 ° or less can be produced by the method described later.
- the titania fine particles that are the core portion of the titania fine particle composite of the present invention are crystallized titanium oxide.
- the crystal type may be either a rutile type or an anatase type, or may be mixed. Further, it may be partially uncrystallized. Of these, rutile crystals that have low surface activity and can be expected to absorb ultraviolet rays are preferred.
- the titania fine particles that are the core part of the titania fine particle composite of the present invention may be those obtained by coating the surface of the titania fine particles with one or more hydrated oxides such as silicon, aluminum, and zirconium. Surface activity can be suppressed by the surface coating of fine particles. However, it should be noted that when the particle diameter is increased by the surface treatment, the absorption efficiency of ultraviolet rays may decrease.
- R represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a carboxyl group or a hydroxy group.
- the hydrogen atom of the alkyl group or alkenyl group is substituted with a carboxyl group, the carbon number of the alkyl group or alkenyl group is defined by the number on the assumption that such substitution is not performed. Is done.
- X represents a hydrogen atom, an alkali metal or a polyoxyalkylene group having 1 to 12 moles added.
- R is preferably a C 1-8 alkyl group or alkenyl group in which a hydrogen atom may be substituted with a carboxyl group or a hydroxy group.
- examples of the carboxylic acid represented by the general formula (1) include acetic acid, propionic acid, and caproic acid.
- examples of the carboxylic acid represented by the general formula (1) include acrylic acid and methacrylic acid.
- the carboxylic acid represented by the general formula (1) includes oxalic acid, malonic acid, tartaric acid, succinic acid, and citric acid. It can illustrate suitably. That is, the carboxylic acid represented by the general formula (1) may be a monocarboxylic acid or a polycarboxylic acid such as a dicarboxylic acid or a tricarboxylic acid, and preferably has 10 or less carbon atoms.
- X is an alkali metal
- examples of X include potassium, sodium and lithium.
- the average number of added moles is preferably 1 to 12, and more preferably 2 to 8.
- the polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.
- an alkali metal salt of a polycarboxylic acid such as a monocarboxylic acid having 10 or less carbon atoms or a dicarboxylic acid or a tricarboxylic acid, or a partial carboxyl group or Those in which polyoxyalkylene is added to the hydroxyl group are particularly preferred.
- the carboxylic acid is a polycarboxylic acid
- a form in which a part thereof is a salt is preferable.
- alkali metal salts include sodium acetate, potassium propionate, sodium acrylate, triethylamine methacrylate, sodium caprate, lithium oxalate, potassium malonate, sodium succinate, potassium citrate, sodium tartrate, etc. it can.
- polyoxyethylene adduct include polyoxyethylene acrylate and polyoxyethylene methacrylate.
- a polymer containing the carboxylic acid and / or carboxylic acid derivative represented by the general formula (1) as a constituent monomer methacrylic acid, acrylic acid or a polyoxyethylene adduct, metal salt or alkali metal salt thereof is used.
- the monomer include a polymer in which an alkenyl group of a carboxylic acid side chain is a polymerization group.
- the polymerization degree of these polymers is preferably 1000 or less.
- the polymer is a homopolymer obtained by polymerizing the constituent monomers, or a compound represented by the general formula (1) such as the constituent monomers and an alkyl (meth) acrylate such as vinyl acetate, vinyl alcohol, styrene, or methyl methacrylate.
- a copolymer with a monomer that does not belong to the group can be suitably exemplified.
- the polymer include polyacrylic acid, sodium polyacrylate, polyethanolamine triethanolamine, polysodium methacrylate, polymethacrylic acid triethylamine, or polyoxyethylene acrylic polymer having an addition number of oxyethylene of 23 mol or less or A polyoxyethylene methacrylic polymer is mentioned.
- the titania fine particle composite of the present invention in which a titania fine particle and a polymer having a carboxylic acid and / or a carboxylic acid derivative represented by the general formula (1) as a constituent monomer are combined can be dispersed in a neutral aqueous solution. .
- the titania fine particle composite of the present invention in which the titania fine particles are complexed with the carboxylic acid and the carboxylic acid derivative represented by the general formula (1) can be dispersed in a hydrophobic solvent.
- the absorption peak of the carbonyl group in the infrared absorption spectrum measured by the KBr tablet method preferably appears at 1535 to 1545 cm ⁇ 1 .
- the infrared absorption spectrum is defined as a spectrum obtained by measurement under the following conditions.
- the neutral aqueous dispersion of the titania fine particle composite of the present invention is dried at 105 ° C. and then pulverized to obtain a measurement powder.
- the measurement powder is a KBr tablet, and the spectrum is measured using a Fourier transform infrared spectrophotometer (FTIR-8300; manufactured by Shimadzu Corporation).
- the titania fine particle composite is uniformly dispersed in a dispersion medium, and can achieve transparency and ultraviolet absorption. Further, as shown in a comparison between Example 1 and Comparative Example 4 described later, a dispersion containing such a titania fine particle composite at a high concentration is a dispersion containing a conventional titania fine particle composite at the same concentration. The viscosity is significantly lower than that.
- the peak of the carbonyl group of the carboxylic acid monomer or polymer is present on the side larger than 1535 to 1545 cm ⁇ 1 , for example, 1558 to 1560 cm ⁇ 1 for sodium polyacrylate.
- the carbonyl group of the carboxylic acid monomer or polymer or the like since the intermolecular interaction between the titania fine particles and the carboxylic acid monomer or polymer is large, the carbonyl group of the carboxylic acid monomer or polymer or the like. It is considered that a part of is bound to the surface of the titania fine particles, and the peak of the carbonyl group appears at 1535 to 1545 cm ⁇ 1 .
- the peak of the carbonyl group does not appear at 1535 to 1545 cm ⁇ 1 , so that the titania fine particle composite of the present invention is used. Can be distinguished from the body.
- the titania fine particle composite having the absorption peak at 1535 to 1545 cm ⁇ 1 can be produced by the method described later.
- the ratio of the titania fine particles to the carboxylic acid monomer or polymer is preferably 60% or more by weight. This weight ratio is preferably 60 to 99%, more preferably 85 to 99%.
- the particle size of the titania fine particle composite is increased, it tends to be difficult to uniformly disperse in the dispersion medium.
- the titania fine particle composite of the present invention has a large intermolecular interaction between the titania fine particles and the carboxylic acid monomer or polymer, the composite effect can be achieved even if the weight ratio of the carboxylic acid monomer or polymer compounded to the titania fine particles is small. Is sufficiently fulfilled, and the fine particles can be uniformly dispersed in the dispersion medium.
- the particle diameter of the titania fine particle composite of the present invention is preferably 0.002 to 5 ⁇ m when used as an ultraviolet absorber. In particular, it is preferably 1 ⁇ m or less. Since the titania fine particle composite of the present invention may have a small amount of carboxylic acid monomer or polymer as described above, the titania fine particle composite has a small particle size and is uniformly dispersed in a dispersion medium. Since the surface area of the fine particles can be increased, it is suitable for an ultraviolet absorber. The particle shape of the titania fine particle composite can be observed with a scanning electron microscope, and the maximum diameter can be measured by installing a scale.
- the titania fine particle composite of the present invention can be produced by the following method.
- the above is gradually added and stirred to obtain a mixture.
- the mixture may be allowed to stand for 1 minute to 1 hour for aging.
- an alkali such as sodium hydroxide is added to and stirred in the mixture until reaching the neutral range (pH 5 to 7.5) to obtain a neutral solution. After neutralization, this neutral solution may be allowed to stand for about 1 minute to 1 hour in order to cause a sufficient complexing reaction. All of the above steps can be performed at room temperature (15 to 30 ° C.).
- the composite reaction of titania fine particles and a carboxylic acid monomer or a polymer starts by addition of the alkali. That is, the anion in which the titania fine particles are dispersed in water (chlorine ions when the acid in the dispersion medium is hydrochloric acid, nitrate ions when the acid in the nitric acid, etc.) is released from the titania fine particles by alkali neutralization.
- An acid monomer or a polymer is complexed with titania fine particles by intermolecular interaction.
- the titania fine particle composite of the present invention is formed by the above steps, but when processing into a skin external preparation, the neutral liquid obtained above was further filtered, and the filtrate was washed with water to remove salts. It can be in a wet cake state.
- a slurry in which the wet cake is re-dispersed in a dispersion medium is preferable for handling as a raw material for an external preparation for skin.
- ultrasonic dispersion may be performed during redispersion. Further, it may be subjected to a mill (ball mill, sand grinder mill, etc.) before redispersion.
- the concentration of titania fine particles in the acidic aqueous dispersion of titania fine particles is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 2.5% by weight or less in order to obtain a uniform dispersion.
- Hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like can be used as the acid added to water in the dispersion medium (dissolving agent) of the acidic aqueous dispersion of titania fine particles, with hydrochloric acid and nitric acid being particularly preferred.
- the pH of the acidic aqueous dispersion of titania fine particles is preferably in the range of 1 to 2.
- the carboxylic acid monomer or polymer may be added directly to the acidic aqueous dispersion of titania fine particles, but it is preferable to make a solution in advance for uniform complexation.
- the concentration of the solution is preferably 0.01 to 1% by weight.
- the solvent a mixed solvent of alcohol and water is suitable, and ethanol, isopropyl alcohol, methanol, or 1,3-butylene glycol can be used as the alcohol.
- the titania fine particles and the carboxylic acid monomer or polymer are preferably blended at a weight ratio of 5: 1 to 14: 1. If the ratio of the carboxylic acid monomer or the polymer is larger than this, the titania fine particle composite becomes sticky, which is not preferable.
- the titania fine particles used in the method for producing a titania fine particle composite of the present invention can be obtained by various known methods.
- a hydrous titanium oxide obtained by neutralizing a water-soluble titanium salt such as titanium tetrachloride or titanium oxysulfate with an alkali a hydrous titanium oxide obtained by hydrolyzing a titanium alkoxide, or a titanium oxysulfate solution.
- titanium hydroxide obtained by heat hydrolysis is heat-aged.
- tin oxide as a transfer agent is added to titanium hydroxide instead of heat aging, and then acid is added to peptize.
- titania fine particles whose surface is coated with one or more hydrated oxides such as silicon, aluminum and zirconium can be obtained by a known method. For example, it can be carried out by mixing the fine particle titania dispersion prepared in advance into a gel produced by neutralization of sodium silicate and depositing it. Alternatively, a soluble salt of a metal such as aluminum can be treated with an acid and deposited in the form of an insoluble metal hydroxide such as aluminum hydroxide in the presence of a fine particle titania dispersion.
- the titania fine particles preferably have a small particle diameter when transparency is desired, or when used for purposes such as ultraviolet absorption and sterilization. The maximum diameter of the titania fine particles is preferably about 0.1 to 0.001 ⁇ m.
- the composition containing the titania fine particle composite of the present invention has a low viscosity in a neutral aqueous dispersion and a very high fluidity. This is because the titania fine particle composite of the present invention is uniformly dispersed in the neutral aqueous dispersion, and thus aggregation between the titania fine particle composites is difficult to occur. Since the viscosity is small, it can be easily processed as a cosmetic, and a fresh feeling of use can be imparted to the cosmetic.
- the titania fine particle composite of the present invention has a large intermolecular interaction between the titania fine particles as the core and the carboxylic acid monomer or polymer, the interaction between the carboxylic acid monomer or polymer is relatively small, and the neutral It can be uniformly dispersed without agglomeration in the aqueous dispersion. For this reason, the transmittance in the visible range is high, and it becomes transparent. Moreover, the surface area of the titania fine particles is increased, and the shielding rate in the ultraviolet region is increased. Due to this property, the cosmetic containing the titania fine particle composite of the present invention can achieve high transparency, and has an effect of being less whitish when applied to the face or body. Moreover, since the titania fine particle composite of the present invention is excellent in ultraviolet light shielding rate, it is suitable for cosmetics having excellent ultraviolet absorption ability.
- the titania fine particle composite of the present invention can be used in cosmetics as an external preparation for skin, for example, sun protection milk, sun care powder, UV protection cosmetics such as sun block, undermec up, foundation, control color, pressed powder, etc.
- Suitable makeup cosmetics, particularly summer makeup cosmetics, and the like can be suitably exemplified.
- the dosage form can be applied to any dosage form such as a two-layer dispersion lotion dosage form, an emulsifier form, a powder dosage form, or an oil dosage form. Since the titania fine particle composite of the present invention can be uniformly dispersed in an aqueous medium, a two-layer dispersion lotion dosage form or an emulsifier form containing an aqueous carrier is particularly preferred.
- the content is preferably 0.5 to 50% by weight, more preferably 1.0 to 30% by weight of the whole composition.
- the skin external preparation of the present invention can contain optional components that are usually used in skin external preparations in addition to such components.
- optional ingredients include, for example, macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated coconut oil Oil, wax, oil such as beeswax, canola wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum , Hydrocarbons such as microcrystalline wax; higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid; oleyl alcohol, cety
- Bengala yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen that may be treated on the surface , Titanium oxide, zinc oxide inorganic pigments; even if the surface is treated Good, pearl agents such as titanium mica, fish phosphorus foil, bismuth oxychloride; red 202, red 228, red 226, yellow 4, blue 404, yellow 5 and red, which may be raked Organic dyes such as No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No.
- Organic powders such as polymethyl methacrylate, nylon powder, organopolysiloxane elastomer; 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldi UV absorbers such as benzoylmethane; lower alcohols such as ethanol and isopropanol; vitamin A or a derivative thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or a derivative thereof, vitamin B such as vitamin B12, vitamin B15 or a derivative thereof; vitamin E such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, vitamin E acetate,
- vitamins such as vitamin D, vitamin H, pantothenic acid, panthetin, pyrroloquinoline quinone, and the like; solvents such as benzyl alcohol, triacetin, crotamiton
- UV absorbers also included as other UV absorbers are paraaminobenzoic UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, and sugar UV absorbers. You may do it.
- Example 1 Acidic aqueous dispersion of titania fine particles A known method, that is, hydrous titanium oxide obtained by hydrolysis of titanium oxysulfate was treated with an alkali, and heated and aged in hydrochloric acid to obtain an acidic aqueous dispersion of titania fine particles. Produced. The titania fine particles in the obtained acidic aqueous dispersion had a rutile crystal structure, and the average particle size was 0.01 ⁇ m. The concentration of this acidic aqueous dispersion was adjusted with pure water to 100 g / L in terms of TiO 2 , and 1 L of the acidic aqueous dispersion of titania fine particles was weighed.
- the acidic aqueous dispersion of titania fine particles obtained in the step (a) was diluted with pure water to give 5 L of titania fine particle aqueous dispersion 5 L in terms of TiO 2 ( A liquid).
- 20 g of polyacrylic acid (molecular weight: 5000, degree of polymerization: about 50) (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 8 L of pure water (liquid B).
- the solution A was gradually added to the solution B at room temperature with stirring, and then aged for 1 hour. Further, the pH was adjusted to 5 with a 2N aqueous sodium hydroxide solution, aged for 1 hour, filtered and washed with pure water to obtain a wet cake.
- the wet cake was repulped into pure water and then ultrasonically dispersed to obtain a neutral aqueous dispersion (solid content concentration 25%, pH 7.5) (sample A) of the titania fine particle composite of the present invention.
- the composition of titania fine particles and polyacrylic acid in the titania fine particle composite sample A was 0.07 parts by weight of polyacrylic acid with respect to 1 part by weight of TiO 2 , and the ratio of the titania fine particles to the titania fine particle composite was a weight ratio. It was 93.5%.
- the re-dispersed aqueous solution of titania fine particle composite produced by the above method was boiled and then filtered, almost no carboxylic acid monomer or polymer was found in the filtrate.
- the titania fine particle composite is uniformly dispersed in the dispersion, it can be said that the titania fine particle composite has increased hydrophilicity compared with the titania fine particle before the composite. Are presumed to be complexed on the surface of the titania fine particles by a strong interaction.
- Example 2 The present invention was carried out in the same manner as in Example 1 except that 20 g of sodium polyacrylate (molecular weight: 5000, degree of polymerization: about 50) (made by Wako Pure Chemical Industries, Ltd.) was used instead of polyacrylic acid. A neutral aqueous dispersion (sample B) of the titania fine particle composite was obtained. In Sample B, the ratio of titania fine particles to titania fine particle composite was 96.0% by weight.
- Example 3 The same treatment as in Example 1 was carried out except that 20 g of polymethacrylic acid (molecular weight: 100000, degree of polymerization: about 1000) (made by Wako Pure Chemical Industries, Ltd.) was used instead of polyacrylic acid.
- the ratio of the titania fine particles to the titania fine particle composite was 92.0% by weight.
- Example 4 The same treatment as in Example 1 was performed except that 20 g of poly (acrylic acid / maleic acid) (molecular weight: 5000, polymerization degree: about 50) (manufactured by Nippon Shokubai Co., Ltd.) was used instead of polyacrylic acid, A neutral aqueous dispersion (sample D) of the titania fine particle composite, which is the titania fine particle composite of the present invention, was obtained. In Sample D, the ratio of the titania fine particles to the titania fine particle composite was 93.0% by weight.
- Example 5 Silica coating treatment on titania fine particles Silica coating treatment was performed on titania fine particles by a known method. That is, the acidic aqueous dispersion of titania fine particles obtained in the step (a) of Example 1 was diluted with pure water, adjusted to 20 g / L, and weighed 5 L (100 g in terms of TiO 2 ). The temperature was raised to 70 ° C., and then 170 mL of a sodium silicate aqueous solution having a SiO 2 equivalent concentration of 400 g / L (12% as SiO 2 with respect to titania fine particles) was added simultaneously with 20% sulfuric acid, and then aged for 30 minutes.
- a sodium silicate aqueous solution having a SiO 2 equivalent concentration of 400 g / L (12% as SiO 2 with respect to titania fine particles
- the pH was adjusted to 9.0 or more with a 10% aqueous sodium hydroxide solution, the pH was adjusted to 3 with a 1% aqueous sulfuric acid solution, filtered and washed with pure water to obtain a wet cake. This wet cake was repulped into pure water and then ultrasonically dispersed to obtain silica-coated titania fine particles A.
- the surface of the titania fine particles was coated with silica, and the content thereof was 0.05 parts by weight in terms of SiO 2 with respect to 1 part by weight of TiO 2 .
- Example E Polyacrylic acid complexing treatment The same treatment as in Example 1 was carried out except that the silica-coated titania fine particles A prepared in (c) were used instead of the acidic aqueous dispersion of titania fine particles.
- the ratio of titania fine particles to titania fine particle composite was 93.0% by weight.
- Example 6 The same treatment as in Example 5 was performed except that 20 g of polymethacrylic acid (molecular weight: 100000, degree of polymerization: about 1000) (made by Wako Pure Chemical Industries, Ltd.) was used instead of polyacrylic acid.
- the ratio of the titania fine particles to the titania fine particle composite was 91.5% by weight.
- Example 7 Silica coating treatment and alumina coating treatment of titania fine particles 1 L of acidic water dispersion (100 g in terms of TiO 2 ) of titania fine particles obtained in the step (a) of Example 1 was used with sodium hydroxide. The pH was adjusted to 9.0 or more, and 30 mL of a 400 g / L sodium silicate aqueous solution (12% as SiO 2 with respect to titania fine particles) was added thereto, the temperature was raised to 90 ° C., and then sulfuric acid was used for 200 minutes. And neutralized to a pH of 7. 80 g of polyaluminum chloride (8% as Al 2 O 3 with respect to titania fine particles) was added to the aqueous suspension.
- silica-alumina-coated titania fine particles B the mixture was neutralized with sodium hydroxide to have a pH of 5.0 and aged for 60 minutes to obtain silica-alumina-coated titania fine particles B.
- the surface of the titania fine particle was coated with silica, and its composition was 0.12 part by weight in terms of SiO 2 with respect to 1 part by weight of TiO 2 .
- the upper layer was coated with alumina, and the content thereof was 0.08 parts by weight in terms of Al 2 O 3 with respect to 1 part by weight of TiO 2 .
- Example G Polyacrylic acid complexing treatment
- the silica / alumina-coated titania fine particles B prepared in (e) were used instead of the acidic aqueous dispersion of titania fine particles.
- the ratio of the titania fine particles to the titania fine particle composite was 91.0% by weight.
- Example 8 The same treatment as in Example 7 was carried out except that 20 g of poly (acrylic acid / maleic acid) (molecular weight: 5000, degree of polymerization: about 50) (manufactured by Nippon Shokubai Co., Ltd.) was used instead of polyacrylic acid, A neutral aqueous dispersion (sample H) of the silica / alumina-coated titania fine particle composite, which is the titania fine particle composite of the present invention, was obtained. In Sample H, the ratio of the titania fine particles to the titania fine particle composite was 92.0% by weight.
- Example 1 (Comparative Example 1) Except that the addition of polyacrylic acid in Example 1 was omitted, the same treatment as in Example 1 was performed, but aggregation occurred in the neutral region, and a stable dispersion could not be obtained.
- Example II A neutral aqueous dispersion (sample I) of the titania fine particle composite was treated in the same manner as in Example 1 except that 20 g of sodium alginate (Wako Pure Chemical Industries, Ltd.) was used instead of polyacrylic acid. Obtained. In Sample I, the ratio of titania fine particles to titania fine particle composite was 85.0% by weight.
- Example 3 The same treatment as in Example 1 was performed except that 20 g of polyvinyl alcohol (molecular weight: 500, polymerization degree: about 5) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of polyacrylic acid, and the titania fine particle composite A neutral aqueous dispersion (Sample J) was obtained.
- the ratio of the titania fine particles to the titania fine particle composite was 80.0% by weight.
- a solution A was prepared by dissolving 200 g of titanium tetrachloride solution (dilute hydrochloric acid solution; 16 to 17% as Ti content) and 4 g of polyacrylic acid in 300 g of isopropyl alcohol. While stirring the solution A at room temperature, 6N sodium hydroxide was gradually added until the pH of the solution reached 6. Furthermore, it was aged at that temperature for 1 hour. Then, it filtered, keeping temperature at 50 degreeC, and decantation and filtration were repeated 3 times using the 50 degreeC water prepared separately, and the wet cake was obtained.
- Example K a neutral aqueous dispersion (solid content concentration 10%, pH 7.5) (sample K) of the titania fine particle composite.
- the composition of titania fine particles and polyacrylic acid in the titania fine particle composite sample K was 0.12 parts by weight of polyacrylic acid with respect to 1 part by weight of titania, and the ratio of the titania fine particles to the titania fine particle composite was 89 by weight. 3%.
- Comparative Example 4 corresponds to the titania fine particle composite described in Patent Document 8 in which titanium is oxidized and polyacrylic acid is combined at the same time.
- ⁇ TG / DTA> Differential thermothermogravimetric simultaneous measurement was performed by the method shown below.
- the neutral aqueous dispersions of Samples A to K were dried at 105 ° C. and then pulverized to obtain measurement powders.
- the powder for measurement was analyzed using a differential thermal thermogravimetric simultaneous measurement apparatus (TG / DTA300; manufactured by SII Nano Technology Co., Ltd.).
- TG / DTA300 manufactured by SII Nano Technology Co., Ltd.
- Table 2 shows the temperature at which the exothermic peak appeared in the measurement chart.
- an exothermic peak appeared on the low temperature side in the titania microparticle composite of the present invention (samples A to H). Specifically, the exothermic peak that appeared at 400 ° C in the mixture of titania fine particles and polyacrylic acid appeared at 240 ° C and 300 ° C in the composite sample A, and the exothermic peak shifted significantly to the low temperature side. I understand. It can also be seen that in the composite of titania fine particles and polyacrylic acid (samples E and G) surface-treated with silica and aluminum oxide, an exothermic peak appeared at 188 ° C. and was also shifted to the low temperature side.
- the intensity of the peak of the same wave number that appears when sodium polyacrylate is used alone is small, and in addition, on the low wave number side (1535 to 1545 cm ⁇ 1 ).
- a peak also appeared.
- the peak of the carbonyl group when measured with polyacrylic acid alone is 1716.7 cm ⁇ 1
- the polyacrylic acid is The same peak intensity at 1558 cm ⁇ 1 as that of sodium polyacrylate alone converted to a salt by neutralization appeared to be small and a peak also appeared at 1543 cm ⁇ 1 .
- the aqueous dispersion (samples A to H) of titania fine particles of the present invention exhibited a smooth liquid. Compared to a typical cream foundation having a viscosity of about 20000 cps, the viscosities of samples A to H are significantly lower. The viscosities of materials I and J were 1-2 orders of magnitude higher than materials AH. Sample K had a concentration of 13.5% by weight or more, and the fluidity was so poor that the rotor could not rotate, and the viscosity could not be measured. From this, it can be seen that the titania fine particle composite of the present invention is uniformly dispersed in a neutral aqueous dispersion, and aggregation between the titania fine particle composites hardly occurs.
- the UV protective cosmetic (bilayer dispersion lotion type) 1 which is an external preparation for the skin of the present invention according to the formulation of Table 6 shown below.
- 2 and UV protective cosmetics 3 and 4 not included in the skin external preparation of the present invention were prepared. That is, the component (a) was stirred and solubilized while being heated at 80 ° C., and the component (b) was dispersed therein to obtain UV protective cosmetics 1 to 4.
- the titania fine particles it became difficult for the titania fine particles to settle and redisperse. It is considered that this was triggered by the addition of other components, and the titania fine particles were aggregated and settled due to the dissociation of the titania fine particles from the titania fine particles.
- the SPF (UV protection index) of UV protection cosmetics 1 to 3 was measured according to the Japan Cosmetic Industry Association Act. The results obtained are shown in Table 7.
- the SPF of the UV protective cosmetics 1 and 2 is higher than the SPF of the UV protective cosmetic 3, and it was confirmed that a high UV protective effect can be obtained by using the composite of the present invention as a cosmetic.
- the UV protective cosmetic 3 was 3 days after the adjustment, and the UV protective cosmetic 4 was 5 days after the adjustment, and the solid content was separated and settled.
- the dispersion stability of the fine particle titanium oxide is poor, and it is considered that they are aggregated and settled.
- UV protective cosmetics water-in-oil type
- Table 8 the formulation shown in Table 8. That is, the components of a and b are weighed and then heated to 80 ° C., and the temperature is adjusted to 80 ° C. in advance.
- UV protective cosmetics 5 to 8 were obtained.
- the UV protective cosmetics 5 and 6 using the titania fine particle composites B and G had a light feel and a refreshing feeling, while the UV protective cosmetic 7 using the titania fine particle dispersion I was used.
- the touch was heavy with sodium alginate. That is, the UV protective cosmetic of the present invention was remarkably excellent in usability.
- the SPF (UV protection index) of UV protection cosmetics 5, 6, 7 and 8 was measured in accordance with the Japan Cosmetic Industry Association Act. Table 9 shows the obtained results.
- the SPF of the UV protective cosmetics 5 and 6 is higher than the SPF of the UV protective cosmetics 7 and 8, and it was confirmed that a high UV protective effect can be obtained by using the composite of the present invention as a cosmetic.
- the UV protective cosmetic 7 was 3 days after the adjustment, and the UV protective cosmetic 8 was 5 days after the adjustment, and the solid content was separated and settled. It is considered that the dispersion stability of the UV protective cosmetic fine particle titanium oxide is poor and is aggregated and precipitated.
- the titania fine particle composite is uniformly dispersed in the cosmetic, so that the surface area of titania that absorbs ultraviolet rays is increased, and the crystallinity of the core titania fine particles is high, so that the ultraviolet absorption effect is enhanced. It is thought to be caused by this.
- the present invention is suitably applied to a skin external preparation such as cosmetics.
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Abstract
Description
しかしながら、これらの文献で用いられているUV吸収剤の多くが油剤であるため、水への溶解性が低く、化粧料としての剤型が限定される場合がある。これらのUV吸収剤を化粧料に用いた場合には、さっぱりとした使用感が得られにくい。そのため、これらのUV吸収剤の夏に多用される紫外線防御用化粧料への使用には限度があった。
しかしながら、酸化チタンや酸化亜鉛はその微粒子の表面活性により水溶液中での均一分散が妨げられやすい。そのため、酸化チタンや酸化亜鉛を化粧基剤に配合すると、不均一な分散となる。その結果、白濁溶液となった化粧料を顔や体に塗布すると白っぽくなってしまったり、UV防御効果が低下したりする問題点があった。また、酸化チタンや酸化亜鉛が増粘剤などの化粧料中の他の配合成分に影響を与え、その機能を低下させたりする問題点等もあった。
そして、かかるチタニア微粒子複合体は、チタニア微粒子の酸性水分散液に前記カルボン酸モノマー又はポリマー等を添加した後中和することにより得られることを見出し、本発明を完成するに至った。
すなわち本発明は以下の通りである。
(1) チタニア微粒子と、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上とが複合化したチタニア微粒子複合体であって、X線粉体回折分析におけるチタニア結晶由来の最大回折強度のピークの半値幅が2.0°以下であるチタニア微粒子複合体。
(式中、Rは水素原子、又は水素原子がカルボキシル基もしくはヒドロキシ基で置換されていても良い炭素数1~15のアルキル基もしくは炭素数1~15のアルケニル基を表し、Xは水素原子、アルカリ金属又は付加モル数1~12のポリオキシアルキレン基を表す)
(2)KBr錠剤法による赤外線吸収スペクトルにおいてカルボニル基由来の吸収ピークが1535~1545cm-1の範囲に存することを特徴とする、(1)に記載のチタニア微粒子複合体。
(3)チタニア微粒子複合体中のチタニア微粒子の割合が、60~99重量%の範囲であることを特徴とする、(1)又は(2)に記載のチタニア微粒子複合体。
(4)前記チタニア微粒子が、1種以上の金属又は珪素の水和酸化物で被覆されていることを特徴とする(1)~(3)の何れかに記載のチタニア微粒子複合体。
(5)一般式(1)に表されるカルボン酸誘導体が、炭素数が10以下のモノ、ジ、又はトリカルボン酸のアルカリ金属塩並びに該カルボン酸のポリオキシアルキレンの付加物からなる群から選択される一種又は二種以上であることを特徴とする、(1)~(4)の何れかに記載のチタニア微粒子複合体。
(6)一般式(1)に表されるカルボン酸及び/又はその誘導体を構成モノマーとする重合物が、ポリアクリル酸又はポリメタクリル酸、ポリアクリル酸又はポリメタクリル酸のアルカリ金属塩、及びポリアクリル酸又はポリメタクリル酸のポリオキシエチレン付加物からなる群から選択される一種又は二種以上であることを特徴とする、(1)~(5)の何れかに記載のチタニア微粒子複合体。
(7)チタニア微粒子の酸性水分散液に、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上を添加した後、中性域に至るまでアルカリを添加することにより調製されるチタニア微粒子複合体。
(式中、Rは水素原子、又は水素原子がカルボキシル基もしくはヒドロキシ基で置換されていても良い炭素数1~15のアルキル基もしくは炭素数1~15のアルケニル基を表し、Xは水素原子、アルカリ金属又は付加モル数1~12のポリオキシアルキレン基を表す)
(8)(1)~(7)何れかに記載のチタニア微粒子複合体を含有してなる組成物。
(9)皮膚外用剤であることを特徴とする、(8)に記載の組成物。
(10)紫外線吸収用であることを特徴とする、(9)に記載の組成物。
(11)チタニア微粒子複合体の製造方法であって、チタニア微粒子の酸性水分散液に、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上を添加して混和液とする工程、及び中性域に至るまで前記混和液にアルカリを添加して中性液とする工程を含む、チタニア微粒子複合体の製造方法。
(式中、Rは水素原子、又は水素原子がカルボキシル基もしくはヒドロキシ基で置換されていても良い炭素数1~15のアルキル基もしくは炭素数1~15のアルケニル基を表し、Xは水素原子、アルカリ金属又は付加モル数1~12のポリオキシアルキレン基を表す)
(12)チタニア微粒子複合体の中性分散液の製造方法であって、チタニア微粒子の酸性水分散液に、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上を添加して混和液とする工程、中性域に至るまで前記混和液にアルカリを添加して中性液とする工程、前記中性液を濾過して濾物を水で洗浄して湿ケーキを得る工程、及び前記湿ケーキを水に再分散させる工程を含む、チタニア微粒子複合体の中性分散液の製造方法。
(式中、Rは水素原子、又は水素原子がカルボキシル基もしくはヒドロキシ基で置換されていても良い炭素数1~15のアルキル基もしくは炭素数1~15のアルケニル基を表し、Xは水素原子、アルカリ金属又は付加モル数1~12のポリオキシアルキレン基を表す)
また、本発明のチタニア微粒子複合体は、一度分散媒から濾別しても、再度分散媒に均一に分散することもできる。
また、本発明のチタニア微粒子複合体の中性分散液は、従来のチタニア微粒子複合体の中性分散液よりも粘度が低いため、化粧料等への加工が容易である。さらに、本発明のチタニア微粒子複合体の中性分散液は、化粧料に高濃度で配合することも可能である。さらに、化粧料の作製の際に他の成分を添加しても、均一な分散状態を維持することができる。
このように、本発明のチタニア微粒子複合体は、実用性・汎用性に優れる。
本発明において「半値幅」は、次の条件で粉体X線回折分析を行うことにより求められる値で定義される。チタニア微粒子複合体の乾燥試料を、粉砕して測定用粉末とする。X線回折装置(PANalytical X’Pert PROMPD;スペクトリス株式会社製)を用いて、前記測定用粉末のX線回折(XRD)測定を行う。CuKα線をX線源とし、管電圧45kV、管電流40mAの条件下、走査角度2θ=5~70°で測定する。得られた回折チャートより最大回折強度のピークの半値幅を求める。
なお、チタニア結晶由来の最大回折強度のピークは、ルチル型結晶の場合は2θ=27.5°に現われ、アナターゼ型結晶の場合は2θ=25.5°に現われる。
X線回折分析チャートにおけるピーク強度は、粉体の結晶面の存在比率を表す。半値幅とは、山形である前記ピークの縦軸の値が山の最大値の半分であるところの2つの横軸の値の差(山の幅)である。一般的に最大回折強度のピークの半値幅は、その粉体の結晶化度を表す。例えば、(101)面に対応するピークの半値幅が小さい場合、すなわちピークがシャープな場合は(101)面での結晶化度が高いことを示すので、結晶性が向上し安定な状態といえる。一方、(101)面に対応するピークの半値幅が大きい場合、すなわちピークがなだらかな場合は、(101)面での結晶化は進んでおらず、アモルファス状態に近いことを示す。本発明のチタニア微粒子複合体においては、半値幅が2.0°以下であると、チタニア微粒子複合体のコアであるチタニア微粒子の結晶性が向上している状態である。
前記半値幅が上記の範囲にある場合、チタニア微粒子複合体は分散媒に均一に分散し、透明性と紫外線吸収性を実現できる。また、後述の実施例1と比較例4の比較で示されるように、このようなチタニア微粒子複合体を高濃度で含有する分散液は、従来のチタニア微粒子複合体を同濃度で含有する分散液よりも著しく粘度が低い。これは、チタニア微粒子と前記カルボン酸モノマー又はポリマー等の分子間相互作用が大きくなるためであると推察される。
前記半値幅が2.0°以下となるチタニア微粒子複合体は、後述の方法により製造できる。
また、本発明のチタニア微粒子複合体のコア部分であるチタニア微粒子は、珪素、アルミニウム、ジルコニウムなどの水和酸化物1種以上でチタニア微粒子の表面を被覆する処理が行われたものでもよい。微粒子の表面被覆によって、表面活性を抑えることができる。ただし、表面処理によって粒子径が大きくなると、紫外線の吸収効率が低下する場合がある点に留意する。
前記Rは、好ましくは、水素原子がカルボキシル基又はヒドロキシ基で置換されていても良い炭素数1~8のアルキル基又はアルケニル基である。前記Rが、非置換のアルキル基である場合、一般式(1)で表わされるカルボン酸としては、酢酸、プロピオン酸及びカプロン酸が挙げられる。前記Rが、非置換のアルケニル基である場合、一般式(1)で表わされるカルボン酸としては、アクリル酸及びメタクリル酸が挙げられる。前記Rが、水素原子がカルボキシル基又はヒドロキシ基で置換されているアルキル基である場合、一般式(1)で表わされるカルボン酸としては、シュウ酸、マロン酸、酒石酸、コハク酸及びクエン酸が好適に例示できる。即ち、一般式(1)で表わされるカルボン酸としては、モノカルボン酸でも、ジカルボン酸やトリカルボン酸等のポリカルボン酸でもよく、炭素数が10以下のものが好ましい。
前記Xが、アルカリ金属である場合、Xとしてはカリウム、ナトリウム及びリチウムが例示できる。前記Xが、ポリオキシアルキレン基である場合、平均付加モル数は1~12が好ましく、2~8がより好ましい。前記ポリオキシアルキレン基としては、ポリオキシエチレン基及びポリオキシプロピレン基が好適に例示できる。
また、一般式(1)で表わされるカルボン酸の誘導体としては、前記炭素数が10以下のモノカルボン酸又はジカルボン酸やトリカルボン酸等のポリカルボン酸のアルカリ金属塩、又は一部のカルボキシル基又は水酸基にポリオキシアルキレンが付加しているものが、特に好ましい。特に、カルボン酸がポリカルボン酸の場合には一部が塩になっている形態が好ましい。このような前記アルカリ金属塩としては、酢酸ナトリウム、プロピオン酸カリウム、アクリル酸ナトリウム、メタクリル酸トリエチルアミン、カプリン酸ナトリウム、シュウ酸リチウム、マロン酸カリウム、コハク酸ナトリウム、クエン酸カリウム、酒石酸ナトリウム等が例示できる。また、前記ポリオキシエチレン付加物にはポリオキシエチレンアクリレート、ポリオキシエチレンメタクリレート等がある。
一般式(1)で表されるカルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物としては、メタクリル酸、アクリル酸乃至はこれらのポリオキシエチレン付加物、金属塩又はアルカリ金属塩を構成モノマーとして、カルボン酸側鎖のアルケニル基が重合基となった重合物を例示できる。これらの重合物の重合度は1000以下が好ましい。
重合物としては、前記構成モノマーが重合したホモポリマー又は、前記構成モノマーと、酢酸ビニル、ビニルアルコール、スチレン又はメタクリル酸メチル等の(メタ)アクリル酸アルキルなどの一般式(1)で表わされる化合物に属さないモノマーとのコポリマーが好適に例示できる。
重合物の具体例としては、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリル酸トリエタノールアミン、ポリメタクリル酸ナトリウム、ポリメタクリル酸トリエチルアミン、又はオキシエチレンの付加数23モル以下のポリオキシエチレンアクリルポリマーもしくはポリオキシエチレンメタクリルポリマーが挙げられる。
チタニア微粒子と一般式(1)で表されるカルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物とが複合化した本発明のチタニア微粒子複合体は、中性水溶液に分散することができる。一方、チタニア微粒子と一般式(1)で表されるカルボン酸及びカルボン酸誘導体とが複合化した本発明のチタニア微粒子複合体は、疎水性溶媒に分散することができる。
本発明において赤外線吸収スペクトルは、次の条件で測定して得られるスペクトルと定義する。本発明のチタニア微粒子複合体の中性水分散液を105℃で乾燥した後、粉砕して測定用粉末とする。測定用粉末をKBr錠剤とし、フーリエ変換赤外分光光度計(FTIR-8300;株式会社島津製作所製)を用いスペクトルを測定する。
前記吸収ピークが上記の範囲にある場合、チタニア微粒子複合体は分散媒に均一に分散し、透明性と紫外線吸収性を実現できる。また、後述の実施例1と比較例4の比較で示されるように、このようなチタニア微粒子複合体を高濃度で含有する分散液は、従来のチタニア微粒子複合体を同濃度で含有する分散液よりも著しく粘度が低い。
一般に前記カルボン酸モノマー又はポリマー等のカルボニル基のピークは1535~1545cm-1より大きい側に存在し、例えばポリアクリル酸ナトリウムでは1558~1560cm-1に存在する。しかし、後述の実施例1に示されるように本発明のチタニア微粒子複合体においては、チタニア微粒子とカルボン酸モノマー又はポリマー等との分子間相互作用が大きいため、カルボン酸モノマー又はポリマー等のカルボニル基の一部がチタニア微粒子の表面に拘束され、カルボニル基のピークが1535~1545cm-1にも現れると考えられる。一方、後述の比較例4に示されるように、特許文献8に記載の従来のチタニア微粒子複合体においては、カルボニル基のピークは1535~1545cm-1には現われないので、本発明のチタニア微粒子複合体と区別できる。
前記吸収ピークが1535~1545cm-1に現われるチタニア微粒子複合体は、後述の方法により製造できる。
本発明のチタニア微粒子複合体は、チタニア微粒子とカルボン酸モノマー又はポリマー等の分子間相互作用が大きいため、チタニア微粒子に複合化するカルボン酸モノマー又はポリマー等の重量割合が小さくても複合化の効果は十分に果たされ、微粒子が分散媒中で均一に分散することが可能となる。
チタニア微粒子複合体の粒子形状は走査型電子顕微鏡による観察することができ、スケールを設置して最大径を測定することもできる。
チタニア微粒子の酸性水分散液に、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上を徐々に添加・攪拌し、混和液を得る。この後、系を十分に均一にするため、この混和液を1分間~1時間程度静置して熟成させてもよい。次いで中性域(pH5~7.5)に至るまで前記混和液に水酸化ナトリウム等のアルカリを添加・攪拌し、中性液を得る。中和後、十分に複合化反応させるため、この中性液を1分間~1時間程度静置してもよい。
以上の工程はすべて、室温(15~30℃)で行うことができる。
チタニア微粒子の酸性水分散液のチタニア微粒子の濃度は、均一な分散液とするためには10重量%以下が好ましく、より好ましくは5重量%以下、さらに2.5重量%以下が好ましい。
チタニア微粒子の酸性水分散液の分散媒(解謬剤)において水に加える酸としては、塩酸、硝酸、硫酸及び燐酸等を用いることができ、塩酸及び硝酸が特に好ましい。また、チタニア微粒子の酸性水分散液のpHは1~2の範囲が好ましい。
中和の際に添加するアルカリとしては、水酸化ナトリウム、水酸化カリウム等を用いることができ、水酸化ナトリウムが特に好ましい。
カルボン酸モノマー又はポリマー等は、チタニア微粒子の酸性水分散液に直接添加してもよいが、予め溶液としておく方が均一な複合化のためには好ましい。溶液とする場合の濃度は、0.01~1重量%が好ましい。溶媒としてはアルコールと水の混合溶媒が適しており、アルコールはエタノール、イソプロピルアルコール、メタノール又は1,3-ブチレングリコールを用いることができる。
チタニア微粒子とカルボン酸モノマー又はポリマー等は、重量比で5:1~14:1で配合することが好ましい。カルボン酸モノマー又はポリマー等の比率がこれよりも多くなると、チタニア微粒子複合体がべたつくので好ましくない。
また、表面が珪素、アルミニウム、ジルコニウムなどの水和酸化物1種以上で被覆されたチタニア微粒子は、公知の方法で得ることができる。例えば、予め作製した微粒子チタニア分散物に湿式で、珪酸ナトリウムの中和によって生じたゲル中に混ぜ込み、沈着させることによって行うことができる。また、微粒子チタニア分散物の存在下、アルミニウム等の金属の可溶性塩を酸で処理して水酸化アルミニウム等の不溶性金属水酸化物のかたちで沈着させて生成させることもできる。
チタニア微粒子は、透明性を望む場合や、紫外線吸収機能や殺菌等の目的で使用する場合は、粒子径が小さいことが好ましい。そのチタニア微粒子の最大径は、概ね0.1~0.001μmが好ましい。
粘度が小さいことにより化粧料として加工しやすく、また化粧料にさっぱりした使用感を付与することができる。
この性質により、本発明のチタニア微粒子複合体を配合した化粧料は高い透明性を実現でき、顔や体に塗布したときに白っぽくなりにくい効果を有する。また、本発明のチタニア微粒子複合体は、紫外光の遮蔽率に優れるため、紫外線吸収能に優れた化粧料に好適となる。
剤形としては二層分散ローション剤形、乳化剤形、粉体剤形或いはオイル剤形等何れの剤形にも応用できる。本発明のチタニア微粒子複合体は水性媒体にも均一に分散できるため、水性担体を含有する二層分散ローション剤形又は乳化剤形が特に好ましい。
発明のチタニア微粒子複合体を皮膚外用剤等の組成物に含有させる場合、含有量としては組成物全体の0.5~50重量%が好ましく、より好ましくは1.0~30重量%である。
(実施例1)
(a)チタニア微粒子の酸性水分散液
公知の方法、すなわちオキシ硫酸チタンの加水分解によって得られた含水酸化チタンをアルカリで処理し、塩酸中で加熱熟成することによってチタニア微粒子の酸性水分散液を作製した。得られた酸性水分散液中のチタニア微粒子は、ルチル型の結晶構造を有しており、平均粒子径は0.01μmであった。この酸性水分散液をTiO2換算で100g/Lに純水で濃度調整し、このチタニア微粒子の酸性水分散液1Lを量り取った。
前記(a)の工程で得られたチタニア微粒子の酸性水分散液を純水で希釈してTiO2換算で20g/Lのチタニア微粒子水分散液5Lとした(A液)。ポリアクリル酸(分子量:5000、重合度:約50)20g(和光純薬工業株式会社製)を純水8Lに溶解させた(B液)。室温にてB液に攪拌しながらA液を徐々に加えた後、1時間熟成させた。さらに2N水酸化ナトリウム水溶液でpHを5に調整し、1時間熟成させ、濾過、純水で洗浄を行い、湿ケーキを得た。この湿ケーキを純水中にリパルプした後、超音波分散して、本発明のチタニア微粒子複合体の中性水分散液(固形分濃度25%、pH7.5)(試料A)を得た。
チタニア微粒子複合体試料A中のチタニア微粒子とポリアクリル酸の各組成は、TiO21重量部に対してポリアクリル酸0.07重量部で、チタニア微粒子複合体に対するチタニア微粒子の割合が、重量比で93.5%であった。
なお、上記の方法で製造したチタニア微粒子複合体の再分散水溶液を煮沸し、その後濾過したところ、濾液中にはカルボン酸モノマー又はポリマー等はほとんど認められなかった。また、分散液中でチタニア微粒子複合体が均一に分散していることから、複合前のチタニア微粒子と比較して、チタニア微粒子複合体は親水性が増しているといえるので、カルボン酸モノマー又はポリマー等は、チタニア微粒子表面に強固な相互作用により複合化しているものと推定される。
ポリアクリル酸に換えて、ポリアクリル酸ナトリウム(分子量:5000、重合度:約50)20g(和光純薬工業株式会社製)を用いた以外は、実施例1と同様の処理を行い、本発明のチタニア微粒子複合体である、チタニア微粒子複合体の中性水分散液(試料B)を得た。
試料Bにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で96.0%であった。
ポリアクリル酸に換えて、ポリメタクリル酸(分子量:100000、重合度:約1000)20g(和光純薬工業株式会社製)を用いた以外は、実施例1と同様の処理を行い、本発明のチタニア微粒子複合体である、チタニア微粒子複合体の中性水分散液(試料C)を得た。
試料Cにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で92.0%であった。
ポリアクリル酸に換えて、ポリ(アクリル酸/マレイン酸)(分子量:5000、重合度:約50)20g(株式会社日本触媒製)を用いた以外は、実施例1と同様の処理を行い、本発明のチタニア微粒子複合体である、チタニア微粒子複合体の中性水分散液(試料D)を得た。
試料Dにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で93.0%であった。
(c)チタニア微粒子へのシリカ被覆処理
公知の方法によりチタニア微粒子にシリカ被覆処理を行った。すなわち、実施例1の(a)の工程で得られたチタニア微粒子の酸性水分散液を純水で希釈して、20g/Lに調整し、5L(TiO2換算で100g)量りとった。70℃に昇温し、次いで、SiO2換算濃度400g/Lのケイ酸ナトリウム水溶液170mL(チタニア微粒子に対してSiO2として12%)を20%硫酸と同時に添加し、その後、30分間熟成した。次いで、10%水酸化ナトリウム水溶液でpHを9.0以上に調整した後、1%硫酸水溶液でpHを3に調整し、濾過、純水で洗浄を行い、湿ケーキを得た。この湿ケーキを純水中にリパルプした後、超音波分散して、シリカ被覆チタニア微粒子Aを得た。この試料Aには、チタニア微粒子の表面にシリカが被覆しており、その含有量はTiO21重量部に対してSiO2換算で0.05重量部であった。
チタニア微粒子の酸性水分散液に換えて、前記(c)で作製したシリカ被覆チタニア微粒子Aを用いた以外は実施例1と同様の処理を行い、本発明のチタニア微粒子複合体である、シリカで被覆チタニア微粒子複合体の中性水分散液(試料E)を得た。
試料Eにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で93.0%であった。
ポリアクリル酸に換えて、ポリメタクリル酸(分子量:100000、重合度:約1000)20g(和光純薬工業株式会社製)を用いた以外は、実施例5と同様の処理を行い、本発明のチタニア微粒子複合体である、シリカで被覆チタニア微粒子複合体の中性水分散液(試料F)を得た。
試料Fにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で91.5%であった。
(e)チタニア微粒子へのシリカ被覆処理、アルミナ被覆処理
実施例1の(a)の工程で得られたチタニア微粒子の酸性水分散液1L(TiO2換算で100g)を、水酸化ナトリウムを用いてpHを9.0以上にし、そこに、400g/Lのケイ酸ナトリウム水溶液を30mL(チタニア微粒子に対してSiO2として12%)添加し、90℃に昇温した後、硫酸を用いて200分かけてpHが7になるように中和した。
上記水性懸濁液にポリ塩化アルミニウムを80g(チタニア微粒子に対しAl2O3として8%)添加した。添加後、水酸化ナトリウムを用いてpHが5.0になるように中和し、60分間熟成して、シリカ-アルミナ被覆チタニア微粒子Bを得た。このシリカ-アルミナ被覆チタニア微粒子Bには、チタニア微粒子の表面にシリカが被覆しており、その組成はTiO21重量部に対してSiO2換算で0.12重量部であった。さらにその上層にアルミナが被覆しており、その含有量はTiO21重量部に対してAl2O3換算で0.08重量部であった。
チタニア微粒子の酸性水分散液に換えて、前記(e)で作製したシリカ・アルミナ被覆チタニア微粒子Bを用いた以外は実施例1と同様の処理を行い、本発明のチタニア微粒子複合体である、シリカ・アルミナ被覆チタニア微粒子複合体の中性水分散液(試料G)を得た。
試料Gにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で91.0%であった。
ポリアクリル酸に換えて、ポリ(アクリル酸/マレイン酸)(分子量:5000、重合度:約50)20g(株式会社日本触媒製)を用いた以外は、実施例7と同様の処理を行い、本発明のチタニア微粒子複合体である、シリカ・アルミナ被覆チタニア微粒子複合体の中性水分散液(試料H)を得た。
試料Hにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で92.0%であった。
実施例1におけるポリアクリル酸の添加を省略した以外は、実施例1と同様の処理を行ったが、中性領域で凝集が生じ、安定な分散液を得ることができなかった。
ポリアクリル酸に換えて、アルギン酸ナトリウム20g(和光純薬工業株式会社製)を用いた以外は、実施例1と同様の処理を行い、チタニア微粒子複合体の中性水分散液(試料I)を得た。
試料Iにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で85.0%であった。
ポリアクリル酸に換えて、ポリビニルアルコール(分子量:500、重合度:約5)20g(和光純薬工業株式会社製)を用いた以外は、実施例1と同様の処理を行い、チタニア微粒子複合体の中性水分散液(試料J)を得た。
試料Jにおいて、チタニア微粒子複合体に対するチタニア微粒子の割合は、重量比で80.0%であった。
イソプロピルアルコール300gに、四塩化チタン溶液(希塩酸溶液;Ti分として16~17%)200g及びポリアクリル酸4gを溶解させA液とした。室温にてA液に攪拌しながら6N水酸化ナトリウムを、溶液のpHが6になるまで徐々に加えた。さらに、その温度で1時間熟成させた。その後、温度を50℃に保って濾過し、別に用意した50℃の水を用いてデカンテーション及び濾過を3回繰り返し、湿ケーキを得た。この湿ケーキを純水中にリパルプした後、超音波分散して、チタニア微粒子複合体の中性水分散液(固形分濃度10%、pH7.5)(試料K)得た。
チタニア微粒子複合体試料K中のチタニア微粒子とポリアクリル酸の各組成はチタニア1重量部に対してポリアクリル酸0.12重量部で、チタニア微粒子複合体に対するチタニア微粒子の割合が、重量比で89.3%であった。
この比較例4は、チタンの酸化とポリアクリル酸との複合化を同時に行う、特許文献8に記載のチタニア微粒子複合体に相当する。
試料A~Kそれぞれの中性水分散液を105℃で乾燥した後、粉砕して測定用粉末とした。X線回折装置(PANalytical X’Pert PROMPD;スペクトリス株式会社製)を用いて、前記測定用粉末のX線回折(XRD)測定を行った。CuKα線をX線源とし、管電圧45kV、管電流40mAの条件下、走査角度2θ=5~70°で測定した。得られた回折チャートより最大回折強度のピークの半値幅を求めた。
得られた結果を表1に示す。試料A~Jでは該半値幅が2.0°以下であったが、試料Kでは該半値幅が2.0°より大きい値となった。
以下に示す方法により示差熱熱重量同時測定(Thermogravimetry/Differential ThermalAnalysis;TG/DTA)を行った。
試料A~Kそれぞれの中性水分散液を105℃で乾燥した後、粉砕して測定用粉末とした。測定用粉末を示差熱熱重量同時測定装置(TG/DTA300;エスアイアイナノテクノロジー株式会社製)を使用し分析した。白金製の試料セルを用い、空気雰囲気下、昇温速度10℃/minで室温から1000℃まで測定を行った。
測定チャートにおいて発熱ピークが出現した温度を表2に示す。チタニア微粒子とポリマーの混合物における発熱ピークに比べ、本発明のチタニア微粒子複合体(試料A~H)では低温側に発熱ピークが出現した。具体的には、チタニア微粒子とポリアクリル酸の混合物では、400℃に出現した発熱ピークが、複合化している試料Aでは240℃及び300℃に出現し、低温側に発熱ピークが大きくシフトしたことがわかる。また、シリカ及び酸化アルミニウムで表面処理されたチタニア微粒子とポリアクリル酸の複合体(試料E,G)では、発熱ピークが188℃に出現し、やはり低温側にシフトしたことがわかる。一方、試料I及びJにでは、チタニア微粒子とポリマーの混合物と同じ温度に発熱ピークが出現した。また、試料Kでは、300℃に発熱ピークが出現したが、240℃には出現しなかった。
TG/DTAで現れる発熱ピークはカルボン酸モノマー又はポリマー等の燃焼や熱分解に由来する重量減少を表すが、これが低温側にシフトしたことから、カルボン酸モノマー又はポリマー等が複合化していない場合よりも低温で熱分解反応が促進していると考えられる。かかる熱分解にはチタニアが関与すると推察されるので、本発明のチタニア微粒子複合体ではチタニア微粒子とカルボン酸モノマー又はポリマー等の分子間相互作用が大きいことが推察される。
以下に示す方法により試料A~Kについて赤外線吸収(FT-IR)スペクトルを測定した。
試料A~Kそれぞれの中性水分散液を105℃で乾燥した後、粉砕して測定用粉末とした。測定用粉末をKBr錠剤とし、フーリエ変換赤外分光光度計(FTIR-8300;株式会社島津製作所製)を用いスペクトルを測定した。
得られたスペクトルにおいてカルボニル基由来のピークが出現した波数を表3に示す。本発明のチタニア微粒子複合体(試料A~H)では、ポリアクリル酸ナトリウム単独のときに出現したのと同じ波数のピークの強度が小さく現れ、加えて低波数側(1535~1545cm-1)にもピークが出現した。具体的には、ポリアクリル酸単独で測定した場合のカルボニル基のピークは1716.7cm-1であるのに対し、チタニア微粒子とポリアクリル酸との複合体(試料A)では、ポリアクリル酸が中和により塩となったポリアクリル酸ナトリウム単独のときと同じ1558cm-1のピーク強度が小さく現れると共に1543cm-1にもピークが現われた。チタニア微粒子とポリアクリル酸ナトリウムとの複合体(試料B)でも、ポリアクリル酸ナトリウム単独のときのピーク(1558~1560cm-1)に加えて1543cm-1にもピークが出現した。
一方、試料Iでは、アルギン酸ナトリウム単独のときと同じ位置にピークが出現し、新たなピークは出現しなかった。すなわち、試料Iにおいてはチタニア微粒子に対してアルギン酸ナトリウムのカルボニル基を介する化学的な複合化は生じておらず、他の何らかの機構によりチタニア微粒子にアルギン酸ナトリウムが付着していると推察される。
また、試料Kでは、ポリアクリル酸が中和により塩となったポリアクリル酸ナトリウム単独のときと同じ位置にのみピークが出現し、新たなピークは出現しなかった。
以下に示す方法によりチタニア微粒子複合体の分散水溶液の粘度を測定した。
試料A~Jそれぞれの中性水分散液(固形分として25重量%)を調製し、単一円筒型回転粘度計(ビスメトロンVA-A1;芝浦システム株式会社製)を用いた。3号ローターを使用し、回転速度60回/分、室温(25℃)で粘度を測定した。Kにおいては固形分25重量%の水分散液の調製が不可能であった。
得られた結果を表4に示す。本発明のチタニア微粒子の分散水溶液(試料A~H)は、さらさらとした液状を呈した。一般的なクリームファンデーションの粘度が約20000cpzであるのに比して、試料A~Hの粘度は著しく低い。資料I及びJの粘度は、資料A~Hに対して1~2オーダー高かった。なお、試料Kは、13.5重量%以上の濃度では、ローターが回転できないほど流動性に乏しく、粘度を測定することができなかった。
このことから、本発明のチタニア微粒子複合体は、中性水分散液中で均一に分散し、チタニア微粒子複合体間の凝集が生じにくいことがわかる。
可視域での透過率及び紫外線遮蔽能を以下に示す方法により評価した。
試料A~Kそれぞれの中性水分散液を0.0050wt%の濃度になるように純水で希釈し、10mm厚の石英セルに充填した後、分光光度計(U-3000;日立製作所株式会社製)に積分球を装着して、280nm~450nmの範囲で透過スペクトルを測定した。得られたスペクトルから310nm及び450nmにおける各透過率を求め、その差も算出した。
得られた結果を表5に示す。試料A~Hは、試料I~Kに比べ、310nmの紫外域での遮蔽能が同等以上であって、しかも波長450nmの可視域での透過率に優れていた。
チタニア微粒子複合体A、Cとチタニア微粒子分散体I、Jを用いて、下記に示す表6の処方に従って、本発明の皮膚外用剤である、紫外線防護化粧料(二層分散ローション剤型)1,2及び本発明の皮膚外用剤に含まれない紫外線防護化粧料3、4を調製した。すなわち、イの成分を80℃で加熱しながら、攪拌、可溶化し、これにロの成分を分散させ、紫外線防護化粧料1~4を得た。
紫外線防護化粧料4については、チタニア微粒子が沈降し再分散することが困難となった。これは他成分を添加したことがきっかけとなり、チタニア微粒子を系に分散させる役割のポリビニルアルコールがチタニア微粒子から解離してしまったことにより、チタニア微粒子が凝集・沈降したと考えられる。
パネラーの背部を用い、日本化粧品工業会法に則り、紫外線防護化粧料1~3のSPF(紫外線防護指数)を測定した。
得られた結果を表7に示す。紫外線防護化粧料1及び2のSPFは紫外線防護化粧料3のSPFに比べて高く、本発明の複合体を化粧料として用いることにより、高い紫外線防護効果が得られることが確認された。また、紫外線防護化粧料3は調整後3日で、紫外線防護化粧料4は調整後5日で、固形分が分離し沈降した。紫外線防護化粧料3及び4では微粒子酸化チタンの分散安定性が悪く、凝集、沈降しているものと考えられる。
チタニア微粒子複合体B、Gとチタニア微粒子分散体I、Jを用いて、表8に示す処方に従い、皮膚外用剤である、紫外線防護化粧料(油中水剤型)を調製した。即ち、イ、ロの成分を秤量し、しかる後にロを80℃に加温し、これを予め80℃に温度調整しておいたイに、攪拌下徐々に加えて乳化した後、攪拌冷却して紫外線防護化粧料5~8を得た。
チタニア微粒子複合体B、Gを用いた紫外線防御化粧料5、6は、軽い感触で、さっぱりとした使い心地であったが、一方チタニア微粒子分散体Iを用いた紫外線防護化粧料7は使用したアルギン酸ナトリウムにより感触が重かった。すなわち、本発明の紫外線防護化粧料は、使用性が格段に優れていた。
パネラーの背部を用い、日本化粧品工業会法に則り、紫外線防護化粧料5、6、7及び8のSPF(紫外線防護指数)を測定した。
得られた結果を表9に示す。紫外線防護化粧料5及び6のSPFは紫外線防護化粧料7及び8のSPFに比べて高く、本発明の複合体を化粧料として用いることにより、高い紫外線防護効果が得られることが確認された。また、紫外線防護化粧料7は調整後3日で、紫外線防護化粧料8は調整後5日で、固形分が分離し沈降した。紫外線防護化粧料微粒子酸化チタンの分散安定性が悪く、凝集、沈降しているものと考えられる。
この結果は、化粧料中でチタニア微粒子複合体が均一に分散しているため紫外線を吸収するチタニアの表面積が大きくなること、及びコアのチタニア微粒子の結晶化度が高いため紫外線吸収効果が高くなることに起因すると考えられる。
Claims (12)
- KBr錠剤法による赤外線吸収スペクトルにおいてカルボニル基由来の吸収ピークが1535~1545cm-1の範囲に存することを特徴とする、請求項1に記載のチタニア微粒子複合体。
- チタニア微粒子複合体中のチタニア微粒子の割合が、60~99重量%の範囲であることを特徴とする、請求項1又は2に記載のチタニア微粒子複合体。
- 前記チタニア微粒子が、1種以上の金属又は珪素の水和酸化物で被覆されていることを特徴とする請求項1~3の何れか一項に記載のチタニア微粒子複合体。
- 一般式(1)に表されるカルボン酸誘導体が、炭素数が10以下のモノ、ジ、又はトリカルボン酸のアルカリ金属塩並びに該カルボン酸のポリオキシアルキレンの付加物からなる群から選択される一種又は二種以上であることを特徴とする、請求項1~4の何れか一項に記載のチタニア微粒子複合体。
- 一般式(1)に表されるカルボン酸及び/又はその誘導体を構成モノマーとする重合物が、ポリアクリル酸又はポリメタクリル酸、ポリアクリル酸又はポリメタクリル酸のアルカリ金属塩、及びポリアクリル酸又はポリメタクリル酸のポリオキシエチレン付加物からなる群から選択される一種又は二種以上であることを特徴とする、請求項1~5の何れか一項に記載のチタニア微粒子複合体。
- 請求項1~7何れか一項に記載のチタニア微粒子複合体を含有してなる組成物。
- 皮膚外用剤であることを特徴とする、請求項8に記載の組成物。
- 紫外線吸収用であることを特徴とする、請求項9に記載の組成物。
- チタニア微粒子複合体の製造方法であって、チタニア微粒子の酸性水分散液に、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上を添加して混和液とする工程、及び中性域に至るまで前記混和液にアルカリを添加して中性液とする工程を含む、チタニア微粒子複合体の製造方法。
(式中、Rは水素原子、又は水素原子がカルボキシル基もしくはヒドロキシ基で置換されていても良い炭素数1~15のアルキル基もしくは炭素数1~15のアルケニル基を表し、Xは水素原子、アルカリ金属又は付加モル数1~12のポリオキシアルキレン基を表す) - チタニア微粒子複合体の中性分散液の製造方法であって、チタニア微粒子の酸性水分散液に、一般式(1)で表されるカルボン酸及びカルボン酸誘導体、並びに前記カルボン酸及び/又はカルボン酸誘導体を構成モノマーとする重合物から選択される一種又は二種以上を添加して混和液とする工程、中性域に至るまで前記混和液にアルカリを添加して中性液とする工程、前記中性液を濾過して濾物を水で洗浄して湿ケーキを得る工程、及び前記湿ケーキを水に再分散させる工程を含む、チタニア微粒子複合体の中性分散液の製造方法。
(式中、Rは水素原子、又は水素原子がカルボキシル基もしくはヒドロキシ基で置換されていても良い炭素数1~15のアルキル基もしくは炭素数1~15のアルケニル基を表し、Xは水素原子、アルカリ金属又は付加モル数1~12のポリオキシアルキレン基を表す)
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CN200980115825.5A CN102015540B (zh) | 2008-05-02 | 2009-04-28 | 二氧化钛微粒复合物和包含该二氧化钛微粒复合物的组合物 |
BRPI0910748-7A BRPI0910748B1 (pt) | 2008-05-02 | 2009-04-28 | Compósito de partícula fina de titânia, composição, e, métodos para produzir um compósito de partícula fina de titânia e para produzir uma dispersão neutra de um compósito de partícula fina de titânia |
CA 2722795 CA2722795C (en) | 2008-05-02 | 2009-04-28 | Titania fine-particle composite and compositons containing the titania fine-particle composite |
EP09738832.6A EP2295378B1 (en) | 2008-05-02 | 2009-04-28 | Titania fine-particle composite and compositons containing the titania fine-particle composite |
US12/989,145 US8945520B2 (en) | 2008-05-02 | 2009-04-28 | Titania fine-particle composite and compositions containing the titania fine-particle composite |
KR20107026978A KR101311636B1 (ko) | 2008-05-02 | 2009-04-28 | 티타니아 미립자 복합체 및 상기 티타니아 미립자 복합체를 함유하는 조성물 |
JP2010510142A JP5624460B2 (ja) | 2008-05-02 | 2009-04-28 | チタニア微粒子複合体及び該チタニア微粒子複合体を含有する組成物 |
AU2009240918A AU2009240918B2 (en) | 2008-05-02 | 2009-04-28 | Titania fine-particle composite and compositons coantining the titania fine-particle composite |
HK11107518.5A HK1153451A1 (en) | 2008-05-02 | 2011-07-19 | Titania fine-particle composite and compositions containing the titania fine-particle composite |
US14/591,402 US9144541B2 (en) | 2008-05-02 | 2015-01-07 | Titania fine-particle composite and compositions containing the titania fine-particle composite |
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US14/591,402 Continuation US9144541B2 (en) | 2008-05-02 | 2015-01-07 | Titania fine-particle composite and compositions containing the titania fine-particle composite |
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CN106380898A (zh) * | 2016-08-31 | 2017-02-08 | 杭州华大海天科技有限公司 | 一种具有蓝色效应的云母钛金色颜料及其制备方法 |
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US20150125501A1 (en) | 2015-05-07 |
TWI446927B (zh) | 2014-08-01 |
EP2295378A4 (en) | 2014-09-17 |
AU2009240918A1 (en) | 2009-11-05 |
RU2464230C2 (ru) | 2012-10-20 |
AU2009240918B2 (en) | 2012-08-23 |
US9144541B2 (en) | 2015-09-29 |
CA2722795A1 (en) | 2009-11-05 |
CA2722795C (en) | 2014-04-22 |
US8945520B2 (en) | 2015-02-03 |
TW201000141A (en) | 2010-01-01 |
EP2295378A1 (en) | 2011-03-16 |
EP2295378B1 (en) | 2017-12-27 |
BRPI0910748A2 (pt) | 2015-09-29 |
JPWO2009133895A1 (ja) | 2011-09-01 |
BRPI0910748B1 (pt) | 2019-03-26 |
KR20110004890A (ko) | 2011-01-14 |
CN102015540B (zh) | 2014-11-26 |
JP5624460B2 (ja) | 2014-11-12 |
KR101311636B1 (ko) | 2013-09-25 |
HK1153451A1 (en) | 2012-03-30 |
RU2010149226A (ru) | 2012-06-10 |
CN102015540A (zh) | 2011-04-13 |
US20110038817A1 (en) | 2011-02-17 |
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