Classifications

• • 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
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
• • 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
  • A61K8/26—Aluminium; Compounds thereof
• • 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
  • A61K8/37—Esters of carboxylic acids
• • 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
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
• • 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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• • 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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
  • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
• • 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
• • 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
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes

Definitions

• the present invention relates to a water-in-oil emulsion composition.
• Patent Document 1 describes a water-in-oil emulsified cosmetic containing a cation-modified clay mineral, a hydrophobically treated color pigment, a phenyl-modified silicone, and a volatile oil, which adheres well to the skin and spreads lightly. , It is described that it spreads easily, the skin has a thin film feeling and a glossy feeling, and the skin surface is uniform and has a beautiful finish.
• Patent Document 1 JP-A-2018-70516
• the present invention provides the following components (A), (B), (C) and (D): (A) a cationically modified clay mineral substituted with a quaternary ammonium ion; (B) a phenyl-modified silicone that is liquid at 25°C; (C) sorbitan fatty acid ester 0.00005 to 0.3% by mass, (D) It relates to a water-in-oil emulsion composition containing a polyether-modified silicone.
• the present inventors found that by using a very small amount of sorbitan fatty acid ester together with a cation-modified clay mineral, a phenyl-modified silicone and a polyether-modified silicone, even if pressure is applied to the cosmetic and the viscosity decreases, the viscosity is easily recovered. It has been found that a water-in-oil emulsified composition having good viscosity stability, excellent spreadability upon application, adhesion to the skin, and finished covering power can be obtained.
• the water-in-oil emulsion composition of the present invention is excellent in viscosity stability even after long-term storage.
• excellent viscosity stability even after long-term storage means that the water-in-oil emulsion composition is pressured by a filling machine or the like, even if the viscosity is reduced. It shows that it is easy to recover to the viscosity before being applied. In addition, it has excellent spreadability when applied, a feeling of adhesion to the skin, and a finished covering power.
• the cation-modified clay mineral of component (A) used in the present invention is substituted with quaternary ammonium ions, and can be used without limitation as long as it is used in ordinary cosmetics.
• quaternary ammonium salt type cationic surfactant a quaternary ammonium salt type cationic surfactant.
• the quaternary ammonium salt-type cationic surfactant has the following formula (1):
• R 1 represents an alkyl group having 10 to 22 carbon atoms or a benzyl group
• R 2 represents a methyl group or an alkyl group having 10 to 22 carbon atoms
• R 3 and R 4 each have 1 carbon atom.
• X represents a halogen atom or a methylsulfate residue
• the cation-modified clay mineral obtained by substituting a quaternary ammonium salt-type cationic surfactant for a layered clay mineral is selected from dimethyldistearylammonium hectorite, dimethyldistearylammonium bentonite, and benzyldimethylstearylammonium hectorite. dimethyldistearylammonium hectorite and benzyldimethylstearylammonium hectorite. More preferred.
• Commercially available products include Benton 38, Benton 38VCG, and Benton 27 (manufactured by Elementis Japan).
• the organically modified clay mineral can also be used as a dispersion diluted with a solvent from the viewpoint of improving workability and being excellent in the effect of thickening oil. Specifically, it is preferable to use a premixed gel in which an organically modified clay mineral is dispersed in a solvent in advance.
• the solvent is not limited as long as it can be thickened by an organically modified clay mineral, but from the viewpoint of oil thickening effect, octyldodecanol, mineral oil, volatile silicone oil, tri(caprylic acid/capric acid) glyceryl, It preferably contains one or more selected from alkyl benzoate (C12-15), and one or more selected from tri(caprylic/capric)glyceryl and alkyl benzoate (C12-15). More preferably, it contains The content of the organically modified clay mineral in the premix gel is preferably 5 to 25% by mass from the viewpoints of improving workability, increasing the viscosity of the oil, and suppressing the oil separation of the thickened oily gel itself.
• Premix gels include Benton gel EUGV containing 10% by mass of cation-modified clay mineral, Benton gel MIOV, Benton gel VS-5 PCV containing 18% by mass, Benton gel PTM containing 15% by mass (manufactured by Elementis Japan), Commercially available products such as BENTONE GEL GTCC V and BENTONE GEL TN V (manufactured by Elementis Specialties) containing 12.5% by mass can be used.
• Component (A) can be used alone or in combination of two or more, and the content is determined to improve viscosity stability, elongation during application, feel of adhesion to the skin, finish covering power, and clean finish feel of the entire face. From the viewpoint of improving the preferably 1.4% by mass or more, more preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 2.5% by mass or less, and 1.8% by mass % or less is particularly preferable.
• the content of component (A) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.5 to 3% by mass in the total composition. 0.8 to 2.5% by mass is even more preferable, and 1.4 to 1.8% by mass is even more preferable.
• Component (B) is a phenyl-modified silicone that is liquid at 25°C.
• liquid means that the viscosity at 25° C. is 10000 mPa ⁇ s or less.
• the viscosity of component (B) at 25° C. is preferably 4000 mPa ⁇ s or less, more preferably 600 mPa ⁇ s or less, even more preferably 200 mPa ⁇ s or less, and even more preferably 50 mPa ⁇ s or less.
• Viscosity measurement conditions B-type viscometer (Model TVB-10, manufactured by Toki Sangyo Co., Ltd.), rotor No. 4, 60 rpm, 60 seconds
• phenyl-modified silicones that are liquid at 25° C.
• examples of phenyl-modified silicones that are liquid at 25° C. include phenyltrimethicone, diphenylsiloxyphenyltrimethicone, diphenyldimethicone, trimethylsiloxyphenyldimethicone, and trimethylpentaphenyltrisiloxysan.
• phenyl trimethicone and diphenylsiloxyphenyl trimethicone from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and a clean finish of the entire face. or two or more, more preferably diphenylsiloxyphenyl trimethicone.
• Component (B) includes SH556 (manufactured by Dow Corning Toray) and DOWSIL SH 556 FLUID) (manufactured by Dow Toray) as phenyl trimethicone; KF-56A (Shin-Etsu Chemical Co., Ltd.) as diphenylsiloxyphenyl trimethicone ), DOWSIL FZ-209 (manufactured by Dow Toray Industries); KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.) as diphenyl dimethicone ); PDM-1000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) as trimethylsiloxyphenyl dimethicone; PH-1555 HRI C.I. F. (manufact
• Component (B) can be used alone or in combination of two or more, and the content of the component (B) is determined to improve viscosity stability, elongation during application, feel of adhesion to the skin, finish covering power, and clean finish feel of the entire face. From the viewpoint of improvement, it is preferably 1% by mass or more in the entire composition, more preferably 2% by mass or more, still more preferably 3% by mass or more, even more preferably 3.5% by mass or more, and 5% by mass or more. 25% by mass or less is preferable, 20% by mass or less is more preferable, 15% by mass or less is even more preferable, 10% by mass or less is even more preferable, and 7% by mass or less is particularly preferable.
• the content of component (B) is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, still more preferably 3 to 15% by mass, and 3.5 to 10% by mass in the total composition. % is even more preferred, and 5 to 7% by mass is even more preferred.
• the mass ratio (A)/(B) of component (A) to component (B) is the stability of viscosity, elongation at the time of application, feeling of adhesion to skin, covering power of finish, and cleanness of the entire face. From the viewpoint of improving the finished feeling, it is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.12 or more, even more preferably 0.15 or more, and more preferably 0.2 or more. , more preferably 0.23 or more, preferably 1 or less, more preferably 0.5 or less, still more preferably 0.45 or less, still more preferably 0.40 or less, more preferably 0.36 or less, 0. 3 or less is even more preferable.
• the mass ratio (A)/(B) of component (A) to component (B) is preferably 0.05 to 1, more preferably 0.1 to 0.5, and 0.12 to 0. 0. 0.45 is more preferred, 0.15 to 0.40 is more preferred, 0.2 to 0.36 is more preferred, and 0.23 to 0.3 is even more preferred.
• Component (C) used in the present invention is a sorbitan fatty acid ester.
• the sorbitan fatty acid ester preferably has an HLB of 1 or more, from the viewpoint of improving stability of viscosity, elongation at the time of application, feeling of adhesion to the skin, covering power of the finish, and feeling of a clean finish on the entire face. 3 or more is more preferable, 10 or less is preferable, 7 or less is more preferable, and 6 or less is even more preferable.
• the HLB of the component (C) sorbitan fatty acid ester is preferably 1-10, more preferably 2-7, and even more preferably 3-6.
• HLB Hydrophilic-Lipophilic Balance
• sorbitan fatty acid esters examples include sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquistearate, and sorbitan sesquioleate, which provide stability of viscosity, elongation when applied, feeling of adhesion to the skin, and covering power of the finish.
• it preferably contains one or more selected from sorbitan monoisostearate, sorbitan monooleate, and sorbitan sesquistearate, sorbitan monoisostearate, and sesquistearic acid. It more preferably contains one or more selected from sorbitan, and more preferably contains sorbitan monoisostearate.
• sorbitan fatty acid ester of component (C) examples include Span 120 (HLB 4.7) (manufactured by Croda) as sorbitan monoisostearate, NIKKOL SS-15V (HLB 4.2) as sorbitan sesquistearate, As sorbitan monooleate, commercially available products such as NIKKOL SO-10V (HLB 4.3) (manufactured by Nikko Chemicals Co., Ltd.) can be used.
• the content of component (C) is 0.00005 mass in the total composition from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and a clean finish feeling of the entire face.
• % or more preferably 0.00007% by mass or more, more preferably 0.00008% by mass or more, even more preferably 0.0001% by mass or more, even more preferably 0.0005% by mass or more, and 0.3% by mass % or less, preferably 0.1 mass % or less, more preferably 0.05 mass % or less, and even more preferably 0.005 mass % or less.
• the content of component (C) is 0.00005 to 0.3% by mass in the entire composition, preferably 0.00007 to 0.1% by mass, more preferably 0.00008 to 0.05% by mass. Preferably, 0.0001 to 0.05% by mass is more preferable, and 0.0005 to 0.005% by mass is even more preferable. Also, the content of component (C) is preferably 0.0001 to 0.3% by mass in the total composition.
• the mass ratio (B)/(C) of component (B) to component (C) is the stability of viscosity, elongation at the time of application, feeling of adhesion to skin, finished covering power, and the entire face. From the viewpoint of improving the clean finish feeling, it is preferably 20 or more, more preferably 60 or more, still more preferably 150 or more, even more preferably 200 or more, even more preferably 2000 or more, preferably 80000 or less, 60000 The following is more preferable, 30000 or less is even more preferable, and 7000 or less is even more preferable.
• the mass ratio (B)/(C) of component (B) to component (C) is preferably 20 to 80,000, more preferably 60 to 60,000, still more preferably 150 to 30,000, and 200 to 30,000. Even more preferably, 2000 to 7000 is even more preferable.
• the polyether-modified silicone of component (D) is commonly used in cosmetics, such as dimethylpolysiloxane having a polyoxyethylene group or a polyoxypropylene group, or dimethylpolysiloxane to which polyethylene glycol is added. , those used in ordinary cosmetics. Incidentally, the dimethylpolysiloxane may be partially fluorine-modified.
• Polyether-modified silicones contain polyoxyethylene or polyoxypropylene groups from the viewpoint of improving viscosity stability, elongation during application, feeling of adhesion to the skin, covering power of the finished product, and a clean finished feeling of the entire face. is preferred, and dimethylpolysiloxane having at least polyoxyethylene groups is more preferred.
• the polyether-modified silicone does not contain a crosslinked silicone.
• a polyether-modified silicone preferably has an HLB of 1 or more from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and a clean finish feeling of the entire face. 3 or more is more preferable, 12 or less is preferable, 10 or less is more preferable, 8 or less is more preferable, and 6 or less is even more preferable.
• HLB is calculated in the same manner as for component (C) above.
• polyether-modified silicones examples include cetyl PEG/PPG-10/1 dimethicone, PEG/PPG-19/19 dimethicone, PEG10-dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and the like. mentioned.
• cetyl PEG/PPG-10/1 dimethicone, PEG/PPG are used from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and a clean finish feeling of the entire face.
• dimethicone preferably contains one or more selected from PEG10-dimethicone, one or two selected from cetyl PEG/PPG-10/1 dimethicone, PEG/PPG-19/19 dimethicone and more preferably cetyl PEG/PPG-10/1 dimethicone.
• Component (D) can be used alone or in combination of two or more, and the content is determined to improve viscosity stability, elongation during application, feel of adhesion to the skin, covering power of finish, and clean finish of the entire face. From the viewpoint of improvement, it is preferably 0.1% by mass or more in the entire composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and preferably 10% by mass or less. % by mass or less is more preferable, and 3% by mass or less is even more preferable.
• the content of component (D) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass in the total composition.
• the water-in-oil emulsified composition of the present invention may further contain (E) an ester oil that is liquid at 25° C. to improve viscosity stability, elongation upon application, and adhesion to the skin. can be done.
• the term "liquid” means that the viscosity at 25°C is 10,000 mPa ⁇ s or less, like the component (B).
• the viscosity of component (E) is measured in the same manner as for component (B).
• ester oil of component (E) those used in ordinary cosmetics may be used.
• monoester oils diester oils such as neopentyl glycol dicaprate, propylene glycol dicaprate, and diisostearyl malate; tri-2-ethylhexanoate glyceryl, tri (caprylic / capric) glyceryl, etc.; and tetraester oils such as dipentaerythrityl isostearate.
• diester oils such as neopentyl glycol dicaprate, propylene glycol dicaprate, and diisostearyl malate
• tetraester oils such as dipentaerythrityl isostearate.
• it preferably contains one or more selected from monoesters, diesters, and triesters, from the viewpoint of improving viscosity stability, elongation during application, and adhesion to the skin. It is more preferable to contain one or more selected from diesters. Also, it is more preferable to use a combination of a monoester and a diester.
• Component (E) can be used alone or in combination of two or more, and the content is 1 in the total composition from the viewpoint of improving viscosity stability, spreadability during application, and adhesion to the skin. It is preferably at least 2% by mass, more preferably at least 2% by mass, still more preferably at least 3% by mass, preferably at most 20% by mass, more preferably at most 15% by mass, further preferably at most 10% by mass.
• the content of component (E) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 10% by mass in the total composition.
• the water-in-oil emulsified composition of the present invention may further contain an oily gelling agent other than component (A) as component (F), which provides viscosity stability, spreadability upon application, and spreadability on the skin. It can improve the feeling of adhesion, the covering power of the finish, and the beautiful finish of the entire face.
• an oily gelling agent any one that is used in ordinary cosmetics and can thicken the oil phase may be used.
• the oily gelling agent of component (F) include crosslinked organopolysiloxane, dextrin fatty acid ester, metal soap, sucrose fatty acid ester, and oily component (wax) that is solid at 25°C.
• crosslinked organopolysiloxane examples include crosslinked dimethylpolysiloxane, crosslinked alkylpolysiloxane, and crosslinked polyether-modified silicone.
• Crosslinked dimethylpolysiloxane is a polymer having a crosslinked structure in which the siloxane skeleton is three-dimensionally crosslinked, and crosslinked alkylpolysiloxane is a crosslinked dimethylpolysiloxane that further has an alkyl group having 6 to 20 carbon atoms. is.
• Crosslinked dimethylpolysiloxanes include (dimethicone/vinyl dimethicone) crosspolymers, and crosslinked alkylpolysiloxanes include (dimethicone/phenyl dimethicone) crosspolymers, (vinyl dimethicone/lauryl dimethicone) crosspolymers, alkyl (C30 -45) Cetearyl dimethicone crosspolymer, cetearyl dimethicone crosspolymer. These may be used as they are in a solid state, or may be used after being uniformly mixed with a liquid oil.
• Examples of the (dimethicone/vinyl dimethicone) crosspolymer include KSG-15 which is a mixture with decamethylcyclopentasiloxane, KSG-16 which is a mixture with low-viscosity dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), methyltri A commercially available product such as TOREFIL (35%) C/TMF (manufactured by Daito Kasei Kogyo Co., Ltd.), which is a mixture with methicone, can be used.
• KSG-15 is a mixture with decamethylcyclopentasiloxane
• KSG-16 which is a mixture with low-viscosity dimethylpolysiloxane
• methyltri A commercially available product such as TOREFIL (35%) C/TMF (manufactured by Daito Kasei Kogyo Co., Ltd.), which is a mixture with methicone,
• the (dimethicone/phenyldimethicone) crosspolymer commercially available products such as KSG-18 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a mixture with methylphenylpolysiloxane, can be used.
• the (vinyl dimethicone/lauryl dimethicone) crosspolymer includes KSG-41 which is a mixture with liquid paraffin, KSG-42 which is a mixture with light isoparaffin, and KSG which is a mixture with glyceryl tri-2-ethylhexanoate.
• alkyl (C30-45) cetearyl dimethicone crosspolymer commercial products such as Velvesil 125 (manufactured by Momentive Performance Materials), which is a mixture with cyclopentasiloxane, can be used.
• cetearyl dimethicone crosspolymer commercially available products such as Velvesil DM (manufactured by Momentive Performance Materials), which is a mixture of dimethicone, can be used.
• the crosslinked polyether-modified silicone examples include (dimethicone/(PEG-10/15)) crosspolymer, (PEG-15/lauryl dimethicone) crosspolymer, (PEG-10/lauryl dimethicone) crosspolymer, and the like.
• the crosslinked polyether-modified silicone is preferably used as a dispersion diluted with a liquid oil, and more preferably a silicone oil, a hydrocarbon oil, or an ester oil. More preferably, silicone oil and hydrocarbon oil are used. Furthermore, it is preferably diluted or dispersed in a volatile hydrocarbon oil, and isododecane is more preferable as the volatile hydrocarbon oil.
• Crosslinked polyether-modified silicones include, for example, KSG-210, KSG-240 ((dimethicone/(PEG-10/15)) crosspolymer); KSG-310, KSG-320, KSG-330 ((PEG-15 / Lauryl dimethicone) crosspolymer); KSG-340 ((PEG-10/lauryl dimethicone) crosspolymer and (PEG-15/lauryl dimethicone) crosspolymer) (both manufactured by Shin-Etsu Chemical Co., Ltd.). can be done.
• the crosslinked organopolysiloxane preferably contains one or more selected from crosslinked alkylpolysiloxane and crosslinked dimethylpolysiloxane, such as (dimethicone/vinyl dimethicone) crosspolymer and (dimethicone/phenyl dimethicone) cross.
• crosslinked alkylpolysiloxane and crosslinked dimethylpolysiloxane such as (dimethicone/vinyl dimethicone) crosspolymer and (dimethicone/phenyl dimethicone) cross.
• Polymers, (vinyl dimethicone/lauryl dimethicone) crosspolymers are more preferred, and (dimethicone/vinyl dimethicone) crosspolymers are even more preferred.
• the dextrin fatty acid ester is an ester of fatty acid and dextrin, the fatty acid preferably has 8 to 24 carbon atoms, more preferably 14 to 18 carbon atoms, and the fatty acid is a linear or branched saturated or unsaturated fatty acid. It is a saturated fatty acid and preferably has an average degree of polymerization of 10-50, more preferably 20-30. Specific examples include dextrin palmitate, dextrin palmitate/2-ethylhexanoate, dextrin stearate, dextrin palmitate/stearate, dextrin oleate, dextrin isopalmitate, dextrin isostearate, and dextrin myristate. .
• the dextrin fatty acid ester is preferably dextrin palmitate, dextrin palmitate/2-ethylhexanoate, and more preferably dextrin palmitate.
• Commercially available products thereof include dextrin palmitate (Rheopearl KL2, Rheopearl KS2, Rheopearl TL2), dextrin palmitate/2-ethylhexanoate (Rheopearl TT2), dextrin myristate (Rheopearl MKL2) and the like manufactured by Chiba Flour Mills. be done.
• waxes such as jojoba wax (melting point: 55°C), Japanese wax (melting point: 55°C), jojoba butter (melting point: 46-54°C), lanolin (melting point: 37-43°C); hydrogenated jojoba oil (melting point: 68°C) , isostearic acid hydrogenated castor oil (melting point: 45 ° C), hydrogenated castor oil (melting point: 84 ° C), hydrogenated palm oil (melting point: 65 ° C), hydrogenated coconut oil (melting point: 70 ° C), cetyl palmitate (melting point: 50 ° C), eicosanedioic acid glyceryl behenate (melting point: 66 ° C), glyceryl behenate, tristearin, tribehenin, shea butter (melting point: 36-45 ° C), dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / steary
• crosslinked organopolysiloxane is used from the viewpoint of improving viscosity stability, elongation during application, feeling of adhesion to the skin, covering power of the finish, and a clean finish feeling of the entire face. , dextrin fatty acid esters, and oily components that are solid at 25°C, more preferably crosslinked organopolysiloxane, and selected from crosslinked dimethylpolysiloxane and crosslinked alkylpolysiloxane.
• Component (F) can be used alone or in combination of two or more, and the content is determined by viscosity stability, elongation during application, feeling of adhesion to skin, covering power of finish, and beautiful finish of the entire face. From the viewpoint of improving the feeling, it is preferably 0.1% by mass or more in the entire composition, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and 0.5% by mass or more. More preferably, it is 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 2% by mass or less. In addition, the content of component (F) is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, even more preferably 0.3 to 5% by mass in the total composition, 0.5 to 2% by mass is even more preferable.
• the water-in-oil emulsion composition of the present invention may further contain (G) a coloring pigment from the viewpoint of improving the covering power of the finish and the feeling of a beautiful makeup finish on the entire face.
• Coloring pigments used in ordinary cosmetics include titanium oxide, zinc oxide, cerium oxide, aluminum oxide, yellow iron oxide, black iron oxide, red iron oxide, Prussian blue, ultramarine blue, chromium oxide, chromium hydroxide, and the like.
• the coloring pigment preferably contains a metal oxide from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and a clean finish feeling of the entire face, such as titanium oxide, It is more preferable to contain one or more selected from zinc oxide, yellow iron oxide, black iron oxide and red iron oxide, and one or more selected from titanium oxide, yellow iron oxide, black iron oxide and red iron oxide. More preferably, it contains
• color pigments can be used as they are, or can be used after being hydrophobized.
• the hydrophobization treatment is not limited as long as it is a treatment applied to ordinary cosmetic powders, and surface treatment agents such as silicone compounds, metal soaps, amino acid compounds, lecithin, oils, and organic titanates are used. , dry processing, wet processing, or the like may be performed.
• surface treatment agents include alkylalkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane and triethoxycaprylylsilane, dimethylpolysiloxane, methyl Silicone compounds such as hydrogen polysiloxane, cyclic silicone, crosslinked silicone, silicone resin, and acrylic-modified silicone; metal soaps such as aluminum stearate, aluminum myristate, zinc stearate, and magnesium stearate; proline, hydroxyproline, alanine , glycine, sarcosine, glutamic acid, aspartic acid, lysine and derivatives thereof; oils such as oils and fats; organic titanates such as isopropyl triisostearoyl titanate;
• the acylated amino acids include salts of acy
• acylated amino acid salts include disodium stearoyl glutamate and sodium lauroyl aspartate, from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and a clean finish of the entire face. It preferably contains one or more selected from, and more preferably contains stearoyl glutamic acid 2Na.
• silicone compounds, acylated amino acids, and organic titanates are selected from the viewpoint of improving viscosity stability, elongation when applied, feeling of adhesion to the skin, covering power of the finish, and the feeling of a clean finish on the entire face.
• Hydrophobization treatment can be performed according to a normal method.
• the treatment amount of the hydrophobic treatment is preferably 0.1 to 15% by mass, more preferably 1 to 12% by mass, based on the amount of the coated powder, from the viewpoint of improving dispersibility in the solvent.
• the content of the color pigment means the content including the hydrophobized agent.
• the color pigment of component (G) can be used alone or in combination of two or more. .1% by mass or more is more preferable, 1% by mass or more is more preferable, 5% by mass or more is even more preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, 25% by mass or less is even more preferable, and 20 % by mass or less is even more preferable. Further, the content of component (G) is preferably 0.01 to 40% by mass in the total composition, more preferably 0.1 to 30% by mass, further preferably 1 to 25% by mass, and 5 to 20% by mass is even more preferable.
• the mass ratio (G)/(C) of component (G) to component (C) is preferably 500 or more, more preferably 5000 or more, from the viewpoint of viscosity stability and cosmetic finish. 8000 or more is more preferable, 10000 or more is still more preferable, 200000 or less is preferable, 100000 or less is more preferable, 60000 or less is more preferable, and 20000 or less is even more preferable. Further, the mass ratio (G)/(C) of component (G) to component (C) is preferably 500 to 200,000, more preferably 5,000 to 100,000, still more preferably 8,000 to 60,000, and 10,000 to 20,000. Even more preferable.
• the water content in the entire composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and more preferably 10% by mass or more, from the viewpoint of viscosity stability and cosmetic finish. It is more preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. Also, the content of water is preferably 0.1 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 10 to 50% by mass in the total composition.
• the water-in-oil emulsified composition of the present invention contains, in addition to the above components, components that are commonly used in cosmetics, such as oil components other than those described above, powders other than those described above, surfactants other than those described above, and water-soluble polymers. , antioxidants, fragrances, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, moisturizing agents, cooling agents, and the like.
• the water-in-oil emulsion composition of the present invention can be produced according to a normal method.
• the water-in-oil emulsion composition of the present invention can be in the form of liquid, milky lotion, paste, cream, gel, and the like.
• the water-in-oil emulsion composition of the present invention preferably has a viscosity at 30° C. of 15,000 mPa ⁇ s or more, preferably 18,000 mPa, from the viewpoint of improving spreadability upon application, adhesion to the skin, and finished covering power.
• the water-in-oil emulsion composition of the present invention preferably has a viscosity at 30° C. of 15,000 to 200,000 mPa s, more preferably 18,000 to 100,000 mPa s, still more preferably 20,000 to 75,000 mPa s, and 22,000 to 22,000 mPa s.
• the water-in-oil emulsified composition of the present invention has a relatively high viscosity, and even if the viscosity is lowered by applying pressure due to filling or the like, the viscosity is easily recovered to that before the pressure was applied. .
• the water-in-oil emulsion composition of the present invention is preferably an external preparation composition, more preferably a skin external preparation composition.
• the water-in-oil emulsified composition of the present invention is preferably a water-in-oil emulsified cosmetic, more preferably a water-in-oil emulsified cosmetic for skin. Cosmetics are more preferred, and make-up cosmetics are even more preferred.
• the water-in-oil emulsified composition of the present invention includes, for example, makeup bases, foundations, concealers; blushers, eyeshadows, mascara, eyeliners, eyebrows, overcoat agents, makeup cosmetics such as lipsticks; It can be applied as UV protection cosmetics such as sunscreen creams; skin care cosmetics such as skin care milky lotions, skin care creams, BB creams, and beauty essences.
• the present invention further discloses the following compositions and the like.
• the cation-modified clay mineral of component (A) is preferably a cation-modified clay mineral obtained by replacing a layered clay mineral with a quaternary ammonium salt-type cationic surfactant, which is dimethyldistearylammonium hect It is more preferable to contain one or more selected from light, dimethyldistearylammonium bentonite, and benzyldimethylstearylammonium hectorite, and one or two selected from dimethyldistearylammonium hectorite and benzyldimethylstearylammonium hectorite.
• the water-in-oil emulsified composition according to ⁇ 1> above which preferably contains at least one seed, and even more preferably contains dimethyldistearylammonium hectory.
• the content of component (A) is preferably 0.01% by mass or more in the entire composition, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and 0 .8% by mass or more is more preferable, 1.4% by mass or more is particularly preferable, 10% by mass or less is preferable, 5% by mass or less is more preferable, 3% by mass or less is more preferable, and 2.5% by mass or less is
• the water-in-oil emulsion composition according to ⁇ 1> or ⁇ 2> which is more preferably 1.8% by mass or less.
• Component (B) preferably has a viscosity at 25°C of 4000 mPa ⁇ s or less, more preferably 600 mPa ⁇ s or less, still more preferably 200 mPa ⁇ s or less, and even more preferably 50 mPa ⁇ s or less.
• the water-in-oil emulsion composition according to any one of ⁇ 1> to ⁇ 3>.
• Component (B) is preferably one or more selected from phenyltrimethicone and diphenylsiloxyphenyltrimethicone, more preferably diphenylsiloxyphenyltrimethicone, above ⁇ 1>
• the content of component (B) is preferably 1% by mass or more in the total composition, more preferably 2% by mass or more, even more preferably 3% by mass or more, and 3.5% by mass or more. More preferably, 5% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, 15% by mass or less is even more preferable, 10% by mass or less is even more preferable, and 7% by mass or less is particularly preferable.
• the preferred water-in-oil emulsion composition according to any one of ⁇ 1> to ⁇ 5>.
• the mass ratio (A)/(B) of component (A) to component (B) is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.12 or more. , more preferably 0.15 or more, more preferably 0.2 or more, still more preferably 0.23 or more, preferably 1 or less, more preferably 0.5 or less, further preferably 0.45 or less, and 0.5.
• the water-in-oil emulsion composition according to any one of ⁇ 1> to ⁇ 6>, which is more preferably 40 or less, more preferably 0.36 or less, and even more preferably 0.3 or less.
• Component (C) preferably has an HLB of 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 7 or less, and even more preferably 6 or less.
• Component (C) is preferably one or more selected from sorbitan monoisostearate, sorbitan monooleate and sorbitan sesquistearate, and is selected from sorbitan monoisostearate and sorbitan sesquistearate.
• the content of component (C) is preferably 0.00007% by mass or more in the total composition, more preferably 0.00008% by mass or more, and even more preferably 0.0001% by mass or more, 0.0005% by mass or more is more preferable, 0.1% by mass or less is preferable, 0.05% by mass or less is more preferable, and 0.005% by mass or less is even more preferable.
• the water-in-oil emulsion composition according to any one of the above. ⁇ 11> The water-in-oil emulsion according to any one of ⁇ 1> to ⁇ 10>, wherein the content of component (C) is preferably 0.0001 to 0.3% by mass in the total composition. Composition.
• the mass ratio (B)/(C) of component (B) to component (C) is preferably 20 or more, more preferably 60 or more, even more preferably 150 or more, and even more preferably 200 or more.
• 2000 or more is more preferable, 80000 or less is preferable, 60000 or less is more preferable, 30000 or less is even more preferable, and 7000 or less is even more preferable, the water-in-oil according to any one of ⁇ 1> to ⁇ 11>. type emulsion composition.
• Component (D) is preferably a dimethylpolysiloxane having a polyoxyethylene group or a polyoxypropylene group, more preferably a dimethylpolysiloxane having at least a polyoxyethylene group, the above ⁇ 1> to ⁇ 12>
• Component (D) preferably has an HLB of 1 or more, more preferably 3 or more, preferably 12 or less, more preferably 10 or less, further preferably 8 or less, and even more preferably 6 or less.
• Component (D) is preferably one or more selected from cetyl PEG/PPG-10/1 dimethicone, PEG/PPG-19/19 dimethicone, and PEG10-dimethicone, It is more preferable to contain one or more selected from PPG-10/1 dimethicone and PEG/PPG-19/19 dimethicone, and cetyl PEG/PPG-10/1 dimethicone is even more preferable.
• the content of component (D) is preferably 0.1% by mass or more in the total composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 10% by mass.
• the water-in-oil emulsion composition according to any one of the above ⁇ 1> to ⁇ 15> which is preferably 5% by mass or less, and further preferably 3% by mass or less.
• Component (E) is preferably one or more selected from monoesters, diesters and triesters, and more preferably contains one or more selected from monoesters and diesters.
• ⁇ 19> The water-in-oil emulsion composition according to ⁇ 17> or ⁇ 18> above, wherein the component (E) is preferably a combination of a monoester and a diester.
• the content of component (E) is preferably 1% by mass or more in the total composition, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 20% by mass or less,
• composition according to any one of ⁇ 1> to ⁇ 20>, further comprising (F) an oily gelling agent other than component (A).
• component (F) is preferably one or more selected from crosslinked organopolysiloxanes, dextrin fatty acid esters, and oily components that are solid at 25°C, more preferably crosslinked organopolysiloxanes.
• crosslinked dimethylpolysiloxane, and crosslinked alkylpolysiloxane more preferably one or more selected from (dimethicone/vinyl dimethicone) crosspolymer, (dimethicone/phenyl dimethicone) crosspolymer, (vinyl dimethicone/ The water-in-oil emulsion composition according to ⁇ 21> above, which preferably contains one or more selected from (lauryl dimethicone) crosspolymers, and particularly preferably (dimethicone/vinyl dimethicone) crosspolymers.
• the content of component (F) is preferably 0.1% by mass or more in the entire composition, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and 0 .5% by mass or more is more preferable, 20% by mass or less is preferable, 10% by mass or less is more preferable, 5% by mass or less is even more preferable, and 2% by mass or less is even more preferable, ⁇ 21> or ⁇ 22>
• the component (G) preferably contains a metal oxide, more preferably one or more selected from titanium oxide, zinc oxide, yellow iron oxide, black iron oxide, and red iron oxide.
• Component (G) is preferably hydrophobized, and the surface treatment agent contains one or more selected from silicone compounds, acylated amino acids, and organic titanates.
• the content of component (G) is preferably 0.01% by mass or more in the total composition, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and 5% by mass. Above is more preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, 25% by mass or less is more preferable, and 20% by mass or less is even more preferable, any one of ⁇ 24> to ⁇ 26>
• the mass ratio (G)/(C) of component (G) to component (C) is preferably 500 or more, more preferably 5000 or more, even more preferably 8000 or more, and even more preferably 10000 or more.
• the content of water is preferably 0.1% by mass or more in the total composition, more preferably 1% by mass or more, still more preferably 10% by mass or more, and preferably 80% by mass or less.
• Viscosity at 30°C is preferably 15,000 mPa s or more, more preferably 18,000 mPa s or more, still more preferably 20,000 mPa s or more, even more preferably 22,000 mPa s or more, and 200,000 mPa s or less.
• the water-in-oil emulsion composition according to any one of the above ⁇ 1> to ⁇ 29> which is preferably 100,000 mPa ⁇ s or less, more preferably 75,000 mPa ⁇ s or less, and even more preferably 50,000 mPa ⁇ s or less.
• the water-in-oil emulsion composition according to any one of the above ⁇ 1> to ⁇ 30> which is preferably an external preparation composition, more preferably a skin external preparation composition.
• it is a water-in-oil type emulsified cosmetic, more preferably a water-in-oil type emulsified cosmetic for skin, more preferably an ultraviolet protection cosmetic or a makeup cosmetic, and is used as a makeup cosmetic.
• ⁇ 37> Use of the water-in-oil emulsion composition according to any one of ⁇ 1> to ⁇ 32> as a make-up cosmetic.
• ⁇ 38> Use for make-up, wherein the water-in-oil emulsion composition according to any one of ⁇ 1> to ⁇ 32> is applied to the skin, preferably the face.
• ⁇ 39> Use of the water-in-oil emulsified composition according to any one of the above ⁇ 1> to ⁇ 32> for producing a water-in-oil emulsified cosmetic.
• Examples 1-12 and Comparative Examples 1-2 A water-in-oil emulsified cosmetic (foundation) having the composition shown in Table 1 was produced, and the viscosity immediately after production and after storage for one month was measured. The spreadability, adhesion to the skin, and covering power were evaluated. The results are also shown in Table 1. In Comparative Examples 1 and 2, since the viscosity was low, the viscosity stability was not evaluated when the pressure was applied by the filling machine.
• Water-in-oil emulsification is achieved by adding and mixing aqueous phase components to an oil phase containing components (A), (B), (C), (D), (E), (F), and (G). I got cosmetics.
• Viscosity measurement For each water-in-oil emulsified cosmetic, the viscosity immediately after production and after storage at 30 ° C. for 1 month was measured at 30 ° C. with a helical viscometer (TVB-10 type, manufactured by Toki Sangyo Co., Ltd.), a rotor H- It was measured by TC, 10 rotations, and 60 seconds of measurement time. Note that these viscosities are obtained without applying the pressure by the filling machine described in (2) below. Viscosity values are shown in Table 1 below. (A): Immediate viscosity (30° C.)/mPa s (B): Viscosity after 1 month (30°C)/mPa s
• Viscosity stability when pressure is applied by a filling machine Pressure is applied to each water-in-oil emulsified cosmetic by a filling machine under the following conditions, 40 g of each water-in-oil emulsified cosmetic is placed in a 50 mL sample bottle, and the viscosity after storage at 30 ° C. for 1 month ( c) was measured in the same manner as in (1) above. Based on these viscosities, the viscosity stability (viscosity recoverability) when pressure was applied by a filling machine was determined by the following formula. The closer to 100% the smaller the change in viscosity, the better.
• Pressure conditions by filling machine Electric piston type filling machine SBK-1-9L manufactured by Arahata Food Machine Co., ⁇ 40 cylinder, nozzle inner diameter ⁇ 5mm, filling time: 0.3 (sec)
• Elongation during application Three professional evaluators applied 0.03 g of each water-in-oil emulsified cosmetic to the skin on the inner side of the forearm using fingers in a size of 2 ⁇ 3 cm 2 , and evaluated the spreadability at the time of application as follows. was evaluated in five stages. The results were indicated by the total points of the three persons. 5; Elongation is very good. 4; Elongation is good. 3; Elongation is slightly good. 2; elongation is not so good. 1; elongation is poor.
• Covering power When 0.25 g of each water-in-oil emulsified cosmetic was applied to the face using fingers, three professional evaluators evaluated the covering power against pores and uneven color according to the following five levels. The results were indicated by the total points of the three persons. 5; Covering power is evident. 4; It has covering power. 3; Slightly covering power. 2; Not much covering power. 1; No covering power.
• Formulation examples 1-9 Water-in-oil emulsified cosmetics having compositions shown in Tables 2 to 4 were produced in the same manner as in Examples 1 to 12. All of the obtained water-in-oil type emulsified cosmetics are easy to recover even if the viscosity is lowered due to the pressure applied by the filling machine, have good viscosity stability, spread when applied, and spread on the skin. It has excellent adhesion and finish covering power.
• Examples 13 and 14 A water-in-oil emulsified cosmetic (foundation) having the composition shown in Table 5 was produced in the same manner as in Examples 1 to 12, and the viscosity was measured immediately after production and after storage for one month, and pressure was applied using a filling machine. Viscosity stability upon application, spreadability upon application, adhesion to skin and covering power were evaluated. The results are also shown in Table 5.

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