WO2022255182A1 - 油中水型乳化組成物 - Google Patents
油中水型乳化組成物 Download PDFInfo
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- WO2022255182A1 WO2022255182A1 PCT/JP2022/021368 JP2022021368W WO2022255182A1 WO 2022255182 A1 WO2022255182 A1 WO 2022255182A1 JP 2022021368 W JP2022021368 W JP 2022021368W WO 2022255182 A1 WO2022255182 A1 WO 2022255182A1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
- 229940098780 tribehenin Drugs 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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Abstract
Description
例えば、特許文献1には、カチオン変性粘土鉱物、疎水化処理された着色顔料、フェニル変性シリコーン及び揮発性油を含有する油中水型乳化化粧料が、肌への付きが良く、伸びが軽く、塗広げやすく、肌に薄膜感、艶感があり、肌表面が均一できれいな仕上がることが記載されている。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物、
(B)25℃で液状のフェニル変性シリコーン、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーン
を含有する油中水型乳化組成物に関する。
また、塗布時の伸び、肌への付着感、仕上がりのカバー力においても、十分満足できるものではなかった。
本発明において、長期保存しても粘度の安定性に優れるとは、油中水型乳化組成物に対して、充填機などによる圧力が加えられたことによる粘度低下が起こっても、圧力が加えられる前の粘度に回復しやすいことを示す。
また、塗布時の伸び、肌への付着感、仕上がりのカバー力にも優れている。
ここで、第四級アンモニウム塩型カチオン界面活性剤は、下記式(1):
で表されるものである。
なかでも、ベンジルジメチルステアリルアンモニウムクロリド、ジメチルジステアリルアンモニウムクロリドから選ばれる1種又は2種以上を含むのが好ましく、ジメチルジステアリルアンモニウムクロリドがより好ましい。
具体的には、有機変性粘土鉱物を予め溶媒に分散させたプレミックスゲルを用いることが好ましい。溶媒としては、有機変性粘土鉱物によって増粘可能であれば制限されないが、油の増粘効果の点から、オクチルドデカノール、ミネラルオイル、揮発性シリコーン油、トリ(カプリル酸/カプリン酸)グリセリル、安息香酸アルキル(C12-15)から選ばれる1種又は2種以上を含むのが好ましく、トリ(カプリル酸/カプリン酸)グリセリル、安息香酸アルキル(C12-15)から選ばれる1種又は2種以上を含むのがより好ましい。
プレミックスゲル中の有機変性粘土鉱物の含有量は、作業性向上の点、油の増粘効果、及び増粘した油性ゲル自体の油分離を抑制する点から、5~25質量%が好ましく、10~20質量%がより好ましく、10~18質量%がさらに好ましい。
プレミックスゲルとしては、カチオン変性粘土鉱物を10質量%含有するベントンゲルEUGV、ベントンゲルMIOV、18質量%含有するベントンゲルVS-5 PCV、15質量%含有するベントンゲル PTM(以上、エレメンティスジャパン社製)、12.5質量%含有するBENTONE GEL GTCC V、BENTONE GEL TN V(以上、Elementis Specialties社製)等の市販品を用いることができる。
成分(B)の25℃における粘度としては、4000mPa・s以下が好ましく、600mPa・s以下がより好ましく、200mPa・s以下がさらに好ましく、50mPa・s以下がよりさらに好ましい。
ここで、粘度は、以下の条件で測定される。
粘度測定条件:B型粘度計(TVB-10型、東機産業社製)、ローターNo.4、60rpm、60秒
なかでも、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、フェニルトリメチコン、ジフェニルシロキシフェニルトリメチコンから選ばれる1種又は2種以上を含むのが好ましく、ジフェニルシロキシフェニルトリメチコンを含むのがより好ましい。
ソルビタン脂肪酸エステルとしては、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、HLBが1以上であるのが好ましく、2以上がより好ましく、3以上がさらに好ましく、10以下が好ましく、7以下がより好ましく、6以下がさらに好ましい。また、成分(C)のソルビタン脂肪酸エステルは、HLBが1~10であるのが好ましく、2~7がより好ましく、3~6がさらに好ましい。
本発明において、HLB(親水性-親油性のバランス〈Hydrophilic-Lipophilic Balance〉)は、界面活性剤の全分子量に占める親水基部分の分子量を示すものであり、グリフィン(Griffin)の式により求められるものである。また、2種以上の非イオン界面活性剤から構成される場合、混合界面活性剤のHLBは、次のようにして求められる。混合界面活性剤のHLBは、各非イオン界面活性剤のHLB値をその配合比率に基づいて相加算平均したものである。
混合HLB=Σ(HLBx×Wx)/ΣWx
HLBxは、非イオン界面活性剤XのHLB値を示す。
Wxは、HLBxの値を有する非イオン界面活性剤Xの質量(g)を示す。
成分(C)のソルビタン脂肪酸エステルとしては、例えば、モノイソステアリン酸ソルビタンとしては、Span 120(HLB4.7)(クローダ社製)、セスキステアリン酸ソルビタンとしては、NIKKOL SS-15V(HLB4.2)、モノオレイン酸ソルビタンとしては、NIKKOL SO-10V(HLB4.3)(以上、日光ケミカルズ社)等の市販品を用いることができる。
また、成分(C)の含有量は、全組成中に0.0001~0.3質量%が好ましい。
ポリエーテル変性シリコーンとしては、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、ポリオキシエチレン基又はポリオキシプロピレン基を有するジメチルポリシロキサンが好ましく、少なくともポリオキシエチレン基を有するジメチルポリシロキサンがより好ましい。
なお、ポリエーテル変性シリコーンには、架橋型のものは含まないことが好ましい。
このようなポリエーテル変性シリコーンは、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、HLBは、1以上が好ましく、3以上がより好ましく、12以下が好ましく、10以下がより好ましく、8以下がさらに好ましく、6以下がよりさらに好ましい。
ここで、HLBは、前記成分(C)と同様に計算される。
ポリエーテル変性シリコーンとしては、セチルPEG/PPG-10/1ジメチコン、PEG/PPG-19/19ジメチコン、PEG10-ジメチコン、PEG-9ポリジメチルシロキシエチルジメチコン、ラウリルPEG-9ポリジメチルシロキシエチルジメチコン等が挙げられる。これらのうち、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、セチルPEG/PPG-10/1ジメチコン、PEG/PPG-19/19ジメチコン、PEG10-ジメチコンから選ばれる1種又は2種以上を含むのが好ましく、セチルPEG/PPG-10/1ジメチコン、PEG/PPG-19/19ジメチコンから選ばれる1種又は2種以上を含むのがより好ましく、セチルPEG/PPG-10/1ジメチコンがさらに好ましい。
成分(E)のエステル油としては、通常の化粧料に用いられるものであれば良く、例えば、パラメトキシケイ皮酸エチルヘキシル、エチルヘキサン酸セチル、ミリスチン酸オクチルドデシル、イソノナン酸イソトリデシル、イソノナン酸イソノニル等のモノエステル油;ジカプリン酸ネオペンチルグリコール、ジカプリン酸プロピレングリコール、リンゴ酸ジイソステアリル等のジエステル油;トリ2-エチルヘキサン酸グリセリル、トリ(カプリル酸/カプリン酸)グリセリル等のトリエステル油;テトライソステアリン酸ジペンタエリスリチル等のテトラエステル油などが挙げられる。
かかる油性ゲル化剤としては、通常の化粧料に用いられるもので、油相を増粘できるものであればいずれでも良い。
成分(F)の油性ゲル化剤としては、例えば、架橋型オルガノポリシロキサン、デキストリン脂肪酸エステル、金属石鹸、ショ糖脂肪酸エステル、25℃で固体の油性成分(ワックス)等が挙げられる。
架橋型ジメチルポリシロキサンとしては、(ジメチコン/ビニルジメチコン)クロスポリマーが挙げられ、架橋型アルキルポリシロキサンとしては、(ジメチコン/フェニルジメチコン)クロスポリマー、(ビニルジメチコン/ラウリルジメチコン)クロスポリマー、アルキル(C30-45)セテアリルジメチコンクロスポリマー、セテアリルジメチコンクロスポリマーが挙げられる。
これらは、固体状のまま使用しても良く、液状油と均一に混合したものを使用しても良い。なかでも、化粧料中への分散性、作業性の点から、液状油によって希釈された分散液として用いるのが好ましく、シリコーン油、炭化水素油、エステル油から選ばれる1種又は2種以上を用いるのが好ましく、シリコーン油、炭化水素油から選ばれる1種又は2種以上を用いるのがより好ましく、ジメチルポリシロキサン、メチルトリメチコン、デカメチルシクロペンタシロキサン、流動パラフィン、軽質イソパラフィンから選ばれる1種又は2種以上を用いるのがさらに好ましく、ジメチルポリシロキサン、メチルトリメチコンから選ばれる1種又は2種以上を用いるのがよりさらに好ましい。
(ジメチコン/フェニルジメチコン)クロスポリマーとしては、メチルフェニルポリシロキサンとの混合物であるKSG-18(信越化学工業社製)などの市販品を用いることができる。
また、(ビニルジメチコン/ラウリルジメチコン)クロスポリマーとしては、流動パラフィンとの混合物であるKSG-41、軽質イソパラフィンとの混合物であるKSG-42、トリ-2-エチルヘキサン酸グリセリルとの混合物であるKSG-43、スクワランとの混合物であるKSG-44(以上、信越化学工業社製)などの市販品を用いることができる。
さらに、アルキル(C30-45)セテアリルジメチコンクロスポリマーとしては、シクロペンタシロキサンとの混合物であるVelvesil 125(モメンティブ・パフォーマンス・マテリアルズ社製)などの市販品を用いることができる。
また、セテアリルジメチコンクロスポリマーとしては、ジメチコンの混合物であるVelvesil DM(モメンティブ・パフォーマンス・マテリアルズ社製)などの市販品を用いることができる。
架橋型ポリエーテル変性シリコーンは、化粧料中への分散性、作業性の点から、液状油によって希釈された分散液として用いるのが好ましく、シリコーン油、炭化水素油、エステル油を用いるのがより好ましく、シリコーン油、炭化水素油を用いるのがよりさらに好ましい。
さらに、揮発性炭化水素油に希釈又は分散されたものが好ましく、揮発性炭化水素油としては、イソドデカンがより好ましい。
架橋型オルガノポリシロキサンとしては、架橋型アルキルポリシロキサン、架橋型ジメチルポリシロキサンから選ばれる1種又は2種以上を含むのが好ましく、(ジメチコン/ビニルジメチコン)クロスポリマー、(ジメチコン/フェニルジメチコン)クロスポリマー、(ビニルジメチコン/ラウリルジメチコン)クロスポリマーがより好ましく、(ジメチコン/ビニルジメチコン)クロスポリマーがよりさらに好ましい。
具体的には、パルミチン酸デキストリン、パルミチン酸/2-エチルヘキサン酸デキストリン、ステアリン酸デキストリン、パルミチン酸/ステアリン酸デキストリン、オレイン酸デキストリン、イソパルミチン酸デキストリン、イソステアリン酸デキストリン、ミリスチン酸デキストリン等が挙げられる。
デキストリン脂肪酸エステルとしては、パルミチン酸デキストリン、パルミチン酸/2-エチルヘキサン酸デキストリンが好ましく、パルミチン酸デキストリンがより好ましい。
これらの市販品としては、千葉製粉社製のパルミチン酸デキストリン(レオパール KL2、レオパール KS2、レオパール TL2)、パルミチン酸/2-エチルヘキサン酸デキストリン(レオパール TT2)、ミリスチン酸デキストリン(レオパール MKL2)等が挙げられる。
着色顔料としては、通常の化粧料に用いられるもので、例えば、酸化チタン、酸化亜鉛、酸化セリウム、酸化アルミニウム、黄酸化鉄、黒酸化鉄、ベンガラ、紺青、群青、酸化クロム、水酸化クロム等の金属酸化物、マンガンバイオレット、チタン酸コバルト等の金属錯体、更にカーボンブラック等の無機顔料;赤色3号、赤色104号、赤色106号、赤色201号、赤色202号、赤色204号、赤色205号、赤色220号、赤色226号、赤色227号、赤色228号、赤色230号、赤色401号、赤色405号、赤色505号、橙色203号、橙色204号、橙色205号、黄色4号、黄色5号、黄色401号、青色1号、青色404号等の合成有機顔料、有機色素及びそのレーキ顔料;β-カロチン、カラメル、パプリカ色素等の天然有機色素等が挙げられ、これらの着色顔料の複合体、これらの着色顔料を硫酸バリウムやタルク等の体質顔料で希釈した混合顔料などが挙げられる。
着色顔料としては、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、金属酸化物を含むのが好ましく、酸化チタン、酸化亜鉛、黄酸化鉄、黒酸化鉄、ベンガラから選ばれる1種又は2種以上を含むのがより好ましく、酸化チタン、黄酸化鉄、黒酸化鉄、ベンガラから選ばれる1種又は2種以上を含むのがさらに好ましい。
疎水化処理としては、通常の化粧料用粉体に施されている処理であれば制限されず、シリコーン系化合物、金属石鹸、アミノ酸系化合物、レシチン、油剤、有機チタネート等の表面処理剤を用い、乾式処理、湿式処理等を行えばよい。
表面処理剤の具体例としては、メチルトリメトキシシラン、エチルトリメトキシシラン、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、トリエトキシカプリリルシラン等のアルキルアルコキシシラン、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、環状シリコーン、架橋型シリコーン、シリコーン樹脂、アクリル変性シリコーン等のシリコーン系化合物;ステアリン酸アルミニウム、ミリスチン酸アルミニウム、ステアリン酸亜鉛、ステアリン酸マグネシウム等の金属石鹸;プロリン、ヒドロキシプロリン、アラニン、グリシン、サルコシン、グルタミン酸、アスパラギン酸、リジン及びそれらの誘導体等のアミノ酸;ステアロイルグルタミン酸、ラウロイルアスパラギン酸、ジラウロイルグルタミン酸リシン、ラウロイルリシン等のアシル化アミノ酸;レシチン、水添レシチン;ポリイソブチレン、ワックス、油脂、脂肪酸等の油剤;イソプロピルトリイソステアロイルチタネート等の有機チタネートなどが挙げられる。
なお、前記アシル化アミノ酸としては、アシル化アミノ酸の塩が含まれ、アシル化アミノ酸の塩としては、Na、Ca、Al、Mg、Zn、Zr、Ti塩が挙げられ、Na、Ca塩から選ばれる1種又は2種以上を含むのが好ましく、Na塩を含むのがより好ましい。また、アシル化アミノ酸塩としては、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、ステアロイルグルタミン酸2Na、ラウロイルアスパラギン酸Naから選ばれる1種又は2種以上を含むのが好ましく、ステアロイルグルタミン酸2Naを含むのがより好ましい。
表面処理剤としては、粘度の安定性、塗布時の伸び、肌への付着感、仕上がりのカバー力、顔全体のきれいな仕上がり感を向上させる観点から、シリコーン系化合物、アシル化アミノ酸、有機チタネートから選ばれる1種又は2種以上を含むのが好ましく、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、アルキルアルコキシシラン、ステアロイルグルタミン酸2Na、ラウロイルアスパラギン酸Na、イソプロピルトリイソステアロイルチタネートから選ばれる1種又は2種以上を含むのがより好ましく、ジメチルポリシロキサン、ステアロイルグルタミン酸2Na、イソプロピルトリイソステアロイルチタネートから選ばれる1種又は2種以上を含むのがさらに好ましく、ステアロイルグルタミン酸2Naがよりさらに好ましい。
疎水化処理の処理量は、溶媒へ分散性向上の点から、被覆粉体の量に対して0.1~15質量%であるのが好ましく、1~12質量%がより好ましい。
なお、着色顔料を疎水化処理した場合、着色顔料の含有量は、疎水化処理した剤を含めての含有量を意味する
本発明の油中水型乳化組成物は、塗布時の伸び、肌への付着感、仕上がりのカバー力を向上させる観点から、30℃における粘度が、15000mPa・s以上であるのが好ましく、18000mPa・s以上がより好ましく、20000mPa・s以上がさらに好ましく、22000mPa・s以上がよりさらに好ましく、200000mPa・s以下が好ましく、100000mPa・s以下がより好ましく、75000mPa・s以下がさらに好ましく、50000mPa・s以下がよりさらに好ましい。また、本発明の油中水型乳化組成物は、30℃における粘度が15000~200000mPa・sであるのが好ましく、18000~100000mPa・sがより好ましく、20000~75000mPa・sがさらに好ましく、22000~50000mPa・sがよりさらに好ましい。
本発明の油中水型乳化組成物は、比較的高粘度で、充填などによる圧力が加えられて粘度が低下した場合であっても、圧力が加えられる前の粘度に回復しやすいものである。
また、本発明の油中水型乳化組成物は、油中水型乳化化粧料とするのが好ましく、皮膚用油中水型乳化化粧料とするのがより好ましく、紫外線防御化粧料、メイクアップ化粧料とするのがさらに好ましく、メイクアップ化粧料とするのがよりさらに好ましい。
本発明の油中水型乳化組成物は、例えば、化粧下地、ファンデーション、コンシーラー;ほお紅、アイシャドウ、マスカラ、アイライナー、アイブロウ、オーバーコート剤、口紅等のメイクアップ化粧料;日やけ止め乳液、日焼け止めクリーム等の紫外線防御化粧料;スキンケア乳液、スキンケアクリーム、BBクリーム、美容液等のスキンケア化粧料などとして適用することができる。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物、
(B)25℃で液状のフェニル変性シリコーン、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーン
を含有する油中水型乳化組成物。
<3>成分(A)の含有量が、好ましくは、全組成中に0.01質量%以上であって、0.1質量%以上がより好ましく、0.5質量%以上がさらに好ましく、0.8質量%以上がよりさらに好ましく、1.4質量%以上がことさら好ましく、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下がさらに好ましく、2.5質量%以下がよりさらに好ましく、1.8質量%以下がことさら好ましい、前記<1>又は<2>記載の油中水型乳化組成物。
<5>成分(B)が、好ましくは、フェニルトリメチコン及びジフェニルシロキシフェニルトリメチコンから選ばれる1種又は2種以上であって、ジフェニルシロキシフェニルトリメチコンを含むのがより好ましい、前記<1>~<4>のいずれか1記載の油中水型乳化組成物。
<7>成分(B)に対する成分(A)の質量割合(A)/(B)が、好ましくは、0.05以上であって、0.1以上がより好ましく、0.12以上がさらに好ましく、0.15以上がよりさらに好ましく、0.2以上がより好ましく、0.23以上がよりさらに好ましく、1以下が好ましく、0.5以下がより好ましく、0.45以下がさらに好ましく、0.40以下がよりさらに好ましく、0.36以下がより好ましく、0.3以下がよりさらに好ましい、前記<1>~<6>のいずれか1記載の油中水型乳化組成物。
<9>成分(C)が、好ましくは、モノイソステアリン酸ソルビタン、モノオレイン酸ソルビタン及びセスキステアリン酸ソルビタンから選ばれる1種又は2種以上であって、モノイソステアリン酸ソルビタン及びセスキステアリン酸ソルビタンから選ばれる1種又は2種以上を含むのがより好ましく、モノイソステアリン酸ソルビタンを含むのがさらに好ましい、前記<1>~<8>のいずれか1記載の油中水型乳化組成物。
<11>成分(C)の含有量が、好ましくは、全組成中に0.0001~0.3質量%である、前記<1>~<10>のいずれか1記載の油中水型乳化組成物。
<12>成分(C)に対する成分(B)の質量割合(B)/(C)が、好ましくは、20以上であって、60以上がより好ましく、150以上がさらに好ましく、200以上がよりさらに好ましく、2000以上がよりさらに好ましく、80000以下が好ましく、60000以下がより好ましく、30000以下がさらに好ましく、7000以下がよりさらに好ましい、前記<1>~<11>のいずれか1記載の油中水型乳化組成物。
<14>成分(D)が、好ましくは、HLBが1以上であって、3以上がより好ましく、12以下が好ましく、10以下がより好ましく、8以下がさらに好ましく、6以下がよりさらに好ましい、前記<1>~<13>のいずれか1記載の油中水型乳化組成物。
<15>成分(D)が、好ましくは、セチルPEG/PPG-10/1ジメチコン、PEG/PPG-19/19ジメチコン、PEG10-ジメチコンから選ばれる1種又は2種以上であって、セチルPEG/PPG-10/1ジメチコン、PEG/PPG-19/19ジメチコンから選ばれる1種又は2種以上を含むのがより好ましく、セチルPEG/PPG-10/1ジメチコンがさらに好ましい、前記<1>~<14>のいずれか1記載の油中水型乳化組成物。
<16>成分(D)の含有量が、好ましくは、全組成中に0.1質量%以上であって、0.5質量%以上がより好ましく、1質量%以上がさらに好ましく、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下がさらに好ましい、前記<1>~<15>のいずれか1記載の油中水型乳化組成物。
<18>成分(E)が、好ましくは、モノエステル、ジエステル、トリエステルから選ばれる1種又は2種以上であって、モノエステル、ジエステルから選ばれる1種又は2種以上を含むのがより好ましい、前記<17>記載の油中水型乳化組成物。
<19>成分(E)が、好ましくは、モノエステルとジエステルを組合わせて用いる、前記<17>又は<18>記載の油中水型乳化組成物。
<20>成分(E)の含有量が、好ましくは、全組成中に1質量%以上であって、2質量%以上がより好ましく、3質量%以上がさらに好ましく、20質量%以下が好ましく、15質量%以下がより好ましく、10質量%以下がさらに好ましい、前記<17>~<19>のいずれか1記載の油中水型乳化組成物。
<22>成分(F)が、好ましくは、架橋型オルガノポリシロキサン、デキストリン脂肪酸エステル、25℃で固体の油性成分から選ばれる1種又は2種以上であって、架橋型オルガノポリシロキサンがより好ましく、架橋型ジメチルポリシロキサン、架橋型アルキルポリシロキサンから選ばれる1種又は2種以上を含むのがさらに好ましく、(ジメチコン/ビニルジメチコン)クロスポリマー、(ジメチコン/フェニルジメチコン)クロスポリマー、(ビニルジメチコン/ラウリルジメチコン)クロスポリマーから選ばれる1種又は2種以上を含むのがよりさらに好ましく、(ジメチコン/ビニルジメチコン)クロスポリマーがことさら好ましい、前記<21>記載の油中水型乳化組成物。
<23>成分(F)の含有量が、好ましくは、全組成中に0.1質量%以上であって、0.2質量%以上がより好ましく、0.3質量%以上がさらに好ましく、0.5質量%以上がよりさらに好ましく、20質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がさらに好ましく、2質量%以下がよりさらに好ましい、前記<21>又は<22>記載の油中水型乳化組成物。
<25>成分(G)が、金属酸化物を含むのが好ましく、酸化チタン、酸化亜鉛、黄酸化鉄、黒酸化鉄、ベンガラから選ばれる1種又は2種以上を含むのがより好ましく、酸化チタン、黄酸化鉄、黒酸化鉄、ベンガラから選ばれる1種又は2種以上を含むのがさらに好ましい、前記<24>記載の油中水型乳化組成物。
<26>成分(G)が、好ましくは、疎水化処理されたものであって、表面処理剤が、シリコーン系化合物、アシル化アミノ酸、有機チタネートから選ばれる1種又は2種以上を含むのが好ましく、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、アルキルアルコキシシラン、ステアロイルグルタミン酸2Na、ラウロイルアスパラギン酸Na、イソプロピルトリイソステアロイルチタネートから選ばれる1種又は2種以上を含むのがより好ましく、ジメチルポリシロキサン、ステアロイルグルタミン酸2Na、イソプロピルトリイソステアロイルチタネートから選ばれる1種又は2種以上を含むのがさらに好ましく、ステアロイルグルタミン酸2Naがよりさらに好ましい、前記<24>又は<25>記載の油中水型乳化組成物。
<28>成分(C)に対する成分(G)の質量割合(G)/(C)が、好ましくは、500以上であって、5000以上がより好ましく、8000以上がさらに好ましく、10000以上がよりさらに好ましく、200000以下が好ましく、100000以下がより好ましく、60000以下がさらに好ましく、20000以下がよりさらに好ましい、前記<24>~<27>のいずれか1記載の油中水型乳化組成物。
<30>30℃における粘度が、好ましくは、15000mPa・s以上であって、18000mPa・s以上がより好ましく、20000mPa・s以上がさらに好ましく、22000mPa・s以上がよりさらに好ましく、200000mPa・s以下が好ましく、100000mPa・s以下がより好ましく、75000mPa・s以下がさらに好ましく、50000mPa・s以下がよりさらに好ましい、前記<1>~<29>のいずれか1記載の油中水型乳化組成物。
<32>好ましくは、油中水型乳化化粧料であって、皮膚用油中水型乳化化粧料がより好ましく、紫外線防御化粧料、メイクアップ化粧料がさらに好ましく、メイクアップ化粧料とするのがよりさらに好ましい、前記<1>~<31>のいずれか1記載の油中水型乳化組成物。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物 0.01~10質量%、
(B)25℃で液状のフェニル変性シリコーン 1~25質量%、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーン 0.1~10質量%
を含有する皮膚外用剤組成物。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物 0.8~2.5質量%、
(B)25℃で液状のフェニル変性シリコーン 3.5~10質量%、
(C)ソルビタン脂肪酸エステル 0.00005~0.05質量%、
(D)ポリエーテル変性シリコーン 0.1~10質量%
を含有する皮膚外用剤組成物。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物 0.01~10質量%、
(B)25℃で液状のフェニル変性シリコーン 1~25質量%、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーン 0.1~10質量%、
(E)25℃で液状のエステル油 1~20質量%、
(F)成分(A)以外の油性ゲル化剤 0.1~20質量%、
(G)着色顔料 0.01~40質量%
を含有する皮膚外用剤組成物。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物 0.8~2.5質量%、
(B)25℃で液状のフェニル変性シリコーン 3.5~10質量%以下、
(C)ソルビタン脂肪酸エステル 0.00005~0.05質量%、
(D)ポリエーテル変性シリコーン 0.1~10質量%、
(E)25℃で液状のエステル油 3~10質量%、
(F)架橋型オルガノポリシロキサン 0.5~2質量%、
(G)着色顔料 5~20質量%
を含有する皮膚外用剤組成物。
<38>前記<1>~<32>のいずれか1記載の油中水型乳化組成物を、皮膚、好ましくは顔に塗布する、メイクアップのための使用。
<39>油中水型乳化化粧料製造のための、前記<1>~<32>のいずれか1記載の油中水型乳化組成物の使用。
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物、
(B)25℃で液状のフェニル変性シリコーン、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーンを配合してなる油中水型乳化組成物。
表1に示す組成の油中水型乳化化粧料(ファンデーション)を製造し、製造直後及び1カ月保存後の粘度を測定するとともに、充填機による圧力を加えた際の粘度安定性、塗布時の伸び感、肌への付着感及びカバー力を評価した。結果を表1に併せて示す。
なお、比較例1及び比較例2は、粘度が低いため、充填機による圧力を加えた際の粘度安定性の評価は行わなかった。
成分(A)、(B)、(C)、(D)、(E)、(F)、(G)を含む油相に、水相成分を加えて混合することにより、油中水型乳化化粧料を得た。
(1)粘度測定:
各油中水型乳化化粧料について、製造直後及び30℃で1か月保存した後の粘度を、30℃において、ヘリカル型粘度計(TVB-10型、東機産業社製)、ロータH-T-C、回転数10、測定時間60秒により測定した。なお、これらの粘度は、下記(2)に記載された充填機による圧力を加えていない。
粘度の数値は、表1中の以下の項目に記載した。
(ア):直後粘度(30℃)/mPa・s
(イ):1か月後粘度(30℃)/mPa・s
各油中水型乳化化粧料に対し、以下の条件の充填機による圧力を加え、各油中水型乳化化粧料40gを50mLのサンプル瓶に入れ、30℃で1か月保存後の粘度(ウ)を、前記(1)と同様にして測定した。
これらの粘度から、下記式により、充填機による圧力を加えた際の粘度安定性(粘度の回復性)を求めた。100%に近いほど、粘度変化が小さいので優れている。
充填機による圧力を加えた際の粘度安定性(粘度の回復性)(%)
=(((ウ):圧力を加えた後の1か月後粘度)/((イ)1か月後粘度))×100
・充填機による圧力の条件:アラハタフードマシン社製、電動型ピストン式充填機 SBK-1-9L、Φ40シリンダー、ノズル内径 Φ5mm、充填時間:0.3(sec)
3名の専門評価者が、各油中水型乳化化粧料0.03gを、指を用いて前腕内側の肌に2×3cm2の大きさに塗布し、塗布時の伸ばしやすさについて、下記の5段階で評価した。結果は、3名の合計点で示した。
5;伸びが非常に良い。
4;伸びが良い。
3;伸びがやや良い。
2;伸びがあまり良くない。
1;伸びが悪い。
3名の専門評価者が、指を用いて各油中水型乳化化粧料0.03gを、指を用いて前腕内側の肌に2×3cm2の大きさに塗布し、1秒に1往復の速さで20秒間マッサージしたとき、化粧料の肌への付着感について、下記の5段階で評価した。結果は、3名の合計点で示した。
なお、肌への付着感とは、20秒マッサージした後に、指が吸い付くように止まる感覚があり、油中水型乳化化粧料が肌に密着して付着した実感があることを示す。
5;付着感が明らかにある。
4;付着感がある。
3;付着感がややある。
2;付着感があまりない。
1;付着感がない。
3名の専門評価者が、各油中水型乳化化粧料0.25gを、指を用いて顔に塗布したとき、毛穴と色ムラに対するカバー力について、下記の5段階で評価した。結果は、3名の合計点で示した。
5;カバー力が明らかにある。
4;カバー力がある。
3;カバー力がややある。
2;カバー力があまりない。
1;カバー力がない。
*1:セチルPEG/PPG-10/1ジメチコン;Evonik Operations GmbH製、ABIL EM 90
*2:PEG/PPG-19/19ジメチコン(50質量%イソパラフィン分散液);ダウ・東レ社製、DOWSIL BY 25-337
*3:イソステアリン酸ソルビタン;Croda Europe Ltd製、スパン 120-LQ-(RB)
*4:メチルトリメチコン;信越化学工業社製、TMF-1.5(-G)
*5:ジフェニルシロキシフェニルトリメチコン;信越化学工業社製、シリコーン KF-56A
*6:メトキシケイヒ酸エチルヘキシル;BASF SE製、ユビナール MC80
*7:ジカプリル酸PG;日本サーファクタント工業社製、NIKKOL SEFSOL-228
*8:(ジメチコン/ビニルジメチコン)クロスポリマー(35質量%メチルトリメチコン分散液)、大東化成工業社製、TOREFIL(35%)C/TMF(ポリマー:35質量%、メチルトリメチコン:65質量%)
*9:(ジメチコン/ビニルジメチコン)クロスポリマー(25質量%ジメチルポリシロキサン分散液);信越化学工業社製、シリコーン KSG-16(ポリマー:25質量%、ジメチルポリシロキサン:75質量%)
*10:N-ステアロイル-Lグルタミン酸二Na 3質量%処理酸化チタン(80質量%シクロペンタシロキサン分散液);三好化成社製、SA/NAI-TR-10/D5(80%)M C D(着色顔料:80質量%、シクロペンタシロキサン:20質量%)
*11:N-ステアロイル-Lグルタミン酸二Na 3質量%処理ベンガラ(65質量%シクロペンタシロキサン分散液);三好化成社製、SA/NAI-R-10/D5(65%)M C D(着色顔料:65質量%、シクロペンタシロキサン:35質量%)
*12:N-ステアロイル-Lグルタミン酸二Na 3質量%処理黄酸化鉄(70質量%シクロペンタシロキサン分散液);三好化成社製、SA/NAI-Y-10/D5(70%)M C D(着色顔料:70質量%、シクロペンタシロキサン:30質量%)
*13:N-ステアロイル-Lグルタミン酸二Na 3質量%処理黒酸化鉄(75質量%シクロペンタシロキサン分散液);三好化成社製、SA/NAI-B-10/D5(75%)M C D(着色顔料:75質量%、シクロペンタシロキサン:25質量%)
*14:ジメチルジステアリルアンモニウムヘクトライト;Elementis Specialties, Inc.(US)、ベントン 38VCG
*15:ベンジルジメルステアリルアンモニウムヘクトライト(12.5質量%(トリ(カプリル酸/カプリン酸)グリセリル・炭酸プロピレン混合液)分散液);Elementis Specialties, Inc.(US)、BENTONE GEL GTCC V (粘土鉱物:12.5質量%)
*16:ベンジルジメルステアリルアンモニウムヘクトライト(12.5質量%(安息香酸アルキル(C12-15)・炭酸プロピレン混合液)分散液);Elementis Specialties, Inc.(US)、BENTONE GEL TN V (粘土鉱物:12.5質量%)
実施例1~12と同様にして、表2~表4に示す組成の油中水型乳化化粧料を製造した。
得られた油中水型乳化化粧料はいずれも、充填機による圧力が加えられたことによる粘度低下が起こっても回復しやすく、粘度の安定性が良好で、塗布時の伸び、肌への付着感、仕上がりのカバー力に優れている。
*18:PEG10-ジメチコン;信越化学工業社製、KF-6017
*19:ジフェニルシロキシフェニルトリメチコン;ダウ・東レ社製、DOWSIL FZ-209
*20:フェニルトリメチコン;ダウ・東レ社製 、DOWSIL SH 556 FLUID
*22:ポリ(N-プロピオニルエチルイミン)変性シリコーン;特開2016-222599号公報、合成例3記載の化合物
*23:2-[4-(ジエチルアミノ)-2-ヒドロキシベンゾイル]安息香酸ヘキシルエステル;BASF SE、ユビナール A PLUS GRANULAR
*24:ジメチコジエチルベンザルマロネート;DSM Nutritional Products Ltd.、パルソールSLX
*25:2,4-ビス-[{4-(2-エチルヘキシルオキシ)-2-ヒドロキシ}-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン;BASF SE、TINOSORB S
*26:微粒子酸化チタン(50質量%シクロペンタシロキサン分散液);三好化成社製、SA-UT-A40/D5
*27:微粒子酸化亜鉛(45質量%シクロペンタシロキサン分散液);テイカ社製、OSMZ300/45%スラリー
*28;ジメチルポリシロキサン処理無水ケイ酸;三好化成社製、MIYOFEEL SA-SB-N1
*29:ジメチルポリシロキサン処理酸化亜鉛;テイカ社製、MZY-505M
*31:水添ポリイソブテン;日油社製、パールリーム 4
*32:ASI処理酸化チタン;大東化成工業社製、BCASI TIO2 MP-701(酸化チタン98質量%に対し、イソプロピルトリイソステアロイルチタネート1.5質量%、ラウロイルアスパラギン酸ナトリウム0.42質量%、塩化亜鉛0.08質量%で被覆処理したもの)
*33:ASI処理ベンガラ;大東化成工業社製、ASI RED R-516P(ベンガラ98質量%に対し、*32と同様の表面処理をしたもの)
*34:ASI処理黄酸化鉄;大東化成工業社製、ASI YELLOW LL-100P(黄色酸化鉄98質量%に対し、*32と同様の表面処理をしたもの)
*35:ASI処理黒酸化鉄;大東化成工業社製、ASI BLACK BL-100P(黒色酸化鉄98質量%に対し、*2と同様の表面処理をしたもの)
実施例1~12と同様にして、表5に示す組成の油中水型乳化化粧料(ファンデーション)を製造し、製造直後及び1カ月保存後の粘度を測定するとともに、充填機による圧力を加えた際の粘度安定性、塗布時の伸び感、肌への付着感及びカバー力を評価した。結果を表5に併せて示す。
Claims (15)
- 次の成分(A)、(B)、(C)及び(D):
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物、
(B)25℃で液状のフェニル変性シリコーン、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーン
を含有する油中水型乳化組成物。 - 成分(C)に対する成分(B)の質量割合(B)/(C)が、20~80000である請求項1記載の油中水型乳化組成物。
- 成分(A)の含有量が、0.01~10質量%である請求項1又は2記載の油中水型乳化組成物。
- 成分(B)の含有量が、1~25質量%である請求項1~3のいずれか1項記載の油中水型乳化組成物。
- 成分(D)の含有量が、0.1~10質量%である請求項1~4のいずれか1項記載の油中水型乳化組成物。
- 成分(C)の含有量が、0.0001~0.3質量%である請求項1~5のいずれか1項記載の油中水型乳化組成物。
- 成分(B)に対する成分(A)の質量割合(A)/(B)が、0.05~1である請求項1~6のいずれか1項記載の油中水型乳化組成物。
- さらに、(E)25℃で液状のエステル油を含有する請求項1~7のいずれか1項記載の油中水型乳化組成物。
- さらに、油性ゲル化剤を含有する請求項1~8のいずれか1項記載の油中水型乳化組成物。
- さらに、着色顔料を含有する請求項1~9のいずれか1項記載の油中水型乳化組成物。
- 皮膚用油中水型乳化化粧料である、請求項1~10のいずれか1項記載の油中水型乳化組成物。
- 請求項1~11のいずれか1項記載の油中水型乳化組成物の、メイクアップ化粧料としての使用。
- 請求項1~11のいずれか1項記載の油中水型乳化組成物を、皮膚、好ましくは顔に塗布する、メイクアップのための使用。
- 油中水型乳化化粧料製造のための、請求項1~11のいずれか1項記載の油中水型乳化組成物の使用。
- 次の成分(A)、(B)、(C)及び(D):
(A)第四級アンモニウムイオンで置換されたカチオン変性粘土鉱物、
(B)25℃で液状のフェニル変性シリコーン、
(C)ソルビタン脂肪酸エステル 0.00005~0.3質量%、
(D)ポリエーテル変性シリコーンを配合してなる油中水型乳化組成物。
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JP2008201701A (ja) * | 2007-02-20 | 2008-09-04 | Tokiwa Corp | 油中水型乳化メーキャップ化粧料 |
JP2010111634A (ja) * | 2008-11-07 | 2010-05-20 | Shiseido Co Ltd | 油中水型乳化ベースメーキャップ化粧料 |
JP2016199482A (ja) * | 2015-04-08 | 2016-12-01 | 株式会社伊勢半 | 油中水乳化型化粧料 |
JP2016222599A (ja) | 2015-05-29 | 2016-12-28 | 花王株式会社 | 油中水型乳化化粧料 |
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JP7067860B2 (ja) | 2016-10-31 | 2022-05-16 | 花王株式会社 | 油中水型乳化化粧料の製造方法 |
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JP2008201701A (ja) * | 2007-02-20 | 2008-09-04 | Tokiwa Corp | 油中水型乳化メーキャップ化粧料 |
JP2010111634A (ja) * | 2008-11-07 | 2010-05-20 | Shiseido Co Ltd | 油中水型乳化ベースメーキャップ化粧料 |
JP2016199482A (ja) * | 2015-04-08 | 2016-12-01 | 株式会社伊勢半 | 油中水乳化型化粧料 |
JP2016222599A (ja) | 2015-05-29 | 2016-12-28 | 花王株式会社 | 油中水型乳化化粧料 |
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CN117425463A (zh) | 2024-01-19 |
TW202312977A (zh) | 2023-04-01 |
EP4349415A1 (en) | 2024-04-10 |
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