WO2023127521A1 - Foam aerosol cosmetic preparation - Google Patents
Foam aerosol cosmetic preparation Download PDFInfo
- Publication number
- WO2023127521A1 WO2023127521A1 PCT/JP2022/046181 JP2022046181W WO2023127521A1 WO 2023127521 A1 WO2023127521 A1 WO 2023127521A1 JP 2022046181 W JP2022046181 W JP 2022046181W WO 2023127521 A1 WO2023127521 A1 WO 2023127521A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- component
- modified silicone
- foam
- present
- Prior art date
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 36
- 239000000443 aerosol Substances 0.000 title claims abstract description 22
- 239000006260 foam Substances 0.000 title abstract description 26
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 239000003380 propellant Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims description 19
- 239000011550 stock solution Substances 0.000 claims description 13
- 239000010419 fine particle Substances 0.000 claims description 7
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- 239000007788 liquid Substances 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract 2
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
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- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 230000000171 quenching effect Effects 0.000 description 1
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- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- UUJLHYCIMQOUKC-UHFFFAOYSA-N trimethyl-[oxo(trimethylsilylperoxy)silyl]peroxysilane Chemical compound C[Si](C)(C)OO[Si](=O)OO[Si](C)(C)C UUJLHYCIMQOUKC-UHFFFAOYSA-N 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
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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
-
- 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
- A61K8/27—Zinc; 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
- A61K8/72—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
- 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
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Definitions
- the present invention relates to an aerosol-type cosmetic that is discharged in foamy form.
- UV protective cosmetics In recent years, various formulations of UV protective cosmetics have been developed. Among them, foaming aerosol type cosmetics are characterized by the fact that they do not drip easily when applied to the palm of the hand and provide a light feel when spread out. popular with general consumers. They are those in which a composition containing an ultraviolet absorber or ultraviolet scattering agent is filled in a pump foam container or an aerosol container together with high-pressure liquefied petroleum gas (LPG) to form foam.
- LPG liquefied petroleum gas
- An object of the present invention is to provide a foaming aerosol type cosmetic that can
- the present inventors have made intensive studies and found that a stock solution that is a water-in-oil emulsified composition using a specific polyether-modified silicone containing finely divided metal oxides whose surfaces have been subjected to a hydrophobizing treatment, and an injection A foaming aerosol-type cosmetic that is excellent in powder redispersibility even when left standing for a long period of time, as well as excellent foam retention and spreadability can be obtained by combining an aerosol with an agent. , completed the present invention.
- a foaming aerosol type cosmetic comprising a stock solution, which is a water-in-oil emulsion composition containing the following components (A) to (D), and a propellant.
- the ratio of the stock solution to the propellant is 85:15 to 98:2 [1].
- Foaming aerosol type cosmetics [3] The foaming aerosol type cosmetic according to [1] or [2], wherein the content of component (B) in the stock solution is 30 to 55% by mass.
- the foaming aerosol-type cosmetic of the present invention even if it is left standing for a long period of time, solidification of the fine particle metal oxide is unlikely to occur and it is excellent in redispersibility, so that it can be stored and used for a long period of time.
- the foamy aerosol-type cosmetic of the present invention does not aggregate powder even when a large amount of finely divided metal oxide is blended, so it forms soft and fine bubbles, spreads smoothly, and evenly coats the cosmetic film. Excellent in sex. Furthermore, it has both good foam retention and spreadability, and is excellent in usability. Therefore, it is useful as a sunscreen cosmetic or make-up cosmetic having a high UV protection effect.
- X to Y includes X and Y and means “X or more and Y or less”.
- Component (A) fine particle metal oxide surface-hydrophobized
- the component (A) used in the present invention is obtained by coating the surface of fine metal oxide particles with a hydrophobizing agent to improve the dispersibility in the oil phase.
- the fine particle metal oxide that can be surface-hydrophobized is not particularly limited as long as it is commonly used in cosmetics, etc.
- examples include zinc oxide, titanium oxide, oxide Cerium, zirconium oxide, iron oxide and the like can be mentioned.
- zinc oxide, titanium oxide, and cerium oxide from the viewpoint of high UV blocking effect by absorbing, scattering, reflecting, and quenching a wide range of UV rays.
- Zinc oxide and/or titanium oxide are more preferable, and zinc oxide is even more preferable.
- the shape of the fine metal oxide particles is not particularly limited, but examples thereof include granular, spherical, spindle-shaped, dendritic, and balloon-shaped. , from the viewpoint of UV protection effect and water resistance, it is preferably granular, spherical, or spindle-shaped.
- the particle size of the fine particle metal oxide is not particularly limited, but the average particle size is preferably 1 nm to 300 nm, more preferably 5 nm to 100 nm, from the viewpoints of reducing whitening, UV protection and water resistance. More preferably, it is 10 nm to 50 nm.
- the average particle size is measured as the volume average particle size (D50) using a laser scattering particle size distribution analyzer (manufactured by HORIBA).
- the surface hydrophobizing agent of component (A) is not particularly limited as long as it is commonly used in cosmetics and the like.
- examples include silicone treating agents, fluorine treating agents, organic titanate treating agents, Fatty acid treating agents, acyl amino acid treating agents and the like can be mentioned.
- silicone treatment agents and organic titanate treatment agents are preferred.
- silicone treatment agents include linear silicones such as low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, amino-modified silicones, alkyl-modified silicones, and alkoxy-modified silicones.
- modified silicones such as trimethylsiloxysilicate and acrylic-silicone graft copolymers, silicone resins, silicone rubbers, partially or fully crosslinked organopolysiloxanes, silylating agents, silane coupling agents, and the like.
- silane coupling agents One or more selected from these can be used. Among them, it is preferable to use silane coupling agents.
- trialkoxyalkylsilanes are preferred.
- a trialkoxyalkylsilane is a compound in which three alkoxy groups and one alkyl group are bonded to a silicon atom, and the alkoxy groups chemically modify the powder surface by reacting with hydroxyl groups on the powder surface. is a compound.
- the alkoxy group in the trialkoxyalkylsilane is preferably an alkoxy group having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group and a propoxy group.
- the alkyl group in the trialkoxyalkylsilane is preferably an alkyl group having 6 to 18 carbon atoms, and preferably includes a hexyl group, an octyl group, a decyl group and an octadecyl group.
- Such trialkoxyalkylsilanes are specifically trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane, triethoxydecylsilane, tri and ethoxyoctadecylsilane.
- one or more selected from trimethoxyoctylsilane and triethoxyoctylsilane is more preferable from the viewpoint of usability such as stability over time and spreadability without creaking.
- organic titanate treating agents include long-chain carboxylic acid-type, pyrophosphate-type, phosphorous acid-type, amino acid-type alkyl titanates, etc., and alkyl titanates having an alkyl group of 8 to 24 carbon atoms are preferred.
- the alkyl titanates of long-chain carboxylic acid type include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, and diisostearoyl titanate.
- pyrophosphate-type alkyl titanates include tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(ditridecylphosphite) titanate and the like, and phosphite-type alkyl titanates include isopropyl tri(dioctylpyrophosphate) titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate and the like.
- amino acid-type alkyl titanates examples include isopropyl tri(N-amidoethyl/aminoethyl) titanate.
- alkyl titanates long-chain carboxylic acid-type alkyl titanates are preferable, and isopropyl triisostearoyl titanate is more preferable, from the viewpoint of stability over time, water resistance, and the like.
- the coating amount of the surface hydrophobizing agent in component (A) is not particularly limited, but from the viewpoint of water resistance and stability over time, the upper limit is , 60% by mass (hereinafter simply abbreviated as “%”) or less, more preferably 40% or less, even more preferably 20% or less, and the lower limit is 2% or more. It is preferably 5% or more, more preferably 10% or more.
- component (A) there are no particular restrictions on the method of surface treatment for component (A), and it can be produced by a generally known method.
- a surface treatment agent and powder particles to be treated are added to a solvent, stirred with a ball mill or the like, dried if necessary, washed with water, and filtered repeatedly to remove contaminants, followed by drying, By pulverizing, the desired surface-treated powder can be obtained.
- component (A) in the present invention is 10 to 20% in the undiluted solution that is the water-in-oil emulsion composition. If it exceeds, the stability over time and the spreadability may be deteriorated.
- Component (A) is preferably 12% or more, more preferably 13% or more, in the undiluted solution.
- Component (A) is preferably 18% or less, more preferably 17% or less, in the undiluted solution.
- Component (B) oil
- the component (B) oil used in the present invention is not particularly limited as long as it is commonly used in cosmetics and the like, and has properties such as solid, paste, and liquid, and physical properties such as polar and non-polar. Also, hydrocarbons, oils and fats, waxes, esters, fatty acids, silicone oils, fluorinated oils and the like can be mentioned regardless of the origin of vegetable oils, mineral oils, synthetic oils and the like.
- hydrocarbons such as isododecane, isohexadecane, light isoparaffin, liquid paraffin (mineral oil), squalane, squalene, ⁇ -olefin oligomer, polybutene, liquid isoparaffin, heavy liquid isoparaffin, polyisobutylene, and hydrogenated polyisobutene.
- Brainssica seed oil avocado oil, almond oil, apricot kernel oil, perilla oil, orange oil, olive oil, kiwi seed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, sage oil, soybean oil, Tea seed oil, corn oil, rapeseed oil, evening primrose oil, camellia oil, persic oil, pearl barley oil, peanut oil, sunflower oil, grape seed oil, meadowfoam oil, rosemary oil, jojoba oil, macadamia nut oil, lavender oil, rose Fats and oils such as hip oil and mink oil; glyceryl tri-2-ethylhexanoate, isotridecyl isononanoate, isononyl isononanoate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, myristic acid Octyld
- Component (B) preferably contains an ester oil from the viewpoint of the solubility of the ultraviolet absorber described later and the feeling of use.
- an ester oil from the viewpoint of the solubility of the ultraviolet absorber described later and the feeling of use.
- propylene glycol dicaprate, alkyl benzoate (C12-15) It is more preferable to contain one or more selected from propylene glycol and cetyl 2-ethylhexanoate (capric acid).
- Component (B) may contain an oil-soluble ultraviolet absorber, and is not particularly limited as long as it is commonly used in cosmetics and the like, and may be solid, pasty, or liquid. .
- an oil-soluble ultraviolet absorber for example, 2-hydroxy-4-methoxybenzophenone, 2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine, salicylic acid- 2-ethylhexyl, ethyl para-dihydroxypropylbenzoate, ethylhexyl methoxycinnamate, 4-tert-4'-methoxydibenzoylmethane, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (diethylaminohydroxybenzoyl hexyl benzoate), Polysilicone-15, 2-ethylhexyl dimethoxybenzy
- ethylhexyl methoxycinnamate para-methoxycinnamate-2-ethylhexyl
- 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester 2,4-bis[ ⁇ 4- (2-ethylhexyloxy)-2-hydroxy ⁇ -phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine
- One or more selected from the group consisting of anilino]-1,3,5-triazine and 4-tert-butyl-4′-methoxydibenzoylmethane is more preferable.
- component (B) in the present invention is not particularly limited, but the lower limit is preferably 30% or more, more preferably 40% or more, in the stock solution that is the water-in-oil emulsion composition. Moreover, as an upper limit, 55% or less is preferable and 50% or less is more preferable. Within this range, the stability over time and spreadability are more excellent, which is more preferable.
- component (C) non-crosslinked polyether-modified silicone used in the present invention is a copolymer having at least an organopolysiloxane group and a hydrophilic group having a plurality of ether structures, and the organopolysiloxane group is It may be a graft copolymer having a hydrophilic group in a side chain as a main chain, or a linear block copolymer in which an organopolysiloxane group and a hydrophilic group are alternately bonded. does not contain a crosslinked structure.
- the organopolysiloxane group may be linear or may have a branched structure, and examples of the hydrophilic group include a polyoxyalkylene group and a polyglyceryl group.
- those having a linear organopolysiloxane group as a main chain include, specifically, polyoxyalkylene-modified organopolysiloxane (commercially available, for example, PEG10-dimethicone). KF-6017" manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyalkylene/alkyl co-modified organopolysiloxane (commercially available, for example, lauryl PEG/PPG-18/18 methicone "5200 Formulation Aid” manufactured by Dow Corning Toray) etc.
- polyoxyalkylene-modified organopolysiloxane commercially available, for example, PEG10-dimethicone
- KF-6017 manufactured by Shin-Etsu Chemical Co., Ltd.
- polyoxyalkylene/alkyl co-modified organopolysiloxane commercially available, for example, lauryl PEG/PPG-18/18 methicone "5200 Formulation Aid” manufactured by Dow Corning Toray
- a main chain having an organopolysiloxane group having a branched structure silicone branched polyether-modified silicone
- PEG-9 polydimethylsiloxyethyl dimethicone commercially available, for example, "KF- 6028” manufactured by Shin-Etsu Chemical Co., Ltd.
- lauryl PEG-9 polydimethylsiloxyethyl dimethicone commercially available, for example, "KF-6038” manufactured by Shin-Etsu Chemical Co., Ltd.
- block copolymer type examples include polyoxyethylene/butylene/dimethylpolysiloxane copolymer (commercially available, for example, "FZ-2250” manufactured by Dow Corning Toray Co., Ltd.), polyoxyethylene/poly Oxypropylene/butylene/dimethylpolysiloxane copolymer (commercially available products include “FZ-2233” manufactured by Dow Corning Toray Co., Ltd., and "SILWET 236-L” manufactured by Nihon Unicar Co., Ltd.).
- Component (C) may be used alone or in combination of two or more.
- the graft copolymer type is preferred, and the hydrophilic group is preferably a polyoxyalkylene chain, particularly polyoxyethylene. Chains are preferred, and non-crosslinked polyether-modified silicones with an oxyethylene degree of polymerization of 7-11 are particularly preferred.
- the organopolysiloxane group those having a branched structure are preferable, and it is more preferable to use both a linear structure and a branched structure.
- the average HLB of component (C) is preferably 1-7, more preferably 2.5-5.
- the HLB Hydrophilic-lipophilic Balance
- HLB "inorganic value (IV)/organic value (OV)” x 10 (Formula 1) (See Yoshio Koda, "Organic Conceptual Diagram -Basics and Applications-", pp. 11-17, Sankyo Publishing, 1984)
- the content of the component (C) in the present invention is not particularly limited. is preferred, and 0.2% or more is more preferred.
- the upper limit is preferably 3% or less, more preferably 2% or less, from the viewpoint of elongation and spreadability.
- Component (D) partially crosslinked polyether-modified silicone
- the component (D) cross-linked polyether-modified silicone used in the present invention is a polymer obtained by three-dimensionally cross-linking organopolysiloxane, and has a hydrophilic group such as a polyoxyalkylene group or a polyglycerin group in the molecule. It may be one in which a group is introduced, and one in which an organic group such as an alkyl group is co-modified.
- Component (D) is not particularly limited, but for example, partially crosslinked polyether-modified silicone such as (dimethicone/(PEG-10/15)) crosspolymer, partially crosslinked such as (PEG-15/lauryl dimethicone) crosspolymer, etc. type alkyl-polyether co-modified silicone, partially cross-linked polyglycerin-modified silicone such as (dimethicone/polyglycerin-3) crosspolymer, partially cross-linked alkyl-polyglycerin co-modified silicone such as (lauryl dimethicone/polyglycerin-3) crosspolymer Examples include modified silicones, and one or more of these can be used.
- Such component (D) is commercially available in the form of a mixture with silicone oil
- “KSG-210" solid content: 20-30%) is a mixture of partially crosslinked polyether-modified silicone and dimethylpolysiloxane.
- “KSG-310” solid content 25-35%
- “KSG-320” solid content 20-30%)
- “KSG-330” as a mixture of partially crosslinked alkyl-polyether co-modified silicone and oil agent (solid content 15-25%)
- KSG-340 solid content 25-35%
- KSG-710 solid content 20-30%) as a mixture of partially crosslinked polyglycerin-modified silicone and dimethylpolysiloxane
- KSG-810 solid content 25-35%
- “KSG-820” solid content 20-30%)
- “KSG-830” as a mixture of partially crosslinked alkyl-polyglycerin co-modified silicone and oil agent ” (solid content 15 to 25%)
- “KSG-840” solid content 25
- component (D) in the present invention is not particularly limited. The above is more preferable. Moreover, as an upper limit, 5% or less is preferable and 3% or less is more preferable. If the component (D) is within this range, it is preferable because it is possible to obtain a product that spreads more easily and has excellent stability over time and foam retention.
- the stock solution of the present invention is a water-in-oil emulsified composition
- an aqueous component such as water or a lower alcohol is added as a component constituting the aqueous phase in a quantitative amount that does not impair the effects of the present invention.
- component (C) surfactants other than component (D)
- powders other than component (A) water-soluble polymers, film-forming agents, antioxidants, pH adjusters, chelating agents, cosmetic ingredients, preservatives agents, fragrances, cooling agents, and the like.
- the aqueous component may be any component as long as it is water or a component soluble in water.
- examples include glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol, glycerin, diglycerin and polyglycerin.
- glycerols such as sorbitol, maltitol, sugar alcohols such as glucose, lower alcohols such as ethanol, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO), polyoxypropylene (9 ) glycerin derivatives such as diglyceryl;
- the method for producing the stock solution of the present invention is not particularly limited, and it is prepared by a conventional method.
- part of component (B) and component (A) are kneaded in advance using a roll mill, bead mill, or the like, and the remainder of component (B), component (C), and component (D) are added and mixed under heating.
- a water-in-oil type composition can be obtained by adding an aqueous component to the uniformly dispersed mixture and emulsifying it.
- the propellant used in the present invention contains a liquefied gas obtained by liquefying a gas that is gas at atmospheric pressure under high pressure.
- a gas that is gas at atmospheric pressure under high pressure.
- hydrocarbons having 2 to 5 carbon atoms include hydrocarbons having 2 to 5 carbon atoms and ethers such as dimethyl ether and diethyl ether.
- hydrocarbons having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane.
- LPG liquefied petroleum gas
- propane and butane as main components is preferable, and it is preferable to use one adjusted to a pressure of 0.3 to 0.8 MPa at 20°C.
- the propellant of the present invention can contain carbon dioxide, nitrogen, argon, etc. within a range that does not impair the effects of the present invention.
- the filling ratio of the stock solution to the propellant in the foaming aerosol type cosmetic of the present invention is preferably 85:15 to 98:2, more preferably 90:10 to 96:4, in mass ratio. Within this range, the stability is excellent even when left standing for a long period of time, and the foam retention is also good, which is preferable.
- the filling method of the foaming aerosol type cosmetic of the present invention is not particularly limited, but a stock solution prepared by a conventional method is filled in a pressure-resistant container, an aerosol valve is fixed to the container, and a propellant is injected through the valve. . Furthermore, an aerosol product can be obtained by attaching an injection member according to the purpose to the aerosol valve.
- the foamy aerosol-type cosmetic of the present invention has an ultraviolet protection effect, so it can be applied as a makeup base, foundation, daytime serum, sunscreen, and the like.
- Examples 1 to 11 and Comparative Examples 1 to 3 Foaming aerosol-type sunscreens
- Foaming aerosol-type sunscreens having the compositions shown in Table 1 below were prepared by the following production method, and foam retention, stability over time, and elongation The spreadability was evaluated and judged according to the evaluation method and judgment criteria shown below, and the results are also shown in Table 1.
- KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- KSG-210 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 20 to 30%
- KSG-710 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 20 to 30%
- KSG-310 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 25 to 35%
- Rheopearl ISK2 (manufactured by Chiba Flour Milling Co., Ltd.)
- KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- the foaming aerosol type sunscreens of Examples 1 to 11 are all excellent in foam retention and have good stability over time, so they are used in a fine foam state until the end. It was possible to do so, it spread smoothly, and it was excellent also in an ultraviolet protection effect.
- Comparative Example 1 in which the component (A) was excessive, was inferior in all evaluation items due to caking.
- Comparative Example 2 in which the component (C) was not blended, caused caking and was inferior in terms of foam retention and stability over time.
- Comparative Example 3 in which the component (D) was not blended was inferior in foam retention due to insufficient emulsifying power, and was also inferior in spreadability.
- Example 12 Non-chemical sunscreen (ingredient) (%) (1) Triethoxyoctylsilane-treated zinc oxide (Note 8) 20 (2) Stearic acid-treated titanium oxide (Note 9) 5 (3) Polyhydroxy stearic acid 0.3 (4) PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 0.2 (5) cetyl ethylhexanoate 15 (6) Dimethicone (6CS) 5 (7) Diphenyl dimethicone (Note 10) 5 (8) Diphenylsiloxyphenyl trimethicone (Note 11) 5 (9) PEG-10 dimethicone (Note 12) 0.7 (10) (Dimethicone/(PEG-10/15)) crosspolymer (Note 3) 1 (11) Talc 5 (12) Mica 1 (13) Ethanol 7 (14) Purified water remaining amount (15) Na chloride 0.3 (16) 1,3-butylene glycol 5 (17) Glycerin 1 (18) Dipropylene glyco
- A Uniformly mix and disperse components (7) to (10).
- B Components (1) to (6) are uniformly powder-dispersed.
- C Add B to A and mix and disperse uniformly.
- D Components (11) and (12) are added to C and uniformly mixed and dispersed.
- E Components (13) to (22) are uniformly mixed.
- F E is added to D and emulsified to obtain a water-in-oil emulsion composition.
- 10 parts of liquefied petroleum gas 0.4 MPa
- the non-chemical sunscreen of Example 12 had excellent stability over time, achieved both good foam retention and good spreadability, and had a uniform cosmetic film, as well as an excellent UV protection effect.
- Example 13 Base cosmetics (ingredients) (%) (1) Triethoxyoctylsilane (4%) treated zinc oxide (35 nm) 15 (2) PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 0.5 (3) cetyl ethylhexanoate 15 (4) Dimethicone (6CS) 5 (5) Diphenyl dimethicone (Note 10) 5 (6) Diphenylsiloxyphenyl trimethicone (Note 11) 5 (7) PEG-10 dimethicone (Note 12) 0.7 (8) (Dimethicone/(PEG-10/15)) crosspolymer (Note 10) 1 (9) Dimethicone (2%) treated talc 5 (10) Mica 1 (11) Ethanol 7 (12) Purified water remaining amount (13) Na chloride 0.3 (14) 1,3-butylene glycol 5 (15) Glycerin 1 (16) Phenoxyethanol 0.3 (17) Red 226 0.01 (18) Gunjo 0.05
- the base cosmetic of Example 13 was excellent in stability over time, had a uniform cosmetic film because it achieved both good foam retention and spreadability, and was also excellent in UV protection effect.
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Abstract
[Problem] The present invention addresses the problem of providing a foam aerosol cosmetic preparation which is capable of having both good foam retainability and good spreadability, while exhibiting excellent long-term stability even if a large amount of a fine particulate metal oxide is added thereto for the achievement of high ultraviolet light shielding performance. A foam aerosol cosmetic preparation according to the present invention, which has solved the problem, is characterized by being composed of a propellant and a starting material liquid that is a water-in-oil emulsion composition containing the components (A) to (D) described below. (A) a surface-hydrophobized fine particulate metal oxide in an amount of 10% by mass to 20% by mass in the starting material liquid
(B) an oil agent
(C) an uncrosslinked polyether-modified silicone
(D) a partially crosslinked polyether-modified silicone
Description
本発明は、泡沫状に吐出されるエアゾール型化粧料に関する。
The present invention relates to an aerosol-type cosmetic that is discharged in foamy form.
近年、様々な剤型の紫外線防御化粧料の開発が行われており、中でも泡沫性エアゾール型化粧料は、手のひらに塗布した際に垂れ落ちしにくいことや、伸び広げる時に軽い感触が得られることから一般消費者に好まれている。それらは、紫外線吸収剤や紫外線散乱剤を含有する組成物を、ポンプフォーマー容器や、高圧の液化石油ガス（ＬＰＧ）と共にエアゾール容器に充填して泡沫を形成するものであるが、より良好な使用感や品質向上のため、種々の検討がなされてきた。（例えば特許文献１～４参照）。
In recent years, various formulations of UV protective cosmetics have been developed. Among them, foaming aerosol type cosmetics are characterized by the fact that they do not drip easily when applied to the palm of the hand and provide a light feel when spread out. popular with general consumers. They are those in which a composition containing an ultraviolet absorber or ultraviolet scattering agent is filled in a pump foam container or an aerosol container together with high-pressure liquefied petroleum gas (LPG) to form foam. Various studies have been made to improve usability and quality. (See Patent Documents 1 to 4, for example).
紫外線防御化粧料においては、紫外線防御能を高める目的で、紫外線を反射および散乱させる微粒子金属酸化物を多量に配合する必要がしばしばある。しかし、これらをエアゾールという特殊環境下で保存すると、経時的にケーキング（粉体どうしが凝集固化した状態）が発生し、再分散しづらいという安定性不良を起こしたり、化粧膜が不均一になったりする場合があった。しかし、先行文献に開示された技術では、ケーキングによる経時安定性不良については、何ら検討されていない。また、泡保持性と伸び広がりの良さの両立の点においても、満足のいくものではなかった。
In UV protective cosmetics, it is often necessary to add a large amount of fine metal oxide particles that reflect and scatter UV rays in order to increase the UV protection ability. However, if these are stored in the special environment of an aerosol, caking (a state in which the powders aggregate and solidify) occurs over time, causing poor stability such as difficulty in redispersion and uneven cosmetic film. There was a case. However, in the techniques disclosed in the prior art documents, no consideration has been given to deterioration of stability over time due to caking. In addition, it was not satisfactory in terms of both good foam retention and good spreadability.
そこで本発明では、紫外線防御能のために微粒子金属酸化物を多量に配合しても、経時安定性に優れるため化粧膜の均一性が高く、さらに泡保持性と伸び広がりのよさを両立することができる泡沫性エアゾール型化粧料を提供することを課題とする。
Therefore, in the present invention, even if a large amount of fine particle metal oxide is blended for ultraviolet protection, the uniformity of the cosmetic film is high due to excellent stability over time, and it is possible to achieve both foam retention and spreadability. An object of the present invention is to provide a foaming aerosol type cosmetic that can
かかる実情において本発明者は、鋭意検討した結果、表面疎水化処理された微粒子金属酸化物を含有して、特定のポリエーテル変性シリコーンを用いた油中水型乳化組成物である原液と、噴射剤とを組み合わせてエアゾールとすることにより、長期間静置されても粉体の再分散性に優れるとともに、泡保持性および伸び広がりにも優れた泡沫性エアゾール型化粧料が得られることを見出し、本発明を完成させた。
Under such circumstances, the present inventors have made intensive studies and found that a stock solution that is a water-in-oil emulsified composition using a specific polyether-modified silicone containing finely divided metal oxides whose surfaces have been subjected to a hydrophobizing treatment, and an injection A foaming aerosol-type cosmetic that is excellent in powder redispersibility even when left standing for a long period of time, as well as excellent foam retention and spreadability can be obtained by combining an aerosol with an agent. , completed the present invention.
すなわち、本発明は以下を提供するものである。
［１］次の成分（Ａ）～（Ｄ）を含有する油中水型乳化組成物である原液と、噴射剤とからなる泡沫性エアゾール型化粧料。
（Ａ）表面疎水化処理された微粒子金属酸化物 前記原液中１０～２０質量％
（Ｂ）油剤
（Ｃ）非架橋型ポリエーテル変性シリコーン
（Ｄ）部分架橋型ポリエーテル変性シリコーン
［２］前記原液と噴射剤の割合が８５：１５～９８：２である［１］に記載の泡沫性エアゾール型化粧料。
［３］前記原液中における成分（Ｂ）の含有量が３０～５５質量％である［１］又は［２］に記載の泡沫性エアゾール型化粧料。 That is, the present invention provides the following.
[1] A foaming aerosol type cosmetic comprising a stock solution, which is a water-in-oil emulsion composition containing the following components (A) to (D), and a propellant.
(A) Fine particle metal oxide surface-hydrophobicized 10 to 20% by mass in the stock solution
(B) Oil agent (C) Non-crosslinked polyether-modified silicone (D) Partially crosslinked polyether-modified silicone [2] The ratio of the stock solution to the propellant is 85:15 to 98:2 [1]. Foaming aerosol type cosmetics.
[3] The foaming aerosol type cosmetic according to [1] or [2], wherein the content of component (B) in the stock solution is 30 to 55% by mass.
［１］次の成分（Ａ）～（Ｄ）を含有する油中水型乳化組成物である原液と、噴射剤とからなる泡沫性エアゾール型化粧料。
（Ａ）表面疎水化処理された微粒子金属酸化物 前記原液中１０～２０質量％
（Ｂ）油剤
（Ｃ）非架橋型ポリエーテル変性シリコーン
（Ｄ）部分架橋型ポリエーテル変性シリコーン
［２］前記原液と噴射剤の割合が８５：１５～９８：２である［１］に記載の泡沫性エアゾール型化粧料。
［３］前記原液中における成分（Ｂ）の含有量が３０～５５質量％である［１］又は［２］に記載の泡沫性エアゾール型化粧料。 That is, the present invention provides the following.
[1] A foaming aerosol type cosmetic comprising a stock solution, which is a water-in-oil emulsion composition containing the following components (A) to (D), and a propellant.
(A) Fine particle metal oxide surface-hydrophobicized 10 to 20% by mass in the stock solution
(B) Oil agent (C) Non-crosslinked polyether-modified silicone (D) Partially crosslinked polyether-modified silicone [2] The ratio of the stock solution to the propellant is 85:15 to 98:2 [1]. Foaming aerosol type cosmetics.
[3] The foaming aerosol type cosmetic according to [1] or [2], wherein the content of component (B) in the stock solution is 30 to 55% by mass.
本発明の泡沫性エアゾール型化粧料によれば、長期間静置されても微粒子金属酸化物の固化が生じにくく再分散性に優れるため、長期にわたっての保存と使用が可能である。また、本発明の泡沫状エアゾール型化粧料は、微粒子金属酸化物を多量に配合しても粉体の凝集がないため、ふんわりときめ細かい泡を形成し、滑らかな伸び広がりで、化粧膜の均一性にも優れる。さらに、泡保持性と伸び広がりのよさを両立し、使用性にも優れるものである。そのため、高い紫外線防御効果を有する日焼け止め化粧料や、メイクアップ化粧料として有用なものである。
According to the foaming aerosol-type cosmetic of the present invention, even if it is left standing for a long period of time, solidification of the fine particle metal oxide is unlikely to occur and it is excellent in redispersibility, so that it can be stored and used for a long period of time. In addition, the foamy aerosol-type cosmetic of the present invention does not aggregate powder even when a large amount of finely divided metal oxide is blended, so it forms soft and fine bubbles, spreads smoothly, and evenly coats the cosmetic film. Excellent in sex. Furthermore, it has both good foam retention and spreadability, and is excellent in usability. Therefore, it is useful as a sunscreen cosmetic or make-up cosmetic having a high UV protection effect.
以下、本発明の実施の形態を説明する。なお、本発明は、以下の実施の形態のみには限定されない。本明細書において、範囲を示す「Ｘ～Ｙ」は、ＸおよびＹを含み、「Ｘ以上Ｙ以下」を意味する。
Embodiments of the present invention will be described below. In addition, the present invention is not limited only to the following embodiments. In the present specification, the range “X to Y” includes X and Y and means “X or more and Y or less”.
＜原液：油中水型乳化組成物＞
（成分（Ａ）：表面疎水化処理された微粒子金属酸化物）
本発明に用いられる成分（Ａ）は、疎水化処理剤を用いて微粒子金属酸化物の表面を被覆処理したものであり、油相中への分散性を向上させるものである。 <Undiluted solution: water-in-oil emulsion composition>
(Component (A): fine particle metal oxide surface-hydrophobized)
The component (A) used in the present invention is obtained by coating the surface of fine metal oxide particles with a hydrophobizing agent to improve the dispersibility in the oil phase.
（成分（Ａ）：表面疎水化処理された微粒子金属酸化物）
本発明に用いられる成分（Ａ）は、疎水化処理剤を用いて微粒子金属酸化物の表面を被覆処理したものであり、油相中への分散性を向上させるものである。 <Undiluted solution: water-in-oil emulsion composition>
(Component (A): fine particle metal oxide surface-hydrophobized)
The component (A) used in the present invention is obtained by coating the surface of fine metal oxide particles with a hydrophobizing agent to improve the dispersibility in the oil phase.
成分（Ａ）において、表面疎水化処理され得る微粒子金属酸化物としては、化粧料等に通常に用いられるものであれば、特に限定されるものではないが、例えば、酸化亜鉛、酸化チタン、酸化セリウム、酸化ジルコニウム、酸化鉄等が挙げられる。これらの中でも、広範囲の紫外線を吸収、散乱、反射、消光等することにより紫外線を遮断する効果が高いという観点から、酸化亜鉛、酸化チタン、及び酸化セリウムから選択される１種又は２種以上であることが好ましく、酸化亜鉛及び／又は酸化チタンであることがより好ましく、酸化亜鉛であることがさらに好ましい。
In component (A), the fine particle metal oxide that can be surface-hydrophobized is not particularly limited as long as it is commonly used in cosmetics, etc. Examples include zinc oxide, titanium oxide, oxide Cerium, zirconium oxide, iron oxide and the like can be mentioned. Among these, one or more selected from zinc oxide, titanium oxide, and cerium oxide from the viewpoint of high UV blocking effect by absorbing, scattering, reflecting, and quenching a wide range of UV rays. Zinc oxide and/or titanium oxide are more preferable, and zinc oxide is even more preferable.
また微粒子金属酸化物の形状としては、特に限定されるものではないが、例えば粒状、球状、紡錘状、樹枝状、バルーン状等が挙げられ、組成物中での分散性向上による白浮きの低減、紫外線防御効果及び耐水性の観点から、粒状、球状、紡錘状であることが好ましい。
The shape of the fine metal oxide particles is not particularly limited, but examples thereof include granular, spherical, spindle-shaped, dendritic, and balloon-shaped. , from the viewpoint of UV protection effect and water resistance, it is preferably granular, spherical, or spindle-shaped.
微粒子金属酸化物の粒径としては、特に限定されないが、白浮きの低減、紫外線防御能及び耐水性の観点から、平均粒子径が１ｎｍ～３００ｎｍであることが好ましく、５ｎｍ～１００ｎｍであることがより好ましく、１０ｎｍ～５０ｎｍであることがより好ましい。なお、本発明において平均粒子径は、レーザー散乱式粒度分布計（ＨＯＲＩＢＡ社製）を用い、体積平均粒子径（Ｄ５０）として測定する。
The particle size of the fine particle metal oxide is not particularly limited, but the average particle size is preferably 1 nm to 300 nm, more preferably 5 nm to 100 nm, from the viewpoints of reducing whitening, UV protection and water resistance. More preferably, it is 10 nm to 50 nm. In the present invention, the average particle size is measured as the volume average particle size (D50) using a laser scattering particle size distribution analyzer (manufactured by HORIBA).
成分（Ａ）の表面疎水化処理剤としては、化粧料等に通常に用いられるものであれば、特に限定されるものではないが、例えば、シリコーン処理剤、フッ素処理剤、有機チタネート処理剤、脂肪酸処理剤、アシルアミノ酸処理剤などが挙げられる。これらの中でも、耐水性、経時安定性の観点から、シリコーン処理剤、有機チタネート処理剤から選択される１種又は２種以上であることが好ましい。
The surface hydrophobizing agent of component (A) is not particularly limited as long as it is commonly used in cosmetics and the like. Examples include silicone treating agents, fluorine treating agents, organic titanate treating agents, Fatty acid treating agents, acyl amino acid treating agents and the like can be mentioned. Among these, from the viewpoint of water resistance and stability over time, one or more selected from silicone treatment agents and organic titanate treatment agents are preferred.
シリコーン処理剤としては、例えば、低重合度ジメチルポリシロキサン、高重合度ジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン等の鎖状シリコーン類、アミノ変性シリコーン、アルキル変性シリコーン、アルコキシ変性シリコーン等の変性シリコーン類、トリメチルシロキシケイ酸やアクリル－シリコーングラフト共重合体等のシリコーン樹脂類、シリコーンゴム類、部分又は全架橋オルガノポリシロキサン類、シリル化剤類、シランカップリング剤類等が挙げられ、これらから選択される１種又は２種以上を用いることができる。中でも、シランカップリング剤類を用いることが好ましい。
Examples of silicone treatment agents include linear silicones such as low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, amino-modified silicones, alkyl-modified silicones, and alkoxy-modified silicones. modified silicones, such as trimethylsiloxysilicate and acrylic-silicone graft copolymers, silicone resins, silicone rubbers, partially or fully crosslinked organopolysiloxanes, silylating agents, silane coupling agents, and the like. One or more selected from these can be used. Among them, it is preferable to use silane coupling agents.
シランカップリング剤の中でも、特に限定されないが、トリアルコキシアルキルシランが好ましい。トリアルコキシアルキルシランは、ケイ素原子に三つのアルコキシ基と一つのアルキル基が結合した化合物であり、該アルコキシ基が粉体表面の水酸基等と反応することにより、粉体表面を化学的に修飾する化合物である。該トリアルコキシアルキルシランにおける、アルコキシ基は、炭素数１～３のアルコキシ基が好ましく、メトキシ基、エトキシ基、プロポキシ基が挙げられる。また、該トリアルコキシアルキルシランにおける、アルキル基は、炭素数６～１８のアルキル基が好ましく、ヘキシル基、オクチル基、デシル基、オクタデシル基等が好ましく挙げられる。このようなトリアルコキシアルキルシランは、具体的には、トリメトキシヘキシルシラン、トリメトキシオクチルシラン、トリメトキシデシルシラン、トリメトキシオクタデシルシラン、トリエトキシヘキシルシラン、トリエトキオクチルシラン、トリエトキシデシルシラン、トリエトキシオクタデシルシラン等が挙げられる。これらの中でも、経時安定性、きしみのない伸び広がりという使用性の観点から、トリメトキシオクチルシラン、トリエトキシオクチルシランから選択される１種又は２種以上であることがより好ましい。
Among the silane coupling agents, although not particularly limited, trialkoxyalkylsilanes are preferred. A trialkoxyalkylsilane is a compound in which three alkoxy groups and one alkyl group are bonded to a silicon atom, and the alkoxy groups chemically modify the powder surface by reacting with hydroxyl groups on the powder surface. is a compound. The alkoxy group in the trialkoxyalkylsilane is preferably an alkoxy group having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group and a propoxy group. The alkyl group in the trialkoxyalkylsilane is preferably an alkyl group having 6 to 18 carbon atoms, and preferably includes a hexyl group, an octyl group, a decyl group and an octadecyl group. Such trialkoxyalkylsilanes are specifically trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane, triethoxydecylsilane, tri and ethoxyoctadecylsilane. Among these, one or more selected from trimethoxyoctylsilane and triethoxyoctylsilane is more preferable from the viewpoint of usability such as stability over time and spreadability without creaking.
有機チタネート処理剤としては、長鎖カルボン酸型、ピロリン酸型、亜リン酸型、アミノ酸型等のアルキルチタネート等が挙げられ、炭素数８～２４のアルキル基を有するアルキルチタネートが好ましい。前記アルキルチタネートは、具体的には、長鎖カルボン酸型のアルキルチタネートとしては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、ジイソステアロイルエチレンチタネート等が挙げられ、ピロリン酸型アルキルチタネートとしては、テトライソプロピルビス（ジオクチルホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシルホスファイト）チタネート等が挙げられ、亜リン酸型アルキルチタネートとしては、イソプロピルトリ（ジオクチルピロホスフェート）チタネート、ビス（ジオクチルピロホスフェート）オキシアセテートチタネート、ビス（ジオクチルピロホスフェート）エチレンチタネート等が挙げられ、アミノ酸型アルキルチタネートとしては、イソプロピルトリ（Ｎ－アミドエチル・アミノエチル）チタネート等が挙げられる。これらアルキルチタネートの中でも、経時安定性、耐水性等の点から、長鎖カルボン酸型のアルキルチタネートが好ましく、イソプロピルトリイソステアロイルチタネートがより好ましい。
Examples of organic titanate treating agents include long-chain carboxylic acid-type, pyrophosphate-type, phosphorous acid-type, amino acid-type alkyl titanates, etc., and alkyl titanates having an alkyl group of 8 to 24 carbon atoms are preferred. Specifically, the alkyl titanates of long-chain carboxylic acid type include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, and diisostearoyl titanate. ethylene titanate and the like, and pyrophosphate-type alkyl titanates include tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(ditridecylphosphite) titanate and the like, and phosphite-type alkyl titanates include isopropyl tri(dioctylpyrophosphate) titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate and the like. and examples of amino acid-type alkyl titanates include isopropyl tri(N-amidoethyl/aminoethyl) titanate. Among these alkyl titanates, long-chain carboxylic acid-type alkyl titanates are preferable, and isopropyl triisostearoyl titanate is more preferable, from the viewpoint of stability over time, water resistance, and the like.
成分（Ａ）における表面疎水化処理剤の被覆量は、特に限定されるものではないが、耐水性及び経時安定性の観点から、処理前の微粒子金属酸化物の質量に対して、上限としては、６０質量％（以降、単に「％」と略す）以下であることが好ましく、４０％以下であることがより好ましく、２０％以下であることがさらにより好ましく、下限としては、２％以上であることが好ましく、５％以上であることがより好ましく、１０％以上であることがさらにより好ましい。
The coating amount of the surface hydrophobizing agent in component (A) is not particularly limited, but from the viewpoint of water resistance and stability over time, the upper limit is , 60% by mass (hereinafter simply abbreviated as “%”) or less, more preferably 40% or less, even more preferably 20% or less, and the lower limit is 2% or more. It is preferably 5% or more, more preferably 10% or more.
成分（Ａ）における表面処理の方法は、特に制限はなく、通常公知の方法で製造できる。例えば、溶媒に表面処理剤と処理を施される粉体粒子を添加し、ボールミル等で撹拌処理した後、必要に応じて乾燥し、水洗、濾過を繰返し、夾雑物を除去した後、乾燥、粉砕することにより、目的の表面処理粉体を得ることができる。また、表面処理剤である数種類の化合物を同時に表面処理することもでき、何れか一つの化合物で予め表面処理をしてから、更に他の化合物を表面処理することもできる。
There are no particular restrictions on the method of surface treatment for component (A), and it can be produced by a generally known method. For example, a surface treatment agent and powder particles to be treated are added to a solvent, stirred with a ball mill or the like, dried if necessary, washed with water, and filtered repeatedly to remove contaminants, followed by drying, By pulverizing, the desired surface-treated powder can be obtained. In addition, it is also possible to simultaneously treat the surface with several kinds of compounds that are surface treatment agents, or to perform surface treatment in advance with any one of the compounds and then further surface-treat with other compounds.
本発明における成分（Ａ）の含有量は、油中水型乳化組成物である原液中、１０～２０％であり、１０％未満であると、紫外線防御効果が得られなかったり、２０％を超えると、経時安定性や伸び広がりに劣ったりする場合がある。また成分（Ａ）は、原液中の１２％以上であることが好ましく、１３％以上であることがより好ましい。また成分（Ａ）は、原液中の１８％以下であることが好ましく、１７％以下であることがより好ましい。
The content of component (A) in the present invention is 10 to 20% in the undiluted solution that is the water-in-oil emulsion composition. If it exceeds, the stability over time and the spreadability may be deteriorated. Component (A) is preferably 12% or more, more preferably 13% or more, in the undiluted solution. Component (A) is preferably 18% or less, more preferably 17% or less, in the undiluted solution.
（成分（Ｂ）：油剤）
本発明に用いられる成分（Ｂ）油剤は、化粧料等に一般に用いられるものであれば、特に限定されるものではく、固体、ペースト状、液状等の性状や、極性、非極性等の物性、また植物油、鉱物油、合成油等の由来を問わず、炭化水素類、油脂類、ロウ類、エステル類、脂肪酸類、シリコーン油類、フッ素系油等が挙げられる。具体的には、イソドデカン、イソヘキサデカン、軽質イソパラフィン、流動パラフィン（ミネラルオイル）、スクワラン、スクワレン、α－オレフィンオリゴマー、ポリブテン、流動イソパラフィン、重質流動イソパラフィン、ポリイソブチレン、水添ポリイソブテン等の炭化水素類；アブラナ種子油、アボカド油、アルモンド油、アンズ核油、エゴマ油、オレンジ油、オリーブ油、キウイ種子油、ゴマ油、小麦胚芽油、米胚芽油、コメヌカ油、サフラワー油、セージ油、大豆油、チャ種子油、トウモロコシ油、ナタネ油、月見草油、ツバキ油、パーシック油、ハトムギ油、ピーナッツ油、ひまわり油、ブドウ種子油、メドウフォーム油、ローズマリー油、ホホバ油、マカデミアナッツ油、ラベンダー油、ローズヒップ油、ミンク油等の油脂類；トリ２－エチルヘキサン酸グリセリル、イソノナン酸イソトリデシル、イソノナン酸イソノニル、２－エチルヘキサン酸セチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、パルミチン酸－２－エチルヘキシル、ミリスチン酸オクチルドデシル、トリオクタン酸グリセリル、トリ（カプリル・カプリン酸）グリセリル、ジイソステアリン酸グリセリル、トリイソステアリン酸グリセリル、デカイソステアリン酸デカグリセリル（デカイソステアリン酸ポリグリセリル－１０）、ジカプリン酸プロピレングリコール、ジ（カプリル酸／カプリン酸）プロピレングリコール、ジカプリン酸ネオペンチルグリコール、トリイソステアリン酸ポリグリセリル、リンゴ酸ジイソステアリル、ジエチルヘキサン酸ネオペンチルグリコール、テトライソステアリン酸ペンタエリトリット、テトラ２－エチルヘキサン酸ペンタエリトリット、ペンタイソステアリン酸ジペンタエリトリット、炭酸ジアルキル、シクロヘキサン－１，４－ジカルボン酸ビスエトキシジグリコール、ダイマージリノレイル水添ロジン縮合物、安息香酸アルキル（Ｃ１２－１５）等のエステル類；オレイン酸、イソステアリン酸等の脂肪酸類；オレイルアルコール、２－オクチルドデカノール、２－デシルテトラデカノール、イソステアリルアルコール、２－ヘキシルデカノール等の高級アルコール類；ジメチルポリシロキサン（ジメチコン）、メチルトリメチコン、メチルフェニルポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、テトラメチルテトラハイドロジェンシクロテトラシロキサン、テトラメチルテトラフェニルシクロテトラシロキサン、テトラメチルテトラトリフロロプロピルシクロテトラシロキサン、ペンタメチルペンタトリフロロプロピルシクロペンタシロキサン、ポリエーテル変性メチルポリシロキサン、オレイル変性メチルポリシロキサン、ポリビニルピロリドン変性メチルポリシロキサン等のシリコーン油類；パーフルオロポリエーテル、パーフルオロデカン、パーフルオロオクタン等のフッ素系油剤類；酢酸ラノリン、ラノリン脂肪酸イソプロピル、ラノリンアルコール等のラノリン誘導体類；油溶性紫外線吸収剤等が挙げられ、これらの１種又は２種以上を用いることができる。 (Component (B): oil)
The component (B) oil used in the present invention is not particularly limited as long as it is commonly used in cosmetics and the like, and has properties such as solid, paste, and liquid, and physical properties such as polar and non-polar. Also, hydrocarbons, oils and fats, waxes, esters, fatty acids, silicone oils, fluorinated oils and the like can be mentioned regardless of the origin of vegetable oils, mineral oils, synthetic oils and the like. Specifically, hydrocarbons such as isododecane, isohexadecane, light isoparaffin, liquid paraffin (mineral oil), squalane, squalene, α-olefin oligomer, polybutene, liquid isoparaffin, heavy liquid isoparaffin, polyisobutylene, and hydrogenated polyisobutene. ;Brassica seed oil, avocado oil, almond oil, apricot kernel oil, perilla oil, orange oil, olive oil, kiwi seed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, sage oil, soybean oil, Tea seed oil, corn oil, rapeseed oil, evening primrose oil, camellia oil, persic oil, pearl barley oil, peanut oil, sunflower oil, grape seed oil, meadowfoam oil, rosemary oil, jojoba oil, macadamia nut oil, lavender oil, rose Fats and oils such as hip oil and mink oil; glyceryl tri-2-ethylhexanoate, isotridecyl isononanoate, isononyl isononanoate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, myristic acid Octyldodecyl, glyceryl trioctanoate, caprylic-capric triglyceride, glyceryl diisostearate, glyceryl triisostearate, decaglyceryl decaisostearate (polyglyceryl-10 decaisostearate), propylene glycol dicaprate, di(caprylic/capric) Acid) Propylene glycol, neopentyl glycol dicaprate, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol diethylhexanoate, pentaerythritol tetraisostearate, pentaerythritol tetraisostearate, pentaerythritol tetra-2-ethylhexanoate, dipentylisostearate Esters such as pentaerythritol, dialkyl carbonate, bisethoxydiglycol cyclohexane-1,4-dicarboxylate, dimer dilinoleyl hydrogenated rosin condensate, alkyl benzoate (C12-15); Fatty acids; higher alcohols such as oleyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol and 2-hexyldecanol; dimethylpolysiloxane (dimethicone), methyltrimethicone, methylphenylpolysiloxane, octamethyl Cyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetratrifluoropropylcyclotetrasiloxane, pentamethylpentatrifluoropropylcyclopentasiloxane, polyether-modified Silicone oils such as methylpolysiloxane, oleyl-modified methylpolysiloxane, and polyvinylpyrrolidone-modified methylpolysiloxane; fluorine-based oils such as perfluoropolyether, perfluorodecane, and perfluorooctane; lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol lanolin derivatives such as; oil-soluble ultraviolet absorbers;
本発明に用いられる成分（Ｂ）油剤は、化粧料等に一般に用いられるものであれば、特に限定されるものではく、固体、ペースト状、液状等の性状や、極性、非極性等の物性、また植物油、鉱物油、合成油等の由来を問わず、炭化水素類、油脂類、ロウ類、エステル類、脂肪酸類、シリコーン油類、フッ素系油等が挙げられる。具体的には、イソドデカン、イソヘキサデカン、軽質イソパラフィン、流動パラフィン（ミネラルオイル）、スクワラン、スクワレン、α－オレフィンオリゴマー、ポリブテン、流動イソパラフィン、重質流動イソパラフィン、ポリイソブチレン、水添ポリイソブテン等の炭化水素類；アブラナ種子油、アボカド油、アルモンド油、アンズ核油、エゴマ油、オレンジ油、オリーブ油、キウイ種子油、ゴマ油、小麦胚芽油、米胚芽油、コメヌカ油、サフラワー油、セージ油、大豆油、チャ種子油、トウモロコシ油、ナタネ油、月見草油、ツバキ油、パーシック油、ハトムギ油、ピーナッツ油、ひまわり油、ブドウ種子油、メドウフォーム油、ローズマリー油、ホホバ油、マカデミアナッツ油、ラベンダー油、ローズヒップ油、ミンク油等の油脂類；トリ２－エチルヘキサン酸グリセリル、イソノナン酸イソトリデシル、イソノナン酸イソノニル、２－エチルヘキサン酸セチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、パルミチン酸－２－エチルヘキシル、ミリスチン酸オクチルドデシル、トリオクタン酸グリセリル、トリ（カプリル・カプリン酸）グリセリル、ジイソステアリン酸グリセリル、トリイソステアリン酸グリセリル、デカイソステアリン酸デカグリセリル（デカイソステアリン酸ポリグリセリル－１０）、ジカプリン酸プロピレングリコール、ジ（カプリル酸／カプリン酸）プロピレングリコール、ジカプリン酸ネオペンチルグリコール、トリイソステアリン酸ポリグリセリル、リンゴ酸ジイソステアリル、ジエチルヘキサン酸ネオペンチルグリコール、テトライソステアリン酸ペンタエリトリット、テトラ２－エチルヘキサン酸ペンタエリトリット、ペンタイソステアリン酸ジペンタエリトリット、炭酸ジアルキル、シクロヘキサン－１，４－ジカルボン酸ビスエトキシジグリコール、ダイマージリノレイル水添ロジン縮合物、安息香酸アルキル（Ｃ１２－１５）等のエステル類；オレイン酸、イソステアリン酸等の脂肪酸類；オレイルアルコール、２－オクチルドデカノール、２－デシルテトラデカノール、イソステアリルアルコール、２－ヘキシルデカノール等の高級アルコール類；ジメチルポリシロキサン（ジメチコン）、メチルトリメチコン、メチルフェニルポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、テトラメチルテトラハイドロジェンシクロテトラシロキサン、テトラメチルテトラフェニルシクロテトラシロキサン、テトラメチルテトラトリフロロプロピルシクロテトラシロキサン、ペンタメチルペンタトリフロロプロピルシクロペンタシロキサン、ポリエーテル変性メチルポリシロキサン、オレイル変性メチルポリシロキサン、ポリビニルピロリドン変性メチルポリシロキサン等のシリコーン油類；パーフルオロポリエーテル、パーフルオロデカン、パーフルオロオクタン等のフッ素系油剤類；酢酸ラノリン、ラノリン脂肪酸イソプロピル、ラノリンアルコール等のラノリン誘導体類；油溶性紫外線吸収剤等が挙げられ、これらの１種又は２種以上を用いることができる。 (Component (B): oil)
The component (B) oil used in the present invention is not particularly limited as long as it is commonly used in cosmetics and the like, and has properties such as solid, paste, and liquid, and physical properties such as polar and non-polar. Also, hydrocarbons, oils and fats, waxes, esters, fatty acids, silicone oils, fluorinated oils and the like can be mentioned regardless of the origin of vegetable oils, mineral oils, synthetic oils and the like. Specifically, hydrocarbons such as isododecane, isohexadecane, light isoparaffin, liquid paraffin (mineral oil), squalane, squalene, α-olefin oligomer, polybutene, liquid isoparaffin, heavy liquid isoparaffin, polyisobutylene, and hydrogenated polyisobutene. ;Brassica seed oil, avocado oil, almond oil, apricot kernel oil, perilla oil, orange oil, olive oil, kiwi seed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, sage oil, soybean oil, Tea seed oil, corn oil, rapeseed oil, evening primrose oil, camellia oil, persic oil, pearl barley oil, peanut oil, sunflower oil, grape seed oil, meadowfoam oil, rosemary oil, jojoba oil, macadamia nut oil, lavender oil, rose Fats and oils such as hip oil and mink oil; glyceryl tri-2-ethylhexanoate, isotridecyl isononanoate, isononyl isononanoate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, myristic acid Octyldodecyl, glyceryl trioctanoate, caprylic-capric triglyceride, glyceryl diisostearate, glyceryl triisostearate, decaglyceryl decaisostearate (polyglyceryl-10 decaisostearate), propylene glycol dicaprate, di(caprylic/capric) Acid) Propylene glycol, neopentyl glycol dicaprate, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol diethylhexanoate, pentaerythritol tetraisostearate, pentaerythritol tetraisostearate, pentaerythritol tetra-2-ethylhexanoate, dipentylisostearate Esters such as pentaerythritol, dialkyl carbonate, bisethoxydiglycol cyclohexane-1,4-dicarboxylate, dimer dilinoleyl hydrogenated rosin condensate, alkyl benzoate (C12-15); Fatty acids; higher alcohols such as oleyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol and 2-hexyldecanol; dimethylpolysiloxane (dimethicone), methyltrimethicone, methylphenylpolysiloxane, octamethyl Cyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetratrifluoropropylcyclotetrasiloxane, pentamethylpentatrifluoropropylcyclopentasiloxane, polyether-modified Silicone oils such as methylpolysiloxane, oleyl-modified methylpolysiloxane, and polyvinylpyrrolidone-modified methylpolysiloxane; fluorine-based oils such as perfluoropolyether, perfluorodecane, and perfluorooctane; lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol lanolin derivatives such as; oil-soluble ultraviolet absorbers;
成分（Ｂ）は、後述する紫外線吸収剤の溶解性および使用感の観点から、エステル油を含有することが好ましく、中でもジカプリン酸プロピレングリコール、安息香酸アルキル（Ｃ１２－１５）、ジ（カプリル酸／カプリン酸）プロピレングリコール、２－エチルヘキサン酸セチルから選択される１種又は２種以上を含有することがより好ましい。
Component (B) preferably contains an ester oil from the viewpoint of the solubility of the ultraviolet absorber described later and the feeling of use. Among them, propylene glycol dicaprate, alkyl benzoate (C12-15), It is more preferable to contain one or more selected from propylene glycol and cetyl 2-ethylhexanoate (capric acid).
成分（Ｂ）には油溶性紫外線吸収剤が含まれてもよく、化粧料等に一般に用いられるものであれば、特に限定されず、固形状、ペースト状、液状のいずれの性状のものでもよい。具体的には、例えば、２－ヒドロキシ－４－メトキシベンゾフェノン、２，４，６－トリアニリノ－ｐ－（カルボ－２’－エチルヘキシル－１’－オキシ）－１，３，５－トリアジン、サリチル酸－２－エチルヘキシル、パラジヒドロキシプロピル安息香酸エチル、メトキシケイヒ酸エチルヘキシル、４－ｔｅｒｔ－４’－メトキシジベンゾイルメタン、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（ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル）、ポリシリコーン－１５、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸２－エチルヘキシル、２，２’－メチレンビス［６－（２Ｈ－ベンゾトリアゾール－２イル）－４－（１，１，３，３－テトラメチルブチル）フェノール］、２，４－ビス［｛４－（２－エチルヘキシロキシ）－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（ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン）、ジメチコジエチルベンザルマロネート等が挙げられる。紫外線防御効果の観点からは、メトキシケイヒ酸エチルヘキシル（パラメトキシケイヒ酸－２エチルヘキシル）、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、２，４－ビス［｛４－（２－エチルヘキシロキシ）－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、２，４，６－トリス［４－（２－エチルヘキシルオキシカルボニル）アニリノ］－１，３，５－トリアジン及び４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタンからなる群から選択される一種又は２種以上がより好ましい。
Component (B) may contain an oil-soluble ultraviolet absorber, and is not particularly limited as long as it is commonly used in cosmetics and the like, and may be solid, pasty, or liquid. . Specifically, for example, 2-hydroxy-4-methoxybenzophenone, 2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine, salicylic acid- 2-ethylhexyl, ethyl para-dihydroxypropylbenzoate, ethylhexyl methoxycinnamate, 4-tert-4'-methoxydibenzoylmethane, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (diethylaminohydroxybenzoyl hexyl benzoate), Polysilicone-15, 2-ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate, 2,2′-methylenebis[6-(2H-benzotriazol-2yl)-4-(1,1,3, 3-tetramethylbutyl)phenol], 2,4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (bisethylhexyloxyphenol methoxyphenyltriazine), dimethicodiethylbenzalmalonate and the like. From the viewpoint of UV protection effect, ethylhexyl methoxycinnamate (para-methoxycinnamate-2-ethylhexyl), 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 2,4-bis[{4- (2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl) One or more selected from the group consisting of anilino]-1,3,5-triazine and 4-tert-butyl-4′-methoxydibenzoylmethane is more preferable.
本発明における成分（Ｂ）の含有量は、特に限定されないが、油中水型乳化組成物である原液中に、下限としては、３０％以上が好ましく、４０％以上がより好ましい。また、上限としては、５５％以下が好ましく、５０％以下がより好ましい。この範囲であると、経時安定性、伸び広がりの良さに、より優れるためより好ましい。
The content of component (B) in the present invention is not particularly limited, but the lower limit is preferably 30% or more, more preferably 40% or more, in the stock solution that is the water-in-oil emulsion composition. Moreover, as an upper limit, 55% or less is preferable and 50% or less is more preferable. Within this range, the stability over time and spreadability are more excellent, which is more preferable.
（成分（Ｃ）：非架橋型ポリエーテル変性シリコーン）
本発明に用いられる成分（Ｃ）非架橋型ポリエーテル変性シリコーンとは、少なくともオルガノポリシロキサン基と、複数のエーテル構造を有する親水基とを有する共重合体であり、該オルガノポリシロキンサン基を主鎖として側鎖に親水基を有するグラフト共重合体であっても、オルガノポリシロキサン基と親水基とが、交互に結合した直鎖状のブロック共重合体であってもよいが、分子内には架橋構造を含まないものである。前記オルガノポリシロキサン基は、直鎖状であっても、分岐構造を有していてもよく、また前記親水基としては、ポリオキシアルキレン基やポリグリセリル基等が挙げられる。 (Component (C): non-crosslinked polyether-modified silicone)
The component (C) non-crosslinked polyether-modified silicone used in the present invention is a copolymer having at least an organopolysiloxane group and a hydrophilic group having a plurality of ether structures, and the organopolysiloxane group is It may be a graft copolymer having a hydrophilic group in a side chain as a main chain, or a linear block copolymer in which an organopolysiloxane group and a hydrophilic group are alternately bonded. does not contain a crosslinked structure. The organopolysiloxane group may be linear or may have a branched structure, and examples of the hydrophilic group include a polyoxyalkylene group and a polyglyceryl group.
本発明に用いられる成分（Ｃ）非架橋型ポリエーテル変性シリコーンとは、少なくともオルガノポリシロキサン基と、複数のエーテル構造を有する親水基とを有する共重合体であり、該オルガノポリシロキンサン基を主鎖として側鎖に親水基を有するグラフト共重合体であっても、オルガノポリシロキサン基と親水基とが、交互に結合した直鎖状のブロック共重合体であってもよいが、分子内には架橋構造を含まないものである。前記オルガノポリシロキサン基は、直鎖状であっても、分岐構造を有していてもよく、また前記親水基としては、ポリオキシアルキレン基やポリグリセリル基等が挙げられる。 (Component (C): non-crosslinked polyether-modified silicone)
The component (C) non-crosslinked polyether-modified silicone used in the present invention is a copolymer having at least an organopolysiloxane group and a hydrophilic group having a plurality of ether structures, and the organopolysiloxane group is It may be a graft copolymer having a hydrophilic group in a side chain as a main chain, or a linear block copolymer in which an organopolysiloxane group and a hydrophilic group are alternately bonded. does not contain a crosslinked structure. The organopolysiloxane group may be linear or may have a branched structure, and examples of the hydrophilic group include a polyoxyalkylene group and a polyglyceryl group.
前記グラフト共重合体タイプのうち、直鎖構造のオルガノポリシロキサン基を主鎖とするものとしては、具体的には、ポリオキシアルキレン変性オルガノポリシロキサン（市販品として、例えばＰＥＧ１０－ジメチコンである「ＫＦ－６０１７」信越化学工業社製）、ポリオキシアルキレン・アルキル共変性オルガノポリシロキサン（市販品として、例えばラウリルＰＥＧ／ＰＰＧ－１８／１８メチコンである「５２００ Ｆｏｒｍｕｌａｔｉｏｎ Ａｉｄ」東レ・ダウコーニング社製）等が挙げられる。また、分岐構造を有するオルガノポリシロキサン基を主鎖とするもの（シリコーン分岐型ポリエーテル変性シリコーン）としては、具体的には、ＰＥＧ－９ポリジメチルシロキシエチルジメチコン（市販品として、例えば「ＫＦ－６０２８」信越化学工業社製）、ラウリルＰＥＧ－９ポリジメチルシロキシエチルジメチコン（市販品として、例えば「ＫＦ－６０３８」信越化学工業社製）等が挙げられる。
Among the above-mentioned graft copolymer types, those having a linear organopolysiloxane group as a main chain include, specifically, polyoxyalkylene-modified organopolysiloxane (commercially available, for example, PEG10-dimethicone). KF-6017" manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyalkylene/alkyl co-modified organopolysiloxane (commercially available, for example, lauryl PEG/PPG-18/18 methicone "5200 Formulation Aid" manufactured by Dow Corning Toray) etc. Further, as a main chain having an organopolysiloxane group having a branched structure (silicone branched polyether-modified silicone), specifically, PEG-9 polydimethylsiloxyethyl dimethicone (commercially available, for example, "KF- 6028" manufactured by Shin-Etsu Chemical Co., Ltd.), lauryl PEG-9 polydimethylsiloxyethyl dimethicone (commercially available, for example, "KF-6038" manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
前記ブロック共重合体タイプとしては、具体的には、ポリオキシエチレン・ブチレン・ジメチルポリシロキサン共重合体（市販品として、例えば「ＦＺ－２２５０」東レ・ダウコーニング社製）、ポリオキシエチレン・ポリオキシプロピレン・ブチレン・ジメチルポリシロキサン共重合体（市販品として、「ＦＺ－２２３３」東レ・ダウコーニング社製、「ＳＩＬＷＥＴ ２３６－Ｌ」日本ユニカー社製）等が挙げられる。
Specific examples of the block copolymer type include polyoxyethylene/butylene/dimethylpolysiloxane copolymer (commercially available, for example, "FZ-2250" manufactured by Dow Corning Toray Co., Ltd.), polyoxyethylene/poly Oxypropylene/butylene/dimethylpolysiloxane copolymer (commercially available products include "FZ-2233" manufactured by Dow Corning Toray Co., Ltd., and "SILWET 236-L" manufactured by Nihon Unicar Co., Ltd.).
成分（Ｃ）は、必要に応じて１種又は２種以上を用いることができるが、これらの中でも、グラフト共重合体タイプが好ましく、親水基としてはポリオキシアルキレン鎖が好ましく、特にポリオキシエチレン鎖が好ましく、さらにはオキシエチレンの重合度が７～１１である非架橋型ポリエーテル変性シリコーンが特に好ましい。また、オルガノポリシロキサン基としては、分岐構造を有するものが好ましく、直鎖構造を有するものと、分岐構造を有するものを併用することが、さらにより好ましい。また、成分（Ｃ）の平均ＨＬＢは１～７が好ましく、２．５～５がより好ましい。なお、本発明におけるＨＬＢ（Ｈｙｒｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ Ｂａｌａｎｃｅ）とは、親水性－親油性のバランスを示す指標であり、小田・寺村らによる下記（式１）で計算されるものであり、平均ＨＬＢとは加重平均値とする。
ＨＬＢ＝「無機性値（ＩＶ）／有機性値（ＯＶ）」×１０・・・（式１）
（甲田善生著、「有機概念図－基礎と応用－」、１１～１７頁、三共出版、１９８４年発行参照） Component (C) may be used alone or in combination of two or more. Among these, the graft copolymer type is preferred, and the hydrophilic group is preferably a polyoxyalkylene chain, particularly polyoxyethylene. Chains are preferred, and non-crosslinked polyether-modified silicones with an oxyethylene degree of polymerization of 7-11 are particularly preferred. Moreover, as the organopolysiloxane group, those having a branched structure are preferable, and it is more preferable to use both a linear structure and a branched structure. The average HLB of component (C) is preferably 1-7, more preferably 2.5-5. The HLB (Hydrophile-Lipophile Balance) in the present invention is an index showing the hydrophilic-lipophilic balance, and is calculated by the following (formula 1) by Oda and Teramura et al. Use the weighted average.
HLB = "inorganic value (IV)/organic value (OV)" x 10 (Formula 1)
(See Yoshio Koda, "Organic Conceptual Diagram -Basics and Applications-", pp. 11-17, Sankyo Publishing, 1984)
ＨＬＢ＝「無機性値（ＩＶ）／有機性値（ＯＶ）」×１０・・・（式１）
（甲田善生著、「有機概念図－基礎と応用－」、１１～１７頁、三共出版、１９８４年発行参照） Component (C) may be used alone or in combination of two or more. Among these, the graft copolymer type is preferred, and the hydrophilic group is preferably a polyoxyalkylene chain, particularly polyoxyethylene. Chains are preferred, and non-crosslinked polyether-modified silicones with an oxyethylene degree of polymerization of 7-11 are particularly preferred. Moreover, as the organopolysiloxane group, those having a branched structure are preferable, and it is more preferable to use both a linear structure and a branched structure. The average HLB of component (C) is preferably 1-7, more preferably 2.5-5. The HLB (Hydrophile-Lipophile Balance) in the present invention is an index showing the hydrophilic-lipophilic balance, and is calculated by the following (formula 1) by Oda and Teramura et al. Use the weighted average.
HLB = "inorganic value (IV)/organic value (OV)" x 10 (Formula 1)
(See Yoshio Koda, "Organic Conceptual Diagram -Basics and Applications-", pp. 11-17, Sankyo Publishing, 1984)
本発明における成分（Ｃ）の含有量は、特に限定されないが、油中水型乳化組成物である原液中に、下限としては、経時安定性および泡保持性の観点から、０．１％以上が好ましく、０．２％以上がより好ましい。また、上限としては、伸び広がりの観点から、３％以下が好ましく、２％以下がより好ましい。
The content of the component (C) in the present invention is not particularly limited. is preferred, and 0.2% or more is more preferred. In addition, the upper limit is preferably 3% or less, more preferably 2% or less, from the viewpoint of elongation and spreadability.
（成分（Ｄ）：部分架橋型ポリエーテル変性シリコーン）
本発明に用いられる成分（Ｄ）架橋型ポリエーテル変性シリコーンは、オルガノポリシロキサンを三次元的に架橋結合させて得られる重合物のうち、分子中にポリオキシアルキレン基やポリグリセリン基等の親水基を導入したものであり、さらにアルキル基等の有機基を共変性したものであってもよい。 (Component (D): partially crosslinked polyether-modified silicone)
The component (D) cross-linked polyether-modified silicone used in the present invention is a polymer obtained by three-dimensionally cross-linking organopolysiloxane, and has a hydrophilic group such as a polyoxyalkylene group or a polyglycerin group in the molecule. It may be one in which a group is introduced, and one in which an organic group such as an alkyl group is co-modified.
本発明に用いられる成分（Ｄ）架橋型ポリエーテル変性シリコーンは、オルガノポリシロキサンを三次元的に架橋結合させて得られる重合物のうち、分子中にポリオキシアルキレン基やポリグリセリン基等の親水基を導入したものであり、さらにアルキル基等の有機基を共変性したものであってもよい。 (Component (D): partially crosslinked polyether-modified silicone)
The component (D) cross-linked polyether-modified silicone used in the present invention is a polymer obtained by three-dimensionally cross-linking organopolysiloxane, and has a hydrophilic group such as a polyoxyalkylene group or a polyglycerin group in the molecule. It may be one in which a group is introduced, and one in which an organic group such as an alkyl group is co-modified.
成分（Ｄ）は、特に限定されないが、例えば、（ジメチコン／（ＰＥＧ－１０／１５））クロスポリマー等の部分架橋型ポリエーテル変性シリコーン、（ＰＥＧ－１５／ラウリルジメチコン）クロスポリマー等の部分架橋型アルキル・ポリエーテル共変性シリコーン、（ジメチコン／ポリグリセリン－３）クロスポリマー等の部分架橋型ポリグリセリン変性シリコーン、（ラウリルジメチコン／ポリグリセリン－３）クロスポリマー等の部分架橋型アルキル・ポリグリセリン共変性シリコーンが挙げられ、これらを１種又は２種以上用いることができる。
Component (D) is not particularly limited, but for example, partially crosslinked polyether-modified silicone such as (dimethicone/(PEG-10/15)) crosspolymer, partially crosslinked such as (PEG-15/lauryl dimethicone) crosspolymer, etc. type alkyl-polyether co-modified silicone, partially cross-linked polyglycerin-modified silicone such as (dimethicone/polyglycerin-3) crosspolymer, partially cross-linked alkyl-polyglycerin co-modified silicone such as (lauryl dimethicone/polyglycerin-3) crosspolymer Examples include modified silicones, and one or more of these can be used.
このような成分（Ｄ）は、シリコーン油との混合物の形態で市販されており、部分架橋型ポリエーテル変性シリコーンとジメチルポリシロキサンとの混合物として「ＫＳＧ－２１０」（固形分２０～３０％）、部分架橋型アルキル・ポリエーテル共変性シリコーンと油剤との混合物として「ＫＳＧ－３１０」（固形分２５～３５％）、「ＫＳＧ－３２０」（固形分２０～３０％）、「ＫＳＧ－３３０」（固形分１５～２５％）及び「ＫＳＧ－３４０」（固形分２５～３５％）、部分架橋型ポリグリセリン変性シリコーンとジメチルポリシロキサンの混合物として「ＫＳＧ－７１０」（固形分２０～３０％）、部分架橋型アルキル・ポリグリセリン共変性シリコーンと油剤との混合物として、「ＫＳＧ－８１０」（固形分２５～３５％）、「ＫＳＧ－８２０」（固形分２０～３０％）、「ＫＳＧ－８３０」（固形分１５～２５％）、及び「ＫＳＧ－８４０」（固形分２５～３５％）（以上、信越化学工業社製）が挙げられる。
Such component (D) is commercially available in the form of a mixture with silicone oil, and "KSG-210" (solid content: 20-30%) is a mixture of partially crosslinked polyether-modified silicone and dimethylpolysiloxane. , "KSG-310" (solid content 25-35%), "KSG-320" (solid content 20-30%), "KSG-330" as a mixture of partially crosslinked alkyl-polyether co-modified silicone and oil agent (solid content 15-25%) and "KSG-340" (solid content 25-35%), "KSG-710" (solid content 20-30%) as a mixture of partially crosslinked polyglycerin-modified silicone and dimethylpolysiloxane , "KSG-810" (solid content 25-35%), "KSG-820" (solid content 20-30%), "KSG-830" as a mixture of partially crosslinked alkyl-polyglycerin co-modified silicone and oil agent ” (solid content 15 to 25%), and “KSG-840” (solid content 25 to 35%) (manufactured by Shin-Etsu Chemical Co., Ltd.).
本発明における成分（Ｄ）の含有量は、特に限定されないが、油中水型乳化組成物である原液中に、固形分換算で、下限としては０．０５％以上が好ましく、０．１％以上がより好ましい。また、上限としては５％以下が好ましく、３％以下がより好ましい。成分（Ｄ）がこの範囲であれば、より軽い伸び広がりで経時安定性および泡保持性に優れたものが得られるため好ましい。
The content of component (D) in the present invention is not particularly limited. The above is more preferable. Moreover, as an upper limit, 5% or less is preferable and 3% or less is more preferable. If the component (D) is within this range, it is preferable because it is possible to obtain a product that spreads more easily and has excellent stability over time and foam retention.
本発明の原液は、油中水型乳化組成物であるため、上記の成分以外に、水相を構成する成分として、水、低級アルコール等の水性成分を、本発明の効果を損なわない量的、質的範囲において、必要に応じて含有することができる。例えば、成分（Ｃ）、成分（Ｄ）以外の界面活性剤、成分（Ａ）以外の粉体、水溶性高分子、皮膜形成剤、酸化防止剤、ｐＨ調整剤、キレート剤、美容成分、防腐剤、香料、清涼剤等を含有することができる。
Since the stock solution of the present invention is a water-in-oil emulsified composition, in addition to the above components, an aqueous component such as water or a lower alcohol is added as a component constituting the aqueous phase in a quantitative amount that does not impair the effects of the present invention. , in the qualitative range, can be contained as necessary. For example, component (C), surfactants other than component (D), powders other than component (A), water-soluble polymers, film-forming agents, antioxidants, pH adjusters, chelating agents, cosmetic ingredients, preservatives agents, fragrances, cooling agents, and the like.
水性成分としては、水及び水に可溶な成分であれば何れでもよく、例えば、プロピレングリコール、１，３－ブチレングリコール、ジプロピレングリコール、ポリエチレングリコール等のグリコール類、グリセリン、ジグリセリン、ポリグリセリン等のグリセロール類、ソルビトール、マルチトール、グルコースなどの糖アルコール類、エタノール等の低級アルコール類、ポリオキシブチレンポリオキシエチレンポリオキシプロピレングリセリルエーテル（３ＢＯ）（８ＥＯ）（５ＰＯ）、ポリオキシプロピレン（９）ジグリセリル等のグリセリン誘導体類等が挙げられる。
The aqueous component may be any component as long as it is water or a component soluble in water. Examples include glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol, glycerin, diglycerin and polyglycerin. glycerols such as sorbitol, maltitol, sugar alcohols such as glucose, lower alcohols such as ethanol, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO), polyoxypropylene (9 ) glycerin derivatives such as diglyceryl;
本発明の原液の製造方法は、特に限定されるものではなく、常法により調製される。例えば、成分（Ｂ）の一部と成分（Ａ）を、予めロールミルやビーズミル等を用いて混練し、成分（Ｂ）の残部及び成分（Ｃ）、成分（Ｄ）を加えて加熱混合して均一に分散したものに、水性成分を加えて乳化して油中水型の組成物を得ることができる。
The method for producing the stock solution of the present invention is not particularly limited, and it is prepared by a conventional method. For example, part of component (B) and component (A) are kneaded in advance using a roll mill, bead mill, or the like, and the remainder of component (B), component (C), and component (D) are added and mixed under heating. A water-in-oil type composition can be obtained by adding an aqueous component to the uniformly dispersed mixture and emulsifying it.
＜噴射剤＞
本発明に用いられる噴射剤は、大気圧において気体であるガスを高圧下で液状にした液化ガスを含有するものであり、化粧料等に一般に用いられるものであれば、特に限定されるものではないが、炭素数２～５の炭化水素類、ジメチルエーテル、ジエチルエーテル等のエーテル類が挙げられる。炭素数２～５の炭化水素としては、具体的に、エタン、プロパン、ｎ－ブタン、イソブタン、ｎ－ペンタン、イソペンタン、ネオペンタン等が挙げられる。これらの中でも、プロパン、ブタンを主成分とする液化石油ガス（ＬＰＧ）が好ましく、２０℃条件下にて圧力が０．３～０．８ＭＰａに調整したものを用いることが好ましい。この範囲の圧力に調整した液化ガスを用いることで、泡保持性を向上させることができる。 <Propellant>
The propellant used in the present invention contains a liquefied gas obtained by liquefying a gas that is gas at atmospheric pressure under high pressure. However, it includes hydrocarbons having 2 to 5 carbon atoms and ethers such as dimethyl ether and diethyl ether. Specific examples of hydrocarbons having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane. Among these, liquefied petroleum gas (LPG) containing propane and butane as main components is preferable, and it is preferable to use one adjusted to a pressure of 0.3 to 0.8 MPa at 20°C. By using a liquefied gas adjusted to a pressure within this range, foam retention can be improved.
本発明に用いられる噴射剤は、大気圧において気体であるガスを高圧下で液状にした液化ガスを含有するものであり、化粧料等に一般に用いられるものであれば、特に限定されるものではないが、炭素数２～５の炭化水素類、ジメチルエーテル、ジエチルエーテル等のエーテル類が挙げられる。炭素数２～５の炭化水素としては、具体的に、エタン、プロパン、ｎ－ブタン、イソブタン、ｎ－ペンタン、イソペンタン、ネオペンタン等が挙げられる。これらの中でも、プロパン、ブタンを主成分とする液化石油ガス（ＬＰＧ）が好ましく、２０℃条件下にて圧力が０．３～０．８ＭＰａに調整したものを用いることが好ましい。この範囲の圧力に調整した液化ガスを用いることで、泡保持性を向上させることができる。 <Propellant>
The propellant used in the present invention contains a liquefied gas obtained by liquefying a gas that is gas at atmospheric pressure under high pressure. However, it includes hydrocarbons having 2 to 5 carbon atoms and ethers such as dimethyl ether and diethyl ether. Specific examples of hydrocarbons having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane. Among these, liquefied petroleum gas (LPG) containing propane and butane as main components is preferable, and it is preferable to use one adjusted to a pressure of 0.3 to 0.8 MPa at 20°C. By using a liquefied gas adjusted to a pressure within this range, foam retention can be improved.
本発明の噴射剤には、上記液化ガスに加え、本発明の効果を妨げない範囲で、二酸化炭素、窒素、アルゴン等を含有することができる。
In addition to the above liquefied gas, the propellant of the present invention can contain carbon dioxide, nitrogen, argon, etc. within a range that does not impair the effects of the present invention.
＜泡沫性エアゾール型化粧料＞
本発明の泡沫性エアゾール型化粧料における原液と噴射剤の充填割合は、質量比で８５：１５～９８：２が好ましく、さらに好ましくは９０：１０～９６：４である。この範囲であると、長期間静置されても安定性に優れ、泡保持性も良好となるため好ましい。 <Foamable aerosol type cosmetics>
The filling ratio of the stock solution to the propellant in the foaming aerosol type cosmetic of the present invention is preferably 85:15 to 98:2, more preferably 90:10 to 96:4, in mass ratio. Within this range, the stability is excellent even when left standing for a long period of time, and the foam retention is also good, which is preferable.
本発明の泡沫性エアゾール型化粧料における原液と噴射剤の充填割合は、質量比で８５：１５～９８：２が好ましく、さらに好ましくは９０：１０～９６：４である。この範囲であると、長期間静置されても安定性に優れ、泡保持性も良好となるため好ましい。 <Foamable aerosol type cosmetics>
The filling ratio of the stock solution to the propellant in the foaming aerosol type cosmetic of the present invention is preferably 85:15 to 98:2, more preferably 90:10 to 96:4, in mass ratio. Within this range, the stability is excellent even when left standing for a long period of time, and the foam retention is also good, which is preferable.
本発明の泡沫性エアゾール型化粧料の充填方法としては、特に限定されないが、常法により調製した原液を耐圧容器に充填し、容器にエアゾールバルブを固着した後、該バルブを通じて噴射剤を注入する。更に、前記エアゾールバルブに、目的に応じた噴射部材を取り付けることによりエアゾール製品とすることができる。
The filling method of the foaming aerosol type cosmetic of the present invention is not particularly limited, but a stock solution prepared by a conventional method is filled in a pressure-resistant container, an aerosol valve is fixed to the container, and a propellant is injected through the valve. . Furthermore, an aerosol product can be obtained by attaching an injection member according to the purpose to the aerosol valve.
本発明の泡沫性エアゾール型化粧料は、紫外線防御効果を有するため、化粧用下地、ファンデーション、日中用美容液、日焼け止め料などとして適用可能である。
The foamy aerosol-type cosmetic of the present invention has an ultraviolet protection effect, so it can be applied as a makeup base, foundation, daytime serum, sunscreen, and the like.
実施例１～１１及び比較例１～３：泡沫性エアゾール型日焼け止め料
下記表１に示す組成の泡沫性エアゾール型日焼け止め料を下記製造方法により調製し、泡保持性、経時安定性、伸び広がりのよさについて、以下に示す評価方法及び判定基準により評価判定し、結果を併せて表１に示す。 Examples 1 to 11 and Comparative Examples 1 to 3: Foaming aerosol-type sunscreens Foaming aerosol-type sunscreens having the compositions shown in Table 1 below were prepared by the following production method, and foam retention, stability over time, and elongation The spreadability was evaluated and judged according to the evaluation method and judgment criteria shown below, and the results are also shown in Table 1.
下記表１に示す組成の泡沫性エアゾール型日焼け止め料を下記製造方法により調製し、泡保持性、経時安定性、伸び広がりのよさについて、以下に示す評価方法及び判定基準により評価判定し、結果を併せて表１に示す。 Examples 1 to 11 and Comparative Examples 1 to 3: Foaming aerosol-type sunscreens Foaming aerosol-type sunscreens having the compositions shown in Table 1 below were prepared by the following production method, and foam retention, stability over time, and elongation The spreadability was evaluated and judged according to the evaluation method and judgment criteria shown below, and the results are also shown in Table 1.
（注１）ＫＦ－６０１７（信越化学工業社製）
（注２）ＫＦ－６０２８（信越化学工業社製）
（注３）ＫＳＧ－２１０（信越化学工業社製）：固形分２０～３０％
（注４）ＫＳＧ－７１０（信越化学工業社製）：固形分２０～３０％
（注５）ＫＳＧ－３１０（信越化学工業社製）：固形分２５～３５％
（注６）レオパール ＩＳＫ２（千葉製粉社製）
（注７）ＫＰ－５４５（信越化学工業社製） (Note 1) KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) KSG-210 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 20 to 30%
(Note 4) KSG-710 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 20 to 30%
(Note 5) KSG-310 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 25 to 35%
(Note 6) Rheopearl ISK2 (manufactured by Chiba Flour Milling Co., Ltd.)
(Note 7) KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
（注２）ＫＦ－６０２８（信越化学工業社製）
（注３）ＫＳＧ－２１０（信越化学工業社製）：固形分２０～３０％
（注４）ＫＳＧ－７１０（信越化学工業社製）：固形分２０～３０％
（注５）ＫＳＧ－３１０（信越化学工業社製）：固形分２５～３５％
（注６）レオパール ＩＳＫ２（千葉製粉社製）
（注７）ＫＰ－５４５（信越化学工業社製） (Note 1) KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) KSG-210 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 20 to 30%
(Note 4) KSG-710 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 20 to 30%
(Note 5) KSG-310 (manufactured by Shin-Etsu Chemical Co., Ltd.): solid content 25 to 35%
(Note 6) Rheopearl ISK2 (manufactured by Chiba Flour Milling Co., Ltd.)
(Note 7) KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
（製造方法）
（実施例１～１１及び比較例１～３）
Ａ：成分（４）～（１１）、（１４）～（１６）、（１９）、（２０）を均一に混合溶解する。
Ｂ：成分（１）～（３）と成分（１２）、（１３）の半量を均一に分散する。
Ｃ：ＡにＢを加え、均一に混合分散する。
Ｄ：Ｃに成分（１７）、（１８）および成分（１２）、（１３）の残量を加え、均一に混合分散する。
Ｅ：成分（２１）～（２４）を均一に混合する。
Ｆ：ＤにＥを加え乳化し、油中水型乳化組成物を得る。
Ｇ：Ｆ１００部をエアゾール型耐圧容器に充填後、噴射剤として液化石油ガス（０．４ＭＰａ）５部を充填し、泡沫性エアゾール型日焼け止め料を得た。 (Production method)
(Examples 1 to 11 and Comparative Examples 1 to 3)
A: Components (4) to (11), (14) to (16), (19) and (20) are uniformly mixed and dissolved.
B: Components (1) to (3) and half of components (12) and (13) are uniformly dispersed.
C: Add B to A and mix and disperse uniformly.
D: Add components (17) and (18) and the remainder of components (12) and (13) to C, and uniformly mix and disperse.
E: Mix components (21) to (24) uniformly.
F: E is added to D and emulsified to obtain a water-in-oil emulsion composition.
After filling 100 parts of G:F into an aerosol-type pressure-resistant container, 5 parts of liquefied petroleum gas (0.4 MPa) was filled as a propellant to obtain a foaming aerosol-type sunscreen.
（実施例１～１１及び比較例１～３）
Ａ：成分（４）～（１１）、（１４）～（１６）、（１９）、（２０）を均一に混合溶解する。
Ｂ：成分（１）～（３）と成分（１２）、（１３）の半量を均一に分散する。
Ｃ：ＡにＢを加え、均一に混合分散する。
Ｄ：Ｃに成分（１７）、（１８）および成分（１２）、（１３）の残量を加え、均一に混合分散する。
Ｅ：成分（２１）～（２４）を均一に混合する。
Ｆ：ＤにＥを加え乳化し、油中水型乳化組成物を得る。
Ｇ：Ｆ１００部をエアゾール型耐圧容器に充填後、噴射剤として液化石油ガス（０．４ＭＰａ）５部を充填し、泡沫性エアゾール型日焼け止め料を得た。 (Production method)
(Examples 1 to 11 and Comparative Examples 1 to 3)
A: Components (4) to (11), (14) to (16), (19) and (20) are uniformly mixed and dissolved.
B: Components (1) to (3) and half of components (12) and (13) are uniformly dispersed.
C: Add B to A and mix and disperse uniformly.
D: Add components (17) and (18) and the remainder of components (12) and (13) to C, and uniformly mix and disperse.
E: Mix components (21) to (24) uniformly.
F: E is added to D and emulsified to obtain a water-in-oil emulsion composition.
After filling 100 parts of G:F into an aerosol-type pressure-resistant container, 5 parts of liquefied petroleum gas (0.4 MPa) was filled as a propellant to obtain a foaming aerosol-type sunscreen.
（評価方法：（ａ）泡保持性）
実施例１～１１及び比較例１～３の泡沫性エアゾール型日焼け止め料について、手のひらとエアゾールの噴射口を２ｃｍの距離とし、ピンポン玉程度を手のひらに噴射した時の泡状態から、経時変化を観察し、下記の評価基準により判定した。
［評価基準］
（評価） ：（判定）
噴射後３０秒経過した時点において、
噴射直後の泡の外観が維持されている ： ◎
噴射後２０秒経過した時点において、
噴射直後の泡の外観が維持されている ： 〇
噴射後１０秒経過した時点において、
噴射直後の泡の外観が維持されている ： △
噴射後１０秒経過するまでの間に泡の外観が顕著に変化し、
維持されない ： × (Evaluation method: (a) foam retention)
For the foaming aerosol-type sunscreens of Examples 1 to 11 and Comparative Examples 1 to 3, the distance between the palm and the aerosol injection port was 2 cm, and the change over time was observed from the foam state when a ping-pong ball size was injected into the palm. It was observed and judged according to the following evaluation criteria.
[Evaluation criteria]
(Evaluation) : (Judgment)
30 seconds after injection,
Appearance of foam immediately after injection is maintained : ◎
20 seconds after injection,
The appearance of the foam immediately after injection is maintained: ○ 10 seconds after injection,
Appearance of foam is maintained immediately after spraying : △
The appearance of the foam changed significantly until 10 seconds after injection,
Not maintained: ×
実施例１～１１及び比較例１～３の泡沫性エアゾール型日焼け止め料について、手のひらとエアゾールの噴射口を２ｃｍの距離とし、ピンポン玉程度を手のひらに噴射した時の泡状態から、経時変化を観察し、下記の評価基準により判定した。
［評価基準］
（評価） ：（判定）
噴射後３０秒経過した時点において、
噴射直後の泡の外観が維持されている ： ◎
噴射後２０秒経過した時点において、
噴射直後の泡の外観が維持されている ： 〇
噴射後１０秒経過した時点において、
噴射直後の泡の外観が維持されている ： △
噴射後１０秒経過するまでの間に泡の外観が顕著に変化し、
維持されない ： × (Evaluation method: (a) foam retention)
For the foaming aerosol-type sunscreens of Examples 1 to 11 and Comparative Examples 1 to 3, the distance between the palm and the aerosol injection port was 2 cm, and the change over time was observed from the foam state when a ping-pong ball size was injected into the palm. It was observed and judged according to the following evaluation criteria.
[Evaluation criteria]
(Evaluation) : (Judgment)
30 seconds after injection,
Appearance of foam immediately after injection is maintained : ◎
20 seconds after injection,
The appearance of the foam immediately after injection is maintained: ○ 10 seconds after injection,
Appearance of foam is maintained immediately after spraying : △
The appearance of the foam changed significantly until 10 seconds after injection,
Not maintained: ×
（評価方法：（ｂ）経時安定性）
透明ガラス耐圧容器に充填した実施例１～１１及び比較例１～３の泡沫性エアゾール型日焼け止め料を、４０℃にて１か月保管後、室温に戻して３０回振盪し、内容物中の粉体の再分散状態（ケーキングのなさ）を観察し、下記の評価基準により判定した。
［評価基準］
（評価） ：（判定）
全体が均一に再分散する ： ◎
微量に分散していない粉体が存在するが、良好に再分散する ： 〇
分散していない粉体が存在する ： △
明らかなケーキングが観察される ： × (Evaluation method: (b) stability over time)
The foaming aerosol-type sunscreen materials of Examples 1 to 11 and Comparative Examples 1 to 3 filled in a transparent glass pressure container were stored at 40 ° C. for 1 month, then returned to room temperature and shaken 30 times. The state of redispersion of the powder (absence of caking) was observed and evaluated according to the following evaluation criteria.
[Evaluation criteria]
(Evaluation) : (Judgment)
The whole is evenly re-dispersed : ◎
Although there is a small amount of undispersed powder, it is redispersed well: 〇 There is undispersed powder: △
Obvious caking observed: ×
透明ガラス耐圧容器に充填した実施例１～１１及び比較例１～３の泡沫性エアゾール型日焼け止め料を、４０℃にて１か月保管後、室温に戻して３０回振盪し、内容物中の粉体の再分散状態（ケーキングのなさ）を観察し、下記の評価基準により判定した。
［評価基準］
（評価） ：（判定）
全体が均一に再分散する ： ◎
微量に分散していない粉体が存在するが、良好に再分散する ： 〇
分散していない粉体が存在する ： △
明らかなケーキングが観察される ： × (Evaluation method: (b) stability over time)
The foaming aerosol-type sunscreen materials of Examples 1 to 11 and Comparative Examples 1 to 3 filled in a transparent glass pressure container were stored at 40 ° C. for 1 month, then returned to room temperature and shaken 30 times. The state of redispersion of the powder (absence of caking) was observed and evaluated according to the following evaluation criteria.
[Evaluation criteria]
(Evaluation) : (Judgment)
The whole is evenly re-dispersed : ◎
Although there is a small amount of undispersed powder, it is redispersed well: 〇 There is undispersed powder: △
Obvious caking observed: ×
（評価方法：（ｃ）伸び広がりのよさ）
化粧料評価専門パネル１０名に、実施例１～１１及び比較例１～３の泡沫性エアゾール型日焼け止め料を使用してもらい（ピンポン玉程度を手のひらに噴射した後、前腕部に塗布する）、滑らかに塗布できるかどうか、各自が下記の評価基準に従って５段階評価し、サンプル毎に評点を付し、更に全パネルの評点の平均点を下記の判定基準に従って判定した。
［評価基準］
（評点）：（結果）
５点 ： 非常に良好
４点 ： 良好
３点 ： 普通
２点 ： やや不良
１点 ： 不良
［判定基準］
（評点の平均点） ：（判定）
４．５点以上 ： ◎
３．５点以上４．５点未満 ： 〇
２．５点以上３．５点未満 ： △
１．０点以上２．５点未満 ： × (Evaluation method: (c) good spreadability)
A panel of 10 cosmetics evaluation specialists was asked to use the foaming aerosol-type sunscreens of Examples 1 to 11 and Comparative Examples 1 to 3 (after spraying a ping-pong ball size on the palm, apply it to the forearm). , Whether or not it can be applied smoothly, each person evaluated in five stages according to the following evaluation criteria, gave a score to each sample, and further determined the average score of all the panel scores according to the following evaluation criteria.
[Evaluation criteria]
(Rating): (Result)
5 points: very good 4 points: good 3 points: normal 2 points: somewhat poor 1 point: poor [Criteria]
(Average score) : (Judgment)
4.5 points or more: ◎
3.5 points or more and less than 4.5 points: 〇 2.5 points or more and less than 3.5 points: △
1.0 points or more and less than 2.5 points: ×
化粧料評価専門パネル１０名に、実施例１～１１及び比較例１～３の泡沫性エアゾール型日焼け止め料を使用してもらい（ピンポン玉程度を手のひらに噴射した後、前腕部に塗布する）、滑らかに塗布できるかどうか、各自が下記の評価基準に従って５段階評価し、サンプル毎に評点を付し、更に全パネルの評点の平均点を下記の判定基準に従って判定した。
［評価基準］
（評点）：（結果）
５点 ： 非常に良好
４点 ： 良好
３点 ： 普通
２点 ： やや不良
１点 ： 不良
［判定基準］
（評点の平均点） ：（判定）
４．５点以上 ： ◎
３．５点以上４．５点未満 ： 〇
２．５点以上３．５点未満 ： △
１．０点以上２．５点未満 ： × (Evaluation method: (c) good spreadability)
A panel of 10 cosmetics evaluation specialists was asked to use the foaming aerosol-type sunscreens of Examples 1 to 11 and Comparative Examples 1 to 3 (after spraying a ping-pong ball size on the palm, apply it to the forearm). , Whether or not it can be applied smoothly, each person evaluated in five stages according to the following evaluation criteria, gave a score to each sample, and further determined the average score of all the panel scores according to the following evaluation criteria.
[Evaluation criteria]
(Rating): (Result)
5 points: very good 4 points: good 3 points: normal 2 points: somewhat poor 1 point: poor [Criteria]
(Average score) : (Judgment)
4.5 points or more: ◎
3.5 points or more and less than 4.5 points: 〇 2.5 points or more and less than 3.5 points: △
1.0 points or more and less than 2.5 points: ×
表１の結果から明らかなように、実施例１～１１の泡沫性エアゾール型日焼け止め料は、いずれも泡保持性に優れ、経時安定性も良好であるため、最後まで細かな泡状態で使用することが可能であり、滑らかな伸び広がりで、紫外線防御効果にも優れたものであった。
一方、成分（Ａ）が過剰である比較例１は、ケーキングが生じるため、全ての評価項目において劣るものであった。また成分（Ｃ）を配合していない比較例２は、ケーキングが生じ、泡保持性および経時安定性について劣るものであった。さらに成分（Ｄ）を配合していない比較例３は、乳化力が不足することから泡保持性が劣り、さらに伸び広がりの良さの点でも劣るものであった。 As is clear from the results in Table 1, the foaming aerosol type sunscreens of Examples 1 to 11 are all excellent in foam retention and have good stability over time, so they are used in a fine foam state until the end. It was possible to do so, it spread smoothly, and it was excellent also in an ultraviolet protection effect.
On the other hand, Comparative Example 1, in which the component (A) was excessive, was inferior in all evaluation items due to caking. Comparative Example 2, in which the component (C) was not blended, caused caking and was inferior in terms of foam retention and stability over time. Furthermore, Comparative Example 3, in which the component (D) was not blended, was inferior in foam retention due to insufficient emulsifying power, and was also inferior in spreadability.
一方、成分（Ａ）が過剰である比較例１は、ケーキングが生じるため、全ての評価項目において劣るものであった。また成分（Ｃ）を配合していない比較例２は、ケーキングが生じ、泡保持性および経時安定性について劣るものであった。さらに成分（Ｄ）を配合していない比較例３は、乳化力が不足することから泡保持性が劣り、さらに伸び広がりの良さの点でも劣るものであった。 As is clear from the results in Table 1, the foaming aerosol type sunscreens of Examples 1 to 11 are all excellent in foam retention and have good stability over time, so they are used in a fine foam state until the end. It was possible to do so, it spread smoothly, and it was excellent also in an ultraviolet protection effect.
On the other hand, Comparative Example 1, in which the component (A) was excessive, was inferior in all evaluation items due to caking. Comparative Example 2, in which the component (C) was not blended, caused caking and was inferior in terms of foam retention and stability over time. Furthermore, Comparative Example 3, in which the component (D) was not blended, was inferior in foam retention due to insufficient emulsifying power, and was also inferior in spreadability.
実施例１２：ノンケミカル日焼け止め料
（成分） （％）
（１）トリエトキシオクチルシラン処理酸化亜鉛（注８） ２０
（２）ステアリン酸処理酸化チタン（注９） ５
（３）ポリヒドロキシステアリン酸 ０．３
（４）ＰＥＧ－９ポリジメチルシロキシエチルジメチコン（注２）０．２
（５）エチルヘキサン酸セチル １５
（６）ジメチコン（６ＣＳ） ５
（７）ジフェニルジメチコン（注１０） ５
（８）ジフェニルシロキシフェニルトリメチコン（注１１） ５
（９）ＰＥＧ－１０ジメチコン（注１２） ０．７
（１０）（ジメチコン／（ＰＥＧ－１０／１５））クロスポリマー（注３）
１
（１１）タルク ５
（１２）マイカ １
（１３）エタノール ７
（１４）精製水 残量
（１５）塩化Ｎａ ０．３
（１６）１，３－ブチレングリコール ５
（１７）グリセリン １
（１８）ジプロピレングリコール ０．５
（１９）ヒアルロン酸 ０．１５
（２０）トレハロース ０．０５
（２１）カワラヨモギエキス ０．０１
（２２）フェノキシエタノール ０．３ Example 12: Non-chemical sunscreen (ingredient) (%)
(1) Triethoxyoctylsilane-treated zinc oxide (Note 8) 20
(2) Stearic acid-treated titanium oxide (Note 9) 5
(3) Polyhydroxy stearic acid 0.3
(4) PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 0.2
(5) cetyl ethylhexanoate 15
(6) Dimethicone (6CS) 5
(7) Diphenyl dimethicone (Note 10) 5
(8) Diphenylsiloxyphenyl trimethicone (Note 11) 5
(9) PEG-10 dimethicone (Note 12) 0.7
(10) (Dimethicone/(PEG-10/15)) crosspolymer (Note 3)
1
(11) Talc 5
(12) Mica 1
(13) Ethanol 7
(14) Purified water remaining amount (15) Na chloride 0.3
(16) 1,3-butylene glycol 5
(17) Glycerin 1
(18) Dipropylene glycol 0.5
(19) hyaluronic acid 0.15
(20) Trehalose 0.05
(21) Kawara mugwort extract 0.01
(22) Phenoxyethanol 0.3
（成分） （％）
（１）トリエトキシオクチルシラン処理酸化亜鉛（注８） ２０
（２）ステアリン酸処理酸化チタン（注９） ５
（３）ポリヒドロキシステアリン酸 ０．３
（４）ＰＥＧ－９ポリジメチルシロキシエチルジメチコン（注２）０．２
（５）エチルヘキサン酸セチル １５
（６）ジメチコン（６ＣＳ） ５
（７）ジフェニルジメチコン（注１０） ５
（８）ジフェニルシロキシフェニルトリメチコン（注１１） ５
（９）ＰＥＧ－１０ジメチコン（注１２） ０．７
（１０）（ジメチコン／（ＰＥＧ－１０／１５））クロスポリマー（注３）
１
（１１）タルク ５
（１２）マイカ １
（１３）エタノール ７
（１４）精製水 残量
（１５）塩化Ｎａ ０．３
（１６）１，３－ブチレングリコール ５
（１７）グリセリン １
（１８）ジプロピレングリコール ０．５
（１９）ヒアルロン酸 ０．１５
（２０）トレハロース ０．０５
（２１）カワラヨモギエキス ０．０１
（２２）フェノキシエタノール ０．３ Example 12: Non-chemical sunscreen (ingredient) (%)
(1) Triethoxyoctylsilane-treated zinc oxide (Note 8) 20
(2) Stearic acid-treated titanium oxide (Note 9) 5
(3) Polyhydroxy stearic acid 0.3
(4) PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 0.2
(5) cetyl ethylhexanoate 15
(6) Dimethicone (6CS) 5
(7) Diphenyl dimethicone (Note 10) 5
(8) Diphenylsiloxyphenyl trimethicone (Note 11) 5
(9) PEG-10 dimethicone (Note 12) 0.7
(10) (Dimethicone/(PEG-10/15)) crosspolymer (Note 3)
1
(11) Talc 5
(12) Mica 1
(13) Ethanol 7
(14) Purified water remaining amount (15) Na chloride 0.3
(16) 1,3-butylene glycol 5
(17) Glycerin 1
(18) Dipropylene glycol 0.5
(19) hyaluronic acid 0.15
(20) Trehalose 0.05
(21) Kawara mugwort extract 0.01
(22) Phenoxyethanol 0.3
（注８）ＭＺＸ－５０８ＯＴＳ（テイカ社製）
（注９）ＭＴ－０１（テイカ社製）
（注１０）ＫＦ－５４（信越化学工業社製）
（注１１）ＫＦ－５６（信越化学工業社製）
（注１２）ＫＦ－６０１７Ｐ（信越化学工業社製） (Note 8) MZX-508OTS (manufactured by Tayca)
(Note 9) MT-01 (manufactured by Tayka)
(Note 10) KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 11) KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 12) KF-6017P (manufactured by Shin-Etsu Chemical Co., Ltd.)
（注９）ＭＴ－０１（テイカ社製）
（注１０）ＫＦ－５４（信越化学工業社製）
（注１１）ＫＦ－５６（信越化学工業社製）
（注１２）ＫＦ－６０１７Ｐ（信越化学工業社製） (Note 8) MZX-508OTS (manufactured by Tayca)
(Note 9) MT-01 (manufactured by Tayka)
(Note 10) KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 11) KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 12) KF-6017P (manufactured by Shin-Etsu Chemical Co., Ltd.)
（製造方法）
Ａ：成分（７）～（１０）を均一に混合・分散する。
Ｂ：成分（１）～（６）を均一に粉体分散する。
Ｃ：ＡにＢを加え、均一に混合分散する。
Ｄ：Ｃに成分（１１）、（１２）を加え、均一に混合分散する。
Ｅ：成分（１３）～（２２）を均一に混合する。
Ｆ：ＤにＥを加え乳化し、油中水型乳化組成物を得る。
Ｇ：Ｆ９０部をエアゾール型耐圧容器に充填後、噴射剤として液化石油ガス（０．４ＭＰａ）１０部を充填し、ノンケミカル日焼け止め料を得た。 (Production method)
A: Uniformly mix and disperse components (7) to (10).
B: Components (1) to (6) are uniformly powder-dispersed.
C: Add B to A and mix and disperse uniformly.
D: Components (11) and (12) are added to C and uniformly mixed and dispersed.
E: Components (13) to (22) are uniformly mixed.
F: E is added to D and emulsified to obtain a water-in-oil emulsion composition.
After filling 90 parts of G:F into an aerosol-type pressure-resistant container, 10 parts of liquefied petroleum gas (0.4 MPa) was filled as a propellant to obtain a non-chemical sunscreen.
Ａ：成分（７）～（１０）を均一に混合・分散する。
Ｂ：成分（１）～（６）を均一に粉体分散する。
Ｃ：ＡにＢを加え、均一に混合分散する。
Ｄ：Ｃに成分（１１）、（１２）を加え、均一に混合分散する。
Ｅ：成分（１３）～（２２）を均一に混合する。
Ｆ：ＤにＥを加え乳化し、油中水型乳化組成物を得る。
Ｇ：Ｆ９０部をエアゾール型耐圧容器に充填後、噴射剤として液化石油ガス（０．４ＭＰａ）１０部を充填し、ノンケミカル日焼け止め料を得た。 (Production method)
A: Uniformly mix and disperse components (7) to (10).
B: Components (1) to (6) are uniformly powder-dispersed.
C: Add B to A and mix and disperse uniformly.
D: Components (11) and (12) are added to C and uniformly mixed and dispersed.
E: Components (13) to (22) are uniformly mixed.
F: E is added to D and emulsified to obtain a water-in-oil emulsion composition.
After filling 90 parts of G:F into an aerosol-type pressure-resistant container, 10 parts of liquefied petroleum gas (0.4 MPa) was filled as a propellant to obtain a non-chemical sunscreen.
実施例１２のノンケミカル日焼け止め料は、経時安定性に優れ、泡保持性と伸び広がりの良さを両立するため化粧膜が均一であり、紫外線防御効果にも優れたものであった。
The non-chemical sunscreen of Example 12 had excellent stability over time, achieved both good foam retention and good spreadability, and had a uniform cosmetic film, as well as an excellent UV protection effect.
実施例１３：下地化粧料
（成分） （％）
（１） トリエトキシオクチルシラン（４％）処理酸化亜鉛（３５ｎｍ）
１５
（２）ＰＥＧ－９ポリジメチルシロキシエチルジメチコン（注２）０．５
（３）エチルヘキサン酸セチル １５
（４）ジメチコン（６ＣＳ） ５
（５）ジフェニルジメチコン（注１０） ５
（６）ジフェニルシロキシフェニルトリメチコン（注１１） ５
（７）ＰＥＧ－１０ジメチコン（注１２） ０．７
（８）（ジメチコン／（ＰＥＧ－１０／１５））クロスポリマー（注１０）
１
（９）ジメチコン（２％）処理タルク ５
（１０）マイカ １
（１１）エタノール ７
（１２）精製水 残量
（１３）塩化Ｎａ ０．３
（１４）１，３－ブチレングリコール ５
（１５）グリセリン １
（１６）フェノキシエタノール ０．３
（１７）赤２２６ ０．０１
（１８）グンジョウ ０．０５ Example 13: Base cosmetics (ingredients) (%)
(1) Triethoxyoctylsilane (4%) treated zinc oxide (35 nm)
15
(2) PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 0.5
(3) cetyl ethylhexanoate 15
(4) Dimethicone (6CS) 5
(5) Diphenyl dimethicone (Note 10) 5
(6) Diphenylsiloxyphenyl trimethicone (Note 11) 5
(7) PEG-10 dimethicone (Note 12) 0.7
(8) (Dimethicone/(PEG-10/15)) crosspolymer (Note 10)
1
(9) Dimethicone (2%) treated talc 5
(10) Mica 1
(11) Ethanol 7
(12) Purified water remaining amount (13) Na chloride 0.3
(14) 1,3-butylene glycol 5
(15) Glycerin 1
(16) Phenoxyethanol 0.3
(17) Red 226 0.01
(18) Gunjo 0.05
（成分） （％）
（１） トリエトキシオクチルシラン（４％）処理酸化亜鉛（３５ｎｍ）
１５
（２）ＰＥＧ－９ポリジメチルシロキシエチルジメチコン（注２）０．５
（３）エチルヘキサン酸セチル １５
（４）ジメチコン（６ＣＳ） ５
（５）ジフェニルジメチコン（注１０） ５
（６）ジフェニルシロキシフェニルトリメチコン（注１１） ５
（７）ＰＥＧ－１０ジメチコン（注１２） ０．７
（８）（ジメチコン／（ＰＥＧ－１０／１５））クロスポリマー（注１０）
１
（９）ジメチコン（２％）処理タルク ５
（１０）マイカ １
（１１）エタノール ７
（１２）精製水 残量
（１３）塩化Ｎａ ０．３
（１４）１，３－ブチレングリコール ５
（１５）グリセリン １
（１６）フェノキシエタノール ０．３
（１７）赤２２６ ０．０１
（１８）グンジョウ ０．０５ Example 13: Base cosmetics (ingredients) (%)
(1) Triethoxyoctylsilane (4%) treated zinc oxide (35 nm)
15
(2) PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 0.5
(3) cetyl ethylhexanoate 15
(4) Dimethicone (6CS) 5
(5) Diphenyl dimethicone (Note 10) 5
(6) Diphenylsiloxyphenyl trimethicone (Note 11) 5
(7) PEG-10 dimethicone (Note 12) 0.7
(8) (Dimethicone/(PEG-10/15)) crosspolymer (Note 10)
1
(9) Dimethicone (2%) treated talc 5
(10) Mica 1
(11) Ethanol 7
(12) Purified water remaining amount (13) Na chloride 0.3
(14) 1,3-butylene glycol 5
(15) Glycerin 1
(16) Phenoxyethanol 0.3
(17) Red 226 0.01
(18) Gunjo 0.05
（製造方法）
Ａ：成分（５）～（８）を均一に混合分散する。
Ｂ：成分（１）～（４）、を均一に粉体分散する。
Ｃ：ＡにＢを加え、均一に混合分散する。
Ｄ：Ｃに成分（９）、（１０）を加え、均一に混合分散する。
Ｅ：成分（１１）～（１８）を均一に混合する。
Ｆ：ＤにＥを加え乳化し、油中水型乳化組成物を得る。
Ｇ：Ｆ９５部をエアゾール型耐圧容器に充填後、噴射剤として液化石油ガス（０．４ＭＰａ）５部を充填し、下地化粧料を得た。 (Production method)
A: Components (5) to (8) are uniformly mixed and dispersed.
B: Components (1) to (4) are uniformly powder-dispersed.
C: Add B to A and mix and disperse uniformly.
D: Components (9) and (10) are added to C and uniformly mixed and dispersed.
E: Components (11) to (18) are uniformly mixed.
F: E is added to D and emulsified to obtain a water-in-oil emulsion composition.
After filling 95 parts of G:F into an aerosol-type pressure-resistant container, 5 parts of liquefied petroleum gas (0.4 MPa) was filled as a propellant to obtain a base cosmetic.
Ａ：成分（５）～（８）を均一に混合分散する。
Ｂ：成分（１）～（４）、を均一に粉体分散する。
Ｃ：ＡにＢを加え、均一に混合分散する。
Ｄ：Ｃに成分（９）、（１０）を加え、均一に混合分散する。
Ｅ：成分（１１）～（１８）を均一に混合する。
Ｆ：ＤにＥを加え乳化し、油中水型乳化組成物を得る。
Ｇ：Ｆ９５部をエアゾール型耐圧容器に充填後、噴射剤として液化石油ガス（０．４ＭＰａ）５部を充填し、下地化粧料を得た。 (Production method)
A: Components (5) to (8) are uniformly mixed and dispersed.
B: Components (1) to (4) are uniformly powder-dispersed.
C: Add B to A and mix and disperse uniformly.
D: Components (9) and (10) are added to C and uniformly mixed and dispersed.
E: Components (11) to (18) are uniformly mixed.
F: E is added to D and emulsified to obtain a water-in-oil emulsion composition.
After filling 95 parts of G:F into an aerosol-type pressure-resistant container, 5 parts of liquefied petroleum gas (0.4 MPa) was filled as a propellant to obtain a base cosmetic.
実施例１３の下地化粧料は、経時安定性に優れ、泡保持性と伸び広がりの良さを両立するため化粧膜が均一であり、紫外線防御効果にも優れたものであった。
The base cosmetic of Example 13 was excellent in stability over time, had a uniform cosmetic film because it achieved both good foam retention and spreadability, and was also excellent in UV protection effect.
The base cosmetic of Example 13 was excellent in stability over time, had a uniform cosmetic film because it achieved both good foam retention and spreadability, and was also excellent in UV protection effect.
Claims (3)
- 次の成分（Ａ）～（Ｄ）を含有する油中水型乳化組成物である原液と、噴射剤とからなる泡沫性エアゾール型化粧料。
（Ａ）表面疎水化処理された微粒子金属酸化物 前記原液中１０～２０質量％
（Ｂ）油剤
（Ｃ）非架橋型ポリエーテル変性シリコーン
（Ｄ）部分架橋型ポリエーテル変性シリコーン A foaming aerosol type cosmetic comprising a stock solution which is a water-in-oil emulsion composition containing the following components (A) to (D) and a propellant.
(A) Fine particle metal oxide surface-hydrophobicized 10 to 20% by mass in the stock solution
(B) Oil agent (C) Non-crosslinked polyether-modified silicone (D) Partially crosslinked polyether-modified silicone - 前記原液と噴射剤の割合が８５：１５～９８：２である請求項１に記載の泡沫性エアゾール型化粧料。 2. The foaming aerosol type cosmetic according to claim 1, wherein the ratio of said concentrate to propellant is 85:15 to 98:2.
- 前記原液中における成分（Ｂ）の含有量が３０～５５質量％である請求項１又は２に記載の泡沫性エアゾール型化粧料。 3. The foaming aerosol type cosmetic according to claim 1, wherein the content of component (B) in said stock solution is 30 to 55% by mass.
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| JP2021212843 | 2021-12-27 | ||
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Citations (3)
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|---|---|---|---|---|
| JP2018108966A (en) * | 2017-01-04 | 2018-07-12 | 株式会社コーセー | Aerosol type cosmetic |
| JP2020094046A (en) * | 2018-12-05 | 2020-06-18 | 株式会社コーセー | Aerosol cosmetic |
| JP2021011472A (en) * | 2019-07-03 | 2021-02-04 | 株式会社コーセー | Aerosol cosmetic |
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2022
- 2022-12-15 WO PCT/JP2022/046181 patent/WO2023127521A1/en unknown
- 2022-12-23 TW TW111149641A patent/TW202339699A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018108966A (en) * | 2017-01-04 | 2018-07-12 | 株式会社コーセー | Aerosol type cosmetic |
| JP2020094046A (en) * | 2018-12-05 | 2020-06-18 | 株式会社コーセー | Aerosol cosmetic |
| JP2021011472A (en) * | 2019-07-03 | 2021-02-04 | 株式会社コーセー | Aerosol cosmetic |
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