WO2022054820A1 - Oil-in-water emulsion composition - Google Patents

Oil-in-water emulsion composition Download PDF

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Publication number
WO2022054820A1
WO2022054820A1 PCT/JP2021/032951 JP2021032951W WO2022054820A1 WO 2022054820 A1 WO2022054820 A1 WO 2022054820A1 JP 2021032951 W JP2021032951 W JP 2021032951W WO 2022054820 A1 WO2022054820 A1 WO 2022054820A1
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Prior art keywords
oil
dimethicone
silicone elastomer
examples
silicone
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PCT/JP2021/032951
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French (fr)
Japanese (ja)
Inventor
亮 古川
圭太 西田
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株式会社 資生堂
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Priority to CN202180055896.1A priority Critical patent/CN116075289A/en
Publication of WO2022054820A1 publication Critical patent/WO2022054820A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • 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 oil-in-water emulsified composition.
  • the oil-in-water emulsified composition is widely used as a base for external skin preparations such as skin cosmetics that are directly applied to the skin because it gives a refreshing and moist feel when applied to the skin.
  • the oil-in-water emulsified composition contains a silicone elastomer because it has the effects of reducing stickiness and squeaking of the skin after application and softening the skin (for example, Patent Documents 1 and 2).
  • dimethicodiethylbenzalmalonate is a kind of ultraviolet absorber in the UV-B region (ultraviolet-B: 280 to 320 nm), but its ultraviolet protection ability is lower than that of other ultraviolet absorbers, and its ultraviolet protection ability is low.
  • SPF unsun protection factor
  • Patent Document 3 describes dimethicodiethylbenzalmalonate and 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3).
  • an object of the present invention is to provide an oil-in-water emulsified composition capable of improving the absorbance even if a silicone elastomer is blended. ..
  • the oil-in-water emulsified composition of the present invention (A) Dimethicodiethylbenzalmaronate and (B) Silicone elastomer and (C) A surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone, and Is included.
  • the oil-in-water emulsified composition of the present invention preferably contains (D) an oil-soluble ultraviolet absorber other than (A) dimethicodiethylbenzalmalonate in an amount of 8% by mass or more based on the total amount of the composition.
  • the mass ratio of (B) silicone elastomer to (C) a surfactant having HLB 8 or less having a hydrocarbon group having 4 or more carbon atoms in the dimethicone main chain is preferably 0.5 to 10.
  • the mass ratio of (B) silicone elastomer to (A) dimethicodiethylbenzalmalonate is preferably 0.1 to 2.
  • the oil-in-water emulsified composition of the present invention (A) Dimethicodiethylbenzalmaronate and (B) Silicone elastomer and (C) Since the dimethicone main chain contains a surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms, the absorbance can be improved even if a silicone elastomer is blended.
  • the oil-in-water emulsified composition of the present invention (A) Dimethicodiethylbenzalmaronate and (B) Silicone elastomer and (C) A surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone, and Is included.
  • a surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone, and Is included (Is included.
  • HLB hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone
  • each component will be described in detail.
  • POE is an abbreviation for polyoxyethylene
  • PEG is an abbreviation for polyethylene glycol
  • PPG is an abbreviation for polypropylene glycol.
  • Dimethicodiethylbenzalmalonate Dimethicodiethylbenzalmaronate contained in the oil-in-water emulsified composition of the present invention is a silicone-modified compound liquid at room temperature and is also called polysilicone-15.
  • Dimethicodiethylbenzalmalonate is a known ultraviolet absorber and a commercially available product can be used. Examples thereof include “PARSOL SLX" (DSM Nutritional Products).
  • the blending amount of (A) dimethicodiethylbenzalmalonate is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and further 0.5 by mass with respect to the total amount of the composition. It is preferably ⁇ 5% by mass. When it is 0.1% by mass or more with respect to the total amount of the composition, the absorbance can be further improved, and when it is 10% by mass or less, better usability can be ensured.
  • silicone elastomer crosslinked silicone contained in the oil-in-water emulsifying composition of the present invention is not particularly limited, but is not particularly limited, but is a dimethicone crosspolymer, a dimethicone / vinyldimethicone crosspolymer (polysilicone 11).
  • One or more selected from the group is preferably used.
  • the silicone elastomer When preparing the oil-in-water emulsified composition of the present invention, it is preferable to blend the silicone elastomer in the form of a swelled product swollen with an oil that is liquid at room temperature. This further improves the dispersibility and stability of the crosslinked silicone.
  • the liquid oil content used for swelling include liquid silicone oil, liquid hydrocarbon oil, liquid ester oil, liquid higher fatty acid and the like, and in particular, low viscosity at room temperature (25 ° C.), for example, liquid of 100 mPa ⁇ s or less. Oil is preferred. The preferred viscosity range is 1 to 100 mPa ⁇ s.
  • the mixing ratio of the crosslinked silicone and the liquid oil is preferably 5:95 to 40:60 in terms of mass ratio.
  • the fact that the liquid oil swelling material is within this mass ratio makes the preparation of an oil-in-water emulsified composition more suitable.
  • liquid oil swelling product of the silicone elastomer a commercially available product can be used, and examples of the commercially available product include the following.
  • the swelling product of dimethicone crosspolymer 9040 silicone elastomer blend (mixture of dimethicone crosspolymer and decamethylcyclopentasiloxane with 12% crosslinked product) and 9041 silicone elastomer blend (dimethicone crosspolymer, crosslinked with dimethicone 5 mPa ⁇ s mixture).
  • the swellings of the dimethicone / vinyl dimethicone crosspolymer include KSG-15 ((dimethicone / vinyl dimethicone) crosspolymer, a mixture of cyclopentasiloxane with a crosslinked product of 4 to 10%), and KSG-16 ((dimethicone / vinyldimethicone)).
  • GRANSIL DMG-50 a mixture of polymer-11 and dimethicone 50 mPa ⁇ s, about 26% crosslinked
  • GRANSIL PM a mixture of polysilicone-11 and phenyltrimethicone, about 2 crosslinkeds.
  • GRANSIL ININ a mixture of polysilicone-11 and isononyl isononanoate with a crosslinked product of about 15% (above, manufactured by GRANT) and the like.
  • the swelling product of dimethicone / phenylvinyl dimethicone crosspolymer is KSG-18A (a mixture of (dimethicone / phenylvinyl dimethicone) crosspolymer and diphenylsiloxyphenyltrimethicone with a crosslinked product of 10 to 20%) (manufactured by Shin-Etsu Chemical Co., Ltd.). And so on.
  • the swellings of the vinyl dimethicone / lauryl dimethicone cross-polymer include KSG-41 ((vinyl dimethicone / lauryl dimethicone) cross-polymer, 25-30% crosslinked product of a mixture of mineral oils), KSG-42 ((vinyl dimethicone / lauryl)).
  • Dimethicone Cross-polymer, cross-linked product of isododecane 20-30%), KSG-43 ((vinyl dimethicone / lauryl dimethicone) cross-polymer, cross-linked product of trioctanoin 25-35%), KSG-44 ((Vinyl dimethicone / lauryl dimethicone) cross-polymer, cross-linked product is 25-35% in a mixture of squalane) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.
  • VELVESIL 125 a mixture of alkyl (C30-45) cetearyl dimethicone crosspolymer and cyclopentasiloxane, the crosslinked product is about 12.5%
  • VELVESIL Plus A mixture of alkyl (C30-45) cetearyl dimethicone crosspolymer, cyclopentasiloxane, PEG / PPG-20 / 23 dimethicone 5 mPa ⁇ s, and the crosslinked product is about 20%
  • Examples of the swelling product of cetearyl dimethicone cross polymer include VELVESIL DM (a mixture of cetearyl dimethicone cross polymer and dimethicone 5 mPa ⁇ s with a crosslinked product of about 17%) (manufactured by Momentive Performance Materials).
  • KSG-210 solid content 20-30%) as a mixture of partially crosslinked polyether-modified silicone and dimethylpolysiloxane
  • KSG-51 as a mixture with cyclic fluorine-containing silicone such as fluoroalkyl group-containing cyclic organopolysiloxane.
  • Examples of the mixture of partially crosslinked polyglycerin-modified silicone and dimethylpolysiloxane include KSG-710 (solid content 20 to 25%) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
  • alkyl group-containing crosslinked polyether-modified silicone examples include mineral oil PEG-15 lauryldimethicone crosspolymer (“KSG-310”; manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and isododecane PEG-15 lauryldimethicone crosspolymer (“KSG-320”).
  • Trioctanoin PEG-15 lauryl dimethicone crosspolymer (“KSG-330 ”; manufactured by Shinetsu Chemical Industry Co., Ltd.), Squalane PEG-15 lauryl dimethicone cross polymer PEG-10 lauryl dimethicone cloth
  • KSG-340 manufactured by Shin-Etsu Chemical Industry Co., Ltd.
  • dimethicone PEG-15 / laurylpolydimethylsiloxyethyl dimethicone
  • KSG360Z manufactured by Shin-Etsu Chemical Industry Co., Ltd.
  • alkyl group-containing crosslinked polyglycerin-modified silicone examples include mineral oil (lauryldimethicone / polyglycerin 3) crosspolymer (“KSG-810”; manufactured by Shin-Etsu Chemical Co., Ltd.) and isododecane (lauryldimethicone / polyglycerin 3) cloth.
  • Polymer (“KSG-820; manufactured by Shin-Etsu Chemical Co., Ltd.”), trioctanoin (lauryldimethicone / polyglycerin 3) cross-polymer (“KSG-830"; manufactured by Shin-Etsu Chemical Co., Ltd.), squalane (lauryldimethicone / poly).
  • Glycerin 3) Crosspolymer (“KSG-840”; manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.
  • the blending amount of the silicone elastomer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and further preferably 2 to 7% by mass with respect to the total amount of the composition.
  • the blending amount is 0.1% by mass or more, the effect of reducing the stickiness and squeak of the skin after application and the effect of softening the skin can be obtained, and when it is 10% by mass or less, the stability of the composition is improved. It can be secured more.
  • the mass ratio ((B) component / (A) component) of the (B) silicone elastomer to (A) dimethicodiethylbenzalmalonate is preferably 0.1 to 2, more preferably 0.12 to 1. It is preferably .95, more preferably 0.15 to 1.8.
  • the mass ratio (B) / (A) is 0.1 or more, the usability becomes smoother without stickiness, and when it is 2 or less, the absorbance can be further improved.
  • (C) Surfactant of HLB8 or less having a hydrocarbon group having 4 or more carbon atoms in the dimethicone main chain
  • Preferred examples of the surfactant having an HLB of 8 or less include an alkyl group-containing polyether-modified silicone, an alkyl group-containing polyglycerin-modified silicone, and the like.
  • the mechanism of action in which the absorbance is dramatically improved by blending the component (C) is not always clear, but it is considered to be related to the improvement in the dispersion of the silicone elastomer (B).
  • alkyl group-containing polyether-modified silicone examples include lauryl PEG-9 polydimethylsiloxyethyl dimethicone: silicone SC0928SL (manufactured by Shin-Etsu Chemical Co., Ltd.), cetyl PEG / PPG-10 / 1 dimethicone: ABIL EM180 (manufactured by Goldschmidt), and the like. Can be mentioned.
  • alkyl group-containing polyglycerin-modified silicone examples include laurylpolyglyceryl-3 polydimethylsiloxyethyl dimethicone (“KF-6105”; manufactured by Shin-Etsu Chemical Co., Ltd.) and bisbutyldimethicone polyglyceryl-3 (silicone KF-6109 (Shin-Etsu Chemical) as a commercial product). (Made by Kogyo Co., Ltd.))) and the like.
  • the blending amount of the component (C) is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.9% by mass, and further preferably 0.05 to 0.8% by mass with respect to the total amount of the composition. % Is preferable.
  • the blending amount is 0.01% by mass or more, the absorbance can be further improved, and when it is 1% by mass or less, the stickiness can be further reduced.
  • the mass ratio of the (B) silicone elastomer to the component (C) is preferably 0.5 to 10, more preferably 0.55 to 9, and further 0.6. It is preferably ⁇ 8.
  • the mass ratio (B) / (C) is 0.5 or more, the stickiness can be further reduced, and when it is 10 or less, the absorbance can be further improved.
  • the oil-in-water emulsified composition of the present invention preferably contains (D) an oil-soluble UV absorber other than (A) dimethicodiethylbenzalmalonate.
  • the oil-soluble ultraviolet absorber is not particularly limited as long as it is conventionally used in cosmetics. For example, methoxycinnamic acid derivative, salicylic acid derivative, benzoyl derivative, camphor derivative, paraaminobenzoic acid derivative, triazine derivative, ⁇ , ⁇ -diphenylacrylate derivative and benzophenone derivative can be mentioned.
  • the oil-soluble ultraviolet absorber may be blended in one kind or a combination of two or more kinds, if necessary.
  • methoxycinnamic acid derivative examples include octylmethoxycinnamate or ethylhexyl methoxycinnamate (eg, "Pulsole MCX”; Hoffman-La Roche), isopropyl methoxycinnamate, and isoamyl methoxycinnamate (eg, "Neo Heliopan E1000”; Herman).
  • cinnoxate, DEA methoxycinnamate, diisopropylmethylsilicate, glyceryl-ethylhexanoate-dimethoxycinnamate, di- (2-ethylhexyl) -4'-methoxybenzalmaronate, etc. are exemplified. ..
  • salicylic acid derivative examples include homosalate (“Eusolex HMS”; Lona / EM Industries), ethylhexyl salicylate (octyl salicylate, for example, “NeoHeliopan OS”; Herman and Reimer), Examples thereof include dipropylene glycol salicylate (eg, "Dipsal”; Skele), TEA salicylate (eg, "Neo Heliopan TS”; Herman and Reimer).
  • homosalate (“Eusolex HMS”; Lona / EM Industries)
  • ethylhexyl salicylate octyl salicylate, for example, “NeoHeliopan OS”; Herman and Reimer
  • dipropylene glycol salicylate eg, "Dipsal”; Skele
  • TEA salicylate eg, "Neo Heliopan TS”; Herman and Reimer
  • benzoyl derivative examples include 4-tert-butyl-4'-methoxydibenzoylmethane (for example, "Pulsole 1789”).
  • camphor derivative examples include terephthalylidene-3,3'-dikanfur-10,10'-disulfonate, 4-methylbenzylidenecamphor and the like.
  • para-aminobenzoic acid derivative examples include para-aminobenzoic acid (PABA) ethyl, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA (for example, "Escalol 507"; ISP), glyceryl PABA, and PEG-25-PABA (for example, "" Ubinal P25 ”; BASF), hexyl diethylaminohydroxybenzoylbenzoate (eg,“ Ubinal A Plus ”) and the like are exemplified.
  • PABA para-aminobenzoic acid
  • triazine derivative examples include bisethylhexyloxyphenol methoxyphenyltriazine (for example, “Tinosorb S”; Ciba Specialty Chemicals), ethylhexyltriazone (for example, “Ubinal T150”; BASF), and dietihexylbutamide.
  • Triazone eg, "Uvasorb HEB”; Sigma 3V
  • 2,4,6-tris diisobutyl-4'-aminobenzalmaronate
  • -s-triazine 2,4,6-tris [ 4- (2-Ethylhexyloxycarbonyl) anilino] -1,3,5-triazine and the like are exemplified.
  • ⁇ , ⁇ -diphenylacrylate derivative examples include octocrylene (for example, “Ubinal N539T”; BASF).
  • benzophenone derivative examples include benzophenone-1 (eg, "Ubinal 400"; BASF), benzophenone-2 (eg, “Ubinal D50”; BASF), benzophenone-3 or oxybenzone (eg, "Ubinal M40"; BASF), benzophenone.
  • the blending amount of the (D) oil-soluble ultraviolet absorber is preferably 8% by mass or more, more preferably 9 to 20% by mass, and further preferably 10 to 18% by mass with respect to the total amount of the composition. It is preferable to have.
  • the blending amount of the oil-soluble ultraviolet absorber is 8% by mass or more with respect to the total amount of the composition, so that the ultraviolet protection ability can be further enhanced.
  • the oil-in-water emulsified composition of the present invention can contain other optional ingredients that can be blended in ordinary cosmetics and quasi-drugs as long as the effects of the present invention are not impaired.
  • Other optional components include, but are not limited to, oils such as liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, synthetic ester oils, and silicone oils, powder components, coloring agents, and moisturizers. , Aqueous thickeners, dispersants, preservatives, fragrances, various chemicals and the like.
  • Liquid fats and oils include, for example, avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, sesame oil, persic oil, wheat germ oil, southern ka oil, sunflower oil, flaxseed oil, safflower oil, cottonseed oil, and eno oil. , Soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, triglycerin and the like.
  • solid fats and oils examples include coconut oil, palm oil, hardened palm oil, palm oil, palm kernel oil, mokuro kernel oil, hydrogenated oil, mokuro, and hardened castor oil.
  • waxes examples include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, montan wax, nukarou, capoc wax, sugar cane wax, hexyl laurate, jojoba wax, cellac wax, POE cholesterol ether and the like.
  • hydrocarbon oil examples include liquid paraffin, zokerite, squalane, pristan, paraffin, selecin, squalene, petrolatum, microcrystalline wax, hydrogenated polydecene and the like.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tortic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid ( DHA) and the like.
  • Synthetic ester oils include isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate.
  • silicone oil examples include chain polysiloxane (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxane (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane).
  • chain polysiloxane eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.
  • cyclic polysiloxane eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane.
  • Silicone resin Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) forming a three-dimensional network structure, etc. Be done.
  • various modified polysiloxanes amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.
  • the powder component examples include ultraviolet scattering agents such as zinc oxide and titanium oxide, extender pigments such as talc, mica and kaolin, and polymer powders such as polyethylene powder, polymethyl methacrylate powder and nylon powder.
  • ultraviolet scattering agents such as zinc oxide and titanium oxide
  • extender pigments such as talc, mica and kaolin
  • polymer powders such as polyethylene powder, polymethyl methacrylate powder and nylon powder.
  • moisturizer examples include polyhydric alcohols such as glycerin, 1,3-butylene glycol, dipropylene glycol and propylene glycol, and water-soluble polymers such as trehalose, hyaluronic acid and chondroitin sulfate.
  • polyhydric alcohols such as glycerin, 1,3-butylene glycol, dipropylene glycol and propylene glycol
  • water-soluble polymers such as trehalose, hyaluronic acid and chondroitin sulfate.
  • aqueous thickener examples include succinoglycan, (dimethylacrylamide / acryloyldimethyltaurine Na) crosspolymer, cellulose gum, carboxyvinyl polymer, xanthan gum, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer and the like. ..
  • the oil-in-water emulsification composition of the present invention is, for example, an oil-in-water emulsification in which a component constituting the oil phase and a component constituting the aqueous phase are separately mixed and the oil phase is added to the aqueous phase for emulsification. It can be produced according to a conventional method of composition (cosmetics).
  • the oil-in-water emulsified composition of the present invention can be provided as cosmetics in various dosage forms such as liquid, milky, creamy, gelled, and bavarois. Further, the oil-in-water emulsified composition of the present invention can be provided as a skin care cosmetic, a sunscreen cosmetic, a cosmetic containing a coloring agent, a foundation, a makeup base, and a BB cream.
  • Example 1 An oil-in-water emulsified composition was prepared according to the formulation shown in Table 1 below, and the prepared composition was evaluated according to the following criteria.
  • the oil-in-water emulsified composition of the example had a high peak top value and integrated value of absorbance even when the silicone elastomer was blended.
  • Comparative Example 1 containing no component (C) and Comparative Examples 2 and 3 not containing dimethicodiethylbenzalmalonate the peak top value and the integrated value of the absorbance were significantly lowered.
  • Comparative Example 3 even if the amount of octocrylene, which is most used as being useful for sun care cosmetics, was increased, the peak top value and the integrated value of Examples were not reached.

Abstract

[Problem] To provide an oil-in-water emulsion composition capable of improving absorbance even when a silicone elastomer is mixed. [Solution] An oil-in-water emulsion composition includes (A) a dimethicodiethylbenzalmalonate, (B) a silicone elastomer, and (C) a surfactant with an HLB of at most 8 having a hydrocarbon group having at least 4 carbon atoms in a main chain of dimethazone.

Description

水中油型乳化組成物Oil-in-water emulsification composition
　本発明は、水中油型乳化組成物に関するものである。 The present invention relates to an oil-in-water emulsified composition.
　水中油型乳化組成物は、肌に塗布した際に爽やかでしっとりした感触が得られることから、肌に直接適用される皮膚化粧料等の皮膚外用剤の基剤として広く用いられている。特に、水中油型乳化組成物には、塗布後の肌のべたつきやきしみの軽減、皮膚を柔軟化する効果があることから、シリコーンエラストマーが配合されている（例えば特許文献１や２）。 The oil-in-water emulsified composition is widely used as a base for external skin preparations such as skin cosmetics that are directly applied to the skin because it gives a refreshing and moist feel when applied to the skin. In particular, the oil-in-water emulsified composition contains a silicone elastomer because it has the effects of reducing stickiness and squeaking of the skin after application and softening the skin (for example, Patent Documents 1 and 2).
　ところで、ジメチコジエチルベンザルマロネートは、ＵＶ－Ｂ領域（ultraviolet-B：２８０～３２０ｎｍ）の紫外線吸収剤の一種であるが、他の紫外線吸収剤に比べて、紫外線防御能力が低く、その配合量を多くして高いＳＰＦ（sun protection factor）製品を目指す場合には、高配合によるきしみや油っぽさといった問題を有している。このような問題に鑑み、特許文献３には、ジメチコジエチルベンザルマロネートと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］とを組み合わせて配合した日焼け止め化粧料に、特定構造の両末端シリコーン変性グリセリンを配合することで、高いＳＰＦを有する製品を製造する場合であっても、優れた使用感が得られることが記載されている。 By the way, dimethicodiethylbenzalmalonate is a kind of ultraviolet absorber in the UV-B region (ultraviolet-B: 280 to 320 nm), but its ultraviolet protection ability is lower than that of other ultraviolet absorbers, and its ultraviolet protection ability is low. When aiming for a high SPF (sun protection factor) product with a large amount of compounding, there are problems such as squeak and oiliness due to the high compounding amount. In view of such problems, Patent Document 3 describes dimethicodiethylbenzalmalonate and 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3). 3-Tetramethylbutyl) Phenol] is blended with sunscreen cosmetics, and by blending double-ended silicone-modified glycerin with a specific structure, it is excellent even when producing products with high SPF. It is described that a feeling of use can be obtained.
国際公開第２０１３／０４７１９６号International Publication No. 2013/047196 特許第５５８８１６４号Patent No. 5588164 特許第５４６９３１９号Patent No. 5469319
　一般に、シリコーンエラストマーを配合すると吸光度が低下することが知られている。今般、シリコーンエラストマーの分散に特定の界面活性剤を用いたところ、吸光度が飛躍的に向上し、さらにその分散体にジメチコジエチルベンザルマロネートを配合してみたところ、吸光度が相乗的に向上することを見出し本発明に至った。 Generally, it is known that the absorbance decreases when a silicone elastomer is blended. Recently, when a specific surfactant was used to disperse the silicone elastomer, the absorbance dramatically improved, and when dimethicodiethylbenzalmaronate was added to the dispersion, the absorbance synergistically improved. It was found that this was done, and the present invention was reached.
　すわなち、本発明は上記知見に基づきなされたものであり、シリコーンエラストマーが配合されていても吸光度を向上させることが可能な水中油型乳化組成物を提供することを目的とするものである。 That is, the present invention has been made based on the above findings, and an object of the present invention is to provide an oil-in-water emulsified composition capable of improving the absorbance even if a silicone elastomer is blended. ..
　本発明の水中油型乳化組成物は、
　（Ａ）ジメチコジエチルベンザルマロネートと、
　（Ｂ）シリコーンエラストマーと、
　（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤と、
を含むものである。 The oil-in-water emulsified composition of the present invention
(A) Dimethicodiethylbenzalmaronate and
(B) Silicone elastomer and
(C) A surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone, and
Is included.
　本発明の水中油型乳化組成物は、（Ａ）ジメチコジエチルベンザルマロネート以外の（Ｄ）油溶性紫外線吸収剤を組成物全量に対し８質量％以上含むことが好ましい。 The oil-in-water emulsified composition of the present invention preferably contains (D) an oil-soluble ultraviolet absorber other than (A) dimethicodiethylbenzalmalonate in an amount of 8% by mass or more based on the total amount of the composition.
　（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤に対する（Ｂ）シリコーンエラストマーの質量比は０．５～１０であることが好ましい。 The mass ratio of (B) silicone elastomer to (C) a surfactant having HLB 8 or less having a hydrocarbon group having 4 or more carbon atoms in the dimethicone main chain is preferably 0.5 to 10.
　（Ａ）ジメチコジエチルベンザルマロネートに対する（Ｂ）シリコーンエラストマーの質量比は０．１～２であることが好ましい。 The mass ratio of (B) silicone elastomer to (A) dimethicodiethylbenzalmalonate is preferably 0.1 to 2.
　本発明の水中油型乳化組成物は、
　（Ａ）ジメチコジエチルベンザルマロネートと、
　（Ｂ）シリコーンエラストマーと、
　（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤と、を含むので、シリコーンエラストマーが配合されていても吸光度を向上させることができる。 The oil-in-water emulsified composition of the present invention
(A) Dimethicodiethylbenzalmaronate and
(B) Silicone elastomer and
(C) Since the dimethicone main chain contains a surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms, the absorbance can be improved even if a silicone elastomer is blended.
　以下、本発明を詳細に説明する。
　本発明の水中油型乳化組成物は、
　（Ａ）ジメチコジエチルベンザルマロネートと、
　（Ｂ）シリコーンエラストマーと、
　（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤と、
を含むものである。
　以下、各成分について詳細に説明する。
　なお、以下において、ＰＯＥはポリオキシエチレン、ＰＥＧはポリエチレングリコール、ＰＰＧはポリプロピレングリコールの略である。 Hereinafter, the present invention will be described in detail.
The oil-in-water emulsified composition of the present invention
(A) Dimethicodiethylbenzalmaronate and
(B) Silicone elastomer and
(C) A surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone, and
Is included.
Hereinafter, each component will be described in detail.
In the following, POE is an abbreviation for polyoxyethylene, PEG is an abbreviation for polyethylene glycol, and PPG is an abbreviation for polypropylene glycol.
（Ａ）ジメチコジエチルベンザルマロネート
　本発明の水中油型乳化組成物に含まれるジメチコジエチルベンザルマロネートは常温で液状のシリコーン変性化合物で、ポリシリコーン－１５とも呼ばれる。（Ａ）ジメチコジエチルベンザルマロネートは公知の紫外線吸収剤であり市販品を使用でき、例えば、「ＰＡＲＳＯＬ　ＳＬＸ」（ＤＳＭ　Ｎｕｔｒｉｔｉｏｎａｌ　Ｐｒｏｄｕｃｔｓ）が挙げられる。（Ａ）ジメチコジエチルベンザルマロネートの配合によって、さらに吸光度が相乗的に向上する作用機序は必ずしも明らかではないが、後述する（Ｂ）シリコーンエラストマーが構成する分子の穴に（Ａ）ジメチコジエチルベンザルマロネートが入り込むことで、（Ｂ）シリコーンエラストマーによる吸光度の低下を抑制することができるものと考えられる。 (A) Dimethicodiethylbenzalmalonate Dimethicodiethylbenzalmaronate contained in the oil-in-water emulsified composition of the present invention is a silicone-modified compound liquid at room temperature and is also called polysilicone-15. (A) Dimethicodiethylbenzalmalonate is a known ultraviolet absorber and a commercially available product can be used. Examples thereof include "PARSOL SLX" (DSM Nutritional Products). Although the mechanism of action in which (A) dimethicodiethylbenzalmalonate further synergistically improves the absorbance is not always clear, (A) dimethi is formed in the hole of the molecule composed of (B) silicone elastomer, which will be described later. It is considered that the inclusion of codiethylbenzalmalonate can suppress the decrease in absorbance due to (B) the silicone elastomer.
　（Ａ）ジメチコジエチルベンザルマロネートの配合量は、組成物全量に対して０．１～１０質量％であることが好ましく、より好ましくは０．３～８質量％、さらには０．５～５質量％であることが好ましい。組成物全量に対して０．１質量％以上であることで、吸光度をより向上させることができ、１０質量％以下であることでより良好な使用性を確保することができる。 The blending amount of (A) dimethicodiethylbenzalmalonate is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and further 0.5 by mass with respect to the total amount of the composition. It is preferably ~ 5% by mass. When it is 0.1% by mass or more with respect to the total amount of the composition, the absorbance can be further improved, and when it is 10% by mass or less, better usability can be ensured.
（Ｂ）シリコーンエラストマー
　本発明の水中油型乳化組成物に含まれるシリコーンエラストマー（架橋型シリコーン）は、特に限定されるものではないが、ジメチコンクロスポリマー、ジメチコン／ビニルジメチコンクロスポリマー（ポリシリコーン１１）、ジメチコン／フェニルビニルジメチコンクロスポリマー、ビニルジメチコン／ラウリルジメチコンクロスポリマー、ラウリルポリジメチルシロキシエチルジメチコン／ビス－ビニルジメチコンクロスポリマー、アルキル（Ｃ３０－４５）セテアリルジメチコンクロスポリマー、セテアリルジメチコンクロスポリマーからなる群より選択される１種または２種以上が好ましく用いられる。 (B) Silicone Elastomer The silicone elastomer (crosslinked silicone) contained in the oil-in-water emulsifying composition of the present invention is not particularly limited, but is not particularly limited, but is a dimethicone crosspolymer, a dimethicone / vinyldimethicone crosspolymer (polysilicone 11). , Dimethicone / phenylvinyldimethicone crosspolymer, vinyldimethicone / lauryldimethicone crosspolymer, laurylpolydimethylsiloxyethyl dimethicone / bis-vinyldimethicone crosspolymer, alkyl (C30-45) cetearyl dimethicone crosspolymer, cetearyl dimethicone crosspolymer. One or more selected from the group is preferably used.
　本発明の水中油型乳化組成物を調製するに際しては、シリコーンエラストマーを、常温で液状の油分で膨潤した膨潤物の形態で配合することが好ましい。これにより、架橋型シリコーンの分散性および安定性がさらに向上する。
　膨潤に用いられる液状油分としては、例えば液状シリコーン油、液状炭化水素油、液状エステル油、液状高級脂肪酸などが挙げられ、特に、常温（２５℃）で低粘度、例えば、１００ｍＰａ・ｓ以下の液状油分が好ましい。好ましい粘度範囲は、１～１００ｍＰａ・ｓである。
　好ましい配合形態であるシリコーンエラストマーの液状油膨潤物において、架橋型シリコーンと液状油の混合の比率は質量比で、５：９５～４０：６０が好適である。液状油膨潤物がこの質量比の範囲にあることで、水中油型乳化組成物の調製がより好適となる。 When preparing the oil-in-water emulsified composition of the present invention, it is preferable to blend the silicone elastomer in the form of a swelled product swollen with an oil that is liquid at room temperature. This further improves the dispersibility and stability of the crosslinked silicone.
Examples of the liquid oil content used for swelling include liquid silicone oil, liquid hydrocarbon oil, liquid ester oil, liquid higher fatty acid and the like, and in particular, low viscosity at room temperature (25 ° C.), for example, liquid of 100 mPa · s or less. Oil is preferred. The preferred viscosity range is 1 to 100 mPa · s.
In the liquid oil swelling product of the silicone elastomer, which is a preferable compounding form, the mixing ratio of the crosslinked silicone and the liquid oil is preferably 5:95 to 40:60 in terms of mass ratio. The fact that the liquid oil swelling material is within this mass ratio makes the preparation of an oil-in-water emulsified composition more suitable.
　シリコーンエラストマーの液状油膨潤物は、市販されているものを用いることも可能であり、市販品の例としては、以下のようなものが挙げられる。
　ジメチコンクロスポリマーの膨潤物としては、９０４０シリコーンエラストマーブレンド（ジメチコンクロスポリマー、デカメチルシクロペンタシロキサンの混合物で架橋物は１２％）、９０４１シリコーンエラストマーブレンド（ジメチコンクロスポリマー、ジメチコン５ｍＰａ・ｓの混合物で架橋物は１６％）、９０４５シリコーンエラストマーブレンド（ジメチコンクロスポリマー、デカメチルシクロペンタシロキサンの混合物で架橋物は１２．５％）、ＥＬ－８０４０ＩＤシリコーンオーガニックブレンド（ジメチコンクロスポリマー、イソドデカンの混合物で架橋物は１６％）（以上、東レ・ダウコーニング株式会社製）等が挙げられる。 As the liquid oil swelling product of the silicone elastomer, a commercially available product can be used, and examples of the commercially available product include the following.
As the swelling product of dimethicone crosspolymer, 9040 silicone elastomer blend (mixture of dimethicone crosspolymer and decamethylcyclopentasiloxane with 12% crosslinked product) and 9041 silicone elastomer blend (dimethicone crosspolymer, crosslinked with dimethicone 5 mPa · s mixture). 16%), 9045 Silicone Elastomer Blend (mixture of dimethicone crosspolymer, decamethylcyclopentasiloxane, 12.5% crosslinked), EL-8040ID Silicone Organic Blend (mixture of dimethicone crosspolymer, isododecane, crosslinked) 16%) (above, manufactured by Toray Dow Corning Co., Ltd.) and the like.
　ジメチコン／ビニルジメチコンクロスポリマーの膨潤物としては、ＫＳＧ－１５（（ジメチコン／ビニルジメチコン）クロスポリマー、シクロペンタシロキサンの混合物で架橋物は４～１０％）、ＫＳＧ－１６（（ジメチコン／ビニルジメチコン）クロスポリマー、ジメチコン６ｍＰａ・ｓの混合物で架橋物は２０～３０％）、ＫＳＧ－１６１０（（ジメチコン／ビニルジメチコン）クロスポリマー、メチルトリメチコンの混合物で架橋物は１５～２０％）（以上、信越化学工業社製）、ＧＲＡＮＳＩＬ　ＧＣＭ（ポリシリコーン－１１とオクタメチルシク ロテトラシロキサンの混合物で架橋物は約６％）、ＧＲＡＮＳＩＬ ＧＣＭ－５（ポリシ リコーン－１１とデカメチルシクロペンタシロキサンの混合物で架橋物は約６％）、ＧＲ ＡＮＳＩＬ　ＩＤＳ（ポリシリコーン－１１とイソデカンの混合物で架橋物は約７％）、 ＧＲＡＮＳＩＬ　ＤＭＧ－３（ポリシリコーン１１とジメチコン３ｍＰａ・ｓの混合物で、架橋物は約１２％）、ＧＲＡＮＳＩＬ ＤＭＧ－６（ポリシリコーン－１１とジメチコン６ｍＰａ・ｓの混合物 で架橋物は約１８％）、ＧＲＡＮＳＩＬ　ＤＭＧ－２０（ポリシリコーン－１１とジメチ コン２０ｍＰａ・ｓの混合物で架橋物は約２５％）、ＧＲＡＮＳＩＬ ＤＭＧ－５０（ポ リシリコーン－１１とジメチコン５０ｍＰａ・ｓの混合物で架橋物は約２６％）、ＧＲＡ ＮＳＩＬ　ＰＭ（ポリシリコーン－１１とフェニルトリメチコンの混合物で架橋物は約２ ０％）、ＧＲＡＮＳＩＬ ＩＮＩＮ（ポリシリコーン－１１とイソノナン酸イソノニルの 混合物で架橋物は約１５％）（以上、ＧＲＡＮＴ社製）等が挙げられる。 The swellings of the dimethicone / vinyl dimethicone crosspolymer include KSG-15 ((dimethicone / vinyl dimethicone) crosspolymer, a mixture of cyclopentasiloxane with a crosslinked product of 4 to 10%), and KSG-16 ((dimethicone / vinyldimethicone)). A mixture of cross-polymer and dimethicone 6 mPa · s with a crosslinked product of 20 to 30%), KSG-1610 (a mixture of (dimethicone / vinyl dimethicone) cross-polymer and methyltrimethicone with a cross-linked product of 15 to 20%) (above, Shinetsu) (Manufactured by Kagaku Kogyo Co., Ltd.), GRANSIL GCM (mixture of polysilicone-11 and octamethylcyclotetrasiloxane, about 6% crosslinked), GRANSIL GCM-5 (crosslinked with polymer-11 and decamethylcyclopentasiloxane) Approximately 6%), GR ANSIL IDS (mixture of polymer-11 and isodecane, approximately 7% crosslinked), GRANSIL DMG-3 (mixture of polymer 11 and dimethicone 3 mPa · s, crosslinked approximately 12) %), GRANSIL DMG-6 (a mixture of polymer-11 and dimethicon 6 mPa · s, about 18% crosslinked), GRANSIL DMG-20 (a mixture of polysilicone-11 and dimethicon 20 mPa · s, about 18% crosslinked). 25%), GRANSIL DMG-50 (a mixture of polymer-11 and dimethicone 50 mPa · s, about 26% crosslinked), GRANSIL PM (a mixture of polysilicone-11 and phenyltrimethicone, about 2 crosslinkeds). 0%), GRANSIL ININ (a mixture of polysilicone-11 and isononyl isononanoate with a crosslinked product of about 15%) (above, manufactured by GRANT) and the like.
　ジメチコン／フェニルビニルジメチコンクロスポリマーの膨潤物としては、ＫＳＧ－１８Ａ（（ジメチコン／フェニルビニルジメチコン）クロスポリマー、ジフェニルシロキシフェニルトリメチコンの混合物で架橋物は１０～２０％）（信越化学工業社製）等が挙げられる。 The swelling product of dimethicone / phenylvinyl dimethicone crosspolymer is KSG-18A (a mixture of (dimethicone / phenylvinyl dimethicone) crosspolymer and diphenylsiloxyphenyltrimethicone with a crosslinked product of 10 to 20%) (manufactured by Shin-Etsu Chemical Co., Ltd.). And so on.
　ビニルジメチコン／ラウリルジメチコンクロスポリマーの膨潤物としては、ＫＳＧ－４１（（ビニルジメチコン／ラウリルジメチコン）クロスポリマー、ミネラルオイルの混合物で架橋物は２５～３０％）、ＫＳＧ－４２（（ビニルジメチコン／ラウリルジメチコン）クロスポリマー、イソドデカンの混合物で架橋物は２０～３０％）、ＫＳＧ－４３（（ビニルジメチコン／ラウリルジメチコン）クロスポリマー、トリオクタノインの混合物で架橋物は２５～３５％）、ＫＳＧ－４４（（ビニルジメチコン／ラウリルジメチコン）クロスポリマー、スクワランの混合物で架橋物は２５～３５％）（以上、信越化学工業社製）等が挙げられる。 The swellings of the vinyl dimethicone / lauryl dimethicone cross-polymer include KSG-41 ((vinyl dimethicone / lauryl dimethicone) cross-polymer, 25-30% crosslinked product of a mixture of mineral oils), KSG-42 ((vinyl dimethicone / lauryl)). Dimethicone) Cross-polymer, cross-linked product of isododecane 20-30%), KSG-43 ((vinyl dimethicone / lauryl dimethicone) cross-polymer, cross-linked product of trioctanoin 25-35%), KSG-44 ((Vinyl dimethicone / lauryl dimethicone) cross-polymer, cross-linked product is 25-35% in a mixture of squalane) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.
　アルキル（Ｃ３０－４５）セテアリルジメチコンクロスポリマーの膨潤物としては、ＶＥＬＶＥＳＩＬ　１２５（アルキル（Ｃ３０－４５）セテアリルジメチコンクロスポリマー、シクロペンタシロキサンの混合物で架橋物は約１２．５％）、ＶＥＬＶＥＳＩＬ　Ｐｌｕｓ（アルキル（Ｃ３０－４５）セテアリルジメチコンクロスポリマー、シクロペンタシロキサン、ＰＥＧ／ＰＰＧ－２０／２３ジメチコン５ｍＰａ・ｓの混合物で架橋物は約２０％）（以上、モメンティブ・パフォーマンス・マテリアルズ社製）等が挙げられる。 As the swelling product of alkyl (C30-45) cetearyl dimethicone crosspolymer, VELVESIL 125 (a mixture of alkyl (C30-45) cetearyl dimethicone crosspolymer and cyclopentasiloxane, the crosslinked product is about 12.5%), VELVESIL Plus. (A mixture of alkyl (C30-45) cetearyl dimethicone crosspolymer, cyclopentasiloxane, PEG / PPG-20 / 23 dimethicone 5 mPa · s, and the crosslinked product is about 20%) (The above is manufactured by Momentive Performance Materials). And so on.
　セテアリルジメチコンクロスポリマーの膨潤物としては、ＶＥＬＶＥＳＩＬ　ＤＭ（セテアリルジメチコンクロスポリマー、ジメチコン５ｍＰａ・ｓの混合物で架橋物は約１７％）（モメンティブ・パフォーマンス・マテリアルズ社製）等が挙げられる。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はＫＳＧ－２１０（固形分２０～３０％）、フルオロアルキル基含有環状オルガノポリシロキサン等の環状フッ素含有シリコーンとの混合物としてはＫＳＧ －５１（固形分１５～２５％）、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はＫＳＧ－７１０（固形分２０～２５％）（以上、信越化学工業社製）等が挙げられる。 Examples of the swelling product of cetearyl dimethicone cross polymer include VELVESIL DM (a mixture of cetearyl dimethicone cross polymer and dimethicone 5 mPa · s with a crosslinked product of about 17%) (manufactured by Momentive Performance Materials). KSG-210 (solid content 20-30%) as a mixture of partially crosslinked polyether-modified silicone and dimethylpolysiloxane, and KSG-51 as a mixture with cyclic fluorine-containing silicone such as fluoroalkyl group-containing cyclic organopolysiloxane. Examples of the mixture of partially crosslinked polyglycerin-modified silicone and dimethylpolysiloxane (solid content 15 to 25%) include KSG-710 (solid content 20 to 25%) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
　アルキル基含有架橋型ポリエーテル変性シリコーンとしては、ミネラルオイル・ＰＥＧ－１５ラウリルジメチコンクロスポリマー（「ＫＳＧ－３１０」；信越化学工業社製）、イソドデカン・ＰＥＧ－１５ラウリルジメチコンクロスポリマー（「ＫＳＧ－３２０」；信越化学工業社製）、トリオクタノイン・ＰＥＧ－１５ラウリルジメチコンクロスポリマー（「ＫＳＧ－３３０」；信越化学工業社製）、スクワラン・ＰＥＧ－１５ラウリルジメチコンクロスポリマー・ＰＥＧ－１０ラウリルジメチコンクロスポリマー（「ＫＳＧ－３４０」；信越化学工業社製）、ジメチコン・（ＰＥＧ－１５／ラウリルポリジメチルシロキシエチルジメチコン（「ＫＳＧ３６０Ｚ」；信越化学工業社製）等が挙げられる。 Examples of the alkyl group-containing crosslinked polyether-modified silicone include mineral oil PEG-15 lauryldimethicone crosspolymer (“KSG-310”; manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and isododecane PEG-15 lauryldimethicone crosspolymer (“KSG-320”). ”; Trioctanoin PEG-15 lauryl dimethicone crosspolymer (“KSG-330 ”; manufactured by Shinetsu Chemical Industry Co., Ltd.), Squalane PEG-15 lauryl dimethicone cross polymer PEG-10 lauryl dimethicone cloth Examples include polymers (“KSG-340”; manufactured by Shin-Etsu Chemical Industry Co., Ltd.), dimethicone (PEG-15 / laurylpolydimethylsiloxyethyl dimethicone (“KSG360Z”; manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and the like.
　アルキル基含有架橋型ポリグリセリン変性シリコーンとしては、ミネラルオイル・（ラウリルジメチコン／ポリグリセリン３）クロスポリマー（「ＫＳＧ－８１０」；信越化学工業社製）、イソドデカン・（ラウリルジメチコン／ポリグリセリン３）クロスポリマー（「ＫＳＧ－８２０；信越化学工業社製」）、トリオクタノイン・（ラウリルジメチコン／ポリグリセリン３）クロスポリマー（「ＫＳＧ－８３０」；信越化学工業社製）、スクワラン・（ラウリルジメチコン／ポリグリセリン３）クロスポリマー（「ＫＳＧ－８４０」；信越化学工業社製）等が挙げられる。 Examples of the alkyl group-containing crosslinked polyglycerin-modified silicone include mineral oil (lauryldimethicone / polyglycerin 3) crosspolymer (“KSG-810”; manufactured by Shin-Etsu Chemical Co., Ltd.) and isododecane (lauryldimethicone / polyglycerin 3) cloth. Polymer ("KSG-820; manufactured by Shin-Etsu Chemical Co., Ltd."), trioctanoin (lauryldimethicone / polyglycerin 3) cross-polymer ("KSG-830"; manufactured by Shin-Etsu Chemical Co., Ltd.), squalane (lauryldimethicone / poly). Glycerin 3) Crosspolymer (“KSG-840”; manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.
　シリコーンエラストマーの配合量は、組成物全量に対し０．１～１０質量％であることが好ましく、より好ましくは１～８質量％、さらには２～７質量％であることが好ましい。配合量が０．１質量％以上であることでより塗布後の肌のべたつきやきしみの軽減、皮膚を柔軟化する効果が得られ、１０質量％以下であることで、組成物の安定性をより確保することができる。 The blending amount of the silicone elastomer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and further preferably 2 to 7% by mass with respect to the total amount of the composition. When the blending amount is 0.1% by mass or more, the effect of reducing the stickiness and squeak of the skin after application and the effect of softening the skin can be obtained, and when it is 10% by mass or less, the stability of the composition is improved. It can be secured more.
　（Ａ）ジメチコジエチルベンザルマロネートに対する（Ｂ）シリコーンエラストマーの質量比（（Ｂ）成分／（Ａ）成分）は０．１～２であることが好ましく、より好ましくは０．１２～１．９５、さらには０．１５～１．８であることが好ましい。質量比（Ｂ）／（Ａ）が０．１以上であることでよりべたつきのない滑らかな使用性となり、２以下であることで吸光度をより向上させることができる。 The mass ratio ((B) component / (A) component) of the (B) silicone elastomer to (A) dimethicodiethylbenzalmalonate is preferably 0.1 to 2, more preferably 0.12 to 1. It is preferably .95, more preferably 0.15 to 1.8. When the mass ratio (B) / (A) is 0.1 or more, the usability becomes smoother without stickiness, and when it is 2 or less, the absorbance can be further improved.
（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤
　本発明の水中油型乳化組成物に含まれる（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤（以下、単に（Ｃ）成分ともいう）としては、アルキル基含有ポリエーテル変性シリコーン、アルキル基含有ポリグリセリン変性シリコーン等を好適に挙げることができる。（Ｃ）成分の配合によって吸光度が飛躍的に向上する作用機序は必ずしも明らかではないが、（Ｂ）シリコーンエラストマーの分散が向上することが関係していると考えている。 (C) Surfactant of HLB8 or less having a hydrocarbon group having 4 or more carbon atoms in the dimethicone main chain (C) A hydrocarbon group having 4 or more carbon atoms in the dimethicone main chain contained in the oil-in-water emulsifying composition of the present invention. Preferred examples of the surfactant having an HLB of 8 or less (hereinafter, also simply referred to as the component (C)) include an alkyl group-containing polyether-modified silicone, an alkyl group-containing polyglycerin-modified silicone, and the like. The mechanism of action in which the absorbance is dramatically improved by blending the component (C) is not always clear, but it is considered to be related to the improvement in the dispersion of the silicone elastomer (B).
　アルキル基含有ポリエーテル変性シリコーンとしては、ラウリルＰＥＧ－９ポリジメチルシロキシエチルジメチコン：シリコーンＳＣ０９２８ＳＬ（信越化学工業社製）、セチルＰＥＧ／ＰＰＧ－１０／１ジメチコン：ＡＢＩＬ ＥＭ１８０（ゴールドシュミット社製）等が挙げられる。 Examples of the alkyl group-containing polyether-modified silicone include lauryl PEG-9 polydimethylsiloxyethyl dimethicone: silicone SC0928SL (manufactured by Shin-Etsu Chemical Co., Ltd.), cetyl PEG / PPG-10 / 1 dimethicone: ABIL EM180 (manufactured by Goldschmidt), and the like. Can be mentioned.
　アルキル基含有ポリグリセリン変性シリコーンとしては、ラウリルポリグリセリル－３ポリジメチルシロキシエチルジメチコン（「ＫＦ－６１０５」；信越化学工業社製）、ビスブチルジメチコンポリグリセリル－３（市販品としてシリコーンＫＦ－６１０９（信越化学工業社製））等が挙げられる。 Examples of the alkyl group-containing polyglycerin-modified silicone include laurylpolyglyceryl-3 polydimethylsiloxyethyl dimethicone (“KF-6105”; manufactured by Shin-Etsu Chemical Co., Ltd.) and bisbutyldimethicone polyglyceryl-3 (silicone KF-6109 (Shin-Etsu Chemical) as a commercial product). (Made by Kogyo Co., Ltd.))) and the like.
　（Ｃ）成分の配合量は、組成物全量に対し０．０１～１質量％であることが好ましく、より好ましくは０．０３～０．９質量％、さらには０．０５～０．８質量％であることが好ましい。配合量が０．０１質量％以上であることでより吸光度を向上させることができ、１質量％以下であることで、べたつきをより低減することができる。 The blending amount of the component (C) is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.9% by mass, and further preferably 0.05 to 0.8% by mass with respect to the total amount of the composition. % Is preferable. When the blending amount is 0.01% by mass or more, the absorbance can be further improved, and when it is 1% by mass or less, the stickiness can be further reduced.
　（Ｃ）成分に対する（Ｂ）シリコーンエラストマーの質量比（（Ｂ）成分／（Ｃ）成分）は０．５～１０であることが好ましく、より好ましくは０．５５～９、さらには０．６～８であることが好ましい。質量比（Ｂ）／（Ｃ）が０．５以上であることでべたつきをより低減することができ、１０以下であることでより吸光度を向上させることができる。 The mass ratio of the (B) silicone elastomer to the component (C) (component (B) / component (C)) is preferably 0.5 to 10, more preferably 0.55 to 9, and further 0.6. It is preferably ~ 8. When the mass ratio (B) / (C) is 0.5 or more, the stickiness can be further reduced, and when it is 10 or less, the absorbance can be further improved.
（Ｄ）油溶性紫外線吸収剤
　本発明の水中油型乳化組成物は、（Ａ）ジメチコジエチルベンザルマロネート以外の（Ｄ）油溶性紫外線吸収剤を含むことが好ましい。
　（Ｄ）油溶性紫外線吸収剤は、従来から化粧料に使用されているものであればよく特に限定されない。例えば、メトキシケイヒ酸誘導体、サリチル酸誘導体、ベンゾイル誘導体、カンファー誘導体、パラアミノ安息香酸誘導体、トリアジン誘導体、β，β－ジフェニルアクリレート誘導体およびベンゾフェノン誘導体が挙げられる。油溶性紫外線吸収剤は、必要に応じて１種または２種以上の組み合わせで配合することができる。 (D) Oil-soluble UV absorber The oil-in-water emulsified composition of the present invention preferably contains (D) an oil-soluble UV absorber other than (A) dimethicodiethylbenzalmalonate.
(D) The oil-soluble ultraviolet absorber is not particularly limited as long as it is conventionally used in cosmetics. For example, methoxycinnamic acid derivative, salicylic acid derivative, benzoyl derivative, camphor derivative, paraaminobenzoic acid derivative, triazine derivative, β, β-diphenylacrylate derivative and benzophenone derivative can be mentioned. The oil-soluble ultraviolet absorber may be blended in one kind or a combination of two or more kinds, if necessary.
　メトキシケイヒ酸誘導体としては、オクチルメトキシシンナメートまたはメトキシケイヒ酸エチルヘキシル（例えば「パルソールＭＣＸ」；ホフマン－ラ・ロシュ社）、メトキシケイヒ酸イソプロピル、メトキシケイヒ酸イソアミル（例えば「ネオ・ヘリオパンＥ１０００」；ハーマン・アンド・レイマー社）、シンノキセート、ＤＥＡメトキシシンナメート、メチルケイヒ酸ジイソプロピル、グリセリル－エチルヘキサノエート－ジメトキシシンナメート、ジ－（２－エチルヘキシル）－４’－メトキシベンザルマロネートなどが例示される。 Examples of the methoxycinnamic acid derivative include octylmethoxycinnamate or ethylhexyl methoxycinnamate (eg, "Pulsole MCX"; Hoffman-La Roche), isopropyl methoxycinnamate, and isoamyl methoxycinnamate (eg, "Neo Heliopan E1000"; Herman). And Reimer), cinnoxate, DEA methoxycinnamate, diisopropylmethylsilicate, glyceryl-ethylhexanoate-dimethoxycinnamate, di- (2-ethylhexyl) -4'-methoxybenzalmaronate, etc. are exemplified. ..
　サリチル酸誘導体としては、ホモサレート（「ユーソレックス（Ｅｕｓｏｌｅｘ）ＨＭＳ」；ロナ／ＥＭインダストリーズ社）、エチルヘキシルサリチレート（サリチル酸オクチル、例えば「ネオ・ヘリオパン（ＮｅｏＨｅｌｉｏｐａｎ）ＯＳ」；ハーマン・アンド・レイマー社）、ジプロピレングリコールサリチレート（例えば「ディピサル（Ｄｉｐｓａｌ）」；スケル社）、ＴＥＡサリチラート（例えば「ネオ・ヘリオパンＴＳ」；ハーマン・アンド・レイマー社）などが例示される。 Examples of the salicylic acid derivative include homosalate (“Eusolex HMS”; Lona / EM Industries), ethylhexyl salicylate (octyl salicylate, for example, “NeoHeliopan OS”; Herman and Reimer), Examples thereof include dipropylene glycol salicylate (eg, "Dipsal"; Skele), TEA salicylate (eg, "Neo Heliopan TS"; Herman and Reimer).
　ベンゾイル誘導体としては、４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン（例えば「パルソール１７８９」）などが例示される。 Examples of the benzoyl derivative include 4-tert-butyl-4'-methoxydibenzoylmethane (for example, "Pulsole 1789").
　カンファー誘導体としては、テレフタリリデン－３，３’－ジカンフル－１０，１０’－ジスルフォン酸塩、４－メチルベンジリデンカンファーなどが例示される。 Examples of the camphor derivative include terephthalylidene-3,3'-dikanfur-10,10'-disulfonate, 4-methylbenzylidenecamphor and the like.
　パラアミノ安息香酸誘導体としては、パラ－アミノ安息香酸（ＰＡＢＡ）エチル、エチル－ジヒドロキシプロピルＰＡＢＡ、エチルヘキシル－ジメチルＰＡＢＡ（例えば「エスカロール５０７」；ＩＳＰ社）、グリセリルＰＡＢＡ、ＰＥＧ－２５－ＰＡＢＡ（例えば「ユビナールＰ２５」；ＢＡＳＦ社）、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（例えば「ユビナールＡプラス」）などが例示される。 Examples of the para-aminobenzoic acid derivative include para-aminobenzoic acid (PABA) ethyl, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA (for example, "Escalol 507"; ISP), glyceryl PABA, and PEG-25-PABA (for example, "" Ubinal P25 ”; BASF), hexyl diethylaminohydroxybenzoylbenzoate (eg,“ Ubinal A Plus ”) and the like are exemplified.
　トリアジン誘導体としては、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（例えば「チノソーブ（Ｔｉｎｏｓｏｒｂ）Ｓ」；チバ・スペシャリティー・ケミカルズ社）、エチルヘキシルトリアゾン（例えば「ユビナールＴ１５０」；ＢＡＳＦ社）、ジエチヘキシルブタミドトリアゾン（例えば「ユバソーブ（Ｕｖａｓｏｒｂ）ＨＥＢ」；シグマ３　Ｖ社）、２，４，６－トリス（ジイソブチル－４’－アミノベンザルマロナート）－ｓ－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－トリアジンなどが例示される。 Examples of the triazine derivative include bisethylhexyloxyphenol methoxyphenyltriazine (for example, "Tinosorb S"; Ciba Specialty Chemicals), ethylhexyltriazone (for example, "Ubinal T150"; BASF), and dietihexylbutamide. Triazone (eg, "Uvasorb HEB"; Sigma 3V), 2,4,6-tris (diisobutyl-4'-aminobenzalmaronate) -s-triazine, 2,4,6-tris [ 4- (2-Ethylhexyloxycarbonyl) anilino] -1,3,5-triazine and the like are exemplified.
　β，β－ジフェニルアクリレート誘導体としては、オクトクリレン（例えば「ユビナールＮ５３９Ｔ」；ＢＡＳＦ社）などが例示される。 Examples of the β, β-diphenylacrylate derivative include octocrylene (for example, “Ubinal N539T”; BASF).
　ベンゾフェノン誘導体としては、ベンゾフェノン－１（例えば「ユビナール４００」；ＢＡＳＦ社）、ベンゾフェノン－２（例えば「ユビナールＤ５０」；ＢＡＳＦ社）、ベンゾフェノン－３またはオキシベンゾン（例えば「ユビナールＭ４０」；ＢＡＳＦ社）、ベンゾフェノン－４（例えば「ユビナールＭＳ４０」；ＢＡＳＦ社）、ベンゾフェノン－５、ベンゾフェノン－６（例えば「ヘリソーブ（Ｈｅｌｉｓｏｒｂ）１１」；ノルクアイ社）、ベンゾフェノン－８（例えば「スペクトラ－ソーブ（Ｓｐｅｃｔｒａ－Ｓｏｒｂ）ＵＶ－２４」；アメリカン・シアナミド社）、ベンゾフェノン－９（例えば「ユビナールＤＳ－４９」；ＢＡＳＦ社）、ベンゾフェノン－１２などが例示される。 Examples of the benzophenone derivative include benzophenone-1 (eg, "Ubinal 400"; BASF), benzophenone-2 (eg, "Ubinal D50"; BASF), benzophenone-3 or oxybenzone (eg, "Ubinal M40"; BASF), benzophenone. -4 (eg, "Ubinal MS40"; BASF), Benzophenone-5, Benzophenone-6 (eg, "Helisorb 11"; Norquay), Benzophenone-8 (eg, "Spectra-Sorb" UV- 24 ”; American Cyanamide), Benzophenone-9 (eg,“ Ubinal DS-49 ”; BASF), Benzophenone-12 and the like are exemplified.
　本発明において、（Ｄ）油溶性紫外線吸収剤の配合量は、組成物全量に対して８質量％以上であることが好ましく、より好ましくは９～２０質量％、さらには１０～１８質量％であることが好ましい。（Ｄ）油溶性紫外線吸収剤の配合量は、組成物全量に対して８質量％以上であるで、紫外線防御能をより高めることができる。 In the present invention, the blending amount of the (D) oil-soluble ultraviolet absorber is preferably 8% by mass or more, more preferably 9 to 20% by mass, and further preferably 10 to 18% by mass with respect to the total amount of the composition. It is preferable to have. (D) The blending amount of the oil-soluble ultraviolet absorber is 8% by mass or more with respect to the total amount of the composition, so that the ultraviolet protection ability can be further enhanced.
　本発明の水中油型乳化組成物は、通常の化粧料や医薬部外品に配合可能な他の任意成分を、本発明の効果を阻害しない範囲で配合することができる。他の任意成分としては、限定するものではないが、例えば、液体油脂、固体油脂、ロウ類、炭化水素油、高級脂肪酸、合成エステル油、シリコーン油などの油分、粉末成分、色剤、保湿剤、水性増粘剤、分散剤、防腐剤、香料、各種薬剤等が挙げられる。 The oil-in-water emulsified composition of the present invention can contain other optional ingredients that can be blended in ordinary cosmetics and quasi-drugs as long as the effects of the present invention are not impaired. Other optional components include, but are not limited to, oils such as liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, synthetic ester oils, and silicone oils, powder components, coloring agents, and moisturizers. , Aqueous thickeners, dispersants, preservatives, fragrances, various chemicals and the like.
　液体油脂としては、例えば、アボカド油、ツバキ油、マカデミアナッツ油、トウモロコシ油、オリーブ油、ナタネ油、ゴマ油、パーシック油、小麦胚芽油、サザンカ油、ヒマシ油、アマニ油、サフラワー油、綿実油、エノ油、大豆油、落花生油、茶実油、カヤ油、コメヌカ油、シナギリ油、日本キリ油、ホホバ油、胚芽油、トリグリセリン等が挙げられる。 Liquid fats and oils include, for example, avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, sesame oil, persic oil, wheat germ oil, southern ka oil, sunflower oil, flaxseed oil, safflower oil, cottonseed oil, and eno oil. , Soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, triglycerin and the like.
　固体油脂としては、例えば、カカオ脂、ヤシ油、硬化ヤシ油、パーム油、パーム核油、モクロウ核油、硬化油、モクロウ、硬化ヒマシ油等が挙げられる。 Examples of solid fats and oils include coconut oil, palm oil, hardened palm oil, palm oil, palm kernel oil, mokuro kernel oil, hydrogenated oil, mokuro, and hardened castor oil.
　ロウ類としては、例えば、ミツロウ、カンデリラロウ、綿ロウ、カルナウバロウ、ベイベリーロウ、イボタロウ、モンタンロウ、ヌカロウ、カポックロウ、サトウキビロウ、ラウリン酸ヘキシル、ホホバロウ、セラックロウ、ＰＯＥコレステロールエーテル等が挙げられる。 Examples of the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, montan wax, nukarou, capoc wax, sugar cane wax, hexyl laurate, jojoba wax, cellac wax, POE cholesterol ether and the like.
　炭化水素油としては、例えば、流動パラフィン、オゾケライト、スクワラン、プリスタン、パラフィン、セレシン、スクワレン、ワセリン、マイクロクリスタリンワックス、水添ポリデセン等が挙げられる。 Examples of the hydrocarbon oil include liquid paraffin, zokerite, squalane, pristan, paraffin, selecin, squalene, petrolatum, microcrystalline wax, hydrogenated polydecene and the like.
　高級脂肪酸としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、オレイン酸、ウンデシレン酸、トール酸、イソステアリン酸、リノール酸、リノレイン酸、エイコサペンタエン酸（ＥＰＡ）、ドコサヘキサエン酸（ＤＨＡ）等が挙げられる。 Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tortic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid ( DHA) and the like.
　合成エステル油としては、ミリスチン酸イソプロピル、オクタン酸セチル、ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、ステアリン酸ブチル、ラウリン酸ヘキシル、ミリスチン酸ミリスチル、オレイン酸デシル、ジメチルオクタン酸ヘキシルデシル、乳酸セチル、乳酸ミリスチル、酢酸ラノリン、ステアリン酸イソセチル、イソステアリン酸イソセチル、１２－ヒドロキシステアリン酸コレステリル、ジ－２－エチルヘキサン酸エチレングリコール、ジペンタエリスリトール脂肪酸エステル、モノイソステアリン酸Ｎ－アルキルグリコール、ジカプリン酸ネオペンチルグリコール、リンゴ酸ジイソステアリル、ジ－２－ヘプチルウンデカン酸グリセリン、トリ－２－エチルヘキサン酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、テトラ－２－エチルヘキサン酸ペンタエリスリトール、トリ－２－エチルヘキサン酸グリセリン、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、トリイソステアリン酸トリメチロールプロパン、セチル２－エチルヘキサノエート、２－エチルヘキシルパルミテート、トリミリスチン酸グリセリン、トリ－２－ヘプチルウンデカン酸グリセライド、ヒマシ油脂肪酸メチルエステル、オレイン酸オレイル、アセトグリセライド、パルミチン酸２－ヘプチルウンデシル、アジピン酸ジイソブチル、Ｎ－ラウロイル－Ｌ－グルタミン酸－２－オクチルドデシルエステル、アジピン酸ジ－２－ヘプチルウンデシル、エチルラウレート、セバシン酸ジ－２－エチルヘキシル、ミリスチン酸２－ヘキシルデシル、パルミチン酸２－ヘキシルデシル、アジピン酸２－ヘキシルデシル、セバシン酸ジイソプロピル、コハク酸２－エチルヘキシル、クエン酸トリエチル等が挙げられる。 Synthetic ester oils include isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate. , Lanorin acetate, Isocetyl stearate, Isocetyl isostearate, Cholesteryl 12-hydroxystearate, Di-2-ethylhexanoate ethylene glycol, Dipentaerythritol fatty acid ester, N-alkylglycol monoisostearate, Neopentyl glycol dicaprate, Apple Diisostearyl Acid, Di-2-Heptylundecanoate Glycerin, Tri-2-ethylhexanoic Acid Trimethylol Propane, Triisostearate Trimethylol Propane, Tetra-2-ethylhexanoate Pentaerythritol, Tri-2-ethylhexanoate Glycerin , Trioctanoate glycerin, triisopalmitate glycerin, triisostearate trimethylolpropane, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl Estel, oleyl oleate, acetglyceride, 2-heptyl undesyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamate-2-octyldodecyl ester, di-2-heptyl undesyl adipate, ethyl laurate, sebacine Examples thereof include di-2-ethylhexyl acid, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.
　シリコーン油としては、例えば、鎖状ポリシロキサン（例えば、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、ジフェニルポリシロキサン等）；環状ポリシロキサン（例えば、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、ドデカメチルシクロヘキサシロキサン等）、３次元網目構造を形成しているシリコーン樹脂、シリコーンゴム、各種変性ポリシロキサン（アミノ変性ポリシロキサン、ポリエーテル変性ポリシロキサン、アルキル変性ポリシロキサン、フッ素変性ポリシロキサン等）等が挙げられる。
　上記の各油分は、１種または２種以上を適宜組み合わせて用いることができる。 Examples of the silicone oil include chain polysiloxane (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxane (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane). (Sasiloxane, etc.)) Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) forming a three-dimensional network structure, etc. Be done.
Each of the above oil components may be used alone or in combination of two or more.
　粉末成分としては、酸化亜鉛、酸化チタン等の紫外線散乱剤、タルク、マイカ、カオリン等の体質顔料、ポリエチレン粉末、ポリメタクリル酸メチル粉末、ナイロン粉末等のポリマー粉末等が挙げられる。 Examples of the powder component include ultraviolet scattering agents such as zinc oxide and titanium oxide, extender pigments such as talc, mica and kaolin, and polymer powders such as polyethylene powder, polymethyl methacrylate powder and nylon powder.
　保湿剤としては、例えば、グリセリン、１，３－ブチレングリコール、ジプロピレングリコール、プロピレングリコール等の多価アルコール、トレハロース、ヒアルロン酸、コンドロイチン硫酸等の水溶性高分子等が挙げられる。 Examples of the moisturizer include polyhydric alcohols such as glycerin, 1,3-butylene glycol, dipropylene glycol and propylene glycol, and water-soluble polymers such as trehalose, hyaluronic acid and chondroitin sulfate.
　水性増粘剤としては、例えば、サクシノグリカン、（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポリマー、セルロースガム、カルボキシビニルポリマー、キサンタンガム、（アクリル酸ヒドロキシエチル／アクリロイルジメチルタウリンＮａ）コポリマー等が挙げられる。 Examples of the aqueous thickener include succinoglycan, (dimethylacrylamide / acryloyldimethyltaurine Na) crosspolymer, cellulose gum, carboxyvinyl polymer, xanthan gum, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer and the like. ..
　本発明の水中油型乳化組成物は、例えば、油相を構成する成分と水相を構成する成分とを別々に混合し、水相に油相を加えて乳化するなどといった、水中油型乳化組成物（化粧料）の常法に従って製造することができる。 The oil-in-water emulsification composition of the present invention is, for example, an oil-in-water emulsification in which a component constituting the oil phase and a component constituting the aqueous phase are separately mixed and the oil phase is added to the aqueous phase for emulsification. It can be produced according to a conventional method of composition (cosmetics).
　本発明の水中油型乳化組成物は、液状、乳液状、クリーム状、ジェル状、ババロア状等のさまざまな剤型の化粧料として提供されうる。
　また、本発明の水中油型乳化組成物は、スキンケア化粧料、日焼け止め化粧料、色剤を配合した化粧料、ファンデーション、化粧下地、ＢＢクリームとして提供することができる。 The oil-in-water emulsified composition of the present invention can be provided as cosmetics in various dosage forms such as liquid, milky, creamy, gelled, and bavarois.
Further, the oil-in-water emulsified composition of the present invention can be provided as a skin care cosmetic, a sunscreen cosmetic, a cosmetic containing a coloring agent, a foundation, a makeup base, and a BB cream.
　以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれによってなんら限定されるものではない。配合量は特記しない限りすべて質量％である。 The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Unless otherwise specified, all blending amounts are mass%.
（実施例１～３および比較例１～３）
　下記表１に示す処方で水中油型乳化組成物を作製し、作製した組成物について、以下の基準で評価した。 (Examples 1 to 3 and Comparative Examples 1 to 3)
An oil-in-water emulsified composition was prepared according to the formulation shown in Table 1 below, and the prepared composition was evaluated according to the following criteria.
（ピークトップ値）
　測定プレート（Ｓプレート）（５×５ｃｍのＶ溝ＰＭＭＡ板、ＳＰＦＭＡＳＴＥＲ－ＰＡ０１）に各例の組成物（サンプル）を２ｍｇ／ｃｍ２の量で滴下し、６０秒間指で塗布し、１５分間乾燥した後に、形成された塗膜の吸光度を株式会社日立製作所社製Ｕ－３５００型自記録分光光度計にて吸光度を測定した。無塗布のプレートをコントロールとし、吸光度（Ａｂｓ）を以下の式で算出し、吸光度の最大値ピークをピークトップ値とした。
　Ａｂｓ＝－ｌｏｇ（Ｔ／Ｔｏ）
　Ｔ：サンプルの透過率、Ｔｏ：無塗布の透過率 (Peak top value)
The composition (sample) of each example was added dropwise to a measurement plate (S plate) (5 × 5 cm V-groove PMMA plate, SPFMASTER-PA01) in an amount of 2 mg / cm 2 , applied with a finger for 60 seconds, and dried for 15 minutes. After that, the absorbance of the formed coating film was measured with a U-3500 type self-recording spectrophotometer manufactured by Hitachi, Ltd. Using the uncoated plate as a control, the absorbance (Abs) was calculated by the following formula, and the maximum value peak of the absorbance was taken as the peak top value.
Abs = -log (T / To)
T: Sample transmittance, To: Uncoated transmittance
＜吸光度（Ａｂｓ）積算値の測定＞
　測定プレート（Ｓプレート）（５×５ｃｍのＶ溝ＰＭＭＡ板、ＳＰＦＭＡＳＴＥＲ－ＰＡ０１）に各例の組成物（サンプル）を２ｍｇ／ｃｍ２の量で滴下し、６０秒間指で塗布し、１５分間乾燥した後に、形成された塗膜の吸光度を株式会社日立製作所社製Ｕ－３５００型自記録分光光度計にて測定した。無塗布のプレートをコントロールとし、吸光度（Ａｂｓ）を以下の式で算出し、２８０ｎｍ～４００ｎｍにおける測定値を積算し、吸光度積算値を求めた。
　Ａｂｓ＝－ｌｏｇ（Ｔ／Ｔｏ）
　Ｔ：サンプルの透過率、Ｔｏ：無塗布の透過率 <Measurement of integrated absorbance (Abs)>
The composition (sample) of each example was added dropwise to a measurement plate (S plate) (5 × 5 cm V-groove PMMA plate, SPFMASTER-PA01) in an amount of 2 mg / cm 2 , applied with a finger for 60 seconds, and dried for 15 minutes. After that, the absorbance of the formed coating film was measured with a U-3500 type self-recording spectrophotometer manufactured by Hitachi, Ltd. Using the uncoated plate as a control, the absorbance (Abs) was calculated by the following formula, and the measured values at 280 nm to 400 nm were integrated to obtain the integrated absorbance value.
Abs = -log (T / To)
T: Sample transmittance, To: Uncoated transmittance
　処方および評価結果を表１に示す。なお、表に示す成分のうち、主だったものの市販品名を以下に示す。
・(アクリレーツ/アクリル酸アルキル(Ｃ１０－Ｃ３０)）クロスポリマー：ＰＥＭＵＬＥＮ　ＴＲ－２（Ｌｕｂｒｉｚｏｌ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃ．製）・（アクリロイルジメチルタウリンアンモニウム／メタクリル酸ベヘネス－２５）クロスポリマー：ＡＲＩＳＴＯＦＬＥＸ　ＨＭＢ（クラリアントＧＭＢＨ社製）
・ビスブチルジメチコンポリグリセリル－３：シリコーンＫＦ－６１０９（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：シリコーンＳＣ０９２８ＳＬ（信越化学工業社製）
・セチルＰＥＧ／ＰＰＧ－１０／１ジメチコン：ＡＢＩＬ ＥＭ１８０（ゴールドシュミット社製）
・ラウリルベタイン：アノンＢＬ－ＳＦ（日油株式会社製）
・ポリシリコーン－１１／ジメチコン（３ＣＳ）：Ｇｒａｎｓｉｌ　ＤＭＧ－３（（ＧＲＡＮＴ　ＩＮＤＵＳＴＲＩＥＳ社製）
・ジメチコジエチルベンザルマロネート：パルソールＳＬＸ（ＤＳＭ　Ｎｕｔｒｉｔｉｏｎａｌ　Ｐｒｏｄｕｃｔｓ社製） The prescription and evaluation results are shown in Table 1. Of the components shown in the table, the names of the main commercial products are shown below.
-(Acryloyl / alkyl acrylate (C10-C30)) cross-polymer: PEMULEN TR-2 (rubrizol Advanced Materials, Inc.)-(Acryloyldimethyltaurine ammonium / behenes methacrylate-25) cross-polymer: ARISTOFLEX HMB (Clariant GMBH) Made by the company)
-Bisbutyldimethicone polyglyceryl-3: Silicone KF-6109 (manufactured by Shin-Etsu Chemical Co., Ltd.)
-Lauryl PEG-9 polydimethylsiloxyethyl dimethicone: Silicone SC0928SL (manufactured by Shin-Etsu Chemical Co., Ltd.)
-Cetyl PEG / PPG-10 / 1 dimethicone: ABIL EM180 (manufactured by Goldschmidt)
・ Lauryl betaine: Anon BL-SF (manufactured by NOF CORPORATION)
Polysilicone-11 / Dimethicone (3CS): Gransil DMG-3 ((manufactured by GRANT INDUSTRIES)
Dimethicodiethylbenzalmaronate: Parsole SLX (manufactured by DSM Nutritional Products)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例の水中油型乳化組成物はシリコーンエラストマーが配合されていても吸光度のピークトップ値、積算値ともに高かった。一方、（Ｃ）成分を含まない比較例１や（Ａ）ジメチコジエチルベンザルマロネートを含まない比較例２や３では吸光度のピークトップ値、積算値が優位に低下した。特に、比較例３はサンケア化粧品に有用であるとして最も使用されているオクトクリレンを増量しても実施例のピークトップ値、積算値には及ばなかった。 As shown in Table 1, the oil-in-water emulsified composition of the example had a high peak top value and integrated value of absorbance even when the silicone elastomer was blended. On the other hand, in Comparative Example 1 containing no component (C) and Comparative Examples 2 and 3 not containing dimethicodiethylbenzalmalonate, the peak top value and the integrated value of the absorbance were significantly lowered. In particular, in Comparative Example 3, even if the amount of octocrylene, which is most used as being useful for sun care cosmetics, was increased, the peak top value and the integrated value of Examples were not reached.

Claims (4)

  1. 　（Ａ）ジメチコジエチルベンザルマロネートと、
    　（Ｂ）シリコーンエラストマーと、
    　（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤と、
    を含む水中油型乳化組成物。     (A) Dimethicodiethylbenzalmaronate and
    (B) Silicone elastomer and
    (C) A surfactant having an HLB of 8 or less having a hydrocarbon group having 4 or more carbon atoms in the main chain of dimethicone, and
    An oil-in-water emulsified composition containing.
  2. 　前記（Ａ）ジメチコジエチルベンザルマロネート以外の（Ｄ）油溶性紫外線吸収剤を組成物全量に対し８質量％以上含む請求項１記載の水中油型乳化組成物。 The oil-in-water emulsified composition according to claim 1, which contains (D) an oil-soluble ultraviolet absorber other than (A) dimethicodiethylbenzalmalonate in an amount of 8% by mass or more based on the total amount of the composition.
  3. 　前記（Ｃ）ジメチコン主鎖に炭素数４以上の炭化水素基を有するＨＬＢ８以下の界面活性剤に対する（Ｂ）シリコーンエラストマーの質量比が０．５～１０である請求項１または２記載の水中油型乳化組成物。 The oil in water according to claim 1 or 2, wherein the mass ratio of the (B) silicone elastomer to the surfactant having an HLB 8 or less having a hydrocarbon group having 4 or more carbon atoms in the (C) dimethicone main chain is 0.5 to 10. Molded emulsion composition.
  4. 　前記（Ａ）ジメチコジエチルベンザルマロネートに対する前記（Ｂ）シリコーンエラストマーの質量比が０．１～２である請求項１、２または３記載の水中油型乳化組成物。 The oil-in-water emulsified composition according to claim 1, 2 or 3, wherein the mass ratio of the (B) silicone elastomer to the (A) dimethicodiethylbenzalmaronate is 0.1 to 2.
PCT/JP2021/032951 2020-09-09 2021-09-08 Oil-in-water emulsion composition WO2022054820A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010047538A (en) * 2008-08-22 2010-03-04 Shiseido Co Ltd Sunscreen cosmetic
JP2015510897A (en) * 2012-03-19 2015-04-13 ザ プロクター アンド ギャンブルカンパニー Superabsorbent polymers and silicone elastomers for use in skin care compositions
JP2016523983A (en) * 2013-07-22 2016-08-12 ザ プロクター アンド ギャンブル カンパニー Stable and high salt content skin care composition
JP2018168134A (en) * 2017-03-30 2018-11-01 株式会社コーセー Oil-in-water type cosmetic

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010047538A (en) * 2008-08-22 2010-03-04 Shiseido Co Ltd Sunscreen cosmetic
JP2015510897A (en) * 2012-03-19 2015-04-13 ザ プロクター アンド ギャンブルカンパニー Superabsorbent polymers and silicone elastomers for use in skin care compositions
JP2016523983A (en) * 2013-07-22 2016-08-12 ザ プロクター アンド ギャンブル カンパニー Stable and high salt content skin care composition
JP2018168134A (en) * 2017-03-30 2018-11-01 株式会社コーセー Oil-in-water type cosmetic

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