JP6789631B2 - High internal phase emulsion composition for improving SPF and rheology - Google Patents

Description

The present invention relates to cosmetic compositions for keratinous substances such as skin, and more specifically to cosmetic compositions in the form of oil-in-oil (O / W / O) polyphasic emulsions.

Emulsion compositions are commonly used in the cosmetic and dermatological fields because they are pleasing to use due to the exhilaration that the aqueous phase can provide. Emulsions include oil-in-water emulsions (O / W-type emulsions), water-in-oil emulsions (W / O-type emulsions), multi-phase emulsions of water-in-water emulsions (W / O / W-type emulsions), and oil-in-oil oils. It can take the form of a multiphase emulsion (O / W / O type emulsion). To date, several prior art documents have disclosed compositions in the form of polyphasic emulsions.

For example, US-A-5,814,321 is a partial ester derived from a polyhydric alcohol and fatty acid that retains at least 3 hydroxyl groups, 30-90% by weight oil phase A), nonionic surfactant B). 0.5-30% by weight emulsifier containing), and hydroxy fatty acid triglyceride C) (where the hydroxy groups of fatty acids are polyoxyethyleneized in 20-60 ethylene oxide units), E) 0.01-10% by weight Amino acids or salts thereof, and 0.01-10% by weight non-reducing sugars or sugar alcohols having at least 5 hydroxyl groups in the molecule, and 5-65% by weight aqueous phase D) (biologically acceptable and effective). An oil-in-water oil containing a water-in-oil type oil-based adjuvant phase containing (containing an amount of an antigen) and an outer aqueous phase F) containing 0.2 to 20% by mass of an emulsifier containing a nonionic surfactant. Discloses a medium-water oil-based adjuvant vaccine.

In addition, highly internal aqueous phase W / O emulsions consisting of large amounts of water are also known in the cosmetic and dermatological fields.

For example, US-A-2003 / 0064046 discloses a water-in-oil emulsion cosmetic composition with a high internal aqueous phase, which is (A) one or more of 0.1 to 10.0% by weight. Crosslinkable polyether-modified silicones having a specific structure in quantity, and (B) one or more specific structure-based polyether-modified silicones having an aqueous phase component content of at least 50% by weight. including.

In addition, JP-A-2010-132620 discloses a water-in-oil emulsified cosmetic that contains the following ingredients (A), (B), (C) and (D): It contains and meets the following requirements (1) and (2). Ingredients: (A) selected from one or more glycerin monooleate, glycerin monoisostearate and polyoxyethylene glyceryl monostearate; (B) aqueous ingredients; (C) oily ingredients; And (D) powder. Requirements: (1) Internal aqueous phase obtained by dividing the sum of the masses of the aqueous components of component (B) by the sum of the masses of the aqueous components of component (A) and component (B) and the oily component of component (C). The ratio of glycerin monooleate is at least 50%; (2) for component (A), the purity of glycerin monooleate is at least 90% by weight based on the total amount of glycerin monooleate, glycerin dioleate and glycerin trioleate. Yes; the purity of glycerin monoisostearate is at least 90% by weight relative to the total amount of glycerin monoisostearate, glycerin diisostearate and glycerin triisostearate; and the purity of polyoxyethylene glyceryl monostearate is monoisostearic acid. It is at least 90% by mass based on the total amount of polyoxyethylene glyceryl, polyoxyethylene glyceryl distearate and polyoxyethylene glyceryl tristearate.

These emulsion compositions are commonly used in sun care cosmetics for keratinous substances such as the skin. For Suncare products, good UV protection is one of the key features.

US-A-5,814,321 US-A-2003 / 0064046 JP-A-2010-132620 US-A-5364633 US-A-5411744 EP669323 US2,463,264

J. Soc. Cosm. Chem., 1954 (Volume 5), pp. 249-256 By F. Puisieux and M. Seiller, Galenica 5: Les systemes disperses [Dispersed systems] --Volume I --Agents de surface et emulsions [Surface agents and emulsions] --Chapter IV --Notions de HLB et de HLB critique [Notions of HLB and of critical HLB], pp. 153-194, Chapter 1.1.2., Determination de HLB par voie experimentale [Experimental determination of HLB], pp. 164-180 "Handbook of Surfactants", by M.R.Porter, Blackie & Son Publishers (Glasgow and London), 1991, pp. 116-178 Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics ASTM Standard 445 Appendix C

An object of the present invention is to provide an O / W / O polyphasic emulsion composition for keratin substances such as skin, preferably a cosmetic sun care O / W / O polyphasic emulsion composition, which has an improved UV protection effect. It is to be.

The above object of the present invention is a multiphase emulsion of oil in oil having an external oil phase, a large amount of internal aqueous phase in the external oil phase, and an internal oil phase dispersed as droplets in the large amount of internal aqueous phase. A composition in the form of (O / W / O type emulsion)
(a) At least one surfactant with an HLB of less than 13 and
(b) At least one oil and
(c) At least one UV shield and
(d) Including water
It can be achieved with a composition in which the amount of the large amount of internal aqueous phase is 60% by weight or more relative to the total mass of the composition and the droplet diameter of the internal oil phase is less than 200 nm.

The droplet diameter of the internal oil phase can be less than 150 nm, preferably less than 120 nm.

The amount of the large amount of the internal aqueous phase can be in the range of 60 to 99% by mass, preferably 70 to 95% by mass, and more preferably 80 to 90% by mass with respect to the total mass of the composition.

(a) The HLB value of the surfactant can be less than 12, preferably less than 10.

The viscosity of the composition can be 1 to 500 Pa · s, preferably 10 to 400 Pa · s, more preferably 50 to 350 Pa · s, and even more preferably 100 to 300 Pa · s at 25 ° C.

The amount of the internal oil phase may be in the range of 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass with respect to the total mass of the composition. it can.

The oil (b) in the external oil phase is an ester oil such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglyceride such as capryl caprylglyceride, sarcosinate such as isopropyl lauroyl sarcosate, and a hydrocarbon oil such as isohexadecane. , And mineral oils such as paraffin can be selected.

(a) Surfactant is a monoester of a polyol preferably selected from glycerol, sorbitan and diglycerol and a fatty acid containing 8 to 24 carbon atoms, preferably selected from isolauric acid and oleic acid. Specifically, they are esters of polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate, and glyceryl oleate, preferably polyether-modified dimethicone such as PEG / PPG-18 / 18 dimethicone and PEG-15 / lauryl dimethicone. Polyethers such as crosspolymers and nonionic surfactants, which are silicone surfactants that are alkyl-modified dimethicone crosspolymers, and polyoxyethylene alkyl ethers such as polyoxyethylene (3) to (17) lauryl ether carboxylic acids. It can be selected from anionic surfactants that are carboxylic acids.

(a) The amount of the surfactant can be in the range of 0.1 to 20% by mass, preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass with respect to the total mass of the composition.

The amount of the external oil phase may be in the range of 1% by mass to 40% by mass, preferably 2% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass with respect to the total mass of the composition. it can.

The oil (b) in the external oil phase is an ester oil such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglyceride such as capryl caprylglyceride, sarcosinate such as isopropyl lauroyl sarcosate, and a hydrocarbon oil such as isohexadecane. , Paraffin and other mineral oils, and silicone oils.

The composition may contain less than 10% by weight, preferably less than 5% by weight, water-soluble solvent with respect to the total mass of the composition.

Examples of the (c) UV shielding agent include both hydrophilic and hydrophobic UV shielding agents, and (c) the amount of the UV shielding agent is 1 to 40% by mass based on the total mass of the composition. It can be preferably in the range of 2 to 30% by mass, more preferably 5 to 20% by mass.

The present invention also relates to a cosmetic method for a keratin substance such as skin, and includes a step of applying the composition according to the present invention to the keratin substance.

The present invention also relates to a method of protecting a keratin substance from ultraviolet rays, and includes a step of applying the composition according to the present invention to the keratin substance.

This is an example of a schematic diagram of the O / W / O emulsion of the present invention.

As a result of diligent studies, the present inventors have found that in the sun care composition of O / W / O emulsion, introduction of a nano-sized oil phase into an aqueous phase can surprisingly improve the UV protection effect. It was.

In addition, the inventors have also found that incorporating a nano-sized oil phase into an O / W / O emulsion can improve its stability.

Therefore, the composition according to the present invention, preferably a cosmetic composition for a keratin substance, preferably for the skin, comprises an external oil phase, a large amount of internal aqueous phase in the external oil phase, and a large amount of internal aqueous phase. An O / W / O type emulsion having an internal oil phase dispersed therein.
(a) At least one surfactant with an HLB of less than 13 and
(b) At least one oil and
(c) At least one UV shield and
(d) Including water
An O / W / O type emulsion in which the amount of the large amount of the internal aqueous phase is 60% by mass or more with respect to the total mass of the composition, and the particle size of the internal oil phase is less than 200 nm.

The compositions according to the invention can exhibit an improved UV protection effect.

Hereinafter, the composition according to the present invention will be described in detail.

[Composition]
The composition according to the present invention takes the form of an O / W / O emulsion having an external oil phase, a large amount of internal aqueous phase in the external oil phase, and an internal oil phase dispersed in a large amount of internal aqueous phase. The external oil phase forms a continuous oil phase. The large amount of internal aqueous phase is in an amount of 60% by mass or more with respect to the total mass of the composition. The internal oil phase forms nano-sized droplets with a size of less than 200 nm. The composition comprises (a) at least one surfactant having an HLB of less than 13, (b) at least one oil, (c) at least one UV shield, and (d) water. And include.

It is preferable that the composition according to the present invention is a cosmetic composition, specifically a cosmetic sun care composition for keratin substances such as skin.

The compositions according to the invention can exhibit an improved UV protection effect. In addition, the compositions according to the invention can have good stability even when they are completely free of thickeners or even when they contain very small amounts of thickeners.

First, the structure of O / W / O of the composition according to the present invention will be described below.

(External oil phase)
The external oil phase in the O / W / O emulsion of the present invention is a continuous oil phase and (b) contains at least one oil. (b) In addition to the oil, the external oil phase may contain other hydrophobic / fat-soluble components such as hydrophobic UV shields and fat-soluble cosmetic active ingredients.

The amount of the external oil phase is not limited, but is generally 1% by mass to 40% by mass, preferably 2% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass, based on the total mass of the composition. The range.

(Large amount of internal aqueous phase)
The large amount of internal aqueous phase in the O / W / O emulsion of the present invention is (d) water and other hydrophilic / water-soluble components such as hydrophilic UV shields, hydrophilic organics allowed as cosmetics. Includes solvent (water-soluble solvent), thickener and neutralizer.

The large amount of internal aqueous phase results in a high internal phase emulsion (HIPE). Due to the large amount of aqueous phase, the shape of the droplets in the aqueous phase is generally polyhedral. In addition, a large amount of aqueous phase can contain a large amount of water, which can impart a refreshing sensation to the composition according to the invention when applied to the skin.

The large amount of internal aqueous phase forms micro-sized droplets. The size of the internal aqueous phase can be 1 μm or more, preferably less than 20 μm, more preferably less than 10 μm. The aqueous droplet diameter can be measured using, for example, a particle size distribution measuring device (VASCO, Cordouan Technologies).

The amount of the large amount of the internal aqueous phase is 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass of the composition. The upper limit of the amount of the large amount internal aqueous phase is not limited, but generally, it can be less than 99% by mass, preferably less than 95% by mass, and more preferably less than 90% by mass with respect to the total mass of the composition.

(Internal oil phase)
The internal oil phase in the O / W / O emulsion of the present invention forms droplets dispersed in a large amount of the internal aqueous phase and (b) contains at least one oil. (b) In addition to the oil, the internal oil phase may contain other hydrophobic / fat-soluble components such as hydrophobic UV shields and fat-soluble cosmetic active ingredients.

The internal oil phase forms nano-sized droplets. The droplet diameter of the internal oil phase is less than 200 nm, preferably less than 150 nm, more preferably less than 120 nm. In general, the droplet diameter of the internal oil phase is greater than 1 nm, preferably greater than 5 nm, more preferably greater than 10 nm. The droplet diameter of the oil phase is a number average particle diameter, and can be measured using, for example, a particle size distribution measuring device (VASCO, Cordouan Technologies).

The amount of the internal oil phase is not limited, but is generally 0.5% to 15% by weight, preferably 1% to 10% by weight, more preferably 2% to 5% by weight, based on the total weight of the composition. The range.

Surprisingly, we have found that nano-sized internal oil droplets in an O / W / O emulsion can improve the UV protection effect of the compositions according to the invention.

In addition, the present inventors have found that nano-sized internal oil droplets in an O / W / O emulsion can impart viscosity to the composition, thus improving the stability of the composition. Therefore, the compositions according to the invention are stable even when they contain virtually no thickener, or even when they contain a very small amount of thickener.

In one embodiment of the invention, the composition according to the invention is substantially free of thickeners, preferably less than 5% by weight, more preferably less than 1% by weight, based on the total mass of the composition. Contains thickeners.

The viscosity of the composition according to the present invention is not particularly limited. The viscosity can be measured at 25 ° C. using a rheometer, for example, a DHR2 rheometer (TA instrument) with a parallel plate arrangement. Preferably, the viscosity of the composition without any thickener is, for example, 25 ° C. and 0.01 to 1000 1 / s, 1 to 500 Pa · s, preferably 10 to 400 Pa · s, more preferably 50 to 350 Pa · s. It can be in the range of s, and even more preferably 100 to 300 Pa · s. In addition, the composition can have Newtonian fluid properties.

Moreover, the stability of the composition according to the invention can be characterized by its high yield stress value. Yield stress, as used herein, means the maximum stress at which the material maintains its structure. Beyond this stress, the material tends to flow or destabilize. In other words, high yield stresses help improve stability. High yield stress values can be calculated from shear rate response force curves measured at 25 ° C. using, for example, a rheometer, eg, a DHR2 rheometer with a parallel plate arrangement (TA instrument). Preferably, the yield stress value of the O / W / O multiphase emulsion according to the present invention is, for example, 25 ° C. and 0.01 to 1000 1 / s, and may be more than 30 Pa, preferably more than 50 Pa, and more preferably more than 70 Pa. it can.

FIG. 1 shows an example of a schematic diagram of the O / W / O emulsion of the present invention. This figure is for reference only and does not limit the scope of the invention. As shown in FIG. 1, the emulsion of the present invention has a polyphase structure, the outer oil phase forms a continuous oil phase in the emulsion, and a large amount of the internal aqueous phase is a polyhedral liquid in the outer oil phase. Droplets can be formed, forming nano-sized droplets in which the internal oil phase is dispersed in a large amount of the internal aqueous phase.

Next, the components of the composition according to the present invention will be described below.

(a) Surfactants The compositions according to the invention include (a) at least one surfactant having an HLB (hydrophilic lipophilic balance) of less than 13. Two or more kinds of (a) surfactants may be used in combination. Therefore, a single type of surfactant or a combination of different types of surfactants can be used.

The term HLB (“hydrophilic lipophilic balance”) is well known to those skilled in the art and refers to the hydrophilic lipophilic balance of surfactants. The HLB or hydrophilic lipophilic balance of surfactants used in accordance with the present invention can be found in the HLB by Griffin as defined in Publication J. Soc. Cosm. Chem., 1954 (Volume 5), pp. 249-256. Galenica 5: Les systemes disperses [Dispersed systems] --Volume I --Agents de surface et emulsions [Surface agents and emulsions], or published experimentally and with the following titles by F. Puisieux and M. Seiller: ] --Chapter IV --Notions de HLB et de HLB critique [Notions of HLB and of critical HLB], pp. 153-194, Chapter 1.1.2., Determination de HLB par voie experimentale [Experimental determination of HLB], pp. 164-180 It is the HLB described in.

Preferably, the (a) surfactant used in the composition has an HLB value of less than 12, more preferably less than 10. When two or more surfactants are used, their HLB values can be determined by the mass average of the HLB values of all the surfactants.

It is preferable to consider the calculated HLB value. The calculated HLB is defined as the following coefficients:
Calculated HLB = 20 x molar mass of hydrophilic portion / total molar mass.

Preferably, the lipophilic moiety of the surfactant consists of either a carbon atom and a hydrogen atom, or a silicon atom and a hydrogen atom.

The surfactant used in the composition according to the present invention can be selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Preferably, (a) the surfactant is selected from nonionic surfactants and anionic surfactants.

Nonionic Surfactants Nonionic surfactants are naturally well-known compounds [for example, in this regard, "Handbook of Surfactants", by MR Porter, Blackie & Son Publishers (Glasgow and London). , 1991, pp. 116-178].

Therefore, (a) the surfactant can be selected from, for example, esters of alcohols, α-diols, alkylphenols, and fatty acids, and these compounds are ethoxylated, propoxylated or glycerolified, for example. It may have at least one fatty chain containing 8 to 30 carbon atoms, the number of ethylene oxide or propylene oxide groups in the range of 2 to 50, and the number of glycerol groups in the range of 1 to 30. It is possible.

(a) The surfactant can preferably be selected from monooxyalkyleneized, polyoxyalkyleneed, monoglycerolized or polyglycerolized nonionic surfactants. More specifically, the oxyalkylene unit is an oxyethylene unit, an oxypropylene unit, or a combination thereof, and is preferably an oxyethylene unit.

Examples of monooxyalkyleneed or polyoxyalkyleneed nonionic surfactants that can be mentioned include
Monooxyalkyleneized or polyoxyalkyleneized (C _{8 to} C ₂₄ ) alkylphenols,
Saturated or unsaturated, linear or branched, monooxyalkyleneized or polyoxyalkyleneized C _8- C ₃₀ alcohols,
Saturated or unsaturated, linear or branched, monooxyalkyleneated or polyoxyalkyleneized C _8- C ₃₀ amides,
Saturated or unsaturated, linear or branched esters of C _{8 to} C ₃₀ acids with polyalkylene glycols,
Saturated or unsaturated, linear or branched, monooxyalkylene or polyoxyalkyleneized esters of C _{8 to} C ₃₀ acids with sorbitol,
Saturated or unsaturated, monooxyalkylene or polyoxyalkyleneized vegetable oils,
Condensations of ethylene oxide and / or propylene oxide, among others, alone or as a mixture.

Surfactants preferably contain a molar number of ethylene oxide and / or propylene oxide between 1 and 100, most preferably between 2 and 50. Advantageously, the nonionic surfactant does not contain any oxypropylene units.

According to one of the embodiments of the present invention, the polyoxyalkyleneized nonionic surfactants are polyoxyethylene glycol fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylene glycol ester (fatty acid). (Polyethylene glycol ester).

Examples of polyoxyethylene fatty alcohols (or C _{8 to} C ₃₀ alcohols) that can be mentioned include ethylene oxide adducts of lauryl alcohol, especially those containing 7 to 50 oxyethylene units, more specifically. Containing 6-12 oxyethylene units (Laures-7 to Laures-12 in CTFA name); Ethylene oxide adducts of behenyl alcohol, especially those containing 5-50 oxyethylene units (Behenes-in CTFA name) 5 to Behenes-50); ethylene oxide adducts of cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing 7 to 30 oxyethylene units (CTFA name: ceteares-7 to ceteares-30) , Ethylene oxide adducts of cetyl alcohol, especially those containing 7-30 oxyethylene units (CTFA name: Ceteth-7 to Ceteth-30); Stearyl alcohol ethylene oxide adducts, especially 7-30 oxyethylene units (CTFA name: Steares-7 to Steares-30), Ethylene oxide adducts of isostearyl alcohol, especially those containing 8 to 50 oxyethylene units (CTFA name: Isosteares-8 to Isosteares-50) , And mixtures thereof.

Monoglycerolized or polyglycerolized As an example of a nonionic surfactant, monoglycerolized or polyglycerolized C _{8 to} C ₄₀ alcohols are preferably used.

Specifically, monoglycerolized or polyglycerolized C _8- C ₄₀ alcohols have the following formula:
RO- [CH ₂ -CH (CH ₂ OH) -O] _m -H or RO- [CH (CH ₂ OH) -CH ₂ O] _m -H
(During the ceremony,
R represents a linear or branched C _{8 to} C ₄₀ , preferably C _{8 to} C ₃₀ alkyl or alkenyl group.
m represents a number in the range 1-30, preferably 1.5-10)
Corresponds to.

Examples of suitable compounds in the context of the present invention are lauryl alcohol containing 4 mol glycerol (INCI name: polyglyceryl-4 lauryl ether), lauryl alcohol containing 2 mol glycerol (INCI). Name: polyglyceryl-2 lauryl ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: polyglyceryl-4 oleyl ether), oleyl alcohol containing 2 mol of glycerol (INCI) Name: Polyglyceryl-2 oleyl ether), cetearyl alcohol containing 2 mol glycerol, cetearyl alcohol containing 6 mol glycerol, oleocetyl alcohol containing 6 mol glycerol, and 6 mol glycerol. Octadecanol.

Alcohols may represent a mixture of alcohols in the same way that the value of m represents a statistical value, even if multiple polyglycerolated fatty alcohols coexist in the form of a mixture in commercial products. It means good.

Among monoglycerolized or polyglycerolated alcohols, C ₈ / C ₁₀ alcohols containing 1 mol of glycerol, C ₁₀ / C ₁₂ alcohols containing 1 mol of glycerol, and C ₁₂ alcohols containing 1.5 mol of glycerol. It is preferable to use it.

Monoglycerolized or polyglycerolized C _{8 to} C ₄₀ fatty acid esters have the following formula:
R'O-[CH ₂ -CH (CH ₂ OR'')-O] _m -R'' or R'O-[CH (CH ₂ OR''')-CH ₂ O] _m -R''
(During the ceremony,
Each of R', R'' and R''' is independently a hydrogen atom, or a linear or branched C _{8 to} C ₄₀ , preferably C _{8 to} C ₃₀ alkyl-CO-group or alkenyl. Represents a -CO- group, provided that at least one of R', R'' and R'''is not a hydrogen atom
m represents a number in the range 1-30, preferably 1.5-10)
Can be equivalent to.

Examples of polyoxyethyleneylated fatty acid esters that can be mentioned include additions of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, particularly 9-100 oxyethylene units. Includes, for example laurate PEG-9 to PEG-50 laurate (CTFA name: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA name: PEG-9 palmitate) From PEG-50 palmitate); PEG-9 to PEG-50 steerate (CTFA name: PEG-9 steerate to PEG-50 steerate); PEG-9 to PEG-50 palmito steerate; PEG There are -9 to PEG-50 behenates (CTFA names: PEG-9 behenates to PEG-50 behenates); polyethylene glycol 100 EO monostearate (CTFA names: PEG-100 steerates); and mixtures thereof.

According to one of the embodiments according to the invention, the nonionic surfactant is saturated or unsaturated with a polyol and, for example, 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms. Esters with chain-bearing fatty acids and their polyoxyalkyleneized derivatives containing 10-200, more preferably 10-100 oxyalkylene units, such as C _8- C ₂₄ , preferably C _12- C. Monoglyceryl ester or polyglyceryl ester of one or more fatty acids of ₂₂ and its polyoxyalkyleneized derivative containing preferably 10 to 200, more preferably 10 to 100 oxyalkylene units; C _{8 to} C ₂₄ , A sorbitol ester of one or more fatty acids, preferably C _{12 to} C ₂₂ , and its polyoxyalkyleneized derivative, preferably containing 10 to 200, more preferably 10 to 100 oxyalkylene units; C ₈ to C. ₂₄ , preferably sugar (scrose, maltose, glucose, fructose, sorbitol, sorbitan and / or alkylglycose) esters of one or more fatty acids C _12- C ₂₂ , and preferably 10-200, more preferably 10 Its polyoxyalkyleneized derivatives containing ~ 100 oxyalkylene units; ethers of fatty alcohols; ethers of sugars with fatty alcohols of C ₈ ~ C ₂₄ , preferably C ₁₂ ~ C ₂₂ ; and mixtures thereof. can do.

Glyceryl esters of fatty acids include glyceryl laurate (mono-, di- and / or glyceryl tri-laurate), especially glyceryl monolaurate (CTFA name: glyceryl laurate, sold by Taiyo Kagaku Co., Ltd.), stearic acid. Glyceryl (mono-, di- and / or tri-glyceryl stearate) (CTFA name: glyceryl stearate), glyceryl monooleate (CTFA name: glyceryl oleate, sold by Taiyo Kagaku Co., Ltd.) or ricinolic acid Glyceryl, as well as mixtures thereof, can be cited and, as their polyoxyalkyleneized derivatives, mono-, di- or triesters of fatty acids with polyoxyalkyleneized glycerol (polyalkylene glycols of fatty acids, glycerol). Mono-, di- or triester with ether), preferably polyoxyethylene stearic acid (mono-, di- and / or tristearic acid) glyceryl, such as PEG-20 stearic acid (mono-, di-and / Or tristearic acid) glyceryl can be cited.

Mixtures of these surfactants, such as products containing glyceryl stearate and PEG-100 stearate marketed by Uniqema under the name ARLACEL 165, and glyceryl stearate (mono) marketed by Goldschmidt under the name TEGIN. Products containing glyceryl stearate and glyceryl distearate) and potassium stearate (CTFA name: glyceryl stearate SE) and the like can also be used.

Examples of fatty acid polyglyceryl esters include products containing 2 to 10 glycerol units, such as polyglyceryl monolaurate, specifically diglyceryl monolaurate (CTFA name: polyglyceryl laurate-2, Taiyo Kagaku Co., Ltd.) (Sold by), oleic acid ester, myristic acid ester, capric acid ester or stearic acid ester, containing 2 to 10 glycerol units, mono (iso) polyglyceryl stearate, containing 2 to 10 glycerol units, Polyglyceryl dioleate containing 2-10 glycerol units, polyglyceryl dilaurate containing 2-10 glycerol units, polyglyceryl dimyristate containing 2-10 glycerol units, birds containing 2-10 glycerol units Polyglyceryl myristate, polyglyceryl trioleate containing 2-10 glycerol units, and polyglyceryl tricaprylate containing 2-10 glycerol units.

The sorbitol esters of C _{8 to} C ₂₄ fatty acids and their polyoxyalkyleneized derivatives are sorbitan palmitate, sorbitan isostearate, sorbitan oleate, sorbitan stearate, sorbitan sesquioleate, sorbitan laurate, sorbitan caprylate and trioleic acid. Esters of sorbitan, as well as fatty acids and alkoxylated sorbitan containing, for example, 20-100 EOs, such as sorbitan monooleate (CTFA name: sorbitan oleate, sold by Croda), named by ICI Span 60 Polysorbate monostearate (CTFA name: sorbitan stearate) sold by ICI, sorbitan monopalmitate (CTFA name: sorbitan palmitate) sold by ICI under the name Span 40, and Tween 65 by ICI. You can choose from commercially available sorbitan tristearate 20 EO (CTFA name: polysorbate 65), polyethylene sorbitan trioleate (polysorbate 85), or compounds marketed by Uniqema under the trade name Tween 20 or Tween 60. it can.

As an ester of the fatty acid and glucose or alkyl glucose, glucose palmitate, alkyl glucose sesquistearate, such as methyl sesquistearate, alkyl glucose palmitate, such as methyl glucose palmitate or ethyl glucose palmitate, methyl glucoside fatty acid ester, Diester of methyl glucoside and oleic acid (CTFA name: methyl glucose dioleate), mixed ester of methyl glucoside and a mixture of oleic acid / hydroxystearic acid (CTFA name: methyl glucose dioleic acid / hydroxystearate), methyl glucoside And isostearic acid (CTFA name: methyl glucose isostearate), methyl glucoside and lauric acid (CTFA name: methyl lauric acid), methyl glucoside and isostearic acid, a mixture of monoester and diester (CTFA name: methyl glucose laurate). CTFA name: Methylglucose sesquiisostearate), a mixture of methylglucoside and stearate, monoester and diester (CTFA name: Methylglucose sesquistearate), and in particular products marketed under the name Glucate SS by AMERCHOL. , And a mixture of these can be cited.

As an ethoxylated ether of fatty acid and glucose or alkyl glucose, ethoxylated ether of fatty acid and methyl glucose, particularly methyl glucose and stearic acid such as a product marketed by AMERCHOL under the name Glucam E-20 distearate. Polyethylene glycol ether of diester with about 20 mol of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate), a mixture of methyl-glucose and stearic acid monoester and diester, with about 20 mol of ethylene oxide Polyethylene glycol ether (CTFA name: PEG-20 methyl glucose sesquistearate), specifically a product marketed by AMERCHOL under the name Glucamate SSE-20, and a product marketed by GOLD SCHMIDT under the name Grillocose PSE-20. Products, as well as mixtures thereof, can be cited, for example.

As sucrose esters, palmito-saccharose stearate, sucrose stearate and sucrose monolaurate can be cited, for example.

Alkyl polyglucosides can be used as the sugar ethers, for example, products marketed under the name MYDOL 10 by Kao Chemical, products marketed under the name PLANTAREN 2000 by Henkel, and ORAMIX NS by the name Seppic. Ethers of sugars containing decyl glucoside and C _{8 to} C ₂₄ fatty alcohols, such as those marketed in 10, are marketed under the name ORAMIX CG 110 by Seppic or under the name LUTEN SOL GD 70 by BASF. Capril glucosides such as products, lauryl glucosides such as products marketed under the name PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucosides such as products marketed under the name PLANTACARE 818 / UP by Henkel, for example. Settostearyl glucoside, sometimes mixed with setostearyl alcohol, commercially available by Seppic under the name MONTANO V 68, by Goldschmidt under the name TEGO-CARE CG90, and by Henkel under the name EMULGADE KE3302, by Seppic. Arakidyl glucoside in the form of a mixture of arachidyl and behenyl alcohol and arachidyl glucoside, commercially available in 202, for example, a mixture of cetyl and stearyl alcohol, marketed under the name MONTANO V 82 by Seppic (35/65) The form of cocoyl ethyl glucoside, as well as mixtures thereof, can be specifically cited.

A glyceride mixture of alkoxylated vegetable oils, such as a mixture of ethoxylated (200 EO) palm glycerides and copra (7 EO) glycerides, can also be cited.

The nonionic surfactant according to the invention preferably contains an alkenyl or branched C _12- C ₂₂ acyl chain, such as an oleyl group or an isostearyl group. More preferably, the nonionic surfactant according to the invention is PEG-20 glyceryl triisostearate.

According to one of the embodiments according to the invention, the nonionic surfactant is a copolymer of ethylene oxide and propylene oxide, in particular the following formula:
HO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H
(During the ceremony,
a, b and c are integers such that a + c is in the range 2-100 and b is in the range 14-60)
Can be selected from copolymers of these, as well as mixtures thereof.

Specifically, among these nonionic surfactants, a monoester of a polyol and a fatty acid is preferably used in the present invention. Glycerol, sorbitan and diglycerol are particularly preferable as the polyol, and lauric acid and oleic acid are particularly preferable as the fatty acid. The most preferred esters are polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate and glyceryl oleate.

According to one of the embodiments according to the invention, the nonionic surfactant is a copolymer of ethylene oxide and propylene oxide, in particular the following formula:
HO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H
(During the ceremony,
a, b and c are integers such that a + c is in the range 2-100 and b is in the range 14-60)
Can be selected from copolymers of these, as well as mixtures thereof.

According to one of the embodiments of the present invention, the nonionic surfactant can be selected from silicone surfactants. Non-limiting examples are those disclosed in the patent documents US-A-5364633 and US-A-5411744.

The silicone surfactant is preferably prepared by the following formula (I):

[During the ceremony,
R ₁ , R ₂ and R ₃ are independent of each other, C _{1 to} C ₆ alkyl groups or-(CH ₂ ) _x- (OCH ₂ CH ₂ ) _y- (OCH ₂ CH ₂ CH ₂ ) _z -OR ₄ groups. At least one group of R ₁ , R ₂ or R ₃ is not an alkyl group
R ₄ is a hydrogen, alkyl or acyl group;
A is an integer in the range 0-200
B is an integer in the range 0-50, where A and B cannot be equal to 0 at the same time.
x is an integer in the range 1-6
y is an integer in the range 1-30;
z is an integer in the range 0-5]
Can be a compound of.

According to a preferred embodiment of the invention, in the compound of formula (I), the alkyl group is a methyl group, x is an integer in the range 2-6 and y is in the range 4-30. Is an integer of.

An example of a silicone surfactant of formula (I) can be given as follows formula (II):

(During the ceremony,
A is an integer in the range 20-105, B is an integer in the range 2-10, and y is an integer in the range 10-20)
It is a compound of.

Further examples of silicone surfactants of formula (I) can be given as formula (III) :.
_{H- (OCH 2 CH 2) y} - (CH 2) 3 - [(CH 3) 2 SiO] A '- (CH 2) 3 - (OCH 2 CH 2) y -OH (III)
(During the ceremony,
A'and y are integers in the range 10-20)
It is a compound of.

The compounds of the invention that may be used are those sold by Dow Corning under the names DC5329, DC7439-146, DC2-5695 and Q4-3667. Compounds DC5329, DC7439-146 and DC2-5695 are compounds of formula (III), where A is 22 and B is 2 and y is 12, respectively; A is 103 and A is 103. B is 10 and y is 12; A is 27, B is 3, and y is 12. Compound Q4-3667 is a compound of formula (III), in which A is 15 and y is 13.

Specifically, as the silicone surfactant, an alkyldimethicone copolyxane, particularly an alkyl group having 10 to 22 carbon atoms, 2 to 50 oxyethylene groups, and 2 to 50 oxypropylene groups can be used. What you have, such as products marketed under the name Abil EM-90 by Goldschmidt, setyl dimethicone copolyxane (INCI name: cetyl PEG / PPG-10 / 1 dimethicone); lauryl dimethicone copolypolyxane (INCI name: lauryl PEG / PPG-18 / 18 methicone), and, for example, a mixture of about 91% lauryl dimethicone copoly polyol and about 9% isostearyl alcohol, commercially available under the name DOW CORNING 5200 FORMULATION AID by Dow Corning; dimethicone copolyxane, Among those having 2 to 50 oxyethylene groups and 2 to 50 oxypropylene groups, for example, a polyether-modified linear or branched having 18 oxyethylene groups and 18 oxypropylene groups. A polysiloxane polymer (PEG / PPG-18 / 18 dimethicone sold by Shin-Etsu Chemical Industry Co., Ltd.), for example, DC-3225C or DC2-5225C (INCI name: cyclopentasiloxane / PEG /) named by Dow Corning. PPG-18 / 18 Dimethicone), a mixture of 18 oxyethylene groups and 18 oxypropylene groups, cyclopentasiloxane, water and (10/88/2) dimethicone copoly polyols, or Those having 14 oxyethylene groups and 14 oxypropylene groups (PEG / PPG-14 / 14 dimethicone), eg, 14 oxyethylene groups and 14 commercially available by Goldschmidt under the name Abil EM-97. Examples thereof include a mixture of a dimethicone copolyol having (85/15) with an oxypropylene group of (INCI name: bis-PEG / PPG-14 / 14 dimethicone / cyclopentasiloxane).

Further, the silicone surfactant includes a cross-linked siloxane elastomer, for example a polyether-substituted or unsubstituted, dimethicone / copolypoly crosspolymer, dimethicone and dimethicone / PEG-10 / 15 crosspolymer, substituted or unsubstituted. Included are dimethicone / polyglyceryl crosspolymers, dimethicone and dimethicone / polyglycerin-3 crosspolymers. Such suitable emulsifying crosslinked siloxane elastomers include, for example, the polyether-modified dimethicone crosspolymer of the name "KSG-210" [INCI name is dimethicone (and) dimethicone / PEG-10 / 15 crosspolymer], and the name "KSG-". 710 ”polyglycerin-modified dimethicone crosspolymer [INCI name is dimethicone (and) dimethicone / polyglycerin-3 crosspolymer] sold or made, both available from ShinEtsu Silicones of America, Inc. (Aklon, Ohio). .. Among the crosslinked siloxane elastomers modified with polyether, crosslinked siloxane elastomers modified with polyether and alkyl chains, such as PEG-10 / lauryldimethicone crosspolymer and PEG-15 / lauryldimethicone crosspolymer (Shinetsu Chemical Industry Co., Ltd.) The names "KSG-310", "KSG-320", "KSG-330" or "KSG-340") are preferably used in the present invention. In crosslinked siloxane elastomers modified with polyethers and alkyl chains, the number of polyether units can be 2 to 50, preferably 5 to 20, and the number of alkyl chains is 8 to 24, preferably 12 to 22. Contains 1 carbon atom.

Anionic Surfactants Specific examples of anionic surfactants include phosphates and alkyl phosphates, carboxylates, sulfosuccinates, amino acid derivatives, alkyl sulfates, alkyl ether sulfates, sulfonates, You can choose from isethionic acid salts, taur phosphate salts, polyoxyethylene alkyl ether carboxylic acids, alkyl sulfoacetates, polypeptides, and mixtures thereof.

1) Phosphates and alkyl phosphates can be, for example, monoalkyl phosphates and dialkyl phosphates, for example sold by Kao Chemical Co., Ltd. under the name MAP 20®. Lauryl monophosphate, potassium salt of dodecyl phosphate as a mixture (mainly diester) of monoester and diester sold under the name Crafol AP-31® by Cognis, named Crafol AP- by Cognis A mixture of octyl phosphate monoester and diester sold under 20®, ethoxylated (7 mol EO) phosphorus sold under the name Isofol 12 7 EO-Phosphate Ester® by Condea A mixture of monoesters and diesters of 2-butyl octyl acid, mono (C _12- C ₁₃ ) sold by Uniqema under reference numbers Arlatone MAP 230K-40® and Arlatone MAP 230T-60®. ) Potassium or triethanolamine salts of alkyl phosphates, potassium lauryl phosphate sold by Rhodia Chimie under the name Dermalcare MAP XC-99 / 09®, and sold by Uniqema under the name Arlatone MAP 160K. It is potassium cetyl phosphate.

2) Carboxylates include:
--Amid Ether Carboxylate (AEC), for example Sodium Lauryl Amide Ether Carboxylate (3 EO), sold by Kao Chemical under the name Akypo Foam 30®,
--Polyoxyethyleneated carboxylates, such as sodium oxyethyleneated (6 EO) lauryl ether carboxylate (65/25/10, C ₁₂ ~) sold by Kao Chemicals under the name Akypo Soft 45 NV® C _{14 to} C ₁₆ ), polyoxyethylated fatty acids and carboxymethylated fatty acids derived from olive oil sold under the name Olivem 400 (registered trademark) by Biologia E Tecnologia, or Nikkol ECTD-6 NEX by Nikko Chemicals Co., Ltd. Sodium oxyethyleneated (6 EO) tridecyl ether carboxylate sold under (registered trademark), as well as
-Fatty acid salts with C _{6 to} C ₂₂ alkyl chains neutralized with organic or inorganic bases such as potassium hydroxide, sodium hydroxide, triethanolamine, N-methylglucamine, lysine and arginine (soap) ..

3) Specific examples of amino acid derivatives of amino acid alkali salts include the following:
--Sarcosine sarcosine, for example sodium lauroyl sarcosine sold under the name Sarkosyl NL 97® by Ciba or under the name Oramix L30® by Seppic, named Nikkol Sarcosinate MN by Nikko Chemicals Co., Ltd. Sodium myristyl sarcosine sold under (registered trademark), or sodium palmitoyl sarcosine sold under the name Nikkol Sarcosinate PN® by Nikko Chemicals Co., Ltd.,
--Alanate, for example N-lauroyl-N-methylamide sold by Nikko Chemicals Co., Ltd. under the name Sodium Nikkol Alaninate LN 30 (registered trademark) or by Kawaken Fine Chemicals Co., Ltd. under the name Alanone ALE (registered trademark). Sodium propionate, or triethanolamine N-lauroyl-N-methylalanine, sold by Kawaken Fine Chemicals Co., Ltd. under the name Alanone ALTA®,
--Glutamic acid, for example monococoyl glutamate triethanolamine sold by Ajinomoto Co., Inc. under the name Acylglutamate CT-12®, lauroyl glutamate sold by Ajinomoto Co., Inc. under the name Acylglutamate LT-12® Triethanolamine,
--Aspartate, for example a mixture of N-lauroyl aspartate triethanolamine and N-myristoyl aspartate triethanolamine, sold by Mitsubishi Chemical Corporation under the name Asparack®,
--Glycine derivatives (glycine salts), such as sodium N-cocoyl glycine, sold by Ajinomoto Co., Inc. under the names Amilite GCS-12® and Amilite GCK 12.
--Citric acid monoesters of oxyethyleneated (9 mol) coco alcohols, such as citrates, sold by Goldschmidt under the name Witconol EC 1129,
--Galacturonic acid salt, eg sodium dodecyl D-galactoside uronate sold by Soliance.

4) Sulfosuccinates can be, for example, oxyethyleneated (3 EO) sold by Witco under the names Setacin 103 Special® and Rewopol SB-FA 30 K 4®. Lauryl (70/30, C ₁₂ / C ₁₄ ) alcohol monosulfosuccinate, disodium salt of hemisulfosuccinic acid from C _{12 to} C ₁₄ alcohols sold under the name Setacin F Special Paste® by Zschimmer Schwarz , Sold under the name Standapol SH 135® by Cognis, disodium oxyethyleneated (2 EO) oleamide sulfosuccinate, sold under the name Lebon A-5000® by Sanyo Kasei Kogyo Co., Ltd. Oxyethyleneated (5 EO) lauramide monosulfosuccinate, a disodium salt of oxyethyleneated (10 EO) laurylcitrate monosulfosuccinic acid, sold by Witco under the name Rewopol SB CS 50®, Alternatively, it is a ricinolic acid monoethanolamide monosulfosuccinate sold by Witco under the name Rewoderm S 1333®. Further available are polydimethylsiloxane sulfosuccinates such as PEG-12 dimethicone disodium sulfosuccinate sold by MacIntyre under the name Mackanate-DC 30.

5) Alkyl sulfates can be, for example, triethanolamine lauryl sulphate (CTFA name: TEA lauryl sulphate), for example, products sold under the name Empicol TL40 FL by Huntsman, or Texapon T42 by Cognis. Products sold at, these products are 40% aqueous solutions. Further mentioned is ammonium lauryl sulphate (CTFA name: ammonium lauryl sulphate), such as the products sold by Huntsman under the name Empicol AL 30FL, which is a 30% aqueous solution.

6) Alkyl ether sulfates can be, for example, sodium lauryl ether sulfate (CTFA name: sodium laureth sulfate), such as those sold by Cognis under the names Texas N40 and Texas AOS 225 UP, or Cognis. It is ammonium lauryl ether sulfate (CTFA name: ammonium laureth sulfate) such as that sold by the company under the name Standapol EA-2.

7) Examples of sulfonates include α-olefin sulfonates, eg, Witconate AOS Protege, sold by Stepan under the name Bio-Terge AS-40®, by Witco. (R) and Sulframine AOS PH 12 (R) sold by, or Stepan Company name Bio-Terge AS-40 CG sold (R) alpha-olefin sodium sulfonate by (C ₁₄ ~ C ₁₆ ), a secondary sodium olefin sulfonate sold under the name Hostapur SAS 30® by Clariant; or a linear alkylaryl sulfonate, eg, Manrosol SXS 30® by Manro. ), Manrosol SXS40® and Manrosol SXS93® are sodium xylene sulfonates.

8) Examples of isethionic acid salts include acyl isethionic acid salts, for example, sodium cocoyl isethionate, such as products sold by Jordan under the name Jordapon CIP®.

9) Taurinate can be mentioned as the sodium salt of palm kernel oil methyl taurate sold by Clariant under the name Hostapon CT Pate®; N-acyl-N-methyl taurate, eg. Sodium N-cocoyl-N-methyltaurate sold by Clariant under the name Hostapon LT-SF® or by Nikko Chemicals Co., Ltd. under the name Nikkol CMT-30-T® , Sodium palmitoyl methyl taurate sold under the name Nikkol PMT® by Nikko Chemicals Co., Ltd., or sodium stearoyl methyl taurate sold under the name Sunsoft O-30S by Nikko Chemicals Co., Ltd.

10) Polyoxyethylene alkyl ether carboxylic acid can be mentioned, for example, formula (IV) :.
RO [CH ₂ O] _u [(CH ₂ ) _x CH (R') (CH ₂ ) _y (CH ₂ ) _z O] _v [CH ₂ CH ₂ O] _w CH ₂ COOH (IV)
(During the ceremony,
R is a hydrocarbon group containing 6 to 40 carbon atoms.
u, v and w represent numbers in the range 0-60, independent of each other.
x, y and z represent numbers from 0 to 13 independently of each other.
R'represents hydrogen, alkyl, preferably C _{1 to} C ₁₂ alkyl;
The sum of x + y + z is greater than or equal to 0)
It is a compound corresponding to.

In formula (IV), R is linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted. Examples of substituents are monovalent functional groups such as halogen atoms, hydroxyl groups, C _{1 to} C ₆ alkoxy groups, amino groups, C _{1 to} C ₆ alkylamino groups, C _{1 to} C ₆ Dialkylamino group, nitro group, carbonyl group, acyl group, carboxyl group, cyano group and the like. Typically, R is a linear or branched, acyclic C _{6 to} C ₄₀ alkyl or alkenyl group, or C _{1 to} C ₄₀ alkylphenyl group, more typically C ₈ ~ C ₂₄ alkyl group or alkenyl group, or C ₄ ~ C ₂₀ alkylphenyl group, and more typically C ₁₀ ~ C ₁₈ alkyl group or alkenyl group, or C ₆ ~ C ₁₆ alkylphenyl group. It may be substituted; u, v, w are independent of each other, typically numbers 2-20, more typically numbers 3-17, most typically 5-15. X, y, z are independent of each other, typically numbers from 2 to 13, more typically numbers from 1 to 10, and most typically numbers from 0 to 8.

The polyoxyethylene alkyl ether carboxylic acid corresponding to formula (IV) can be obtained by alkoxylation of alcohol ROH with ethylene oxide as a single alkoxide, or by alkoxylation with several alkoxides followed by oxidation. Can be done. The numbers u, v and w represent the degree of alkoxylation, respectively. At the molecular level, the numbers u, v and w, as well as the total degree of alkoxylation can only be integers containing zero, but at the macroscopic level they are mean values in the form of fractions. Examples of the fatty ether carboxylic acid include polyoxyalkyleneized (C _{6 to} C ₃₀ ) alkyl ether carboxylic acids and salts thereof, and more specifically polyoxyethyleneated (C _{6 to} C ₃₀ ) alkyl ether carboxylic acids and salts thereof; Examples thereof include polyoxyalkyleneized (C _{6 to} C ₃₀ ) alkylaryl ether carboxylic acids and salts thereof; and polyoxyalkyleneized (C _{6 to} C ₃₀ ) alkylamide ether carboxylic acids. Preferably, the fatty ether carboxylic acid is a polyoxyethylene (3)-(17) lauryl ether carboxylic acid.

Suitable polyoxyethylene alkyl ether carboxylic acids include, but are not limited to, the following representative examples referred to by their INCI name: butoxinol-5-19 carboxylic acids, capriles-4-25 carboxylic acids, Cose-7 Carboxylic Acid, C _9-15 Palace-6-8 Carboxylic Acid, Deces-7 Carboxylic Acid, Laures-3-17 Carboxylic Acid, eg Laures-5 Carboxylic Acid, PPG-6-Laures-6 Carboxylic Acid, PPG -8-Staires-7 Carboxylic Acid, Milles-3-5 Carboxylic Acid, Nonoxinol-5-10 Carboxylic Acid, Octes-3 Carboxylic Acid, Octoxinol-20 Carboxylic Acid, Ores-3-10 Carboxylic Acid, PPG -3-Decess-2 Carboxylic Acid, Caprice-2 Carboxylic Acid, Ceteth-13 Carboxylic Acid, Decess-2 Carboxylic Acid, Hexes-4 Carboxylic Acid, Isosteares-6-11 Carboxylic Acid, Tordeces-3-12 Carboxylic Acid, Trideces -3 to 19 carboxylic acids, Undeces-5 carboxylic acids, and mixtures thereof.

Preferably, (a) the surfactant used in the composition according to the invention is preferably selected from polyols selected from glycerol, sorbitan and diglycerol, preferably selected from isolauric acid and oleic acid, 8 Monoesters with fatty acids containing ~ 24 carbon atoms, specifically polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate and glyceryl oleate, preferably PEG / PPG-18 / 18 Polyether-modified dimethicone such as dimethicone, polyether such as PEG-15 / lauryl dimethicone crosspolymer, and silicone surfactant which is an alkyl-modified dimethicone crosspolymer, nonionic surfactant and polyoxyethylene (3) to ( 17) It can be selected from anionic surfactants which are polyoxyethylene alkyl ether carboxylic acids such as lauryl ether carboxylic acid.

Representative examples of the surfactants used in the present invention and their HLV values are shown below.

The amount of (a) surfactant in the composition according to the present invention is not limited and is 0.1 to 20% by mass, preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total mass of the composition. Can be in the range of.

(b) Oil The composition according to the invention comprises (b) at least one oil. Two or more kinds of (b) oils may be used in combination. Therefore, a single type of oil or a combination of different types of oil can be used. In the present invention, (b) oil can be contained in both the outer oil phase and the inner oil phase.

As used herein, the expression "oil" means an aliphatic compound or substance in the form of a liquid or paste (non-solid) at room temperature (25 ° C.) under atmospheric pressure (760 mmHg). These oils may be volatile or non-volatile, preferably non-volatile.

(b) The oil may be a non-polar oil such as a hydrocarbon oil or a silicone oil; a polar oil such as a vegetable oil or an animal oil, and an ester oil or an ether oil; or a mixture thereof.

Hydrocarbon oils can be selected from:
--Linear or branched, optionally cyclic, C _{6 to} C ₁₆ lower alkanes. Examples can be hexane, undecane, dodecane, tridecane and isoparaffin, such as isohexadecane, isododecane and isodecan, and
--Linear or branched hydrocarbons containing more than 16 carbon atoms such as liquid paraffin, liquid petrolatum, polydecene and hydrogenated polyisobutene, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (eg liquid paraffin), paraffin, petrolatum or petrolatum, naphthalene and the like. Hydrocarboned polyisobutene, isoeikosan, and decene / butene copolymers; and mixtures thereof.

Examples of silicone oils include, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane; cyclic organopolysiloxanes such as octamethylcyclotetra. Siloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc .; and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxane (PDMS), and liquid polyorganosiloxanes containing at least one aryl group.

These silicone oils may also be organically modified. The organically modified silicones that can be used according to the present invention are as defined above and are silicone oils containing one or more organic functional groups bonded via hydrocarbon groups in the structure.

Organopolysiloxane is defined in great detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile.

When they are volatile, silicones are more specifically selected from those with boiling points between 60 ° C and 260 ° C, and even more specifically from the following:
(i) A cyclic polydialkyl siloxane containing 3 to 7, preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxanes sold under the name Volatile Silicone® 7207 by Union Carbide or under the name Silbione® 70045 V2 by Rhodia, Volatile Silicone by Union Carbide. Decamethylcyclopentasiloxane sold by Rhodia under the name Silbione® 70045 V5, and dodecamethylcyclopentasiloxane sold by Momentive Performance Materials under the name Silsoft 1217, and It is a mixture of these. Further mentioned are cyclocopolymers of the following type, such as dimethylsiloxane / methylalkylsiloxane, such as Silicone Volatile® FZ 3109, sold by Union Carbide.

D'' in the formula

And D'is

Is.

Further examples include a mixture of cyclic polydialkylsiloxane and an organosilicon compound, such as a mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50), and octamethylcyclotetrasiloxane and oxy-1. , 1'-Bis (2,2,2', 2', 3,3'-hexatrimethylsilyloxy) is a mixture with neopentane.
(ii) A linear volatile polydialkylsiloxane containing 2 to 9 silicon atoms and having a viscosity of 5 × 10 ^-6 m ² / s or less at 25 ° C. An example is the decamethyltetrasiloxane sold under the name SH 200, especially by Toray Silicone. Silicones belonging to this category are also described in articles published in Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicone is measured at 25 ° C. according to ASTM Standard 445 Appendix C.

Non-volatile polydialkylsiloxanes can also be used. These non-volatile silicones are more specifically selected from polydialkylsiloxanes, among which mainly polydimethylsiloxanes containing a trimethylsilyl terminal group can be mentioned.

Among these polydialkylsiloxanes, the following commercial products can be mentioned without limitation:
--Silbione® 47 and 70 047 series or Mirasil® oils sold by Rhodia, eg Oil 70 047 V 500 000,
--Mirasil® series oils sold by Rhodia,
--200 series oils from Dow Corning, eg DC200 with a viscosity of 60000 mm ² / s,
--Viscasil® oil from General Electric and certain SF series oils from General Electric (SF 96, SF 18).

Further mentioned are polydimethylsiloxanes containing dimethylsilanol end groups, known by the name Dimethiconol (CTFA), such as 48 series oils from Rhodia.

Among silicones containing an aryl group, there are polydiarylsiloxanes, particularly polydiphenylsiloxanes and polyalkylarylsiloxanes. Examples that can be given are products sold under the following names:
--Silbione® oil 70 641 series from Rhodia,
--Rhodorsil® 70 633 and 763 series oils from Rhodia,
--Oil from Dow Corning Dow Corning 556 Cosmetic Grade Fluid,
--PK series silicone from Bayer, eg product PK20,
--Specific SF series oils from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

Examples of vegetable oils include flaxseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, southern ka oil, sunflower oil, red flower oil, jojoba oil, sunflower oil, almonds. Oils, rapeseed oils, sesame oils, soybean oils, peanut oils, and mixtures thereof.

Examples of animal oils include, for example, squalene and squalene.

Examples of synthetic oils are alkane oils such as isodecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

Ester oil, preferably a saturated or unsaturated, liquid esters of linear or branched, C ₁ -C ₂₆ aliphatic monoacid or polyacid, and a saturated or unsaturated, linear or branched ramified, a C ₁ -C ₂₆ aliphatic monoalcohol or liquid esters of polyalcohols, the total number of carbon atoms of these esters is 10 or more.

Preferably, in the ester of monoalcohol, at least one of the alcohols and acids from which the ester of the invention is derived is branched.

Among the monoesters of monoacids and monoalcohols are ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carboxylate, alkyl myristate, such as isopropyl myristate or ethyl myristate, isocetyl stearate. , 2-Ethylhexyl isononanoate, isononyl isononanoate, isodesyl neopentanoate and isostearyl neopentanoate.

Esters of C _{4 to} C ₂₂ dicarboxylic acids or tricarboxylic acids and C _{1 to} C ₂₂ alcohols, and monocarboxylic acids, dicarboxylic acids or tricarboxylic acids, and non-sugars C _{4 to} C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or Esters with pentahydroxy alcohols can also be used.

Particularly mentioned are diethyl sebacate, isopropyl lauroyl sarcosate, diisopropyl sebacate, bis sebacate (2-ethylhexyl), diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis adipate (dioctyl adipate). 2-Ethylhexyl), diisostearyl adipate, bis maleate (2-ethylhexyl), triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactic acid, glyceryl trioctanoate, trioctyldodecyl citrate, citrate Trioleyl acid, neopentyl glycol diheptate, and diethylene glycol diisononanonate.

As the ester oil, sugar esters and diesters of C _{6 to} C ₃₀ , preferably C _{12 to} C ₂₂ fatty acids can be used. The term "sugar" means an oxygen-retaining hydrocarbon compound that contains several alcohol functional groups, contains or does not contain aldehyde or ketone functional groups, and contains at least 4 carbon atoms. Is recalled. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that can be mentioned include sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives such as methyl. Derivatives, such as methyl glucose.

Fatty acid sugar esters are particularly from the group comprising esters or ester mixtures of the above-mentioned sugars with linear or branched, saturated or unsaturated C _{6 to} C ₃₀ preferably C _{12 to} C ₂₂ fatty acids. You can choose. If they are unsaturated, these compounds can have 1-3 conjugated or unconjugated carbon-carbon double bonds.

Esters in this modified form can also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters include, for example, oleic acid ester, lauric acid ester, palmitic acid ester, myristic acid ester, bechenic acid ester, coconut oil fatty acid ester, stearic acid ester, linoleic acid ester, linolenic acid ester, capric acid ester and arachidonic acid. It may be an ester, or a mixture thereof, for example, a mixed ester of an oleopalmitic acid ester, an oleostearic acid ester, and a palmitostearic acid ester, and pentaerythrityl tetraethylhexanoate.

More specifically, monoesters and diesters, especially monooleic acid or dioleic acid esters of sucrose, glucose or methyl glucose, stearic acid esters, behenic acid esters, oleopalmitic acid esters, linoleic acid esters, are used. Linolenic acid ester and oleostearic acid ester.

An example that can be mentioned is the product sold by Amerchol under the name Glucate® DO, which is methylglucose dioleate.

Examples of preferred ester oils include, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanate, octyldodecyl octanate, isodecyl neopentate, myristyl propionate, 2-Ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylic acid / caprylic acid, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprilyl carbonate, isopropyl lauroyl sarcosate, isononyl isononanoate, palmitate Ethylhexyl, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, tri (2-ethylhexanoic acid) glyceryl, tetra (2-ethylhexanoic acid) pentaerythricyl, succinic acid 2-Ethylhexyl, diethyl sebacate, and mixtures thereof.

Examples of artificial triglycerides include, for example, caprylicaprilyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, tri (capric acid) / Caprylic acid) glyceryl and tri (caprylic acid / caprylic acid / linolenic acid) glyceryl.

(b) The oil is preferably selected from non-polar hydrocarbon oils that are liquid at room temperature, more specifically mineral oils such as paraffin.

It is also preferred that (b) the oil be selected from oils having a molecular weight of less than 600 g / mol.

Preferably, (b) the oil has a low molecular weight, such as less than 600 g / mol, more preferably less than 500 g / mol, specifically less than 400 g / mol, and has a short chain hydrocarbon ester or ether oil (C). _{1 to} C ₁₈ , eg isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dicaprylyl carbonate, ethylhexyl palmitate, dicaprilyl ethers, especially sarcosinates such as isopropyl lauroyl sarcosinate), hydrocarbon oils with short chain alkyl (C) _{1 to} C ₁₈ , eg isododecane, isohexadecan and squalane), and short chain alcohol-type oils, such as octyldodecanol, are selected.

(b) The oil is not a hydrocarbon oil, an ester of C _{4 to} C ₂₂ dicarboxylic acid or tricarboxylic acid and C _{1 to} C ₂₂ alcohol, and C _{4 to} C ₂₂ monocarboxylic acid, dicarboxylic acid or tricarboxylic acid. It is also preferred to be selected from the group consisting of the sugars C _{4 to} C ₂₆ dihydroxy, C _{4 to} C ₁₅ trihydroxy, esters with tetrahydroxy or pentahydroxy alcohols, and mixtures thereof.

(b) The oil is an ester oil such as isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dicaprylyl carbonate, ethylhexyl palmitate, dicaprylyl ether, and sarcosinate such as iropropyl lauroyl sarcosate, artificial such as capryl caprylyl glyceride. It is also preferred to choose from triglycerides, as well as silicone oils.

The amount of (b) oil in the composition according to the present invention is not limited, but is 1 to 40% by mass, preferably 2 to 30% by mass, and more preferably 5 to 20% by mass with respect to the total mass of the composition. Can be a range.

Preferably, the oil (b) constituting the internal oil phase is an ester oil such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglyceride such as capryl caprylglyceride, sarcosinate such as isopropyl lauroyl sarcosinate, isohexadecane and the like. It is selected from the group consisting of hydrocarbon oils and mineral oils such as paraffin.

The amount of (b) oil in the internal oil phase of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

Preferably, the oil (b) constituting the external oil phase is an ester oil such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglyceride such as capryl capryl glyceride, sarcosinate such as isopropyl lauroyl sarcosinate, iso. It is selected from the group consisting of hydrocarbon oils such as hexadecane, mineral oils such as paraffin, and silicone oils.

The amount of (b) oil in the external oil phase of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

(c) UV Shielding Agent The composition according to the invention contains (c) at least one UV shielding agent. Two or more UV shielding agents may be used in combination. Therefore, a single type of UV shielding agent or a combination of different types of UV shielding agents can be used.

The term "UV" includes the UV-B region (wavelength 260-320 nm) and the UV-A region (wavelength 320-400 nm) herein. Thus, UV shielding means any material that has a shielding effect at wavelengths in the UV-A and / or UV-B region. Preferably, the composition according to the invention can cover both UV-A and UV-B regions.

In the present invention, the UV shielding agent can be an organic UV shielding agent. Both hydrophilic UV shields and hydrophobic UV shields can be used in the compositions according to the invention.

The term "hydrophilic UV-shielding agent" is used herein to block UV light and be completely soluble in the molecular state in the aqueous phase, or in the aqueous phase of an O / W / O emulsion. It is understood to mean any agonist that can be dispersed in colloidal form (eg in micellar form). Therefore, the hydrophilic UV shield can be incorporated into the internal aqueous phase of the present invention.

The term "hydrophobic UV shield" is used herein to block ultraviolet light and be completely soluble in the molecular state in the oil phase, or in the oil phase of an O / W / O emulsion. It is understood to mean any agonist that can be dispersed in colloidal form (eg in micellar form). Therefore, the hydrophobic UV shield can be incorporated into the external and internal oily phases of the present invention.

(Hydrophilic UV shield)
The hydrophilic UV shields used for the present invention are active in the UV-A and / or UV-B regions, preferably in both the UV-A and UV-B regions, alone or in combination. Can be.

Hydrophilic UV-A shielding agents include, but are not limited to:
Benzylidene camphor derivatives, such as terephthalilidene camphor sulfonic acid, such as those manufactured by Chimex under the name "Mexoryl SX",
Bisbenzoxazolyl derivatives, such as those described in EP669323 and US2,463,264, more specifically the compound phenyldibenzimidazole tetrasulfonate disodium sold by Haarmann & Reimer under the trade name "Neo Heliopan AP". ..

Hydrophilic UV-B shielding agents include, but are not limited to:
p-Aminobenzoic acid (PABA) derivatives such as PABA, PABA glyceryl and PABA PEG-25, such as those sold by BASF under the name "Uvinul P25",
Phenylbenzimidazole derivatives, such as phenylbenzimidazole sulfonic acid, commercially available under the name "Eusolex 232" by Merck, and phenyldivene imidazole disodium tetrasulfonate, under the name "Neo Heliopan AP" by Haarmann & Reimer. Commercially available, phenylbenzimidazole sulfonic acid, eg, those sold under the trade name "Eusolex 232" by Merck, in particular.
Ferulic acid,
Salicylic acid,
Methoxycinnamate DEA,
Benzylidene camphorsulfonic acid, eg, manufactured by Chimex under the name "Mexoryl SL",
Camphor benzalkonium methosulfate, for example manufactured by Chimex under the name "Mexoryl SO".

Hydrophilic UV-A and UV-B shielding agents include, but are not limited to:
Benzophenone-4, eg, those sold by BASF under the trade name "Uvinul MS40", benzophenone-5, and benzophenone-9.

Preferably, the hydrophilic UV shield is selected from the group consisting of benzylidene camphor derivatives such as terephthalidene dicamer sulfonic acid and phenylbenzimidazole derivatives such as phenylbenzimidazole sulfonic acid.

The amount of the hydrophilic UV shielding agent in the composition is 1% by mass to 40% by mass, preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass with respect to the total mass of the composition. It can be mass%.

(Hydrophobic UV shield)
The hydrophobic shielding agent of the present invention can be blended in both the external oil phase and the internal oil phase, or in either the external oil phase or the internal oil phase.

The hydrophobic UV shield used for the present invention is active in the UV-A and / or UV-B regions, preferably in both the UV-A and UV-B regions, alone or in combination. Can be.

Examples of the hydrophobic UV-A shielding agent used in the present invention include, but are not limited to, aminobenzophenone compounds, dibenzoylmethane compounds, anthranilic acid compounds and 4,4-diarylbutadiene compounds.

An example of an aminobenzophenone compound is n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, which is an alternative name for diethylamino sold by BASF under the trade name "Uvinul A +". It is hydroxybenzoylhexylbenzoate (DHHB).

Examples of dibenzoylmethane compounds include 4-isopropyldibenzoylmethane sold by Merck under the name "Eusolex 8020" and 1- (4-methoxy) sold by Quest under the name "Pongamol". -1-benzofuran-5-yl) -3-phenylpropane-1,3-dione, 1- (4- (tert-butyl) phenyl) -3- (2-hydroxyphenyl) propane-1,3-dione, And Hoffmann-La Roche is a butylmethoxydibenzoylmethane sold under the trade name "Parsol 1789".

An anthranilic acid compound can be mentioned is menthyl anthranylate, which is marketed by Symrise under the name "NEO HELIPAN MA".

Examples of 4,4-diarylbutadiene compounds include 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, and diphenylbutadiene malonate and malononitrile.

Examples of the hydrophobic UV-B shielding agent used in the present invention include triazine compounds, para-aminobenzoic acid compounds, salicylic acid compounds, silicic acid ester compounds, β, β-diphenyl acrylate compounds, benziliden camphor compounds, and imidazoline. Examples include, but are not limited to, compounds, benzalmalonate compounds and mecosyanine compounds.

Examples of triazine compounds include ethylhexyltriazone, which is marketed by BASF under the name "UVINUL T-150", and diethylhexylbutamidotriazone, which is marketed by SIGMA 2V under the name "UVASORB HEB". 2,4,6-Tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine, 2,4,6-tris (diisobutyl 4'-aminobenzalmaronate) -s-triazine, 2,4- Bis (dineopentyl 4'-aminobenzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine, 2,4-bis (n-butyl 4'-aminobenzoate) -6- (amino It is propyltrisiloxane) -s-triazine.

Examples of para-aminobenzoic acid derivatives include para-aminobenzoic acid (PABA), for example, PABA (para-aminobenzoic acid) ethyl, PABA ethyldihydroxypropyl, and the name "ESCALOL 5972" from ISP. It is a commercially available PABA ethylhexyldimethyl.

Examples of salicylic acid compounds include homosalate marketed by Rona / EM industries under the name "Eusolex HMS" and ethylhexyl salicylate marketed by Symrise under the name "NEO HELIOPAN OS".

Examples of cinnamic acid ester compounds are ethylhexyl methoxycinnamate, isopropyl ethoxycinamic acid, and "NEO HELIOPAN E 1000", which are marketed by DSM NUTRITIONAL PRODUCTS under the name "PARSOL MCX". Commercially available isoamyl methoxycinnamate, diisopropyl methylsilicate, sinoxate, and glyceryl dimethoxycinnamate ethylhexanate.

Examples of β, β-diphenyl acrylate compounds include octocrylene marketed by BASF under the name "UVINUL N539" and etucrylene marketed by BASF under the name "UNIVUL N35".

Benzylidene camphor compounds can be listed as 3-benzylidene camphor marketed under the name "MEXORYL SD" by CHIMEX, methylbenzylene camphor marketed under the name "EUSOLEX 6300" by MERCK, and named by CHIMEX. It is a polyacrylamide methylbenzylene camphor marketed in "MEXORYL SW".

An example of an imidazoline compound is ethylhexyl dimethoxybenzylenedioxoimidazoline propionate.

Examples of benzalmalonate compounds include polyorganosiloxanes containing a benzalmalonate moiety, such as polysilicone-15 commercially available under the name "Parsol SLX" by DSM NUTRITIONAL PRODUCTS, and di-neopentyl. It is 4'-methoxybenzalmalonate.

Hydrophobic UV-A and UV-B shielding agents used in the present invention include, but are not limited to:
--Benzophenone compounds, such as benzophenone-1, marketed by BASF under the name "UVINUL 400", benzophenone-2 marketed by BASF under the name "UNIVUL 500", and marketed by BASF under the name "UVINUL M40". Benzophenone-3 or oxybenzone, benzophenone-6 marketed under the name "Helisorb 11" by norquay, benzophenone-8, benzophenone-10 marketed under the name "Spectra-Sorb UV-24" by American Cyanamid , Benzophenone-11, and Benzophenone-12,
—— Benzotriazole compounds, such as drometrizole trisiloxane, marketed by Rhodia Chimie under the name “Silatrizole”, and bumetrizole, marketed by CIBA-GEIGY under the name “TINOGUARTD AS”.
--Bis-resolcinyltriazine, for example, bis-ethylhexyloxyphenylmethoxyphenyltriazine commercially available under the name "TINOSORB S" by CIBA-GEIGY, as well as
--Benzoxazole compounds, such as 2,4-bis [5- (1-dimethylpropyl) benzoxazole-2-yl (4-phenyl) imino] marketed by Sigma 3V under the name "Uvasorb K2A" -6- (2-Ethylhexyl) imino-1,3,5-triazine.

Preferably, the hydrophobic UV shielding agent is a cinnamic acid ester compound such as ethylhexyl methoxycinnamate, isopropyl ethoxycinnamate, isoamyl methoxycinnamate, diisopropyl methylsilicate, synoxate, and ethylhexanoic acid dimethoxycinnamate. Selected from glyceryl.

The amount of the hydrophobic UV shielding agent in the internal oil phase is not limited, but can be 0.1 to 5% by weight, preferably less than 2% by weight, based on the total mass of the composition. The amount of the hydrophobic UV shielding agent in the external oil phase is not limited, but can be 1 to 15% by weight, preferably less than 5% by weight, based on the total mass of the composition.

Generally, the amount of (c) UV shielding agent, including hydrophilic and hydrophobic UV shielding agents, is 1-40% by mass, preferably 2-30% by mass, more preferably 5 with respect to the total mass of the composition. It can be ~ 20% by mass.

(d) Water The composition according to the invention comprises (d) water. (d) Water constitutes the massive internal aqueous phase of the present invention.

(d) The amount of water is not limited and can be 40-99% by mass, preferably 50-95% by mass, more preferably 60-90% by mass, based on the total mass of the composition. The amount of water (d) in the large amount of internal aqueous phase can be more than 60% by mass, preferably more than 70% by mass, more preferably more than 80% by mass, based on the total mass of the aqueous phase.

(Other ingredients)
The compositions according to the invention may also contain at least one additional ingredient.

The composition according to the invention may contain at least one thickener. The thickeners used in the compositions according to the invention include water-soluble polymers such as high molecular weight cross-linked homopolymers of acrylates and acrylate / C _10-30 alkyl acrylate crosspolymers such as Carbopol®. And Pemulen®; anionic acrylate polymers such as Salcare® AST, and cationic acrylate polymers such as Salcare® SC96; acrylamide propyltrimonium chloride / acrylamide; hydroxyethyl methacrylate polymer, steareth-10. Allyl ether / acrylate copolymer; Acryn / Behenes-25 methacrylate polymer known as Aculyn® 28; Polyglyceryl methacrylate, acrylate / steares-20 methacrylate polymer; Bentnite; Gum such as alginate, caragenan, acacia gum, gum arabic , Gatti gum, Karaya gum, tragacanth gum, guar gum; guar hydroxypropyltrimonium chloride, xanthan gum or gellan gum; cellulose derivatives such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl carboxyethyl cellulose, hydroxymethyl carboxypropyl cellulose, ethyl cellulose, sulfated cellulose, hydroxypropyl Cellulose, methyl cellulose, hydroxypropyl methyl cellulose, microcrystalline cellulose; agar; pectin; gelatin; starch and its derivatives; chitosan and its derivatives such as hydroxyethyl chitosan; polyvinyl alcohol, PVM / MA copolymers, PVM / MA decadiencross polymers, poly Examples thereof include (ethylene oxide) -based gelling agents, sodium carbomeres, and mixtures thereof.

Preferably, the compositions of the present invention are substantially free of thickeners. Preferentially, the composition according to the invention comprises a thickener of less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight, based on the total mass of the composition.

The composition according to the present invention may contain at least one cosmetic active ingredient. The term "active ingredient" as used herein means an organic compound having any cosmetic or dermatological effect. Preferably, the active ingredient used in the composition is selected from skin whitening ingredients, anti-aging ingredients, antioxidant ingredients and fragrances.

Examples of skin whitening ingredients include L-ascorbic acid and its derivatives, such as ascorvir tetraisopalmitate, alkoxysalicylic acid, hydroquinone glycosides and their derivatives, tranexamic acid and its derivatives, resorcinol or resorcinol derivatives, such as phenyl. Ethyl resorcinol, ascoric acid and its derivatives, ellagic acid, and resveratrol. Preferably, the skin whitening ingredient is selected from resorcinol or resorcinol derivatives.

Examples of anti-aging components include vitamins such as retinol, saponin, and allantoin.

Examples of antioxidant components include carotenoids such as β-cryptoxanthin, tocopherols and their derivatives, and flavonoids.

These cosmetic active ingredients can be blended in the outer oil phase and / or the inner oil phase. The amount of the cosmetic active ingredient in the internal oil phase is not limited, but can be 0.1 to 5% by mass, preferably less than 2% by mass, based on the total mass of the composition. The amount of the cosmetic active ingredient in the external oil phase is not limited, but can be 1 to 15% by mass, preferably less than 5% by mass, based on the total mass of the composition.

The saturation of these cosmetic active ingredients in the oil phase is preferably 0.7-1. The degree of saturation is defined herein as the ratio of the concentration of active ingredient in the oil phase to the maximum solubility of the active ingredient in the oil phase, as measured at room temperature and at atmospheric pressure.

The composition according to the present invention may contain at least one kind of hydrophilic organic solvent (water-soluble solvent) acceptable for cosmetics in a large amount of internal aqueous phase. Hydrophilic solvents used in the compositions according to the invention include, for example, substantially linear or branched lower monoalcohols having 1 to 8 carbon atoms such as ethanol, propanol, butanol, isopropanol and Isobutanol; aromatic alcohols such as asbenzyl alcohol and phenylethyl alcohol; polyols or polyol ethers such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, ethylene glycol monomethyl ether, monoethyl ether and mono Butyl ethers, propylene glycol ethers such as propylene glycol monomethyl ether, diethylene glycol alkyl ethers such as diethylene glycol monoethyl ether or monobutyl ether; polyethylene glycols such as PEG-4, PEG-6 and PEG-8, and derivatives thereof.

The amount of the hydrophilic organic solvent in the composition can be less than 10% by mass, preferably less than 5% by mass, based on the total mass of the composition. In one embodiment of the invention, the composition is free of hydrophilic organic solvents.

In addition, the composition according to the invention may contain a neutralizing agent, such as ethanolamine, in a large amount of internal aqueous phase. The amount of the neutralizing agent is not limited, but can be 1% by mass to 10% by mass based on the total mass of the composition.

The compositions according to the invention may contain other additives commonly used in cosmetics. Additives are anionic, cationic, nonionic or amphoteric polymers; peptides and their derivatives; protein hydrolysates; swelling agents and penetrants; (b) natural or synthetic thickeners for oils; Acidifying agents; Inorganic or organic fillers; Antioxidants; Preservatives; Antibacterial agents; Suspensions; Metal ion sequestering agents; Ovibrants; Dyes; Inorganic UV shielding agents; Vitamin or provitamins; Moisturizers; Self-tanning It can be selected from the group consisting of compounds; anti-wrinkle active ingredients; preservatives; stabilizers; and mixtures thereof.

The amount of the additional component is not limited, but can be from 0.1% to 30% by weight based on the total mass of the composition according to the present invention.

The composition can be in the form of lotions, milky lotions, creams, gels, pastes or serums.

The composition exhibits a pH that cares for the skin, generally in the range of 3-8, preferably 4.5-7.

The composition according to the present invention can be produced by two steps including a step of preparing a nanoemulsion and a step of preparing a large amount of internal phase emulsion. The step of preparing the nanoemulsion can be carried out by a low energy method known in the art. Specifically, the step of preparing the nanoemulsion involves (a) a surfactant, (b) an oil and (d) a water component, and (c) a UV shield and other components, or together. Rather, it can be carried out, for example, by gently mixing at room temperature (25 ° C.). The step of preparing a large amount of internal phase emulsion is to mix the resulting nanoemulsion with (b) oil and (a) surfactant at high speed, eg, with or without UV shielding agent (DAC). It can be carried out by mixing at room temperature for 2-4 minutes at 2750 rpm using 400 FVZ, Hauschild Engineering).

[Makeup method]
The composition according to the present invention can preferably be used as a sun care composition. In particular, the compositions according to the invention can be intended for application to keratinous substances such as skin, scalp and / or lips, preferably skin. Therefore, the compositions according to the invention can be used in cosmetic methods for the skin.

The use of a cosmetic method or cosmetic for a keratin substance such as skin according to the present invention includes at least a step of applying the composition according to the present invention to the keratin substance. The present invention also relates to a method of protecting a keratin substance from ultraviolet rays, includes a step of applying the composition according to the present invention to the keratin substance, and also relates to a method of absorbing ultraviolet light, and applies the composition according to the present invention. The step of subjecting the keratin substance to ultraviolet light is included. These methods can be defined as non-therapeutic methods.

The compositions according to the invention can be used in topical sun care compositions in the form of lotions, milky lotions, creams, gels, pastes or serums.

The present invention will be described in more detail by way of examples. However, these examples should not be construed as limiting the scope of the invention.

(Example 1 and Comparative Example 1)
The following compositions according to Example 1 shown in Table 1 (Table 2) were prepared as follows. All numerical values for the amount of ingredients are based on "mass%" as an active raw material in Table 1 (Table 2).

First, O / W nanoemulsion was prepared by the following method:
20 g of ethylhexyl palmitate, 10 g of ethylhexyl methoxycinnamate, 30 g of laureth-5 carboxylic acid (HLB = 9.5, obtained from Kao Chemical Co., Ltd.) and 40 g of water were mixed using a magnetic stirrer. The premix was diluted 20-fold with an aqueous phase containing 3 g of phenylbenzimidazole sulfonic acid, 13 g of terephthalilidene dicamer sulfonic acid, 4 g of triethanolamine and 75 g of water. The final composition of the nanoemulsion is ethylhexyl palmitate 1 g, ethylhexyl methoxycinnamate 0.5 g, laures-5 carboxylic acid 1.5 g, phenylbenzimidazole sulfonic acid 2.85 g, terephthalylidene dicamer sulfonic acid 12.35 g, triethanolamine. It consists of 3.8g and 78g of water.

Second, O / W / O multiphase emulsions were prepared by the following methods:
85 g of O / W nanoemulsion was premixed with 10 g of isohexadecane and 5 g of PEG-15 / lauryl dimethicone crosspolymer (HLB <8, obtained from Shin-Etsu Chemical Co., Ltd.). The obtained premix was further mixed at 2750 rpm for 3 minutes using a high-speed mixer (DAC 400 FVZ, Hauschild Engineering) to obtain an O / W / O multiphase emulsion.

For Comparative Example 1 in Table 1, O / W emulsions were prepared by the following methods:

Ethylhexyl palmitate 1 g, ethylhexyl methoxycinnamate 0.5 g, laures-5 carboxylic acid 1.5 g, phenylbenzimidazole sulfonic acid 2.85 g, terephthalidene dikanfer sulfonic acid 12.35 g, triethanolamine 3.8 g and water 78 g, magnetically A milky O / W emulsion was prepared by mixing together using a stirrer.

Second, 85 g of O / W emulsion was premixed with 10 g of isohexadecane and 5 g of PEG-15 / lauryl dimethicone crosspolymer (HLB <8, obtained from Shinetsu Chemical Co., Ltd.). The obtained premix was further mixed at 2750 rpm for 3 minutes using a high-speed mixer (DAC 400 FVZ, Hauschild Engineering) to obtain an O / W / O multiphase emulsion.

[Evaluation]
The compositions according to Example 1 and Comparative Example 1 were evaluated as follows.

(Drop diameter)
Using a particle size distribution measuring device (Vasco, Cordouan Technologies), the droplet diameters of the oil phases of the O / W nanoemulsion of Example 1 and the O / W emulsion of Comparative Example 1 were measured, and these were O / Obtained during the W / O emulsion preparation process. At 25 ° C., the refractive index of water was 1.33 and the viscosity was 0.89 cp.

The droplet diameter of the internal aqueous phase of the O / W / O multiphase emulsion was determined using an OLYMPUS GX 71 (Olympus Optical Co., Ltd.) microscope.

(SPF)
Samples for measuring SPF values, 20 mg each of the compositions according to Example 1 and Comparative Example 1, were placed in dots on a plate (Helio plate HD 6, PMMA, 50 mmx50 mm), then they were placed three times. Prepared by spreading it on the plate with your fingers. In vitro SPF values were calculated from UV absorption data measured with a UV spectrophotometer (UV-2000S, Labsphere Inc) for diffuse transmission of samples in the wavelength range 250-450 nm.

(viscosity)
The steady-state shear viscosity was measured at 25 ° C. with a set gap of 0.2 mm using a DHR2 rheometer (TA instrument) with a parallel plate arrangement (40 mm). The sample amount was 2 g, and a shear rate of 0.01 to 1000 1 / s was applied.

(Yield stress)
The yield stress values of the compositions according to Example 1 and Comparative Example 1 were calculated from the shear rate response force curves, where these parameters were set using a DHR2 rheometer (TA instrument) with a parallel plate arrangement (40 mm). The measurement was performed at 25 ° C. with a gap of 0.2 mm. The sample amount was 2 g, and a shear rate of 0.01 to 1000 1 / s was applied.

The compositions of Example 1 and Comparative Example 1 and the results of their evaluation are shown in Table 1.

As shown in Table 1 (Table 2), the composition according to Example 1 exhibited an improved UV protection effect due to its high SPF value. In addition, it also exhibited good stability due to its high viscosity. In contrast, the composition according to Comparative Example 1 containing macro-sized oil droplets as the internal oil phase exhibited inferior UV protection and lower viscosity.

In addition, the composition according to Example 1 containing nano-sized oil droplets as the internal oil phase exhibited better stability due to its high yield stress value. In contrast, the composition according to Comparative Example 2 containing macro-sized oil droplets as the internal oil phase exhibited lower stability.

(Examples 2 to 3 and Comparative Example 2)
The following compositions according to Examples 2 to 3 and Comparative Example 2 shown in Table 2 (Table 3) were used in place of PEG-15 / lauryl dimethicone crosspolymer in Example 2 with glyceryl oleate (HLB = 2.8, solar chemistry). In Example 3, polyglyceryl laurate-2 (HLB = 8.5, obtained from Taiyo Kagaku Co., Ltd.) was used, and in Comparative Example 2, polysorbate 80 (HLB = 15, Croda) was used. Was prepared in the same manner as in Example 1 above, except that (obtained from) was used.

[Evaluation]
The compositions according to Examples 2 to 3 and Comparative Example 2 were evaluated as follows.

(Observation of appearance)
The appearance of the O / W / O polyphasic emulsion according to Examples 2 to 3 and Comparative Example 2 was visually observed to confirm the formation of the polyphasic emulsion.

The compositions of Examples 2 to 3 and Comparative Example 2 and the results of observing the appearance are shown in Table 2 (Table 3).

As shown in Table 2, the compositions according to Examples 2 and 3 each containing a surfactant having an HLB of less than 13 were able to form a polyphasic emulsion. In contrast, the composition according to Comparative Example 2 containing a surfactant having an HLB of 13 was unable to form a polyphasic emulsion.

Claims (15)

A composition in the form of a multiphase emulsion of oil in oil, comprising an external oil phase, a large amount of internal aqueous phase in the external oil phase, and an internal oil phase dispersed as droplets in the large amount of internal aqueous phase. There,
(a) At least one surfactant with an HLB of less than 13 and
(b) At least one oil and
(c) At least one UV shield and
(D) Including water
The amount of said multimeric internal aqueous phase is not less than 60% by weight relative to the total weight of the composition, droplet size of the internal oil phase, der less than 200nm is, droplet size of the large amount internal aqueous phase is A composition that is 1 μm or larger . Droplet size of the internal oil phase, a 150nm less than A composition according to claim 1. The composition according to claim 1 or 2, wherein the amount of the large amount of the internal aqueous phase is in the range of 60 to 99 % by mass with respect to the total mass of the composition. (a) HLB surfactant, 12 is less than A composition according to any one of claims 1 to 3. The composition according to any one of claims 1 to 4, which has a viscosity of 1 to 500 Pa · s at 25 ° C. The composition according to any one of claims 1 to 5, wherein the amount of the internal oil phase is in the range of 0.5% by mass to 15% by mass with respect to the total mass of the composition. (B) oil of the internal oil phase is an ester oil, preparative triglycerides, Sa Rukoshineto, coal hydrocarbon oil is selected from及beauty mineral oil, the composition according to any one of claims 1 to 6 Stuff. (a) surfactant, and Po triol, an 8 monoester of fatty acid containing 24 carbon atoms, or a sheet recone surfactants, nonionic surfactants, positive as well polyoxyethylene alkyl The composition according to any one of claims 1 to 7, which is selected from an anionic surfactant which is an ether carboxylic acid. (a) The composition according to any one of claims 1 to 8, wherein the amount of the surfactant is in the range of 0.1 to 20 % by mass with respect to the total mass of the composition. The amount of external oil phase, relative to the total weight of the composition ranges from 1 wt% to 3 0% by weight, the composition according to any one of claims 1 to 9. (B) oil of the outer oil phase is an ester oil, preparative triglycerides, Sa Rukoshineto, coal hydrocarbon oil, mineral oil, and is selected from silicone oils, according to any one of claims 1 to 10 Composition. By weight, containing 10 wt% less than the water-soluble solvent, the composition according to any one of claims 1 to 11. Any one of claims 1 to 12, wherein the amount of (c) UV shielding agent, including both hydrophilic and hydrophobic UV shielding agents, is in the range of 1-40 % by mass with respect to the total mass of the composition. The composition according to the section. To keratin materials, comprising the step of applying a composition according to any one of claims 1 to 13, cosmetic process for Ke keratin materials. A method for protecting a keratin substance from ultraviolet rays, which comprises a step of applying the composition according to any one of claims 1 to 13 to the keratin substance.

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