JP2003511235A - Stable multiple emulsion composition - Google Patents

Abstract

(57) Abstract: W 1 _{/ O} emulsion comprises an inner aqueous phase containing a benefit agent and an oil phase surrounding it, the external isotropic aqueous phase is found to ambient, amide-containing anionic surfactants external surfactant phase is discloses _W 1 _{-O-W 2} emulsion containing no active agent. A method for stabilizing a multiple oil composition is also disclosed.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to liquid surfactant compositions comprising multiple emulsions, such as liquid shower gels or liquid shampoos. In particular, the present invention relates to multiple emulsion compositions that can include high levels of surfactants, but that are nevertheless stable (eg, microscopically stable). In another embodiment, the composition microscopically maintains multiple emulsion droplet integrity while macroscopically having little or no phase separation. The present invention also relates to methods of stabilizing multiple emulsion compositions.

BACKGROUND OF THE INVENTION Multiple emulsion systems (generally defined as systems in which water / oil and oil / water emulsions coexist) are highly beneficial, but they allow for the incorporation of benefit agents and enhanced delivery. Because. Thus, for example, in the area of cosmetics and pharmaceuticals, multiple emulsions have been used for many years to deliver cosmetic or pharmacological benefit agents (eg Vesper).
See U.S. Pat. No. 5,306,498 by ini, or U.S. Pat. No. 5,567,426 by Nadaud et al.).

Generally, however, the level of cleansing surfactant in such multiple emulsion systems (eg high HLB, eg 10 or more, preferably 1
The emulsion becomes less stable as the number of HLBs (having 2 or more) increases. Thus, for example, the level of cleansing surfactant in almost all cosmetic and pharmaceutical compositions mentioned in the prior art is below 5% by weight of the composition. When the amount is large, the stability becomes low and phase separation occurs.

US Pat. Nos. 5,656,280 and 5,589,177 (Herb et al.)
And their European equivalents EP717,978 and EP715,842 describe the stabilization of multiple emulsions in compositions containing high levels of conditioning surfactants. However, the stable multiple emulsion compositions disclosed therein contain a stabilizing liquid crystal, i.e. a surfactant which must form a layered liquid crystal (i.e. a conditioning surfactant). The described composition in which the surfactant forms an isotropic phase (see, for example, US Pat.
, 589, 177, lines 30-44, column 29, Example 29) was unstable (see column 34. Example 29 stability is only 5 minutes). This time, the Applicant et al. Surprisingly found that even though the surfactant phase of the composition of the present invention was an isotropic surfactant phase, it was found that this multiple emulsion had room temperature when measured at a temperature of about 25 ° C. It was found that even when evaluated for at least 2 weeks, preferably 4 weeks or longer, more preferably 8 weeks or longer, the emulsion did not disintegrate into a single emulsion.

Compositions containing an isotropic surfactant phase are advantageous over compositions containing a layered liquid crystal phase that can be formed with a fairly wide range of surfactants, and include foam / foam (
laser).

Therefore, it is an object of the present invention to provide a composition having a surfactant phase which is not limited to a layered phase.

Another object of the invention is to provide a surfactant phase (which is an isotropic phase) that contains high levels of surfactant but does not destabilize multiple emulsions.

In a second embodiment, by using a specific selection of external surfactant system in combination with a stabilizing natural rubber polymer that forms a gelled external aqueous phase containing a relatively high concentration of surfactant. It has further been found that the composition can be stabilized for a long time (in addition to being microscopically stable as described above). A composition using a similar technique (ie, a gelled outer aqueous phase) is described by Vesperiini in US Pat. No. 5,306,498, Ve.
US Patent No. 4,083,798 by Rsteeg, US Patent No. 5,332,595 by Gaonkar, US Patent No. 5,576, by Fructus.
064 and 5,656,263, and U.S. Pat. No. 5,567,426 by Nadaud. However, in the disclosed prior art compositions, the level of high HLB external surfactant is only 5% in one example and in most cases is zero.

Accordingly, yet another object of the present invention is to provide a gelled isotropic external surfactant phase that contains high levels of surfactant, maintains the integrity of multiple emulsion droplets and does not phase separate the composition. Is to provide.

BRIEF SUMMARY OF THE INVENTION In one embodiment, Applicants et al., Now obtain a multiple emulsion system that includes high levels of surfactants that form an isotropic phase, whereby multiple emulsions provide the desired benefit agents. It has been found that they can be delivered (eg in the internal oil phase) and at the same time the stability of the multiple emulsions can be maintained. In the past, it has been difficult or impossible to produce stable multiple emulsions in the presence of high levels of surfactants that form an isotropic phase. In a preferred embodiment, the surfactant system comprises anionic and amphoteric surfactants and the level of surfactant is about 10.5% by weight or more of the total composition.

The present invention further relates to a method of stabilizing the aforementioned multiple emulsion system.

[0012]   More specifically, the present invention relates to water-in-oil-water (W₁-OW_Two) Multiple Emergy
Water in oil (W₁/ O) the emulsion itself is composed of solute and optional
Internal aqueous phase containing surfactant (W₁); Oil phase O (low HLB milk) surrounding the internal water phase
Agents, eg oils mixed with emulsifiers having an HLB of less than 10); and aqueous W₁During ~
Alternatively, it includes a topically active compound which may be in O. W₁O phase is cleansing
Surfactants, optionally topically active compounds (first optional topically active compounds
, Which may be the same as or different from), and an aqueous isotropic phase containing an optional solute (W _Two ) Surrounded by. (Some solutes are almost always present in the surfactant or pH
It is understood that it is formed when adjusting). Surfactant phase W_TwoIs an amide group
Must not contain anionic surfactants with.

Another essential feature is that the oil in the O phase must not contain more than 50% unsaturated compounds or be volatile silicones (eg silicones with viscosities below 10 centistokes). That is.

As mentioned above, the present invention requires prior art (eg, US Pat. No. 5) to require that the aqueous phase W ₂ (eg, the external aqueous phase) contains a surfactant system capable of forming stabilized liquid crystals. ，
656,280). In contrast, the present application requires that the external aqueous phase be isotropic. The isotropic phase is formed by choosing a specific surfactant system that must not contain anionic surfactants with amide groups.

By definition, the lamellar phase is the liquid crystal phase, while the isotropic phase is the micelle. Optically, the lamellar phase exhibits birefringence under polarized light, while the micellar phase does not exhibit this feature.

Specifically, the present invention is a W ₁ -O-W ₂ multiple emulsion composition comprising: (1) about 1% to 99% by weight, preferably 2% to 90% by weight of the composition. %, More preferably 5% to 80% W ₁ / O emulsion, (a) about 1% to 99% of the emulsion, (i) water; (ii) 0.01 to 30% solute; And (iii) an internal aqueous phase containing 0 to 30% of an optional surfactant; (b) about 0.1% to about 99%, preferably 0.5 to 95% of the emulsion.
%, More preferably 1 to 80%, surrounding the internal aqueous phase and comprising a non-volatile silicone compound, a volatile hydrocarbon compound, a non-volatile hydrocarbon compound or mixtures thereof; (c) about 0.1 of the emulsion. To 20% by weight, preferably 1 to 15% by weight, more preferably 1.5 to 15% by weight, a non-silicon-containing surfactant or surfactant mixture having an HLB value of about 10 or less, an oil-soluble silicon-based interface. An active agent, a surfactant emulsifier selected from oil-soluble polymeric surfactants and mixtures thereof, and (d) a locally effective, which can be found in the aqueous phase (a) and / or the oil phase (b) In an amount (eg 0.01 to 40% by weight, preferably 0.05 to 15)
Wt%) of the first topically active compound and (2) about 1 to 99% by weight, preferably 20 to 95% by weight of an external isotropic anion containing a non-amide anion and / or other surfactant. It includes an emulsion containing an aqueous phase W ₂ . The composition contains a non-amide anion and an amphoteric surfactant, the ratio of the first surfactant (preferably anionic surfactant) to the amphoteric surfactant being 100: 1.
To 1: 100 is preferred. The composition optionally contains a second topically active compound that performs the same, similar or different function as the first topically active compound, usually 0-40% by weight of the external phase, and an optional solute. Surfactants typically comprise about 2-80% of the aqueous phase.

W ₁ -O-W ₂ multiple emulsion compositions are stable (eg, they usually do not break at room temperature for at least 2 weeks into a simple emulsion) and have exceptional aesthetic and functional properties. Indicates. W 1 _{-O-W 2} multiple emulsion compositions are liquids or creams, it can be effectively delivered to one or more topically-active compounds from a single composition to the skin or hair.

In a second embodiment, Applicants et al. Have now demonstrated an external surfactant system in combination with a stabilized natural rubber polymer that forms a gelled external aqueous phase containing a relatively high concentration of surfactant. When selected for, a multiple emulsion system is formed that allows the delivery of the desired benefit agent, while at the same time maintaining both the integrity of the multiple emulsion droplets and the physical stability of the composition (ie, the bottom transparency produced by phase separation). Layer is less than 20 volume percent of the total sample volume for at least 45 days at room temperature).

Specifically, this embodiment relates to the selection of natural rubber polymers and surfactants or combinations of surfactants that form a gelled external water phase for the multiple emulsions described above.

The invention therefore further relates to W ₁ —O—W ₂ multiple emulsions, wherein the W ₁ O phase is surrounded by an external aqueous isotropic phase W ₂ , as well as an optional topically active compound. And the optional solute also comprises an emulsion surrounded by a stabilized natural rubber polymer.

It is essential that the natural rubber stabilizer and the selected surfactant form a gel. It is also essential that, as in the first embodiment, the surfactant phase W ₂ should not contain anionic surfactants having amide groups. Moreover, the W ₂ surfactant phase must be isotropic. This isotropic phase is formed by choosing a specific surfactant system that must not contain anionic surfactants with amide groups.

Oils in the O phase (eg gas oil, hexadecane, octyl palmitate) are (1
) Must not contain more than 50% unsaturated compounds, or (2) Volatile silicone (
For example, it should not be silicone having a viscosity of 10 centistokes or less).

As mentioned above, the present invention is a prior art technique, US Pat. No. 5,306,498 (Ve
sperini), No. 4,083,798 (Versteeg), No. 5,33.
2,595 (Gaonkar), 5,567,064 and 5,656.
No. 263 (Fructus), and No. 5,567,426 (Nadaud)
), Since Applicants et al.'S invention uses a surfactant level of 10.5% or higher, while the aforementioned composition uses an external surfactant level of only 0-5%. Is.

Specifically, the present invention is further a W ₁ -O-W ₂ multiple emulsion composition comprising: (1) about 1% to 99% by weight, preferably 2% to 90% by weight of the composition. % By weight, more preferably 5% to 80%, more preferably 5% to 50% W ₁ / O.
An emulsion comprising: (a) about 1% to 99% of the emulsion; (i) water; (ii) 0.01 to 30% solute; and (iii) 0 to 30% optional surfactant. (B) from about 0.5% to about 99%, preferably from 1 to 80% of the emulsion, surrounding the internal water phase, a non-volatile silicone compound, a volatile hydrocarbon compound, a non-volatile hydrocarbon. An oil phase comprising a compound or mixtures thereof; (c) about 0.1 to 20% by weight of the emulsion, preferably 1 to 15% by weight, more preferably 1.5 to 15% by weight 1.5 to 15% by weight, Surfactant milk selected from non-silicon-containing surfactants or surfactant mixtures having an HLB value of about 10 or less, oil-soluble silicon-based surfactants, oil-soluble polymer-based surfactants and mixtures thereof. Agent, and (d) the aqueous phase (a) and / or the oil phase (b) can be found in the topically effective amount (e.g., 0.01 to 40 wt%, preferably from 0.05 15
Wt%) of the first topically active compound and (2) about 1 to 99% by weight, preferably 20 to 95% by weight of an external isotropic anion containing a non-amide anion and / or other surfactant. It includes an emulsion containing an aqueous phase W ₂ .

The composition contains all non-amide anions or all amphoteric surfactants or a combination of the two of which 60% by weight or more are anionic surfactants. Surfactants are usually about 2-80% aqueous phase and 0.01-10% stabilized natural rubber polymer.
including.

The composition optionally comprises a second topically active compound which performs the same, similar or different function as the first topically active compound, usually 0-40% by weight of the external phase and an optional solute. It is preferred to use nonionic rubber polymers in systems where the outer surfactant phase W2 consists entirely of anionic surfactants or contains most anionic surfactants. Conversely, it is preferred to use anionic rubber polymers in systems where the external surfactant phase W2 consists entirely of amphoteric surfactants or contains most amphoteric surfactants.

W ₁ -O-W ₂ multiple emulsion compositions are physically stable (eg, they typically do not phase separate at room temperature for at least 45 days) and exhibit exceptional aesthetic and functional properties. W 1 _{-O-W 2} multiple emulsion compositions are liquids or creams, it can be effectively delivered to one or more topically-active compounds from a single composition to the skin or hair.

Brief Description of the Drawings Figure 1 relating to the first embodiment of the present invention is a schematic diagram, Figure 1A shows a stable multiple emulsion in which the W ₁ / O phase is surrounded by the W ₂ phase, FIG. 1B shows the multiple emulsions disintegrating into a single O / (W ₁ + W ₂ ) emulsion.

FIGS. 2 and 3, both relevant to the second embodiment of the present invention, show a plot of viscosity against Haake RV06 spindle speed. In FIG. 2, when 3% by weight of anionic natural rubber (eg, carrageenan) is added to an amphoteric surfactant (eg, cocamidopropyl betaine), a gelling external W2 phase, ie, shear fluidization (shear thi).
It is clear that a viscoelastic solution is obtained which exhibits a ‘nning’ behavior. In Figure 3,
Anionic surfactant (eg, sodium laureth sulfate) and nonionic natural rubber (eg,
It is clear that the addition of 1% by weight locust bean) gives a gelled external W2 phase. In each of these cases, the addition of rubber to the surfactant was W2
The rheology of the phase was changed from Newton low viscosity to shear fluidized, high viscosity gel. This gelling extrinsic (W2) phase with the selection of appropriate surfactants and stabilizers helps the composition to be pourable without phase separation of the multiple emulsions.
A viscosity of at least 6000 cps at a spindle speed of 5 rpm and a viscosity of about 9000 cps at 50 rpm is preferred to make the composition phase stable and pourable.

[0030] DETAILED DESCRIPTION first embodiment of the invention, the present _invention provides a W 1 _{-O-W 2} multiple emulsion composition, comprising 99% of _W 1 / O emulsion from (1) 1 , W ₁ (containing water, solute and optional surfactant) from about 1% to 99%, and O phase (containing oil compound and low HLB emulsifier) 0.1 to 99%, topically active compound Is an emulsion which may be present in the W ₁ phase, the O phase or both, and (2) an external aqueous phase containing non-amide anions and / or other surfactants, which phase is an anionic surfactant, amphoteric Approximately 1% to 99% by weight aqueous phase, which preferably comprises a surfactant, an optional second topically active compound, and a solute.
Relating to an emulsion.

The external water phase W2 (1 to 99% of the total emulsion) differs from the art in that it is an isotropic aqueous surfactant phase rather than a layered phase. These compositions are
A relatively large amount of surfactant (ie 10.5% or more, preferably 11% to 75% by weight, more preferably 12% to 60% by weight of the composition, while maintaining the integrity of the multiple emulsion, More preferably 13 to 60% by weight, more preferably 15 to 60% by weight, more preferably 16 to 55% by weight, more preferably 17 to 50% by weight).
Unless the surfactant system and oil are specifically selected as described herein, such multiple emulsion compositions generally break very quickly into simple emulsions (see Figure 1). Please refer).

[0032]   In a second embodiment, the present invention provides the integrity of multiple emulsion droplets.
W that is maintained and the composition does not phase separate₁-OW_TwoRegarding multiple emulsions
It These formulations   (1) 1 to 99% W₁/ O emulsion and W₁(Water, solute and
About 1% to 99% (containing optional surfactant) and O phase (oil compound or
And 0.5 to 99% (including low HLB emulsifiers), the topical active compound is W ₁ Phase, an emulsion that may be present in the O phase or both, and   (2) Non-amide anion and / or amphoteric surfactant, stabilized natural rubber poly
An external aqueous phase comprising a mer, an optional second topically active compound, and a solute
% To 99% by weight.

The external water phase W2 is isotropic and at a high concentration (ie, 15% by weight or more, preferably 16% by weight or more, preferably 17 to 75% by weight, more preferably 20 to 70% by weight of the composition). %, More preferably 22 to 60% by weight, more preferably 25 to 50% by weight) surfactant. It is essential that the natural rubber stabilizer and the selected surfactant form a gel. Unexpectedly the applicants,
It has been found that the external surfactant W2 consists entirely of anionic surfactants or that nonionic rubber polymers must be used in systems containing the majority of anionic surfactants. Conversely, the external surfactant W2 must consist entirely of amphoteric surfactant or the anionic rubber polymer must be used in systems containing most of the amphoteric surfactant. This differs from the prior art in that the external phase this time contains a high level of cleansing surfactant and the choice of stabilizing polymer is constrained by the criticality.

[0034]   Next, the present invention will be described in more detail.

Water-in-oil (W ₁ / O) emulsion A W ₁ / O emulsion comprises water, an internal water phase W ₁ containing a solute and an optional surfactant, and an oil phase O.

[0036]   Generally, the water, solute and first topically active compound are W₁Of / O emulsion
Although included in the partially aqueous phase, the active compound may be in the oil phase provided it is oil compatible. sand
W, W₁The phase is a droplet containing water, a solute and possibly a first topically active compound.
including. For example, a droplet containing water, a solute and a first topically active compound (W₁)
Has a diameter ranging from about 0.01 to about 75 and is used in membranes or films containing an oil phase.
It may be wrapped. Therefore, the internal water phase (W₁) Contents are W₁-OW _Two External water phase of multiple emulsion (W_Two) Does not contact.

The primary W ₁ / O emulsion is in an amount of about 1% to about 99%, preferably 2% to 90%, more preferably about 5% to about 80% by weight of the multiple emulsion composition. in present in _W 1 _{-O-W 2} multiple emulsion composition. The main W ₁ / O emulsion is suitably present in an amount of about 10% to about 80%.

Internal Water Phase The internal water phase (W1) is contained in an amount of about 1% to about 99% by weight of the emulsion, and the oil phase separates the external water phase (W ₂ ) and the internal water phase (W ₁ ) of the emulsion. is doing.

The internal aqueous phase (W ₁ ) of the present W ₁ -O-W ₂ multiple emulsion compositions generally comprises water, a solute and an optional first locally active compound (either in the oil phase or in both phases). May be found in). The internal aqueous phase may further contain additional locally active compounds and / or
Alternatively, it can include an optional water-soluble compound that can provide the desired aesthetic or functional effect such as a scent.

The aqueous phase (W ₁ ) is from about 1% to about 99% by weight of the W ₁ / O emulsion, preferably about 10% to about 95%, more preferably about 25% to about 95%.
It is included by weight percent.

Topically Active Compounds A variety of topically active compounds can be incorporated into the W ₁ / O emulsion as the _first topically active compound. When found in the W ₁ phase, the topically active compounds are water-soluble or dispersible in water and include both cosmetics and other compounds that act on contact with the skin or hair. The first topically active compound is present in an amount sufficient to perform its intended function, usually from about 0.01% to about 4% by weight of the W ₁ O emulsion.
It is present in an amount of 0% by weight, preferably 0.05 to 15% by weight.

The first topically active compound is usually washed off from the skin or hair, whereas it remains on the skin or hair after application. However, in some cases, the first topically active compound is designed to be washed off the skin or hair after the compound has performed its intended function.

The first topically active compound can be incorporated into the aqueous or oil phase of the primary emulsion, or both. Whether a particular first topically active compound is incorporated into the aqueous or oily phase of the primary emulsion is related to the water solubility of the topically active compound. In a preferred embodiment, the first topically active compound is water soluble and is incorporated into the internal W ₁ aqueous phase. However, more hydrophobic drugs can be used in the oil phase.

The term “water-soluble” as used herein means water-soluble or dispersible in water. The water-soluble compound has a water solubility of at least 0.1 g (gram) per 100 ml (ml) of water and produces a true solution. The water-soluble compound may be water-soluble in nature, or may be made water-soluble by adding a solubilizing agent such as a coupling agent, a cosurfactant, or a solvent. The water-dispersible compound has been dispersed in water for at least the time required to produce a primary W ₁ / O emulsion, ie, at least about 1 hour.

Furthermore, topically active compounds can be incorporated into the external aqueous phase W ₂ to enhance efficacy.

Thus, the topically active compound may be any one or a combination of cosmetic compounds, medically active compounds or other compounds useful for topical application to the skin or hair. Such topical active compounds include hair and skin conditioners, hair and skin cleansers, hair fixatives.
, Hair dye, hair growth promoter, deodorant, skin care compound, permanent wave compound, hair relaxer, hair styling agent (hair s)
and antibacterial compounds, antifungal compounds, anti-inflammatory compounds, topical anesthetics, sunscreens and other cosmetically and medically topically active compounds.

According to one aspect of the invention, the topically active compound comprises a water soluble hair conditioner such as a quaternary ammonium compound. Although quaternary ammonium compounds are important to hair and are excellent hair conditioners, it is well known that they are incompatible with anionic surfactants and dyes. Therefore, the quaternary ammonium compound is generally applied to the hair from a separate conditioning composition rather than a component of the shampoo conditioner composition or anionic dye-based composition.

Water soluble quaternary ammonium compounds suitable for the purposes of this application have the following general structural formula:

[0049]

[Chemical 1] [Wherein R ₁ is an alkyl group containing about 8 to about 18 carbon atoms, and R ₂ is an alkyl group containing about 8 to about 18 carbon atoms, a hydrogen atom, a methyl group, an ethyl group,
R ₃ is selected from a hydroxymethyl group and a hydroxyethyl group, R ₃ is selected from a benzyl group, a hydrogen atom, an ethyl group, a methyl group, a hydroxymethyl group and a hydroxyethyl group, and R ₄ is a hydrogen atom, a methyl group, an ethyl group, a hydroxy group. Selected from methyl and hydroxyethyl groups, X is an anion. The quaternary nitrogen of the water soluble quaternary ammonium compound may also be part of a heterocyclic nitrogen containing group such as morpholine or pyridine. The anion of the quaternary ammonium compound may be a common anion such as chloride, methosulfate, ethosulfate, nitrate, bromide, tosylate, acetate, or phosphate.

The water soluble quaternary ammonium compound can have one or more long chain alkyl groups containing from about 8 to about 18 carbon atoms. The long chain alkyl group may also contain, in addition to, or instead of, carbon and hydrogen atoms, a bond or similar water solubilizing bond. The remaining two or three substituents on the quaternary nitrogen of the quaternary ammonium compound are hydrogen; or benzyl, or a short chain alkyl or hydroxyalkyl group such as a methyl, ethyl, hydroxymethyl or hydroxyethyl group; A combination, which may be the same or different.

Water-soluble quaternary ammonium compounds include lautrimonium chloride (lautrim).
onium); Quaternium-16; lauralkonium chloride; olearkonium chloride
onium); dilauryl dimonium chloride
); Cetalkonium chloride; dicetyldimonium chloride; laurylpyridinium chloride; cetylpyridinium chloride; soyatrimonium chloride; polyquaternium-6; polyquaternium-7
Guar hydroxypropyltrimonium chloride (guarhydroxypr
polyquaternium-11; polyquaternium-5; polyquaternium-10; polyquaternium-24; cetrimonium chloride; polyquaternium-24; mitrimonium chloride; PEG-2 Cocomonium
ium) chloride; PEG-2 cocoyl quaternium-4; PEG-15 cocoyl quaternium-4; PEG-2 stearyl quaternium-4; PEG-
2 oleyl quaternium-4; and PEG15 oleyl quaternium-4
And a mixture thereof, the compound name is hereinafter referred to as CTFA Dictionary, and is referred to as CTFA Cosmetic.
ic Ingredient Dictionary, 4th Edition, 1991, Cosmetic, Toiletry and Fragrance Asso
Cation, Inc. More provided. Other water-soluble quaternary ammonium compounds are described in CTFA Cosmetic Ingred, incorporated herein by reference.
ient Handbook, 1st edition, 1988 (hereinafter CTFA Handb
(books), pages 40-42.

Other water-soluble hair conditioners are also suitable as the first topically active compound. Such hair conditioners include aliphatic amine salts, ethoxylated aliphatic amine salts, dimethicone copolyols.
lyol), protonated polyethyleneimine, protonated ethoxylated polyethyleneimine, soluble animal collagen, lauramin oxide, cationic polymer,
It includes, but is not limited to, many other water soluble hair conditioners and mixtures thereof listed in CTFA Handbook, pages 71-73, which are incorporated herein by reference.

In addition to hair conditioners, skin conditioners can be used as the first topical active compound. Skin conditioning agents include humectants such as fructose, glucose, glycerin, propylene glycol, glycereth-26, mannitol and urea; pyrrolidone carboxylic acid; hydrolyzed lecithin; coco-betaine; cysteine hydrochloride; glutamine; PPG-. 15; sodium gluconate; potassium aspartate; oleylbetaine, thiamine hydroxychloride; sodium laureth sulfate; sodium hyaluronate; hydrolyzed protein; hydrolyzed keratin; amino acids; amine oxides; vitamins A, E
And water-soluble derivatives of D; amino-functional silicones; ethoxylated glycerin;
Alpha-hydroxy acids and their salts; PEG-24 hydrogenated lanolin, water-soluble fatty oil derivatives such as almond oil, grape seed oil and castor oil; CTFA
Many other water-soluble skin conditioners listed in Handbook, pages 79-84 (incorporated herein by reference); and mixtures thereof, are included, but are not limited to. Other conditioners include lactic acid,
Alpha hydroxy acids such as glycolic acid or salts thereof are included.

The first topically active compound may also be a hair fixative or film former that imparts style-retaining properties to the hair, ie sets the hair. Hair fixatives are usually homopolymers, copolymers, or terpolymers. The polymer may be a nonionic, amphoteric, anionic or cationic polymer. Examples of hair fixatives include acrylamide copolymers; acrylamide / sodium acrylate copolymers; polystyrene sulfonates; polyethylene oxides; water dispersible polyesters; cationic celluloses; acrylate / ammonium methacrylate copolymers; aminoethyl acrylate phosphate / acrylate copolymers; polyacrylamides; polyacrylamides. Polyquaternium-1; Polyquaternium-2; Polyquaternium-4; Polyquaternium-4; Polyquaternium-5; Polyquaternium-7; Polyquaternium-8; Polyquaternium-9; Polyquaternium -10; Polyquaternium-11; Polyquaternium-12; Polyquaternium-13; Polyquaternium-14
Polyquaternium-15; polyquaternium-16; polyquaternium-28; PVP (polyvinylpyrrolidone); PVP / dimethylaminoethyl methacrylate copolymer; PVP / ethyl methacrylate / methacrylic acid copolymer; carboxylated polyvinyl acetate; vinyl / Caprolactam / PVP / Dimethylaminoethyl Methacrylate Copolymer (GAFFIX VC713); P
VP / Vinyl Acetate Copolymer; Sodium Acrylate / Vinyl Alcohol Copolymer; Carrageenan Sodium; Vinyl Acetate / Crotonic Acid Copolymer; Many other water soluble hairs listed on pages 73-74 of CTFA Handbook, incorporated herein by reference. Fixatives; and mixtures thereof, but are not limited thereto. Many hair fixatives are also disclosed in US Pat. No. 5,277,899, which is incorporated herein by reference.

The first topically active compound is also m-aminophenol hydrochloride, p-aminophenol sulfate, 2,3-diaminophenol hydrochloride, 1,5-naphthalenediol, phenylenediamine hydrochloride, sodium picramate. , Water-soluble cationic dyes, water-soluble anionic dyes, water-soluble FD & C dyes such as Blue No. 1, Blue No. 2, Red No. 3, Red No. 4, or Red No. 40, Yellow No. 10, Red No. 22 or Red No. 28, etc. And water-soluble hair dyes such as, but not limited to, the water-soluble D & C dyes, and pyrogallol. Many other hair dyes are listed on pages 70-71 of the CTFA Handbook, which is incorporated herein by reference.

The first topically active compound may also be an antioxidant such as ascorbic acid or erythorbic acid; a distyryl biphenyl derivative, stilbene or a stilbene derivative,
It may be an optical bleaching agent or an optical brightening agent such as a pyralozine derivative or a coumarin derivative. In addition, a self-tanning compound such as dihydroxyacetone, or a hair growth promoting substance, or a hair bleaching agent such as perboronic acid or persulfate may be the first topically active compound.

The first topically active compound may also be a deodorant compound such as an astringent salt or a bioactive compound. Astringent salts include organic and inorganic salts of aluminum, zirconium, zinc and mixtures thereof. The anion of the astringent salt is
For example, sulfate, chloride, chlorohydroxide, alum, formate, lactate, benzyl sulfonate or phenyl sulfonate. Exemplary types of antiperspirant astringent salts include aluminum halides, aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides,
And mixtures thereof.

[0058]   Exemplary aluminum salts include aluminum chloride and the general formula Al_Two(OH) _x O_yXH_TwoO (wherein Q is chlorine, bromine or iodine, and x is about 2 to about 5)
And x + y is about 6, x and y are not necessarily integers, and X is about 1
From about 6 to about 6). Exemplary
Zirconium compounds include zirconium oxy salts and zirconium hydroxy.
Salts, which are also called zirconyl salts and zirconyl hydroxy salts,
General empirical formula ZrO (OH)_2-nzL_z(In the formula, z changes from about 0.9 to about 2.
Is not necessarily an integer, n is a valence of L, 2-nz is 0 or more,
L is halide, nitrate, sulfamate, sulfate, and their
Selected from the mixture).

Accordingly, exemplary deodorant compounds include aluminum bromohydrate,
Potassium alum, sodium aluminum chloryl hydroxy lactate, aluminum sulfate, aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrate, aluminum-zirconium polychlorohydrate complexed with glycine, aluminum-zirconium trichlorohydrate, aluminum-zirconium octachloro. Hydrate, aluminum sesquichlorohydrate, aluminum sesquichlorohydrex PG, aluminum chlorohydrex PEG, aluminum zirconium octachlorohydrex glycine complex, aluminum zirconium pentachlorohydrex glycine complex, aluminum zirconium tetrachlorohydrex glycine complex, aluminum Jill Aluminum trichlorohydrex glycine complex, aluminum chlorohydrex PG, zirconium chlorohydrate, aluminum dichlorohydrate, aluminum dichlorohydrate PEG, aluminum dichlorohydrate PG, aluminum sesquichlorohydrate PG, aluminum chloride, aluminum zirconium pentachlorohydrate Rate, CTFA
Many other useful antiperspirant compounds listed in Handbook, page 56 (incorporated herein by reference), and mixtures thereof, are included, but are not limited to.

In addition to astringent salts, deodorant compounds include, for example, cetyltrimethylammonium bromide, cetylpyridinium chloride, benzethonium chloride, diisobutylbenzoxyethoxyethyl-dimethylbenzylammonium chloride, sodium N-laurylsarcosine, N-poly Methylsarcosine sodium, lauroyl sarcosine, N-
Myristolyl glycine, N-lauroyl sarcosine potassium, and bacteriostatic quaternary ammonium compounds such as stearyl trimethyl ammonium chloride; or bioactive compounds; or, for example, alkali metal carbonates and bicarbonates,
And carbonates or bicarbonates such as ammonium and tetraalkyl carbonates and bicarbonates.

Furthermore, as the first topically active compound, an amount sufficient to perform the intended function,
Other compounds can be included in the main emulsion. For example, if the composition is intended for sunscreen, benzophenone-4, trihydroxycinnamic acid and its salts, tannic acid, uric acid, dihydroxynaphthalic acid quinine salt, anthranilate, diethanolamine methoxycinnamate, p-
Compounds such as aminobenzoic acid, phenylbenzimidazole sulfonic acid, PEG-25p-aminobenzoic acid or triethanolamine salicylate can be incorporated into the internal aqueous W ₁ phase.

Further, dioxybenzone, ethyl 4- [bis (hydroxypropyl)] aminobenzoate, glyceryl aminobenzoate, homosalate, methyl anthranilate, octocrylene (o).
ctocrylene), octyl methoxycinnamate, octyl salicylate, oxybenzone, padimate O, red petrolatum (petr)
olatum), titanium dioxide, 4-menthylbenzylidene camphor, benzophenone-1, benzophenone-2, benzophenone-7, benzophenone-1.
Sunscreen compounds such as 2, isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, zotocrylene, or zinc oxide can be incorporated into the oil phase of the main emulsion. Other sunscreen compounds soluble in the aqueous or organic phase are CTFA Handbook 87 and 87.
Listed on the page, which is hereby incorporated by reference.

Similarly, an antifungal compound; an antibacterial compound; an anti-inflammatory compound; a local anesthetic; a drug for rashes, skin diseases and dermatitis; Can be included in things. For example, analgesics such as benzocaine, dyclonine hydrochloride, aloe; anesthetics such as butamben picrate, lidocaine hydrochloride, xylocaine; povidone-iodo, polymyxin-bacitracin sulfate, zinc-neomycin sulfate-
Antibacterial agents such as hydrocortisone, chloramphenicol, methylbenzethonium chloride, and erythromycin; anthelmintic agents such as lindane; deodorants such as chlorophyllin copper complex, aluminum chloride, aluminum chloride hexahydrate, and methylbenzethonium chloride; benzoyl peroxide , Erythromycin benzoyl peroxide, clindamycin phosphate, and acne preparations such as 5,7-dichloro-8-hydroxyquinoline. Alcomethasone dipropionate (
Alcometasone, betamethasone velerate and other anti-inflammatory agents; o-amino-p-toluenesulfonamide monoacetate and other burns ointments; monobenzone and other depigmenting agents; active steroid acinonide (aci)
nonide), diflurazone diacetate, hydrocortisone and other dermatitis therapeutic agents; methylbenzethonium chloride and other diaper rash therapeutic agents; mineral oil, PEG-4
Emollients and moisturizers such as dilaurate, lanolin oil, petrolatum, mineral waxes; fungicides such as butocouazole, haloprogen, clotrimazole; O-[(2-
Anti-herpetic agents such as (hydroxyethoxy) -methyl] guanine; anti-pruritic agents such as alcomethasone dipropionate, betamethasone valerate and isopropyl myristate MSD; 2- (acetyloxy) -9-fluoro-1 ', 2', 3 ',
4'-tetrahydro-11-hydroxypregna-1,4-dieno [16,17
-B] naphthalene-3,20-dione and 21-chloro-9-fluoro-1 '
, 2 ', 3', 4'-Tetrahydro-11b-hydroxypregna-1,4-dieno [16z, 17-b] naphthalene-3,20-dione and other steroids. Any other drug that can be administered topically can be incorporated into the compositions of the invention in an amount sufficient to perform its intended function. Other topically active compounds are described in Remington's Pharmaceutical, which is incorporated herein by reference.
Sciences, 17th Edition, Merck Publishing Co, E
aston, Pa. (1985), pp. 773-891 and 1054-10.
They are listed on page 48 (hereinafter Remington's).

The first topically active compound described above is designed to remain on the skin or hair to perform its intended function. However, in certain circumstances, the first topically active compound which is washed off the skin or hair may be incorporated into the internal aqueous W ₁ phase of the main emulsion.

For example, a W ₁ —O—W ₂ multiple emulsion composition designed as a permanent wave composition can incorporate a reducing agent in the external aqueous phase as the second locally active compound. After applying the W ₁ -O-W ₂ composition to the hair and contacting the composition with the hair for a time sufficient to reduce the hair, the external aqueous phase is rinsed from the hair and small droplets of the main emulsion on the hair. Leave.

The primary emulsion has an oxidizing agent incorporated therein as the first topically active compound. When the oil phase, preferably the volatile oil phase, evaporates from the primary emulsion, the oxidant is released, neutralizing the hair and any reducing agent that remains on the hair. The excess oxidant can then be washed off the hair in a second washing step.

Exemplary but non-limiting oxidizing agents for use as the first topically active compound are ammonium persulfate, hydrogen peroxide, potassium bromate, potassium chromate, potassium persulfate, sodium bromate, sodium carbonate. , Peroxide, sodium iodate, sodium perborate, sodium persulfate, urea peroxide, and mixtures thereof. The oxidizing agent may also be a second topically active compound if the first topically active compound is a hair conditioner. Further, the second topically active compound may be a bleaching agent (ie an oxidizer) and the first topically active compound may be a hair dye.

In a preferred embodiment of the invention, the topically active compound must not be cationic in nature, especially when anionic surfactants are used.

Water Since there is sufficient water in the water phase, the water phase contains from about 1% to about 99% by weight of W ₁ O. The total water present in the W ₁ -O-W ₂ multiple emulsion composition is from about 30% to about 99.9%, usually from about 40% to about 9% by weight of the composition.
It is 5% by weight.

Solute The internal aqueous phase must also contain an oil-insoluble solute. Introduce solute to balance osmotic pressure. Solutes that can be added include alkali metal chlorides, sulfates, nitrates, benzoates and acetates and sugars, and sugar derivatives such as glucose and sucrose. If the solute is added to the internal aqueous phase, it comprises 0.01 to 30% by weight, preferably 0.1 to 20%, most preferably 0.5 to 15%.

Optional Ingredients Surfactants are generally added to the outer W ₂ phase, although it is possible to add surfactants to the inner aqueous phase. The surfactant can be any of the surfactants discussed below with respect to the W ₂ phase.

The internal aqueous phase may also include optional ingredients conventionally included in topically applied compositions. These optional ingredients include, but are not limited to, dyes, perfumes, preservatives, antioxidants, detackifying agents, and similar types of compounds. Optional ingredients are included in the internal aqueous phase of the primary emulsion in amounts sufficient to perform their intended function.

[0073]   O phase   Major W₁/ O emulsions also include from about 0.5% to about 9% by weight of the emulsion.
9% by weight, preferably about 0.75% to about 80% by weight, most preferably about 1
% To about 70% by weight oil phase. Is the oil phase an oil and a low HLB surfactant?
Consists of The oil phase is the internal aqueous W of the main emulsion₁The phase is encapsulated and has a diameter of about 0.
Droplets of 1 to about 1,000μ, preferably about 1 to about 500μ are formed. did
Therefore, the oil phase is W₁-OW_TwoMain emulsion of multiple emulsion composition
To provide a barrier between the internal and external water phases of the liquid. The oil phase is W ₁ Provides sufficient barrier even if it constitutes only 0.5% by weight of O emulsion
To do.

[0074]   oil   The oil may be volatile (except silicone) or non-volatile.

Volatile oils include volatile hydrocarbon oils that evaporate during the process of drying the skin or hair, thereby releasing the internal aqueous W ₁ phase containing the first topically active compound to the skin or hair. Contact. It is desirable for this oil to be free of volatile silicones, as volatile silicones tend to destabilize multiple emulsions.

In one embodiment, the oil may include a combination of volatile oils (excluding silicones) and non-volatile oils. In this embodiment, the oil can be designed to evaporate at a preselected temperature and provide a controlled release of the first topically active compound at the preselected temperature. The preselected temperature is that provided by a hair dryer or during normal hair drying with a curling iron.

As mentioned above, oils also have certain functional properties as long as the topically active compound does not adversely affect the W ₁ -O-W ₂ multiple emulsion composition (eg, does not impart instability to the emulsion). Alternatively, a water-insoluble topically active compound may be included in an amount sufficient to impart an aesthetic effect (eg, emollient).

Although the oil may incorporate a topically active compound, it is preferred that the topically active compound be incorporated in the internal aqueous phase.

Volatile oils are volatile hydrocarbon compounds, such as hydrocarbons having from about 10 to about 30 carbon atoms, in which the W ₁ -O-W ₂ multiple emulsion composition is applied to the skin or hair. However, it is preferred to include a compound having sufficient volatility to slowly volatilize from the skin or hair after subsequent washing off. Preferred volatile hydrocarbon compounds have about 12 to about 24 carbon atoms and have a temperature of about 100 ° C to about 2
It is an aliphatic hydrocarbon having a boiling point of 50 ° C. Volatile hydrocarbon compounds perform the same function as volatile silicone compounds and provide essentially the same benefits.

Volatile hydrocarbon compounds incorporated into the primary emulsion include, for example, isododecane and isohexadecane, ie, Presperse, Inc. ,
South Plainfield, N.M. J. Commercially available from PERMET
HYL 99A, PERMETHYL 101A and PERMETHYL 1
02A is included. Other exemplary volatile hydrocarbon compounds are represented by general structural formula (I), wherein m is 2-5.

[0081]

[Chemical 2]

[0082]   Another exemplary volatile hydrocarbon compound is ISOPAR M (Exxon Ch
electrical Co. C, commercially available from Baytown, Tex_Thirteen~ C ₁₄ Isoparaffin). Volatile hydrocarbons must be less than 50% unsaturated
Is preferred.

As mentioned above, the oil may also be a non-volatile oil. Non-volatile oils include non-volatile silicone compounds, non-volatile hydrocarbons, or mixtures thereof. Non-volatile oils preferably contain compounds containing less than 50% unsaturation. The non-volatile oil phase does not evaporate from the skin or hair. Therefore, the first topically active compound is released by rubbing the skin or hair to rupture the W ₁ / O emulsion. Non-volatile oils have a boiling point of about 250 ° C. or higher at atmospheric pressure.

Exemplary non-volatile silicone compounds include polyalkyl siloxanes, polyaryl siloxanes or polyalkylaryl siloxanes. Mixtures of these non-volatile silicone compounds are also useful. Nonvolatile silicone is 2
About 10 to about 60,000 cs at 5 ° C., typically about 350 to about 10,000 cs
A non-functional siloxane or siloxane mixture having a viscosity of. A viscosity of at least 600,000 cs at 20 ° C. as described in US Pat. No. 4,902,499 (incorporated herein by reference), and at least about 500,000.
So-called "cured silicones" having a weight average molecular weight of are also useful in the compositions of the present invention. Phenyltrimethicone is also useful as a non-volatile silicone compound.

The non-volatile silicone compound is preferably a mixture of a low molecular weight polydimethylsiloxane fluid and a high molecular weight polydimethylsiloxane rubber in a weight ratio of about 2: 1. Preferred silicone rubbers include the following general formula [wherein n is a number from about 2,000 to about 15,000, preferably from about 2,000 to about 7,000. ] Linear and branched polydimethylsiloxanes.

[0086]     (CH_Three)_ThreeSiO- [Si (CH_Three)_TwoO] n-Si (CH_Three)_Three   Silicone rubbers useful in the compositions of the present invention are General Elac
tric Company, Waterford, N.M. Y. And Dow Co
running Corp. , Midland, Michigan, etc.
Commercially available from commercial sources.

Non-volatile oils can also include non-volatile hydrocarbon compounds such as mineral oils.
Other exemplary non-volatile hydrocarbon compounds that can be used include, but are not limited to, branched 1-decene oligomers such as 1-decene dimer or polydecene.

The oil also optionally comprises (1) jojoba oil, wheat germ oil or prucerine (
oil, such as purcellin) oil, or (2) further comprising a water-insoluble emollient, such as, for example, an ester having at least about 10 carbon atoms, preferably about 10 to about 32 carbon atoms. it can.

Suitable esters include aliphatic alcohols having from about 8 to about 20 carbon atoms and aliphatic or aromatic carboxylic acids containing from 2 to about 12 carbon atoms, or vice versa. To aliphatic alcohols having from 2 to about 12 carbon atoms with aliphatic or aromatic carboxylic acids having from about 20 carbon atoms are included. Esters are straight or branched. The ester preferably has a molecular weight of less than about 500. Thus, suitable esters include, for example, (a) aliphatic monohydric alcohol esters such as myristyl propionate, isopropyl isostearate, isopropyl myristate, cetyl palmitate, cetyl acetate, cetyl propionate, cetyl stearate, isodecyl. Neopentanonate, cetyl octanoate, isocetyl stearate, (b) aliphatic di- and tri-esters of polycarboxylic acids such as diisopropyl adipate, diisostearyl fumarate, dioctyl adipate, and citric acid triisostearyl, (c) aliphatic polyhydric alcohol esters, such as propylene glycol dipelargonate, aliphatic esters of (d) aromatic acids, e.g., C ₁₂ -C benzoic acid ₅ alcohol esters, octyl salicylate, sucrose benzoate, and include dioctyl phthalate, but are not limited thereto.

Many other esters are available on CTFA Handbook at pages 24-26 (
(Incorporated herein by reference).

Low HLB Emulsifier The O phase of the present invention also comprises from about 0.1% to about 30% by weight of the oil, preferably about 1%.
% To about 15% by weight low HLB emulsifier.

Low HLB emulsifiers are non-silicon containing surfactants, or HLB values of less than about 10 (
That is, it may comprise a mixture of non-silicon containing surfactants having an HLB value of from about 0.1 to less than about 10, an oil soluble silicon based surfactant, an oil soluble polymer based surfactant, or a mixture thereof. . The silicon-free surfactant or surfactant mixture preferably has an HLB value of from about 1 to about 7, and from about 3 to about 6.
Is more preferable. As used herein, the term oil soluble refers to oil phase 10
It means a compound which has a solubility of at least 0.1 g per 0 ml and produces a true solution.

The HLB value of certain surfactants is determined by McCutcheon's Emulsif.
iers and Detergents, North Americana
nd International Editions, MC Publish
ing, Glen Rock, NJ (1993) (hereinafter McCutcheon '
s) can be found in Alternatively, the HLB value for a particular surfactant can be estimated by dividing the weight percent of oxyethylene in the surfactant by 5 (for surfactants containing only ethoxy moieties). Further, the HLB value of the surfactant mixture can be estimated by the following formula.

HLB = (wt.% A) (HLB _A ) + (wt.% A) (HLB _B ) [wherein wt. % A and wt. % B is the weight percent of surfactants A and B, respectively, in the silicon-free surfactant mixture, and HLB _A and HLB _B are the HLB values of surfactants A and B, respectively. ] Suitable low HLB surfactants may be silicone based or non-silicone containing surfactants.

[0095] Silicon Suitable types of non-containing nonionic surfactants, fatty _(C 6 _{~C 22)} polyoxyethylene ethers of alcohols, fatty _(C 6 _{~C 22)} alcohol polyoxyethylene / polyoxypropylene Including but not limited to ethers, ethoxylated alkylphenols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, and mixtures thereof.

Suitable silicon-free nonionic surfactants are ethoxylated alcohols with HLB values of about 0.1 to about 10. A particularly preferred ethoxylated alcohol is laureth-1, i.e. lauryl alcohol ethoxylated with an average of 1 mole of ethylene oxide. Other suitable ethoxylated alcohols include laureth-2, laureth-3 and laureth-4. About 0.1 to about 10 H
Many other suitable nonionic surfactants with LB are McCutcheon.
pp. 229-236 (incorporated herein by reference). Other exemplary non-silicon containing nonionic surfactants having HLB values of about 0.1 to about 10 include ethoxylated nonylphenol, ethoxylated octylphenol, ethoxylated dodecylphenol, ethoxylated with up to 4 ethylene oxide moieties. fatty _(C 6 _{~C 22)} alcohol, oleth (oleth) -2, steareth (steareth) -3, steareth-2, ceteth (ceteth)
-2, oleth-3, and mixtures thereof, but are not limited thereto.

The emulsifier can also include a non-silicon containing surfactant mixture having an HLB value of about 1 to about 10. The mixture has an acceptable HLB value, ie about 0.1 to about 1
A sufficient amount of surfactant having 0 and a high HLB value, ie from about 1 to about 10
A sufficient amount of a surfactant mixture having the above, wherein the surfactant mixture is about 1
To about 10 total HLB values. Exemplary, but non-limiting, nonionic surfactants having high HLB values are listed in McCutcheon's pages 236-246, incorporated herein by reference.

A preferred non-silicone containing surfactant is PEG30 dipolyhydroxystearate.

An exemplary oil-soluble silicon-based surfactant is Dow Corning Co. , M
idland, Mich. Commercially available from DOW CORNING 322
Dimethicone copolyols, which are dimethylsiloxane polymers with polyoxyethylene and / or polyoxypropylene side chains such as 5C and 5225C FORMULATION AID. Dimethicone copolyols have a total of about 15 or less ethylene oxide and / or propylene oxide monomer units in the side chain. Dimethicone copolyols are traditionally used in conjunction with silicones, where the silicon-containing surfactant is highly soluble in volatile or non-volatile silicone compounds, very insoluble in water, and low on low skin. This is because it is irritating.

Another exemplary, but non-limiting, oil-soluble silicon-based surfactant is Goldsch
midt Chemical Corporation, Hopewell, V
a. Alkyl dimethicone copolyols such as cetyl dimethicone copolyol commercially available from ABIL® EM90 as commercially available from K.K. The alkyl dimethicone copolyol has the following structure.

[0101]

[Chemical 3] [In the formula,   p is a number from 7 to 17,   q is a number from 1 to 100,   m is a number from 1 to 40,   n is a number from 0 to 200,   PE has a molecular weight of about 250 to about 2000 (C_TwoH_FourO)_a(C_ThreeH ₆ O)_b-H, a and b are in the weight ratio C_TwoH_FourO / C_ThreeH₆O is 100 /
It is selected to be 0 to 20/80. ]   The surfactant phase can also include oil-soluble polymeric surfactants. In oil
Polymeric surfactants that can form water emulsions are
Completely covers the surface of the drop, firmly adheres to the oil-water interface, and the external oil phase is a polymer
It is a good solvent for the stabilizing part of the system surfactant,
It has the advantage that it is thick enough to guarantee stability. These surface activities
Agents include ethoxy, propoxy and / or similar alkylene oxide monomers.
-Units such as butoxy are included. Oil-soluble polymer surfactant is a surfactant
, But is not physically or chemically crosslinked in solution.

Therefore, oil-soluble polymeric surfactants are distinguished from polymeric gelling agents such as polyacrylic acid or polymethacrylic acid.

Thus, exemplary oil-soluble polymeric surfactants include, but are not limited to, polyoxyethylene-polyoxypropylene block copolymers, and similar polyoxyalkylene block copolymers. Oil-soluble block copolymers typically have less than about 20 wt% ethylene oxide. Specific non-limiting oil-soluble polymer surfactants include poloxamer 101, poloxamer 105, PPG-2-Buteth-3, PPG-3-Butech-5, PPG-5-Butek-. 7, PPG-7-Butek-10,
PPG-9-butes-12, PPG-12-butes-16, PPG-15-butes-20, PPG-20-butes-30, PPG-24-butes-27, PPG
-28-butes-35, and PEG-15 butanediol. Another useful oil-soluble polymeric surfactant is a polyoxyethylene-polyoxypropylene block copolymer of a polyamine having less than about 40 wt% ethylene oxide, namely ethylenediamine.

The non-silicon-containing surfactant, the silicon-containing surfactant, or the hydrophobic portion of the polymer-based surfactant is sufficiently soluble in the oil phase, and a sufficient amount of the surfactant is present in the oil phase. Stabilize the primary W ₁ / O emulsion. In one embodiment where the oil phase comprises a silicone compound, the surfactant phase is a silicon-based surfactant, from about 10 to about 14.
Included are non-silicon containing surfactants, oil soluble polymer based surfactants, or mixtures thereof, which have a hydrophobic portion which preferably contains 1 carbon atom. When the hydrophobic portion of the silicon-free surfactant is saturated and contains about 14 or more carbon atoms, the silicon-free surfactant is insoluble in the silicone phase and the major W ₁ / O 2
The emulsion is unstable. If the hydrophobic portion contains less than about 10 carbon atoms, the primary W ₁ / O emulsion will tend to coalesce, ie the emulsion droplets will coalesce to form larger droplets. The amount of surfactant phase needed to provide the desired W ₁ / O droplet diameter to the primary emulsion varies with the amount of aqueous phase in the primary emulsion and is readily determined by one of ordinary skill in the art.

[0105]   A particularly preferred emulsifier is cetyl dimethicone copolyol.

External Water Phase In a first embodiment, the external water phase (W ₂ ) of the W ₁ -O-W ₂ multiple emulsion comprises an isotropic mixture of surfactant phases (US Pat. No. 5,656,56). 280
(As opposed to the lamellar phase of No.). As mentioned above, this external phase comprises non-amide anionic surfactants and / or other surfactants. Non-amide group anionic surfactant comprising 1 to 99% surfactant system and amphoteric surfactant comprising 1 to 99% surfactant system comprising anionic surfactant in combination with amphoteric surfactant. Is preferred. The key to the present invention is the ability to maintain stable multiple emulsions at much higher levels of surfactant than previously thought.

In a second embodiment, the outer aqueous phase (W ₂ ) of the W ₁ —O—W ₂ multiple emulsion is a relatively high level of surfactant forming an isotropic phase, usually 0 of the outer phase.
-40% by weight of the second topically active compound, which has the same, similar, or different function as the first topically active compound, a solute, and 0.01 to 10% by weight of the stabilized natural rubber polymer. The composition contains all non-amide anions or all amphoteric surfactants, or a mixture of both. Surfactants typically contain about 2 to 80% aqueous phase.

Both anionic surfactants of the above embodiments include, for example, primary alkane (eg, C _{8 to} C ₂₂ ) sulfonate, primary alkane (eg, C _{8 to} C ₂₂ ) disulfonate, C _{8 to} C ₂₂ alkene. _sulfonates, C 8 _{-C 22} hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS);
Alternatively, it may be an aromatic sulfonate such as an alkylbenzene sulfonate.

The anionic surfactant may also be an alkyl sulphate (eg C _{12 to} C ₁₈ alkyl sulphate) or an alkyl ether sulphate (including alkyl glyceryl ether sulphate). Suitable alkyl ether sulphates include those having the general formula:

RO (CH ₂ CH ₂ O) _n SO ₃ M [wherein R is an alkyl or alkenyl group having about 8 to 18 carbons, preferably 12 to 18 carbons, and n is 1. Having a mean value greater than or equal to 0, preferably between 2 and 3, M is a stabilizing cation such as sodium, potassium, ammonium or substituted ammonium. ] Ammonium and sodium lauryl ether sulphate are preferred.

Anionic surfactants also include alkyl sulfosuccinates (including mono and dialkyls, eg, C _{6 to} C ₂₂ sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates, C ₈ -C ₂₂ alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyalkyl phosphate esters, acyl lactates, C ₈ -C ₂₂ monoalkyl succinates and maleates, may be sulphoacetates, and acyl isethionates.

The sulfosuccinate may be a monoalkyl sulfosuccinate having the formula:

R ⁴ O ₂ CCH ₂ CH (SO ₃ M) CO ₂ M [wherein R ⁴ is C ₈ -C ₂₂ alkyl and M is a stabilizing cation as defined above. ] Alkoxylated citrate sulfosuccinates; and alkoxylated sulfosuccinates such as:

[0114]

[Chemical 4] [Wherein n = 1 to 20 and M is as defined above. ] Sarcosinates are generally represented by the formula _{RCON (CH 3) CH 2 CO} 2 M, wherein, R is _{C 22} alkyl from _{C 8,} M is a solubilizing cation.

[0115]   Taurate is generally represented by the following equation.

R ² CONR ³ CH ₂ CH ₂ SO ₃ M [wherein R ² is C ₈ -C ₂₀ alkyl, R ³ is C ₁ -C ₄ alkyl, and M is a solubilizing cation. ] Another type of anionic surfactant is a carboxylate, such as:

[0117] R- _{(CH 2} CH ₂ O) in n _CO 2 M [wherein, R is _{C 20} alkyl from _{C 8,} n is 0 to 20, M is as defined above. Another carboxylate that can be used is, for example, Montei by Seppic.
is an amidoalkyl polypeptide carboxylate, such as ne LCQ®.

Other surfactants that can be used are C _{8 to} C ₁₈ acyl isethionates. These esters include alkali metal isethionates and 6 to 18 carbon atoms and 2
Prepared by reaction with a mixed aliphatic fatty acid having an iodine value of less than 0. At least 75% of the mixed fatty acids have 12 to 18 carbon atoms and up to 25% have 6 to 10 carbon atoms.

When an acyl isethionate is present, generally about 0.5 to 1 of the total composition.
5% by weight, preferably about 1 to about 10%.

The acyl isethionate may be an alkoxylated isethionate as described in Ilardi et al., US Pat. No. 5,393,466, incorporated herein by reference. This compound has the following general formula:

[0121]

[Chemical 5] [Wherein R is an alkyl group having 8 to 18 carbons, m is an integer of 1 to 4, X and Y are hydrogen or an alkyl group having 1 to 4 carbons, and M ⁺ Is, for example, a monovalent cation such as sodium, potassium or ammonium. Generally, the anionic component is about 1 to 30% by weight of the composition, preferably 2 to 2
5%, most preferably 5 to 20% by weight of the composition.

Zwitterionic and Amphoteric Surfactants Zwitterionic surfactants are exemplified by surfactants, which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, and include aliphatic radicals. May be straight or branched, one of the aliphatic substituents containing from about 8 to about 18 carbon atoms and one containing an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. contains. The general formulas for these compounds are as follows:

[0123]

[Chemical 6] Wherein R ² is alkyl, alkenyl, or about 8 to about 18 carbon atoms, 0
Is a hydroxyalkyl radical containing from about 10 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety, Y is selected from nitrogen, phosphorus, and sulfur atoms, and R ³ is from about 1 to about 3 An alkyl or monohydroxyalkyl group containing carbon atoms, X is 1 when Y is a sulfur atom, Y
Is 2 when is nitrogen or phosphorus, R ⁴ is alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms, and Z is selected from carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups. Is a radical. ] Examples of such a surfactant include 4- [N, N-di (2-hydroxyethyl) -N-octadecylammonio]
-Butane-1-carboxylate, 5- [S-3-hydroxypropyl-S-hexadecylsulfonio] -3-hydroxypentane-1-sulfate, 3- [P, P-diethyl-P-3,6. 9-trioxatetradexosylphosphonio] -2-hydroxypropane-1-phosphate, 3- [N, N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio] -propane-1-phosphonate, 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate, 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-1-sulfonate, 4- [N, N-di (2-hydroxyethyl) -N- (2-hydroxydodecyl) ammonio] -butane-1-carboxylate, 3- [S-ethyl-S- (3-dodecoxy-2-hydroxypropyl) sulfonio] -propane-1-phosphate, 3- [P, P-dimethyl-P-dodecylphosphonio] -propane-1-phosphonate, Included are 5- [N, N-di (3-hydroxypropyl) -N-hexadecylammonio] -2-hydroxy-pentane-1-sulfate.

Amphoteric surfactants that can be used in the present invention contain at least one acid group. It may be a carboxylic acid group or a sulfonic acid group. Generally, it must include alkyl or alkenyl groups containing 7 to 18 carbon atoms.

Suitable amphoteric surfactants within the general formula above include simple betaines of the formula:

[0126]

[Chemical 7] Wherein R ¹ is alkyl or alkenyl of 7 to 18 carbons and R ² and R ³ are each independently alkyl, hydroxyalkyl or carboxyalkyl containing 2 to 3 carbon atoms. . ] R ¹ is in particular at least half, preferably at least three-quarters of the group R ¹ is 10
It may also be a mixture of C ₁₂ and C ₁₄ alkyl groups derived from coconut, so as to have 4 to 14 carbon atoms. R ² and R ³ are preferably methyl.

[0127]   Another possibility is that the amphoteric surfactant is a sulfobetaine of the formula:

[0128]

[Chemical 8] [In formula, m is 2 or 3. _{Or, - (CH 2) 3 SO} - 3 is that it is a variation which is replaced by the following equation.

[0129]

[Chemical 9] [Wherein R ¹ , R ² and R ³ are as defined above. ] Amphoteric / zwitterionic surfactants generally comprise from about 1 to 30% by weight of the composition, preferably from 2 to 25%, more preferably from 5 to 20%.

In addition to one or more anions and amphoteric and / or zwitterionic, the surfactant phase can optionally contain nonionic surfactants.

Nonionic surfactants which can be used are in particular compounds having a hydrophobic group and a reactive hydrogen atom, such as aliphatic alcohols, acids, amides or alkylphenols and alkylene oxides, especially ethylene oxide alone or ethylene oxide and propylene oxide. Reaction products of. Specific nonionic surfactant compounds are alkyl _(C 6 _{~C 22)} phenol - ethylene oxide condensates,
Aliphatic _(C 8 ~C ₁₈₎ condensation products of primary or secondary linear or branched alcohols with ethylene oxide, and ethylene oxide with a product produced by the condensation of the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic surfactant compounds include long chain quaternary amine oxides, long chain quaternary phosphine oxides and dialkyl sulfoxides.

The nonionic surfactant may also be a sugar amide, such as a polysaccharide amide. Specifically, US Pat. No. 5,389,2 by Au et al., Incorporated herein by reference.
One of the lactobionamides described in No. 79, or K, incorporated herein by reference.
One of the sugar amides described in patent 5,009,814 by Elkenberg may be used as a surfactant.

Other surfactants that can be used are those described in Parran Jr. US Patent No. 3,7
No. 23,325, and the alkyl polysaccharide nonionic surfactant is Ll.
U.S. Pat. No. 4,565,647 to enado, both of which are incorporated herein by reference.

[0134]   A preferred alkyl polysaccharide is an alkyl polyglycoside of the formula:

[0135]     R^TwoO (C_nH_2nO)_t(Glycosyl)_x [In the formula, R^TwoIs about 10 to about 18 alkyl groups, preferably about 12 to 14
Alkyls containing 1 carbon atom, alkylphenyls, hydroxyalkyls,
Selected from droxyalkylphenyl and mixtures thereof, n being 0 to 3
, Preferably 2, t is from 0 to about 10, preferably 0, and x is 1.
It is from 3 to about 10, preferably 1.3 to about 2.7. ] Glycosyl
It is preferably derived from glucose. To prepare these compounds,
The alcohol or alkyl polyethoxy alcohol is first produced and then the glucose
Or a glucose source to produce a glucoside (bonded at the 1-position). Next
Thus, additional glycosyl units were added to the 1-position and the preceding glycosyl units 2-, 3-, 4-
And / or it can be attached between the 6-position, preferably predominantly the 2-position.

[0136]   Nonionic surfactants comprise 0 to 10% by weight of the composition.

According to a second embodiment, the external water phase should also comprise from about 0.01 to 10% by weight of stabilized natural rubber polymer. In systems where the external surfactant W2 consists entirely of nonionic surfactant or contains a majority (60% or more) of nonionic surfactant, it is preferred to use nonionic gum polymers.

Non-ionic species polysaccharides are especially soluble and dispersible in anionic surfactants and anion-rich surfactant systems. One such stabilizer is guar gum, which is structurally composed of a straight chain of D-mannose and a D-galactose side chain that is present on almost all other mannose units. The usual ratio of mannose to galactose is about 2: 1 and the molecular weight is usually around 100,000 to 1,000,000. Another useful stabilizer is locust bean gum, a galactomannan consisting of a backbone of D-mannose units and a single galactose side chain approximately every fourth unit. Similar to guar gum, the approximate molecular weights are 100,000 and 1,000,
It is between 000.

Whether the external surfactant W2 consists entirely of amphoteric surfactant or most (50% or more)
In the system containing the amphoteric surfactant, the anionic gum polymer is preferable. They may be seaweed polysaccharides, exudate polysaccharides, or microbial polysaccharides.

A preferred anionic seaweed polysaccharide is carrageenan, or Irish moss, which is a complex mixture of sulfated polysaccharides. Carrageenan alternates with α-1,3 and β-1,4
A mixture of galactans having varying proportions of half ester sulphates linked by glycosidic bonds and linked to one or more hydroxyl groups of the galactose unit. The molecular weight typically ranges from 100,000 to 1,000,000.

A preferred anionic exudate polysaccharide is tragacanth, which is a complex mixture of acidic polysaccharides containing galacturonic acid, galactose, fucose, xylose, and arabinose. Another preferred anionic exudate polysaccharide is karaya gum, a partially acetylated high molecular weight polysaccharide containing L-rhamnose, D-galactose, D-galacturonic acid, and D-glucuronic acid residues.

The most preferred amphoteric or amphoteric surfactant systems are microbial anionic heteropolysaccharide gums, with xanthan gum being most preferred. The major structure of these microbial gums contains two glucose units, two mannose units, and one glucuronic acid unit.

Unless otherwise indicated in the operating and comparative examples, or otherwise indicated, all quantities in the present description indicating the amounts or ratios of materials or conditions or reactions, physical properties of materials and / or uses are: It should be understood that it is modified by the word "about".

As used herein, the term “comprising” is intended to include the presence of the indicated feature, integer, step, component, but one or more feature, integer, step, component or It is not intended to exclude the presence or addition of that group.

Unless otherwise stated, all percentages used are intended to be weight percentages.

Definition and Measurement of Stability (for purposes of the first embodiment) Sodium ISE: To measure the stability of multiple emulsions, a sodium ion sensitive electrode (Corning 476138) was attached to the Orion EA92.
It was connected to a 0 expandable ion analyzer.

Multiple emulsion samples were purposely prepared with very low internal NaCl concentration. That is, the separated bottom phase Na ion concentration served as a quick indicator of multiple emulsion stability.

In case of multiple emulsion failure, NaCl is released from the internal phase,
The NaCl concentration in the outer aqueous phase increases due to the higher initial salt concentration in the inner phase. A plot of the sodium ion concentration of the separated phase against the storage time shows a positive slope (
Na ion concentration increases with time).

In the case of stable multiple emulsions, NaCl is retained in the inner phase and only water is released in the outer phase. The plot of sodium ion concentration in the separated phase against storage time shows a negative slope (Na ions gradually dilute over time) or little slope (water was released in the early stages).

5 g of the separated external aqueous (bottom) phase is taken up in a separating funnel and milli-Q water 45
diluted to 50 g. 50g of 0.5M triethanolamine (TEA)
Was added to maintain the ionic strength and equalize the activity coefficient.

The standard product was obtained by taking samples 1, 2, 3, 4 and 5 g of the original external phase and
It was prepared by diluting with 11-Q water 49, 48, 47, 46, and 45 g to 50 g. As above, 50 g of 0.5M TEA was added to each sample.

Each of the standard sample and the separated emulsion sample was measured for sodium ion activity (concentration) using a sodium ion sensitive electrode.

Multiple emulsions showing zero or negative slope for 30 days storage at room temperature (20-25 ° C.) were considered stable. Conversely, emulsions that showed a positive slope within the same time were considered unstable.

Definition and measurement of stability (for the second embodiment) Multiple emulsion stability is determined by collecting a fixed amount of the separated aqueous phase (if any) and weighing the collected material for 45 days. It was measured later. This weight was then divided by the total weight of product in the separatory funnel to determine percent separation.

Multiple Emulsion Preparation (For Both Embodiments) Main (W ₁ / O) Emulsion Oil Phase: Oil and oil soluble surfactant (low HLB emulsifier) were mixed together at room temperature using overhead stirring.

Internal Aqueous Phase (W ₁ ): A sodium chloride solution having an appropriate concentration with or without a topical active compound was prepared, and the pH was adjusted to 7.0.

W ₁ / O Preparation: The oil phase (O) was filled in a container. Side scraper (60-8
The salt / topically active compound solution (W ₁ ) was gradually added to the oil phase with an addition funnel over 10-12 minutes with mixing at 0 rpm). Slow addition of the aqueous phase under low shear mixing is essential to obtain a stable primary emulsion. When the aqueous phase was completely added, the side scraper mixing speed was reduced to 40 rpm and the homogenizer was switched on. Homogenization was carried out at room temperature for 3 minutes at 8000, 9500 and 13,500 rpm, respectively. The heat generated during the homogenization process raised the temperature of the batch to about 35 ° C.

Multiple Emulsions External Water Phase (W ₂ ): The external water phase was prepared in a jacketed vessel by mixing the secondary surfactant into the main surfactant at 60 ° C. with vigorous mixing.
The pH of each surfactant solution was adjusted to 7.0 in advance. The surfactant solution with gel-like viscosity was centrifuged at 7000 rpm for 20 minutes to remove the entrapped air.

W ₁ / O / W ₂ Preparation: The main emulsion (W ₁ / O) was charged to a smaller scale vessel, followed by the external aqueous phase (W ₂ ). The mixture was hand mixed with a spatula for 15 seconds. This was followed by side scraper mixing at 70-105 rpm for 8 minutes (if a low speed was found to be inappropriate, use a higher speed).
Insert a small spatula as a baffle into the container to ensure good mixing around the center spindle of the side scraper. The resulting multiple emulsion was transferred to a 250 ml separatory funnel and awaited separation of the aqueous phase for emulsion stability analysis.

Examples 1 to 37 relate to the first embodiment, and 38 to 59 relate to the second embodiment.

[0161]     Example   The following components were used in the experiment as described below.

[0162]

[Table 1]

Examples 1-14 The following examples were prepared to demonstrate the effect of various anionic surfactants mixed with an amphoteric surfactant (eg betaine) on the stability of multiple emulsions.

[0164]

[Table 2]

As can be seen, anionic surfactants with amide groups destabilize multiple emulsions (compare Examples 8 to 14 and Examples 1 to 7).

Examples 15-21 The effect of the amphoteric surfactant / anionic surfactant ratio on stability, if any,
To measure it, the following example was prepared.

[0167]

[Table 3]

As mentioned above, the emulsion was stable regardless of the amphoteric surfactant / anionic surfactant ratio.

Examples 1 and 22 The following examples show that multiple emulsions are stable for various types of amphoteric surfactants.

[0170]

[Table 4]

Examples 23 and 24 The following compositions were prepared and demonstrated that nonionic and amphoteric surfactants also form stable multiple emulsions.

[0172]

[Table 5]

Examples 1 and 25-28 From the table below, stable multiple emulsions are produced when the composition of the oil phase is less than 50% unsaturated hydrocarbon compounds, ie sunflower oil is above 50%. It was found to have a composition that was an unsaturated hydrocarbon compound.

[0174]

[Table 6]

[0175]   Examples 29-31   The following examples were prepared to demonstrate the effect of low HLB emulsifier concentration.

[0176]

[Table 7]

Examples 2, 32 and 33 The following examples were prepared to demonstrate whether multiple emulsions are stable for a wide range of surfactant / oil ratio compositions.

[0178]

[Table 8]

[0179]   As can be seen, stability was maintained over a wide range of surfactant / oil ratios.

Examples 2, 34-37 Compositions 2 and 34 to demonstrate the stability of multiple emulsions when a skin benefit agent or hair styling polymer is incorporated into the W1 phase.
~ 37 was prepared.

[0181]

[Table 9]

Apparently, in Examples 34 and 35, the incorporation of benefit agent did not affect the stability of the multiple emulsions. Examples 36 and 37 demonstrate the criticality that the stability of multiple emulsions is adversely affected when using cationic hair styling polymers in systems containing anionic surfactants.

[0183]   Material (for second embodiment) and Examples 38-59   The following components were used in the experiment as described below.

[0184]

[Table 10]

[0185]   Examples 38-43

[0186]

[Table 11]

The control Example 38 has a Newtonian anion external W ₂ phase (SLES),
40% phase separation over 45 days. Examples 2 and 3 show that gelling the external phase with a nonionic natural rubber stabilizer prevents phase separation by incorporating locust bean gum or delays phase separation by incorporating guar gum. ing. Example 41 shows that locust bean gum also gels another anionic surfactant, sodium lauryl sulfate. Example 42 shows that octyl palmitate is replaced with gas oil. In Example 43 Applicants et al. Attempted to incorporate anionic gum into the anionic surfactant, but the W2 phase was not homogeneous. Examples 39-42 demonstrate the criticality that the gum must be nonionic when the surfactant is anionic.

[0188]   Examples 44-51

[0189]

[Table 12]

The control Example 44 has Newtonian amphoteric external W ₂ phase (betaine) and 45
50% phase separation over day. Examples 45-49 show that gelling the external phase with an anionic natural rubber stabilizer prevents phase separation by incorporating xanthan gum or delays phase separation by incorporating tragacanth gum, karaya gum, or carrageenan. Is shown. Example 49 shows that xanthan gum also gels another amphoteric surfactant, coco amphoglycinate. Example 50 shows that octyl palmitate is replaced with gas oil. In Example 51 we attempted to incorporate a nonionic gum into the amphoteric surfactant, but the W2 phase was not homogeneous. Examples 45-5
0 demonstrates the criticality that the gum must be anionic when the surfactant is amphoteric.

[0191]   Examples 52-59

[0192]

[Table 13]

Example 52 is a control with an anionic surfactant as the major surfactant. Examples 53 and 54 show that the phase separation is hindered when a non-ionic gum stabilizer (locust bean) is used, whereas the phase separation is still close to the control when an anionic gum stabilizer (xanthan) is used. Shows. Example 56 shows that the anionic surfactant ratio can be varied from 13: 2 to 9: 6 without phase separation. Conversely, Example 56 is a control with amphoteric surfactant as the predominant surfactant. Examples 57 and 58 prevent phase separation when anionic gum stabilizer (xanthan) is used, while nonionic gum stabilizer (
It shows that the phase separation is still close to the control when locust beans) are used. Example 59 shows that the anionic surfactant ratio can be varied from 11: 4 to 7.5: 7.5 without phase separation.

These examples demonstrate the criticality that a nonionic gum stabilizer must be used if the predominant surfactant is anionic.
Furthermore, if the surfactant mixture is more than half the amphoteric surfactant, an anionic gum stabilizer must be used.

[Brief description of drawings]

FIG. 1A shows a stable multiple emulsion in which the W ₁ / O phase is surrounded by the W ₂ phase.

FIG. 1B shows multiple emulsions disintegrating into a single O / (W ₁ + W ₂ ) emulsion.

[Fig. 2]   Figure 8 shows a plot of viscosity against Haake RV06 spindle speed.

[Figure 3]   Figure 8 shows a plot of viscosity against Haake RV06 spindle speed.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01F 17/54 B01F 17/54 C11D 1/82 C11D 1/82 3/04 3/04 3/18 3 / 18 3/22 3/22 3/37 3/37 3/38 3/38 17/08 17/08 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM ), AE, AG, AL, AM, AT, AU, AZ, B , BB, BG, BR, BY, BZ, CA, CH, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX , MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Basdevan, Chirchtierai Barahan USA, Illinois 60047, Chicago, Rolling Meadows, East Golf Road 3100, Unilever Home and Personal Care You Est Ai. (72) Inventor No, Henry Lewis United States, New Jersey 07649, Oladel, Utdland Avenyu 848 (72) Inventor Gandolhuo, François Jeerrard United States, New York 11220, Brutskrin, Sixties Street Street 712 (72) Inventor Munchine, Kanuni United States, New York 10025, New York, West One Handled Streets 216 F term (reference) 4C083 AA121 AB032 AB331 AB332 AC011 AC022 AC302 AC712 AC782 AD071 AD072 AD151 AD152 AD201 AD202 AD351 BB04 BB05 CC23 CC38 DD34 EE01 4D077 AB10 AC02 BA04 BA07 BA12 BA13 CA03 DD29Y DD55Y DE01Y DE07Y 4G065 AA01 AA02 AB01Y AB32Y BA01 BA03 BA05 BA07 BA13 BB06 CA06 DA08 EA01 EA07 402003 A21 EB37 EB41 ED02 ED04 FA16 FA37

Claims (17)

[Claims] 1. A W ₁ -O-W ₂ multiple emulsion comprising: (1) from 1% by weight of the composition to 99% by weight of a W ₁ / O emulsion, (a) from 1% by weight of the emulsion. 99% by weight of (i) water; (ii) 0.
01 to 30% by weight of emulsion solute; and (iii) 0 to 30% of optional surfactant in internal aqueous phase; (b) 0.1% to 99% by weight of internal aqueous phase of emulsion. A surrounding oil phase, wherein the oil is selected from volatile hydrocarbons, non-volatile hydrocarbons, non-volatile silicones and mixtures thereof; (c) 0.1 to 20% by weight of emulsion, about 10 or less. A non-silicon-containing surfactant or surfactant mixture having an HLB value of, an oil-soluble silicon-based surfactant, a surfactant emulsifier selected from oil-soluble polymer-based surfactants and mixtures thereof, and (d) water An emulsion comprising a topically effective amount of a first topically active compound that can be found in phase (a), oil phase (b) or both, and (2) 1 to 99% by weight external, etc. A water phase W ₂ which comprises (a) 2 to 80% by weight of a surfactant phase of a non-amide anion or nonionic surfactant in combination with at least one amphoteric surfactant, or An aqueous phase comprising a mixture thereof and having a ratio of anionic and / or nonionic surfactants to amphoteric surfactants of 100: 1 to 1: 100, (b) optionally 0 to 60% by weight of the external phase A second topically active compound of
And (c) an emulsion comprising an aqueous phase W ₂ with an optional solute. 2. A W ₁ -O-W ₂ multiple emulsion comprising: (1) 1% to 99% by weight of the composition of W ₁ / O emulsion, and (a) 1% by weight of the emulsion. 99% by weight of (i) water; (ii) 0.
01 to 30% by weight emulsion solute; and (iii) an internal aqueous phase containing an optional surfactant; (b) 0.1% to about 99% by weight of the emulsion, in an oil phase surrounding the internal aqueous phase. Wherein the oil is an oil phase selected from volatile hydrocarbons, non-volatile hydrocarbons, non-volatile silicones and mixtures thereof; (c) 0.1-20% by weight of the emulsion, having an HLB value of about 10 or less. A non-silicon-containing surfactant or a surfactant mixture, an oil-soluble silicon-based surfactant, an oil-soluble polymer-based surfactant and a surfactant emulsifier selected from a mixture thereof, and (d) an aqueous phase (a) , the oil phase (b) or an emulsion comprising a first topically active compound topically effective amount can be found in both, and (2) 1 to 99 wt% of the external isotropic aqueous phase W ₂ And (a) an aqueous phase of 2 to 80% by weight of a surfactant phase, comprising a non-amide anion surfactant, or an amphoteric surfactant or a mixture of the two, (i) 60% by weight or more Is an anionic surfactant or (ii) 50% by weight of an amphoteric surfactant in the aqueous phase, (b) 0-60% by weight of the external phase of the second topically active compound, (c) optional. And (d) 0.01 to 10% of a nonionic natural rubber stabilizer when 60% or more of the surfactant phase in (2) (a) (i) above is an anionic surfactant, Or 0.01 to 10% of anionic natural rubber stabilizer when 50% or more of the surfactant phase in (2) (a) (ii) above is an amphoteric surfactant, and in any case Even multiple emulsion droplets have their integrity Maintain an emulsion comprising an aqueous phase W ₂ which comprises a stabilizer multiple emulsion composition is not phase separate. 3. Emulsion according to claim 1 or 2, which comprises from 2 to 90% by weight of W ₁ / O emulsion. 4. The emulsion according to claim 3, comprising 5 to 80% by weight of W ₁ / O emulsion. 5. The emulsion according to any one of claims 1 to 4, wherein the solute in the internal aqueous phase is alkali metal chloride, sucrose or glucose. 6. The oil phase comprises 1 to 80% internal W ₁ / O phase.
The emulsion according to any one of 1. 7. The emulsion according to any one of claims 1 to 6, wherein the hydrocarbon is a saturated vegetable oil. 8. The emulsion according to claim 7, wherein the oil is 50% or more saturated. 9. The emulsion according to claim 8, wherein the oil is 85% or more saturated. 10. The emulsion according to claim 1, wherein the emulsifier (c) is cetyl dimethicone copolyol. 11. The topical active compound (1) (d) is lactic acid.
0. The emulsion according to any one of 0. 12. The emulsion according to claim 10, wherein the topically active compound (2) (b) is also lactic acid. 13. The emulsion according to claim 1, wherein the topically active compound is a nonionic hair styling polymer. 14. The emulsion according to claim 1, wherein the topically active compound is PVP. 15. The emulsion according to claim 1, which is stable at a temperature of 25 ° C. after 2 weeks. 16. The emulsion according to claim 15, which is stable after 30 days. 17. The emulsion according to any one of claims 1 to 16, wherein the natural rubber stabilizing polymer is locust bean gum or guar gum.