CN107007481A - A kind of multiple emulsion compositons and preparation method thereof - Google Patents

A kind of multiple emulsion compositons and preparation method thereof Download PDF

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Publication number
CN107007481A
CN107007481A CN201710251864.4A CN201710251864A CN107007481A CN 107007481 A CN107007481 A CN 107007481A CN 201710251864 A CN201710251864 A CN 201710251864A CN 107007481 A CN107007481 A CN 107007481A
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water
oil
emulsion
compositons
mixed liquor
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CN201710251864.4A
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CN107007481B (en
Inventor
倪向梅
李洪海
苏海波
张云岭
洪奇
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SHANGHAI INOHERB COSMETIC CO Ltd
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SHANGHAI INOHERB COSMETIC CO Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/066Multiple emulsions, e.g. water-in-oil-in-water
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20Halogens; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/23Sulfur; Selenium; Tellurium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31Hydrocarbons
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4993Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48Thickener, Thickening system

Abstract

The present invention provides a kind of multiple emulsion compositons, wherein, the micella that oil-in-water emulsifiers the first grease of parcel is mutually formed is dispersed in aqueous phase as interior phase, and the interior micella mutually formed of water-in-oil emulsifier parcel is dispersed in the second grease phase.Present invention also offers the preparation method of the emulsion, including:The mixed liquor of first grease phase and oil-water emulsifiers is added into aqueous phase, oil-in-water emulsion is prepared, emulsion oil-in-water is added in the mixed liquor containing water-in-oil emulsifier and the second grease phase as interior, stirs, obtains multiple emulsion compositons.The multiple emulsion compositons that the present invention is provided, the emulsification particle diameter of the first grease phase is smaller, the height temperature stability with more wide temperature range, can meet and use and transport under various circumstances.The greasy feeling of traditional water-in-oil emulsion is avoided in addition and with Consumer's Experience more preferably clearly sense, water moisture feeling and moisture feeling, there is broader practice prospect in household chemicals field.

Description

A kind of multiple emulsion compositons and preparation method thereof
Technical field
The invention belongs to cosmetic technical field, it is related to a kind of emulsion compositions and preparation method thereof, more particularly to it is a kind of Multiple emulsion compositons and preparation method thereof.
Background technology
With the continuous improvement of people's living standards, consumer is for beauty, the requirement more and more higher of skin-protection product, no longer Meet daily basic skin care demand, it is often more important that pursue good experience sense while skin care demand is met.At present, city The brand and species of skin-care cosmetics are various on field, are analyzed from formula composition, generally with oil-in-water type and water-in-oil type Skin care item it is in the majority.
Water-in-oil type skin care item are made up of aqueous phase, oil phase and water-in-oil emulsifier, and the form of system is with small by water The form of drop is scattered in oil, and oil phase is foreign minister or decentralized medium, is relatively moistened when using, but is often also compared greasy and general It is glossy, it is generally suitable for dry skin or autumn and winter uses.It is strong, easily general in order to overcome water-in-oil type skin care item to stick soapy feeling Glossy defect, many cosmetics companies all develop oil-in-water type skin care item in succession, and oil-in-water type skin care item are grease type things Matter is scattered in the Heterodisperse system formed in aqueous phase with fine droplet state, and oil phase is wrapped in the aqueous phase of outside, kept away Exempt from the greasy feeling of water-in-oil type skin care item, and be more presented as water moisture feeling, therefore liked by consumers in general, so Creams class cosmetics still account for dominant contribution with oil-in-water type in the market.
Such as Application No.:201510018080.8, invention and created name:Cosmetic composition, passes through polymer film-forming agent Combination with silica can produce equably the cosmetics of covering wrinkle immediately there is provided a kind of on skin.Preparation method For:Aqueous and oily matter is well mixed at different temperatures respectively, then added oil phase in aqueous phase, most backward aqueous phase and Film forming agent is added in the mixed liquor of oil phase, cosmetic composition is obtained.
Although oil-in-water type skin care item salubrious water profit relatively when in use, there is also moist degree it is not lasting enough the drawbacks of, Some oil-in-water type skin care item are long-acting moist in order to pursue, and often add the more moist lubricant component that degree is high, closure is strong, It has impact on its original water and moisten salubrious use feeling.By taking the oil-in-water skin care product of emulsion-type as an example, it is to be added directly into oil phase In aqueous phase, it is mixed with and forms through emulsification, the particle of oil phase is larger in skin care item.It is additionally, since emulsion and belongs to thermodynamics in itself Unstable state, oil-phase component is intended to polymerization, therefore cosmetics are in transportation, or in shelf life, easily occurs Oil phase polymerize the phenomenon for causing emulsion particle diameter to become big, even the phenomenon of water-oil separating occurs when serious, when particularly skin care item are long Between be placed on hotter or colder area, water-oil separating phenomenon is more obvious, and these defects limit the use scope of skin care item, Also it is unfavorable for the long distance transportation of skin care item.
The content of the invention
The present invention the problem of exist for prior art there is provided a kind of high temperature performance is excellent, that customer experience is good is many Gravity emulsion composition and preparation method thereof.
The first aspect of the invention is to provide a kind of multiple emulsion compositons, and the multiple emulsion compositons include:
Wherein, aqueous phase includes polyalcohol and deionized water, and content of the polyalcohol in the emulsion is
0.5-15wt%, content of the deionized water in the emulsion is >=30.5wt%.
The first micella that the first grease of the oil-in-water emulsifiers parcel is mutually formed, which is dispersed in the aqueous phase, forms water Oil-in emulsion, the second micella of water-in-oil emulsifier parcel emulsion oil-in-water formation is dispersed in the second grease phase In;The disperse polyol is in the first grease phase, and/or the second grease phase and/or aqueous phase.
In a preferred embodiment, the oil-water emulsifiers wrap up the particle diameter for the first micella that the first grease is mutually formed For 3-50 μm, preferably 5-30 μm, such as 8 μm, 15 μm, 20 μm.
In a preferred embodiment, the multiple emulsion compositons can also include thickener, co-stabilizer and other Any one or a few combination in additive.
In a preferred embodiment, the content of the thickener is 0.1-2.0wt%, the content of the co-stabilizer 0.5-3.0wt%, the content of other additives is 0.3-2wt%.
In a preferred embodiment, the multiple emulsion compositons include:
In a preferred embodiment, the water-in-oil emulsifier is any one or a few group in methyl-silicone oil Close, it is preferable that the methyl-silicone oil is selected from following any one or several combinations:Cetyl PEG/PPG-10/1 polydimethylsiloxanes Alkane, KSG-210, PEG-9 dimethyl silicone polymers, PEG-10 polydimethylsiloxanes Alkane, KF-6028, lauryl PEG-9 polydimethylsiloxanes ethyl poly dimethyl silicon Oxygen alkane, lauryl PEG-10 tri- (trimethylsiloxy group) silica ethyl polymethyl siloxane.
In a preferred embodiment, the oil-in-water emulsifiers are hydrophilic non-ionic surfactant, are preferably Selected from polysorbate, hydrogenated castor grease and/or ether, ceteth ester and/or ether, decyl tetradecyl alcohol polyether ester and/or In ether, polyglyceryl fatty acid ester any one or a few combination, more preferably polysorbate -20, polysorbate -60, Polyoxyethylene Sorbitan Monooleate etc., Cremophor RH40, PEG-60 rilanit specials, PPG-4- ceteths -20, PPG-8 whales Ceryl alcohol polyethers -20, PPG-6- decyl tetradecyl alcohols polyethers -12, PPG-6- decyl tetradecyl alcohols polyethers -20, PPG-6- decyl tetradecyl alcohols Polyethers -30, Natrulon H-10 stearate, Natrulon H-10 palmitate, Natrulon H-10 myristinate, Natrulon H-10 bay Any one or a few combination in acid esters, wherein PEG is polyethylene glycol, and PPG is polypropylene glycol.
In a preferred embodiment, the first described grease and/or the second grease are selected from fatty alcohol, aliphatic acid, glycerine Any one or a few combination in ester, siloxanes, alkane and ester, preferably comprises following at least one compound or a variety of Combination:Caprylic/capric triglyceride, dimethyl silicone polymer, ring five dimethyl silicone polymer, diphenyl polydimethylsiloxanes Alkane, phenyl polymethyl siloxane, saualane, glycerine three (thylhexoic acid) ester, the heptanoate of neopentyl glycol two, but be not limited only to above-mentioned In the grease classification referred to, the conventional other kinds grease of cosmetic formulations and silicone oil are all contained in.
In a preferred embodiment, described polyalcohol be polyethylene glycol, it is propane diols, glycerine, 1,3-BDO, double sweet One or more kinds of combinations of oil, dipropyl glycol, trimethylolpropane, xylitol, sorbierite, maltitol.
In a preferred embodiment, described co-stabilizer is inorganic salts, makes an addition to interior aqueous phase, selected from following any One or more combination:Calcium chloride, sodium chloride, potassium chloride, magnesium chloride, magnesium sulfate.
In a preferred embodiment, the thickener is gum arabic, carrageenan, duckweed mother-in-law glue, twelve month yam glue, thorn It is locust bean gum, methylcellulose, hydroxypropyl methyl cellulose, sodium cellulose glycolate, hydroxyethyl cellulose, polyacrylamide, poly- It is vinyl alcohol, pectic acid sodium, Sodium L-arginate, ethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyethylene glycol oxide, poly- Any one or a few combination in acrylic acid, Sodium Polyacrylate etc..
In a preferred embodiment, other described additives is in preservative, chelating agent, aromatic, antioxidants etc. Any one or a few combination, it is preferable that according to formula actual conditions can also add antiallergic releive, whitening, it is anti-ageing, protect Wet, anti-acne the effects such as property composition.
The second aspect of the invention is to provide a kind of preparation method of multiple emulsion compositons, comprised the following steps:
Emulsion oil-in-water is prepared, it is standby;
1.0-5.0wt% water-in-oil emulsifiers, 2.0-20.0wt% the second grease phases are mixed, mixed dissolution completely, is obtained To the 3rd mixed liquor;
The emulsion oil-in-water prepared is added in the 3rd mixed liquor, stirs, prepares institute The multiple emulsion compositons stated.
Wherein, the preparation method of the emulsion oil-in-water comprises the following steps:
Step 1, mix under the conditions of 60-80 DEG C 0.2-2.0wt% oil-in-water emulsifiers, 0.5-10wt% polyalcohols, 0-1.0%wt% water is cooled to normal temperature to uniform, obtains the first mixed liquor, standby;
Step 2, by the greases of 1-15wt% first mutually be slowly added to dropwise in the first mixed liquor prepared by step 1, stirring extremely Emulsification is complete, obtains the second mixed liquor;
Step 3, the second mixed liquor that step 2 is obtained is slowly added in 30-96wt% deionized water, stirs, obtain Emulsion oil-in-water.
Wherein described first grease phase and/or the second grease are mutually selected from fatty alcohol, aliphatic acid, glyceride, siloxanes, alkane With any one or a few combination in ester, following at least one compound or multiple combinations are preferably comprised:Caprylic/capric The poly- methyl silicon of triglycerides, dimethyl silicone polymer, ring five dimethyl silicone polymer, diphenyl dimethicone, phenyl Oxygen alkane, saualane, glycerine three (thylhexoic acid) ester, the heptanoate of neopentyl glycol two, but it is not limited only to the above-mentioned grease classification referred to, In the conventional other kinds grease of cosmetic formulations and silicone oil are all contained in.
In a preferred embodiment, the preparation method comprises the following steps:
Emulsion oil-in-water is prepared, it is standby;
1.0-5.0wt% water-in-oil emulsifiers, 2.0-20.0wt% the second grease phases are mixed, mixed dissolution completely, is obtained To the 3rd mixed liquor;
The emulsion oil-in-water prepared is added in the 3rd mixed liquor, stirs, prepares institute The multiple emulsion compositons stated.
Wherein, the preparation method of the emulsion oil-in-water comprises the following steps:
Step 1, mix under the conditions of 60-80 DEG C 0.2-2.0wt% oil-in-water emulsifiers, 0.5-10wt% polyalcohols, 0-1.0%wt% water is cooled to normal temperature to uniform, obtains the first mixed liquor, standby;
Step 2, by the greases of 1-15wt% first mutually be slowly added to dropwise in the first mixed liquor prepared by step 1, stirring extremely Emulsification is complete, obtains the second mixed liquor;
Step 3, by 1.0-2.0wt% co-stabilizers, 0.2-1.0wt% thickeners and 0.5-1.0wt% other additives Add in 40-90wt% deionized waters, stirring mixed dissolution is uniform, obtains the 4th mixed liquor.
Step 4, the second mixed liquor for preparing step 2 are added in the 4th mixed liquor prepared by step 3, and stirring obtains water Oil-in emulsion.
The third aspect of the invention be to provide the cosmetics that a kind of foregoing emulsion is coated on skin surface and/ Or the application in skin care item.
Wherein, the emulsion includes:
Wherein, aqueous phase includes polyalcohol and deionized water, and content of the polyalcohol in the emulsion is 0.5- 15wt%, content of the deionized water in the emulsion is >=30.5wt%.
The first micella that the first grease of the oil-in-water emulsifiers parcel is mutually formed, which is dispersed in the aqueous phase, forms water Oil-in emulsion, the second micella of water-in-oil emulsifier parcel emulsion oil-in-water formation is dispersed in the second grease phase In;The disperse polyol is in the first grease phase, and/or the second grease phase and/or aqueous phase.
The fourth aspect of the invention is providing a kind of multiple emulsion compositons included as described in above any Cosmetics and/or skin care item.
The multiple emulsion compositons that the present invention is provided, the emulsification particle diameter of the first grease phase is smaller, and minimum reaches several microns. Multiple emulsion compositons have the height temperature stability of more wide temperature range, after being tested within the temperature range of -15 DEG C -49 DEG C, Do not occur it is serious be layered, the wild effect such as coarse, water outlet, fully meet and used under varying environment and high/low temperature is transported Condition.Avoid in addition traditional water-in-oil emulsion greasy feeling and with Consumer's Experience more preferably clearly sense, water moisture feeling and moisten Sense, has broader practice prospect in household chemicals field.
Brief description of the drawings
The microphotograph for the multiple emulsion compositons that Fig. 1 provides for the present invention;
Fig. 2 is the partial enlarged drawing of black wire part in Fig. 1;
Fig. 3 is the microphotograph of water-in-oil emulsion prepared by prior art;
Fig. 4 is multiple emulsion photo of the constant temperature after 3 months at different temperatures prepared by embodiment five;
The photo that Fig. 5 is the water-in-oil emulsion for preparing of comparative example one after -15 DEG C of constant temperature 3 months.
Embodiment
Clear, complete description is carried out to technical scheme below in conjunction with specific embodiment.It is as described below to be The different modes case of the object of the invention, effect and technical characteristic is embodied, is not intended to limit the scope of the present invention.
Embodiment one is to embodiment ten
Oil-in-water emulsifiers, polyalcohol, a small amount of first deionized water are added in mass ratio into emulsification pot first, After being well mixed under the conditions of 60-80 DEG C, normal temperature is cooled to, the first mixed liquor is obtained.Persistently stirred with 400-600rpm rotating speed First mixed liquor, and it is slowly added to the first grease phase dropwise thereto, stirring is complete to emulsifying, and obtains the second mixed liquor, standby.
Co-stabilizer, thickener, waterborne-type preservation, chelating agent and antioxidant are sequentially added second in mass ratio In ionized water, stirred under the conditions of 60-80 DEG C with 100-500rpm rotating speeds to being completely dissolved, obtain the 4th mixed liquor, wherein, increase Thick dose, preservative, chelating agent and antioxidant are conventional commercial product, not as claimed object, as long as Meet Functional Requirement.The 4th mixed liquor is persistently stirred with 100-500rpm rotating speeds under the conditions of 60-80 DEG C, and thereto The second mixed liquor is slowly added to, emulsion oil-in-water is obtained, normal temperature is cooled to standby.
Water-in-oil emulsifier, oil-solvent preservative, the second grease phase and essence are mixed, at normal temperatures with 100-500rpm Rotating speed stirring and dissolving completely, obtains the 3rd mixed liquor;Emulsion oil-in-water obtained above is slowly added in the 3rd mixed liquor, Stir, prepare milky multiple emulsion compositons.Wherein, each component content of the multiple emulsion compositons is prepared As shown in table 1, table 2.
Wherein, first, second in the first deionized water, the second deionized water be according to deionized water order of addition not It is distinguish between, the species without referring to deionized water together, the first deionized water, the second deionized water are deionized water.
The content of table 1, each component into embodiment five of embodiment one
The content of table 2, each component into embodiment ten of embodiment six
The structure of multiple emulsion compositons
The structure of emulsion prepared by embodiment five is observed under the microscope, wherein, microscope parameter is:OL-350II things Mirror, the coaxial high power varifocal mirrors of MX-10C, zoom ratio is 750X, and microscopical resolution ratio is 0.22 μm, microphotograph such as Fig. 1, Shown in Fig. 2, as seen from Figure 1, Figure 2, the multiple emulsion that the present invention is provided is three-phase structure, the company that outside is mutually formed for the second grease Phase oil-in-water emulsion forms the unordered micella bead of multiple long-range orders, short distance, these glue in continuous phase, water-in-oil emulsifier parcel Shu little Qiu is dispersed in the second grease phase.Oil-water emulsifiers wrap up the first grease and mutually form the smaller micella of multiple particle diameters Bead is dispersed in aqueous phase, the oil-in-water structure inside formation, and disperse polyol is in the first grease phase, the second grease phase and aqueous phase In.As shown in Figure 2, in the emulsion that the present invention is provided, the particle diameter of the first grease phase is generally 5-30 μm, from the figure 3, it may be seen that with routinely Indicated in tens microns, such as Fig. 3 85.60 μm and 119.85 of water-in-oil emulsion average grain diameter prepared by emulsifying technology μm, the particle diameter of the little particulate in Fig. 3 is also 30 μm or so, it is seen then that the particle diameter for the multiple emulsion that the present invention is provided is than conventional oil bag The particle diameter of water emulsion is smaller.
Emulsion intercalation method is tested
In order to assess the emulsion intercalation method that the present invention is provided, emulsion prepared by embodiment one to embodiment ten exists respectively A period of time is stood under different temperatures, within the temperature range of -15-49 DEG C, the emulsion that the present invention is provided under different temperatures is determined Stability, emulsion intercalation method prepared by embodiment one to embodiment five, as shown in table 3, embodiment six to embodiment ten are made Standby emulsion intercalation method, as shown in table 4.
Table 3, embodiment one to embodiment five provide emulsion intercalation method
Table 4, embodiment six to embodiment ten provide emulsion intercalation method
As shown in Table 3, the multiple emulsion that embodiment one is prepared to embodiment five, it is permanent in -15 DEG C to 49 DEG C temperature ranges Stability is good in the temperature experimentation of 2 months, can keep more uniform state.After -15 DEG C are kept for 3 months, Viscosity has risen after the multiple emulsion that only prepared by embodiment two and example IV is maintained 2-3 months at -15 DEG C, but not Occur it is serious be layered, the unstable phenomenon such as coarse, water outlet, do not influence the normal of product to use, other keep preferably State.Under 49 DEG C of the condition of high temperature, after constant temperature is kept for 3 months, multiple emulsion prepared by embodiment one to embodiment five Outward appearance is showed well, keeps preferably uniform state.Fig. 4 is that emulsion prepared by embodiment five experienced -15 DEG C to 49 DEG C Appearance stability photo after being maintained 3 months in temperature range, as shown in Figure 4, constant temperature is after 3 months, and each group product appearance is good It is good, maintain preferably uniform state.
As shown in Table 4, the emulsion that embodiment six is prepared to embodiment ten, in the range of -15 DEG C to 49 DEG C, the perseverance of 3 months After warm off-test, there is viscosity after being maintained 3 months at -15 DEG C and risen now in the emulsion that only prepared by embodiment seven and embodiment nine As viscosity is declined slightly after embodiment seven is maintained 3 months at 49 DEG C, and the multilayer emulsion of remaining each group can keep more uniform shape State, is maintained to its fine and smooth glossy stable outward appearance, do not occur it is serious be layered, the unstable phenomenon such as coarse, water outlet.
Comparative example one
First by polyalcohol, deionized water, co-stabilizer be proportionally added into emulsification pot in, under the conditions of 60-80 DEG C with 100-500rpm rotating speeds are mixed, and dissolving is complete, obtains aqueous phase mixed liquor, W/O emulsifying agents, grease and other lipophilies are added Plus agent is mixed to being uniformly dissolved with the stirring of 100-200rpm rotating speeds, obtains oil phase mixed liquor.Under normal temperature condition, oil phase is kept to mix The rotating speed for closing liquid is constant, and the aqueous phase mixed liquor prepared is slowly added into oil phase mixed liquor, water-in-oil emulsion, each group is obtained The content divided is as shown in table 5:
The content of each component in table 5, comparative example one
Emulsion intercalation method test prepared by comparative example one
In order to assess the emulsion intercalation method of the preparation of comparative example one, emulsion prepared by comparative example one exists respectively A period of time is stood under different temperatures, within the temperature range of -15-49 DEG C, the emulsion of comparative example one under different temperatures is determined Stability, as shown in table 6 and Fig. 5.
Emulsion intercalation method prepared by table 6, comparative example one
Emulsion prepared by comparative example one maintains 3 months by stability test at room temperature, but maintains 1- at -15 DEG C Viscosity has rising within 2 months, occurs demulsifying phenomenon during to 3 months, as shown in Figure 5.Maintain 2-3 viscosity occur in individual month at 49 DEG C to slightly have The phenomenon of decline.
Recruitment evaluation
For the use of the multiple emulsion relatively more of the invention provided and prior art, such as emulsion prepared by comparative example one Sensory difference, has randomly choosed embodiment three, embodiment five, embodiment six and embodiment eight, and skin is carried out with comparative example one Feel contrast test.With the entitled object of the average age Fu Gan expert groups of 30 years old 20, the assessment using perceived direction is carried out.Assessment side Method is the corresponding score value of selection corresponding index in 1-15 points, as follows:
By scoring each side, use feeling assessment result is embodied in table 7.
Multiple emulsion prepared by table 7, the present invention is compared with emulsion use feeling prepared by comparative example one
Index classification Embodiment three Embodiment five Embodiment six Embodiment eight Comparative example one
Spreadability 8.2 8.5 8.4 8.6 9.2
Smear salubrious sense 9.2 9.6 9.4 9.2 8.0
Smear water moisture feeling 9.5 9.2 9.6 9.0 8.5
Smooth feeling 11.4 11.6 11.3 11.7 10.3
Use rear moisture feeling 10.7 10.4 10.3 10.5 9.4
As shown in table 7, the oil that the multiple emulsion that the present invention is provided is prepared with comparative example one using prior art Bag aqueous emulsion is compared, and be clearly felt that has skin sense difference when in use in terms of spreadability, water moisture feeling, smooth feeling and moisture feeling. The emulsion of the invention provided is embodied a concentrated expression of compared with water-in-oil emulsion, is easier to sprawl relatively in skin surface, and avoid The greasy feeling of water-in-oil emulsion and with the salubrious sense, water moisture feeling more liked by consumer, and the emulsion that provides of the present invention exists After being smeared on skin, skin is more smooth, also more moistens.
The emulsion that the present invention is provided, than the stability that water-in-oil emulsion has more wide temperature range, fully meets difference Long-term use and high/low temperature traffic condition under environment.Emulsion emulsifiers particle diameter made from the method provided using the present invention is smaller, Emulsion is more uniform and stable, and the presence of multiplet is also observed under the microscope.And during skin surface smearing, The water-in-oil emulsion that the multiple emulsion is compared, feels, the moisture feeling after water moisture feeling and use with preferably salubrious, therefore in day Change field has a good application prospect.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and Modification, all should be contained within the scope of the invention.

Claims (10)

1. a kind of multiple emulsion compositons, it is characterised in that the multiple emulsion compositons include:
Wherein, aqueous phase includes polyalcohol and deionized water, and content of the polyalcohol in the emulsion is 0.5-15wt%, Content of the deionized water in the emulsion is >=30.5wt%;
The first micella that the first grease of the oil-in-water emulsifiers parcel is mutually formed, which is dispersed in the aqueous phase, forms oil-in-water Type emulsion, the second micella of water-in-oil emulsifier parcel emulsion oil-in-water formation is dispersed in the second grease phase;Institute Disperse polyol is stated in the first grease phase, and/or the second grease phase and/or aqueous phase.
2. multiple emulsion compositons according to claim 1, it is characterised in that the oil of oil-water emulsifiers parcel first The particle diameter of first micella of lipid phase formation is 3-50 μm.
3. multiple emulsion compositons according to claim 1, it is characterised in that the multiple emulsion compositons also include increasing Any one or a few combination in thick dose, co-stabilizer and other additives;The content of the thickener is 0.1- 2.0wt%, the content 0.5-3.0wt% of the co-stabilizer, the content of other additives is 0.3-2wt%.
4. the multiple emulsion compositons according to claim any one of 1-3, it is characterised in that the multiple emulsion compositons Including:
5. the multiple emulsion compositons according to claim any one of 1-3, it is characterised in that the water-in-oil emulsifier choosing From any one or a few following combination:Cetyl PEG/PPG-10/1 dimethyl silicone polymers, dimethyl silicone polymer PEG- 10/15 cross-linked polymer, PEG-9 dimethyl silicone polymers, KF6017, PEG-9 polydimethylsiloxanes second Base dimethyl silicone polymer, lauryl KF-6028, lauryl PEG-10 tri- (three Methyl siloxy) silica ethyl polymethyl siloxane.
6. the multiple emulsion compositons according to claim any one of 1-3, it is characterised in that the oil-in-water emulsifiers For hydrophilic non-ionic surfactant, the hydrophilic non-ionic surfactant is selected from polysorbate, rilanit special It is any in ester and/or ether, ceteth ester and/or ether, decyl tetradecyl alcohol polyether ester and/or ether, polyglyceryl fatty acid ester One or more combination.
7. a kind of preparation method of multiple emulsion compositons, it is characterised in that comprise the following steps:
Emulsion oil-in-water is prepared, it is standby;
Mix 1.0-5.0wt% water-in-oil emulsifiers, 2.0-20.0wt% the second grease phases, mixed dissolution completely, obtains the Three mixed liquors;
The emulsion oil-in-water prepared is added in the 3rd mixed liquor, stirred, is prepared described Multiple emulsion compositons;
Wherein, the preparation method of the emulsion oil-in-water comprises the following steps:
Step 1, mixing 0.2-2.0wt% oil-in-water emulsifiers, 0.5-10wt% polyalcohols, 0- under the conditions of 60-80 DEG C 1.0%wt% water is cooled to normal temperature to uniform, obtains the first mixed liquor, standby;
Step 2, by the greases of 1-15wt% first mutually be slowly added to dropwise in the first mixed liquor prepared by step 1, stirring to emulsify Completely, the second mixed liquor is obtained;
Step 3, the second mixed liquor that step 2 is obtained is slowly added in 30-96wt% deionized water, stirs, obtain water bag Water emulsion.
8. the preparation method of multiple emulsion compositons according to claim 7, it is characterised in that comprise the following steps:
Emulsion oil-in-water is prepared, it is standby;
Mix 1.0-5.0wt% water-in-oil emulsifiers, 2.0-20.0wt% the second grease phases, mixed dissolution completely, obtains the Three mixed liquors;
The emulsion oil-in-water prepared is added in the 3rd mixed liquor, stirred, is prepared described Multiple emulsion compositons;
Wherein, the preparation method of the emulsion oil-in-water comprises the following steps:
Step 1, mixing 0.2-2.0wt% oil-in-water emulsifiers, 0.5-10wt% polyalcohols, 0- under the conditions of 60-80 DEG C 1.0%wt% water is cooled to normal temperature to uniform, obtains the first mixed liquor, standby;
Step 2, by the greases of 1-15wt% first mutually be slowly added to dropwise in the first mixed liquor prepared by step 1, stirring to emulsify Completely, the second mixed liquor is obtained;
Step 3,1.0-2.0wt% co-stabilizers, 0.2-1.0wt% thickeners and 0.5-1.0wt% other additives are added In 40-90wt% deionized waters, stirring mixed dissolution is uniform, obtains the 4th mixed liquor.
Step 4, the second mixed liquor for preparing step 2 are added in the 4th mixed liquor prepared by step 3, and stirring obtains oil-in-water Type emulsion.
9. a kind of application of the multiple emulsion compositons as described in claim any one of 1-3, it is characterised in that the multiple emulsion Composition is used for the cosmetics and/or skin care item for being coated in skin surface.
10. a kind of cosmetics and/or skin care item, it is characterised in that the cosmetics and/or skin care item include claim 1-3 Multiple emulsion compositons described in any one.
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CN107684529A (en) * 2017-08-21 2018-02-13 上海相宜本草化妆品股份有限公司 A kind of microemulsified facial mask liquid and preparation method thereof
CN110897918A (en) * 2019-12-25 2020-03-24 广州欧正化妆品技术研究院有限公司 Polyglycerol compound emulsifier and preparation method thereof
CN113730303A (en) * 2021-09-17 2021-12-03 欧诗漫生物股份有限公司 Method for preparing multiple emulsions by using single type emulsifier and ice crystal cream for repairing after-sun
CN113786354A (en) * 2021-10-29 2021-12-14 守正创新生物科技(天津)有限公司 N-terminal modified recombinant human fibronectin-based multiple emulsion and preparation method thereof
CN114015516A (en) * 2021-11-19 2022-02-08 烟台新时代健康产业日化有限公司 Cleaning agent for water-in-oil type substance and preparation and use methods thereof
CN115607462A (en) * 2022-10-12 2023-01-17 上海飞创科贸有限公司 Pre-dispersed calcium ions, pre-dispersion method thereof and application of pre-dispersed calcium ions in depilatory products
CN115737461A (en) * 2022-12-15 2023-03-07 诺斯贝尔化妆品股份有限公司 Ion-rich cream and preparation method thereof
CN116326753A (en) * 2023-04-04 2023-06-27 天津艾尔森生物科技有限公司 Preparation method of essence with multiple emulsion structure
CN117462433A (en) * 2023-12-27 2024-01-30 拉芳家化股份有限公司 Low-temperature-resistant washing-free moisturizing double-layer hair care spray emulsion and preparation method thereof

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CN103040633A (en) * 2013-01-05 2013-04-17 拉芳家化股份有限公司 Oil/water/silicone oil multiphase emulsion and preparation method
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Publication number Priority date Publication date Assignee Title
CN107684529A (en) * 2017-08-21 2018-02-13 上海相宜本草化妆品股份有限公司 A kind of microemulsified facial mask liquid and preparation method thereof
CN110897918A (en) * 2019-12-25 2020-03-24 广州欧正化妆品技术研究院有限公司 Polyglycerol compound emulsifier and preparation method thereof
CN113730303A (en) * 2021-09-17 2021-12-03 欧诗漫生物股份有限公司 Method for preparing multiple emulsions by using single type emulsifier and ice crystal cream for repairing after-sun
CN113730303B (en) * 2021-09-17 2024-04-05 欧诗漫生物股份有限公司 Method for preparing multiple emulsion by using single type emulsifier and repairing ice crystal cream after sun
CN113786354A (en) * 2021-10-29 2021-12-14 守正创新生物科技(天津)有限公司 N-terminal modified recombinant human fibronectin-based multiple emulsion and preparation method thereof
CN113786354B (en) * 2021-10-29 2023-05-12 守正创新生物科技(天津)有限公司 N-terminal modified recombinant human fibronectin-based multiple emulsion and preparation method thereof
CN114015516B (en) * 2021-11-19 2024-02-23 烟台新时代健康产业日化有限公司 Cleaning agent for water-in-oil substance and preparation and use methods thereof
CN114015516A (en) * 2021-11-19 2022-02-08 烟台新时代健康产业日化有限公司 Cleaning agent for water-in-oil type substance and preparation and use methods thereof
CN115607462A (en) * 2022-10-12 2023-01-17 上海飞创科贸有限公司 Pre-dispersed calcium ions, pre-dispersion method thereof and application of pre-dispersed calcium ions in depilatory products
CN115737461A (en) * 2022-12-15 2023-03-07 诺斯贝尔化妆品股份有限公司 Ion-rich cream and preparation method thereof
CN116326753B (en) * 2023-04-04 2023-11-14 天津艾尔森生物科技有限公司 Preparation method of essence with multiple emulsion structure
CN116326753A (en) * 2023-04-04 2023-06-27 天津艾尔森生物科技有限公司 Preparation method of essence with multiple emulsion structure
CN117462433A (en) * 2023-12-27 2024-01-30 拉芳家化股份有限公司 Low-temperature-resistant washing-free moisturizing double-layer hair care spray emulsion and preparation method thereof
CN117462433B (en) * 2023-12-27 2024-04-12 拉芳家化股份有限公司 Low-temperature-resistant washing-free moisturizing double-layer hair care spray emulsion and preparation method thereof

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