WO1996018383A1 - Stable water-in-synthetic hydrocarbon fluid emulsions - Google Patents
Stable water-in-synthetic hydrocarbon fluid emulsions Download PDFInfo
- Publication number
- WO1996018383A1 WO1996018383A1 PCT/US1994/014417 US9414417W WO9618383A1 WO 1996018383 A1 WO1996018383 A1 WO 1996018383A1 US 9414417 W US9414417 W US 9414417W WO 9618383 A1 WO9618383 A1 WO 9618383A1
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- WO
- WIPO (PCT)
- Prior art keywords
- composition
- hlb value
- fluid
- ionic emulsifier
- weight percent
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 42
- 239000012530 fluid Substances 0.000 title claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 title description 2
- 229930195733 hydrocarbon Natural products 0.000 title description 2
- 150000002430 hydrocarbons Chemical class 0.000 title description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 20
- -1 fatty acid diester Chemical class 0.000 claims abstract description 11
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims abstract description 7
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 6
- 239000008158 vegetable oil Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 29
- 239000003995 emulsifying agent Substances 0.000 claims description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 239000007762 w/o emulsion Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000600 sorbitol Substances 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- KJYGRYJZFWOECQ-UHFFFAOYSA-N [2-hydroxy-3-[2-hydroxy-3-[2-hydroxy-3-(16-methylheptadecanoyloxy)propoxy]propoxy]propyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)COCC(O)COC(=O)CCCCCCCCCCCCCCC(C)C KJYGRYJZFWOECQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004909 Moisturizer Substances 0.000 claims description 3
- 229930003427 Vitamin E Natural products 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001333 moisturizer Effects 0.000 claims description 3
- 229930003231 vitamin Natural products 0.000 claims description 3
- 235000013343 vitamin Nutrition 0.000 claims description 3
- 239000011782 vitamin Substances 0.000 claims description 3
- 229940088594 vitamin Drugs 0.000 claims description 3
- 229940046009 vitamin E Drugs 0.000 claims description 3
- 235000019165 vitamin E Nutrition 0.000 claims description 3
- 239000011709 vitamin E Substances 0.000 claims description 3
- 230000001166 anti-perspirative effect Effects 0.000 claims description 2
- 239000003213 antiperspirant Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 239000002781 deodorant agent Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 239000000077 insect repellent Substances 0.000 claims description 2
- 230000000475 sunscreen effect Effects 0.000 claims description 2
- 239000000516 sunscreening agent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 9
- 239000004615 ingredient Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000003974 emollient agent Substances 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- PMRDEUXZGUOOLS-UHFFFAOYSA-N 2,3-dihydroxypropyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO.CCCCCCCCCCCCCCCC(=O)OCC(O)CO PMRDEUXZGUOOLS-UHFFFAOYSA-N 0.000 description 1
- JKXYOQDLERSFPT-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO JKXYOQDLERSFPT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 229940125715 antihistaminic agent Drugs 0.000 description 1
- 239000000739 antihistaminic agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008278 cosmetic cream Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000008250 pharmaceutical cream Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
Definitions
- This invention relates generally to water-in-oil type emulsions and more particularly to stable, high water content, water-in-oil type emulsions having alpha-olefin oligomer fluids such as polydecene fluids as the continuous phase, which can be formed at ambient temperatures.
- Alpha-olefin oligomer fluids often referred to in the art as "polyalphaolefins", have been used to replace mineral oils in a number of applications including personal care products such as lotions and creams.
- Cosmetic products containing polyalphaolefin fluids are described, for example, in published Japanese patent applications SHO (1977) - 72832 and SHO (1978) - 27772.
- High water content water-in-oil emulsions are desirable from the standpoint of cost, less oily feel, and an enhanced cooling effect ("freshness") due to evaporation of the larger amount of water.
- a problem associated with high water content, water-in-oil emulsions made from alpha- olefin oligomer fluids, such as the commercially available polydecenes, is emulsion stability, especially when the products are subjected to several freeze-thaw cycles.
- Freeze-thaw stable, long shelf life water-in-oil emulsions using alpha-olefin oligomer fluids have now been provided by using certain combinations of non-ionic emulsifiers.
- the emulsions can be formed at ambient temperatures, which saves energy.
- a freeze-thaw stable water-in-oil emulsion composition comprising:
- non-ionic emulsifier system consisting essentially of a polyglyceryl fatty acid diester type non- ionic emulsifier having a HLB value of less than about 5, a non-ionic emulsifier having a HLB value of from about 8 to
- Polyalphaolefin fluids are hydrogenated, branched chain liquids which are prepared by oligomerizing alpha- olefins which have from about 6 to 20 and, preferably, 8 to 14 carbon atoms.
- Preferred polyalphaolefins for use in the emulsion compositions of the invention have kinematic vis ⁇ cosities at 100°C of from about 2 to 20 cSt and especially preferred are polydecenes having viscosities of from about
- the fluids constitute the external or continuous phase and in cosmetic applications act as an emollient.
- the fluids are, preferably, present in amounts of from about 5 to 40 and, more preferably, from about 9 to 25 weight percent of the emulsion compositions.
- the water is preferably present in the range of from about 50 to 85 weight percent of the emulsion compositions and more preferably from about 65 to 75 weight percent.
- the non-ionic emulsifier system includes a poly- glyceryl fatty acid diester type non-ionic emulsifier which has a HLB value of less than about 5.0 and preferably from about 4.0 to 4.9.
- Non-limiting examples include tri- glyceryl dioleate, diglyceryl dipalmitate and the like.
- Preferred are branched alkyl chain esters such as triglyceryldiisostearate.
- the emulsifier system also includes a non-ionic emulsifier which has a HLB value of from about 8 to 10.
- Preferred are polyoxyethylene sorbitan esters of fatty acids such as PEG (40) sorbitol septaoleate.
- the system can also include an ethoxylated vegetable oil type non-ionic emulsifier which has a HLB value of less than about 5 and preferably from about 4.0 to
- the amounts of the emulsifier components are chosen to provide a combined HLB value of from about 5 to 7 depending upon the emulsifier system used and, preferably in a two-component system, about 5.9 for polydecenes, which value has been found to provide freeze-thaw and storage stable polydecene containing water-in-oil emulsions.
- the combined HLB value is a straight line relationship which can be readily calculated by multiplying the proportion of each emulsifier in the system by its HLB value and adding up the resulting values, as is known in the art.
- emulsifiers having HLB values above 10 will provide the required HLB value for the system, They do not provide stable emulsions.
- the use of a vegetable oil type emulsifier in a two component emulsifier system does not provide a stable emulsion.
- the total amount of emulsifiers in the emulsion compositions will range from about 2 to 10 weight percent and, preferably, from about 4 to 7 weight percent.
- the emulsions also contain from about 0.1 to 0.5 weight percent an emulsion stabilizer.
- Non-limiting examples of such inorganic salts include alkali metal salts, alkaline earth metal salts and aluminum salts of inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid.
- Preferred inorganic salts include potassium sulfate, magnesium sulfate, potassium chloride, magnesium chloride and aluminum chloride.
- Other types of stabilizers, such as fatty acid salts could be used.
- the emulsions can be used in a variety of applications such as drilling fluids and health care products such as pharmaceutical and cosmetic creams and lotions.
- the health care product emulsions will include one or more appropriate ingredients selected from emollients, preservatives, humectants, fragrances, thickeners, moisturizers, antifoam agents, opacifiers, colorants, covering agents, and active agents such as pharmaceuticals (antibiotics, antiseptics, antifungals, antihistamines, analgesics, etc.) vitamins, sunscreens, insect repellents, deodorants, antiperspirants, cleaning agents, moisturizers, and the like. Normally the total amount of these additive ingredients will not exceed about 10 wt. percent of the total emulsion composition.
- the emulsions can be made by mechanical mixing techniques as known in the art at ambient temperatures, e.g. about 20 to 30°C.
- a stable water-in-oil emulsion is prepared at room temperature using the following ingredients:
- the emulsifier system has a HLB value of about 6.4.
- the emulsion is prepared by adding Part B to Part A with mixing at 25-30°C until a uniform mixture is obtained (about 1 hour) .
- Part C is then added with mixing to provide a lotion.
- the emulsion is stable through three freeze-thaw cycles and oven aging of 45°C for over one month.
- the vitamin E helps to provide a stable emulsion.
- a stable water-in-oil emulsion is prepared at room temperature using the following formulation.
- the emulsifier system (6.9 weight percent surfactants) has a HLB of about 5.9.
- the emulsion is prepared by adding Part B to Part A with mixing at room temperature (25 to 30°C) until a uniform mixture is obtained. The mixture is then homogenized for three minutes. The water-in-oil emulsion is stable through three freeze thaw cycles and oven aging for one month.
- a stable water-in-oil emulsion is prepared at room temperature using the following formulation:
- Stable water-in-oil emulsions are formed using the same ingredients and process as in Example 2 except that 3.8 parts of triglyceryl-3-diisostearate, 1.2 part of OE (40)-sorbitol septaoleate and 23.5 parts of polydecene (5.0 weight percent surfactants) are used.
- Stable water-in-oil emulsions are formed using the same ingredients and process as in Example 2 except that 3.0 parts of triglyceryl-3-diisostearate, 1.0 part of POE (40)-sorbitol septaoleate, and 24.5 parts polydecene (4.0 weight percent surfactants) are used.
- a water-in-oil emulsion is prepared using the formulation as in Example 2, except that 5.2 parts of triglyceryl-3-diisostearate is replaced by 5.2 parts of PEG-7 hydrogenated castor oil. The resulting emulsion is not stable.
- a water-in-oil emulsion is prepared as in Example 2 except that the emulsifier system (6.9 weight percent surfactants HLB 5.9) is 6.1 parts of Span 60 sorbitan mono- ester or stearic acid (HLB 4.7) and 0.8 parts of Tween 60 POE derivative of sorbitan mono-ester of stearic acid (HLB 14.9).
- HLB 5.9 weight percent surfactants
- HLB 5.9 weight percent surfactants HLB 5.9 is 6.1 parts of Span 60 sorbitan mono- ester or stearic acid (HLB 4.7) and 0.8 parts of Tween 60 POE derivative of sorbitan mono-ester of stearic acid (HLB 14.9).
- the emulsion is not stable.
- a water-in-oil emulsion is prepared as in Example
- emulsifier system (6.9 weight percent surfactants HLB 5.9) is 5.98 parts of Brij 72 stearyl alcohol ethoxylate (HLB 4.9) and 0.92 part of Brig 76 stearyl alcohol ethoxylate (HLB 12.4).
- HLB 4.9 Brij 72 stearyl alcohol ethoxylate
- HLB 12.4 0.92 part of Brig 76 stearyl alcohol ethoxylate
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
Abstract
Freeze-thaw stable water-in-oil emulsions include: an external phase comprising a polyalphaolefin fluid; an internal aqueous phase which contains a polyglyveryl fatty acid diester type non-ionic emulsifier having a HLB value of less than about 5, a non-ionic emulsifier having a HLB value of above about 8 and, optionally, an ethoxylated vegetable oil type non-ionic emulsifier having a HLB value of less than about 5, and an emulsion stabilizer.
Description
STABLE WATER-IN-SYNTHETIC HYDROCARBON FLUID EMULSIONS
This invention relates generally to water-in-oil type emulsions and more particularly to stable, high water content, water-in-oil type emulsions having alpha-olefin oligomer fluids such as polydecene fluids as the continuous phase, which can be formed at ambient temperatures.
Alpha-olefin oligomer fluids, often referred to in the art as "polyalphaolefins", have been used to replace mineral oils in a number of applications including personal care products such as lotions and creams. Cosmetic products containing polyalphaolefin fluids are described, for example, in published Japanese patent applications SHO (1977) - 72832 and SHO (1978) - 27772.
High water content water-in-oil emulsions are desirable from the standpoint of cost, less oily feel, and an enhanced cooling effect ("freshness") due to evaporation of the larger amount of water. A problem associated with high water content, water-in-oil emulsions made from alpha- olefin oligomer fluids, such as the commercially available polydecenes, is emulsion stability, especially when the products are subjected to several freeze-thaw cycles.
Freeze-thaw stable, long shelf life water-in-oil emulsions using alpha-olefin oligomer fluids have now been provided by using certain combinations of non-ionic emulsifiers. The emulsions can be formed at ambient temperatures, which saves energy.
- l -
In accordance with this invention there is provided a freeze-thaw stable water-in-oil emulsion composition comprising:
an external phase comprising a polyalphaolefin fluid;
an internal aqueous phase;
a non-ionic emulsifier system consisting essentially of a polyglyceryl fatty acid diester type non- ionic emulsifier having a HLB value of less than about 5, a non-ionic emulsifier having a HLB value of from about 8 to
10 and, optionally, an ethoxylated vegetable oil non-ionic emulsifier having a HLB value of less than about 5; and
an emulsion stabilizer.
Polyalphaolefin fluids are hydrogenated, branched chain liquids which are prepared by oligomerizing alpha- olefins which have from about 6 to 20 and, preferably, 8 to 14 carbon atoms. Preferred polyalphaolefins for use in the emulsion compositions of the invention have kinematic vis¬ cosities at 100°C of from about 2 to 20 cSt and especially preferred are polydecenes having viscosities of from about
2 to 12 cSt. These fluids constitute the external or continuous phase and in cosmetic applications act as an emollient. The fluids are, preferably, present in amounts of from about 5 to 40 and, more preferably, from about 9 to 25 weight percent of the emulsion compositions. The water is preferably present in the range of from about 50 to 85
weight percent of the emulsion compositions and more preferably from about 65 to 75 weight percent.
The non-ionic emulsifier system includes a poly- glyceryl fatty acid diester type non-ionic emulsifier which has a HLB value of less than about 5.0 and preferably from about 4.0 to 4.9. Non-limiting examples include tri- glyceryl dioleate, diglyceryl dipalmitate and the like. Preferred are branched alkyl chain esters such as triglyceryldiisostearate. The emulsifier system also includes a non-ionic emulsifier which has a HLB value of from about 8 to 10. Preferred are polyoxyethylene sorbitan esters of fatty acids such as PEG (40) sorbitol septaoleate. The system can also include an ethoxylated vegetable oil type non-ionic emulsifier which has a HLB value of less than about 5 and preferably from about 4.0 to
4.9 such as PEG-7 hydrogenated castor oil.
The amounts of the emulsifier components are chosen to provide a combined HLB value of from about 5 to 7 depending upon the emulsifier system used and, preferably in a two-component system, about 5.9 for polydecenes, which value has been found to provide freeze-thaw and storage stable polydecene containing water-in-oil emulsions. The combined HLB value is a straight line relationship which can be readily calculated by multiplying the proportion of each emulsifier in the system by its HLB value and adding up the resulting values, as is known in the art. Although emulsifiers having HLB values above 10 will provide the required HLB value for the system, They do not provide stable emulsions. Likewise, the use of a vegetable oil
type emulsifier in a two component emulsifier system does not provide a stable emulsion. In general, the total amount of emulsifiers in the emulsion compositions will range from about 2 to 10 weight percent and, preferably, from about 4 to 7 weight percent.
The emulsions also contain from about 0.1 to 0.5 weight percent an emulsion stabilizer. Preferred are inorganic acid salts. Non-limiting examples of such inorganic salts include alkali metal salts, alkaline earth metal salts and aluminum salts of inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid. Preferred inorganic salts include potassium sulfate, magnesium sulfate, potassium chloride, magnesium chloride and aluminum chloride. Other types of stabilizers, such as fatty acid salts could be used.
The emulsions can be used in a variety of applications such as drilling fluids and health care products such as pharmaceutical and cosmetic creams and lotions. The health care product emulsions will include one or more appropriate ingredients selected from emollients, preservatives, humectants, fragrances, thickeners, moisturizers, antifoam agents, opacifiers, colorants, covering agents, and active agents such as pharmaceuticals (antibiotics, antiseptics, antifungals, antihistamines, analgesics, etc.) vitamins, sunscreens, insect repellents, deodorants, antiperspirants, cleaning agents, moisturizers, and the like. Normally the total amount of these additive ingredients will not exceed about 10 wt. percent of the total emulsion composition.
The emulsions can be made by mechanical mixing techniques as known in the art at ambient temperatures, e.g. about 20 to 30°C.
The invention is further illustrated by, but is not intended to be limited to, the following examples wherein parts are parts-by-weight unless otherwise indicated.
Example 1
A stable water-in-oil emulsion is prepared at room temperature using the following ingredients:
Ingredient Function Amount
Part A
PEG-7 Hydrogenated Castor Oil Emulsifier 1.7
(HLB 4.7) Triglyceryl-3-Diisostearate ) Emulsifier 2.7
(HLB 4.7 POE (40)-Sorbitol Septaoleate Emulsifier 2.5
(HLB 9.5) Vitamin E Vitamin 5.0 Polydecene (4 cSt at 100°C) Emollient 16.6
Part B Glycerin Humectant 3.0
Magnesium Sulfate Stabilizer 0.3 Water Diluent 67.2
- D -
Part C
Propylene Glycol & Diazolidinyl Preservative 1.0 Urea & Methylparaben & Polyparaben
The emulsifier system has a HLB value of about 6.4. The emulsion is prepared by adding Part B to Part A with mixing at 25-30°C until a uniform mixture is obtained (about 1 hour) . Part C is then added with mixing to provide a lotion. The emulsion is stable through three freeze-thaw cycles and oven aging of 45°C for over one month. The vitamin E helps to provide a stable emulsion.
Example 2
A stable water-in-oil emulsion is prepared at room temperature using the following formulation.
Inσredient Function Amount
Part A
Triglyceryl-3-Diisostearate Emulsifier 5.2 POE (40) - Sorbitol Septaoleate Emulsifier 1.7 Polydecene (4 cSt at 100βC) Emollient 21.6
Part B Glycerin Humectant 3.0
Magnesium Sulfate Stabilizer 0.3 Water Diluent 68.2
The emulsifier system (6.9 weight percent surfactants) has a HLB of about 5.9. The emulsion is prepared by adding Part B to Part A with mixing at room temperature (25 to 30°C) until a uniform mixture is obtained. The mixture is then homogenized for three minutes. The water-in-oil emulsion is stable through three freeze thaw cycles and oven aging for one month.
Example 3
A stable water-in-oil emulsion is prepared at room temperature using the following formulation:
Ingredient Amount
Part A
PEG-7 hydrogenated Castor oil 1.95
Triglyceryl diisostearate 3.25 POE (40)-sorbitol septaoleate 1.7
Polydecene (2 cSt at 100°C) 21.6
Part B
Glycerin 3.0
MgS04 0.3 Water 68.2
Example 4
Stable water-in-oil emulsions are formed using the same ingredients and process as in Example 2 except that 3.8 parts of triglyceryl-3-diisostearate, 1.2 part of
OE (40)-sorbitol septaoleate and 23.5 parts of polydecene (5.0 weight percent surfactants) are used.
Example 5
Stable water-in-oil emulsions are formed using the same ingredients and process as in Example 2 except that 3.0 parts of triglyceryl-3-diisostearate, 1.0 part of POE (40)-sorbitol septaoleate, and 24.5 parts polydecene (4.0 weight percent surfactants) are used.
The advantages of the above emulsions include:
(1) Stability - these emulsions are stable after three freeze-thaw cycles and oven aging at 45°C for over one month.
(2) Silky Feel - the polydecene-containing lotion gives silkier, less greasy feel than mineral oil- containing ones.
(3) Energy Saving - Since these emulsions were prepared at room temperature it saves energy to prepare them.
(4) Low Cost - These emulsions can employ a large internal aqueous phase and still be freeze-thaw stable.
Comparison 1
A water-in-oil emulsion is prepared using the formulation as in Example 2, except that 5.2 parts of triglyceryl-3-diisostearate is replaced by 5.2 parts of PEG-7 hydrogenated castor oil. The resulting emulsion is not stable.
Comparison 2
A water-in-oil emulsion is prepared as in Example 2 except that the emulsifier system (6.9 weight percent surfactants HLB 5.9) is 6.1 parts of Span 60 sorbitan mono- ester or stearic acid (HLB 4.7) and 0.8 parts of Tween 60 POE derivative of sorbitan mono-ester of stearic acid (HLB 14.9). The emulsion is not stable.
Comparison 3
A water-in-oil emulsion is prepared as in Example
2 except that emulsifier system (6.9 weight percent surfactants HLB 5.9) is 5.98 parts of Brij 72 stearyl alcohol ethoxylate (HLB 4.9) and 0.92 part of Brig 76 stearyl alcohol ethoxylate (HLB 12.4). The emulsion is not stable.
Claims
1. A freeze-thaw stable water-in-oil emulsion composition comprising:
an external phase comprising a polyalphaolefin fluid;
an internal aqueous phase;
a non-ionic emulsifier system consisting essentially of a polyglyceryl fatty acid diester type non- ionic emulsifier having a HLB value of less than about 5, a non-ionic emulsifier having a HLB value of from about 8 to
10 and, optionally, an ethoxylated vegetable oil type non- ionic emulsifier having a HLB value of less than about 5; and
an emulsion stabilizer.
2. The composition of claim 1 wherein said poly-alphaolefin fluid is derived from an α-olefin monomer having from 8 to 14 carbon atoms and has a kinematic viscosity of from about 2 to 12 cSt at 100°.
3. The composition of claim 2 wherein said poly- alphaolefin fluid is polydecene.
. The composition of claim 3 wherein said emulsifier system has a HLB value of from about 5 to 7, and said emulsion stabilizer is magnesium sulfate.
5. The composition of claim 1 which includes at least one agent selected from the group consisting of fragrances, pharmaceutical compounds, sunscreens, insect repellents, vitamins, antiperspirants, cleaning agents, moisturizers, and deodorants.
6. The composition of claim 1 wherein said emulsifier system consists essentially of a polyglyceryl fatty acid diester type non-ionic emulsifier having a HLB value less than about 5 and a non-ionic emulsifier having a HBL of from about 8 to 10.
7. The composition of claim 6 wherein the polyalphaolefin fluid is polydecene and the HLB value of the emulsifier system is about 5.9.
8. The composition of claim 1 wherein the amount of polyalphaolefin fluid is from about 5 to 40 weight percent of the emulsion composition and the amount of water is from about 50 to 85 weight percent of the emulsion composition.
9. The composition of claim 1 which includes said ethoxylated vegetable oil type non-ionic emulsifier.
10. A freeze-thaw stable water-in-oil emulsion composition comprising:
an external phase which comprises a polydecene fluid having a kinetic viscosity of from about 2 to 4 cSt at 100°C, said fluid making up from about 9 to 25 weight percent of said composition; an external aqueous phase the water in said aqueous pahse making up from about 65 to 75 weight percent of said composition;
a non-ionic emulsifier system consisting essentially of triglyceryl diisostearate and POE (40) -
Sorbitol septaoleate in proportions to provide a combined HLB value of about 5.9; and
magnesium sulfate.
11. A freeze-thaw stable water-in-oil emulsion composition comprising:
an external phase which comprises a polydecene fluid having a kinetic viscosity of from about 2 to 4 cSt at 100°C, said fluid making up from about 9 to 25 weight percent of said composition;
an external aqueous phase the water in said aqueous phase making up from about 65 to 75 weight percent of said composition;
a non-ionic emulsifier system consisting essentially of triglyceryl diisostearate, POE (40) - Sorbitol septaoleate, and PEG-7 hydrogenated castor oil in proportions to provide a combined HLB value of about 6.4;
vitamin E; and
magnesium sulfate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US1994/014417 WO1996018383A1 (en) | 1994-12-15 | 1994-12-15 | Stable water-in-synthetic hydrocarbon fluid emulsions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US1994/014417 WO1996018383A1 (en) | 1994-12-15 | 1994-12-15 | Stable water-in-synthetic hydrocarbon fluid emulsions |
Publications (1)
Publication Number | Publication Date |
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WO1996018383A1 true WO1996018383A1 (en) | 1996-06-20 |
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PCT/US1994/014417 WO1996018383A1 (en) | 1994-12-15 | 1994-12-15 | Stable water-in-synthetic hydrocarbon fluid emulsions |
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RU2785396C2 (en) * | 2017-11-15 | 2022-12-07 | Эс.Си.ДЖОНСОН ЭНД САН, ИНК. | Frost-resistant emulsion water-in-oil compositions for purification and/or polishing |
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