WO1997000667A1 - Stable hydroalcoholic compositions - Google Patents
Stable hydroalcoholic compositions Download PDFInfo
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- WO1997000667A1 WO1997000667A1 PCT/US1996/008924 US9608924W WO9700667A1 WO 1997000667 A1 WO1997000667 A1 WO 1997000667A1 US 9608924 W US9608924 W US 9608924W WO 9700667 A1 WO9700667 A1 WO 9700667A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/342—Alcohols having more than seven atoms in an unbroken chain
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
- A61K8/604—Alkylpolyglycosides; Derivatives thereof, e.g. esters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/02—Local antiseptics
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
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- 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
- the present invention relates to compositions useful as skin disinfectants, surgical hand preparations, patient skin preparations and antimicrobial hand lotions. More specifically the invention relates to stable hydroalcoholic compositions which are thickened using mixed emulsifier systems.
- Hand disinfection is generally accomplished using antimicrobial soaps with water. These soaps are usually formulated to include either povidone-iodine (usually 7.5% by weight) or chlorhexidine gluconate (CHG) (usually 2 or 4% by weight) as the active antimicrobial agent. In addition, these formulated soaps may contain surfactants and possibly low levels of humectants such as glycerin. Hand disinfection is also accomplished using presurgical scrub replacements.
- Presurgical scrub replacements ideally achieve bacterial kill equal to or better than a traditional soap and water scrub and in a shorter period of time. Additionally, they maintain or improve the skin's natural barrier to microbial and chemical contamination while providing acceptable tactile properties.
- Examples of presurgical scrub replacements include hydroalcoholic gels which generally include high levels of either ethanol or isopropanol as the disinfecting agent and also include a thickener and optionally include a humectant (e.g. glycerin).
- thickeners used in hydroalcoholic gels have been based on anionic polymers such as polyacrylic acid (sold under the tradename Carbopol by BF Goodrich Specialty Polymers and Chemicals Division of Cleveland, Ohio).
- US Patent 4,915,934 to Tomlinson discloses the use of CHG- containing antiseptic foams based on hydroalcoholic solvents, a fatty alcohol, and a surfactant.
- the surfactant is selected from the group of ethoxylated sorbitan alkylates, ethoxylated fatty alcohols, and ethoxylated nonyl phenols.
- Formulating stable viscous hydroalcoholic emulsions is difficult for two reasons.
- 40% by weight ethanol in water has a surface tension of approximately 31 dyne/cm compared to pure water which has a surface tension of about 72 dyne/cm at 20°C.
- a hydroalcoholic solution at 60% by weight ethanol has a dramatically decreased surface tension as compared to water.
- Such a composition has a surface tension of approximately 27 dyne/cm at 20°C.
- Second, many surfactants typically used in cosmetic emulsions become completely or partially soluble in hydroalcoholic systems.
- US Patent Number 4,956,170 to Lee discloses a hydroalcoholic skin moisturizing/conditioning antimicrobial gel.
- the gel comprises 60-75% ethanol and 0.4-2% of a polymeric thickening agent.
- the formulations also comprise polyethoxylated non-ionic surfactants/emulsifiers to stabilize the added emollient oils in addition to a fatty alcohol.
- US Patent Number 5,167,950 to Lins discloses an antimicrobial aerosol mousse having a high alcohol content.
- the mousse comprises alcohol, water, a polymeric gelling agent and a surfactant system comprising a C16-C22 alcohol, aerosol propellant and a non-ionic polyethoxylated surfactant.
- compositions useful as products for skin disinfection such as presurgical hand preps, patient preps, and lotions.
- the preferred formulations of this invention in general, have a very nice feel after both single and multiple applications. Additionally, preferred formulations maintain or improve the skin condition after multiple applications and no slimy or abnormal feeling is noticed during post application hand washing.
- this invention achieves bacterial, fiingal, and viral kill equal to or better than a traditional soap and water scrub in a shorter period of time while maintaining or improving the skin's natural barrier to microbial and chemical contaminants.
- the invention overcomes the shortcomings of past compositions by providing a viscous composition which includes a high concentration of a lower alcohol but does not require a polymeric thickener to make the composition viscous. Further, the composition has a cosmetically elegant feel and may be dispensed as a lotion or as a foam.
- This invention provides a composition
- a composition comprising a lower alcohol and water in a weight ratio of about 35:65 to 100:0, between at least 0.5% and 8.0% by weight thickener system comprised of at least two emulsifiers, each emulsifier present in at least 0.05% by weight wherein the emulsifiers are selected such that the composition free of auxiliary thickeners has a viscosity of at least 4,000 centipoise at 23 degrees C and wherein each emulsifier is comprised of at least one hydrophobic group and at least one hydrophilic group, wherein: (i) the hydrophobic group is comprised of an alkyl group of at least 16 carbon atoms; an alkenyl group of at least 16 carbon atoms; or an aralkyl or an aralkenyl group of at least 20 carbon atoms; and (ii) the hydrophilic group is comprised of an amide having the structure - NHR"' where R"' is comprised of hydrogen or
- M is a positively charged counter ion present in a molar ratio necessary to achieve a net neutral charge on the emulsifier and is selected from the group consisting of hydrogen, sodium, potassium, lithium, ammonium, calcium, magnesium or N+R ⁇ where each R' is independently an alkyl group of 1 to 4 carbon atoms optionally substituted with N, O, or S; and optionally alcohol; and/or polyethylene glycol bonded to said hydrophobic group through an ether or ester bond having 2-150 moles of ethylene oxide units per mole of hydrophobe, polyethylene glycol/polypropylene glycol polymers having 2-150 moles of ethylene oxide units per mole of hydrophobe and optionally terminated by C1-C36 alkyl or alkaryl ester; and/or esters of polyhydric alcohols and their polyethoxylated derivatives; and sorbitan and polyethoxylated sorbitan; as well as combinations of these groups.
- This invention further provides a method of preparing a stable hydroalcoholic composition
- a method of preparing a stable hydroalcoholic composition comprising the steps of preparing a thickener system comprised of at least two emulsifiers, each emulsifier present in at least 0.05% by weight in the composition wherein said emulsifiers are selected such that the composition free of auxiliary thickeners has a viscosity of at least 4,000 centipoise at 23 degrees C and wherein each emulsifier is comprised of at least one hydrophobic group and at least one hydrophilic group, wherein: (i) the hydrophobic group is comprised of an alkyl group of at least 16 carbon atoms; an alkenyl group of at least 16 carbon atoms; or an aralkyl or an aralkenyl group of at least 20 carbon atoms; and (ii) the hydrophilic group is comprised of an amide having the structure -NHR"' wherein R'" is comprised of hydrogen or an
- R" is hydrogen or an alkyl or alkylene group optionally substituted with nitrogen, oxygen, or sulfur atoms; or an alkylene carboxyl group, which alkyl or and L' is -CO 2 -M, -OP(O)(O-) 2 M, (-O) 2 P(O)O-M, -SO 2 O-M or -OSO 2 O-M;
- M is a positively charged counter ion present in a molar ratio necessary to achieve a net neutral charge on the emulsifier and is selected from the group consisting of hydrogen, sodium, potassium, lithium, ammonium, calcium, magnesium or N+R'3 where each R' is independently an alkyl group of 1 to 4 carbon atoms optionally substituted with N, O, or S;
- This invention also provides a method of preparing a stable hydroalcoholic composition comprising the steps of: (a) heating a thickener system to a temperature sufficient to melt said thickener system, wherein the thickener system is comprised of at least two emulsifiers, each emulsifier present in the composition in at least 0.5% by weight wherein said emulsifiers are selected such that the composition free of auxiliary thickeners has a viscosity of at least 4,000 centipoise at 23 degrees C and wherein each emulsifier is comprised of at least one hydrophobic group and at least one hydrophilic group, wherein: (i) the hydrophobic group is comprised of an alkyl group of at least 16 carbon atoms; an alkenyl group of at least 16 carbon atoms; or an aralkyl or an aralkenyl group of at least 20 carbon atoms; and (ii) the hydrophilic group is comprised of an amide having the structure - NHR 1 " where R'
- R" is hydrogen or an alkyl or alkylene group optionally substituted with nitrogen, oxygen, or sulfiir atoms, or an alkylene carboxyl group, which alkyl or alkylene carboxyl group comprises 1 to 6 carbon atoms;
- L' is -CO 2 -M, -OP(O)(O-) 2 M, (-O) 2 P(O)O-M, -SO 2 O"M or
- M is a positively charged counter ion present in a molar ratio necessary to achieve a net neutral charge on the emulsifier and is selected from the group consisting of hydrogen, sodium, potassium, lithium, ammonium, calcium- magnesium or N+R ⁇ where each R' is independently an alkyl group of 1 to 4 carbon atoms optionally substituted with N, O.
- Ambient temperature refers to the temperature range between about 21 and 25 degrees C.
- auxiliary thickeners refers to additives (other than the emulsifiers which comprise the thickener system described below) which increase the viscosity ofthe solvent phase even in the absence ofthe thickener system. Certain auxiliary thickeners may act synergistically with the thickener system to increase the viscosity ofthe resultant formula. Auxiliary thickeners include but are not limited to soluble and swellable polymers and associative colloidal thickeners such as silica, magnesium aluminum silicate, and the like. "Emollient” as used herein refers broadly to materials which are capable of maintaining or improving the moisture level, compliance, or appearance of the skin when used repeatedly.
- Emmulsifier as used herein is synonymous with “surfactant” and refers to molecules comprising hydrophilic (polar) and hydrophobic (non-polar) regions on the same molecule.
- Emmulsion refers to a stable dispersion of one liquid in a second immiscible liquid.
- “Lotion” means liquid or cream free of any propellant.
- Melt temperature Tm as used herein refers to the temperature at which compositions or emulsions ofthe present invention dramatically lose viscosity.
- Polymer as used herein refers to a natural or synthetic molecule having repetitive units and a number average molecular weight of at least 20,000.
- solvent solvent system
- hydroalcoholic solvent refer to the alcohol and water combination in the present invention.
- “Stable” as used herein refers to a composition that displays less than or equal to 10% by volume separation after centrifuging at 2275 x g for 30 minutes at ambient temperature.
- Thickener system refers to a combination of at least two emulsifiers each present in a concentration of at least 0.05% by weight capable of providing a viscosity of at least 4,000 centipoise at 23 °C to the compositions of the present invention without auxiliary thickeners.
- the invention provides a composition comprised of a lower chain alcohol, water, and thickening system.
- Alcohols used in the present invention are first discussed followed by a discussion of thickening systems.
- Ingredients which are optionally added to the composition such as antimicrobial agents and emollients are then discussed followed by a discussion of how to prepare compositions ofthe present invention.
- Alcohol used in the present invention is a lower hydrocarbon chain alcohol such as a C1-C4 alcohol.
- the alcohol is chosen from ethanol, 2-propanol, or n-propanol, and most preferably ethanol.
- Ethanol is a preferred alcohol since it provides broad spectrum and quick killing of microbes and has an odor acceptable to consumers such as doctors, nurses and clinicians.
- the invention anticipates that a single alcohol may be used or that a blend of two or more alcohols may comprise the alcohol content ofthe composition.
- the alcohol to water ratio in the present invention is between about 35:65 and 100:0 by weight.
- Compositions having alcohol to water ratios within the range 40:60 and 95:5 range ensure an efficacious immediate bacterial kill.
- the alcohol:water ratio is between about 50:50 and 85:15, more preferably between about 60:40 and about 75:25, and most preferably the alcohokwater ratio is between about 64:36 and 72:28 by weight.
- Higher alcohol to water ratios are used in a preferred embodiment for optimum antimicrobial activity and to ensure the composition is fast drying.
- the thickener system useful in this invention affects the cosmetic attributes ofthe final composition.
- hand preps and lotions ofthe invention have the following desirable cosmetic attributes.
- the composition should not result in excessive clumping of glove powder beneath powdered surgical gloves and should not affect the integrity ofthe glove material.
- the composition should maintain an acceptable viscosity at 25°C and preferably up to 35°C.
- formulations are stable to heat and cool cycles (heating up to 50°C or higher and cooling to ambient temperature) as well as freeze/thaw cycles (cooling to -30°C and warming to ambient temperature). All of these cosmetic attributes are affected by the types and amounts of emulsifiers chosen which comprise the thickener system ofthe present invention and are discussed below.
- compositions of this invention have a viscosity of at least 4,000cps at 23°C, preferably at least 20,000cps, more preferably at least 50,000cps and most preferably about 80,000 to 500,000cps measured using a very low shear viscometer such as Brookfield LVDV-I+ viscometer and T spindles with a heliopath adapter. Since the emollient system and other optional ingredients may affect the viscosity (either positively or negatively), the measured viscosity is that ofthe final composition without any added auxiliary thickeners.
- the viscosity ofthe present invention is imparted by a thickener system comprised of at least two emulsifiers.
- at least one ofthe emulsifiers is a solid at room temperature comprising at least one long chain hydrocarbon of at least 16 carbon atoms, preferably at least 18 carbon atoms, and more preferably at least 22 carbon atoms.
- Emulsifiers of this invention are comprised of molecules having hydrophilic (polar) and hydrophobic (non-polar) regions on the same molecule and conform to the general structure:
- R represents a hydrophobic group and L represents a hydrophilic group.
- R comprises an alkyl group of at least 16 carbon atoms, preferably 18 carbon atoms and more preferably 20 carbon atoms and most preferably at least about 22 carbon atoms; alkenyl group of at least 16 carbon atoms, preferably 18 and most preferably 20 carbon atoms; or aralkyl or aralkenyl group of at least 20 carbon atoms, preferably at least 24 carbon atoms and most preferably at least 26 carbon atoms.
- R is unbranched.
- "L” is further comprised of zwitterionic compounds having the structure -N + (R") 2 (CHQ) X L
- R" is hydrogen or an alkyl or alkylene group optionally substituted with nitrogen or oxygen or sulfur atoms, or an alkylene carboxyl group, which alkyl or alkylene carboxyl group comprises 1 to 6 carbon atoms;
- Q is hydrogen or hydroxyl;
- x is 1 to 4; and
- L' is comprised of -CO 2 " M or -OP(O)(O-) 2 M or (-O) 2 P(O)O " M or
- M is a positively charged counter ion present in a molar ratio necessary to achieve a net neutral charge on the emulsifier and is selected from the group consisting of hydrogen, sodium, potassium, lithium, ammonium, calcium, magnesium or N " ⁇ 3 where each R' is independently an alkyl group of 1 to 4 carbon atoms optionally substituted with N, O, or S.
- L is optionally alcohol; and/or polyethylene glycol bonded to said hydrophobe through an ether or ester bond having 2-150 moles of ethylene oxide units per mole of hydrophobe, polyethylene glycol/polypropylene glycol copolymers having 2-150 moles of ethylene oxide plus propylene oxide units per mole of hydrophobe and optionally terminated by C1-C36 alkyl or alkaryl ester; and/or esters and ethers of polyhydric alcohols and their polyethoxylated derivatives; and/or sorbitan and polyethoxylated sorbitan, as well as combinations of these groups, e.g. a polyethoxylated polyglucoside.
- "a" and "b" are independently 1 to 4.
- the hydrophobic and hydrophilic groups on non-ionic emulsifiers are generally selected to have a hydrophile/Iipophile balance (HLB) of 2 to 20 and more preferably 4 to 16. Furthermore, the weight average HLB ofthe thickener system is preferably 4 to 16 and more preferably 8 to 12. (For example, a thickener system comprised of 40% by weight of an emulsifier with an HLB of 10 and 60% by weight of an emulsifier with an HLB of 15 has a weight average HLB of 13.)
- HLB hydrophile/Iipophile balance
- the emulsifiers which comprise thickener systems may be chosen from a single class of surfactants (e.g., a mixture of chain length alkyl polyglucosides) but is preferably a mixture of emulsifier classes.
- Many commercially available emulsifiers are actually comprised of a mixture of chain lengths.
- some behenyl alcohol as commercially supplied is actually a mixture of alcohols consisting of primarily C22 and C20 fractions but contain detectable levels of C24, C18 and C16 fractions.
- the chain lengths specified herein refer to the number average chain length.
- each emulsifier must be present in a concentration of at least 0.05% and more preferably at least 0.1% by weight to be considered a component of a thickener system.
- Thickener systems ofthe present invention are capable of achieving high viscosities at relatively low total emulsifier concentrations.
- the total concentration of emulsifiers present as a thickener system is generally less than about 8% by weight, preferably less than about 5% by weight, more preferably less than 4% by weight, and most preferably less than 3% by weight ofthe total composition ofthe present invention.
- an emulsifier is considered part ofthe thickener system if its presence in the formula results in an increase in the viscosity ofthe composition. If a certain emulsifier does not result in increasing the viscosity ofthe composition, it is considered an emollient or stabilizer as defined below.
- compositions ofthe present invention which are substantially free of polymeric thickening agents have a "melt temperature" (Tm). If compositions are heated above this melt temperature, they dramatically lose viscosity.
- the compositions ofthe present invention preferably have melt temperatures greater than 25°C in order to maintain a high viscosity at room temperature. More preferably the melt temperature is greater than 35°C in order to maintain viscosity once applied to the skin.
- the most preferred formulations have a melt temperature greater than 40°C in order to allow shipping and handling without ref ⁇ geration.
- Thickener systems affect the melt temperature of a given composition. In order to obtain a preferred melt temperature a preferred thickener system includes at least one emulsifier which is solid at ambient temperature.
- all emulsifiers of a thickener system are solid at ambient temperature to increase the melt temperature ofthe resultant composition.
- the structure of emulsifiers in a thickener system affects the melt temperature ofthe resultant composition.
- at least one emulsifier in a thickener system is capable of promoting a crystalline structure. Crystallinity is promoted by long straight chain alkyl groups, therefore, at least one emulsifier preferably comprises a saturated straight chain hydrocarbon of at least 16, preferably at least 18 and most preferably at least 20 carbon atoms. Certain hydrophilic head groups have been found to particularly promote association and crystallization.
- Suitable crystalline emulsifiers include alkyl alcohols, alkyl polyglucosides, polyglycerol alkyl esters, C1-C4 esters of alkyl alcohols, C1-C4 esters of alkyl carboxylates, optionally substituted alkyl amides, alkyl betaines and alkyl phosphates or phospholipids, alkyl quaternary amines, alkyl amine oxides polyethoxylated alkyl alcohols and alkyl esters of polyethylene glycol.
- the emulsifier chain length also helps to determine the maximum level of ethanol which can be used in the composition and the concentration of emulsifiers required in the thickener system.
- concentration of ethanol increases the chain length ofthe hydrocarbon chains in a thickening system must also increase in order to maintain a melt temperature over 35°C.
- the Montanov 68 (C16/C18 alkyl polyglucoside)/Brij 76 (polyethoxylated C18 alcohol) thickener system requires approximately 5% total emulsifier to achieve a suitable viscosity.
- a similar system based on C22 hydrophobes achieves a suitable viscosity at only 2% total emulsifier.
- the nature and size of hydrophilic head groups of emulsifiers are important and help to determine which thickening systems produce viscous stable systems. Certain combinations of emulsifiers will produce viscous stable emulsions. Without being bound by theory, it is believed that the size, charge, and degree of hydrogen bonding are important parameters to determine how emulsifiers interact.
- Many preferred thickener systems are capable of producing viscoelastic compositions which are very stable. By varying the ratio of emulsifiers, the degree of elasticity can be adjusted from almost a purely viscous composition to a highly elastic and even stringy composition. If emollients are added, increasing the elasticity ofthe system imparts added stability to prevent separation of immiscible emollients. Excessive elasticity, however, is not preferred since an elastic composition usually does not provide a cosmetically appealing product. Addition of certain emulsifiers with at least two hydrophobic components has been shown to limit the viscoelasticity while ensuring viscous stable compositions. A favored class of multiple hydrophobic component emulsifiers are quaternary ammonium salts conforming substantially to the following structure:
- R' and R" are long chain alkyl or alkenyl hydrocarbon chains of at least 16 carbon atoms;
- R 1 " is a short chain alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl;
- R"" is equivalent to either R' or R'" and is preferably equivalent to R'"; and X is a halogen, R'"SO 3 -, R'"SO 4 -, or R'"CO 2 -
- Some preferred structures include distearyldimethylammonium chloride, dibehenyldimethylammonium chloride, and dibehenyldimethylammonium methosulfate, while dibehenyldimethylammonium methosulfate is a more preferred structure.
- Suitable multiple hydrophobic emulsifiers include dialkylglycerol esters, trialkylglycerol esters, polyglycerol alkyl esters, ethylene glycol dialkylesters, polyethylene glycol dialkylesters, dialkylamides of diamines such as ethylene diamine, polyalkylesters of pentaerythritol and dialkyi (optionally ethoxylated) phosphates, and alkyl esters of polyethyoxylated alkyl alcohols.
- emulsifier classes are offered as nonlimiting examples of suitable emulsifiers for use in the present invention. Examples of some preferred emulsifiers are provided for each emulsifier class.
- an emulsifier must be present with at least one coemulsifier to provide a thickener system to produce stable viscous compositions.
- Nonlimiting examples of preferred alkyl or alkenyl polyglucoside emulsifiers include cetearyl glucoside sold as Montanov 68 by Seppic, Inc. of Fairfield, New Jersey; Behenyl glucoside, produced experimentally as Essai 624 MP, an alkyl polyglucoside prepared with 92% C-22 alcohol and corn-derived glucoside by Seppic, Inc.; and oleyl glucoside.
- R is as defined above and R' is C1-C4 branched or straight chain alkyl optionally substituted in available positions by hydroxyl groups.
- Some preferred short chain esters of long chain alcohols or acids include but are not limited to methyl behenate sold as Kemester 9022 by Witco,
- Rg-OH where Rg is a straight or branched chain alkyl or alkenyl hydrocarbon chain of at least 16 carbon atoms, preferably at least 18 and most preferably at least 20 carbon atoms; or an aralkyl or alkenyl group of at least 22 carbon atoms, preferably at least
- Nonlimiting examples of preferred alkyl and alkenyl alcohol emulsifiers useful in a thickener system ofthe invention include stearyl alcohol available as Lanette 18 from Henkel's Emery Division of Cincinnati, Ohio; Behenyl
- Alcohol available as Lanette 22 from Henkel Oleyl alcohol available as Novol from Croda
- C-24 alcohol available as Unilin 350 from Petrolite of Tulsa, Oklahoma C31 alcohol available as Unilin 425 from Petrolite
- each Rj is independently hydrogen or a straight chain alkyl group of at least
- Some examples of preferred polyglycerol ester emulsifiers useful in a thickener system ofthe present invention include but are not limited to decaglycerol monostearate available as Polyaldo 10-1-S from Lonza Inc. of Fairlawn, New Jersey; tetraglycerol monostearate available as Tetraglyn 1-S from Barnet Products Co ⁇ oration of Paterson, New Jersey; and decaglyceroltetrabehenate.
- R2 is the same as R3 or a long chain alkyl or alkenyl hydrocarbon chain of at least 16 carbon atoms, preferably at least 18 and more preferably at least 20 carbon atoms optionally substituted in available positions by N, O, and S; or an aralkyl or aralkenyl group of at least 22 carbon atoms, preferably at least 24 carbon atoms, and most preferably at least 26 carbon atoms;
- R3 is a short chain alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl;
- R4 is equivalent to either R2 or R3 and is preferably equivalent to R3- and
- Nonlimiting examples of quaternary amine emulsifiers include dibehenyldimethylammonium methosulfate available as Incroquat DBM-90 from Croda; behenyltrimethylammonium chloride available as Nikkol CA-2580 from Barnet; and tallowtrimethylammonium chloride available as Arquad T-27W from Akzo Chemicals, Inc. of Chicago, Illinois.
- R, R , and R3 are as defined above and R and R3 may also be selected from polyethoxylated or polyproxylated alkyl or alkenyl alcohol chains having 1-50 moles of ethylene oxide or propylene oxide groups per mole of emulsifier and
- emulsifiers from the class of tertiary amines and their protonated salts useful in a thickener system ofthe invention include but are not limited to behenamidopropyldimethylamine available as Incromine BB from Croda; behenamidopropyldimethylamine gluconate; tallowdimethylamine hydrochloride; dihydrogenated tallow methyl amine; stearyl diethanolamine hydrochloride; polyethoxylated stearyl diethanolamine hydrochloride. 7.
- behenamidopropyldimethylamine available as Incromine BB from Croda
- behenamidopropyldimethylamine gluconate tallowdimethylamine hydrochloride
- dihydrogenated tallow methyl amine dihydrogenated tallow methyl amine
- stearyl diethanolamine hydrochloride polyethoxylated stearyl diethanolamine hydrochloride.
- R2, R3 and R_ are as defined above.
- Nonlimiting examples of emulsifiers from the class of amine oxides suitable in a thickener system ofthe invention include behenamine oxide (behenyldimethylamine oxide) available as Incromine B-30P from Croda; stearamine oxide available as Incramine Oxide S from Croda; behenamidopropyldimethyl amine oxide; and bis(2- hydroxyethyl)tallow amine oxide available as Aromox T/12 from Akzo.
- emulsifiers from the class of polyethoxylated alcohols and esters include but are not limited to Steareth-2 available as Brij 72 from ICI Americas Inc. of Wilmington, DE; Steareth-10 available as Brij 76 from ICI; beheneth-5 available as Nikkol BB-5 from Barnet Products Inc.; beheneth-10 available as Nikkol BB-10 from Barnet; C31 alkyl- 10EO available as Unithox 450 from Petrolite Corp. of Tulsa, OK; C31 alkyl-40 EO available as Unithox 480 n from Steareth-2 available as Brij 72 from ICI Americas Inc. of Wilmington, DE; Steareth-10 available as Brij 76 from ICI; beheneth-5 available as Nikkol BB-5 from Barnet Products Inc.; beheneth-10 available as Nikkol BB-10 from Barnet; C31 alkyl- 10EO available as Unithox 450 from Petrolite Corp. of Tulsa, OK; C31 alkyl-40
- Nonlimiting examples of emulsifiers from the class of zwitterions useful in a thickener system ofthe invention include StearamidopropylPG- dimmonium chloride phosphate available as Phospholipid S V from Mona Industries of Paterson, New Jersey; and behenyl betaine available as Incronam B-40 from
- R and R 7 are as defined above.
- examples of some preferred emulsifiers from the class of alkyl and alkenyl amides useful in a thickener system ofthe invention include but are not limited to behenamide available as Kemamide B from Witco; stearamide available as Uniwax 1750 from Petrolite; Behenamidopropyldimethyl amine available as Incromine BB from Croda; stearyldiethanolamide available as Lipamide S from Lipo Chemicals Inc. of Paterson, NJ; and Erucamide available as Armid E from Akzo. 11. Esters and Ethers of Polyhydric Alcohols
- esters and ethers examples include glycerol monobehenate, pentaerythritol distearate and glycerol tribehenate.
- Esters and ethers of polyethoxylated polyhydric alcohols are also useful. For example, these include but are not limited to polyethoxylated glycerol monostearate, polyethoxylated penta erythritol behenate, polyethoxylated propylene glycol monostearate.
- R ⁇ 2 is an alkyl or alkenyl group of at least 16 carbon atoms, preferably at least 18 carbon atoms and most preferably at least 20 carbon atoms optionally comprising oxygen, nitrogen, or sulfiir atoms within or substituted upon the alkyl or alkenyl chain or a polyethoxylated and/or polypropoxylated alkyl or alkenyl group which alkyl or alkenyl group comprises at least 16 carbon atoms, preferably at least 18 carbon atoms and most preferably at least 20 carbon atoms optionally comprising oxygen, nitrogen, or sulfur atoms within or substituted upon the alkyl or alkenyl chain and R12 is a polyethoxylated or polypropoxylated substituent or a copolymer of ethylene oxide and propylene oxide, these polymeric subunits are present in amounts of 1 to 100 moles, preferably 1 to 20 moles per mole of hydrophobe; L is sulfate (— OSO2O "
- M is hydrogen (IT), sodium (Na + ), potassium (K + ), lithium (Li + ), ammonium (NH4 + ), calcium (Ca + 2).
- B comprises 3 to 7 atoms selected from the group consisting of carbon, nitrogen, sulfur and oxygen atoms which complete the nitrogen-containing heterocyclic ring; and wherein R may be substituted in available positions with oxygen, nitrogen or sulfiir atoms; a and c are independently 1 or 2; b and d are independently 1, 2 or 3; and e is equal to (c times d)/b.
- Nonlimiting examples of preferred emulsifiers from the anionic class of emulsifiers suitable for use in a thickener system ofthe invention include behenic acid available as Croacid B from Croda, Inc.; stearyl phosphate available as Sippostat 0018 from Specialty Industrial Products, Inc. of Spartanburg, SC; and sodium stearate available from Witco.
- R13 is H or CR12 and each v is independently 0-30.
- Fatty acid esters of sorbitan and its polyethoxylated derivatives, polyoxyethylene derivatives of mono and poly-fatty esters are also examples of additional emulsifiers useful in the present invention.
- composition ofthe invention is believed to be that of an emulsion.
- a classic definition of an emulsion is a stable dispersion of one liquid in a second immiscible liquid.
- the present composition is preferably formed using at least one emulsifier which is a wax at room temperature.
- compositions ofthe present invention are not well characterized, they are believed to be a viscous stable mixture of a solid, semisolid, or liquid phase in a second liquid phase.
- hydrophobic emulsifiers and immiscible emollients form an "oil” or hydrophobic phase which is dispersed in the hydroalcoholic liquid phase to form an "oil” in “water” emulsion.
- the hydroalcoholic phase is referred to herein as the "water” phase. Since many preferred emulsions are somewhat viscoelastic, these emulsions are believed to be liquid crystalline emulsions which have been cooled below the crystallization temperatures ofthe chosen emulsifiers to form a semi ⁇ crystalline gel-like network.
- compositions ofthe present invention may also exist as combinations of these structures.
- Liquid crystalline and coagel phases in aqueous systems are described in "Application of Emulsion Stability Grafs to Mobile and Semisolid O/W Emulsions," Cosmetics and Toiletries. Vol. 101, pp 73-92 (1986), and “Influence of Long Chain Alcohols (or Acids) and Surfactants on the Stability and Consistencies of Cosmetic Lotions and Creams," Cosmetics and Toiletries. Vol. 92, pp. 21-28 (1977).
- the exact type of molecular association that occurs depends on many factors including the nature, size, and physical and chemical states ofthe polar and hydrocarbon portions ofthe emulsifiers which comprise the thickener system at a specified temperature.
- Emulsifiers other than those required in the composition to provide a thickener system may also be added as emollients or stabilizers. These emulsifiers are referred to herein as auxiliary emulsifiers.
- auxiliary emulsifiers For example, certain emollients are also comprised of hydrophobic and hydrophilic regions and are useful in the present invention since they are believed to become incorporated into the liquid crystalline network. These emollients tend to enhance the stability ofthe composition as is discussed more fully below.
- certain dimethicone copolyol surfactants can actually improve the stability of fo ⁇ nulations inco ⁇ orating emollients. This is also discussed in more detail below.
- compositions ofthe present invention may optionally include ingredients such as salts, emollients, stabilizers, antimicrobials, fragrances, therapeutic agents, propellants and additional emulsifiers.
- ingredients such as salts, emollients, stabilizers, antimicrobials, fragrances, therapeutic agents, propellants and additional emulsifiers.
- the melt temperature ofthe compositions ofthe present invention may be increased by adding salts.
- concentration of salt As the concentration of salt is increased, the ratio of emulsifiers will often need to change in order to maintain a stable composition. It is important to choose salts which do not create an unstable system and are compatible with any antimicrobials present in the system. For example, chlorhexidine digluconate (CHG) will precipitate rapidly in the presence of halide salts above a concentration of about O.lM. Therefore, if a system includes CHG, preferably gluconate salts such as triethanolamine gluconate or sodium gluconate, are used. Stabilizers
- a stable composition is one which does not separate more than 10% by volume after centrifuging at 2275 x g for 30 minutes as measured at the longitudinal midpoint ofthe sample tube. It is also recognized that stability may be time dependent due to crystallization of emulsifiers and/or emollients present in the system, coalescence of emollients, emulsifiers and the like and, therefore, preferred compositions do not exhibit separation of more than 10% after standing for 6 months at ambient conditions.
- Two types of stabilizers are useful in the present invention. These include (1) those stabilizers that complex with emulsifier hydrophilic head groups, and (2) those that associate with the emulsifier hydrophobic tails. Certain stabilizers may perform both functions.
- emulsifiers comprising 1,2 diol-containing head groups such as alkylpolyglucosides, monoalkylglycerides, and polyglycerol alkyl esters
- head groups such as alkylpolyglucosides, monoalkylglycerides, and polyglycerol alkyl esters
- borate ions complex with adjacent head groups which may increase the association of hydrophobic tails by holding them in close proximity.
- Natural or synthetic polymers comprised of pendent long chain alkyl groups (greater than 12 and preferably greater than 16 carbon atoms) such as stearyl modified cellulose derivatives, stearyl modified proteins such as wheat protein, stearyl modified collagen and the like are capable of stabilizing compositions ofthe present invention.
- Such added components may also increase the melt temperature of compositions ofthe present invention. It is believed that the pendent alkyl groups in these polymers associate by Van der Waals interactions with the hydrophobes of a thickening system, thereby enhancing the stability ofthe crystalline structure. Polymeric thickeners which do not have associative pendent alkyl chains may also increase the melt temperature presumably by increasing the viscosity ofthe continuous phase.
- a nonlimiting example of such thickeners are quaternary celluloses such as CelquatTM 230M as available from National Starch of Bridgewater, New Jersey.
- stearyldimonium hydroxypropyl cellulose commercially available as Crodacel QS from Croda Inc., Parsippany, NJ is added as a stabilizer.
- Emollients are typically added to hand lotions or hand preps because they act to increase the moisture content ofthe stratum corneum. Emollients are generally separated into two broad classes based on their function. The first class of emollients function by forming an occlusive barrier to prevent water evaporation from the stratum corneum. The second class of emollients penetrate into the stratum corneum and physically bind water to prevent evaporation. The first class of emollients is subdivided into compounds which are waxes at room temperature and compounds which are liquid oils. The second class of emollients includes those which are water soluble and are often referred to as humectants.
- the thickener system is considered separate and distinct from any emollients which may be added even though it is recognized that the emulsifiers may function as occlusive emollients and aid in maintaining or improving the skin condition.
- Emollients are included in a preferred embodiment ofthe invention and preferably comprise between about 3 and 30%, more preferably between about 4 and 20% and most preferably between about 5 and 12% by weight ofthe formulation.
- the ratio of wax to liquid emollients (oils and humectants) in a prefe ⁇ ed embodiment ofthe invention is between about 5:1 to 1:5 and preferably between about 1 :3 to 3 : 1.
- Emollients may be selected from any ofthe classes known in the art. A general list of useful emollients appears in US patent 4,478,853 and EPO patent application 0 522 624 Al and in the CTFA Cosmetic Ingredient Handbook published by The Cosmetic, Toiletry, and Fragrance Association, Wash. D.C. (1992) under the listings "Skin Conditioning agents,” “emollients,” “humectants,” “miscellaneous” and “occlusive.”
- emollients are chosen from the following nonlimiting list of general emollients, occlusive emollients and humectants.
- general emollients include short chain alkyl or aryl esters (C1-C6) of long chain straight or branched chain alkyl or alkenyl alcohols or acids (C8-C36) and their polyethoxylated derivatives; short chain alkyl or aryl esters (C1-C6) of C4- C12 diacids or diols optionally substituted in available positions by -OH; alkyl or aryl C1-C9 esters of glycerol, pentaerythritol, ethylene glycol, propylene glycol, as well as polyethoxylated derivatives of these and polyethylene glycol; C12-C22 alkyl esters or ethers of polypropylene glycol; C12-C22 alkyl esters or ethers of poly
- occlusive emollients include cyclic dimethicones, polydialkylsiloxanes, polyaryl/alkylsiloxanes, long chain (C8 - C36) alkyl and alkenyl esters of long straight or branched chain alkyl or alkenyl alcohols or acids; long chain (C8 - C36) alkyl and alkenyl amides of long straight or branched chain (C8- C36) alkyl or alkenyl amines or acids; hydrocarbons including straight and branched chain alkanes and alkenes such as squalene, squalane, and mineral oil; polysiloxane polyalkylene copolymers, dialkoxy dimethyl polysiloxanes, short chain alkyl or aryl esters (C1-C6) of C12-C22 diacids or diols optionally substituted
- Nonlimiting examples of preferred humectant type emollients include glycerol, propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol, pantothenol, gluconic acid salts and the like.
- emollients may also affect the viscosity, stability, and melt temperature of a composition. It is anticipated that a single emollient may be added to the present invention or two or more emollients may be added to the composition. A wide range of emollients may be added to the formulations ofthe present invention. Preferably wax and oil type emollients along with water soluble emollients are used.
- emollient systems are comprised of humectants in addition to occlusive wax and oil emollients in concentrations which achieve a moisturizing but not greasy composition which maintains and improves the condition ofthe skin upon repeated use.
- emollients are non-comedogenic and are chosen to ensure no skin irritation or sensitization reaction occurs. This is particularly critical since the composition ofthe present invention will likely be worn in an occluded condition under surgical gloves.
- emollients should be chosen which do not affect the integrity ofthe glove material.
- hydrocarbon emollients such as mineral oil and petrolatum can detrimentally affect the tear strength of surgical gloves
- these emollients may need to be avoided for compositions employed as presurgical disinfectants.
- emollients may be added to the present compositions, they may be present in four distinct regions.
- the emollients could occur (1) as a soluble species in the solvent phase, (2) dispersed as emulsified droplets within the mixed emulsifier micelle or crystalline gel network, (3) inco ⁇ orated into the mixed emulsifier micelle or crystalline gel network, or (4) as a separate and distinct emulsion.
- emollients can affect the melt temperature of a composition. Those emollients that are soluble or dispersible in the solvent phase tend to have little or no affect on the melt temperature and are therefore preferred. These emollients include the humectant and general emollients. The most preferred general emollients are those which are essentially insoluble in water but soluble in the hydroalcoholic solvent. These emollients are also prefe ⁇ ed since they remain soluble and uniformly dispersed even above the melt temperature so that upon cooling to room temperature a uniform composition results. In addition, they are also believed to have little effect on surgical gloves. Such general emollients typically do not have alkyl or alkenyl chains greater than about 14, preferably not greater than 12 and most preferably not greater than about 9 carbon atoms.
- emollients which are insoluble in the hydroalcoholic solvent may associate with the emulsifiers ofthe thickener system and/or become inco ⁇ orated into the micelle or crystalline gel network.
- Prefe ⁇ ed emollients within this class are those emollients that are very hydrophobic since they tend to maintain a high melt temperature. For example, hexadecane was found to increase the viscoelasticity of certain thickener systems.
- Those emollients which are capable of associating with and disrupting the emulsifiers ofthe thickener system tend to decrease the melt temperature and may influence the stability ofthe composition.
- Certain branch alkyl esters of greater than about 12 carbon atoms per hydrophobe have been found to be particularly effective at decreasing the melt temperature. For example, trioctyldodecyl citrate has been found to significantly decrease the melt temperature of some systems.
- Emollients which become inco ⁇ orated into the thickener system tend to decrease the melt temperature.
- laureth-4 (Brij 30) appears to inco ⁇ orate into the thickener system since it does not phase out when heated above the melt temperature at concentrations below about 1% by weight.
- Laureth-4 also tends to decrease the melt temperature ofthe composition.
- Certain emollients which are insoluble in the hydroalcoholic solvent can be emulsified in what is believed to be a separate and distinct emulsion. These emollients have little affect on the melt temperature of a composition.
- certain cyclic silicones, polysiloxanes, and dialkoxypolysiloxanes can be emulsified in hydroalcoholic solvents using polyether/polysiloxane copolymers surfactants. Cyclic silicones such as DC344 (available from Dow Corning of Midland, Michigan) in the presence of certain polyether/polysiloxane copolymers such as Abil B88183 available from Goldschmidt Chemical Co ⁇ .
- Rg is a polyether substituted alkyl group with the structure:
- R9 is an alkyl group of 1 to 6 carbon atoms
- RlO is hydrogen or an alky group of 1-22 carbon atoms; and R ⁇ 1 is an alkyl group of 1 to 22 carbon atoms or phenyl.
- compositions ofthe present invention are nonlimiting examples of emulsifier/emollient components which improve thickening/stability of compositions ofthe present invention.
- wax emulsifiers/emollients have been found to be particularly useful and include solid waxy esters such as: Myristyl Myristate, Cetyl Palmitate, Myristyl Stearate, Stearyl Behenate, Behenyl Isostearate, Isostearyl Behenate, Behenyl Behenate, Lauryl Behenate, Behenyl Erucate. These have the following formula:
- R1-CO2-R2 where: R ⁇ is at least C14 carbon atoms;
- R2 is an alkyl or alkenyl of at least 4 carbon atoms.
- Long chain hydrocarbon di-esters, tri-esters, of polyhydric alcohols with melting point greater than 23 °C include solid esters such as glycerol tribehenate and sorbitan tristearate.
- Pure lanolins and lanolin derivatives e.g. hydrogenated lanolin provide excellent emolliency but can also improve the stability ofthe emulsion when used in combination with oil emollients.
- Petrolatums provide excellent emolliency and can also improve the stability ofthe emulsion when used in combination with oil emollients.
- Petrolatums are mixtures of oily and waxy long chain hydrocarbons.
- Microcrystalline waxes and branched hydrocarbon waxes with a melting point greater than 50°C and a molecular weight greater than 400 includes but is not limited to Vybar 103 which is a branched hydrocarbon with a number average molecular weight of 2800 and is available from Petrolite Co ⁇ . of Tulsa, Oklahoma and UltraflexTM which is a microcrystalline wax also available from Petrolite Co ⁇ .
- Oxidized waxes and modified hydrocarbon waxes may find application in the present invention. These are prepared from waxes modified by oxidation, salts of oxidized waxes, maleic anhydride adducts of polyolefins and urethane derivatives of oxidized synthetic or petroleum waxes. Applicable waxes could include Petrolite' s Cardis or Petronauba microcrystalline and polyethylene-based oxidized products, Polymekon (salts) and Ceramer (anhydride adducts).
- Fully saturated homopolymers of polyethylene or copolymers of various alkene monomers may be used to form polymers with a molecular weight at or below 3,000 with a melting point below 130°C and low melt viscosities.
- Applicable waxes could include Polywax® available from Petrolite Co ⁇ .
- the formulations may also comprise a fragrance. If fragrances are included the fragrances must be chosen carefully since some fragrances are known to cause skin irritation and/or sensitization reactions. Antimicrobials
- compositions ofthe present invention may be added to enhance the antimicrobial action ofthe compositions ofthe present invention. This may be particularly desirable in critical uses such as presurgical hand scrubs or presurgical patient skin scrub replacements.
- Suitable additional antimicrobials include iodine and its complexed forms such as povidone/iodine, chlorhexidine salts such as chlorhexidine digluconate (CHG), parachlorometaxylenol (PCMX), hexachlorophene, phenols, surfactants comprising a long chain hydrophobe (C12-C22) and a quaternary group, triclosan, Lauricidin, quaternary silanes, hydrogen peroxide, phenols, silver, silver salts such as silver chloride, silver oxide and silver sulfadiazine and the like.
- the antimicrobial level should be adjusted to the minimum level which maintains a low bacteriological count for 6 and most preferably for 12 hours after application.
- the most prefe ⁇ ed additional antimicrobial is chlorhexidine since it is capable of ensuring long term antimicrobial efficacy. If chlorhexidine is added to the present invention it is preferably present as a soluble salt.
- the diacetate and digluconate salts are prefe ⁇ ed.
- the most prefe ⁇ ed antimicrobial is chlorhexidine digluconate (CHG).
- CHG is preferably present at a concentration of 0.05-5.0%, more preferably from 0.1 - 3% and most preferably from 0.25-2% by weight.
- Chlorhexidine is a bis(diguanide) and therefore is very basic and is capable of forming multiple ionic bonds with anionic materials.
- chlorhexidine- containing thickener system are preferably based on non-ionic and or cationic emulsifiers. Certain zwitterionic, very insoluble, or non-precipitating anionic emulsifiers may also be useful.
- compositions ofthe present invention may also be formulated into an aerosol foam or mousse by addition of an appropriate propellant.
- the propellant must be chosen to ensure proper delivery from the container to prevent clogging ofthe valve.
- the propellant can be chosen from chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorinated alkanes, and lower alkanes (C1-C5) as well as nitrous oxide dimethyl ether and other solvent-soluble propellants.
- Preferred propellants are lower alkanes such as propane, butane, and isobutane since these result in a dramatic loss in viscosity making the formulation easy to dispense.
- a 70/30 mixture of propane/isobutane is a particularly prefe ⁇ ed embodiment.
- the antimicrobial lotion is first formulated and charged into an appropriate pressure rated container. If convenient, the formulation may be heated above the melt temperature in order to facilitate filling. The propellant is then added under pressure at approximately 2-30% preferably 3-20% by volume. The propellant may form a separate layer or may remain emulsified in the composition.
- compositions of this invention may be compounded with UV absorbers and oils to deliver fast-drying sunscreens.
- Antimicrobials such as benzoyl peroxide may also be added to the formulations and the formulations may be useful as an acne medication.
- the systems of this invention may also be formulated with barrier compounds to form barrier creams and lotions.
- Materials which may be added to provide barrier protection for use as skin barriers to protect against diaper rash include but are not limited to 0.1 to 60% aldioxa, allantoin, aluminum acetate, aluminum hydroxide, bismuth subnitrate, boric acid, calamine, cellulose (microporous), cholecalciferol, cocoa butter, cod liver oil (in combination), colloidal oatmeal, cysteine hydrochloride, dexpanthenol, dimethicone, glycerin kaolin, lanolin (in combination), live yeast cell derivative, mineral oil, peruvian balsam, peruvian balsam oil, petrolatum, protein hydrolysate (1 -leucine, 1 -isoleucine, 1 -methionine, 1- phenylalanine, and l-tyrosine), racemethionine, shark liver oil, sodium bicarbonate, sulfur, talc, tannic acid, topical starch, vitamin A white petrolatum, zinc acetate
- Formulations are also contemplated containing antifungal agents for treating fungal infections ofthe skin such as athlete's foot and the like.
- compositions ofthe present invention may be prepared by a variety of techniques.
- the process can often be as simple as adding the thickener system to the hydroalcoholic solvent at a temperature above the melting point ofthe emulsifiers, mixing briefly and cooling.
- the components are preferably subjected to high shear (e.g. homogenized) for a limited time period while above the melting point of the thickener system followed by low shear mixing while cooling.
- the system should be mixed under high shear long enough to ensure a very small "droplet" size, however, excessive high shear mixing may result in decreased viscosity and stability.
- the cooling rate may be important depending on the particular thickener system. Certain thickener systems can be homogenized and then allowed to cool slowly, however, rapid cooling appears beneficial for most systems.
- the order of adding the components may also affect the stability and viscosity ofthe system. In general it works well to melt the mixed emulsifiers with aqueous-insoluble emollients together in one vessel. The hydroalcoholic solvent and any aqueous miscible emollients are mixed in a second vessel. Both components are heated above the melting temperature ofthe thickener system. The hot liquid components are mixed together rapidly followed by approximately 1 to 5 minutes of homogenization for typical batches under 500 grams. While still low in viscosity the system is stirred using moderate agitation and cooled.
- viscosity was measured at 23 °C at ambient pressure using a Brookfield LVDV-I * viscometer equipped with a model D Brookfield heliopath and T spindles B-F.
- the spindle and speed was chosen for each particular sample such that the viscometer was operating in the middle of its range. All samples were allowed to equilibrate at 23°C for 24 hours prior to measurement.
- the viscosity is taken at the lowest speed possible while staying within 20-80% ofthe viscometer range and more preferably between 30-70% ofthe range. In all cases the sample size and container geometry was chosen to ensure that there were no wall effects.
- wall effects it is meant the viscosity value is not affected by the container and is essentially equivalent to the viscosity taken in an infinitely large container. For this reason lower viscosity samples required a larger sample size to accommodate the larger spindles.
- the following table outlines prefe ⁇ ed spindles for various sample viscosities.
- the viscosity of each sample was taken as the highest relatively stable reading achieved oh the first path the spindle traversed using the heliopath adapter.
- the stability of samples was measured 24 hours after conditioning at ambient conditions by placing 12ml of a formulation that formed a lotion/cream in a 15ml graduated centrifuge tube. The tube was then centrifuged in a Labofuge B (Heraeus Sepatech GmbH, Model 2650, rotor 2150 and buckets #2101) at 3000 ⁇ m (2275 x g when measured at the longitudinal midpoint ofthe sample tube) for 30 minutes at 23 °C. Stability is recorded as a volume percent separation in the Examples below.
- Labofuge B Heraeus Sepatech GmbH, Model 2650, rotor 2150 and buckets #2101
- the melt temperature was measured by placing approximately 15 grams sample in a 25cc sealed glass vial and placing the vial in a water bath. The temperature ofthe bath was increased periodically in discrete increments and the contents checked after approximately 1 hour at a given temperature. The melt temperature was taken as the temperature at which the mixture became very low in viscosity.
- MIC Minimum Inhibitory Concentration
- Aureus ATCC 14154 (lab strain 502) grown on trypticase soy agar plates was resuspended in Mueller-Hinton Broth to a cell density of 0.6-1.2x10 6 colony forming units per milliliter.
- Chlorhexidine samples were prepared by adjusting CHG to 512 ⁇ g/ml in Mueller-Hinton Broth and serially diluting in two-fold steps in Mueller-Hinton Broth.
- the CHG-containing Mueller-Hinton Broth was placed in 96-well sterile microliter plates and each well was inoculated with the bacteria. The plates were then incubated for 24-48 hrs at 37°C. Bacterial growth was determined visually by comparing the plates. The MIC was determined as the lowest concentration of CHG that resulted in complete kill ofthe test organism.
- compositions of this invention are preferably formulated with emollients to achieve a moisturized but relatively dry feel. Lotions with excessive emollients tend to be perceived as greasy and can result in excessive clumping ofthe powder under surgical gloves.
- the formulations of this invention do not provide a tacky or sticky feel even in high humidity environments throughout the application process.
- the invention formulations preferably yield a smooth, soft, non-tacky, and moisturized feeling. Testing ofthe cosmetic or tactile properties ofthe compositions was conducted with preferably greater than ten evaluators who applied a premeasured amount of product, approximately 2ml.
- Example 1 Alkyl Polyglucoside Thickener Svstems An alkyl polyglucoside emulsifier having an alkyl chain of 16 to 18 carbons was obtained as Montanov 68 from Seppic Inc. of Fairfield, NJ. This highly crystalline emulsifier was combined with other emulsifiers to form thickener systems in a hydroalcoholic solvent. The solvent was either 60:40 or 68:32 ethanol:water by weight. 200 proof ethanol and distilled water were used. The Montanov 68/co- emulsifier ratio was varied keeping the total emulsifier concentration fixed at 5% by weight according to the following table: Formulation (grams)
- Emulsifier A B C D Emulsifier A B C D
- Each co-emulsifier/Montanov 68 composition was prepared using the following procedure:
- the hydroalcoholic solvent was heated to 75°C in a sealed jar.
- the mixture was homogenized at maximum speed for 4 minutes using a Silverson L4R homogenizer available from Silverson Machines, Waterside England.
- the vessel was then immersed in 15-20°C water with moderate agitation using an overhead paddle impeller for 20 minutes.
- Nikkol BB-5 (beheneth-5) 60:40 240,000cps 2200 cps 29300cps 26600 0% separation 0% 0% 0% 0%
- Nikkol BB-5 (beheneth-5) 68:32 1500 48000 57000 25000
- Nikkol BB-10 (beheneth-20) 68:32 32000 6800 450 NS
- Armid 18 (octadecenamine) 60:40 ⁇ 100 NS NS NS
- the size ofthe hydrophilic group influences the stability and viscosity even within the group of mixed emulsifiers which produce stable systems. For example, as the degree of ethoxylation increases, the hydrophilic group size increases and, in general, the peak viscosity decreases. For example, within the ceteth series (Brij 52-58) the maximum viscosity is 240,000cps for Ceteth-2 whereas Ceteth-20 had only a maximum viscosity of 60,000cps. Similar results were found for the steareth series (Brij 72-78) and the beheneth series (Nikkol BB series).
- a series of 15 formulations were prepared using a three component mixture design based on the results of Example 1.
- the following concentration ranges were investigated using a solvent ratio of 68:32 ethanol: water.
- formulae E and F were chosen for use as base systems to which a third emulsifier was added to further increase the viscosity.
- the third emulsifier was added at concentrations of 0.3, 0.8, 1.3 and 1.8% by weight keeping the ratio of Montanov 68 and Brij 72 at the ratios found effective in formulations E and F of Example 2 according to the following table:
- the solvent used was 68:32 ethanol:water.
- the formulations were prepared and subsequently tested for stability and viscosity.
- the third co-emulsifiers used were behenyl alcohol (Lanette 22, Henkel Co ⁇ .) and stearamide diethanolamine (Lipamide S, Lipo Chemical of Paterson, New Jersey). The following viscosity results were found:
- Example 4 Effect of Shear on Viscosity and Stability Formulation C from Example 2 was used as a base system to test the effect of varying levels of shear on the resulting viscosity and stability ofthe compositions.
- the thickener and the solvent were heated to 75°C in separate containers.
- the solvent was added to the emulsifiers rapidly and the composition mixed as described below:
- a hand shaken for less than 1 minute B ⁇ hand shaken for less than 1 minute, sealed and placed on a roller for 4 hours at 50
- This example investigated the effects of adding various polymers ((1) polymers containing pendant alkyl groups and (2) linear and soluble in the solvent and (3) crosslinked and swellable in the solvent) to a thickener system.
- the polymers used were:
- Crodacel QS Crodacel QS (Croda, Inc. of Parsippany, New Jersey)- Stearyldimonium hydroxypropyloxyethyl cellulose
- Quatrisoft LM-200 Stearyldimonium hydroxypropyloxyethyl cellulose
- the polymers were added to the formulations at levels of 0.1, 0.25, 0.37, 0.5 and 0.75% by weight according to the following table:
- Example 2 The formulations were prepared as in Example 1 except the polymers were added to the solvent (68:32 ethanol:water by weight) prior to mixing. Note that formula number refers to weight percent polymer. If the polymer was supplied in water, the water in the solvent system was corrected to reflect the exact formulation shown above. The results are shown below:
- Crodacel QS with pendant stearyl groups has a synergistic effect on the viscosity ofthe composition. This is evident since the polymer itself contributes little thickening. Crodacel QS is supplied as a 20% aqueous solution and at concentrations under 1% by weight the viscosity of this polymer in 68:32 ethanol: water is less than 50cps. It is believed that this polymer associates with the thickener system in the formulation. The Quatrisoft polymer also contributed to thickening the formulations. The Crodacel QS and Quatrisoft polymer formulations with the peak viscosity were prepared again except that the polymer was added to the thickener system after the composition was prepared and cooled to room temperature.
- a preferred method of preparing the formulations is adding the polymer to the hot solvent before adding the thickener system so that the polymer and emulsifiers can interact while above the melt temperature.
- the Crodacel formulations were also found to be stable, showing no separation.
- Example 1 The procedure of Example 1 was used to prepare the formulations except emollients were either added to the hot solvent or the thickener system prior to mixing. Glycerine and Quamectant were added to the solvent. Other emollients were added to the thickener system. The viscosity results are shown below:
- sodium borate was added to a premade alkylpolyglucoside thickener composition. It is believed that the borate ion associates with adjacent polyglucose hydrophilic head groups to hold them in the "micelle" structure thus elevating the melt temperature.
- a solution of sodium borate in water was added to a concentration of 0.7% by weight to the formulation of Example 6A containing Fitoderm squalane. The resulting formulation with sodium borate was visibly thicker with a higher melt temperature. The sample without borate melted rapidly when dispensed into the palm of a hand. The sample with borate did not melt when dispensed into the hand.
- the base formulation was prepared according to Example 1 with the Crodacel QS added to the solvent system prior to mixing.
- the borate solutions were added to yield the weight percent borate shown in the table below after the thickener system had cooled to room temperature. The following observations and melt temperatures were recorded:
- Formulations containing 7% Montanov 68, 1.76% Brij 76, 0.5% Crodacel QS polymer (on a solids basis) were prepared in accordance with Example 5.
- percent solvent was held constant at 90.74% but the ratio of ethanol: water was varied from 50:50 to 68:32.
- the melt temperature was measured as described above.
- Example 9 Antimicrobial Efficacy of Compositions Containing Chlorhexidine Gluconate
- the following thickener systems were produced with and without chlorhexidine gluconate (CHG) to determine if the CHG is effectively delivered in a thickener system.
- CHG chlorhexidine gluconate
- the borate pH 5 solution from Example 7 was used.
- MIC Minimum Inhibitory Concentration
- Example 11 A Presurgical Antimicrobial Hand Lotion Using an Alkylpolyglucoside Containing Thickener System
- the resulting formulation had an ethanol:water ratio of 68:32. This formulation was applied to hands repeatedly throughout the day by several volunteers. Hands were washed with Ivory soap between applications. The feel of the lotion was well received and skin condition was maintained.
- Example 12 Alkylpolyglucoside/Polyethoxylated alkyl alcohol/Ester of Short Chain Alcohol/Amine Oxide/Quaternary Amine Thickener Systems
- compositions were prepared by heating separately the solvent (alcohol and water) and the thickener system to 70°C.
- the solvent was rapidly added to the thickener system and homogenized on a Silverson L4R homogenizer. This was followed by 10 minutes of stirring with an overhead inverted "T" paddle stiner with the glass container immersed in a 10-15 °C water bath.
- Compositions A-C were mixed for 10 minutes while C and D were mixed for 4 and 5 minutes respectively.
- the compositions were then cooled to allow the emulsifiers to solidify.
- Kemester 9022 methyl behenate, Witco, Humko Chemical Div. Memphis
- compositions A, B, and C were viscous creams with little elasticity. Visually, sample C was more viscous than B which was more viscous than A. This shows that the amine oxide contributed to the viscosity ofthe compositions.
- Compositions D and E were very viscous and quite elastic in nature. Composition E was significantly thicker. This shows that this quaternary amine contributed to a more elastic composition.
- Samples F and G were opaque white creams of good consistency. Sample G was more viscous than Sample F. Sample F had some syneresis.
- composition A B C D E F G
- Example 13 Long Chain Alkylpolyglucoside/Polyethoxylated alkyl alcohol/Quaternary Amine Thickener System
- a series of 10 formulations were prepared using a three component mixture design with the total emulsifier level fixed at 2% by weight.
- the following concentration ranges were investigated using a solvent ratio of 68:32 ethanol:water further containing 0.5% by weight CHG.
- Eassi 624MP is an alkylpolyglucoside prepared from an alcohol feed stock of 92% by weight behenyl alcohol and was obtained from Seppic Inc., Fairfield, NJ. The product had a melting point of 83°C and a 5% aqueous solution had a pH of 6.4.
- Each formulation was prepared by adding 49 grams solvent at 80°C to 2 grams thickener system at 80°C followed by 45 seconds of homogenization followed by 3 minutes of overhead mixing while immersed in a 15°C water bath. The samples were subsequently diluted to 2% solids by adding 49 grams solvent mixture. Each composition was subsequently tested for viscosity and Tm. The viscosities ofthe resulting formulations ranged from less than 165,000 cps to 309,000 cps. Examples of several prefe ⁇ ed formulations appear below: Sample 1
- Tm (°C) >57°C 52-57 52 52-57 44 52-57
- Example 14 Disinfectant Hand Lotion based on Alkylpolyglucoside
- Disinfectant hand creams/lotions were prepared based on the thickener system of Example 13F.
- the compositions are shown below:
- Silwet 7001 a methyl terminated polyether pendant silicone copolyol having a polyethylene oxide/polypropylene oxide ratio of 40/60 and a molecular weight of
- ***Arcol PPG-725 polypropylene glycol having a molecular weight of approximately 750, Arco Chemical Co.
- 'DC344 D4, D5, cyclodimethicone available from Dow Corning, Midland, MI.
- compositions were prepared by heating the solvent and Silwet to
- Example 15 The formulations for Example 15 (as described in the table below) were prepared by heating the thickener system and the solvent in separate jars to 75°C, rapidly adding the solvent to the thickeners, shaking vigorously, and stirring with an overhead stirrer for 10 minutes while immersed in a 10-15°C water bath. The Tm was measured as described above.
- Samples A, B and C produced stable compositions of varying viscosity. Visual observation showed that sample A had a higher viscosity than B which was higher than C.
- a longer polyglycerol chain length is preferred in this thickener system and even though the longer chain polyglycerol emulsifier is expected to be more soluble in the solvent system, it increased the Tm ofthe formulation.
- Samples A and B were homogenous viscous translucent almost gel ⁇ like compositions. Sample B had a fairly nice feel but was a little tacky.
- Example 17 Polyglycerol ester/Amine Oxide/Quaternary Amine Thickener Systems
- compositions were prepared as described in Example 15. The viscosity (Tm) was measured for each sample.
- Samples C and D returned to a uniform appearance after heating above the melt temperature and allowing to slowly cool.
- compositions were prepared by heating the thickener system and solvent in separate jars to 80°C, rapidly adding the solvent to the thickener, homogenizing for 20 seconds, and stirring with an overhead stiner for 10 minutes while immersed in a 10-15°C water bath. The Tm and viscosity were measured for some ofthe samples.
- Samples B-D produced homogenous compositions of low viscosity.
- Sample A was an opaque viscous cream with a fairly high melt temperature.
- Samples E-H were lower in viscosity and melt temperature than Sample A.
- Samples A and B did not produce stable homogenous compositions.
- Composition C and D produced viscous compositions but composition D appeared non-uniform.
- the melt temperature of Composition C was quite high.
- a series of 18 formulations were prepared using a three component mixture design.
- the total thickener level varied from 2.45 to 4.55% by weight.
- the following concentration ranges were investigated using a solvent ratio of 68:32 ethanol:water.
- compositions were prepared by heating the thickener system and the solvent in separate jars to 75°C, rapidly adding the solvent to the emulsifiers, shaking vigorously, and stirring with an overhead stiner for 5 minutes while immersed in a 10-15°C water bath.
- the melt temperature (Tm), viscosity and stability were measured as described above. All ratios produced stable compositions having a viscosity range of 10,000-270,000cps and a Tm of 45-47°C.
- Elasticity was measured by gently stirring the sample and was judged on a scale of 1-5 where 5 was a very stringy composition and 1 was viscous but not elastic. A few ofthe compositions prepared are shown below:
- composition D is a prefe ⁇ ed formulation since it is high in viscosity at low total solids content (2.83%), has very little elasticity and a high melt temperature.
- This composition was stable with a nice viscosity and a Tm of 41°C.
- compositions were prepared by separately heating the solvent and the thickener system to 65-70°C.
- the solvent was rapidly added to the thickener system followed by stirring with an overhead paddle stiner with the glass container immersed in a 10°C water bath.
- Each composition was mixed for 4.5 minutes after which the compositions cooled sufficiently for the emulsifiers to solidify. All three compositions were viscoelastic.
- the samples appeared pearlescent with macroscopically obvious crystalline regions.
- the crystals appeared macroscopically lamellar in nature. A small amount of syneresis was seen on standing at 23 °C overnight.
- the Tm of sample C was approximately 47°C. (The sample did not melt uniformly and even at 47°C still had some solid regions.)
- compositions were prepared by heating the thickener system and the solvent in separate jars to 75°C, rapidly adding the solvent to the thickener, homogenizing for 40 seconds on a Silverson L4R homogenizer at maximum speed, and stirring with an overhead stiner for 5 minutes while immersed in a 10-15°C water bath.
- Tm, viscosity and stability were measured. Only select ratios produced high viscosity stable compositions having a viscosity range of 76,000-274,000 cps and a Tm of 47-53°C. Stability was measured according to Example 1.
- Several of the formulations are shown below:
- composition C is a particularly prefened formulation since it has a high viscosity, high melt temperature, and little separation. After standing for 1-2 days at 23 °C, all ofthe above formulae showed a small amount of syneresis, i.e. a small amount of clear low viscosity solvent phase separated on the top ofthe sample.
- Oleyl alcohol was incorporated into the formulation shown in Example 22C by adding it to the molten thickeners prior to mixing with the solvent.
- the composition is shown below:
- Component Amount (grams)
- Example 24 Addition of Dialkoxy Dimethicone and Polyether-Polysiloxane Copolymers for Enhanced Stability
- Example 22 had very good viscosity, Tm, and stability properties but showed a slight amount of syneresis on standing. Surprisingly, adding a combination of dialkoxy dimethicone and polyether-polysiloxane copolymers ensured no syneresis and also provided a smooth non-waxy feel.
- the following system was prepared using the thickener ratios identified in Example 22C and the procedure of Example 22. The Abil wax2440 was heated with the emulsifiers while the Abil B88183 was heated in the solvent:
- Abil wax2440 dibehenoxypolydiemthyl siloxane available from Goldschmidt
- Abil B88183 dimethicone copolyol having a EO/PO ratio of 77/23 and a viscosity in water at 35% solids at 25C of 95mm2/sec available from Goldschmidt Chemical Corp., Hopewell, VA.
- the system was stable and showed no signs of syneresis even after 13 days of room temperature storage.
- the melt temperature ofthe base formulation is reduced compared to that of Example 22C most likely due to the increase in the level of ethanol in the solvent.
- Kemester 9022 1.00 0.52 1.00 0.50 1.00 0.51
- Example 25 Repeat Application of a Preferred Hand Lotion Composition
- the formulation was first evaluated in tactile testing by applying 2ml in the palm of one hand and rubbing the lotion thoroughly into both hands. This composition had good cosmetic properties. A panel of five volunteers then applied the lotion as described eight times a day in approximately 1 hour intervals after first washing with water and Ivory liquid soap (Procter and Gamble, Cincinnati, Ohio) and drying the hands thoroughly before each application. This was repeated for a total of 5 days and was conducted during the winter to exaggerate any potential drying effect. The lotion was rated positively in all cosmetic categories surveyed including overall feel, lack of oiliness, moisturization, smoothness during application, and feel while washing. Expert grading was used to judge the condition ofthe skin.
- the skin condition was evaluated initially and at the end of days 3 and 5 and results are shown in the table below.
- Example 26 Polyethoxylated Alcohol/Ester/Quaternary Amine Thickener System
- the following thickener system compositions were prepared by heating the solvent and the thickener system separately to 75°C.
- the solvent was added to the thickener system and homogenized on a Silverson L4R at maximum speed for 45 seconds followed by stirring with an overhead paddle stiner in a glass container immersed in a 20°C water bath.
- Each composition was mixed for 3 minutes and the compositions were cooled sufficiently to allow the thickeners to solidify.
- Unithox 450 is a polyethoxylated alkyl alcohol having an alkyl chain length of approximately 36 carbons and nine units of ethylene oxide having a molecular weight of 2125 available from Petrolite Specialty Polymers Group, Tulsa, OK.
- Formulation A produced a stable thick creamy composition having a Tm of 44-45°C.
- Formulations B and C were quite low in viscosity and Formulation D showed almost no increase in viscosity.
- Example 28 Alkylene Alcohol/Ester/Quaternary Amine Thickener System
- Formulation A was unstable and showed significant phase separation.
- Formulation B was homogenous and had very low viscosity.
- Formulation C was a viscous cream but showed some syneresis on standing.
- Formulation D was opaque and gel-like with a high viscosity and showed only a slight amount of syneresis.
- Composition A was translucent, fairly elastic and low in viscosity.
- Composition B was translucent, pearlescent, and fairly elastic but significantly more viscous then composition A.
- Compositions C and D were pearlescent, slightly opaque, and fairly elastic with higher viscosities.
- Example 30 Alkyl Phospholipid/Polyethoxylated Alkyl Alcohol Thickener System
- Phospholipid SV 1 (35% 1.08 0.81 0.54 0.27 solution in water)
- Viscosity (cps) ⁇ 100 ⁇ 100 6.170 4,590 ⁇ 100 ⁇ 100 6,300 29,400
- Phospholipid SV is a zwitterionic surfactant that is stearamidopropyl PG- dimmonium chloride phosphate (a stearyl derived phospholipid) also containing cetyl alcohol available from Mona Industries Inc. of Paterson, NJ.
- Behenylphospholipid is a behenyl derived phospholipid similar in composition to
- Samples A ,B, E and F were uniform and stable but had low viscosity.
- Samples C, D, G, and H were opaque and pearlescent with higher viscosity values.
- Example 28 The following formulations systems were prepared according to the procedure of Example 28. After measuring the viscosity, CHG was added as a 20% solution to a final concentration of 0.5% by weight. The viscosity was measured again one day later.
- Incronam B-40 behenyl betaine available from Croda Inc. of Parsippeny, NJ. Formulation A and B were opaque with some elasticity.
- Formulations C and D were similar but were more elastic. All formulations were homogenous after adding CHG and the CHG actually increased the viscosity ofthe formulations.
- Behenyl Lactate was prepared by reacting methyl lactate (Aldrich Chemical Company, Inc. of Milwaukee, WI) with Lanette 22 (behenyl alcohol, 90%, Henkel Corp. of Ambler, PA) in a transesterification reaction according to the following method: 0.2 g sodium hydride (60% in mineral oil) was added to 32.6 grams Lanette 22 at 70°C in a 3-neck 250ml glass flask purged with nitrogen and inserted with overhead stiner, Dean Stark trap, thermometer, and condenser. To this was slowly added 9.4g of methyl lactate and the contents were slowly heated to 160°C and held at that temperature for one hour. At this temperature over 2ml of methanol was collected. The contents were heated to 200°C with a nitrogen sweep to remove any volatile components. After approximately 15 minutes at 200°C the contents were cooled. Upon cooling the product crystallized and had a melting point of approximately 57°C.
- Behenyl lactate is a useful emulsifier for the purposes ofthe present invention.
- Behenyl lactate forms homogenous high viscosity emulsions in a variety of systems over a broad range of thickener ratios.
- sample A was low in viscosity
- Samples B-D formed very pearlescent viscoelastic compositions.
- Samples E-L formed very viscous gel-like compositions. The compositions are also stable to CHG addition.
- Example 33 Alkylene Monoglyceride/Ester/Amine Oxide thickener System
- the following thickener systems were prepared by heating separately the solvent and the thickener system to 75°C.
- the solvent was added to the thickener system rapidly followed by homogenization on a Silverson L4R at maximum speed for 15 seconds followed by stirring with an overhead paddle stiner in a glass container immersed in a 5-10°C water bath.
- Each composition was mixed for 3 minutes after which the composition cooled sufficiently for the emulsifiers to solidify.
- the viscosity was measured as described above.
- To each sample was then added CHG as a 20% solution in water to a final concentration of 0.5% by weight.
- the CHG was mixed in well using a spatula and the sample was allowed to equilibrate for 24 hours. The viscosity was then measured again.
- Glycerol monoeurucate 1 1.20 0.90 0.60 0.30
- Composition A was bluish translucent but had a low viscosity.
- Composition B was similar to A but much more viscous than Composition A. 97/00667 PC-7US96/08924
- Composition C was semi-opaque and even more viscous than Composition B.
- Sample D was opaque white with a fairly high viscosity.
- the following example illustrates the pseudoplastic rheology and shear sensitivity ofthe compositions ofthe present invention.
- the viscosity was measured as a function of shear rate using a Rheometrics Dyanamic Analyzer (RDA-II) with a 25mm cone/plate fixture with a cone angle of 0.1 rad at a temperature of 25°C. Entrapped air was removed from the samples prior to testing by centrifugation. The viscosity was measured in steady shear by keeping the rate of rotation constant. This was done over a shear rate range of 0.06 - 40 per second.
- the samples used for this testing were prepared according to Example 1, Sample A (Brij 78) and Example 32, Sample B. The following results were obtained:
- Example 25 90g ofthe formulation of Example 25 was charged to a glass pressure vessel at room temperature. To this was added 7g propane and 3g isobutane. The addition ofthe propellant resulted in a dramatic drop in viscosity. The viscosity appeared to be about the viscosity of water. The formulation appeared as a single emulsified opaque white liquid. After sitting for several days the propellant formed a separate phase but was easily reemulsified by shaking. The formulation produced a white foam.
- the samples were prepared according to the formulae outlined in the table below by placing all components in a 4-oz. jar. The jar was capped and heated to 65°C until all components were dissolved. The jar was then swirled to mix the components, removed from the heat and allowed to cool to ambient temperature. Viscosity measurements were taken as identified in the table. Separation tests were done as outlined in Example 3.
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Also Published As
Publication number | Publication date |
---|---|
AU6044596A (en) | 1997-01-22 |
JP4508294B2 (ja) | 2010-07-21 |
CA2224798A1 (en) | 1997-01-09 |
US20020127253A1 (en) | 2002-09-12 |
EP0833605A1 (en) | 1998-04-08 |
US20030211066A1 (en) | 2003-11-13 |
US20110110869A1 (en) | 2011-05-12 |
JP2009084283A (ja) | 2009-04-23 |
JPH11508252A (ja) | 1999-07-21 |
US5951993A (en) | 1999-09-14 |
EP1374847A1 (en) | 2004-01-02 |
AU715827B2 (en) | 2000-02-10 |
US6352701B1 (en) | 2002-03-05 |
US6562360B2 (en) | 2003-05-13 |
EP2322137A1 (en) | 2011-05-18 |
US20020142018A1 (en) | 2002-10-03 |
US6610315B2 (en) | 2003-08-26 |
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