Classifications

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  • 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
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
  • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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  • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
  • A61K47/22—Heterocyclic compounds, e.g. ascorbic acid, tocopherol or pyrrolidones
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  • A61K8/29—Titanium; Compounds thereof
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• • A—HUMAN NECESSITIES
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  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/35—Ketones, e.g. benzophenone
• • A—HUMAN NECESSITIES
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  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
  • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
• • A—HUMAN NECESSITIES
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  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
• • A—HUMAN NECESSITIES
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  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
• • A—HUMAN NECESSITIES
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  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
  • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
• • A—HUMAN NECESSITIES
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  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
  • A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
• • A—HUMAN NECESSITIES
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  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
  • A61K8/927—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of insects, e.g. shellac
• • A—HUMAN NECESSITIES
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  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
  • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
  • A61K8/9783—Angiosperms [Magnoliophyta]
  • A61K8/9789—Magnoliopsida [dicotyledons]
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  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
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• • A—HUMAN NECESSITIES
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• • A—HUMAN NECESSITIES
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  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
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• • A—HUMAN NECESSITIES
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• • A—HUMAN NECESSITIES
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• • A—HUMAN NECESSITIES
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  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
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• • A—HUMAN NECESSITIES
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  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q9/00—Preparations for removing hair or for aiding hair removal
  • A61Q9/04—Depilatories
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/45—Anti-settling agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
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  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/49—Solubiliser, Solubilising system
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring

Definitions

• This invention relates to personal care formulations that contain certain alkyl ketal ester compounds and to methods for the manufacture of the formulations.
• Personal care formulations are available in a wide range of formulation forms and are used in a wide variety of specialized applications. Because these various types of formulations differ enormously, as do the conditions under which they are used, the individual formulations tend to be formulated specifically for the end-use application for which they are intended. Further, the use of materials based on renewable resources is becoming of increasing interest as formulators redesign their formulations to meet environmental sensitivities of their consumer bases.
• the personal care formulations comprising an alkyl ketal ester having the structure
• a is 0 or an integer of 1 to 12
• b is 0 or 1
• R 2 a divalent C 1-8 group optionally substituted with up to 5 hydroxyl groups
• R 1 is C 1-6 alkyl
• an active agent selected from organic anti-aging agents, organic anti-acne agents, organic skin whiteners, organic ultraviolet light absorbers, organic tanning agents, organic anti-alopecia agents, antifungal agents, anti-dandruff active agents, antimicrobial agents, organic medicinals, depilatory compounds, hair dyes, organic insect repellants, and combinations thereof.
• a waxy personal care formulation comprising a wax, an emollient, and an alkyl ketal ester of structure I.
• a personal care formulation in the form of an emulsion comprises (i) a continuous phase and a disperse phase wherein the continuous phase or the disperse phase is an aqueous phase and the other is an oil phase; or at least two co-continuous phases wherein at least one of the co-continuous phases is an aqueous phase and at least one of the co-continuous phases is an oil phase; and wherein any of the foregoing oil phases comprises at least one of (a) a paraffinic, naphthenic or aromatic mineral oil, (b) a nonionic organic compound having a melting temperature of less than 45° C., a molecular weight of at least 190 Daltons, an amido or ester group, and an alkyl chain containing at least 8 carbon atoms, and a solubility in water of no greater than 1 part in 99 parts of water, (c) a nonionic organosilicone compound having a melting temperature of less than 45° C., and a solubility in water of no
• a personal care formulation comprises an alkyl ketal ester of structure I, and an additional cosmetically acceptable ingredient.
• alkyl ketal esters of Structure I are excellent formulatory ingredients that provide benefit in a wide number of personal care formulations.
• the alkyl ketal esters are excellent solvents for a wide range of materials, including active agents useful in personal care formulations. Many of them are at least partially miscible with water or other organic solvents, or both, as well as a wide range of somewhat hydrophobic materials as are commonly present in personal care formulations.
• the alkyl ketal esters have low volatility. Under normal conditions of manufacture, storage, and use, the alkyl ketal esters are not reactive with many of the other materials that are commonly found in personal care formulations.
• the alkyl ketal esters are useful in a wide range of personal care formulations, including formulations that contain various types of active agents as described below, as well as formulations that do not contain such active agents.
• the alkyl ketal esters can provide a range of benefits to the formulation. The particular benefits seen in any given formulation will depend on the particular ingredients and function of that formulation.
• the alkyl ketal esters of structure I can be used to enhance the solubility of an active agent in a personal care formulation.
• the alkyl ketal ester can be used as a cosolvent with water, as a compatibilizer with water and an organic solvent, as a cosolvent with an organic solvent, as an emulsifier, or a combination comprising of any of one or more of the foregoing.
• an individual ingredient can have more than one type of function, for example a given alkyl ketal ester could function both as a cosolvent and as a compatibilizer.
• the alkyl ketal ester can in some embodiments function as a cosolvent, together with water.
• Many alkyl ketal esters are good solvents for active agents and also have good miscibility in water.
• the presence of such an alkyl ketal ester can allow the concentration of the active agent to be increased, often without the presence of volatile organic compounds (VOCs) such as ethanol, isopropanol, acetone, ethyl acetate, and the like in the formulation. The result in some cases can be a more concentrated low VOC formulation.
• VOCs volatile organic compounds
• the alkyl ketal ester can also perform additional functions, such as compatibilization of aqueous and organic phases, compatibilization or solubilization of certain organic materials into an aqueous phase, emulsification of an oil phase into an aqueous phase or of an aqueous phase into an oil phase.
• the alkyl ketal ester can act as an emulsifier, compatibilizer, or solubilizer for ingredients other than the active agent, or as a co-emulsifier, co-compatibilizer, or co-solubilizer for ingredients other than the active agent, in particular if the alkyl ketal ester is highly water-soluble. Moreover, incorporation of the alky ketal ester can lead to a lighter, less greasy or heavy-feeling formulation, especially compared to many other naturally-derived ingredients.
• the alkyl ketal ester can in some cases function as a cosolvent, either with the alcohol or with an alcohol-water mixture.
• the alkyl ketal ester can in some cases permit an increase in the concentration of the active agent in an alcoholic or alcohol-water phase. In other cases, it can permit the proportion of the alcohol in the cosolvent mixture to be decreased, which has the benefit of reducing VOCs in the formulation and in some cases decreasing the drying effect the formulation has on the skin.
• the alkyl ketal ester can perform additional functions, such as compatibilization, solubilization, or emulsification. In some cases, the alkyl ketal ester can also lead to a lighter, less greasy or heavy-feeling formulation, as before.
• the alkyl ketal ester can in some cases permit the active agent to become dissolved in an aqueous phase, in some cases alone and in other cases in conjunction with one or more other cosolvents. This can in some cases allow a highly water-insoluble active agent to become incorporated into an aqueous-based solution or gel-type form. In some cases, mixtures of alkyl ketal esters having different solubility/solubilizing characteristics can be present in order to accomplish the dissolution of the active agent.
• the alkyl ketal ester can aid in dissolving or compatibilizing such an active agent into an organic phase, or to help compatibilize or emulsify an organic phase containing the active agent with an aqueous phase, forming in this case an emulsified formulation that can be, for example, a cream or lotion.
• the alkyl ketal ester in some cases can allow the level of emollient materials to be reduced or improve formulation feel characteristics.
• the alkyl ketal ester can in some cases aid mutually incompatible materials to be formulated into a stable formulation form.
• the alkyl ketal ester is a valuable ingredient in many emulsified formulations, such as lotions and creams, which include a water-in-oil or oil-in-water emulsion.
• the alkyl ketal ester in many cases can allow hydrophobic organic ingredients to be dissolved into an aqueous phase to produce clear formulations. In many cases, this can be achieved while reducing or eliminating other ingredients from the formulation. For example, volatile organic compounds or emulsifiers can be eliminated or used in reduced quantities.
• alkyl ketal ester can improve the feel of a cosmetic, giving the formulated formulation a lighter, less oily feel while preserving its function and performance. In many cases, formulation viscosity is reduced, which can contribute to the lighter and less greasy feel.
• the alkyl ketal ester is a good solvent for a wide range of materials, it is very useful for making concentrates, which can be let down into water, an alcohol or other diluent.
• alkyl ketal ester in some formulations, it allows the amount of water to be increased in otherwise highly hydrophobic formulations. This can provide a moisturizing function in some cases, or provide other benefits.
• lip care formulations particularly lipsticks, lip glosses, and lip balms, and cuticle balms which are based on waxes and other highly hydrophobic materials.
• the alkyl ketal ester permits up to 3%, up to 4%, up to 5%, or up to 10% by weight of water to be included in the lip care or cuticle care formulation, which can allow the lip care or cuticle care formulation to perform a hydrating function.
• this invention is a formulated personal care formulation comprising an alkyl ketal ester of structure I, and one or more active agent selected from organic anti-aging agents, organic anti-acne agents, organic skin whitening agents, organic ultraviolet light absorbing agents, organic tanning agents, organic anti-alopecia agents, antifungal agents and/or anti-dandruff agents, antimicrobial agents, organic medicinals, depilatory compounds, hair dyes, or organic insect repellants.
• active agent selected from organic anti-aging agents, organic anti-acne agents, organic skin whitening agents, organic ultraviolet light absorbing agents, organic tanning agents, organic anti-alopecia agents, antifungal agents and/or anti-dandruff agents, antimicrobial agents, organic medicinals, depilatory compounds, hair dyes, or organic insect repellants.
• the alkyl ketal ester forms part of a cosolvent mixture with water or with another organic solvent miscible with the alkyl ketal ester at the relative proportions thereof that are present in the formulated personal care formulation, and the active agent is dissolved in the cosolvent mixture.
• the active agents are present in amounts effective to achieve the desired activity, which can vary broadly, depending on the active agent and the product. Thus, an active agent can be present in the formulation in amounts as low as 0.001% by weight, 0.01% by weight, or 0.1% by weight, up to 30% by weight.
• the amount of water used in the formulation can also vary widely based on the active agent and the product, from anhydrous products as described above, to products have from 2 to 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, or 10% by weight of water, based on the total weight of the formulation.
• the formulated personal care formulation includes a compound selected from alpha-hydroxy acids such as lactic acid, 2-hydroxydecanoic acid, 2-hydroxyoctanoic acid and glycolic acid, beta-hydroxy acids such as beta-hydroxy salicylic acid, avobenzone, coenzyme Q10, benzoate-4-methylbenzylidene, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, mexoryl SX, drometrizole trisiloxane, octocrylene, octyl methoxycinnamate, ethylhexyl salicylate, oxybenzone, padimate O, p-aminobenzoic acid (PABA), phenylbenzimidazole sulfonic acid, sulisobenzone, titanium trolamine salicylate, salicylic acid, retinoic acid (including the all-trans isomer known as tretinoin),
• a personal care formulation includes a tanning agent such as dihydroxyacetone, erythrulose, dihydroxyacetone-ortho-ethyl-acetate, canthaxanthin, or afamelanotide. These compounds function as tanning agents, and personal care formulations containing them in sufficient quantities are effective tanning (skin darkening) formulations.
• a tanning agent such as dihydroxyacetone, erythrulose, dihydroxyacetone-ortho-ethyl-acetate, canthaxanthin, or afamelanotide.
• the personal care formulation includes a compound selected from minoxidil and 5-alpha reductase inhibitors such as dutasteride and ketoconazole. These compounds function as anti-alopecia (hair loss prevention) agents; accordingly, personal care formulations containing them are useful in some cases to prevent hair loss.
• a personal care formulation includes a compound selected from zinc pyrithione, selenium sulfide, clotrimazole, tea tree oil, or piroctone olamine. These compounds function as anti-fungal agents, and personal care formulations containing them in sufficient quantities are effective topical anti-fungal treatments (such as for Tinea pedis or Tinea cruris) and/or as anti-dandruff formulations.
• a personal care formulation includes a compound selected from an amphetamine, an antihistamine, methylphenidate, oxymetazoline, tetrahydrolzoline hydrochloride, or psilocybin. These compounds function as vasoconstrictors in some instances and personal care formulations containing them in sufficient quantities are effective as redness reducers (such as in eye drops and anti-redness or anti-puffing creams).
• a personal care formulation includes a compound selected from calcium thioglycolate, sodium thioglycolate, thioglycolic acid, ammonium thioglycolate, butyl thioglycolate, ethanolamine thioglycolate, glyceryl thioglycolate, isooctyl thioglycolate, isopropyl thioglycolate, magnesium thioglycolate, methyl thioglycolate, or potassium thioglycolate.
• These compounds function to modify hair fibers by breaking S—S bonds in keratin; personal care formulations containing them in sufficient quantities are used in depilatories, permanent waves, relaxers, hair straightening, and hair re-styling formulations.
• a personal care formulation includes a compound selected from aluminum zirconium tetrachlorohydrex gly, aluminum chlorohydrate, or aluminum chloride. These agents are anti-perspirants and personal care formulations containing these are often effective as deodorants and anti-perspirants.
• a personal care formulation includes a compound selected from resorcinol (“resorcin”), 1-napthol, p-aminophenol, p-phenylenediamine (and its salts), 4-amino-2-hydroxytoluene, and the like.
• resorcin resorcinol
• 1-napthol p-aminophenol
• p-phenylenediamine and its salts
• 4-amino-2-hydroxytoluene 4-amino-2-hydroxytoluene
• a personal care formulation includes a compound selected from phenoxyethanol, N,N-diethyl-m-toluamide, p-menthane-3,8-diol (active agent in the essential oil of lemon eucalyptus), nepetalactone (catnip oil), citronella oil, permethrin, neem oil, or bog myrtle extract.
• active agents are effective insect repellants; and personal care formulations containing these are often effective as insect repellants.
• the personal care formulation comprises from 0 or 0.001 to 15% by weight of water, specifically, 0 or 0.01 to 12 wt % by weight of water, 0.1 to 10% by weight water, 0.5 to 8% by weight water, or 1 to 5% by weight of water, each based on the total weight of the formulation.
• the personal care formulation is essentially anhydrous, containing no more than 3% by weight water, no more than 2% by weight water, more specifically no more than 1% by weight water.
• the amount of water can be 0%, as low as 0.001%, or 0.01%, or 0.1% by weight, each based on the total weight of the personal care formulation.
• a waxy formulation e.g., a lipstick, lip gloss, lip balm formulation, or a cuticle cream
• a waxy formulation e.g., a lipstick, lip gloss, lip balm formulation, or a cuticle cream
• the lipstick, lip gloss, lip balm, or cuticle cream formulation contains from 0.1 to 10% by weight water, specifically 0.5 to 5% by weight water, each based on the total weight of the persona care formulation.
• These formulations are in stick or other solid form.
• the alkyl ketal ester preferably is a partially or fully water-miscible alkyl ketal ester, as defined below, when the waxy formulation contains more than 0.1% by weight water.
• a formulated personal care formulation in the form of an emulsion in the form of an emulsion.
• the emulsion can have a continuous phase and a disperse phase, one of which is an aqueous phase, and the other of which is an oil phase.
• the emulsion can have at least two co-continuous phases, again wherein at least one of the co-continuous phase is an aqueous phase and at least one of the co-continuous phases is an oil phase.
• the oil phase contains at least one of (a) a paraffinic, naphthenic or aromatic mineral oil, (b) a nonionic organic compound having a melting temperature of less than 45° C., a molecular weight of at least 190 Daltons, an amido or ester group, an alkyl chain containing at least 8 carbon atoms, and a solubility in water of no greater than 1 part in 99 parts of water by weight; (c) a nonionic organosilicone compound having a melting temperature of less than 45° C. and a solubility in water of no greater than 1 part in 99 parts of water by weight; (d) a long chain alcohol; and (e) a wax.
• a paraffinic, naphthenic or aromatic mineral oil a nonionic organic compound having a melting temperature of less than 45° C., a molecular weight of at least 190 Daltons, an amido or ester group, an alkyl chain containing at least 8 carbon atoms, and a solubility in water
• the emulsion further comprises an alkyl ketal ester of structure I.
• the alkyl ketal ester can be present in a continuous phase, a disperse phase, in both a continuous phase and a disperse phase, or at the interface between a continuous and a disperse phase.
• Personal care formulations and products can take the physical form of solids (sticks, bars, powders, etc.), solutions (including solutions containing sufficient gallant or thickener to provide a gel-like consistency), ointments, dispersions (including pastes), or emulsions (including gels, liniments, lotions, creams, or the like). They can be sprayable, in particular the solutions, dispersions, and powders.
• the personal care products can be, for example, bath or shower products, including various hair and body cleaners; eye care products; cosmetics; a fragrance; treatment formulation, including a hair coloring formulation and a; a hair straightening or permanent wave formulation; a nail care formulation; an oral hygiene formulation, including toothpaste and mouthwash; a shave cream; a skin care formulation; a sun care formulation; a lip care formulation; an antiperspirant; or a foot care formulation.
• alkyl ketal esters useful herein include those having the general structure I
• a is 0 or an integer of 1 to 12, specifically 1 to 6, more specifically 1 to 4;
• b is 0 or 1;
• R 2 is a divalent C 1-8 group optionally substituted with up to 5 hydroxyl groups, specifically methylene, ethylidene (>CH—CH 3 ), >CH—CH 2 OH, >C(CH 3 )CH 2 OH, >C(C 2 H 5 )CH 2 OH, >C(CH 2 OH) 2 , >CH—CH(OH)—CH 2 OH, or >CH—(CHOH) 3 —CH 2 OH; and
• R 1 is C 1-6 alky, specifically a C 1-4 alkyl, more specifically a C 1-2 alkyl.
• Some compounds within the scope of Structure I contain one or more chiral carbon atoms, as is the case where b is 0 or R 2 is substituted; structure I does not distinguish among those possible stereoisomers and is intended to include all such stereoisomers.
• a is 1 to 4
• B is 0 or 1
• R 2 is >CH—CH 3 , >CH—CH 2 OH, >C(CH 3 )CH 2 OH, >C(C 2 H 5 )CH 2 OH, >C(CH 2 OH) 2 , >CH—CH(OH)—CH 2 OH, or >CH—(CHOH) 3 —CH 2 OH.
• the alkyl ketal ester When b is 0, the alkyl ketal ester includes a five-membered ring; when b is 1, it includes a six-member ring. In a specific embodiment b is 0.
• b is 0 and R 2 is one of methylene, ethylidene or >CH—CH 2 OH. In other embodiments, b is 1 and R 2 is methylene.
• R 1 contains 1 or 2 carbon atoms.
• Specific alkyl ketal esters include those corresponding to the reaction formulations of 1,2-ethylene glycol with the methyl, ethyl, n-propyl or n-butyl ester of levulinic acid; of 1,2-propylene glycol with the methyl, ethyl, n-propyl or n-butyl ester of levulinic acid; of 1,3-propane diol with the methyl, ethyl, n-propyl or n-butyl ester of levulinic acid; of glycerine with the methyl, ethyl, n-propyl, or n-butyl ester of levulinic acid; of trimethylolethane with the methyl, ethyl, n-propyl, or n-butyl ester of levulinic acid; of trimethylolpropane with the methyl, ethyl, n-propyl, or n-buty
• alkyl ketal esters include those having the following structures II-VI.
• An embodiment includes alkyl ketal esters of structure II
• R 1 is methyl, ethyl, n-propyl, or n-butyl.
• R 1 is methyl
• this structure is referred to herein as “methyl-LGK,” and corresponds to the reaction formulation of methyl levulinate with glycerine.
• Methyl-LGK is miscible with water in all proportions.
• R 1 in structure II is ethyl
• this structure is referred to herein as “ethyl-LGK,” or “Et-LGK” and corresponds to the reaction formulation of ethyl levulinate with glycerine.
• Ethyl-LGK is miscible in water in all proportions.
• Ethyl-LGK also dissolves or is miscible with a large number of hydrophobic and hydrophilic organic compounds to the extent of at least 20 parts of the organic compound in 80 parts of ethyl-LGK.
• organic compounds examples include methanol, ethanol, tetrahydrofuran, acetone, ethyl acetate, ethyl laurate, lauric acid, methylene chloride, toluene, acetic acid, low molecular weight poly(propylene glycol), and castor oil.
• n-propyl-LGK When R 1 in structure II is n-propyl, this structure is referred to herein as “n-propyl-LGK,” and corresponds to the reaction formulation of n-propyl levulinate with glycerine. n-Propyl-LGK is miscible with water to the extent of 1 part per 99 parts water.
• R 1 in structure II is n-butyl
• this structure is referred to herein as “n-butyl-LGK” or “Bu-LGK,” and represents the reaction formulation of n-butyl levulinate with glycerine.
• n-Butyl-LGK is miscible in water to the extent of 1 part per 99 parts of water. It dissolves or is miscible with various organic compounds to the extent of at least 20 parts of the organic compound in 80 parts of N-butyl-LGK.
• organic compounds include alcohols (including ethanol and 1,2-butylene glycol), organic esters (such as C 12-14 alkyl benzoates, isopropyl myristate and octyl palmitate), and many vegetable oils (including castor, corn, soy and safflower oils).
• alcohols including ethanol and 1,2-butylene glycol
• organic esters such as C 12-14 alkyl benzoates, isopropyl myristate and octyl palmitate
• vegetable oils including castor, corn, soy and safflower oils
• R 1 is methyl, ethyl, n-propyl, or n-butyl.
• R 1 is methyl
• the structure is referred to herein as “methyl-LPK” and corresponds to the reaction formulation of methyl levulinate with 1,2-propylene glycol.
• R 1 in structure III is ethyl
• this structure is referred to herein as “ethyl-LPK” or “Et-LPK,” and corresponds to the reaction formulation of ethyl levulinate with 1,2-propylene glycol.
• Ethyl-LPK is miscible in water to the extent of 2.5 parts in 97.5 parts of water.
• Ethyl-LPK dissolves or is miscible with a variety of organic compounds of varying hydrophilicity, to the extent of at least 20 parts of the organic compound in 80 parts of ethyl-LPK.
• organic compounds include, for example, methanol, ethanol, tetrahydrofuran, acetone, ethyl acetate, methylene chloride, toluene, cyclohexane, acetic acid, low molecular weight poly(propylene glycol), mineral oil, castor oil, canola oil, corn oil, and sunflower oil.
• n-butyl-LPK When R 1 in structure III is n-butyl, this structure is referred to herein as “n-butyl-LPK” or “Bu-LPK,” and represents the reaction formulation of n-butyl levulinate with 1,2-propylene glycol.
• n-butyl-LPK dissolves or is miscible with various organic compounds to the extent of at least 20 parts of the organic compound in 80 parts of N-butyl-LPK by weight. Examples of such organic compounds include alcohols (including ethanol and 1,2-butylene glycol), organic esters (such as C 12-14 alkyl benzoates, isopropyl myristate and octyl palmitate), and many vegetable oils (including castor, corn, soy and safflower oils).
• n-butyl-LPK dissolves or is miscible with water to the extent of about 99 parts of water to about 1 part of the part of the N-butyl-LPK by weight.
• R 5 is methyl, ethyl, n-propyl, or n-butyl.
• R 1 is ethyl
• this structure is referred to herein as “ethyl-LEK,” and corresponds to the reaction formulation of ethyl levulinate with 1,2-ethylene glycol.
• Ethyl-LEK is miscible in water to the extent of 5 parts per 95 parts of water by weight.
• R 5 is methyl, ethyl, n-propyl, or n-butyl.
• R 1 is methyl
• this structure is referred to herein as “Me-AcAcGK,” and represents the reaction formulation of methyl acetoacetate with glycerine.
• Et-AcAcGK represents the reaction formulation of ethyl acetoacetate with glycerine.
• Me-AcAcGK and Et-AcAcGK each are miscible with water in all proportions.
• R 1 is methyl, ethyl, n-propyl or n-butyl and R 3 is methyl or ethyl.
• Compounds according to structure VI correspond to the reaction formulation of trimethylolethane (R 3 is methyl) or trimethylolpropane (R 3 is ethyl) and a C 1-6 ester of levulinic acid.
• R 1 is ethyl, and R 3 is methyl
• this structure is referred to herein as “ethyl-LTMEK”
• R 1 is ethyl, and R 3 is ethyl
• this structure is referred to herein as “ethyl-LTMPK.”
• alkyl ketal esters of structures I-VI can be prepared by reacting an alkyl keto ester of structure VII
• ketoesters include C 1 -C 4 alkyl esters of pyruvic acid, acetoacetic acid, levulinic acid, ⁇ -ketobutyric acid, ⁇ -ketoisovaleric acid, 5-ketohexanoic acid, ⁇ -ketoisocaproic acid, 4-acetylbutyric acid, 2-ketopentanoic acid, 3-ketohexanoic acid, 4-ketohexanoic acid, 2-ketooctanoic acid, 3-ketooctanoic acid, 4-ketooctanoic acid, 7-ketooctanoic acid, 2-keto-4-pentenoic acid, and 2-oxo-3-butynoate.
• polyols include ethylene glycol, 1,2-propylene glycol, 1,3-propane diol, glycerine, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, or sorbitol, although reaction conditions must be controlled to produce the mono-derivatives of the last three compounds. This reaction can be performed in the presence of an acid catalyst. A preferred process is described in WO 09/032,905.
• the keto ester is a C 1 -C 4 alkyl ester of levulinic acid (4-oxopentanoic acid).
• Levulinic acid is an abundant feedstock that is prepared on an industrial scale by acidic degradation of hexoses and hexose-containing polysaccharides such as cellulose, starch, sucrose, and the like.
• Other preferred keto esters include C 1 -C 4 alkyl esters of pyruvic acid and acetoacetic acid.
• Especially preferred keto esters include ethyl levulinate, n-propyl levulinate, and n-butyl levulinate.
• miscible and its variations (“miscibility”, “compatibility”, and the like) are used herein as a synonym for “soluble”, i.e., a mixture of the materials by themselves form a “true” solution, in which one material is molecularly dispersed in the other, or in which one material is dispersed as droplets which have a longest dimension of less than 200 nm, such that the mixture is optically clear.
• the longest dimension is a “radius of gyration.”
• a material that is “miscible” or “fully miscible” in another, without further qualification, is miscible with that other material in all proportions, i.e., in mixtures that contain the two components by themselves in all weight ratios from 99:1 to 1:99.
• a fully miscible alkyl ketal ester is soluble in another material, such as water, at all proportions from 99:1 to 1:99.
• a partially miscible alkyl ketal ester is immiscible in another material in proportions from greater than 30 parts of the alkyl ketal ester in 70 parts or less of the other material and miscible in other combinations.
• a sparingly miscible alkyl ketal ester is immiscible in another material or miscible in another material to the extent of less than 10 parts in 90 parts of the other material.
• a material is “immiscible” in another if it is not soluble by itself in that material to the extent of at least 1 part per 99 parts of the other. Unless stated otherwise, miscibility is assessed at 25° C.
• the foregoing alkyl ketal esters can be classified as fully water-miscible, partially water-miscible, or sparingly water-miscible.
• macroscopically uniform it is meant that the formulation is uniform when viewed at a length scale of at least 10 micrometers.
• alkyl ketal ester for a particular personal care formulations will depend at least in part upon the function that the alkyl ketal ester is expected to perform in the formulation, as well as the other ingredients of the formulation. For example, when the alkyl ketal ester is present to solubilize an active agent into an aqueous phase, a partially- or fully-water miscible alkyl ketal ester is selected. If the active agent is highly hydrophobic, a mixture of a partially- or fully-water miscible alkyl ketal ester with a sparingly water-miscible alkyl ketal ester can be used.
• the alkyl ketal ester When the alkyl ketal ester is present to solubilize an active agent into an alcoholic phase or an alcohol/water mixture, the alkyl ketal ester is preferably miscible in the alcohol to the extent of at least 10 parts of the alkyl ketal in 90 parts of alcohol by weight, specifically 30 parts of the alkyl ester in 70 parts by weight of the alcohol, and can be fully miscible in the alcohol.
• Alkyl ketal esters that are fully or partially soluble in the alcohol can be present in a mixture with one or more alkyl ketal esters that are only sparingly soluble in the alcohol.
• the alcohol/miscible alkyl ketal ester mixture can function as a cosolvent mixture in which the sparingly soluble alkyl ketal ester is dissolved, such as the case of Et-LPK in a mixture of Et-LGK/1,3-propanediol/water.
• That other material can be organic compound that is not very soluble in the alcohol, such as a fat or oil, or as shown in one of the examples, a polymer such as polymethylmethacrylate.
• the alkyl ketal ester performs a compatibilization and/or emulsification function, such as to compatibilize or emulsify aqueous and oil phases in an emulsion.
• the alcohol in such an alcoholic phase or alcohol/water mixture is a lower alcohol as described under section (m) below, and is preferably ethanol, 1,2-propylene glycol, glycerol, or 1,3-propane diol.
• the alkyl ketal ester When the alkyl ketal ester is present to dissolve an active agent into an oil phase, the alkyl ketal ester can be a water-immiscible ketal, a partially-water miscible type or a sparingly water-miscible type. It is also possible in some cases to use fully-water-miscible types in that instance.
• the alkyl ketal ester is preferably a fully water-miscible type such as methyl-LGK, ethyl-LGK, methyl-AcAcGK, or a mixture of one or more of them with a partially water-miscible alkyl ketal ester and/or a sparingly soluble alkyl ketal ester such as propyl-LGK, ethyl-LPK, ethyl-LEK and the like.
• a partially water-miscible alkyl ketal ester and/or a sparingly soluble alkyl ketal ester such as propyl-LGK, ethyl-LPK, ethyl-LEK and the like can also be used in aqueous solutions at concentrations beyond their miscibility limits if another water miscible co-solvent is present, for example ethanol, isopropanol, or the like.
• Formulations that take the form of alcohol or alcohol-water solutions in which an active agent is dissolved can contain, such as in the case of ethanol and 1,2-propylene glycol, fully water-miscible alkyl ketal esters, partially water-miscible alkyl ketal esters, sparingly water-miscible alkyl ketal esters, or mixtures thereof.
• the alcohol is 1,3-propane diol
• at least partially water-miscible alkyl ketal esters are preferred, as these tend to be more soluble in 1,3-propane diol.
• Partially and fully water-miscible alkyl ketal esters can form a single-phase solution with ethanol, 1,2-propylene glycol, and/or 1,3-propane diol, into which additional active agents can be dissolved, or an organic phase can be dispersed.
• a sparingly water miscible ketal can be used with 1,3-propane diol and water when combined with coupling agents, like ethanol or a fully-water miscible alkyl ketal ester.
• Gels containing alcohol or alcohol-water solutions in which a gel is suspended can similarly contain fully water-miscible alkyl ketal esters, partially water-miscible alkyl ketal esters, sparingly water-miscible alkyl ketal esters, or mixtures thereof, depending on the alcohol used as described above for alcohol and alcohol-water solutions.
• the alcohol water-solutions can contain from 1 to 99%, 20 to 80%, 30 to 70%, or 40 to 60% by weight of the alcohol and correspondingly from 99 to 1%, 80 to 20%, 70 to 30%, or 60 to 40% by weight of the water, based on the weight of the alcohol and the water.
• Formulations in the form of an emulsion of an oil phase and an aqueous phase can contain a fully water-miscible alkyl ketal ester such as methyl-LGK, ethyl-LGK, methyl-AcAcGK, or partially water-miscible type or a mixture of one or more of them with a sparingly soluble alkyl ketal ester such as propyl-LGK, ethyl-LPK, ethyl-LEK and the like.
• Formulations in which the alkyl ketal ester is present in an oil phase can contain a partially or fully water-miscible alkyl ketal ester, a sparingly soluble alkyl ketal ester such as propyl-LGK, ethyl-LPK, n-butyl-LPK, ethyl-LEK and the like, or a mixture of one or more of a sparingly water-miscible alkyl ketal ester with a partially- or fully-water miscible alkyl ketal ester.
• a sparingly soluble alkyl ketal ester such as propyl-LGK, ethyl-LPK, n-butyl-LPK, ethyl-LEK and the like
• a sparingly soluble alkyl ketal ester such as propyl-LGK, ethyl-LPK, n-butyl-LPK, ethyl-LEK
• Waxy formulations such as lip balms or other hydrophobic formulations in which the alkyl ketal ester is called upon to compatibilize water or another polar compound, such as glycerol, into the formulation typically include a fully water-miscible of alkyl ketal ester such as methyl-LGK, ethyl-LGK, methyl-AcAcGK, or partially water-miscible type, but can also include a sparingly-miscible type.
• compositions are combinations of two or more of the foregoing formulation forms.
• some personal care formulations contain an aqueous phase that contains a dissolved active agent, and further includes an oil phase which can be present, for example, to supply emollients and/or humectants, or to produce a specific formulation form (cream, lotion and the like).
• oil phase which can be present, for example, to supply emollients and/or humectants, or to produce a specific formulation form (cream, lotion and the like).
• a fully-water-miscible alkyl ketal ester might be present in the aqueous phase to help dissolve the active agent
• a partially- or sparingly water-miscible alkyl ketal ester might be present within the oil phase to reduce its viscosity or compatibilize its components.
• Either of these alkyl ketal esters can also perform some emulsifying or compatibilizing function between the aqueous and oil phases.
• a single alkyl ketal ester can perform multiple functions within a personal care formulation, such as dissolving an active agent into an aqueous or oil phase, compatibilizing or emulsifying an aqueous phase with an oil phase, etc.
• the alkyl ketal ester can reside in an aqueous phase, in an alcoholic or alcohol-water phase, or in an oil phase of a personal care formulation, depending on the particular formulation and the particular alkyl ketal ester.
• an alkyl ketal ester can become distributed between aqueous and oil phases of a personal care formulation, due to its solubility in both phases.
• the alkyl ketal ester can reside at the boundary of aqueous and oil phases.
• the amount of alkyl ketal ester present in a personal care formulation depends on the function of the alkyl ketal ester, the other ingredients of the personal care formulation, the specific form of the personal care formulation, and like considerations.
• the formulation comprises 0.001 to 90%, 0.01 to 80%, 0.1 to 70%, or 0.1 to 50% by weight of the alkyl ketal ester based on the total weight of the formulation, although a more typical amount is from 0.5 to 25% by weight, and in many cases from 1 to 10% by weight of the total formulation weight.
• Anti-aging, anti-acne, skin whitening and sun protection formulations can contain 0.001 to 50% of the active agent, specifically from 0.01 to 40% by weight, based on the total weight of the formulation.
• Anti-aging and anti-acne formulations typically are formulated into aqueous and/or ethanolic solutions, or into lotions or creams.
• Sun protection formulations can take the form of clear, low viscosity liquids (as is typical for spray-on formulations, which are often ethanolic or ethanol-water based), or else are lotions or creams.
• Spray-on sun protection formulations typically are aqueous and/or ethanolic solutions or dilute emulsions.
• anti-aging, anti-acne, skin whitening and sun protection active agents are soluble to the extent of at least 5 parts per 95 parts of the alkyl ketal ester in the formulation.
• these include, for example, avobenzone, coenzyme Q10, hydroquinone, oxybenzone, and salicylic acid, all of which are soluble to the extent of at least 5 parts per 95 part of ethyl-LGK, ethyl-LPK, n-Bu-LGK, or a combination thereof.
• the presence of the alkyl ketal ester often allows the amount of ethanol to be reduced, and/or the amount of active agent to be increased at a constant ethanol content, leading to a formulation which is less drying to the skin.
• the ketal may be used to replace a heavy-feeling material that solubilizes the active.
• Some of these active agents such as benzoyl peroxide, resveratrol, glycolic acid, and retinoic acid, tend to have lower solubilities in many alkyl ketal esters, such as ethyl-LGK and ethyl-LPK.
• the alkyl ketal ester can have less of a solubilizing function and can instead (or in addition) function to improve the feel of the formulation or to compatibilize other materials, such as emollients, into the formulation.
• the usage level of the active is well within the solubility range of the active in the ketal, even at the low solubility end.
• Retinoic acid for instance, is commonly used at 0.2% or less in the formulation.
• An anti-aging, anti-acne, skin whitening, or sun protection formulation can contain additional UV absorbing agents, notably inorganic compounds such as titanium dioxide or zinc oxide. These materials are solid particles that typically are dispersed into a lotion or cream formulation.
• Sun protection formulations such as sunscreens often contain a mixture of organic UV absorbing agents, often in order to broaden the range of wavelengths of UV light that are absorbed.
• Such mixture of organic UV agents can include two or more of avobenzone, octylmethoxyl cinnamate, oxybenzone, and ethylhexyl salicylate. These may, in the aggregate, constitute from 0.1 to 50% of the weight of the sunscreen formulation, and more preferably constitute from 2 to 25% by weight thereof.
• a tanning formulation typically contains from 1 to 25%, preferably from 2 to 10% by weight of one or more tanning agents as described before.
• Tanning formulations often are formulated into a lotion or a cream.
• Spray-on tanning formulations are typically aqueous and/or ethanolic solutions.
• a tanning formulation can contain organic UV active agents, as described before, as well as inorganic UV active agents such as titanium dioxide or zinc oxide.
• organic UV active agents can constitute from 0.1 to 50%, specifically 0.1 to 30% of the weight of a tanning formulation, and more specifically from 2 to 25% by weight thereof.
• a mixture of organic UV additives can be present, including a mixture of two or more of avobenzone, octylmethoxyl cinnimate, oxybenzone, and ethylhexyl salicylate.
• Anti-dandruff formulations typically contain from 0.1 to 25%, specifically from 0.5 to 10% by weight of one or more of an anti-fungal agent as described before.
• the formulation form is typically an aqueous solution, aqueous gel, or dilute emulsion containing mostly aqueous phase.
• An anti-dandruff formulation typically contains one or more surfactants, particularly one or more anionic surfactants.
• Sulfosuccinate, lauryl sulfate, and laureth sulfate surfactants and the various fatty acid betaines, or fatty acid amide propyl betaines are preferred types, although others, particularly other anionic surfactants, can be used.
• Surfactants can constitute from 0.1 to 10% by weight of an anti-dandruff formulation.
• the surfactants can function as cleaning agents and/or emulsifiers in the formulation.
• An anti-dandruff agent can contain hair conditioners and other materials as well.
• Anti-alopecia formulations typically contain from 0.1 to 25%, preferably from 1 to 10% of one or more of anti-alopecia agents.
• Formulations of these types typically are formulated into low to medium viscosity fluids, which can contain a propellant and be sprayable, which can be clear solutions in the case of anti-alopecia formulations or opaque emulsions in the case of anti-dandruff formulations.
• These formulations often contain propylene glycol, ethanol, and/or water as a cosolvent mixture, although an advantage of this invention is that levels of propylene glycol and/or ethanol can in some cases be reduced due to the presence of the alkyl ketal ester.
• Chemical treatment formulations for hair include hair straighteners, relaxers, and/permanent wave formulations can contain one or more materials which straighten hair, possibly by breaking sulfur-sulfur bonds in keratin or some other component of hair; among these are the depilatory agents described before. They typically constitute up to 10% by weight of a chemical treatment active agent for hair.
• Chemical treatment formulations for hair can take the form of low viscosity fluids, lotions, creams, or gels.
• a hair styling formulation typically will contain one or more hair fixatives, which hold the hair into a re-styled position.
• the hair fixatives are typically polymeric materials including those indicated under section (g)(1) below. Some of these fixatives can also function as thickeners in a hair straightening and styling formulation.
• the hair fixative typically constitutes from 0.25 to 25 preferably from 0.5 to 15, weight percent of the formulation.
• the hair styling formulation can take the form of an aqueous and/or ethanolic solution, a gel, or a lotion.
• Anti-perspirant formulations contain one or more anti-perspirant agents such as described before. Anti-perspirant formulations typically take the form of a gel, a viscous liquid (for roll-on applications), or a stick.
• a stick or roll-on anti-perspirant typically contains some water, which can constitute from 2 to 60% of the weight of the formulation, and at least 5%, up to 30% by weight of the anti-perspirant agent.
• a topical medicinal formulation can contain one or more medicinal agents such as an amphetamine, antihistamine, methylphenidate, oxymetazoline, tetrahydrolzoline hydrochloride, psilocybin, clotrimazole, tea tree oil, piroctone olamine, chlorhexidine, octenidine, triclosan, sodium 3,5-dibromo-4-hydroxybenzenesulfonate (Dibromol), quaternary ammonium salts such as benzalkonium chloride, cetyl trimethylammonium bromide, cetylpyridinium chloride, and benzethonium chloride, and the like.
• medicinal agents such as an amphetamine, antihistamine, methylphenidate, oxymetazoline, tetrahydrolzoline hydrochloride, psilocybin, clotrimazole, tea tree oil, piroctone olamine, chlorhexidine, octenidine
• Low viscosity fluids which can be sprayable
• Gels are typically aqueous and/or ethanolic
• lotions and creams are typically emulsions containing an aqueous continuous phase and a dispersed or co-continuous phase that contains an emollient.
• Hair dye formulations can include hair dyes such as those described above.
• Hair bleaching formulations can contain a peroxy-type bleaching agent such as hydrogen peroxide.
• the dyes and/or bleaches typically constitute from 0.1 to 5% of the total weight of the formulation in the case of dyes; and from 1 to 20% in the case of bleaches.
• a bleaching formulation can in addition contain an inorganic oxidant such as a persulfate salt, in an amount from 0.1 to 5% by weight.
• Hair dye and bleaching formulations can take the form of low viscosity fluids, lotions, creams, or gels. They can also be prepared in a water-dilutable concentrate form.
• a hair dye or bleaching formulation can contain one or more surfactants which can function to stabilize the emulsion, or as a detergent.
• Depilatory formulations can contain one or more depilatory agents such as those described before. They typically constitute from 1 up to 20% by weight of a depilatory agent. Depilatory formulations often take the form of lotions, creams, or gels.
• An insect repellant formulation comprising an alkyl ketal ester of structure I.
• An insect repellant formulation can contain insect repellants such as phenoxyethanol, N,N-diethyl-m-toluamide, p-menthane-3,8-diol (active agent in the essential oil of lemon eucalyptus), nepetalactone (catnip oil), citronella oil, permethrin, neem oil, or boy myrtle extract. These can constitute from 0.25 to 50% of the total weight of the insect repellant formulation.
• Insect repellant formulations often take the form of low viscosity fluids (which can be sprayable), or lotions.
• a low viscosity insect repellant typically is aqueous and/or ethanolic; water and/or ethanol can constitute up to 98% or more of the weight of such formulations.
• a waxy solid formulation that contains a wax, an emollient, and an alkyl ketal ester of structure I is provided.
• the waxy solid formulation can contain from 0.5 to 20%, 15%, 10%, 8%, 5%, 4%, or 3% by weight water.
• These formulations can be provided in stick or other solid form. They typically contain at least 20% by weight of an oil such as castor oil, a wax (as defined below) and at least 0.5% by weight of an alkyl ketal ester of structure I.
• the alkyl ketal ester can be present in an amount up to 25%, 20%, 15%, or 10% by weight of the formulation.
• the alkyl ketal ester can be a partially or fully water-miscible alkyl ketal ester, as defined below, when the waxy solid formulation contains more than 0.5% by weight water.
• Such formulations include lip formulations such as a lipstick, lip gloss, or lip balm; cuticle creams; and the like.
• waxy formulations include a mixture of one or more waxes with one or more oils and, in the case of lipsticks, one or more pigments.
• Lipsticks and lip balm formulations, as well as cuticle creams, tend to be malleable solids at 25° C., whereas lip glosses tend to be viscous liquids or pastes.
• These formulations are normally characterized as being anhydrous, i.e., containing up to 3% by weight of water.
• a lip care formulation can contain, for example, from 1 to 30% by weight of a wax; from 30-95% by weight of one or more other hydrophobic materials, of which castor oil is typically an important component; and from 1 to 30% by weight of one or more pigments.
• the lipstick or lip balm formulation contains an alkyl ketal ester that is partially or fully miscible with water.
• the presence of the alkyl ketal ester allows for some amount of water to be incorporated into the formulations, while retaining other needed properties such as the necessary rheological characteristics (including, in the case of lipsticks in particular, the ability to retain its stick form) and formulation stability. From 0.5 to 10% or more, preferably from 0.5 to 5% by weight water can be incorporated into a lipstick, lip gloss, or lip balm in this manner.
• the amount of the water-miscible alkyl ketal ester(s) can constitute from 1 to 25% by weight of a waxy formulation such as a lipstick, lip gloss, or lip balm formulation or cuticle cream.
• a waxy formulation such as a lipstick, lip gloss, or lip balm formulation or cuticle cream.
• the alkyl ketal ester is present in a part per part by weight water, if water is present.
• a partially or fully water-miscible alkyl ketal ester can permit water to be incorporated into other normally anhydrous personal care formulations to the extent of up to 10% or more by weight, without significant change in formulation form or function.
• emulsions can be water-in-oil types, oil-in-water types, or types containing co-continuous aqueous and oil phases.
• These formulations typically take the form of low viscosity fluids (in which the disperse phase, which is typically an oil phase, constitutes a small proportion, typically 35% or less or 10% or less by weight of the formulation), lotions, or creams.
• formulations include, for example, hair conditioners, after-shave lotions, various body cleansers, various hand and skin lotions and creams and the like, which do not contain specific active agents as described above.
• Emulsion formulations of these types typically contain from 0.1 to 50% by weight of an alkyl ketal ester of structure I.
• Emulsion formulations including any of the specific types of formulations described herein that have both an aqueous and an oil phase, such as creams, liniments, lotions, some gels, and mousses, typically contain a component selected from classes (a)-(e) below.
• the alkyl ketal ester can reside in the aqueous phase, in the oil phase, in both an aqueous and oil phase, or at the interface between the aqueous and oil phases.
• a lotion and a liniment are generally oil-in-water emulsions, but can be water-in oil emulsions.
• a lotion and a liniment can contain from 0.5 to 25% by weight of one or more materials selected from classes (a)-(e) below.
• a cream is also generally an oil-in-water emulsion, but can be a water-in-oil emulsion.
• a cream can contain from 2 to 80% or more of one or more materials selected from classes (a)-(e) below.
• a cream is an emulsion formulation which is easily deformable but not readily pourable at 25° C.; whereas a lotion is an emulsion formulation which is somewhat viscous (such as having a viscosity of at least 20 cps at 25° C.) but still readily pourable, and used in such a manner.
• Liniments are of similar viscosity to lotions, but are formulated to be applied using friction. Liniments are often formulated using alcohol, acetone, or similar quickly evaporating solvent.
• the alkyl ketal esters can advantageously be used to replace some or a portion of these solvents in a liniment.
• Mousses are generally colloidal dispersions of a propellant (e.g., a liquid propellant or gas) in a liquid or solid phase.
• a propellant e.g., a liquid propellant or gas
• personal care mousse formulations can contain from 5 to 95% by weight water based on the overall formulation, and can contain from 5 to 95% or more of one or more materials selected from classes (a)-(e) below, wherein an alkyl ketal ester can be substituted for the water or the other materials in amounts from 0.1 to 30% by weight, based on the overall weight of the formulation.
• the liquid phase can be in solution or emulsion form.
• the liquid phase of the mousse is an oil-in-water emulsion wherein water is the continuous phase.
• Mousses can also be prepared without water where a suitably volatile propellant is in solution with a viscous nonvolatile material containing the alkyl ketal ester.
• dispersions i.e., a combination of a particulate solid in a liquid or thixotropic liquid, for example a paste.
• a paste is generally a substance that behaves as a solid until a sufficiently large load or stress is applied, at which point it flows like a fluid.
• Dispersions such as pastes can contain from 1 to 90% by weight of the solid, from 10 to 99% by weight of one or more materials selected from classes (a)-(s) (e.g., petroleum jelly), and from 0.1 to 30% by weight of the alkyl ketal ester in place of the one or more materials (a)-(e).
• ointments which are generally mineral oil or petrolatum-based formulations that contain no or very little (less than 5% by weight) of water. Ointments can contain from 1 to 99% or more of one or more materials selected from classes (a)-(s) below. Some ointments can contain particles dispersed therein (e.g., zinc oxide) and can therefore also be classified as dispersions.
• the personal care formulations can also be in the form of gels, which tend to have a higher viscosity than solutions.
• the relatively high viscosity can be the result of a thickened solution, or can include, for example, semisolid emulsions in an alcohol base.
• Gels can contain from 1 to 99% of one or more materials selected from classes (a)-(s) below. Because gels can contain an alcohol base, the alkyl ketal esters can advantageously be used to replace some or a portion of the alcohol.
• the personal care formulations can also be in the form of a solution, wherein all of the components are miscible at room temperature as defined above.
• the solvent can be water, aqueous (containing water and an organic solvent) or organic (e.g., an alcohol). Solutions can contain from 1 to 99% of one or more materials selected from classes (a)-(s) below.
• the personal care formulations can also be in the form of solid, for example, a stick, waxy formulation, or the like.
• Solids can contain from 1 to 99% of one or more materials selected from classes (a)-(s) below. Solids can also optionally contain particulates. It is to be understood that the foregoing classifications are for convenience only, and that some overlap exists between the forms.
• Personal care formulations generally contain additional ingredients, which can be present to perform various functions. Among these are, for example ingredients (a)-(s) as described in more detail below.
• the various ingredients (a)-(s) can be used alone or in combination. More than one type of each ingredient (e.g., two paraffinic oils (a)) can be used. While certain functions may be ascribed to ingredients (a)-(s), it is to be understood that each ingredient may perform the stated function, another function, or more than one function in a personal care formulation.
• Ingredients (a) include paraffinic, naphthenic, or aromatic mineral oil. These materials are often present as all or part of an oil phase in emulsion formulations such as certain lotions and creams. They often function as emollients, by which it is meant a material that tends to soften the skin upon application.
• nonionic organic compounds which have a melting temperature of less than 45° C., a molecular weight of at least 190, contain a amido, or ester group and an alkyl chain containing at least 8 carbon atoms, and a solubility in water of no greater than 1 part in 99 parts of water.
• These materials are often present as all or part of an oil phase in emulsion formulations such as certain lotions and creams.
• Examples of materials (b) include vegetable oils and animal fats and derivatives are useful emollients, including, for example, acai oil, almond oil, aloe vera oil, andiroba oil, annatto oil, avocado oil, babassu oil, borage oil, brazil nut oil, buriti oil, camelina oil, coffee oil, copaiba oil, emu oil, passion fruit oil, almond oil, castor oil, coconut oil, grapeseed oil, jojoba oil, macadamia nut oil, rose hip oil, ajwain oil, angelic root oil, anise oil, aragan oil, asafetida, balsam oil, basil oil, bay oil, bergamot oil, black pepper essential oil, buchu oil, birch oil, camphor, cannabis oil, caraway oil, cardamom seed oil, carrot seed oil, chamomile oil, calamus root oil, cinnamon oil, citronella oil, clary sage, clove leaf oil, coffee, cor
• Other useful nonionic materials (b) include, for example, C 8-24 linear or branched alkyl esters of C 8-24 fatty acids, di-C 8-24 esters of dicarboxylic acids, C 8-24 fatty acid esters of C 8-24 linear or branched alkanoic acids, C 8-24 , especially C 12-15 alkyl benzoates, poly(propylene oxide) esters of C 8-24 fatty acids, di-C 8-24 linear or branched alkyl esters of aromatic diacids, di-C 8-24 fatty acid esters of aromatic diacids, and the like.
• Examples of these include cetyl palmitate, cetearyl ethylhexanoate, ethylene glycol distearate, propylene glycol distearate, glycerol distearate, myristyl myristate, lignoceryl erucate, di-PPG-3 myristyl ether adipate, isostearyl neopentanate, ethylhexyl palmitate, dicaprylyl maleate, diisopropyl dimer dilinoleate, dicetylphthalate, ethylhexyl isononanoate, diethyl phthalate, dimethyl phthalate, dibutyl phthalate, triethylene glycol dibenzoate, butyl stearate, disobutyl adipate, and the like.
• Other useful materials (b) include, for example, C 8-24 linear or branched alkyl amides of C 8-24 fatty acids, di-C 8-24 amides of dicarboxylic acids, C 8-24 fatty acid amides of C 8-24 linear or branched alkanoic acids, poly(propylene oxide) amides of C 8-24 fatty acids, di-C 8-24 linear or branched alkyl amides of aromatic diacids, di-C 8-24 fatty acid amides of aromatic diacids, and the like.
• Ingredients (c) include nonionic organosilicone compounds having a melting temperature of less than 45° C. and a solubility in water of no greater than 1 part in 99 parts of water. Examples are dimethicone and cyclopentasiloxane.
• Ingredients (d) include long chain (eight or more carbon atoms) alcohols such as 1-octanol, 1-decanol, 1-dodecanol, cetyl alcohol, and the like. These alcohols can perform various functions, including thickening and a solvating/compatibilizing function, and can function as emollients as well.
• Ingredients (e) include waxes.
• these waxes perform a skin moisturizing function by depositing onto the skin and forming a barrier to the escape of water from the skin.
• the waxes can function as hair conditioners, or form films upon application (as onto the lips, eyelashes, eyelids, etc.).
• the wax can provide a personal care formulation with a needed physical form (as is the case with lipsticks and lip balm formulations).
• Waxes are hydrophobic (having a solubility in water less than 1 part per 99 parts water), solid but malleable at room temperature, and have a melting temperature of from 45 to 100° C.
• Waxes include synthetic or mineral waxes such as ceresin, montan, ozocerite, peat, paraffin, microcrystalline, polypropylene and other polymerized poly- ⁇ -olefin waxes, substituted amide, petroleum jelly, esterified or saponified waxes, and the like; and waxes of plant or animal origin including beeswax, chinese wax, lanolin, shellac wax, spermaceti, bayberry, candelilla, carnauba, castor, esparto, Japan, ouricury, rice bran or soy waxes.
• synthetic or mineral waxes such as ceresin, montan, ozocerite, peat, paraffin, microcrystalline, polypropylene and other polymerized poly- ⁇ -olefin waxes, substituted amide, petroleum jelly, esterified or saponified waxes, and the like
• waxes of plant or animal origin including beeswax, chinese wax,
• Waxes that have a required HLB of at least 6, or at least 7, at least 8 or at least 10, tend to dissolve more easily in the alkyl ketal esters and are preferred in cases in which the alkyl ketal ester is to dissolve or be dissolved into the wax.
• Ingredients (f) include liquid or low melting (less than 45° C.) hydrocarbons of various types, which can function as cosolvents, conditioners, propellants, or for other purposes. Examples of these include squalene, butane (all isomers), propane, and pentane (all isomers).
• Ingredients (g) include natural, synthetic, or modified organic polymers. Polymers have several primary uses in personal care formulations (some of them being capable of performing multiple functions).
• Polymers (g)(1) include hair fixatives. These polymers include polyvinylpyrrolidone; polyvinylpyrrolidone/vinyl acetate copolymers; polyurethane and polyurethane copolymers and blends; copolymers of vinylpyrrolidone, lauryl methacrylate and optionally one or more other acrylate monomers; copolymers of vinyl pyrrolidone and dimethylaminoethyl methacrylate; copolymers of vinyl caprolactam, vinylpyrrolidone and dimethylaminoethyl methacrylate; copolymers of vinyl pyrrolidone and methacrylamidopropyl trimethylammonium chloride; copolymers of vinylpyrrolidone, vinyl caprolactam and dimethylaminopropyl methacrylamide; vinyl acetate/butyl maleate/isobornyl acrylate copolymers; copolymers of isobutylene, eth
• polymers are dissolved or dispersed in solution (usually water, ethanol, a mixture of water and an alcohol) to form hairsprays, mousses, and gels and are often present in amounts up to 20% by weight in hair sprays, styling gels, and similar hair styling formulations.
• solution usually water, ethanol, a mixture of water and an alcohol
• Polymers based on starch or modified starch can also be used as hair fixatives.
• Polymers (g)(2) include hair conditioning or skin conditioning polymers. These polymers are used in hair care products and skincare products. They can be either water soluble, oil soluble, or dispersed in water. These include hydrolyzed wheat protein and crosspolymers thereof with polyvinylpyrrolidone; many of the Polyquaternium series such as Polyquaternium-4, -7, -10 and -18 and -28; Polyquaternium-4/hydroxypropyl starch copolymers, PEG-50 hydrogenated palm amide; PPG-14 Palmeth-60 hexyl dicarbamate; cetareth-60 myristyl glycol, and the like.
• Polymers (g)(3) include waterproofing polymers. These polymers are dissolved in alcohol or oil phases. They are found in sweat-resistant, water resistant, or rub-resistant formulations for sun care and color cosmetics. These include acrylate polymers and copolymers; polyvinylpyrrolidone and copolymers of vinylpyrrolidone; acrylate/t-octylpropenamide copolymers; polymers and copolymers of polyacrylamide; vinyl acetate/butyl maleate/isobornyl acrylate copolymers; vinyl caprolactam/vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymers; C 30-38 olefin/isopropyl maleate/maleic acid copolymers; triacontanyl polyvinylpyrrolidone polymers; isobutylene/ethyl maleimide/hydroxylethylmaleimide copolymers; acacia Senegal gum; and
• Polymers (g)(4) include polymethylmethacrylate, which is useful as a cosmetic additive for a soft focus effect.
• Polymers (g)(5) include rheology modifiers. These polymers dissolve in a solution or continuous phase of an emulsion and increase viscosity. Usually, these are water soluble polymers that are added to a water phase.
• Rheology-modifying polymers include carbomers, natural gums like xanthan gum and guar gum, alkali swellable latexes, hydroxyethyl cellulose, and starch polymers (including modified starches).
• Polymers (g)(6) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, styrene/acrylates copolymers, acrylates copolymers, polyethylene terephthalate and tosylamide/formaldehyde resins. These polymers are used in nail lacquer that form the continuous coating used in nail polish.
• a surfactant includes ionic (cationic, anionic, or zwitterionic) compounds that contain a hydrocarbon group, specifically an alkyl group, of at least 8 carbon atoms.
• the ionic surfactants include, for example, anionic surfactants which include one or more sulfate, sulfonate or phosphate groups, which are in the neutralized (or “salt”) form; cationic surfactants which include one or more quaternary ammonium or quaternary phosphonium groups, which are in the neutralized (or “salt”) form; one or more zwitterionic groups which can, depending on the pH of the formulation, assume either an anionic or cationic form (as with the betaines, for example), or can assume a cationic or nonionic form (as with the amine oxide surfactants, for example).
• a surfactant additionally includes nonionic molecules that have a highly hydrophobic portion and a highly hydrophilic portion.
• the nonionic surfactants are characterized as having an HLB of at least 4, preferably from 6 to 22.
• HLB HLB of at least 4
• suitable surfactants can be found McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, incorporated herein by reference.
• alkyl benzene sulfonates including C11-16 alkyl benzene sulfonates, alkyl- and alkylether sulfates such as sodium dodecyl sulfate, sodium laureth sulfate, ammonium lauryl sulfate and sodium lauryl ether sulfate; taurates (anionic acylamino alkane surfactants); paraffin sulfonates including C12-18 paraffin-sulfonates, olefin sulfonates, alpha-sulfonates of fatty acids and of fatty acid esters, sulfosuccinate salts, ammonium cocoyl isethionate, ammonium laureth sulfate, ammonium lauryl sulfate, cocoyl sarcosine, diethylhexyl sodium sulfosuccinate, disodium cocamido ME
• nonionic surfactants include alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alkyl polyglucosides such as octyl glucoside, decyl maltoside, isethionates, amides of long chain fatty acids such as cocamide MEA, cocamide DEA, cocamide TEA and polyethoxylated tallow amine, and lauramide surfactants; various amine oxides, alkyl betaines; poly(ethylene oxide)-poly(propylene oxide) copolymers PEG-5 soyamine, PG-hydroxyethyl cellulose stearyldimonium chloride, quaternium-91 & PPG-3 benzyl ether myristate, PEG-50 hydrogenated palm amide capramide DEA, cocamide MIPA, PEG stearates, PEG ditallate, PEG cocamines, PEG soyamines, PEG stearamines,
• Specific cationic surfactants include such as cetylpyridium chloride, benzalkonium chloride, benzethonium chloride Quatenrium-82, dicetyldimonium chloride, dipalmitoylethyldimonium chloride, soytrimonium chloride, Celquat H-100 (cationic cellulose polymer), hydroxyoctacosanyl hydroxylstearate, behentrimonium methosulfate, cetrimonium chloride, and the like. These often function as antimicrobials and antistatic agents in a personal care formulation.
• Specific zwitterionic types of surfactants include dodecyl betaine, dodecyl dimethylamine oxide; such as, alkyl polyglucosides, disodium lauroamphodiacetate, disodium cocoamphodiacetate, sodium lauroamphoacetate, disodium capryloamphodiacetate, sodium amphocarboxylate, sodium cocoamphoacetate, sodium cocoamphopropionate, stearamine oxide, cetyl betaine, cocamidopropyl betaine, babassuamidopropyl betaine, cocamidopropyl hydroxysultaine, cocamidopropylamine oxide, cocamine oxide, cocaminopropionic acid, coco-betaine, coco/sunfloweramidopropyl betaine, dihydroxyethyl tallowamine oxide, disodium caprylamphodiacetate, disodium cocoamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodiacetate, disodium so
• Ingredients (i) include natural or synthetic fragrances, including for example, citrus floral herbal, citrus floral tea, citrus woody, coconut mango, desert flower, dewy morning, eau glacier, floral dove, fresh mint, green aromatic, lemongrass green tea, orange blossom honey, orange mimosa, tropical sunset, vanilla floral musk, vanilla grapefruit, white rose, white tea, menthol, and the like.
• natural or synthetic fragrances including for example, citrus floral herbal, citrus floral tea, citrus woody, coconut mango, desert flower, dewy morning, eau glacier, floral dove, fresh mint, green aromatic, lemongrass green tea, orange blossom honey, orange mimosa, tropical sunset, vanilla floral musk, vanilla grapefruit, white rose, white tea, menthol, and the like.
• Ingredients (j) include botanical extracts such as white tea extract, soy isoflavone extract, red clover extract, passion flower extract, olive extract, green tea extract, grape extract, ginseng extract, chamomile extract, centella asiatica extract, balm mint extract, aloe barbadensis leaf extract, rosemary extract, dulse seaweed extract, acacia extract, acai extract, agave extract, alfalfa extract, almond extract, angelica extract, annatto extract, apple extract, apricot extract, arnica extract, ashwagendha extract, awapuhi extract, bamboo extract, banana extract, basil extract, bearberry extract, beet root extract, bergamot extract, bilberry extract, bitter orange extract, black current extract, black pepper extract, black tea extract, bladderwrack extract, brazil nut extract, buchu extract, burdock extract, butchers broom extract, calendula extract, camu extract, capsicum extract, cardamom extract, carrot extract, cats claw
• John's wort extract strawberry extract, suma extract, sunflower extract, tangerine extract, tea tree extract, thyme extract, tiare extract, valerian root extract, vanilla extract, walnut black extract, watercress extract, white lily extract, white peony tea extract, white willow extract, witch hazel extract, yarrow extract, yerba mate extract, yogurt extract, yohimbe extract, yucca extract, and the like.
• These extracts can be present for fragrance purposes, or as specific active agents in particular formulations.
• Ingredients (k) include natural or synthetic dyes such as quinolines (D&C Yellow 10 and 11), triphenylmethanes (FD&C Blue 1, Green 3 and D&C Blue 4), anthraquinones (D&C Green 5,6 and Violet 2), indigoids (D&C Red 30), Non-azo xanthene (fluoran), xanthenes (D&C Red 22 & Yellow 8), fluorans (D&C Red 21, 27, and Orange 5), D&C Red 36, FD&C Yellow 5, FD&C Yellow 6, D&C Red 33, D&C Red 40, D&C Orange 4, D&C Red No. 6, D&C Red 7, D&C Red 34, sericite, D&C Yellow 10, henna (black, brown, gold brown, mahogany), and the like.
• natural or synthetic dyes such as quinolines (D&C Yellow 10 and 11), triphenylmethanes (FD&C Blue 1, Green 3 and D&C Blue 4), anthraquinones (D&C
• Ingredients (1) include inorganic pigments or pearlizers such as white mica, lead pearl, natural pearlessence, bismuth oxychloride, oxide coated mica ((OCM), titanium dioxide, ferric(III) oxide, aluminum, silica, borosilicate, synthetic mica, mica spheres, titanium, barium sulfate, hectorite, ferric (ammonium) ferrocyanide, cadmium yellow, cadmium red, cadmium green, cadmium orange, carbon black, ivory black, chrome yellow, chrome green, cobalt violet, cobalt blue, cerulean blue, aureolin (cobalt yellow), Han purple, Egyptian blue, Paris green, verdigris, viridian, sanguine, caput mortuum, iron oxide red, red ochre, Venetian red, Prussian blue, yellow ochre, raw sienna, burnt sienna, raw umber, burnt umber, lead white, cremnitz white, Naples yellow, red lead, vermilion
• Ingredients (m) include lower alcohols, including C 1-7 alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 1-hexanol, as well as the various other isomers of pentanol and hexanol; alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propane diol, dipropylene glycol, tripropylene glycol 1,4-butane diol and 1,2-butane diol; triols such as glycerine, and the like. These can function as solvents or cosolvents, or as humectants in personal care formulations.
• C 1-7 alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol,
• Ingredients (n) include glycol ethers, which can function as solvents or cosolvents or but in some cases can perform other functions.
• glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monohexyl ether, and the like.
• Ingredients (o) include active pH adjusters/buffers and chelating agents including 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1,3-propanediol, tris(hydroxymethyl)aminomethane, alpha-hydroxy acids such as lactic acid and glycolic acid), citric acid, citric acid salts, phosphoric acid salts, ascorbic acid salts, triethanolamine, sodium hydroxide, aminomethyl propanol, potassium hydroxide, diethanolamine, sodium carbonate, potassium hydrogen tartrate, levulinic acid, and the like.
• active pH adjusters/buffers and chelating agents including 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1,3-propanediol, tris(hydroxymethyl)aminomethane, alpha-hydroxy acids such as lactic acid and glycolic acid), citric acid, citric acid salts, phosphoric acid salts, ascorbic acid salts, triethanolamine, sodium hydro
• a personal care formulation containing an alkyl ketal ester it is preferred to buffer a personal care formulation containing an alkyl ketal ester to a pH of at least 3.5, especially when the personal care formulation contains a sulfonate or sulfate surfactant, or other sulfonic acid or sulfate salt.
• a pH from 5 to 8 can be used in aqueous formulations.
• Ingredients (p) include organic carboxylic acids having from 2 to 10 carbon atoms.
• Ingredients (q) include inorganic particulates such as clays, magnesium aluminum silicate, magnesium trisilicate, attapulgite, bentonite, hectorite, lithium magnesium silicate, lithium magnesium sodium silicate, montmorillonite, bentonite, smectite clay, boron nitride, silicon nitride, titanium carbide, boron carbide, mullite, coreiderite, and the like.
• inorganic particulates such as clays, magnesium aluminum silicate, magnesium trisilicate, attapulgite, bentonite, hectorite, lithium magnesium silicate, lithium magnesium sodium silicate, montmorillonite, bentonite, smectite clay, boron nitride, silicon nitride, titanium carbide, boron carbide, mullite, coreiderite, and the like.
• Ingredients (r) include non-hydrocarbon propellants such as hydrofluorocarbon 152A, nitrogen, 1,2-trichlorotrifluoroethane, chloropentafluoroethane, dimethyl ether, and the like.
• non-hydrocarbon propellants such as hydrofluorocarbon 152A, nitrogen, 1,2-trichlorotrifluoroethane, chloropentafluoroethane, dimethyl ether, and the like.
• Ingredients (s) include preservatives such as diazolidinyl urea, methyl paraban, propyl paraban, and mixed paraban esters, and the like.
• Formulations containing an alkyl ketal ester, especially a sparingly water-soluble alkyl ketal ester, have been found to be excellent cosmetic removers, particularly if the formulation contains at least 5% and more specifically at least 8% by weight of the alkyl ketal ester.
• the alkyl ketal ester can constitute up to 75%, up to 60% or up to 50% of the weight of a cosmetic remover formulation.
• a cosmetic remover in accordance with the invention can include, in addition to the alkyl ketal ester, water, an alcohol such as ethanol, isopropanol or 1,2- or 1,3-propane diol; one or more of components (a)-(e) above (in which case the cosmetic remover will tend to be in the form of an emulsion which can be in lotion or cream form), or any of the other materials (f)-(s) above.
• Such a cosmetic remover can even be free of surfactants, or contain low (less than 2% by weight) concentrations of surfactants.
• the alkyl ketal esters are also efficient solvents for polymers that are generally present in nail polishes, such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, styrene/acrylates copolymers, acrylates copolymers, polyethylene terephthalate and tosylamide/formaldehyde resins and thus find benefit as solvents in nail polish removers, nail strengthening formulations, and/or nail polishes.
• nail polishes such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, styrene/acrylates copolymers, acrylates copolymers, polyethylene terephthalate and tosylamide/formaldehyde resins
• the personal care formulations described herein satisfy certain continuing needs in the art for formulary ingredients.
• the alkyl ketal esters can be used in a wide range of formulation forms and in a wide variety of specialized applications. Although these various types of formulations differ enormously, as do the conditions under which they are used, the alkyl ketal esters can be used in the formulation of many of them, which greatly simplifies the formulation process.
• formulators of personal care formulations must often simultaneously address formulation needs that are often competing and sometimes even contradictory.
• many personal care formulations contain an active agent that lends a particular functional attribute to the formulation. It can be desirable to increase the concentration of the active agent in a given formulation, or to produce a formulation that contains the active agent in a specific formulation form (such as a solution, dispersion, lotion, cream, stick, gel, or the like), but the formulator is limited by the solubility of the active agent in the other ingredients in the formulation.
• the presence or absence of a specific ingredient that can be an aid to solubility is important.
• VOCs volatile organic compounds
• ethanol can dry the skin and in some cases are to be avoided for that reason, or for other reasons, such as VOC regulations in some jurisdictions.
• VOC regulations in some jurisdictions.
• use of the alkyl ketal esters results in formulations that do not contain VOCs.
• the formulations and products described herein can be low-VOC as defined below.
• alkyl ketal esters can enhance the compatibility amongst the various ingredients of the formulations.
• Many personal care formulation formulations contain both hydrophilic and hydrophobic components. These ingredients tend not to mix into each other.
• emulsifiers, cosolvents, or thickeners can be included so that it becomes kinematically stable. These emulsifiers, cosolvents, and thickeners often play little role in the function or performance of the formulation (i.e., are not active agents), although they can affect the spreading characteristics and feel on the skin.
• compatibilizing ingredients such as volatile or drying organic solvents, for example
• compatibilizers can increase formulation complexity. Formulations that require compatibilization can be very sensitive to small formulational changes. Small changes to a formulation often destabilize it, requiring a new balance of ingredients.
• the alkyl ketal esters can perform the function of emulsifiers, oils, cosolvents, compatibilizers, and like materials. In a further advantage, the alkyl ketal esters enhance the spreading of the formulation, and/or do not feel greasy or heavy.
• Use of the alkyl ketal esters can provide simplified formulations for personal care formulations that still have the needed formulation attributes and functions. In other cases, use of the alkyl ketal esters can reduce the quantities of the various formulary components, and thus can reduce costs and simplify formulating. This can allow a formulator to maintain a simplified raw material inventory and thus reduce associated costs. Use of the alkyl ketal esters can also result in personal care formulation formulations that are more robust to formulation changes.
• Examples 1-6 show the effect of the alkyl ketal esters on solubility of various personal care formulation ingredients. In these tests, clear mixtures as observed without magnification from a distance of, e.g., 0.3 meters are considered to be “miscible,” whereas cloudy or phase separated mixtures are considered to be “immiscible.”
• Salicylic acid was pre-dissolved in ketal and then water was added at room temperature. Observations were made within 5 minutes. Results are shown in Table 5.
• Aloe vera oil is highly immiscible in both ethanol and isopropanol.
• Three-component mixtures of ethyl-LPK, aloe and either ethanol or isopropanol were prepared by mixing the materials at various proportions at room temperature in a vial and shaking. Results are shown in Table 6 (ethanol) and in Table 7 (isopropanol).
• Examples 10-41 show various personal care formulations and products that can be made using the alkyl ketal esters of structure I.
• a model spray sunscreen formulation contained 64.4 parts ethanol, 3 parts of an acrylate/octylacrylamide copolymer, 3 parts of octyldodecanol, 7.5 parts of octinoxate, 4 parts of oxybenzone, 5 parts of octisalate, 3 parts of avobenzone, 2.5 parts of POLYCRYLENE® (CAS No. 862993-96-2), 2.5 parts of octocrylene and 5.1 parts of water.
• Ethanol is a primary ingredient in many hand sanitizer formulations.
• the formulations typically contain one or more emollients such as isopropyl myristate. Water is also commonly added to these formulations to provide hydration or reduce cost, but this tends to make the solution cloudy due to the incompatibility of the emollient with water.
• This formulation retained the balance of emollient and ethanol, while still providing hydration through the presence of water.
• a portion of the ethanol can be replaced with Et-LGK without sacrificing clarity, even at higher water levels.
• a clear solution was obtained when 27 parts isopropyl myristate was mixed with 9 parts of water, 9 parts of ethyl-LGK and 55 parts of ethanol. This reduced ethanol formulation was less drying.
• Example 12A A comparative lotion suitable for use as a moisturizing lotion was prepared in Example 12A.
• Examples 12B and 12C were prepared using 10 parts ethyl-LGK for an equivalent amount of the sesame seed oil and 10 parts ethyl-LPK for an equivalent amount of the sesame seed oil.
• a lotion can be from n-Butyl-LGK as shown in prospective Example 12D as shown in Table 13.
• Carbopol was slowly added and mixed until fully hydrated. The remaining Part A ingredients were added and Part A was heated to 75° C. The ingredients of Part B were combined under mixing at 75° C. Once uniform, Part B was slowly added to Part A with moderate agitation. Once uniform, the solution was cooled to 60-65° C. Part C was then used to adjust the pH to 5.5-6.0 and the batch was cooled to 40° C. Part D was then added to the batch with mixing and then homogenized for 5 minutes or until uniform at 3500 rpm. Further amounts of Part D were added if necessary to adjust the viscosity to 15,000-25,000 cps.
• Example 12B and 12C the result was a light, less greasy formulation compared to comparative example 12A.
• Lotions 12B and 12C also had a silky after-feel absent from example 12A. All formulations remained kinematically stable.
• Example 12B further had the further advantage of being an effective makeup remover. It is expected that Example 12D will also be a light, less greasy kinematically stable product.
• PMMA Polymethyl methacrylate
• emulsion formulation such as a cream or lotion, or as a powder
• PMMA was soluble in ethyl-LPK to the extent of 5 parts of PMMA in 95 parts of ethyl-LPK, and nearly to the same extent in mixtures of ethyl-LPK and ethyl-LGK.
• PMMA was also soluble in various cosolvent mixtures of ethanol and ethyl-LPK or ethanol, water and ethyl-LPK. Therefore, the following in Table 13 are examples of clear serum bases that contained dissolved PMMA, and which formed by themselves, or in admixture with other materials, solution forms that contained dissolved PMMA.
• the triethanol amine was then added to complete Part B.
• the ingredients from Part A were combined except for the acrylates/octylacrylamide copolymer. These components were heated to 80° C. with mixing. The acrylates/octylacrylamide copolymer was then slowly sifted into Part A under constant stirring until dissolved. Part A was then added to Part B and mixed for 15 minutes at 80° C. The mixture was then slowly cooled to room temperature. Example 15 was less viscous, but remained stable for at least four weeks. The modified product had a lighter, less greasy feel.
• Comparative cosmetic remover A and inventive cosmetic removers 13-A through 13-D were prepared from the following formulations.
• the formulations were clear in all cases except for comparative A, which was hazy.
• the formulations were evaluated by rubbing them onto a mascara-coated acrylonitrile-butadiene-styrene sheets, using a cotton swab.
• a “G” rating indicates that the mascara was removed from the substrate after several rubs; a “VG” rating indicates that the mascara was removed from the substrate with minimal rubbing. Results are shown in Table 15.
• an ethanolic insecticide can be prepared that comprises DEET dissolved in a cosolvent mixture of ethanol and ethyl-LPK.
• the presence of the ethyl-LPK allows the ethanol concentration to be reduced, to produce a less drying insecticide formulation.
• a lipstick (Example 18) was prepared from the ingredients in Table 16.
• the Part A ingredients were heated to 80-85 C with mixing.
• the ingredients of Part B were pre-ground.
• the Part B color grind was added to Part A wax/oil mixture.
• the batch was dropped to a temperature of 75° C. and the Part C solution was slowly added to the batch and mixed until the batch was completely homogeneous.
• the formulation was poured into molds to cool.
• Lipsticks (Examples 19-24) were prepared from the ingredients in Table 17.
• Part A was heated at 80-85° C. with mixing.
• Part B was added to Part A while mixing.
• Part C was pre-ground.
• Part A/B was completely melted and clear, Part C color grind was added to the combined Parts A and B.
• the batch temperature was dropped to 75 C and the Part D solution was slowly added to the batch with mixing. The batch was mixed until completely homogeneous. When the batch was uniform, it was poured into molds to cool.
• Part D can be added to combined Parts A and B before addition of Part C, though care should be taken to avoid or minimize water loss.
• the lipstick structure was good in each of Examples 15-21. Samples were aged at 45° C. for 4 weeks to determine stability, and it was found that none of the sticks sweated, showed signs of condensation, or softened when returned to room temperature. There were further no signs of color bleed or color change.
• Hair dye formulations were prepared from the ingredients in Table 19.
• Saturated solutions of each oxidation dye intermediate were prepared in Examples 26A and 27A at pH 10.2, and Examples 26B and 27B at pH 8.5. Three replications were prepared for each example. The saturated solutions were prepared by equilibrating three 50 g samples of each of the variations at 27° C. in a water bath. Once the bases were at the desired temperature, excessive amounts (i.e., more than would dissolve) of p-phenylenediamine, 1-naphthol and p-toluenedaimine sulfate were added to portions of each base pH combinations. The resultant mixtures were maintained at 27° C. for 10 minutes with stirring to dissolve the maximum possible amount of each intermediate under these conditions.
• a calibration curve for dye concentration was prepared by preparing 1.0% (w/w) solutions of the oxidation dye intermediates: p-phenylenediamine (PPD), 1-naphthol and p-toluenediamine sulfate (PTD) were prepared in Solvent A (0.2% EDTA, 0.4% erythorbic acid, 0.4% sodium sulfite, 49.5% DI water (RO filtered), and 49.5% isopropanol). The solutions were diluted stepwise from 1.00% to 0.00001% (10 ppm) and scanned with a Varian DSM 200 from a range of 380 nm to 900. Absorption maxima in the visible range were used to plot concentration curves with an optimal absorbance for viewing at approximately 500 ppm. Results are shown in Table 20.
• Salicylic acid (U.S.P. grade is available from J. T. Baker) was dissolved at 15% solids and 20.8% solids in Et-LGK at room temperature and 50° C., respectively. Both mixtures formed clear uniform solutions at room temperature initially. The mixture at 15% solids was still soluble after 24 hours of storage at room temperature, whereas the mixture at 20.8% solids precipitated.
• Salicylic acid was dissolved at 10% solids in Bu-LGK at 80° C. After 24 hours at room temperature, there was no evidence of precipitation.
• Salicylic acid was dissolved at 11% solids in Et-LPK with no heat. After 24 hours at room temperature, there was no evidence of precipitation. A mixture at 14.3% solids dissolved when heated but precipitated out at room temperature.
• Benzoyl peroxide (USP grade, available as Luperox A70S from Arkema) was dissolved at 5% solids in Et-LGK at 35° C. The solution showed no signs of precipitation after 24 hours at room temperature. A solution at 9.5% solids precipitated at room temperature.
• Retinoic acid (Tretinoin, available from Tokyo Chemical Industry) was dissolved at 2.2% solids in Et-LGK at 80° C. After 1 day at room temperature, there was no sign of precipitation.
• Retinoic acid was dissolved in Bu-LGK at room temperature at 0.25%. After 1 day at room temperature, there was no sign of precipitation. A mixture at 0.5% retinoic acid formed a dispersion.
• Retinoic acid was dissolved in Et-LPK at 0.5% solids at room temperature. After 1 day at room temperature, there was no sign of precipitation. Retinoic acid was dissolved in Et-LPK at 0.84% solids at room temperature. After 1 day at room temperature, there was no sign of precipitation. Retinoic acid was insoluble in Et-LPK at 1.88% solids at room temperature. Retinoic acid was soluble in Et-LPK at 1.88% solids at 80° C.
• Salicylic acid (U.S.P. grade available from J. T. Baker) was dissolved at 15% solids and 20.8% solids in Et-LGK at room temperature and 50° C., respectively. Both mixtures formed clear uniform solutions at room temperature initially. The mixture at 15% solids was still soluble after 24 hours of storage at room temperature, whereas the mixture at 20.8% solids precipitated.
• Salicylic acid was dissolved at 10% solids in Bu-LGK at 80° C. After 24 hours at room temperature, there was no evidence of precipitation.
• Salicylic acid was dissolved at 11% solids in Et-LPK with no heat. After 24 hours at room temperature, there was no evidence of precipitation. A mixture at 14.3% solids dissolved when heated but precipitated out at room temperature.
• Lactic acid (available from Alfa Chem, Ashland Distribution, and Spectrum Chemical Mfg. Corp) forms a homogeneous solution in Et-LGK at a 50/50 ratio. Lactic acid formed a homogeneous solution in Et-LPK at a 50/50 ratio.
• Glycolic acid (available from Lipo Chemicals, Inc. and Spectrum Chemical Mfg. Corp.) was dissolved at 8.33% solids in Et-LGK at room temperature and formed a homogeneous solution. Glycolic acid at 10% solids in Et-LGK did not form a homogeneous solution at room temperature.
• Dimethylmethoxy chromanyl palmitate (available as Chromabright from Liopotec) at 2.03% formed a homogeneous solution in Et-LGK with heat.
• Dimethylmethoxy chromanyl palmitate at 2% formed a homogeneous solution in Et-LPK at room temperature.
• the recommended dosage level is 0.1%.
• Tetrahydrocurcuminoids (available from lotioncrafter.com) was dissolved at 20% solids in Et-LGK at room temperature to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydrocurcuminoids was dissolved at 5% solids in Bu-LGK at 50° C. to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydrocurcuminoids was dissolved at 5% solids in Et-LPK at 50° C. to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• the recommended usage rate is 0.1-1%.
• Resveratrol (available from Enzo Life Sciences) was dissolved at 1% solids in Et-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Resveratrol was dissolved at 0.5% solids in Bu-LGK at 50° C. The mixture was still soluble after 24 hours of storage at room temperature.
• Resveratrol was dissolved at 0.5% solids in Et-LPK at 50° C. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydropiperine (available as Cosmoperine from lotioncrafter.com) was dissolved at 20% solids in Et-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydropiperine was dissolved at 20% solids in Bu-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydropiperine was dissolved at 20% solids in Et-LPK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature. Tetrahydropiperine is a co-ingredient in anti-aging formulations and is thought to improve the bioavailability of active agents.
• Dimethylmethoxy Chromanol (available as Lipochroman-6 from lotioncrafter.com) was dissolved at 2.5% solids in Et-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Dimethylmethoxy Chromanol was dissolved at 2.5% solids in Bu-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Dimethylmethoxy Chromanol was dissolved at 2.5% solids in Et-LPK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• the recommended usage rate is 0.01-0.05%.
• Methyl paraben available from EMD Chemicals, Jeen International Corporation, and The Hallstar Company
• Et-LGK Et-LGK
• Both mixtures formed clear uniform solutions at room temperature initially.
• the mixture at 15% solids was still soluble after 24 hours of storage at room temperature, whereas the mixture at 20.8% solids precipitated.
• Propyl paraben was dissolved at 15% solids and 20.8% solids in Et-LGK at room temperature and 50° C., respectively. Both mixtures formed clear uniform solutions at room temperature initially and remained as clear uniform solutions after 24 hours of storage at room temperature.
• Caprylyl glycol (available from Inolex as Lexgard O) was dissolved at 15% solids and 20.8% solids in Et-LGK at room temperature. Both mixtures formed clear uniform solutions at room temperature initially and remained as clear uniform solutions after 24 hours of storage at room temperature.
• Phenoxyethanol available from Dow Chemical and Spectrum Chemical was soluble at 15% and 20.8% in Et-LGK at room temperature. Both mixtures formed clear uniform solutions at room temperature initially and remained as clear uniform solutions after 24 hours of storage at room temperature.
• Salicylic acid (U.S.P. grade available from J. T. Baker) was dissolved at 15% solids and 20.8% solids in Et-LGK at room temperature and 50° C., respectively. Both mixtures formed clear uniform solutions at room temperature initially. The mixture at 15% solids was still soluble after 24 hours of storage at room temperature, whereas the mixture at 20.8% solids precipitated.
• Salicylic acid was dissolved at 10% solids in Bu-LGK at 80° C. After 24 hours at room temperature, there was no evidence of precipitation.
• Salicylic acid was dissolved at 11% solids in Et-LPK with no heat. After 24 hours at room temperature, there was no evidence of precipitation. A mixture at 14.3% solids dissolved when heated but precipitated out at room temperature.
• Resveratrol (available from Enzo Life Sciences) was dissolved at 1% solids in Et-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Resveratrol was dissolved at 0.5% solids in Bu-LGK at 50° C. The mixture was still soluble after 24 hours of storage at room temperature.
• Resveratrol was dissolved at 0.5% solids in Et-LPK at 50° C. The mixture was still soluble after 24 hours of storage at room temperature.
• p-Phenylene diamine (97% purity, available from Alfa Aesar) was dissolved at 5% solids in Et-LGK at 80° C. and formed a very dark solution with no evidence of precipitation. The active was still soluble after 24 hours of storage at room temperature.
• p-Phenylene diamine partially dissolved at 25% solids in Bu-LGK at 80° C. and formed a dark solution with precipitant on the bottom.
• p-phenylene diamine was dissolved at 5% solids in Bu-LGK at 80° C. and formed a very dark solution with no evidence of precipitation.
• p-Phenylene diamine did not completely dissolve at 5% solids in Et-LPK 80° C. An orange solution with precipitant formed.
• p-phenylene diamine did not completely dissolve at 1% solids in Et-LPK 80° C. An orange solution with precipitant formed. In both cases, the solution turned darker orange with time during storage at room temperature but precipitant remained.
• p-Toluenediamine sulfate (97% purity, available from Aldrich) partially dissolved at 1% solids in Et-LGK at 80° C. The sample formed a brown solution with solid precipitant on the bottom. p-Toluenediamine sulfate partially dissolved at 0.1% solids in Et-LGK at 80° C. The sample formed a brown solution with solid precipitant on the bottom.
• p-Toluenediamine sulfate failed to dissolve at both 1% solids and 0.1% solids in Et-LPK at 80° C.
• the sample formed milky white mixture with solids at the bottom of the vial. No color development occurred.
• Resorcinol (at 99% purity available from Alfa Aesar) was dissolved at 10% solids in Et-LGK at 80° C. with agitation. The mixture was still soluble after 24 hours of storage at room temperature.
• Resorcinol was dissolved at 10% solids in Bu-LGK at 80° C. with agitation. The mixture was still soluble after 24 hours of storage at room temperature.
• Resorcinol was dissolved at 10% solids in Et-LPK at room temperature with agitation. The mixture was still soluble after 24 hours of storage at room temperature.
• m-Aminophenol was dissolved at 5% solids in Et-LPK at 80° C. with agitation. The mixture was still soluble after 24 hours of storage at room temperature.
• a 50/50 mixture of Et-LGK and citronella pure essential oil (Cymbopogon nardus, plant sourced from Indonesia and extracted by steam distillation) was purchased from Wyndmere Naturals) was miscible at room temperature.
• Retinoic acid (Tretinoin, available from Tokyo Chemical Industry) was dissolved at 2.2% solids in Et-LGK at 80° C. After 1 day at room temperature, there was no sign of precipitation.
• Retinoic acid was dissolved in Bu-LGK at room temperature at 0.25%. After 1 day at room temperature, there was no sign of precipitation. A mixture at 0.5% retinoic acid formed a dispersion.
• Retinoic acid was dissolved in Et-LPK at 0.5% solids at room temperature. After 1 day at room temperature, there was no sign of precipitation. Retinoic acid was dissolved in Et-LPK at 0.84% solids at room temperature. After 1 day at room temperature, there was no sign of precipitation. Retinoic acid was insoluble in Et-LPK at 1.88% solids at room temperature. Retinoic acid was soluble in Et-LPK at 1.88% solids at 80° C.
• Salicylic acid was dissolved at 15% solids and 20.8% solids in Et-LGK at room temperature and 50° C., respectively. Both mixtures formed clear uniform solutions at room temperature initially. The mixture at 15% solids was still soluble after 24 hours of storage at room temperature, whereas the mixture at 20.8% solids precipitated.
• Salicylic acid was dissolved at 10% solids in Bu-LGK at 80° C. After 24 hours at room temperature, there was no evidence of precipitation.
• Salicylic acid was dissolved at 11% solids in Et-LPK with no heat. After 24 hours at room temperature, there was no evidence of precipitation. A mixture at 14.3% solids dissolved when heated but precipitated out at room temperature.
• Resveratrol was dissolved at 1% solids in Et-LGK at room temperature. The mixture was still soluble after 24 hours of storage at room temperature.
• Resveratrol was dissolved at 0.5% solids in Bu-LGK at 50° C. The mixture was still soluble after 24 hours of storage at room temperature.
• Resveratrol was dissolved at 0.5% solids in Et-LPK at 50° C. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydrocurcuminoids tetrahydrodiferuloylmethane, available as Tetrahydrocurcuminoids (THC) from lotioncrafter.com
• THC Tetrahydrocurcuminoids
• Tetrahydrocurcuminoids was dissolved at 5% solids in Bu-LGK at 50° C. to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• Tetrahydrocurcuminoids was dissolved at 5% solids in Et-LPK at 50° C. to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• the recommended usage rate is 0.1-1%.
• Hydroquinone (available in 99% purity from Alfa Aesar) was dissolved at 5% solids in Et-LGK at 80° C. with agitation to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• Hydroquinone was dissolved at 10% solids in Et-LPK at 80° C. with agitation to form a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• Dimethylmethoxy chromanyl palmitate (available as Chromabright from Liopotec) at 2.03% formed a homogeneous solution in Et-LGK with heat.
• Dimethylmethoxy chromanyl palmitate at 2% formed a homogeneous solution in Et-LPK at room temperature.
• the recommended dosage level of dimethylmethoxy chromanyl palmitate is 0.1% by weight.
• Erythrulose and Et-LGK were mixed at a ratio of 10/90 at room temperature and formed a clear uniform solution. The mixture was still soluble after 24 hours of storage at room temperature.
• Erythrulose and Bu-LGK were mixed at a ratio of 10/90 at room temperature; the two liquids separated into distinct phases.
• Erythrulose and Et-LPK were mixed at a ratio of 10/90 at room temperature; the two liquids separated into distinct phases.
• Avobenzone (available from Symrise as Neo Heliopan 357 and as Escalol 517 by International Specialty Formulations, Inc. (ISP)) was dissolved at 25% solids in Et-LGK with heat and formed a clear, uniform solution. After 24 hours at room temperature, a precipitate formed. Avobenzone was dissolved at 20% solids in Et-LGK with heat and formed a clear, uniform solution. After 5 days at room temperature, there was no evidence of precipitation.
• ISP International Specialty Formulations, Inc.
• Avobenzone was dissolved at 35% solids in Et-LPK with heat and formed a clear, uniform solution. After 24 hours at room temperature, a precipitate formed. Avobenzone was dissolved at 30% solids in Et-LPK with heat and formed a clear, uniform solution. After 24 hours at room temperature, there was no evidence of precipitation. The solution showed no signs of precipitation after 5 days.
• Oxybenzone (available from BASF as UVINUL M40, Acros Organics (98% purity) and Tokyo Chemical Industry Co.) was dissolved at 10% solids in Et-LGK at room temperature and formed a clear, uniform, yellow solution. After 24 hours at room temperature, there was no evidence of precipitation. Oxybenzone at 25% solids partially dissolved in Et-LGK at room temperature and completely dissolved with heating to 35-40° C. and formed a clear, uniform, yellow solution. Needle-shaped crystals formed over a 48-hour period at room temperature. Oxybenzone dissolved with heat at 20% solids in Et-LGK remained in solution after 24 hours of room temperature storage. Another solution prepared at 18% oxybenzone in Et-LGK showed no signs of precipitation after 5 days.
• Oxybenzone was dissolved at 10% solids in Bu-LGK at room temperature. After 24 hours at room temperature, there was no evidence of precipitation.
• Oxybenzone was dissolved at 40% solids in Et-LPK with heat and formed a clear, uniform, yellow solution. After 24 hours at room temperature, a precipitate formed. Oxybenzone was dissolved at 30% solids in Et-LPK with heat and formed a clear, uniform, yellow solution. After 24 hours at room temperature, there was no evidence of precipitation. The solution showed no signs of precipitation after 5 days.
• Oxybenzone was dissolved at 28.5% solids in Et-LEK at room temperature. Oyxbenzone was dissolved with heat at 37.5% solids in LEK. After 2 weeks at room temperature, there was no sign of precipitation.
• a 50/50 mixture of octyl methoxycinnamate and Bu-LGK was soluble at room temperature.
• the alkyl ketal ester is methyl-LGK, ethyl-LGK, n-propyl-LGK, n-butyl-LGK, ethyl-LPK, n-butyl-LPK, ethyl-LEK, methyl-AcAcGK, ethyl-AcAcGK, ethyl-LTMEK, and ethyl-LTMPK.
• the alkyl ketal ester is ethyl-LGK, ethyl-LPK, n-butyl-LGK, or a combination comprising at least one of the foregoing alkyl ketal esters.
• Antiperspirant formulations are shown in Tables 22A-D.
• non-alcoholic deodorant stick To manufacture the non-alcoholic deodorant stick, combine ingredients of Part A with mixing and heat to 70-80° C. Dust Part B into Part A with mixing. When uniform, cool to desired fill temperature.
• W/O Water-in-oil
• Ingredient weight % Part A Aluminum chlorohydrate 19 (Microdry, Al. Chlorohydrate powder from Reheis Chemical Co.) DI water 25 Part B Stearyl alcohol (CRODACOL S-95) 25.5 Polyglycerol oleate (EMCOL 14, Witco) 5 Sorbitan isostearate (SPAN 120, Croda) 2.5 Caprylic/capric triglyceride 6 (CRODAMOL GTCC, Croda) Alkyl ketal ester* 6 Cyclomethicone (Dow Corning 344 Fluid) 9 Dimethicone (Dow Corning 200 fluid, 350 cst) 2 *Alkyl ketal ester examples: Ex.
• Part A To manufacture the example formulations, weigh Part A and begin heating to 80-85° C. with mixing. Pregrind Part B. When Part A is completely melted and clear, add Part B color grind to Part a wax/oil mixture. When all the color is dispersed and the batch is uniform, pour into molds.
• Part A To manufacture the example formulations, add Part A into a vessel and heat to 75° C. to melt wax, mixing until uniform. Remove from heat and add Part B, stirring well. While still liquid, pour into cosmetic container.
• pre-grind or pre-mix the ingredients of Part C. Add Part A to vessel and heat to 65 C until wax and butter are melted. Slowly add in Part C with mixing and mix until well dispersed. Remove from heat. Add ingredients of Part C to Parts A/B one by one and make sure the formulation is well mixed. Fill into molds while the formulation is still liquid. Allow to cool.
• the example formulations combine the titanium dioxide and the pearl white mica in a mortar, stir very well and thoroughly with the pestle until the color is uniform. Add then the other ingredients of Part B, one after another, mixing well after each addition. Then add Part A to the mortar and blend well, for several minutes or until the ingredients are mixed and the color looks uniform. Fill the eye shadow into an eye shadow jar and press it with a suitable tool into eye shadow containers.
• Part B in advance by stirring in a sealed vessel until dissolved.
• a separate closed vessel combine the ingredients of Part A and heat to 90-95° C. with stirring.
• Part A is clear and well-mixed
• Add Part B and Part C stirring until dissolved.
• Add Parts D through F in sequential order, mixing well with high shear after each addition.
• E ethyl-LPK Ex. F, n-butyl-LPK Ex. G, ethyl-LEK Ex. H, Me-AcAcGK Ex. I, Et-AcAcGK Ex. J, ethyl-LTMEK Ex. K, ethyl-LTMPK
• Powder Cream Blush Ingredient weight % Part A PPG-3 benzyl ether myristate 38 Tribehenin 6 C18-36 acid triglyceride 1 Sorbitan isostearate 1 Methyl paraben 0.2 Propyl paraben 0.1 Part B D&C Red #6 Lake 0.1 D&C Red #7 Lake 0.1 AS 5126 Red Iron oxide color techniques 0.9 AS 5146 Black Iron oxide color techniques 0.2 Alkyl ketal ester* 2 Part C AS Duan Talc 50707 Color techniques 20.4 Mica AS Sericite 5061 Color techniques 14 Bismuth oxychloride 16 *Alkyl ketal ester examples: Ex. A, methyl-LGK Ex. B, ethyl-LGK Ex.
• Part A To manufacture the example formulations, combine Part A and begin homogenizing. Pre-mill Part B until pigments are well blended. Add Part B to Part A and homogenize until pigments are evenly dispersed. Begin heating A/B. Prepare a slurry of Part C and add to Parts A/B and heat to 85° C., maintaining temperature in the 85-90° C. range for 10 minutes. Remove from heat and prepare a second slurry of the ingredients in Part D. Add the slurried of Part D to A/B/C at 77° C. Homogenize until uniform and smooth. Check weight and add water to compensate for any loss, plus another 20 g/kg of formulation. Continue mixing and increase temperature to 77 C. Combine Part E ingredients separately and heat to 77° C.
• one of the alkyl ketal esters is a blend of Et-LGK and an alkyl ketal ester of Exs. B-K.
• the above-described compounds have, in embodiments, one or more isomers.
• an isomer can exist, it should be understood that the invention embodies methods that form any isomer thereof, including any stereoisomer, any conformational isomer, and any cis, trans isomer; isolated isomers thereof; and mixtures thereof.
• any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom.
• a dash (“—”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent.
• —CHO is attached through carbon of the carbonyl group.
• Alkyl groups may be straight-chained or branched. Hydroxyl groups have the formula —OH.
• compositions refers to both a composition that can be used to manufacture a product, and the product itself, i.e., in the form provided to the user.
• compositions can be used to manufacture a product by addition of one or more additional ingredients and/or subjecting the formulation to one or more processing steps, including in some embodiments simply packaging the composition.
• a “low VOC” formulation or product contains no more than 60 wt. % by weight of components that contain at least one carbon atom and meets all of the following conditions: (A) has vapor pressure more than 0.1 mm Hg at 20° C., as determined by ARB Method 310; (B) contains less than 12 carbon atoms, and (C) has a boiling point less than 216° C., as determined by ARB Method 310.
• an “alcohol” means a C1-7 alkanol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, and 1-hexanol, as well as the various other isomers of pentanol and hexanol; alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propane diol, dipropylene glycol, tripropylene glycol 1,4-butane diol and 1,2-butane diol; triols such as glycerine, and the like.
• an alcohol is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 1-hexanol, ethylene glycol, 1,2-propylene glycol, and 1,3-propane diol.

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