EP0927019A1 - Compositions utilisables en cosmetologie - Google Patents

Compositions utilisables en cosmetologie

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Publication number
EP0927019A1
EP0927019A1 EP98918925A EP98918925A EP0927019A1 EP 0927019 A1 EP0927019 A1 EP 0927019A1 EP 98918925 A EP98918925 A EP 98918925A EP 98918925 A EP98918925 A EP 98918925A EP 0927019 A1 EP0927019 A1 EP 0927019A1
Authority
EP
European Patent Office
Prior art keywords
extract
peg
cosmetic composition
oil
polymer network
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98918925A
Other languages
German (de)
English (en)
Inventor
Eyal S. Ron
Barry J. Hand
Lev S. Bromberg
Marie Kearney
Matthew E. Schiller
Peter M. Ahearn
Scott Luczak
Thomas H. E. Mendum
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Medlogic Global Corp
Original Assignee
Medlogic Global Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Medlogic Global Corp filed Critical Medlogic Global Corp
Publication of EP0927019A1 publication Critical patent/EP0927019A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/04—Preparations for care of the skin for chemically tanning the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/04—Preparations for permanent waving or straightening the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • 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
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers

Definitions

  • the present invention relates to a cosmetic composition useful in a variety of topical and personal care products, including treatments of disorders and imperfections of the skin or o ⁇ er areas of the body. More particularly, the present invention is directed to a cosmetic composition comprising a poloxamer:poly(acrylic acid) polymer network that can be designed to reversibly gel over a wide range of conditions to provide a composition having a controllable range of viscosities, making it useful in a variety of cosmetic and personal care applications.
  • hydrogels such as cellulosics
  • a hydrogel is a polymer network which absorbs a large quantity of water without the polymer dissolving in water.
  • the hydrophilic areas of the polymer chain absorb water and form a gel region.
  • the extent of gelation depends upon the volume of the solution which the gel region occupies.
  • Reversibly gelling solutions are known in which the solution viscosity increases and decreases with an increase and decrease in temperature, respectively. Such reversibly gelling systems are useful wherever it is desirable to handle a material in a fluid state, but performance is preferably in a gelled or more viscous state.
  • a known material with these properties is a thermal setting gel using block copolymer polyols, available commercially as Pluronic® polyols (BASF,
  • Another known system which is liquid at room temperature, but forms a semi- solid when warmed to about body temperature is formed from tetrafunctional block polymers of polyoxyethylene and polyoxypropylene condensed with ethylenediamine. commercially available as Tetronic® polyols. These compositions are formed from approximately 10% to 50% by weight of the polyol in an aqueous medium. See, U.S. Patent No. 5,252.318.
  • compositions including Pluronic® and Tetronic® polyols commercially available forms of poly(ethylene glycol)/poly(propylene glycol) block copolymers, significant increases in viscosity (5- to 8-fold) upon a simultaneous change in temperature and pH are observed only at much higher polymer levels. See, Figs. 3-6 of Joshi et al.
  • WO 95/24430 disclose block and graft copolymers comprising a pH-sensitive polymer component and a temperature-sensitive polymer component.
  • the block and graft copolymers are well-ordered and contain regularly repeating units of the pH-sensitive and temperature-sensitive polymer components.
  • the copolymers are described as having a lower critical solution temperature (LCST), at which both solution-to-gel transition and precipitation phase transition occur.
  • LCST critical solution temperature
  • Light transmission is reduced, which may be undesirable in many applications, where the aesthetic characteristics of the composition are of some concern.
  • the known systems which exhibit reversible gelation art limited in that they require large solids content and/or in that the increase in viscosity less than 10- fold.
  • a cosmetic composition which incorporates a poloxamer:poly(acrylic acid) polymer network as a cosmetically acceptable carrier.
  • the polymer network comprises a poloxamer component randomly bonded to a poly(acrylic acid), or PAA. component in an aqueous-based medium, the polymer network being capable of aggregating in response to an increase in temperature.
  • the reverse thermal viscosifying poloxamer:poly(acrylic acid) polymer network includes random covalent bonding between the poly(acrylic acid) component and the poloxamer component of the network.
  • the polymer network may also include some unbound or "free" poloxamer or other additives which contribute to or modify the characteristic properties of the polymer composition.
  • the cosmetic composition includes a cosmetic agent selected to provide a preselected cosmetic effect.
  • cosmetic agent as that term is used herein, it is meant that the additive imparts a cosmetic effect.
  • a cosmetic effect is distinguishable from a pharmaceutical effect in that a cosmetic effect relates to the promoting bodily attractiveness or masking the physical manifestations of a disorder or disease.
  • a pharmaceutic seeks to treat the source or symptom of a disease or physical disorder. It is noted however, that the same additives may have either a cosmetic or pharmaceutical effect, depending upon the amounts used and die manner of administration.
  • Cosmetic as that term is used herein, it is meant the cosmetic and personal-care applications intended to promote bodily attractiveness or to cover or mask the physical manifestations of a disorder or disease.
  • Cosmetics include those products subject to regulation under the FDA cosmetic guidelines, as well as sunscreen products, acne products, skin protectant products, anti-dandruff products, and deodorant and antiperspirant products.
  • gelation or viscosification, as that term is used herein, it is meant a drastic increase in the viscosity of the polymer network solution. Gelation is dependent on the initial viscosity of the solution, but typically a viscosity increase in the range of preferably 2- to 100-fold, and preferably 5- to 50-fold, and more preferably 10- to 20- fold is observed in the polymer network which is used in d e preparation of the cosmetic compositions of the invention. Such effects are observed in a simple polymer network solution and the effect may De modified by the presence of other components in the cosmetic composition.
  • polystyrene resin is a triblock copolymer derived from poIy(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) blocks.
  • the poloxamer is capable of responding to a change in temperature by altering its degree of association and/or agglomeration.
  • the aggregation may be in the form of micelle formation, precipitation, labile crosslinking or other factors.
  • the poly(acrylic acid) component includes poly(acrylic acid) and its salts.
  • the poly(acrylic acid) supports and interacts with the poloxamer component so that a multi-material, responsive polymer network is formed.
  • the interaction of the poloxamer and poly(acrylic acid) exhibits a synergistic effect, which magnifies the effect of the poloxamer component in viscosifying and/or gelling the solution.
  • the novel interaction between the constituent polymers components of the polymer network permits formation of gels at very low solids content. Gelation and/or viscosification is observed in aqueous solutions having about 0.01 to 20 wt% of the poloxamer component and about 0.01 to 20 wt% of the poly(acrylic acid) component.
  • a typical reversibly gelling polymer network may be comprised of less than about 4 wt% of total polymer solids (e.g., poloxamer and poly(acrylic acid))and even less dian lwt% total polymer solids while still exhibiting reverse thermal viscosification.
  • total polymer solids e.g., poloxamer and poly(acrylic acid)
  • d e total solids content including additives of a reversibly gelling polymer network composition may be much higher.
  • the viscosity of the gel increases at least ten-fold with an increase in temperature of about 5°C at pH 7 and 1 wt% polymer. Viscosity increases may be even greater over a larger temperature range at pH 7 and 1% polymer network content.
  • the relative proportion of poloxamer and poly(acrylic acid) may vary dependent upon the desired properties of the polymer composition.
  • the poloxamer is present in a range of about 1 to 20 wt% and the poly(acrylic acid) is present in a range about of 99 to 80 wt%.
  • the poloxamer component is present in a range of about 21 to 40 wt% and the poly(acrylic acid) component is present in a range of about 79 to 60 wt%.
  • the poloxamer component is present in a range of about 41 to 50 wt% and the poly(acrylic acid) component is present in a range of about 59 to 50 wt%.
  • the poloxamer component is present in a range of about 51 to 60 wt% and the poly(acrylic acid) component is present in a range of about 49 to 40 wt%.
  • me poloxamer component is present in a range of about 61 to 90 wt% and the poly(acrylic acid) component is present in a range of about 39 to 20 wt%.
  • d e poloxamer component is present in a range of about 81 to 99 wt% and me poly(acrylic acid) component is present in a range of about 19 to 1 w ⁇ %.
  • the poloxame ⁇ poly(acrylic acid) polymer network described above is included in a cosmetic composition to improve the flow characteristics, thickness and other properties of the composition.
  • the composition includes additional cosmetic agents. such as are needed for the cosmetic purpose of the composition.
  • Additives also may be included to modify die polymer network performance, such as to increase or decrease the temperature of the liquid-to-gel transition and/or to increase or decrease the viscosity of the responsive polymer composition.
  • the poloxamer:poly(acrylic acid) polymer network is incorporated into a cosmetic compositions to impart thickening properties to the cosmetic composition at the use and/or application temperature. Such thickening properties include enhanced overall viscosity, as well as a desirable viscosity response with temperature.
  • the polymer network may be useful as a diickener in pH ranges where other thickeners are not effective.
  • the poloxamer:poly(acrylic acid) polymer network is incorporated into a cosmetic composition to stabilize and solubilize hydrophobic agents in the cosmetic composition.
  • the polymer network may be included to increase emulsion stability. Many emulsions, i.e.. suspension of small droplets or particles of a first material in a second material, lose viscosity upon heating. As will be demonstrated herein, the poloxamer:poly(acrylic acid) polymer network retains its emulsifying properties even with temperature increase.
  • composition may be included in the composition to impart emolliency to the composition.
  • the composition may also act as a film-forming agent after it has been applied to die skin. This film-forming agent may be used as a barrier to prevent water loss from the skin which contributes to the moisturization of the skin.
  • the poloxamer:poly(acrylic acid) poiymer network may be included as an additive in cosmetic applications to prevent viscosity loss at elevated temperatures.
  • Figure 1 is a graph of viscosity vs. temperature for a 1 wt%, 2 wt% and 3 wt% responsive polymer network aqueous composition of a poloxamer/poly(acrylic acid) (1 : 1) at pH 7.0 measured at a shear rate of 0.44 sec "1 ;
  • Figure 2 is a graph of viscosity vs. temperature for a 1 wt% poloxamer: poly(acrylic acid) polymer network composition demonstrating reversibility of the viscosity response;
  • Figure 3 shows die viscosity response of a 2 wt% poloxamer:poly(acrylic acid) polymer composition at various shear rates;
  • Figure 4 shows a viscosity response curve for a 2 wt% poloxamer: poly(acrylic acid) polymer network composition prepared wim nominal mixing and stirring and prepared using high shear homogenization (8000 rpm, 30 min);
  • Figure 5 is a graph of viscosity vs. temperature for a 1 wt% poloxamer: poly(acrylic acid) polymer network composition at various pHs;
  • Figure 6 is a graph of viscosity vs. temperature for a 1 wt% poloxamer: poly(acrylic acid) polymer network composition with and without addition ol 0.25 wt% KC1;
  • Figure 7 is a graph of viscosity vs. temperature for a 1 wt% poloxamer: poly(acrylic acid) polymer network composition with and without addition of 0.5 wt% acetamide MEA;
  • Figure 8 is a graph of viscosity vs. temperature for a 1 wt% poloxamer: poly(acrylic acid) polymer network composition wi out and with 5 wt%, 10 wt% and 20 wt% added ethanol, respectively;
  • Figure 9 is an illustration of a reversibly gelling polymer network used as an emuisifier and stabilizer for a hydrophobic agent
  • Figure 10 is a schematic illustration of me poloxamer:poly(acrylic acid) polymer network below and above the transition temperature illustrating die aggregation of the hydrophobic poloxamer regions;
  • Figure 1 1 is a graph of viscosity vs. pH for a 1 wt% responsive polymer network aqueous composition of a poloxamer/poly(acrylic acid) (1 :1) measured at a shear rate of 0.44 sec "1 ;
  • Figure 12 is a plot of viscosity vs. temperature for (a) a 1 wt% responsive polymer network aqueous composition of Pluronic® F127 poloxamer/poly(acrylic acid) (1 : 1) and (b) a 1 wt% physical blend of Pluronic® F127 poloxamer/poly(acrylic acid) (1 : 1) at pH 7.0 measured at a shear rate 0.22 sec "1 ;
  • Figure 13 is a plot of viscosity vs. temperature for a 1 wt% responsive polymer network aqueous composition of Pluronic® F88 poloxamer/poly(acrylic acid) (1 : 1) at pH 7.0 measured at a shear rate 2.64 sec " ';
  • Figure 14 is a graph of the viscosity vs. temperature effect for a responsive polymer network composition of 2 wt% Pluronic® PI 04 poloxamer/poly(acrylic acid) (1 : 1) in deionized water at pH 7.0 measured at shear rate of 22 sec "1 ;
  • Figure 15 is plot of viscosity vs. temperature for a responsive polymer network composition of 2 w ⁇ % Pluronic® F123 poloxamer/poly(acrylic acid) (1 : 1) at pH 7.0 measured at a shear rate of 22 sec " ':
  • Figure 16 is a plot of viscosity vs. temperature for 1 wt% made of series of poloxamers and poly(acrylic acid) (1 : 1) in deionized water at a shear rate of 132 sec '1 ;
  • Figure 17 is a plot showing release of hemoglobin from a poloxamer/poly(acrylic acid) polymer network of the invention.
  • Figure 18 is a plot showing the release of lysozyme from the poloxamer/poly(acrylic acid) polymer complex of the invention:
  • Figure 19 is a plot showing release of insulin from a poloxamer/poly(acrylic acid) polymer network composition of the invention:
  • Figure 20 is a plot of viscosity vs. temperature for a poloxamer/poly(acrylic acid) polymer network composition (a) before and (b) after sterilization by autoclave;
  • Figure 21 is a plot of viscosity vs. temperature for an oil-free moisturizing formulation prepared from (a) a responsive polymer network composition of the invention and (b) a conventional oil-in-water formulation;
  • Figure 22 is a plot of equilibrium solubility of estradiol (A, B) and progesterone (C, D) in aqueous solutions (pH 7) of Pluronic® F127 (A, C) and responsive polymer network (B, D) vs. temperature;
  • Figure 23 is a plot of the ratio of equilibrium solubilities of estradiol in responsive polymer network and water vs. polymer concentration in the responsive polymer network solutions;
  • Figure 24 is a plot of the effect of loading fluorescein on the onset of gelation of responsive polymer network vs. total polymer concentration in responsive polymer network solution (pH 7.0);
  • Figure 25 is a plot of die percentage of a) estradiol and b) progesterone release from responsive polymer network vs. time;
  • Figure 26 is a plot of the rate of progesterone release and macroscopic viscosity vs. polymer concentration
  • Figure 27 is a plot of the percentage of progesterone release vs. polymer concentration in responsive polymer network and, Figure 28 is a plot of the relative diffusivity of poly(styrene) latex panicles in water and responsive polymer network.
  • the present invention is directed to a cosmetic composition
  • a cosmetic composition comprising a cosmetically acceptable carrier comprising a novel poloxamer:poly acrylic acid) polymer network.
  • the polymer network functions as a temperature sensitive thickening agent, and in addition possesses surfactant and emulsifying capabilities which may be beneficial to the cosmetic composition.
  • the polymer network composition according to the invention includes a poloxamer component randomly bonded to a poly(acrylic acid) component. The two polymer components may interact with one another on a molecular level.
  • the polymer network contains about 0.01-20 wt% each of poloxamer and poly(acrylic acid).
  • Exemplary polymer network- compositions range from about 1 : 10 to about 10:1 poloxamer:poly(acrylic acid).
  • Polymer network gel compositions which exhibit a reversible gelation at body temperature (25-40°C) and or at physiological pH (ca. pH 3.0-9 0) and even in basic environments up to pH 13 (hair care) are particularly
  • a 1 : 1 poloxamer:poly(acrylic acid) polymer network at appropriate pH exhibits flow properties of a liquid at about room temperature, yet rapidly thickens into a gel consistency of at least about five times greater, preferably at least about 10 times greater, and even more preferably at least about 30 times and up to 100 times greater, viscosity upon increase in temperature of about 10 °C and preferably about 5 °C.
  • the reversibly gelling polymer network of the present invention exhibit gelation even at very low polymer concentrations.
  • polymer network compositions at pH 7 comprising about 0.5 wt% poloxamer component and about 0.5 wt% PAA exhibits a significant increase in viscosity from a free-flowing liquid (50 cps) to a gel (6000 cps).
  • the observed gelation takes place at low solids contents, such as less tiian 20 wt% or preferably less than about 10 wt%, or more preferably less than about 2.5 wt% or most preferably less than about 0.1 wt%.
  • only a small amount by weight of the polymer network need be incorporated into a cosmetic composition in order to provide me desired thickening or viscosifying effect.
  • the reverse viscosification effect at low polymer concentrations provides clear, colorless gels which are particularly well-suited to cosmetic applications. For example, very little residue is formed upon dehydration which may be important in some applications, such as in topically applied cosmetics.
  • An additional advantage of d e polymer network of the invention is that it remains clear and translucent above and below the critical temperature or pH. These characteristics of me reversibly gelling polymer network make it well suited for use in cosmetic compositions.
  • the polymer network of the present invention technology may be added to cosmetic formulations to increase the diickness and viscosity of die composition.
  • the poloxamer:poly(acrylic acid) polymer network possesses hydrophobic regions capable of aggregation.
  • the aggregation of the polymer network of the present invention is temperature sensitive.
  • die inventive polymer network of the present invention may have a transition temperature (i.e. temperature of aggregation) above room temperature so that die cosmetic composition is of low viscosity at or below room temperature and is of high viscosity at or around body temperature (body temperature includes both surface and internal body temperature).
  • body temperature includes both surface and internal body temperature.
  • a composition may be prepared at low temperatures while the polymer network is in a low viscosity state. Mixing of ingredients under low viscosity is expected to be easier, thus simplifying the manufacturing process. Yet, the resultant mixture would be of increased viscosity at use temperatures.
  • a cosmetic composition comprising poloxamer:poly(acrylic acid) polymer network may be spread ti inly to allow for even application, due to its low viscosity at room temperature, but will thicken and "fill" the skin contours upon warming up to body surface temperature.
  • d e composition may be applied d rough a nozzle d at provides high shear to reduce viscosity, yet the composition regains its viscosity after application to d e skin. This contrasts with conventional formulations which permanently lose viscosity after being subjected to high shear.
  • the composition may be formulated and applied as a liquid, spray, semi-solid gel, cream, ointment, lotion, stick, roll-on formulation, mousse, pad-applied formulation, and film-forming formulation.
  • the poloxamer:poly(acrylic acid) polymer network may also be included in a cosmetic composition for use as a stabilizing, solubilizing or emulsifying agent for a hydrophobic component of the cosmetic formulation.
  • the strong hydrophilic regions of the poloxamer resulting from aggregation and micelle formation create hydrophobic domains which may be used to solubilize and control release of hydrophobic agents. Similar micelle-based systems have been shown to protect trapped peptides against enzymatic degradation from surface enzymes.
  • the reversibly gelling polymer network of the present invention is a unique polymer composition designed to abruptly change its physical characteristics or the characteristics and properties of materials mixed d erewith with a change in temperature.
  • d e structure of the polymer network involves a random bonding of die poloxamer onto the backbone of die poly(acrylic acid).
  • a portion of the poloxamer which is present during d e polymerization reaction which forms the poly(acrylic acid) is bonded to the backbone of the forming poly(acrylic acid) dirough hydrogen abstraction and subsequent reaction. See detailed discussion of die mechanism, below.
  • the combination of the poly(acrylic acid) and randomly bonded poloxamer gives the composition its unique properties. Any free poloxamer remaining after polymerization of PAA remains associated with the random co-polymer, resulting in a miscible composition.
  • Free poloxamer may also be present in the polymer network composition; however, its presence is not required in order to observe reverse thermal viscosification.
  • the poly(acrylic acid) may be linear, branched and/or crosslinked. Poly(acrylic acid) is capable of ionization with a change in pH of the solution. By ionization, as tiiat term is used witii respect to poly(acrylic acid), it is meant the formation of d e conjugate base of the acrylic acid, namely acrylate.
  • poly(acrylic acid) includes both ionized and non-ionized versions of me polymer. Changes in ionic strength may be accomplished by a change in pH or by a change in salt concentration.
  • the viscosifying effect of the polymer network is partly a function of the ionization of d e poly(acrylic acid); however, reverse thermal gelling may occur without ionization. Changes to the ionic state of the polymer causes the polymer to experience attractive (collapsing) or repulsive (expanding) forces. Where there is no need or desire for the composition to be applied in a high viscosity state, it may be possible to prepare the composition as non-ionized poly(acrylic acid). The body ' s natural buffering ability will adjust the pH of the applied composition to ionize the poly(acrylic acid) and diereby develop its characteristic viscosity.
  • the poloxamer possesses regions of hydrophobic character, e.g., polypropylene glycol) blocks, and hydrophilic character, e.g.. poiy(ethylene glycol) blocks.
  • the poloxamer may be linear or branched.
  • Suitable poloxamers include triad block copolymers of poly(ethylene glycol) and poly(propylene glycol) having the general formula (P
  • poly(propylene glycol) represents the hydrophobic portion of the polymer and poly(etirylene glycol) represents the hydrophilic portion of die polymer.
  • Pluronic® polymers BASF are commercially available for a in the range of 16 to 48 and b ranging from 54-62.
  • One or more poloxamers may be used in die reversibly gelling polymer network composition of the present invention.
  • the reversibly gelling responsive polymer networks compositions of me present invention are highly stable and do not exhibit any phase separation upon standing or upon repeated cycling between a liquid and a gel state. Samples have stood at room temperature for more than three months without any noticeable decomposition, clouding, phase separation or degradation of gelation properties. This is in direct contrast to polymer blends and aqueous mixed polymer solutions, where phase stability and phase separation is a problem, particularly where the constituent polymers are immiscible in one anotiier.
  • Figure 1 is a graph of viscosity vs. temperature for 1 wt%, 2 wt% and 3 wt% polymer network compositions comprising 1 : 1 poloxamer:poly(acrylic acid), hydrated and neutralized.
  • the viscosity measurements were taken on a Bro ⁇ kfield viscometer at a shear rate of 0.44 sec " ' at pH 7.0. All solutions had an initial viscosity of about 1080 cP and exhibited a dramatic increase in viscosity to gel point at about 35°C.
  • poloxamer:poly(acrylic acid) polymer network composition does not permanently loose viscosity after being subjected to high shear conditions.
  • the poloxamer:poly(acrylic acid) polymer network composition remains unaffected by such shear conditions as homogenization.
  • Figure 4 compares die viscosity response curve of a 2 wt% poloxamer:poly(acrylic acid) polymer composition prepared with nominal mixing (simple lime) and stirring with that of a polymer composition of similar composition prepared using high shear homogenization designated by a ticked line (8000 rpm, 30 min). No significant decrease in viscosity is observed.
  • the responsive polymer network may also include additives for influencing die performance of the polymer composition, such as the transition temperature and the viscosity of the polymer composition above me transition temperature.
  • additives for influencing die performance of the polymer composition such as the transition temperature and the viscosity of the polymer composition above me transition temperature.
  • the following list is not intended to be exhaustive but rather illustrative of the broad variety of additives which can be used.
  • solvents e.g., 2-propanol, ethanol, acetone, 1,2- pyrrolidinone, N-methylpyrrolidinone
  • salts e.g., calcium chloride, sodium chloride, potassium chloride, sodium or potassium phosphates, borate buffers, sodium citrate
  • preservatives benzalkonium chloride, phenoxyethanol, sodium hydroxymediylglycinate.
  • ethylparaben benzoyl alcohol, methylparaben, propylparaben.
  • humectant/moisturizers acetamide MEA, lactimide MEA, hydrolyzed collagen, mannitol, pandienol, glycerin
  • lubricants hyaluronic acid, mineral oil, PEG-60-lanolin, PPG-12-PEG-50-lanolin, PPG-2 myristyl ether propionate
  • surfactants may be divided into tiiree classes: cationic, anionic, and nonionics.
  • An example of a cationic surfactant used is ricinoleamidopropyl ethyldimonium ed osulfate (Lipoquat R).
  • Anionic surfactants include sodium dodecyl sulfate and etiier sulfates such as Rhodapex CO-436.
  • Nonionic surfactants include Surfynol CT-111, TG, polyoxyediylene sorbitan fatty acid esters such as Tween 65 and 80, sorbitan fatty acid esters such as Span 65, alkylphenol ethoxylates such as Igepal CO-210 and 430, dimethicone copolyols such as Dow Corning 190, 193, and Silwet L7001.
  • polymers including xanthan gum.
  • cellulosics such as hydroxyethylcellulose (HEC), carbomethoxycellulose (CMC), lauryldimonium hydroxypropyl oxyethyl cellulose (Crodacel QL). hydroxypropylcellul.se (HPC), and hydroxypropylmethylcellulose (HPMC).
  • HEC hydroxyethylcellulose
  • CMC carbomethoxycellulose
  • HPC hydroxypropylcellul.se
  • HPMC hydroxypropylmethylcellulose
  • Poloxamers may also be used as additives.
  • Examples include bodi the Pluronic® polyols having an (P 1 ) a (P : ) b (P ⁇ ) a structure such as Pluronic® F38. L44. P65, F68. F88. L92, P103. P104. P105. F108. L 122 and F127, as well as the reverse
  • Pluronic® R series (P : ) a (P,) b (Pi) a structure such as Pluronic® 17R2 and 25R8.
  • Other miscellaneous materials include propylene glycol. urea, triethanolamine. alkylphenol etiioxylates (Iconol series), and linear alcohol alkoxylates (Plurafac series).
  • Additives affect the viscosity of the compositions differently depending upon the nature of the additive and its concentration. Some additives will affect the initial or final viscosity, whereas others will affect d e temperature range of the viscosity response, or both.
  • Potassium chloride and acetamide MEA are two examples of additives which decrease the final viscosity of the composition (see, Example 30).
  • KC1 (0.25%) added to a 1 wt% reversibly gelling polymer composition reduces the viscosity by about 3000 cps. See, Figure 6.
  • the humectant, acetamide MEA lowers the viscosity of a 1 wt% solution by approximately 1,500 cps (see, Figure 7).
  • Glycerin, etiianol and dimetiiicone copolymer have been shown to affect d e temperature range over which the viscosity response occurs. Glycerin shifts the transition temperature to a slightly lower range from an initial 24-34 °C to about 24- 30 °C, but does not affect die final viscosity (see, Example 44). The effect of ethanol on d e viscosity is different at different concentration levels. At 5 wt% and 10 wt% added ethanol, die transition temperature is shifted to lower ranges, e.g., 24-29 °C and 20-29 ° C. respectively. At 20 wt% added ethanol.
  • d e composition not only exhibits a lowering of the transition temperature, but also a marked increase in initial and final viscosity. See, Figure 8. Dimethicone copolymer ( 1 wt%) also changed the transition temperature, but in this instance the transition temperature range was raised to 28- 41 ° C. Thus, proper selection of additives permits me formulator to adjust d e transition temperature to various ranges.
  • the polymer network compositions of the present invention may be utilized for a wide variety of cosmetic and personal care applications. To prepare a cosmetic composition, an effective amount of cosmetically active agent(s) which imparts the desirable cosmetic effect is incorporated into the reversibly gelling polymer network composition of the present invention.
  • the selected agent is water soluble, which will readily lend itself to a homogeneous dispersion through out the reversibly gelling polymer network composition; however, the polymer network has been demonstrated to significantly solubilize or suspend hydrophilic agents in order to improve formulation homogeneity (see. Example 36). It is also preferred that the agent(s) is nonreactive with the polymer network composition. For materials which are not water soluble, it is also within die scope of the invention to disperse or suspend powders or oil (lipophilic materials) throughout the polymer network composition. It will also be appreciated tiiat some applications may require a sterile environment.
  • the reversibly gelling polymer network compositions of the present invention may be prepared under sterile conditions.
  • An additional feature of the reversibly gelling polymer composition is mat is prepared from constituent polymers that have known accepted toxicological profiles.
  • the poloxamer:poly(acrylic acid) polymer network has been evaluated under Good Laboratory Practice (GLP) standard protocols known in the art for toxicity in animal models and found to exhibit no toxic effects. The results of the toxicity study are summarized in the following Table 1. The non-toxicity of the polymer network makes it an ideal candidate for use in cosmetic compositions. Table 1. Toxicity data for 6% poloxamer: poly(acry lie acid) solution at pH 7.
  • Exemplary cosmetic and personal care applications for which the reversibly gelling polymer network composition may be used include, but are not limited to, baby products, such as baby shampoos, lotions, powders and creams: bath preparations, such as bath oils, tablet and salts, bubble baths, bath fragrances and bath capsules; -eye makeup preparations, such as eyebrow pencil, eyeliner, eye shadow, eye lotion, eye makeup remover and mascara; fragrance preparations, such as colognes and toilet waters, powders and sachets; noncoloring hair preparations, such as hair conditioner, hair spray, hair straighteners, permanent waves, rinses shampoos, tonics, dressings and otiier grooming aids; color cosmetics; hair coloring preparations such as hair dye, hair tints, hair shampoos, hair color sprays, hair lighteners and hair bleaches; makeup preparations such as face powders, foundations, leg and body paints, lipstick, makeup bases, rouges and makeup fixatives; manicuring preparations such as basecoats and undercoats,
  • the cosmetic composition may be in any form. Suitable forms include but are not limited to lotions, creams, sticks, r ⁇ ll-ons formulations, mousses, aerosol sprays, pad-applied formulations, and film-forming formulations.
  • the foregoing list is exemplary only. Because the reversibly gelling polymer network composition of die present invention is suited for application under a variety of physiological conditions, a wide variety of cosmetically active agents may be incorporated into and administered from the polymer network composition.
  • additional cosmetically acceptable carriers may be included in die composition, such as by way of example only, emollients, surfactants, humectants, powders and other solvents.
  • the cosmetic composition also may include additional components, which serve to provide additional aspects of the cosmetic affect or to improve the stability and/or administration of the cosmetic.
  • Such additional components include, but are not limited to, preservatives, abrasives, acidulents, antiacne agents, anti-aging agents, antibacterials, anticaking, anticaries agents, anticellulites, antidandruff, antifungal, anti-inflammatories, anti-irritants, antimicrobials, antioxidants, astringents, anitperspirants, antiseptics, antistatic agents, astringents, binders, buffers, additional carriers, chelators, cell stimulants, cleansing agents, conditioners, deodorants, dipilatories, detergents, dispersants, emollients, emulsifiers, enzymes, essential oils, exfoliants, fibers, film forming agents, fixatives, foaming agents, foam stabilizers, foam boosters, fungicides, gellants, glosser.
  • preservatives include, but are not limited to, preservatives, abrasives, acidulents, antiacne agents, anti-aging
  • hair conditioner hair set resins, hair sheen agents, hair waving agents, humectants.
  • lubricants moisture barrier agents, moisturizers, ointment bases, opacifier. plasticizer. polish, polymers, powders, propellant, protein, refatting agents, sequestrant, silicones.
  • Suitable materials which serve the additive functions listed here are well known in the cosmetic industry.
  • compositions of the invention include a safe and effective amount of a cosmetically active agent.
  • Safe and effective means an amount high enough to significantly positively modify the condition to be treated or the cosmetic effect to be obtained, but low enough to avoid serious side effects.
  • Preservatives can be desirably incorporated into the cosmetic compositions of die invention to protect against the growth of potentially harmful microorganisms.
  • Suitable preservatives include, but are not limited to, alkyl esters of para- hydroxybenzoic acid, hydantoin derivatives, parabens, propioniate salts, triclosan tricarbanilide, tea tree oil, alcohols, farnesol, farnesol acetate, hexachlorophene and quaternary ammonium salts, such as benzoiconjure, and a variety of zinc and aluminum salts.
  • Cosmetic chemists are familiar with appropriate preservatives and may selects that which provides die required product stability. Preservatives are preferably employed in amounts ranging from about 0.0001% to 2% by weight of the composition.
  • Emollients can be desirably incorporated into the cosmetic compositions of die invention to provide lubricity to the formulation.
  • Suitable emollients may be in the form of volatile and nonvolatile silicone oil. highly branched hydrocarbons and synti etic esters. Amounts of emollients may be in the range of about 0.1-30 wt%, and preferably about 1-20 wt%.
  • suitable silicones include cyclic or linear pol dimethylsiloxanes, polyalkylsiloxanes, polyalkylarylsiloxanes and polyether siloxanes.
  • ester emollients include alkenyl esters of fatty acids, polyhydric alcohols, such as ethylene glycol mono and di-fatty acid esters, polyethylene glycol and the like, ether-esters, such as fatty acid esters of ethoxylated fatty alcohols, wax esters, such as beeswax, spermaceti, mysristyl myristate and stearyl stearate. and sterol esters, such as cholesterol fatty acids.
  • ether-esters such as fatty acid esters of ethoxylated fatty alcohols
  • wax esters such as beeswax, spermaceti, mysristyl myristate and stearyl stearate.
  • sterol esters such as cholesterol fatty acids.
  • a variety of oily emollients may be employed in the compositions of this invention. These emollients may be selected from one or more of the following classes: 1.
  • Triglyceride esters such as vegetable and animal fats and oils. Examples include castor oil. cocoa butter, safflower oil, cottonseed oil. corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, squalene. Kikui oil and soybean oil; 2. Acetoglyceride esters, such as acetylated monoglycerides; 3.
  • Ethoxylated glycerides such as ethoxylated glyceryl monostearate: 4.
  • Alkyl esters of fatty acids having 10 to 20 carbon atoms such as. methyl, isopropyl, and butyl esters of fatty acids, and including hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate decyl stearate, isopropyl isostearate, diisopropyl adipate. diisohexvl adipate.
  • alkenyl esters of fatty acids having 10 to 20 carbon atoms such as oleyl myristate, oleyl stearate, and oleyl oleate and the like; 6. fatty acids having 10 to 20 carbon atoms, such as pelargonic, lauric, myristic, palmitic, stearic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, arachidic, behenic, and erucic acids and die like; 7.
  • fatty alcohols having 10 to 20 carbon atoms such as, lauryl, myristyl, cetyl, hexadecyl, stearyl, isostearyl, hydroxystearyl, oleyl, ricinoleyl, behenyl, erucyl, and 2-octyl dodecanyl alcohols are examples of satisfactory fatty alcohols and d e like, 8.
  • fatty alcohol ethers such as ethoxylated fatty alcohols of 10 to 20 carbon atoms including the lauryl, cetyl, stearyl, isostearyl, oleyl. and cholesterol alcohols, having attached thereto from 1 to 50 ethylene oxide groups or 1 to 50 propylene oxide groups: 9.
  • Lanolin and derivatives such as lanolin, lanolin oil, lanolin wax.
  • lanolin alcohols lanolin fatty acids, isopropyl lanolate.
  • ethylene glycol mono and di-fatty acid esters diedrylene glycol mono-and di-fatty acid esters, polyed ylene glycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol polyfatty esters, ethoxylated glyceryl monostearate, 1,2-butylene glycol monostearate, 1,2-butylene glycol distearate.
  • polyoxyetivylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters; 12. wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate: 13. beeswax derivatives, e.g. polyoxyethylene sorbitol beeswax; 14. vegetable waxes including carnauba and candelilla waxes; 15. phospholipids such as lecitiiin and derivatives; 16. sterol including cholesterol and cholesterol fatty acid esters; 17. amides such as fatty acid amides, ethoxylated fatty acid amides, solid fatty acid alkanolamides.
  • Humectants may be added to the composition to increase the effectiveness of die emollient, to reduce scaling, to stimulate removal of built-up scale and improve skin feel.
  • suitable humectants include polyhydric alcohols, such as glycerol, polyalkylene glycols, alkylene polyols dieir derivatives, propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1,2,6-hexanetriol, etiioxylated glycerol, propoxylated glycerol and the like.
  • polyhydric alcohols such as glycerol, polyalkylene glycols, alkylene polyols dieir derivatives, propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol, hydroxypropyl
  • the amount of humectant may be in the range of about 0.5-30 wt% and preferably between 1-15 wt%.
  • active substances may be advantageously employed.
  • suitable active agents which may be incorporated into the cosmetic composition include anti-aging active substances, anti-wrinkle active substances, hydrating or moisturizing or slimming active substances, depigmenting active substances, substances active against free radicals, anti- irritation active substances, sun protective active substances, anti-acne active substances, firming-up active substances, exfoliating active substances, emollient active substances, and active substances for the treating of skin disorders such as dermatitis and the like.
  • one or more moisturizers may be used, such as glycerin or urea, in combination with one or more precursor agents for the biosythesis of structural proteins, such as hydroxyproline, collagen peptides and the like.
  • At least one ketolytic agent or an alpha-hydroxyacid such as salicylic acid or 5-n-octanoicsalicylic acid may be used in combination with at least on liporegulating agent such as caffeine.
  • At least one keratolytic agent is used in combination with a depigmenting agent such as hydroquinone, tyrosinasee inhibitor (kosic acid), ascorbic acid, kojic acid and sodium metabisulfite an the like.
  • a depigmenting agent such as hydroquinone, tyrosinasee inhibitor (kosic acid), ascorbic acid, kojic acid and sodium metabisulfite an the like.
  • a depigmenting agent such as hydroquinone, tyrosinasee inhibitor (kosic acid), ascorbic acid, kojic acid and sodium metabisulfite an the like.
  • a depigmenting agent such as hydroquinone, tyrosinasee inhibitor (kosic acid), ascorbic acid, kojic acid and sodium metabisulfite an the like.
  • vitamin E asgainst COO radicals
  • superoxide dismutase asgainst O 2 free radicals
  • sugar and caffeine asgainst OH
  • moisturizers in the case of anti-aging, moisturizers, sunscreens, alpha-hydroxyacids, salicylic acid or surface restructuring agents may be used in combination witii enzymes for the repair of DNA, vascular protective agents or phospholipids rich in oligoelements and polyunsaturated fatty acids.
  • keratolytics such as salicylic acid, sulfur, lactic acid, glycolic, pyruvic acid, urea, resorcinol and N- acetylcvsteine, and retinoids.
  • retinoids such as retinoic acid and its derivatives may be used.
  • non-steroidal anti- inflammatory agents such as propionic acid derivatives, acetic acid, fenamic acid derivatives, biphenylcarboxylic acid derivatives, oxicams. including but not limited to aspirin, acetaminophen, ibuprofen. naproxen. benoxaprofen, flurbiprofen, fenbufen, ketoprofen. indoprofen. pirprofen, carporfen, and bucloxic acid and the like.
  • NSAIDS non-steroidal anti- inflammatory agents
  • Antimicrobial drugs preferred for inclusion in compositions of the present invention include salts of ⁇ -lactam drugs. quinolone drugs, ciprofloxacin, norfloxacin. tetracycline, er ⁇ hromycin. amikacin, triclosan. doxycycline, capreomycin. chlorhexidine, chlortetracycline, oxytetracycline. clindamycin, ed ambutol. hexamidine isethionate, metronidazole, pentamidine, gentamicin. kanamycin. lineomycin. methacycline. methenamine, minocycline, neomycin, netilmicin, paromomycin. streptomycin, tobramycin. miconazole and amanfadine and the like.
  • suitable agents include 2-ed ylhexyl p-methoxycinnamate, 2-ethylhexyl N.N-dimethyl-p- aminobenzoate, p-aminobenzoic acid, 2-phenyl p-meti oxycinnamate, 2-eti ⁇ ylhexyl octocrylene, oxybenzone, homomenmyl salicylate, octyl salicylate, 4,4' -methoxy- 1- butyldibenzoylmethen, 4-isopropyl dibenzoylmediane, 3-benzylidene camphor, 3-(4- methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof and the like.
  • the sunscreening agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit different ultra-violet radiation absorption spectra.
  • One of the chromophore moieties absorbs predominantly in the UVB radiation range and the otiier absorbs strongly in die UNA radiation range.
  • These sunscreening agents provide higher efficacy, broader UN absorption, lower skin penetration and longer lasting efficacy relative to conventional sunscreens.
  • the sunscreens can comprise from about 0.5% to about 20% of die compositions useful herein. Exact amounts will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen against erythema.
  • tanning agents include, dihydroxyacetone, glyceraldehyde. indoles and their derivatives, and the like.
  • the composition may include cleansing surfactants.
  • Cleansing surfactants are cationic, anionic. amphoteric or non-ionic surfactants which are water-soluble and produce a consumer-acceptable amount of foam.
  • ⁇ onionic surfactants are well-known materials and have been used in cleansing compositions. Therefore, suitable nonionic surfactants include, but are not limited to, compounds in the classes known as alkanolamides, block copolymers of ethylene and propylene. ethoxylated alcohols, ethoxylated alkylphenols, alkyl polyglycosides and mixtures diereof.
  • die nonionic surfactant can be an ethoxylated alkylphenol.
  • alkylphenol having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, d e etirylene oxide being present in an amount equal to at least about 8 moles ethylene oxide per mole of alkylphenol.
  • Examples of compounds of this type include nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of phenol; dodecylphenol condensed with about 12 moles of ediylene oxide per mole of phenol; dinonylphenol condensed widi about 15 moles of ethylene oxide per mole of phenol; octylphenol condensed with about ten moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
  • a wide variety of acids, bases, buffers, and sequestrants can be utilized to adjust and/or maintain die pH and ionic strengtii of die compositions useful in d e instant invention.
  • Materials useful for adjusting and/or maintaining d e pH and/or d e ionic strength include sodium carbonate, sodium hydroxide, hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, sodium acetate, sodium hydrogen phosphate, sodium dihydrogen phosphate, citric acid, sodium citrate, sodium bicarbonate, triethanolamine, EDTA, disodium EDTA, tetrasodium EDTA, and the like.
  • the polymer network may be useful as a solubilization agent in cosmetic and personal care applications.
  • a self-assembling system comprising the reversibly gelling polymer network exhibits thermogelation. pH sensitivity, and d e ability to solubilize hydrophobic agents in aqueous media.
  • PAA poly(acrylic acid)
  • the resulting copolymer network is bioadhesive and can be applied in a number of therapies.
  • the materials described in this invention combine "reverse" thermoviscosification mucoadhesion, solubilization of hydrophobic and difficult to manage moieties, easy formulation, and protection of agents from degradation to provide a superior medium for cosmetic and personal care products.
  • d e polymer network will have the ability to act as a primary emulsifier witiiout any (or with very little) addition of traditional surfactant.
  • the responsive polymer network will also act as a stabilizer for oil-soluble ingredients that would conventionally need to be solubilized by oils in formulation.
  • the hydrophobic portion of the polymer network (PPO) forms domains which act as reservoirs for an oil- soluble or hydrophobic additive, such as an oil droplet, as is illustrated in Figure 9.
  • poloxamer:poly(acrylic acid) polymer network compositions are valuable materials in the formulation of cosmetic and personal care products.
  • they may be useful as rheology modifiers, provide a cushioning effect on :ne skin, offer barrier properties and controlled release of actives.
  • the polymer composition may serve as a surfactant and is compatible with most ingredients used in the cosmetic industry.
  • the above properties of the poloxamer:poly(acrylic acid) polymer network provides a cosmetic composition that spreads evenly and smoothly and which leaves a lubricious feel to the skin.
  • a sensory evaluation was conducted with seven random volunteers in order to determine the sensory effect of a cream formulation on the skin.
  • An oil-free cosmetic formulation was prepared substantially as set forth in Example 33(b) and was compared to Nivea Oil Free, a product of Beiersdorf of Germany.
  • the aggregation process may be understood as occurring as shown in Figure 10, in which a backbone 20 represent poly( acrylic acid), a thin band 24 represents the hydrophobic poly(propylene) glycol region of the poloxamer and a thick band 26 represents the hydrophilic poly(ethylene glycol) region of the poloxamer.
  • a backbone 20 represent poly( acrylic acid)
  • a thin band 24 represents the hydrophobic poly(propylene) glycol region of the poloxamer
  • a thick band 26 represents the hydrophilic poly(ethylene glycol) region of the poloxamer.
  • the polymer network is randomly arranged, as is shown in Figure 10(a).
  • the hydrophobic regions 24 associate to form aggregations or micelles 28, as is shown in Figure 10(b).
  • the association increases die effective molecular weight of die polymer network composition with the corresponding increase in viscosity.
  • a general method of making the poloxame ⁇ PAA polymer network compositions of the present invention comprises solubilization of the poloxamer in acrylic acid monomer, followed by polymerization of the monomer to P.AA.
  • Polymerization may be accomplished by addition of a polymerization initiator or by irradiation techniques.
  • the initiator may be a free radical initiator, such as chemical free radical initiators and uv or gamma radiation initiators. Conventional free radical initiators may be used according to the invention, including, but in no way limited to ammonium persulfate. benzoin ethyl ether, benzyl peroxide.
  • the poloxamer component may be dissolved in an acrylic acid/water mixture instead of pure monomer. It may be desirable to remove unreacted monomer and or free poloxamer from the resultant polymer network. This ma ' y be accomplished using conventional techniques, such as. by way of example, dialysis or sohxlet extraction.
  • the scheme for bonding of poloxamer to acrylic acid may involve initiation (eq 1), hydrogen abstraction from the propylene or ethylene moiety of me poloxamer (eq 3), and attachment to acrylic acid via addition across the unsaturated bond (eq 10). Propagation (eq 8) leads to the final PAA.
  • the mechanism may proceed by initiation according to eqs. (1) and (2). propagation to form PAA (eq.8), a chain transfer reaction to generate a reactive poloxamer moiety (eq. 5), followed by addition of die reactive poloxamer moiety to die unsaturated bond of acrylic acid (eq. 10) and subsequent propagation of the PAA chain.
  • the polymer network may include a plurality of poly(acrylic acid)) units bonded to a single poloxamer unit or, alternatively, a plurality of poloxamer units bound to a single PAA backbone. Combinations of tiiese alternatives are also a possibility.
  • Reverse phase polymerization may be used to prepare polymer network beads by dispersion of the poloxamer and acrylic acid monomer mixture in a nonpolar solvent such as hexane or heptane.
  • the aggregating polymer/monomer solution is dispersed with agitation in the nonpolar solvent in order to suspend droplets of the solution.
  • Polymerization of the monomer is initiated by conventional means (i.e.. addition of a initiator or irradiation) in order to polymerize the monomer and form responsive polymer network beads. See, U.S.S.N. 08/276.532 filed July 18, 1995 and entitled “Useful Responsive Polymer Gel Beads" for further information on the preparation of polymer gel beads, herein incorporated by reference.
  • Such a method may be particularly desirable to provide a heat sink for the heat generated in the exothermic polymerization reaction.
  • polymer network complexes and aqueous gelling solutions of d e present invention may be understood with reference to the following examples, which are provided for the purposes of illustration and which are in no way limiting of the invention.
  • Example 1 This example describes d e syntiiesis of a polymer network and an aqueous responsive polymer network solution prepared using a triblock polymer of poly(ethylene glycol) and poly(propylene glycol), Pluronic® F27 polyol, and poly(acrylic acid). This example also characterizes the gelation and d e physical properties of the resultant polymer network.
  • Block copolymer of poly(propylene glycol) (PPG) and polyethylene glycol) (PEG) having triad ABA structure (PEG) A (PPG) B (PEG) A (Pluronic® F127 NF polyol, Poloxamer 407 NF polyol, where "F” means Flakes, "12” means 12X300 3600 - MW of the PPG section of the block copolymer, "7” PEG in die copolymer is 70 wt%, and nominal molecular weight is 12,600) from BASF (3.0 g) was dissolved in 3.0 g acrylic acid (Aldrich).
  • Viscosity measurements A known amount of me resultant polymer was suspended in 100 ml deionized water into which NaOH was added. Following swelling for 3 days while stirring, the pH of the resulting fine suspension was adjusted to 7. Samples of 15 ml each were taken, and pH in each vial was adjusted to desired value by addition of 1 M HCl or NaOH. Samples were then kept overnight and their viscosities were measured at different temperatures using Brookfield viscometer using either an SC4-18 or an SC4-25 spindle.
  • Figure 12 is a viscosity vs. temperature graph comparing the gelling characteristics of d e responsive polymer network composition and die physical blend.
  • the blend prepared by physically mixing of the triblock PEG/PPG/PEG polymer and poly(acrylic acid) did not exhibit viscosifying effect eitiier as a function of temperature or pH.
  • Example 2 This example describes a standard operating procedure for the manufacture of the reversible gelling polymer network.
  • a NaOH solution was prepared by dissolving 131.8 g NaOH pellets in 131.8 mL Dl water (50% solution). The NaOH was allowed to dissolve completely. The NaOH solution will be used to convert a percentage of the acrylic acid to sodium aery late in situ.
  • Acrylic acid monomer 4 kg is charged into a monomer feed tank and agitated at 250 rpm. NaOH is added slowly. The precipitate formed as the acrylic acid is ueutralized to sodium acrylate is allowed to dissolve.
  • Pluronic® F127 (3.5 kg) is slowly added to die monomer feed tank. Pluronic® F127 is dissolved under continued agitation.
  • Norpar 12 (a refined C-12 alkane) is added to d e reaction vessel (37 L). The mixture is agitated at 100 rpm. Stabilizer solution of Ganex V-126 is prepared in 2L Norpar 12 and added to the reactor under agitation. A reaction vessel was degassed using a nitrogen sparge introduced from the bottom of reactor and was continued throughout the reaction. Initiator (13.63 g Lauryl peroxide and 4.23 g Vazo 52 in 0.7 kg acrylic acid monomer) is introduced into die monomer solution. The monomer solution was transferred to the reaction vessel. Agitation was increased to 150 rpm. Nitrogen sparging continued for an additional 20 minutes and then heating began. Heating began at a rate of 0.5-1.0 X/min up to
  • the reaction began to exotherm at about 45-50 X and is allowed to continue witiiout cooling until a maximum is reached. It is ien cooled to 75 X using forced cooling. The reaction continued for 12 hours and was d en cooled to 35 X.
  • the slurry was transferred into pails and the polymer beads were allowed to settle. The slurry was filtered through Buchner Funnels with filter paper (11 ⁇ m pore size) until the bulk of die Norpar had been removed from the beads. The beads were washed d ree times with heptane. The filtered beads were transferred to a Pyrex drying tray and spread on die tray in a uniform layer. The beads were dried under vacuum for 4 hours at 40-50 X. The dried beads were analyzed as follows. Elemental analysis. The elemental analysis was performed by Quantitative
  • TGA Thermal Gravimetric Analysis
  • the effect of botii die bonded and non-bonded poloxamer on the gelation properties of the responsive polymer network has been determined by extraction of d e non-bonded poloxamer from die material.
  • Such extraction studies have established diat die graft co-polymer alone exhibits the characteristic reverse thermal gelation of the composition; however, the presence of non-bonded poloxamer component modulates d e gelation process.
  • the non-bonded poloxamer component can affect d e temperature of transition (from liquid to gel) and die degree of transition and assists in a more controlled and reproducible transition.
  • Bound poloxamer determination bv ethylene oxide fEO titration was performed as follows. A 5 gm sample of the product polymer was extracted in dichloroethane for three hours at reflux temperatures. The solid is removed and dried under a vacuum for 12 hours at room temperature. The dry material is then analyzed using ASTM method D 2959-95, "Standard Test Method for Ethylene Oxide Content". The amount of EO in the sample is related to the amount of poloxamer bound to the polymer. The typical result is approximately 15 % by weight of EO. The relative amount of free poloxamer may be varied dependent upon die relative proportions of starting materials and the method of polymerization.
  • d e residual solids presumably contain only poloxamer which is bonded to die poly(acrylic acid), i.e. , a graft co-polymer, the material still shows strong viscosification when it is neutralized and dissolved in water.
  • the temperature of viscosification is increased substantially and d e degree of viscosification per gram of total solids is increased by removal of free poloxamer.
  • die free poloxamer plays a role in modifying d e extent and temperature of viscosification.
  • the poloxamer undergoes conformational changes and changes to die critical micelle concentration as a function of temperature.
  • the poloxamer will change from an open, non-aggregated form to a micellular, aggregated form with changes in temperature.
  • Residual acrylic monomer determination by gas chromatography was determined by GC analysis using a Hewlet Packard GC 5890A, using a HP-FFDAP-TPA 10 m x 0.53 mm x l ⁇ m column. The sample was extracted and run in metiianol. Using an internal standard ratio, the sample was compared to a one point calibration. The typical results for this assay were below 70 ppm acrylic acid monomer.
  • Residual Norpar solvent bv GC Residual Norpar solvent bv GC.
  • the residual Norpar in d e sample was determined by GC using the above method and comparing the Norpar peaks to that of a standard. The typical results were below 1.5 wt%.
  • Differential scanning calorimetrv fDSCV The DSC was performed by Massachusetts Material Research. Inc.. West Boylston. MA using a temperature ramp from 30 to 350 X at 5 X/min. The resolution for the system was set to 4 (l.OX/min for all slope changes). The assay yielded one endothermic event at 265 X, typically 270 J/g.
  • Example 10 The following example demonstrates the effect of hydrophilic/hydrophobic ratio on the gelling temperature.
  • Polymer network compositions were prepared from the following poloxamers shown in Table 3. Table 3. Composition of poloxamers investigated.
  • the poloxamer (3.0 g) was dissolved in 3.0 g acrylic acid. The solution was deaerated by N 2 bubbling for 20 min. and following addition of the 100 :1 of freshly prepared saturated solution of ammonium persulfate in deionized water was kept at 70 °C for 16 h resulting in a strong whitish polymer. A sample of the polymer obtained (0.4 g) was suspended in 40 ml deionized water into which NaOH was added. Suspended responsive polymer network particles were allowed to dissolve under constant stirring. The resulting 1 wt% polymer network solutions were subjected to die viscosity measurement at shear rate of 132 or 13.2 sec using a SC4- 18 spindle.
  • Example 11 The following example is related to release of and active agent from a poloxamer: poly(acry lie acid) polymer network. Drug loading and kinetics of release of the protein hemoglobin from poloxamer:poIy(acryIic acid) polymer network is described.
  • Pluronic ® F127 (3.0 g) was dissolved in 3.0 g acrylic acid. The solution was deaerated by N 2 bubbling for 0.5 h and following addition of 100 FI of freshly prepared saturated solution of ammonium persulfate (Kodak) in deionized water was kept at 70°C for 16 h resulting in a transparent polymer. The resultant responsive polymer network obtained (5 g) was suspended in 95 ml deionized water into which NaOH was added. The resulting suspension was allowed to swell for 7 days.
  • a 5 wt% responsive polymer network composition (3 g) was allowed to swell for 16 h in 10 ml of 0.25 mg/ml solution of human hemoglobin (Sigma) in deionized water adjusted to pH 8. The resulting mixture was well shaken and placed into the feed chambers of customized vertical, static, Franz-like diffusion cells made of Teflon. The feed and receiver chambers of the diffusion cells were separated by mesh screens (# 2063). The receiver chamber was continuously stirred by a magnetic bar. The cells were allowed to equilibrate to either 25 or 37 °C (in an oven).
  • the feed and receiver phases consisted of 1 g of the hemoglobin-loaded responsive polymer network and 6 ml of phosphate-buffered saline (pH 7.4), respectively.
  • d e feed phase was made of 1 g of 0.25 mg/ml hemoglobin solution.
  • Samples of the receiver phase was withdrawn from time to time and their absorbance was measured spectrophotometrically at 400 nm.
  • corresponding calibration curves (absorbance in PBS versus hemoglobin concentration) were generated. The results of the kinetic experiment are presented in Figure 17.
  • Example 12 The following example is related to release of an active agent from a poloxamer: poly (aery lie acid) poiymer network. Drug loading and kinetics of release of the protein lysozyme from a polymer network is reported.
  • Lysozyme loading and release A 5 wt% responsive polymer network composition (3 g) was allowed to swell for 16 h in 10 ml of 1 mg/ml solution of chicken egg-white lysozyme (Sigma) and 1.5 mg/ml sodium dodecyl sulfate (Aldrich) in deionized water adjusted to pH 8.5. The resulting mixmre was well shaken and placed into the feed chambers of customized vertical, static, Franz-like diffusion cells made of Teflon. The feed and receiver chambers of the diffusion cells were separated by mesh screens (# 2063). The receiver chamber was continuously stirred by a magnetic bar. The cells were allowed to equilibrate to either 25 or 37 °C (in an oven).
  • the feed and receiver phases consisted of 1 g of the lysozyme-loaded responsive polymer network and 6 ml of phosphate-buffered saline (pH 7.4), respectively.
  • the feed phase was made of 1 g of 1 mg/ml lysozyme solution.
  • the kinetic time commenced. Samples were withdrawn and their absorbance measured spectrophotometrically at 280 nm.
  • a calibration curve was prepared for lysozyme concentration ranging from 0 mg/ml to 0.5 mg/ml in phosphate buffered saline. The results of the kinetic experiment are presented in Figure 18.
  • Example 13 The following example is related to release of an active agent from a poloxamer:poly(acrylic acid) polymer network. Drug loading and kinetics of release of insulin from a responsive polymer network composition is reported. Insulin loading and release. A 5 wt% responsive polymer network composition (3 g) was allowed to swell for 16 h in 10 ml of 5 mg/ml solution of bovine Zn 2+ -insulin (Sigma) in deionized water adjusted to pH 7. The resulting mixmre was well shaken and placed into the feed chambers of customized vertical, static, Franz-like diffusion cells made of Teflon. The feed and receiver chambers of the diffusion cells were separated by mesh screens (# 2063). The receiver chamber was continuously stirred by a magnetic bar.
  • the cells were allowed to equilibrate to either 25 or 37 °C (in an oven).
  • the feed and receiver phases consisted of 1 g of the insulin-loaded responsive polymer network and 6 ml of phosphate-buffered saline (pH 7.4), respectively.
  • the feed phase was made of 1 g of 5 mg/ml insulin solution. After the feed solution had been loaded into the cell, d e timing commenced. Samples were withdrawn and their absorbance was measured spectrophotometrically at 280 nm. A calibration curve was prepared for insulin concentration ranging from 0 mg/ml to 1.25 mg/ml in phosphate buffered saline. The results of the kinetic experiment are presented in Figure 19.
  • the rate of insulin release from responsive polymer network was substantially lowered at 37 °C when compared to that at 25 °C, because of viscosity increase in responsive polymer network at elevated temperamres (see Figure 1).
  • Example 14 This example demonstrates the preparation of a sterile reversibly gelling polymer network aqueous composition and die stability of die composition to sterilization.
  • the polymer network is prepared as described in Example 1 , except that die composition is prepared at 2 wt% Pluronic ® F127 polyol/poly (aery lie acid). After dissolution of the 2 wt% polymer network in water, the viscosity is measured. The composition dien is sterilized by autoclaving at 121 °C, 16 psi for 30 minutes. Viscosity is determined after sterilization. The corresponding curves for viscosity (a) before and (b) after sterilization are shown in Figure 20 and establish that minimal change in die viscosity profile of d e material has occurred with sterilization.
  • Examples 15-30 show additives which may be used to affect die transition temperature overall viscosification of the polymer network composition.
  • a 1 wt% polymer network was prepared in deionized water at pH 7 in which a variety of additives were included in d e composition. The effect of the additive was determined by generation of a Brookfield viscosification curve. Results are reported in Table 4.
  • Example 31 Because of the surfactant nature of the polymer network composition coupled with the gelation effect of d e polymer network composition, it is possible to prepare formulation which are 100% water-based, but which are lubricous and thick.
  • Formulations including a nonionic surfactant formulation An O/W (oil-in- water) emulsion was made by combining me following ingredients utilizing conventional mixing techniques:
  • Formulations including a cationic surfactant formulation An O/W (oil-in- water) emulsion was made by combining the following ingredients utilizing conventional mixing techniques:
  • Formulations including an anionic surfactant formulation An O/W (oil-in- water) emulsion was made by combining me following ingredients utilizing conventional mixing techniques:
  • Example 32 An oil-free, clear, anti-acne treatment is made by combining the following ingredients utilizing conventional mixing techniques:
  • die contents of die first vessel is added to die second vessel, and allowed to mix to homogeneity.
  • the composition displays a flowable clear jelly appearance with excellent spreadability and absorption characteristics at room temperamre, and after heating the formulation to 32°C, the composition thickens to a gel-like consistency.
  • Example 33 (a) Oil-free Moisturizer (formulation I): An oil-free, lubricous moisturizer was made by combing the following ingredients utilizing conventional mixing techniques:
  • the above ingredients were added and processed as described above for the acne composition.
  • the composition displayed a flowable creamy lotion appearance with excellent emolliency, spreadability and absorption characteristics at room temperamre. After heating the formulation to above 26 °C, die composition thickened to a gel-like consistency.
  • the viscosity vs. temperamre curve is shown in Figure 21 and demonstrates that addition of adjuvants to the composition significantly enhances the responsive polymer network maximum viscosity ( > 900,000 cps).
  • the use of the poloxamer: poly(acry lie acid) polymer network in the formulation also imparts a unique viscosification effect after application to the skin, which is not evident in typical commercial O/W emulsion formulations (See, Figure 21b).
  • Oil-free Moisturizer (formulation II): An oil-free, lubricious moisturizer was made by combing the following ingredients utilizing conventional mixing techniques: Table 10.
  • the above ingredients were added and processed as described above for the acne composition.
  • the composition displayed a flowable creamy lotion appearance with excellent emolliency, spreadability and absorption characteristics at room temperamre.
  • me composition thickens to a gel-like consistency.
  • the addition of adjuvants to the composition sigmficantly enhances the polymer network maximum viscosity.
  • Example 34 Sunscreen Lotion. An oil-free, lubricious sunscreen lotion was made by combining the following ingredients utilizing conventional mixing techniques:
  • the above ingredients were added and processed as described above for the acne composition.
  • the composition displayed a flowable creamy lotion appearance with excellent emolliency, spreadability and absorption characteristics at room temperamre. After heating the formulation to above 26 . the composition thickened to a gel-like consistency.
  • the addition of adjuvants to the composition significantly enhances die polymer network maximum viscosity.
  • Example 35 Facial mask. A face mask was made by combing the following ingredients utilizing conventional mixing techniques:
  • the above ingredients were added and processed as described above for the acne composition.
  • the composition displayed a flowable creamy lotion appearance with excellent emolliency, spreadability and absorption characteristics at room temperamre.
  • d e composition thickened to a gel-like consistency.
  • the addition of adjuvants to die composition significantly enhances me polymer network maximum viscosity.
  • Example 36 Facial toner.
  • a face mask was made by combing the following ingredients utilizing conventional mixing techniques:
  • the above ingredients were added and processed as described above for the acne composition.
  • the composition displayed a flowable appearance with excellent emolliency, spreadability and absorption characteristics at room temperamre. After heating the tormulation to above 26 X, the composition thickened to a gel-like consistency.
  • the addition of adjuvants to the composition significantly enhances the polymer network maximum viscosity.
  • Example 36 Solubilization studies of model hydrophobic agents in the poloxamer: polv(acrylic acid) polymer network: estradiol and progesterone. This example is presented to demonstrate the solubilization of a hydrophobic agent in d e polymeric network. Progesterone and estradiol were used as d e hydrophobic agents in this model solubilization study.
  • Acrylic acid (99%), fluorescein (98%), / 3-estradiol (98%), and progesterone (98%) were all obtained from Aldrich and used as received.
  • Pluronic ® F127 NF was obtained from BASF.
  • Poly(oxyethylene-b-oxypropylene-b-oxyethylene)-g-poly(acrylic acid) copolymers (responsive polymer network ) were synthesized by free-radical polymerization of acrylic acid in the presence of poloxamer as described above.
  • the polymer network copolymers discussed here were composed of about 1 : 1 ratio of PAA to poloxamer.
  • the rheological properties of polymer network were assessed using LVDV-II-. and RVDV-II + Brookfield viscometers.
  • the microscopic light scattering of 21 nm poly(styrene) latex particles in deionized water and 1 w% reversibly gelling polymer network was measured using He-Ne laser as described previously (See, Matsuo, E.S. , Orkisz, M. , Sun, S.-T. , Li, Y. , Tanaka, T., Macromolecules, 1994, 27, 6791).
  • the solubility of fluorescein and hormones in aqueous solutions was measured by d e equilibration of excess solubilizate witii the corresponding solution following removal of undissolved species by centrifugation and filtration.
  • Hydrophobic agents were assayed spectrophotometrically at 240 (progesterone) or 280 nm (estradiol), or by using 70/30 w/w H 2 SO 4 /MeOH (Tsilifonis-Chafetz reagent).
  • In vitro hormone release studies were conducted using thermostatted, vertical Franz cells. Spunbonded polypropylene microfilters (micron retention, 15-20) were used as a membrane separating feed and receiver phases in Franz cells. The responsive polymer network, water, ethanol, and 20% PEG in water were observed to wet the membrane. The receiver solutions consisted of 20 w% PEG in water (pH 7) and were stirred by magnetic bars. The feed phases composed of responsive polymer network were loaded widi eitiier estradiol or progesterone. Each hormone was dissolved in etiianol and the resulting solution was added into the responsive polymer network.
  • ⁇ G -RTlnP
  • ⁇ H -R ⁇ lnP/ ⁇ (l/T)
  • ⁇ S ( ⁇ H - ⁇ G)/T (14)
  • Negative ⁇ G values indicate spontaneous solubilization at all temperamres, whereas positive ⁇ H shows that the solubilization was endothermic, similar to the solubilization of estriol, as well as indomethacin, by d e poloxamer.
  • ⁇ S of solubilization was always positive, suggesting d at die more ordered water molecules surrounding hydrophobic estradiol molecules moved to d e less ordered bulk phase when d e estradiol was transferred to the hydrophobic core of PPG segments in responsive polymer network.
  • the aggregation of the PPG segments at elevated temperamres provides not only temporary cross-linking in the gel, but also a diermodynamically "friendly" environment for the hydrophobic drugs. Indeed, one can express the free energy of formation of the aggregate core-water interface in responsive polymer network as:
  • Equation (3) shows that solubilization of a hydrophobic drug of high ⁇ WD should increase the stability of d e aggregate. The solubilization process was found to decrease the critical micellization concentration and substantially increase the micellar core radius in Pluronic surfactants (Hurter, P.N. et al.
  • Figure 27 shows that the relative amount of progesterone penetrating into the receiver phase decreased 4-fold with the increase of total polymer concentration, whereas the total relative amount of progesterone stayed almost constant as t ⁇ tal polymer concentration in the responsive polymer network increased.
  • This result shows the existence of two routes of transport of hydrophobic drugs in our model system. Firstly, the drug inco ⁇ orated into aggregates within die responsive polymer network system can flow dirough the membrane along with die erosion of the responsive polymer network; secondly, the drug not associated wid die responsive polymer network aggregates can diffuse out of the responsive polymer network in the feed phase. The second process should not be related to die viscosity of the responsive polymer network.
  • Abrasive abrades, smoothes, polishes
  • Emollient softens, smoothes skin
  • Emuisifier a surtace-acuve agent (surfactant) that promotes the formation ot water-in-oil or oil-in-water emulsions
  • Absorption base torms water-in-oil emulsions
  • Enzymes complex proteins produced by living cells that catalyze biochemical
  • Aciduient acidifies, lowers pH. neutralizes alkalis reacuons at body temperature
  • Amphote ⁇ c capable of reacting chemically either as an acid or a base:
  • Fiber strands of natural or synthetic polymers for instance, conon. wool, silk, amphoienc surfactants are compatible with anionic and cationic nylon, polyester surfactants
  • Analgesic relieves pain after application to a surface
  • Antacid neutralizes stomach acidity
  • Antibacterial, destrovs mhibits the growth/reproduction of bacte ⁇ a aroma
  • Anti-caking prevents or retards caking of powders, keeps powders free- Flavor, impa ⁇ s a characteristic taste (and aroma) to edible foods and d ⁇ nks. flowing sometimes used in lip products
  • Anti-dandruff retards or eliminates dandruff Foam booster enhances quality and quantity of lather of shampoos
  • Antifoam suppresses loam during mixing
  • Foamer a surface-acuve agent (surfactant) that produces foam, an emulsion ol
  • Anti-irritant reduces, suppresses or prevents lmtauon Foam stabilizer see Foam booster
  • Geilant a gelling agent: forms gels: includes a wide va ⁇ erv of mate ⁇ als such
  • Antioxidant inhibits oxidation and rancidity as polymers, ciavs and soaps
  • Antiperspirant reduces or inhibits perspiration Glosser- tu ishes a surface luster or b ⁇ ghtness. usuallv used in lip or hair products
  • Antipruritic reduces or prevents itching
  • Antiseptic inhibits the growth of microorganisms on the skin or on living tissue Hair conditioner see Conditioner
  • Antistat reduces static by neutralizing electrical charge on a surface Hair dye imparts a new permanent or semi-permanent color to hair
  • Astringent contracts organic tissue otter application Hair-set polymer polvmer and/or resins used to maintain desired hair shape
  • Binder- promotes cohesion ot powders Hair-set resin see Hair-set polymer
  • Bleaching agent lightens color, oxidizing agent Hair waving: see Reducing agent and Neutralize!-
  • Buffer helps maintain original pH (acidity or basicity) of a preparation
  • Hydrotrope enhances water solubility
  • Carrier- a vehicle or base used for a preparation Intermediate basic chemicals which are chemically modified to obtain the desired function
  • Chelate form a complex with trace-metal impurities, usually calcium or iron
  • Lathering agent a surface active agent (surfactant) that torms a loam or lather
  • Colorant adds color, may be a soluble dye or an insoluble pigment on mixing with air in solution: see also Foamer
  • Lubricant reduces f ⁇ cuo ⁇ . smoothes, adds slip
  • Coupling agent aids in solubilization or emulsificauon of incompauble
  • Moisture barrier retards passage of moisture or water components
  • Moisturizer aids in increasing die moisture content of the skin through
  • Decolorant removes color bv adsorption, bleaching or oxidation humectant or barrier action
  • Denaturant used to denature ethyl alcohol
  • Deodorant destroys, masks or inhibits formation of unpleasant odors
  • Oil absorbent see Absorbent powder
  • Depilatory- removes hair chemically Ointment base, an anhydrous mixture of oleaginous components used as a
  • Detergenf a surface-active agent (surfactant) that cleans by emulsifying oils vehicle for medicaments and suspens paniculate soil Opacifier opacifies clear liquids or solids
  • Oxidant oxidizing agent neutralizes reducing agents, bleaching agent
  • Dispersant promotes the formation and stabilization of adispersion or suspension Pearlant imparts a pearlescent texture and luster
  • Pigment a tinelv powdered insoluble substan-e used to import color luster or Stimulant produces a temporary increase in the tunctional octivitv ot an opocitv organism or ⁇ nv ot its pans
  • Surfactant I surface active agent lowers surface tension between two
  • Polish smoothes adds doss and luster or more incompatible phases soaps detergents wetting agents solubizin- agents and emuisifving agents are tvpical surtactams
  • Polvmer ⁇ verv high molecular wei ⁇ ht compound consisting ot repealing surtactants areclassitiedasanionic canonic nonionic and amphotenc structural units anionic surtactams are negativelv charged Lanonic surtactams have
  • Reducing agent reduces a chemical compound usuallv bv donatins electrons Thixotrope the propertv ot certain aels and emulsions ot becomin- more fluid neutralizes oxidizing agents or less viscous when shaken or suited
  • Refatting agent adds oils materials lo ihe surtaLe ot substrates e g skin and UV absorber used as a sunscreen and to protect preparations trom dearadation hair by UV radiation
  • Resin nonvolatile solid or semisolid organic substances obtained from plants UVA absorber jbsoros in the range 20 -400 nanometers mm) as exudates to prepared bv polvme ⁇ zation ot simple molecules
  • UVB absorber absorbs in the range 290 _0 nanometers inmi
  • Siiicone poh e ⁇ c organic silicon compounds which are water resistant contain principally esters ol higher tattv acids and higher lattv alcohols tree
  • Skin protectant protects skin trom en ironmental fattv alcohols lattv acids and hvdrocarbo ⁇ s mav also be present waxes derived trom petroleum products are mainlv high-molecular weight
  • Solubilizer s ⁇ lubi zes usuallv into aqueous vehicles normally insoluble hydrocarbons materials SUL ⁇ as tragrances tlovors oils etc
  • Solvent usuallv liquids capable ot dissol ing other substances interfacial tension facilitating the wetting ot surfaces
  • Jojoba (Buxus chinensis) seed powder Taita ⁇ c acid Serum protein
  • Bladder rack Fucus vesiculosus extract Willow (Salix alba) extra ⁇ Phenyi mercu ⁇ c acetate, Pm benzoate, Pm borate
  • Butcherbroom Ruscus aculeatus extract
  • hazei Haamame s virgimana
  • Rosemarv Rosma ⁇ nus officinalis extract 1- ys ⁇ ne laurovl methionine Ascorbvl oleate. A. palmitate
  • Butcherbroom Ruscus aculeatus extract Soy (Glv ⁇ ne soja) protein p- Hydro xvamsoie
  • Horee chesmut (Aesculia hippocastanum) extract Cetethvldunomum bromide Sage (Salvia officinalis) extra ⁇
  • Aluminum undecvienovl collagen ammo acids PPG-9 diethvlmo um chlo ⁇ de
  • Zinc lactate Aluminum zirconium pentachiorhvdrate PPG-25 diethylmonium chlo ⁇ de
  • Entada phaseoloides extract Isostearvl neopentanoate ammonium ethvi sulfate
  • Eucalvptus (Eucalyptus globulus) extract Wheat ge ⁇ namidopropvl ethvldunomum ethosulfate Maltodext ⁇ n
  • Tormentil extract Euphrasia officinalis extract Tapioca dextnn
  • Astraealus si ⁇ icus extract Cvpress (Cupressus sempervirens) extract Job s tears (Coix lacryma jobu extract
  • Banana Melana (Musa sapie ⁇ tumi extract Doe rose (Rosa cani ⁇ ai hips extract Kiwi (Actimdia chinensis) fruit extract seed oil
  • Bearberrv i Arciostaphvlos uva ursi extract extract Lady s mantle (Alchemilla vulaa ⁇ s) extract
  • Butcherbroom i Ruscus aculeatus extract Ginkgo biloba extract Mangold Cabbage rose I Rosa -entiloliai extract Ginsena ( Panax ginseng) extract Ma ⁇ ne silts Calamus l A ⁇ or ⁇ s calamus I extract Glvcyrrhetinic acid Mat ⁇ cana (Chamomilla recutitai xtract Calendula officinalis extract Glvcyrrhizic acid Meadowsweet (Spiraea ulma ⁇ ai extract Caper (Cappa ⁇ s spinosai extract Glvcvrrhizin ammoniatcd Melon (Cucumis elo) extrau Capsicum trutesce ⁇ s extrau C t oleoresin Golden seal ( Hvdrastis canadensisl root extract MEA iodine Carawav i Camm can 11 extract Goldthread (Coptis japomca I extract Mistleto
  • Clover I T ⁇ tolmm pratensei extract Hops Humuius lupulus I extract Papava iCanca papavai extract Cmdium otficinale rhizome extract C o water
  • Coltsfoot (Tussilaao tartarai leat extract Houttuv a cordata extract Pea ( isum sativum ) extract Comtrev i Svmphvium uitn-inalei leat extrau Hyacinth ( Hvacinthus o ⁇ e ⁇ talis ) extract Peach (Prunus persica I exu-act leat extract Conduranao extract Hydrototvl (Centella asiaticai extract Pelareo ⁇ ium capitatum extract
  • Topical applications or HIV + Lymph-nodes Tel (65) - 7653292 Full Colour Fax (65) - 7653293 Siddha Extracts for post-Chemotheraphy Skin-Damage Treatment PC - Video Teleconferencing (65) 7653292 - For Tech Assistance Functions
  • Pineapple (Ananas sativus i extract Wild agnmonv ( Potenulla anse ⁇ na) extract Tetrahydroxypropyl ethylenedia ⁇ une
  • Plantain Plantain (Plantago major) extract Wild cherry (Prunus serouna) bark extract Tetrasodium EDTA
  • Rhodophvcea extract Cit ⁇ c acid Dandelion (Taraxacum officinale) extract
  • Rhubarb heum palmatuml extract Ethanolamine HCl Echitea glauca extract
  • Saponana orficinalis extract Acrvlates copolymer. sphe ⁇ cal powder Lysimachia toenum-graecum extract
  • Sov Glvcine soiai germ extract, protein, sterol Methvl propanediol Cleansing
  • Swe ⁇ ia chirata extract Tapioca dext ⁇ n 6-(N-Acetvlam ⁇ no ⁇ -4-oxvhexvltnmon ⁇ um chlo ⁇ de
  • Thvme Thvmus vulga ⁇ si extract beta-Alanine diacetic acid Adipic acid/dimethvlaminohvdroxvpropyl
  • Tomato Solanum Ivcopersicum extract Calcium disodium EDTA diethylene t ⁇ amine copolymer
  • Tuberose Panamica extract EDTA Ap ⁇ cot ( Prunus armemaca) kernel oil
  • Vale ⁇ an i Vale ⁇ ana orficinalis ⁇ extract Malic acid Behena ⁇ udopropyl dihvdroxypropyl dimomum
  • Cocamidopropyl dimethylamine C d lactate, C d Hydroxvpropylt ⁇ monium hydrolyzed wheat Proline proptonate protein Propylene glycol stearate Cocamidopropvl dimethvlaminohydroxypropvl Isopropyl hvdroxvbutvramide dimethicone PVP/dimethiconylacrylate/polycarbamyl/ hydrolvzed collagen copolvol polyglvcol ester Cocamidopropvldimomum Isopropvl lanolate PVP/dimethvlam oethylmethacrv late copolymer hvdroxvpropvlhvdrolvzed collagen Isostearamidopropvl betaine.
  • Coco-morpholine oxide Isostearamidopropyl ethvldimomum ethosulfate Quatem ⁇ um-76 hvdrolvzed collagen Coco/oleamidopropvl betaine Isostearamidopropvl laurvlacetodimonium chlo ⁇ de Rapeseedamidopropvl benzvldimonium chlo ⁇ de Cocodimomum hvdroxvpropvl hvdrolvzed hair Isostearamidopropvl morpholine.
  • stearamine Mv ⁇ stamidopropvl beta e.
  • M dimethvlamine Sovamidopropyl betaine S dimethvlamine Dimethvlamidopropvlamuie dimerate Mv ⁇ monium bromide Sovamidopropyl ethvldimomum ethosulfate Disodium hvdrogenated cottonseed glyce ⁇ de Oat (Avena sativa) protein Soyethvl morpholinium ethosulfate sulfosuccmate Oleatmde Soyethvldimomum ethosulfate Disodium laureth sulfosuccmate Oleamidopropvl betaine.
  • N N-dimethvl ammonium chlo Oleamuie oxide Stearamidopropyl ethvldimomum ethosulfate Glutamic acid Oleovl sarcosine Stearamidopropvl morpholine lactate Glvcervl collagenate Olevl betaine Stearamidopropvl PG-dimomum chlo ⁇ de Glv ⁇ ne Olevl dimeihvlamidopropvl ethonium ethosulfate phosphate
  • Salvia miltiorrfuza extract Sodium cocoamphopropionate ⁇ ctoxynol-5. -10
  • Zinc phenol sulfonate Z. ⁇ noleate Sodium C12-15 pareth-25 sulfate Oleth-40
  • Acetvlated mo ⁇ oelyce ⁇ des Colloidal oatmeal Dimethicone propvlethv le ⁇ edi ⁇ mine behenate
  • Cetostean 1 stearate Cetvl C 12 15 parth carboxvlate Cetvl acetate C alcohol Cetvl esters C lactate Cetvl mv nstatc C octanoate Cetvl oleate C p ⁇ lmu ⁇ te Cetvl PPG 2 isodeceth " .. ⁇ rboxv l ⁇ te Cetv I ⁇ L nole ⁇ ie C -.t- ⁇ r ⁇ ie
  • Ethvl li ⁇ olenaie Ethvl li ⁇ olenaie.
  • E minkate Isopentyldiol Octyldodecvl behenate, 0 benzoate
  • Ethyl oleate E oiivate Isopropyl C12-15-pareth-9- arboxylate Octyldodecvl oleate, O ncinoleate
  • Glycereth-7 benzoate Isopropyl PPG-2- ⁇ sodeceth-7 carboxvlate Oleamtne oxide
  • Glycereth-7 dnsononanoate Isopropyl stearate Oleic/palmitoieic/linoleic glvcendes
  • Glycerol tncaprvlate/caprate Isostearyl behenate.
  • Glyceryl adipate Isostearyl diglycervl suc ⁇ nate Orange (Citrus aurantium dulcis) peel wax
  • Glyceryl isostearate G lanolate Isostearvl emcate, I erucvl erucate Orange roughy (Hoplostethus adanticus) od
  • Hybnd safflower (Carthamus tmctonus) oil Lanolin wax PEG-6
  • Isobutvl palmitate I stearate Neem (Meha azadirachta) seed od Pentaervthnrvl isostearate/caprate/caprvlate/adipate
  • Isocetvl behenate I octanoate Neope ⁇ tvl glycol dicaprate Pentaeryth ⁇ tvl stearate Isocetvl palmitate.
  • Poloxamer 105 benzoate PPG- 10 butanediol.
  • PPG-2-buteth-3 PPG-50 cetvl ether.
  • P olevl ether Sorbitan isostearate. S. palmitate
  • PPG-5-laureth-5 Propylene glycol diisostearate.
  • PPG-5 pentaervth ⁇ tvl ether Propylene glycol isostearate. P.g. laurate Steanc acid. S. hydrazide
  • T ⁇ decyl behenate T. cocoate Cet ⁇ m ⁇ nium chlo ⁇ de Glyceryl my ⁇ state. G. oleate
  • T decyl erucate.
  • T ⁇ octyldodecvl curate Decaglycerol monodioleate Hydrogenated soy glvcende
  • Emulsifier Diethvlaminoethvl stearate Isoceted ⁇ -10 stearate
  • Palm acid PEG- 12 dilaurate.
  • PEG-2 cocamine P. distearate PEG-12 laurate, P. oleate PEG-60 hydrogenated castor oil isostearate
  • PEG-2 laurate SE PEG-14 avocado glvcendes PEG-60 shea butter glvcendes
  • PEG-2 oleamine PEG-2 oleamine.
  • P. oleate PEG- 15 castor oil
  • PEG-2 stearate PEG-2 stearate.
  • P. stearate SE PEG- 15 glyceryl isostearate PEG-75
  • PEG-3 C12-C18 alcohols PEG-15 glyceryl ncinoleate PEG-75 dioleate.
  • PEG-3 lanolate PEG-3 lanolate.
  • P. sorbitan oleate PEG- 15 tallow polvami ⁇ e PEG-75 shorea butter glycendes
  • PEG -4 dioleate PEG -4 dioleate.
  • P. diisostearate PEG- 16 hydrogenated castor oil
  • PEG-80 sorbitan laurate
  • PEG-4 dilaurate PEG-4 dilaurate.
  • PEG-16 soy sterol PEG-90 stearate
  • PEG-4 stearate PEG-20 castor oil PEG-4 stearate PEG-20 castor oil.
  • P. dilaurate PEG- 100 lanolin.
  • P. stearate PEG-4 stearate
  • PEG-4 tallate PEG-20 glyceryl laurate PEG-150 dilaurate.
  • PEG-5 castor oil PEG-20 glyceryl oleate PEG- 150 distearate.
  • PEG-5 C12-C18 alcohols PEG-20 glyceryl stearate PEG-150 laurate.
  • Poloxamer 101 ⁇ . 122. 123,124 Sodium nonoxynol- ⁇ phosphate Tissue extract
  • Poloxamer 2 3 8. 33-*. 338,407 Sodium oleate Trideceth-3. -5, -6. -7, -8
  • Sorbitan t ⁇ oleate S. t ⁇ stearate Fermented vegetable
  • Polyglyceryl- 10 disicarate P. isostearate Stearamine oxide Brassica rapa-depressa extract

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention porte sur une composition cosmétique dans un excipient cosmétologique comprenant un réseau de polymères renforçateurs de viscosité par inversion thermique comprenant au moins un composant de poloxamer capable de s'agréger en réponse à une variation de température et fixé aléatoirement à au moins un composant de poly(acide acrylique), et un agent à efficacité cosmétique produisant un effet cosmétique présélectionné, ledit excipient et ledit agent étant placés dans un milieu à base aqueuse.
EP98918925A 1997-05-01 1998-05-01 Compositions utilisables en cosmetologie Withdrawn EP0927019A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US84688397A 1997-05-01 1997-05-01
US846883 1997-05-01
PCT/US1998/008931 WO1998048768A1 (fr) 1997-05-01 1998-05-01 Compositions utilisables en cosmetologie

Publications (1)

Publication Number Publication Date
EP0927019A1 true EP0927019A1 (fr) 1999-07-07

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EP98918925A Withdrawn EP0927019A1 (fr) 1997-05-01 1998-05-01 Compositions utilisables en cosmetologie

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EP (1) EP0927019A1 (fr)
AU (1) AU7174998A (fr)
CA (1) CA2259464A1 (fr)
WO (1) WO1998048768A1 (fr)

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AU7174998A (en) 1998-11-24
WO1998048768A9 (fr) 1999-03-25
WO1998048768A1 (fr) 1998-11-05
CA2259464A1 (fr) 1998-11-05

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