GB2407496A

GB2407496A - Method for forming a polysiloxane film on a biological surface

Info

Publication number: GB2407496A
Application number: GB0324986A
Authority: GB
Inventors: David Gantner; Xavier Thomas
Original assignee: Dow Corning Corp
Current assignee: Dow Silicones Corp
Priority date: 2003-10-27
Filing date: 2003-10-27
Publication date: 2005-05-04
Also published as: GB0324986D0

Abstract

This invention relates to a method for forming a film on a biological surface. The method comprises mixing 5 to 70 wt. % of an alkylene trialkoxysilyl terminated polysiloxane; 0 to 5 wt. % of an alkoxysilane; 0.01 to 5 wt. % of a catalyst; 0 to 25 wt % of a filler; and 1 to 94.99 wt % of a volatile diluent to form a formulation. The formulation is then applied onto a biological surface where it cures in situ on the biological surface to form the film. The resultant film is useful in healthcare and cosmetic applications, as well as pesticidal or herbicidal applications. The preferred formulations include a polysiloxane produced from vinyl-terminated dimethylsiloxane and trimethoxysilylethyl tetramethyldisiloxane, methyltrimethoxysilane as the alkoxysilane, tetra-tert-butyl titanate as the catalyst and hexamethyldisiloxane as the diluent. The formulation may contain an active agent and may be applied to skin, hair, nails, teeth eyes, mucous membranes or to plants.

Description

FAST CURE FILM FORMING FORMULATION

10001] The present invention relates to the use of one-part formulations that rapidly cure on exposure to moisture for forming films in personal and healthcare applications. The formulations comprise an alkylene trialkoxy terminated siloxane; a catalyst; a diluent; and, optionally, an alkoxysilane and/or a filler.

2] Many formulations for forming films are known in the pharmaceutical art.

These include, for example, ointments, salves, creams, lotions, gels, elastomers and the like.

Some of these formulations use silicone-based materials as key components. Silicone based materials are desirable in these formulations since they are generally inert to the body. These products are designed to provide a variety of benefits, for example, moisturize dry skin, mask surface imperfections, allow effective delivery of actives while being cosmetically acceptable during and after application onto various skin areas of the body.

10003] One example of silicon-based materials in film forming formulations is provided in European publication number 465,744. This publication teaches the use of a multi-part formulation including an active agent, a Si-H containing polymer, a polymer having unsaturated groups bound to silicon, a catalyst and a hydrophilic component. This formulation is mixed and applied to the body where it cures and forms a controlled release gel.

4] The prior art methods such as those described in EP 465,744, however, have several disadvantages. For instance, in such methods the person utilizing the formulation must be skilled so as to ensure adequate mixing of the appropriate amounts of component materials in the formulation and then applying the correct amount of the mixed formulation to the desired site before it gels. Similarly, such a method can be an inconvenience and messy for the user. Finally, these methods involve ingredients that may not be desirable for healthcare applications.

5] WO 90/03809 teaches a coating material for forming bandages comprising a siloxane containing bandage material diluted in a volatile polydimethylsiloxane. The . I: ae. c.e ae.e:e 2 .. . .:.... * materials described in this reference, however, are different than those described and claimed herein.

100061 Finally, patent such as U.S. Patent Nos. 3,175,993, 4,772,675, 4, 871,827, 4,888,380, 4,898,910, and 4,906,719 teach silicone sealants comprising an alkylene trialkoxysilyl terminated polysiloxane; an alkoxysilane; and a catalyst. Such references, however, do not teach the compositions or the uses described and claimed herein.

10007] We have now discovered a method of making a film that can avoid many of the above prior art problems and it is, therefore, useful in personal and healthcare applications.

100081 The present invention relates to a method for forming a film on a biological surface. The method comprises mixing 5 to 70 wt. % of an alkylene trialkoxysilyl terminated polysiloxane; 0 to 5 wt. % of an alkoxysilane; 0.01 to 5 wt. % of a catalyst; 0 to 25 wt % of a filler; and 1 to 94.99 wt % of a volatile diluent to form a formulation. The formulation is then applied onto a biological surface, wherein said formulation cures in situ on the biological surface to form a film. The resultant films have many uses in personal and healthcare applications, especially on the skin, where they can serve as, for example, topical drug delivery systems, masking systems for skin protection in dermal treatments, wound dressings and bandages for minor wounds, burns, acute and chronic wounds, skin sealants, skin protective films, scar treatments, exfoliation and hair remover products, deodorizing films, antiperspirant active and fragrance delivery systems, anti-wrinkle patches and moisturizing masks, wherein said film applications have benefits in topical therapies, wound care, surgical closure, scar care, underarm care, foot care, body and face skin care, cosmetics, make-up and foundations. They can likewise be used on other biological surfaces such as hair, nails, teeth, eyes, and mucous membranes as well as similar applications on animals other than humans and a variety of applications on flora.

10009] The present invention relates to using certain formulations for forming films on substrates, preferably biological substrates, where they can serve, for example, as barrier films, cosmetic films, drug delivery mechanisms and the like.

I.: ce. ce. es.. :.

3 e [00101 The first component in the formulations of the present invention comprises alkylene alkoxy terminated polysiloxanes. The polymers may be linear or branched and may be homopolymers, copolymers, or terpolymers. Moreover, the polymers may be a single species or a mixture of different polymers. Typically, it is preferred that these polymers have, on average, at least 1.2 alkylene trialkoxysilyl chain terminations per molecule.

100111 The monomeric units of these polymers may include organic units, such as ethylene, butylene, or oxyalkylene units, but preferably a majority of the monomeric units are siloxy units such as those described by the formula R9sSiO(4-s)/2, where each R9 is independently selected from the group consisting of alkyl groups comprising 1 to about 6 carbon atoms, phenyl, and fluorinated alkyl groups, and s is 0, 1, 2 or 3. Examples of the alkyl groups described by R9 include methyl, ethyl, propyl, butyl and hexyl. An example of the fluorinated alkyl groups described by R9 includes 3,3,3-trifluoropropyl. The preferred polymers comprise polydiorganosiloxanes having repeating units described by the formula (R92SiO2)f -, wherein each R9 is as described above, preferably methyl, and f is a value such that the polymer has a viscosity within a range of about 0.5 to 3000 Pa-s at 250C and preferably within a range of about 5 to 150 Pa-s at 250C.

[00121 These polymers preferably comprise, on average, at least 1.2 alkylene trialkoxysilyl chain terminations per molecule described by formula - ZSiRlx(OR)3-x, wherein each R is independently selected from the group consisting of methyl, ethyl, n propyl, isopropyl, n-butyl, secbutyl, and isobutyl, RI is selected from the group consisting of methyl and ethyl, and x is 0 or 1. In preferred embodiments, each R is independently selected from the group consisting of methyl and ethyl, and x is zero. Z in the above formula is independently selected from the group consisting of divalent hydrocarbon radicals free of aliphatic unsaturation comprising about 2 to 18 carbon atoms and a combination of divalent hydrocarbon radicals and siloxane segments described by the formula: ce. . .e . : : . . . . . 4. . ... . . R9 R9 -G-(SiO)C-Si-G R9 R9 wherein R9 is as defined above, each G is a divalent hydrocarbon radical free of aliphatic unsaturation comprising about 2 to 18 carbon atoms, and c is a whole number from 1 to about 6. Examples of the divalent hydrocarbon radicals describing Z and G include alkylene radicals such as ethylene, propylene, butylene, pentylene, and hexylene; and arylene radicals including phenylene. Preferably, Z is alkylene with ethylene being particularly preferred.

10013] These polymers typically have, on average, at least 1.2 alkylene trialkoxysilyl chain terminations per molecule, and preferably, have, on average, at least 1.5 alkylene trialkoxysilyl chain terminations per molecule. Since these polymers may have on average at least 1.2 alkylene trialkoxysilyl chain terminations per molecule, some polymers may contain other types of chain terminations. Preferably, this other type of chain termination comprises organosilyl chain terminations selected from the group consisting of CH2=CH-SiR92- and R6 3-Si-, where R9 is as defined above and each R6 is independently selected from the group consisting of R9 and vinyl. Examples of organosilyl chain terminations include trimethylsilyl, triethylsilyl, vinyldimethylsilyl, and vinylmethylphenylsilyl.

4] Polysiloxanes useful herein include those described in U.S. Patent Nos. 3,175,993, 4,772,675, 4,871,827, 4,888,380, 4,898,910, 4,906,719, and 4, 962,174, which are hereby incorporated by reference, and can be described, for example, by the formula -e.: te: ; a I C R1x R9 R9 R1x (I) (RO)3 xSi - Z -(sio)fsi-z-si(oR)3-x R9 R9 wherein R. R1, R9, Z. x, and f are as described above. These polymers can be made as described in the above patents.

5] Other polymers useful in this invention are mixtures of the polysiloxanes described by this formula (I) with trialkyl terminated siloxanes and/or the polysiloxanes described by Kamis et al., U.S. Patent No. 4,898,910, which is hereby incorporated by reference, and described, for example, by the formula R9 R9 R9 R1 1 1 1 1 (II) CH2=CH-SiO(SiO)fSi-Z-Si(OR)3-x 1 1 1 R9 R9 R9 wherein R. R1, R9, Z. x and f are as defined above.

l0016l When the polymer comprises mixtures of polysiloxanes described by the above formulas, typically the polysiloxanes will be present in an amount such that 40 percent or less of the chain terminations will be organosilyl chain terminations, and preferably in an amount such that less than 25 percent of the chain terminations are organosilyl chain terminations.

[00171 The most preferred polymers useful in this invention are those polymers described by the polysiloxane formula (1).

6 he tee: ctle elle.e '. :.

10018] The polymers useful herein can also include organic units. One type of organic polymer useful in the invention is the polyoxyalkylene, described by Okawa et al., U.S. Patent No. 5,403,881, and hereby incorporated by reference to show polyoxyalkylene polymers comprising on average at least 1.2 alkylene trialkoxysilyl chain terminations per molecule and methods of preparing these polymers. Other organic units such as polyisobutylenes, polyethylenes, acrylics, amides and the like can also be included.

9] The amount of polymer useful in formulations of the present invention is dependent on the amounts of other components added but is typically in the range of about 5 to about 79.99 weight percent based on the total weight of the formulation. Preferably, the polymer is added in amounts from about 15 to 50 weight percent on the same basis.

10020] The present formulation also includes a catalyst. Although nearly any suitable catalyst (e.g., metal containing materials) will work herein, the preferred agent is a titanium containing material. A preferred titanium material comprises a tetraalkoxytitanium compound described by average formula Ti(OR2)y(0R3)4-y, where each R2 is independently selected from the group consisting of tertiary alkyl radicals and 2,4-dimethyl3-pentyl; each R3 is an independently selected alkyl radical comprising from 1 to about 6 carbon atoms; and y is an average value of from 3 to 4.

1] Examples of tertiary alkyl radicals represented by R2 include tertiary butyl and tertiary amyl. Preferably, each R2 is an independently selected tertiary alkyl radical.

More preferably each R2 is independently selected from the group consisting of a tertiary butyl radical and a tertiary amyl radical.

10022] Examples of alkyl radicals comprising from I to about 6 carbon atoms represented by R3 include methyl, ethyl, n-propyl, isopropyl, nbutyl, sec-butyl, and hexyl.

10023] In this formula, y is an average value of from 3 to 4. Preferably, y is an average value of from about 3.4 to 4, with an average value from about 3.6 to 4 being most preferred.

I. ac: .. ce I. a:e . . . 10024] The amount of catalyst useful in the present formulations is dependent on the amounts of other components added, but is typically used in amounts in the range of about 0.01 to 5 weight percent based on the total weight of the formulation. Preferably, the catalyst is a tetraalkoxytitanium compound and it is added in amounts in the range of about 0.3 to 2.3 weight percent on the same basis. The tetraalkoxytitanium compound may be a single species or a mixture of two or more species.

10025] The formulations of the present invention also include diluents. Such diluents are often necessary to decrease the viscosity of the formulation sufficiently for application.

Examples of diluents include silicon containing diluents such as hexamethyldisiloxane, octamethyltrisiloxane, and other short chain linear siloxanes, cyclic siloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, organic diluents such as butyl acetate, alkalies, alcohols, ketones, esters, hydrofluorocarbons or any other material which can dilute the formulation without adversely affecting any of the component materials of the formulation or the curing time.

6] The above diluents are often used in amounts of up 94.99 wt. % of the formulation. Preferably, the diluent is used in an amount of between about 30 and 90 wt % and more preferably between about 45 and 80 wt % of the formulation. On application, however, the diluent often substantially volatilises leaving the other component materials on the desired site.

7] The present formulations can also comprise an alkoxysilane described by formula R4zSi(OR5)4-z, where each R4 is independently selected from the group consisting of alkyl radicals comprising from l to about 12 carbon atoms and alkenyl radicals comprising from I to about 12 carbon atoms; each R5 is independently selected from the group consisting of methyl and ethyl, and z is l or 2. Preferably z is 1.

8] The alkyl radicals comprising I to about 12 carbon atoms represented by R4 include, for example, methyl, ethyl, isobutyl, hexyl, octyl, and dodecyl. The alkenyl radicals :e e.: .. .. :..

comprising 1 to about 12 carbon atoms represented by R4 include for example vinyl, allyl, butadienyl, and hexenyl. Preferably, each R4 is independently selected from the group consisting of methyl, ethyl, isobutyl and vinyl. More preferably each R4 is methyl.

l0029l Examples of useful alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ethyltrimethoxysilane, octyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, dimethyldiethoxysilane, isobutyltrimethoxysilane, and ethylmethyldiethoxysilane. The partial hydrolyzates of these alkoxysilanes can also be used in the present formulation. Preferred alkoxysilanes include methyltrimethoxysilane and dimethyldimethoxysilane.

[00301 If used, the amount of alkoxysilane is dependent on the amounts of other components added, but is typically in the range of 0.1 to 5 weight percent based on the total weight of the formulation, with amounts in the range of about 0.1 to 2 weight percent on the same basis being preferred. The alkoxysilane may be a single species or a mixture of two or more species.

[00311 The present formulations can also comprise fillers. The fillers can include, but are not limited to, ground, precipitated, and colloidal calcium carbonates which can be untreated or treated with stearate or stearic acid; reinforcing silicas such as fumed silicas, precipitated silicas, and hydrophobed silicas; crushed quartz, ground quartz, alumina, aluminium hydroxide, titanium dioxide, diatomaceous earth, iron oxide, carbon black, and graphite. One class of preferred fillers are synthetic silicas where the surfaces of the silica are modified with silicon compounds to produce a hydrophobic behaviour. These materials differ from one another in surface area, the silicon compound used to treat the silica, and the extent of surface treatment. Such materials are surprisingly able to reduce the viscosity of the film forming formulation. In addition, resinous reinforcing fillers can be used herein to form transparent films. Silica, calcium carbonate, andresinous fillers are especially preferred.

Specific examples include Cab-O-Sil( TS-530 treated filler, Aerosil( R8200 treated filler, and Wacker HDX H2000 treated filler.

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10032] If used, the amount of filler in the formulation is generally that amount which provides the desired properties to the uncured formulation such as viscosity, thixotropy, pigmentation, and UV protection. The amount of filler also depends upon the cured physical properties desired such as tensile strength, elongation, and durometer. Finally, the amount of filler also depends on the amounts of other components added, as well as the hydroxyl content of the specific filler used. Typically, this is an amount in the range of about 0.1 to 25 weight percent based on the total weight of the formulation. Preferably, the filler is added in amounts from about 2 to 15 weight percent on the same basis. The filler may be a single filler or a mixture of two or more fillers.

3] The formulation can also comprise fluorinated fluids, resins, organosiloxane polymers and resins. These materials provide additional properties to the film including but not limited to: softness, flexibility, higher adhesion to substrates like skin and plastic films, pressure sensitive adhesive surface activity, lower coefficient of friction, or lubricity.

Examples of fluorinated fluids are fluorinated siloxanes, trifluoropropylmethyl siloxane.

Examples of resins are rosin type resins and acrylic polymer resins. Examples of organosiloxane polymers are silicone polyethers, silicone polyamides, and silicone acrylic copolymers. Examples of organosiloxane resins are siloxane MQ resins. Other materials such as active agents can also be added to formulations of the present invention. The active agents used in the present invention are generally not critical. They can comprise any solid or liquid material which can be bound in the composition and subsequently released at the desired rate. The active agent should also not interfere with the curing of the silicone formulation to an unacceptable extent. Suitable active agents include cosmetics, personal care, cosmeceuticals, therapeutic or diagnostic materials, pesticides, herbicides, and the like.

[00341 Therapeutic active agents which may be employed include, for example, anti acne agent, antibiotic, antiseptic, antifungal, antibacterial, antimicrobial, biocides, antlinflanunatory, astringents, hormones, anticancer agents, smoking cessation compositions, cardiovascular, histamine blocker, bronchodilator, analgesic, antiarrythmic, antihistamine, alpha- I blocker, beta blocker, ACE inhibitor, diuretic, antiaggregant, sedative, tranquillizer, anticonvulsant, anticoagulant agents, vitamins, antiaging agents, agents for treating gastric :e..: I. .. :e and duodenal ulcers, anticellulites, proteolytic enzymes, healing factors, cell growth nutrients, peptides and others. Specific examples of suitable therapeutic active agents include penicillins, cephalosporins, tetracyclines, macrolides, epinephrine, amphetamines, aspirin, acetominophen, barbiturates, catecholamines, benzodiazepine, thiopental, codeine, morphine, procaine, lidocaine, benzocaine, sulphonamides, ticonazole, perbuterol, ffirosamide, prazosin, prostaglandins, salbutamol, indomethicane, diclofenac, glafenine, dipyridamole, theophylline and retinal.

5] In addition to the therapeutic or diagnostic materials, active, agents could be cosmetics such as perfumes, W protectors, shaving products, deodorants or the like.

Suitable cosmetics are known to those skilled in the art.

100361 The proportion of the active agent employed in the present invention is chosen in accordance with the concentration of the active agent required in the composition to deliver the dosage required at the proposed delivery rate. This may vary within a wide range such as from 0. l to about 70 weight percent, preferably 0. l to 20 weight percent, of the final composition.

[00371 If desired the formulation may also contain other additional ingredients. One advantageous additive is a water scavenger to prevent early curing of the formulation. Other optional ingredients include colorants, colored indicators, other diluents, extenders such as silicone fluids, silicone resins, excipients employed in pharmacy, compounds intended to perform as pH buffers in controlling the environment immediately in and around the formulation, stabilizers, preservatives, surfactants for cellular formulations such as fluorinated silicones, processing aids such as cyclic or linear polydiorganosiloxanes, bioadhesive materials, and hydrophilic, modulating and swellable components or polymers as set forth in EP Publication 465,744. Still other additional ingredients include absorbents for wounds, alginate, polysaccharides, gelatin, collagen, and materials that can decrease the friction on the surface of the cured film and/or change its gloss.

8] Some additional examples of the cosmetics, personal care, and cosmeceutical ingredients and pharmaceutical excipients that may be used herein may be found in the CTFA :. eeec: a. .. :..

ingredient Database and the handbook of pharmaceutical excipients and can include, for example, absorbents, anticaking agents, antioxidants, antistatic agents, astringents, binders, buffering agents, bulking agents, chelating agents, colorants, cosmetic astringents, cosmetic biocides, deodorant agents, emollients, external analgesics, film farmers, flavouring agents, fragrance ingredients, humectants, Iytic agents, moisturizing agents, occlusivity enhancers, opacifying agents, oxidizing and reducing agents, penetration enhancers, pesticides, plasticizers, preservatives, skin bleaching agents, skin conditioning agents, skin protestants, slip modifiers, solubilizing agents, solvents, sunscreen agents, surface modifiers, surfactants and emulsifying agents, suspending agents, thickening agents, viscosity controlling agents including increasing or decreasing agents, UV light absorbers, [0039] Cosmetic, personal care and cosmeccutical ingredients, and pharmaceutical excipients which may be employed are selected, for example, from the following chemical classes: alcohols, fatty alcohols and polyols, aldehydes, alkanolamines, alkoxylated alcohols (e.g. polyethylene glygol derivatives of alcohols and fatty alcohols), alkoxylated amides, alkoxylated amines, alkoxylated carboxylic acids, amides including salts (e.g. ceramides), amines, amino acids including salts and alkyl substituted derivatives, esters, alkyl substituted and acyl derivatives, polyacrylic acids, acrylamide copolymers, adipic acid copolymers, alcohols, aminosilicones, biological polymers and derivatives, butylene copolymers, carbohydrates (e.g. polysaccharides, chitosan and derivatives), carboxylic acids, carbomers, esters, ethers and polymeric ethers (e.g. PEG derivatives, PPG derivatives), glyceryl esters and derivatives, halogen compounds, heterocyclic compounds including salts, hydrophilic colloids and derivatives including salts and gums (e.g. cellulose derivatives, gelatin, xanthan gum, natural gums), imidazolines, inorganic materials (clay, TiO2, ZnO), ketones (e.g. camphor), isethionates, lanolin and derivatives, organic salts, phenols including salts (e.g. parabens), phosphorus compounds (e.g. phosphate derivatives), polyacrylates and acrylate copolymers, protein and enzymes derivatives (e. g. collagen), synthetic polymers including salts, siloxanes and silanes, sorbitan derivatives, sterols, sulfonic acids and derivatives and waxes.

100401 Some examples of anti acne agents are Salicylic acid and Sulfur.

:e ee: e. .. .. :.e Some examples of antifungal agents are Calcium Undecylenate, Undecylenic Acid, Zinc Undec yl enate, an d Povi doneIodine.

Some examples of antimicrobial agents are Alcohol, Benzalkonium Chloride, Benzethonium Chloride, Hydrogen Peroxide, Methylbenzethonium Chloride, Phenol, Poloxamer 188, and Povidone-Iodine.

Some examples of antioxidants are Acetyl Cysteine, Arbutin, Ascorbic Acid, Ascorbic Acid Polypeptide, Ascorbyl Dipalmitate, Ascorbyl Methylsilanol Pectinate, Ascorbyl Palmitate, Ascorbyl Stearate, BHA, p-Hydroxyanisole, BHT, t-Butyl Hydroquinone, Caffeic Acid, Camellia Sinensis Oil, Chitosan Ascorbate, Chitosan Glycolate, Chitosan Salicylate, Chlorogenic Acids, Cysteine, Cysteine HCI, Decyl Mercaptomethylimidazole, Erythorbic Acid, Diarnylhydroquinone, Di-t-Butylhydroquinone, Dicetyl Thiodipropionate, Dicyclopentadiene/t-Butylcresol Copolymer, Digalloyl Trioleate, Dilauryl Thiodipropionate, Dimyristyl Thiodipropionate, Dioleyl Tocopheryl Methylsilanol, Isoquercitrin, Diosmine, Disodium Ascorbyl Sulfate, Disodium Rutinyl Disulfate, Distearyl Thiodipropionate, Ditridecyl Thiodipropionate, Dodecyl Gallate, Ethyl Ferulate, Ferulic Acid, Hydroquinone, Hydroxylamine HCI, Hydroxylamine Sulfate, Isooctyl Thioglycolate, Kojic Acid, Madecassicoside, Magnesium Ascorbate, Magnesium Ascorbyl Phosphate, Melatonin, Methoxy-PEG-7 Rutinyl Succinate, Methylene Di-t-Butylcresol, Methylsilanol Ascorbate, Nordihydroguaiaretic Acid, Octyl Gal late, Phenylthioglycolic Acid, Phloroglucinol, Potassium Ascorbyl Tocopheryl Phosphate, Thiodiglycolamide, Potassium Sulfite, Propyl Gallate, Rosmarinic Acid, Rutin, Sodium Ascorbate, Sodium Ascorbyl/Cholesteryl Phosphate, Sodium Bisulfite, Sodium Erythorbate, Sodium Metabisulfide, Sodium Sulfite, Sodium Thioglycolate, Sorbityl Furfural, Tea Tree (Melaleuca Aftemifolia) Oil, Tocopheryl Acetate, Tetrahexyldecyl Ascorbate, Tetrahydrodiferuloylmethane, Tocopheryl Linoleate/Oleate, Thiodiglycol, Tocopheryl Succinate, Thiodiglycolic Acid, Thioglycolic Acid, Thiolactic Acid, Thiosalicylic Acid, Thiotaurine, Retinol, Tocophereth-5, Tocophereth-10, Tocophereth-12, Tocophereth-18, Tocophereth-50, Tocopherol, Tocophersolan, Tocopheryl Linoleate, Tocopheryl Nicotinate, Tocoquinone, o-Tolyl Biguani de, Tris(Nonylphenyl) Phosphite, Ubiqui none, and Zinc Dibutyldithiocarb am ate.

Some examples of cosmetic biocides are Aluminium Phenolsulfonate, Ammonium Phenolsulfonate, Bakuchiol, Benzalkonium Bromide, Benzalkonium Cetyl Phosphate, Benzalkonium Chloride, Benzalkonium Saccharinate, Benzethonium Chloride, Potassium . . e:. .. .. :.

Phenoxide, Benzoxiquine, Benzoxonium Chloride, Bispyrithione, Boric Acid, Bromochlorophene, Camphor Benzalkonium Methosulfate, Captan, Cetalkonium Chloride, Cetearalkonium Bromide, Cetethyldimonium Bromide, Cetrimonium Bromide, Cetrimonium Chloride, Cetrimonium Methosulfate, Cetrimonium Saccharinate, Cetrimonium Tosylate, Cetylpyridinium Chloride, Chloramine T. Chlorhexidine, Chlorhexidine Diacetate, Chlorhexidine Digluconate, Chlorhexidine Dihydrochloride, p-Chloro-m-Cresol, Chlorophene, pChlorophenol, Chlorothymol, Chloroxylenol, Chlorphenesin, Ciclopirox Olamine, Climbazole, Cloflucarban, Clotrimazole, Coal Tar, Colloidal Sulfur, o-Cymen-5-ol, Dequalinium Acetate, Dequalinium Chloride, Dibromopropamidine Diisethionate, Dichlorobenzyl Alcohol, Dichlorophene, Dichlorophenyl Imidazoldioxolan, Dichloro-m-Xylenol, Diiodomethyltolylsulfone, Dimethylol Ethylene Thiourea, Diphenylmethyl Piperazinylbenzimidazole, Domiphen Bromide, 7-Ethylbicyclooxazolidine, Fluorosalan, Formaldehyde, Glutaral, Hexachlorophene, Hexamidine, Hexamidine Diisethionate, Hexamidine Diparaben, Hexamidine Paraben, Hexetidine, Hydrogen Peroxide, Hydroxymethyl Dioxoazabicyclooctane, Ichthammol, Isopropyl Cresol, Lapyrium Chloride, Lauralkonium Bromide, Lauralkonium Chloride, Laurtrimonium Bromide, Laurtrimonium Chloride, Laurtrimonium Trichlorophenoxide, Lauryl Isoquinolinium Bromide, Lauryl Isoquinolinium Saccharinate, Laurylpyridinium Chloride, Mercuric Oxide, Methenamine, Methenammonium Chloride, Methylbenzethonium Chloride, Myristalkonium Chloride, Myristalkonium Saccharinate, Myrtrimonium Bromide, Nonoxynol-9 Iodine, Nonoxynol-12 Iodine, Olealkonium Chloride, Oxyquinoline, Oxyquinoline Benzoate, Oxyquinoline Sulfate, PEG-2 CocoBenzonium Chloride, PEG-10 Coco-Benzonium Chloride, PEG-6 Undecylenate, PEG-8 Undecylenate, Phenol, o-Phenylphenol, Phenyl Salicylate, Piroctone Olamine, Sulfosuccinylundecylenate, Potassium o-Phenylphenate, Potassium Salicylate, Potassium Troclosene, Propionic Acid, PVP-Iodine, Quaternium8, Quaternium-14, Quaternium-24, Sodium Phenolsulfonate, Sodium Phenoxide, Sodium o-Phenylphenate, Sodium Shale Oil Sulfonate, Sodium Usnate, Thiabendazole, 2,2'-Thiobis(4-Chlorophenol), Thiram, Triacetin,Triclocarban, Triclosan, Trioctyldodecyl Borate, Undecylenamidopropylamine Oxide, Undecyleneth-6, Undecylenic Acid, Zinc Acetate, Zinc Aspartate, Zinc Borate, Zinc Chloride, Zinc Citrate, Zinc Cysteinate, Zinc Dibutyldithiocarbamate, Zinc Gluconate, Zinc Glutamate, Zinc Lactate, Zinc Phenolsulfonate, Zinc Pyrithione, Zinc Sulfate, and Zinc Undecylenate.

: : Some examples of external analgesics are Benzyl Alcohol, Capsicum Oleoresin (Capsicum Frutescens Oleoresin), Methyl Salicylate, Camphor, Phenol, Capsaicin, Juniper Tar (Juniperus Oxycedrus Tar), Phenolate Sodium (Sodium Phenoxide), Capsicum (Capsicum Frutescens), Menthol, Resorcinol, Methyl Nicotinate, and Turpentine Oil (Turpentine).

Some examples of oxidizing agents are Ammonium Persulfate, Calcium Peroxide, Hydrogen Peroxide, Magnesium Peroxide, Melamine Peroxide, Potassium Bromate, Potassium Caroate, Potassium Chlorate, Potassium Persulfate, Sodium Bromate, Sodium Carbonate Peroxide, Sodium Chlorate, Sodium Iodate, Sodium Perborate, Sodium Persulfate, Strontium Dioxide, Strontium Peroxide, Urea Peroxide, and Zinc Peroxide.

Some examples of reducing agents are Ammonium Bisufite, Ammonium Sulfite, Ammonium Thioglycolate, Ammonium Thiolactate, Cystemaine HCI, Cystein, Cysteine HCl, Ethanolamine Thioglycolate, Glutathione, Glyceryl Thioglycolate, Glyceryl Thioproprionate, Hydroquinone, p-Hydroxyanisole, Isooctyl Thioglycolate, Magnesium Thioglycolate, Mercaptopropionic Acid, Potassium Metabisulfite, Potassium Sulfite, Potassium Thioglycolate, Sodium Bisulfite, Sodium Hydrosulfite, Sodium Hydroxymethane Sulfonate, Sodium Metabisulfite, Sodium Sulfite, Sodium Thioglycolate, Strontium Thioglycolate, Superoxide Dismutase, Thioglycerin, Thioglycolic Acid, Thiolactic Acid, Thiosalicylic Acid, and Zinc Formaldehyde Sulfoxylate.

An example of a skin bleaching agent is Hydroquinone.

Some examples of skin protectants are Allantoin, Aluminium Acetate, Aluminium Hydroxide, Aluminium Sulfate, Calamine, Cocoa Butter, Cod Liver Oil, Colloidal Oatmeal, Dimethicone, Glycerin, Kaolin, Lanolin, Mineral Oil, Petrolatum, Shark Liver Oil, Sodium Bicarbonate, Talc, Witch Hazel, Zinc Acetate, Zinc Carbonate, and Zinc Oxide.

Some examples of sunscreen agents are Aminobenzoic Acid, Cinoxate, Diethanolamine Methoxycinnamate, Digalloyl Trioleate, Dioxybenzone, Ethyl 4-[bis(Hydroxypropyl)] Aminobenzoate, Glyceryl Aminobenzoate, Homosalate, Lawsone with Dihydroxyacetone, Menthyl Anthranilate, Octocrylene, Octyl Methoxycinnamate, Octyl Salicylate, Oxybenzone, Padimate O. Phenylbenzimidazole Sulfonic Acid, Red Petrolatum, Sulisobenzone, Titanium Dioxide, and Trolamine Salicylate.

Some examples of UV light absorbing agents are Acetaminosalol, Allatoin PABA, Benzalphthalide, Benzophenone, Benzophenone 1-12, 3-Benzylidene Camphor, Benzylidenecamphor Hydrolyzed Collagen Sulfonamide, Benzylidene Camphor Sulfonic a. c. e: e. en: . . . ee- .:. .. e: Acid, Benzyl Salicylate, Bornelone, Bumetriozole, Butyl Methoxydibenzoylmethane, Butyl PABA, Ceria/Silica, Ceria/Silica Talc, Cinoxate, DEA-Methoxycinnamate, Dibenzoxazol Naphthalene, Di-t-Butyl Hydroxybenzylidene Camphor, Digalloyl Trioleate, Diisopropyl Methyl Cinnamate, Dimethyl PABA Ethyl Cetearyldimonium Tosylate, Dioctyl Butamido Triazone, Diphenyl Carbomethoxy Acetoxy Naphthopyran, Disodium Bisethylphenyl Tiamminotriazine Stilbenedisulfonate, Disodium Distyrylbiphenyl Triaminotriazine Stilbenedisulfonate, Disodium Distyrylbiphenyl Disulfonate, Drometrizole, Drometrizole Trisiloxane, Ethyl Dihydroxypropyl PABA, Ethyl Diisopropylcinnamate, Ethyl Methoxycinnamate, Ethyl PABA, Ethyl Urocanate, Etrocrylene Ferulic Acid, Glyceryl Octanoate Dimethoxycinnamate, Glyceryl PABA, Glycol Salicylate, Homosalate, Isoamyl p Methoxycinnamate, Isopropylbenzyl Salicylate, Isopropyl Dibenzolylmethane, Isopropyl Methoxycinnamate, Menthyl Anthranilate, Menthyl Salicylate, 4-Methylbenzylidene, Camphor, Octocrylene, Octrizole, Octyl Dimethyl PABA, Octyl Methoxycinnamate, Octyl Salicylate, Octyl Triazone, PABA, PEG-25 PABA, Pentyl Dimethyl PABA, Phenylbenzimidazole Sulfonic Acid, Polyacrylamidomethyl Benzylidene Camphor, Potassium Methoxycinnamate, Potassium Phenylbenzimidazole Sulfonate, Red Petrolatum, Sodium Phenylbenzimidazole Sulfonate, Sodium Urocanate, TEA-Phenylbenzimidazole Su]fonate, TEA-Salicylate, Terephthalylidene Dicamphor Sulfonic Acid, Titanium Dioxide, TriPABA Panthenol, Urocanic Acid, and VA/Crotonates/Methacryloxybenzophenone-l Copolymer.

1] Since mixing of the component materials in the formulation causes curing at room temperature in the presence of moisture, the component materials can be mixed and stored in a moisture proof container or they can be stored in a plurality of containers prior to use to inhibit curing prior to use. Moisture proof containers include, for example, single use containers (e.g., foil packets). When using a plurality of containers, one container could, for example, contain the silane and a second could contain the polysiloxanes. Each of the additional components in the formulation is put in the container that is most desirable depending on factors such as stability, viscosity, and interactions. Often, however, it is preferable to include an active agent, if used, in only one of the parts of the formulation in order to preserve its effectiveness. Similarly, it is often desirable to put a diluent in both containers.

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100421 According to the method of the invention, the mixed formulation is applied to the desired site or, alternatively, the component materials of the invention can be applied onto the desired site in a manner that causes mixing. The formulation reacts in the presence of moisture and results in a cured composition. Preferably, the formulations are applied on a biological surface including, but not limited to animal bodies (e.g., human or other animal) and flora.

10043] The formulations of the invention can be applied, for example, by rubbing, painting, spraying, or any other conventional method of applying thin films.

[00441 As noted above, when the formulation is mixed, it cures rapidly at room temperature in the presence of moisture (e.g., within l O minutes, usually within l -2 minutes).

For example, the formulation will cure rapidly on a human or other animal body. If used on an animal, this can minimize the amount time necessary to keep the area immobile while curing takes place.

[00451 The final composition can be in the form of a gel or an elastomer and it can have pores (e.g., foams) or it can be pore-free. If the final composition has pores, the formulations might contain materials such as blowing agents to form the pores.

6] The present invention offers numerous advantages over the prior art. The method described herein allows for a simple method of forming a film on a substrate. As such, a skilled practitioner is not required for application. Moreover, the composition can be formed into a wide variety of shapes and have selected combinations of properties (e.g. bioadhesion, release rate and release profile). Similarly, the formulations and processes described herein don't involve severe conditions (e.g. high temperatures or pressures) that might damage any active agents or substrates used.

[00471 The formulations and resultant compositions herein are generally acceptable on many biological surfaces. The composition may be formed on intact or damaged skin or in a natural or artificial cavity of the body. The cavity may be, for example, the ocular, cee ec: . s: e.

. . a. buccal, nasal, aural, vaginal or rectal cavity or a cavity formed, for example, in a tooth or an open wound.

[00481 The resultant films are typically thin and non-tacky. Films on the order of up to 20 mile (e.g., I to 15 mile) are often obtained. These films can have many physical properties from gels to elastomers so that they are able to withstand many of the pressures exerted during normal activities of a patient.

[00491 The following non-limiting Examples are provided to assist in understanding the invention. Unless indicated, all parts are by weight and all viscosities are at 25 C.

Examples 1-32

0] Formulations of the present invention were made by blending the components listed in Table 1. The polymer used in these Examples was the reaction product of vinyl- terminated dimethylsiloxane with trimethoxysilylethyl tetramethyldisiloxane. The filler used in these Examples was Cab-O-Sil TS- 530 treated filler. The alkoxysilane used in these Examples was methyltrimethoxysi]ane. The catalyst used in these Examples was tetra-tert- butyl titanate in mixed isopropoxy and t-butoxy-titanium complexes. The diluent used in these Examples was hexamethyldisiloxane. The materials were blended by adding, in order, the solvent, filler, polymer, silane, and catalyst to a Lightning rotating shaft mixer.

TABLE 1

Example # _I2345678

Polymer %9.59.09.18.66.66.46.46.2 Filler %0.50.40.40.43.33.23.23.1 Alkoxysilane %0.050.040.40.40.030.030.30.3 Catalyst %0.010.50.010.50.010. 40.010.4 Diluent %9090909090909090 : ..e.: .- t: :: :: '.

. . . . . Example # _91011121t31 t4Lt51 t61 Polymer %66.362.863. 660.346.5 44.745.1 43.5 Filler %3.33.13.23.C23.2 22.422.6 21.7 Alkoxysilane %0.30.33.23.C0.2 0.22.3 2.2 Catalyst %0.073.80.073.60.05 2. 70.04 2.6 Diluent3030303030 3030 30 _looloolooloaloo loo1oo loo Example _ 17 18 _ 20 21 22 23 24 Polymer % 16. 9 16.5 16.6 16.2 15.0 14.6 14.8 14.4 Filler % 2.5 2.5 2.5 2.4 4.5 4.4 4. 4 4.3 Alkoxysilane % 0.2 0.2 0.6 0.6 0.2 0.2 0.5 0.5 Catalyst % 0.3 0.8 0. 3 0.8 0.3 0.7 0.3 0.7 Diluent % 80 80 8C 80 80 80 80 80 _ 100 100 lOC 100 100 100 100 100 Example # _ 25 26 27 28 29 30 31 32 Polymer % 46.4 45.3 45.6 44.5 41.2 40.3 40.6 39.71 Filler % 7.0 6.8 6.8 6. 7 12.4 12.1 12.2 11.9| Alkoxysilane % 0.7 0.7 1.6 1.6 0.6 0.6 1.4 1.4 Catalyst % 0.9 2.3 0.9 2.2 0.8 2.0 0.S 2.0 Diluent _ 45 45 45 45 45 45 45 45 _ 100 100 100 100 100 100 1OC 100

Examples 33-38

1] Materials were made as in Examples 1-32 having the composition as set forth in the following Table 2.

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TABLE 2

Example # 3334 35363738 Polymer %19.1923.03 26.8730.7134.5519.19 Filler %4.85.76 6.727.688.644.8 Alkoxysilane %0.430.52 0.600.690.780.43 Catalyst %0.580.69 0.810.921.040.58 Diluent %75.070.0 65.060.055.075.0 100100 100100100100 [00521 Samples, 0.3 grams, of the above materials were spread in a 1.5- inch diameter circle on a 3M Scotchpak release liner film. The materials were allowed to cure for 24 hours at room temperature. Five-micrometer measurements were taken at different locations around the liner, the readings were averaged and the release liner thickness was deducted to get the result set forth in Table 3.

TABLE 3

Example # % Solids Amount |DrY Film Thickness 33 25 0.3 Mil 34 30 0.3 Mil 35 0.3 7.5 Mil 36 40 0.3 8 Mil 37 45 0.3 10 Mil 38 25 0.3 Mil

Examples 39-47

10053] A 32.5 x 32.5 cm square piece of 3M Scotchpak release liner film was clamped on a tabletop coaler. The shims as indicated in Table 4 were clamped to the outside edges of the release liner. A smooth surfaced coating bar was placed in position. [0054] c:e if.: '. .. :..

10055] Approximately 50 ml of the formulation was poured on the release liner in contact with the coating bar. The coaler was run at medium speed to coat the release liner with the formulation. The formulation was allowed to cure for twenty-four hours at ambient temperature. Five micrometer measurements were taken at different locations around the circle, the readings were averaged and the release liner thickness was deducted to get the result set forth in Table 4.

TABLE 4.

Example # Material from % Solids ShimsDry Film Thickness

Example #

38 25 2 mil1 mil 38 25 5 mil1.5 mil 41 33 25 30 mil5 mil 42 34 30 30 mil6 mil 43 35 35 30 mil7.5 mil 44 36 40 30 mil8 mil 37 45 5 mil3 mil 46 37 45 30 mil10 mil 47 37 45 60 mil17 mil

Examples 48-50

6] Materials from Examples 33, 34 and 36 were cured in an 8 inch X 8 inch Teflon coated pan for 16 hours at room temperature and 4 hours at 100 C. Pieces of the cured material were die cut and their physical properties tested on an Instron Material Tester.

The results are set forth in Table 5.

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TABLE 5

Example # 48 50

Material from 33 34 36

Example #

Tensile (psi) 986 1070 1061 Elongation (%) 625 726 680 100% Modulus 168 157 153 200% Modulus 243 218 227 300% Modulus 347 301 326 (psi) 600% Modulus 919 755 846 (psi) Durometer 46.6 45.9 43.9 (Shore A) Tear (ppi) 121 121 146

Claims

: :. t: t: ë et: : : . : : : e. . . . . . CLAIMS

1. A method for forming a film on a biological surface comprising; mixing 5to 70 wt. % of an alkylene trialkoxysilyl terminated polysiloxane; O to 5 wt. % of an alkoxysilane; 0.01 to 5 wt. % of a catalyst; O to 25 wt % of a filler; and 1 to 94.99 wt % of a volatile diluent to form a formulation; and applying the formulation onto a biological surface, wherein said formulation cures in situ on the biological surface to form the film.

2. The method according to Claim 1 wherein the formulation also comprises an active agent.

3. The method according to Claim 2 wherein the active agent is selected from the group consisting of cosmetics, personal care, cosmeceutical, therapeutic or diagnostic materials, pesticides and herbicides.

4. The method according to Claim 2 wherein the active agent is selected from the group consisting of anti acne agent, antibiotic, antiseptic, antifungal, antibacterial, antimicrobial, biocides, antiinflamatory, astringents, hormones, anticancer agents, smoking cessation compositions, cardiovascular, histamine blocker, bronchodilator, analgesic, antiarrythmic, antihistamine, alpha- I blocker, beta blocker, ACE inhibitor, diuretic, antiaggregant, sedative, tranquillizer, anticonvulsant, anticoagulant agents, vitamins, antiaging agents, agents for treating gastric and duodenal ulcers, anticellulites, proteolytic enzymes, healing factors, cell growth nutrients, peptides, perfumes, W protectors, shaving products and deodorants.

5. The method according to Claim 1 wherein the formulation also comprises cosmetic, personal care or cosmeceutical ingredients and pharmaceutical excipients selected from the group consisting of absorbents, anticaking agents, antioxidants, antistatic agents, astringents, binders, buffering agents, bulking agents, chelating agents, colorants, cosmetic astringents, cosmetic biocides, ct:e t.: .e es. .. as:e deodorant agents, emollients, external analgesics, film farmers, flavouring agents, fragrance ingredients, humectants, lytic agents, moisturizing agents, occlusivity enhancers, opacifying agents, oxidizing and reducing agents, penetration enhancers, pesticides, plasticizers, preservatives, skin bleaching agents, skin conditioning agents, skin protestants, slip modifiers, solubilizing agents, solvents, sunscreen agents, surface modifiers, surfactants and emulsifying agents, suspending agents, thickening agents, viscosity controlling agents including increasing or decreasing agents and UV light absorbers.

6. The method according to Claim 5 wherein the cosmetic, personal care and cosmecoutical ingredients and pharmaceutical excipients are selected from the group consisting of alcohols, fatty alcohols and polyols, aldehydes, alkanolamines, alkoxylated alcohols, alkoxylated amides, alkoxylated amines, alkoxylated carboxylic acids, amides including salts, amines, amino acids including salts and alkyl substituted derivatives, esters, alkyl substituted and acyl derivatives, polyacrylic acids, acrylamide copolymers, adipic acid copolymers, alcohols, aminosilicones, biological polymers and derivatives, butylene copolymers, carbohydrates, carboxylic acids, carbomers, esters, ethers and polymeric ethers, glyceryl esters and derivatives, halogen compounds, heterocyc]ic compounds including salts, hydrophilic colloids and derivatives including salts and gums, imidazolines, inorganic materials, ketones, isethionates, lanolin and derivatives, organic salts, phenols including salts, phosphorus compounds, polyacrylates and acrylate copolymers, protein and enzymes derivatives, synthetic polymers including salts, siloxanes and silanes, sorbitan derivatives, sterols, sulfonic acids and derivatives and waxes.

7. The method according to Claim 1 wherein the biological surface comprises animal skin.

8 The method according to claim 1 wherein the film is less than 20 mils thick.

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9. The method according to Claim l wherein the biological surface comprises flora.

10. The method according to claim 1 wherein the biological surface is skin and the film serves in a capacity selected from the group consisting of topical drug delivery systems, masking systems for skin protection in dermal treatments, wound dressings and bandages for minor wounds, burns, acute and chronic wounds, skin sealants, skin protective films, scar treatments, exfoliation and hair remover products, deodorizing films, antiperspirant active and fragrance delivery systems, anti-wrinkle patches and moisturizing masks, wherein said film applications have benefits in topical therapies, wound care, surgical closure, scar care, underarm care, foot care, body and face skin care, cosmetics, make-up and foundations.

The method according to any of the preceding claims wherein the biological surface is selected from the group consisting of hair, nails, teeth, eyes, and mucous membranes.

12. The method according to any of the preceding claims in which the biological surface is a veterinary application.