Film-forming compositions containing salicylic acid and methods of use

Abstract

Described herein are compositions containing salicylic acid for use as therapeutic articles for specific conditions, and methods for making such articles. The compositions include salicylic acid, a silicone-containing film-forming polymer, a silicate tackifying resin, and an additive, the additive comprising: (i) a nonionic surfactant having an HLB of 5 to 9, (ii) an aminosilicone having an amine number greater than 60, (iii) a cationic silicone polyquaternium, or (iv) a combination thereof. Such compositions can be used for skin treatment applications.

Description

[Technical Field]

[0001] Film-forming compositions containing salicylic acid are discussed along with methods of making the compositions and their use as compatible skin treatments. Summary of the Invention

[0002] It is desirable to identify aesthetically pleasing and compatible skin treatment products that contain salicylic acid.

[0003] In one aspect, a composition for use as a therapeutic article is described. The composition comprises: salicylic acid, a silicone-containing film-forming polymer; a silicate tackifying resin, and additives wherein the additive is (i) a nonionic surfactant having an HLB of 5 to 9, (ii) an aminosilicone having an amine ratio greater than 0.05, (iii) a polyquaternium, or (iv) a combination thereof.

[0004] In one embodiment, the composition is used to treat acne, hi another embodiment, the composition is used to treat warts.

[0005] In another aspect, a method for making a gel composition is described, the method comprising: and combining the first and second parts to produce a gel composition, the gel composition comprising: salicylic acid, a silicone-containing film-forming polymer; silicate tackifying resin, volatile solvents, and an additive, the additive comprising: (i) a nonionic surfactant having an HLB of 5 to 9; (ii) an aminosilicone having an amine ratio greater than 0.05; (iii) a silicone-containing polyquaternium; or (iv) a combination thereof; The first portion comprises salicylic acid in a first portion of a silicone-containing film-forming polymer, and the second portion comprises a second portion of a silicone-containing film-forming polymer.

[0006] The above summary of the invention is not intended to describe every embodiment. The details of one or more embodiments of the invention are also set forth in the following detailed description. Other features, objects, and advantages will be apparent from the detailed description and claims. DETAILED DESCRIPTION OF THE INVENTION

[0007] As used herein, The terms "a," "an," and "the" are used interchangeably and mean one or more; The term "and / or" is used to indicate that either or both of the stated things may occur; for example, A and / or B includes (A and B) and (A or B); "Backbone" refers to the main continuous chain of a polymer; "Crosslinking" refers to the joining of two pre-formed polymer chains using a chemical bond or chemical group; "Interpolymerized" refers to monomers polymerized together to form a polymer backbone; A "monomer" is a molecule that can undergo polymerization and subsequently form part of the basic structure of a polymer. "Polymer" refers to a macrostructure having a number average molecular weight (Mn) of at least 50,000 daltons, at least 100,000 daltons, at least 300,000 daltons, at least 500,000 daltons, at least 750,000 daltons, at least 1,000,000 daltons, or even at least 1,500,000 daltons, as measured using techniques known in the art, such as gel permeation chromatography, and which is not so high as to cause premature gelation of the polymer.

[0008] The term "polydiorganosiloxane" refers to a compound of the formula [ka]

[0009] (In the formula, each R 1 are independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; and the subscript n is independently an integer from 0 to 1500. refers to the bivalent segment of

[0010] As used herein, "film-forming" refers to a composition that, when dried on skin or mucosal tissue under ambient conditions (e.g., 23°C and 50% relative humidity (RH)), forms a continuous layer that does not peel off after simple flexion of the tissue.

[0011] Further herein, the recitations of ranges by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0012] Further, as used herein, the term "at least 1" includes all numbers greater than or equal to 1 (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0013] As used herein, "comprising at least one of" A, B, and C refers to a single element A, a single element B, a single element C, A and B, A and C, B and C, and combinations of all three.

[0014] Silicone-containing film-forming polymers are known to be used to produce conformable bandages. This disclosure relates to the use of similar compositions to produce more aesthetically pleasing treatment options for skin conditions such as acne, warts, calluses, psoriasis, tinea, and ichthyosis. However, as exemplified in U.S. Pat. No. 10,603,405 (Langer-Anderson et al.), all ingredients except for the higher-viscosity silicone-containing film-forming polymer (e.g., SPOx) are mixed together in a primary solvent (e.g., hexamethyldisiloxane) to produce a homogeneous mixture, and the SPOx is then added last to increase the viscosity of the formulation to that of a final gel. When salicylic acid was added to the formulation of U.S. Pat. No. 10,603,405 (where SPOx is added at the end of production to build viscosity), it was found that the salicylic acid did not appear to dissolve and remained as solid particles in solution after production. Because it is important that the functional ingredient (i.e., salicylic acid) be uniformly dispersed throughout the gel, it has been discovered that the order in which the ingredients are mixed and the nature of the ingredients (e.g., additives) are important for achieving a uniform gel solution that allows the composition to be produced under reasonable processing times. Ideally, the resulting composition (i.e., gel and / or dry film) is a single-phase composition that is free of visible solids, and in particular free of solid salicylic acid particulates.

[0015] The compositions of the present disclosure comprise (a) salicylic acid, (b) a silicone-containing film-forming polymer, (c) a silicate tackifying resin, and (d) an additive that is (i) a nonionic surfactant having an HLB of 5-9, (ii) an aminosilicone having an amine number greater than 60, (iii) a silicone polyquaternium, or (iv) a combination thereof. A volatile solvent is used to produce a compatible gel composition that, upon evaporation, provides a therapeutic film.

[0016] Salicylic acid

[0017] The composition of the present disclosure comprises salicylic acid. In one embodiment, the composition comprises at least 0.1, 0.5, or even 1 wt.% salicylic acid, and up to 3, 5, 7, or even 10 wt.% salicylic acid. In one embodiment, the composition comprises at least 5, 8, 10, 15, or even 18 wt.% salicylic acid, and up to 20, 25, 30, or even 35 wt.% salicylic acid. The amount of salicylic acid in the composition can vary depending on whether the composition is in gel or dry form and the skin condition for which the composition is intended.

[0018] Film-forming polymers

[0019] Generally, the majority of the composition comprises a film-forming polymer. The film-forming polymer can form a substantially continuous layer when dried. Suitable film-forming polymers are at least partially soluble in volatile solvents, and include silicone-containing polymers. Particularly suitable silicone-containing polymers include polysiloxane polyamides, silicone polyureas, and silicone polyamines.

[0020] Film-forming polymers are typically soluble in the solvent system used in the gel composition. As used herein, a polymer is "soluble" or "solubilized" if the amount of polymer present in the solvent system is completely dissolved in the solvent system without the polymer precipitating or forming visible swollen gel particles in the solution. As used herein, the term "solubility limit" refers to the maximum amount of a given polymer that can be dissolved in a given solvent system, measured as a percentage of the total weight of the solution. For example, a film-forming polymer may have a solubility limit of at least 5%, 10%, 15%, or even 20% by weight in hexamethyldisiloxane, isooctane, or any other solvent system described herein, based on the total weight of the gel composition.

[0021] Silicone-containing polymers useful in practicing the present disclosure may have an intrinsic viscosity ("IV") of at least 0.9, 1.45, 1.68, or at least 1.8, as measured by the intrinsic viscosity test method of U.S. Pat. No. 8,765,881 (Hayes et al.). Silicone-containing polymers typically have an intrinsic viscosity of less than 3, since polymers with an intrinsic viscosity greater than 3 may be difficult to solubilize in certain circumstances. Low-IV polymers are particularly more soluble in solvents and solvent systems, and therefore may be film-forming agents, but may dry more slowly and remain tacky after application. The IV of the polymer can be adjusted during polymerization of the polymer by varying the initiator, initiator concentration, reaction temperature, reaction solvent, reaction method, and other parameters known to those skilled in the art.

[0022] In one embodiment, suitable silicone-containing polymers include siloxanes and polysiloxane polyamides. Siloxane polymers have unique properties that are primarily due to the physical and chemical characteristics of the siloxane bond. These properties include low glass transition temperatures, thermal and oxidative stability, UV resistance, low surface energy, and low hydrophobicity. However, siloxane polymers often lack tensile strength. The low tensile strength of siloxane polymers can be improved by forming block copolymers. Some block copolymers contain a "soft" siloxane polymer block or segment and any of a variety of "hard" blocks or segments. Particularly suitable elastomeric siloxane-based elastomeric polymers are segmented polymers of Formula I and Formula II below.

[0023] In some embodiments, the silicone-containing polymer is a linear polydiorganosiloxane, a linear polydiorganosiloxane polyamide block copolymer, or a polydiorganosiloxane urethane-containing copolymer, although other silicone-containing polymers may also be useful.

[0024] Polydiorganosiloxanes can have a variety of organic substituents on the silicon carbon atoms of the polysiloxane. For example, each organic substituent can independently be alkyl, haloalkyl, arylalkylenyl, alkylarylenyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo. Polydiorganosiloxanes can be represented by the general formula (Si(R 7 )2O-) (In the formula, R 7 is R in Formula I 7 For any of the embodiments, R may have repeating units of (as defined below). Examples include dimethyl silicone, diethyl silicone, and diphenyl silicone. In some embodiments, R 7 At least 40, 50, 60, 70, 80, 90, 95, 98, or even 99% of the groups can be phenyl, methyl, or a combination thereof. 7 At least 40, 50, 60, 70, 80, 90, 95, 98, or even 99% of the groups are methyl. For example, high molecular weight polydimethylsiloxane (PDMS) having a molecular weight of at least 30,000 grams / mole is commercially available from, for example, Gelest Inc. Morrisville, PA.

[0025] Linear polydiorganosiloxane polyamide block copolymers useful in the practice of the present disclosure include at least two repeating units of Formula I. [ka] In this formula, each R 7is independently alkyl, haloalkyl, arylalkylenyl, alkylarylenyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo. Each Y is independently alkylene, arylalkylene, alkylarylene, or a combination thereof. Subscript n independently ranges from 0 to 1500, and subscript p ranges from 1 to 10. Each group B is independently a covalent bond, alkylene, arylalkylene, alkylarylene, arylene, or a combination thereof. When each group B is a covalent bond, the polydiorganosiloxane polyamide block copolymer of Formula I is called a polydiorganosiloxane polyoxamide block copolymer.

[0026] The group G has the formula R 8 HN-G-NHR 8 Diamine to two -NHR 8 The group R is a divalent group whose residue unit is equal to the residue unit minus the group R. 8 is hydrogen or alkyl (e.g., alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms), or R 8 G and R 8 and G together with the nitrogen to which they are both attached form a heterocyclic group. Each asterisk (*) indicates the point at which the repeat unit is attached to another group within the copolymer, such as another repeat unit of Formula I.

[0027] R in Formula I 7 Suitable alkyl groups for R typically have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Examples of useful alkyl groups include methyl, ethyl, isopropyl, n-propyl, n-butyl, and iso-butyl. 7 In most cases, haloalkyl groups suitable for R have only a portion of the hydrogen atoms of the corresponding alkyl group replaced with halogen. Examples of haloalkyl groups include chloroalkyl and fluoroalkyl groups having 1 to 3 halogen atoms and 3 to 10 carbon atoms. 7Suitable alkenyl groups for R often have 2 to 10 carbon atoms. Examples of alkenyl groups often have 2 to 8, 2 to 6, or 2 to 4 carbon atoms, such as ethenyl, n-propenyl, and n-butenyl. 7 Suitable aryl groups for often have 6 to 12 carbon atoms. Phenyl is one example of an aryl group. The aryl group can be unsubstituted or substituted with alkyl (i.e., it can be an alkylarylenyl group) (the alkyl group can be, for example, an alkyl having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), alkoxy (e.g., an alkoxy having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro). R 7 Suitable arylalkylenyl and alkylarylenyl groups typically have an alkylene group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms. In some arylalkylenyl and alkylarylenyl groups, the aryl group is phenyl and the alkylene group has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. For example, R 7 may be an arylalkylenyl group in which any of these alkylene groups is bonded to a phenyl group.

[0028] In some embodiments, in some repeat units of formula I, R 7 At least 40%, and in some embodiments at least 50%, of the groups are phenyl, methyl, or a combination thereof. For example, R 7 At least 60, 70, 80, 90, 95, 98, or even 99% of the groups can be phenyl, methyl, or a combination thereof. In some embodiments, in some repeat units of Formula I, R 7 At least 40%, or even 50%, of the groups are methyl. For example, R 7 At least 60, 70, 80, 90, 95, 98, or even 99% of the groups may be methyl.7 The groups may be selected from alkyl having at least 2 carbon atoms, haloalkyl, arylalkylenyl, alkylarylenyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo.

[0029] Each Y in Formula I is independently alkylene, arylalkylene, alkylarylene, or a combination thereof. Suitable alkylene groups typically have up to 10, 8, 6, or even 4 carbon atoms. Examples of alkylene groups include methylene, ethylene, propylene, butylene, and the like. Suitable arylalkylene and alkylarylene groups typically have an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. In some arylalkylene and alkylarylene groups, the arylene moiety is phenylene. That is, a divalent arylalkylene or alkylarylene group has a phenylene bonded to an alkylene group having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used herein with respect to the group Y, "combinations thereof" refers to a combination of two or more groups selected from alkylene groups and arylalkylene or alkylarylene groups. For example, the combination can be a single alkylarylene linked to a single alkylene (e.g., alkylene-arylene-alkylene). In one example of an alkylene-arylene-alkylene combination, the arylene is phenylene and each alkylene has 1 to 10, 1 to 6, or even 1 to 4 carbon atoms.

[0030] Each subscript n in Formula I independently ranges from 0 to 1500. For example, subscript n can be up to 1000, 500, 400, 300, 200, 100, 80, 60, 40, 20, or even 10. The value of n is at least 1, 2, 3, 5, 10, 20, or even 40. For example, subscript n can range from 40 to 1500, 0 to 1000, 40 to 1000, 0 to 500, 1 to 500, 40 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to 100, 1 to 80, 1 to 40, or 1 to 20.

[0031] The subscript p ranges from 1 to 10. For example, the value of p is often an integer up to 9, 8, 7, 6, 5, 4, 3, or even 2. The value of p can range from 1 to 8, 1 to 6, or even 1 to 4.

[0032] The group G in formula I is a group of formula R 8 HN-G-NHR 8 From the diamine compound, two amino groups (i.e., -NHR 8 The diamine may have primary or secondary amino groups. 8 is hydrogen or alkyl (e.g., alkyl having 1 to 10, 1 to 6, or even 1 to 4 carbon atoms), or R 8 G and R 8 and G together with the nitrogen to which they are both attached form a heterocyclic group (e.g., a 5- to 7-membered ring). 8 HN-G-NHR 8 is piperazine. In some embodiments, R 8 is hydrogen or alkyl. In some embodiments, both amino groups in the diamine are primary amino groups (i.e., both R 8 groups are hydrogen), the diamine is a diamine represented by the formula H2N-G-NH2.

[0033] In some embodiments, G is alkylene, heteroalkylene, polydiorganosiloxane, arylene, arylalkylene, alkylarylene, or a combination thereof. Suitable alkylenes often have 2 to 10, 2 to 6, or even 2 to 4 carbon atoms. Examples of alkylene groups include ethylene, propylene, and butylene. Suitable heteroalkylenes often are polyoxyalkylenes, such as polyoxyethylene having at least two ethylene units, polyoxypropylene having at least two propylene units, or copolymers thereof. Examples of polydiorganosiloxanes include polydimethylsiloxanes with alkylene end groups. Suitable arylalkylene groups typically contain an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. Some examples of arylalkylene groups are phenylene-alkylene, where the phenylene is bonded to an alkylene having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or even 1 to 4 carbon atoms. Some examples of alkylarylene groups are alkylene-phenylene, where an alkylene having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or even 1 to 4 carbon atoms is bonded to the phenylene. As used herein with respect to the group G, "combinations thereof" refers to combinations of two or more groups selected from alkylene, heteroalkylene, polydiorganosiloxane, arylene, arylalkylene, and alkylarylene. The combination may be, for example, an arylalkylene bonded to an alkylene (e.g., alkylene-arylene-alkylene). In one example of an alkylene-arylene-alkylene combination, the arylene is phenylene and each alkylene has 1 to 10, 1 to 6, or even 1 to 4 carbon atoms.

[0034] In some embodiments, the polydiorganosiloxane polyamide is a polydiorganosiloxane polyoxamide. Polydiorganosiloxane polyoxamides tend to be free of groups having the formula -B-(CO)-NH-, where B is alkylene.

[0035] All of the carbonylamino groups along the backbone of the copolymer material are typically part of an oxalylamino group (i.e., a -(CO)-(CO)-NH- group), where B is a bond. That is, every carbonyl group along the backbone of the copolymer material is bonded to another carbonyl group and becomes part of an oxalyl group. More specifically, polydiorganosiloxane polyoxamides have multiple aminooxalylamino groups.

[0036] Polydiorganosiloxane polyamides are block copolymers and can be elastomeric materials. Unlike many known polydiorganosiloxane polyamides, which are typically formulated as brittle solids or hard plastics, polydiorganosiloxane polyamides can be formulated to contain greater than 50 weight percent polydiorganosiloxane segments, based on the weight of the copolymer. The weight percent of diorganosiloxane in the polydiorganosiloxane polyamide can be increased by using higher molecular weight polydiorganosiloxane segments, providing greater than 60, 70, 80, 90, 95, or even greater than 98 weight percent polydiorganosiloxane segments in the polydiorganosiloxane polyamide. Using higher amounts of polydiorganosiloxane allows for the preparation of elastomeric materials with lower modulus while maintaining adequate strength.

[0037] Some polydiorganosiloxane polyamides can be heated to temperatures up to 200, 225, 250, 275°C, or even up to 300°C without significant material decomposition. For example, when heated in a thermogravimetric analyzer in the presence of air, the copolymers often lose less than 10 weight percent when scanned at a rate of 50°C / minute over the range of 20°C to 350°C. Furthermore, the copolymers can often be heated in air at temperatures such as 250°C for one hour, with no detectable loss of mechanical strength upon cooling, indicating no appreciable decomposition. Linear block copolymers having repeating units of Formula I can be prepared by reacting at least one polydiorganosiloxane-containing precursor with at least one diamine, as described, for example, in U.S. Pat. No. 7,371,464, incorporated herein by reference.

[0038] The diamine may be classified as an organic diamine or a polydiorganosiloxane diamine containing the organic diamine, such as an alkylenediamine, a heteroalkylenediamine (such as a polyoxyalkylenediamine), an arylenediamine, an aralkylenediamine, or an alkylene-aralkylenediamine. The diamine contains only two amino groups, and the resulting polydiorganosiloxane polyoxamide is a linear block copolymer that is often elastomeric, hot-melt processable (e.g., the copolymer can be processed at temperatures up to 250°C or higher without appreciable composition degradation), and soluble in several common organic solvents. In some embodiments, the diamine does not include polyamines containing more than two primary or secondary amino groups. Tertiary amines that do not react with the polydiorganosiloxane-containing precursor may also be present. Furthermore, the diamine utilized in the reaction does not contain any carbonylamino groups. That is, the diamine is not an amide.

[0039] Preferred alkylenediamines (i.e., G is alkylene) include, but are not limited to, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, 2-methylpentamethylene-1,5-diamine (i.e., commercially available from DuPont, Wilmington, Del., under the trade name DYTEK A), 1,3-pentanediamine (commercially available from DuPont under the trade name DYTEK EP), 1,4-cyclohexanediamine, 1,2-cyclohexanediamine (commercially available from DuPont under the trade name DHC-99), 4,4′-bis(aminocyclohexyl)methane, and 3-aminomethyl-3,5,5-trimethylcyclohexylamine.

[0040] Polydiorganosiloxane polyoxamide copolymers can be produced using multiple polydiorganosiloxane precursors, multiple diamines, or a combination thereof. Multiple precursors with different average molecular weights can be mixed with a single diamine or multiple diamines under reactive conditions. For example, the precursor can include a mixture of materials with different values ​​of n, different values ​​of p, or different values ​​of both n and p. Multiple diamines can include, for example, a first diamine that is an organic diamine and a second diamine that is a polydiorganosiloxane diamine. Similarly, a single precursor can be mixed with multiple diamines under reactive conditions.

[0041] The polydiorganosiloxane-containing precursor can be prepared by any known method, hi some embodiments, the precursor is prepared according to the following reaction scheme described in the aforementioned U.S. Pat. No. 7,371,464 (Sherman et al.): [ka]

[0042] The polydiorganosiloxane diamine can be prepared by any known method and can have any suitable molecular weight.

[0043] Further details about suitable polydiorganosiloxane polyamides (including polydiorganosiloxane diamines and especially polydiorganosiloxane polyoxamides) can be found, for example, in U.S. Patent Nos. 8,586,668 (Leir et al.), 5,214,119 (Leir et al.), 5,461,134 (Leir et al.), 5,512,650 (Leir et al.), and 7,371,464 (Sherman et al.), and U.S. Patent Nos. 7,705,101 and 8,431,671 (Sherman et al.). Some polydiorganosiloxane diamines are commercially available, for example, from Shin-Etsu Silicones of America, Inc. (Torrance, CA) and Gelest Inc. (Morrisville, PA).

[0044] Other examples of suitable silicone elastomers include polydiorganosiloxane polyureas, copolymers and blends thereof, such as those described in U.S. Patent Nos. 5,461,134 and 6,007,914 (Joseph et al.). Silicone polyurethane copolymers (SPUs) useful as film-forming polymers in the compositions and methods described herein include block copolymers comprising a silicone block and a second block derived from a polyfunctional isocyanate. In some places herein, the term silicone-polyurea may be used interchangeably with silicone-polyurethane. Useful silicone polyurea block copolymers are disclosed, for example, in U.S. Pat. Nos. 5,512,650, 5,214,119, and 5,461,134, and U.S. Pat. Nos. 6,569,521, 6,664,359 (Melancon et al.), and WO 96 / 35458, WO 98 / 17726, WO 96 / 34028, WO 96 / 34030, and WO 97 / 40103.

[0045] The silicone block may be a compound represented by the general formula (Si(R 7 )2O-)(wherein, R 7 is R in Formula I 7(as defined above for any of the embodiments). Non-limiting examples include dimethyl silicone, diethyl silicone, and diphenyl silicone.

[0046] Polydiorganosiloxane urethane-containing copolymers (part of the SPU material class) useful in the compositions of the present disclosure contain soft polydiorganosiloxane units, hard polyisocyanate residue units, end groups, and, optionally, soft and / or hard organic polyamine residue units. Some polydiorganosiloxane urea-containing copolymers are commercially available from Wacker Chemie AG (Germany) under the trade name "GENIOMER 140." The polyisocyanate residues are polyisocyanates minus the -NCO group, and the organic polyamine residues are organic polyamines minus the -NH group. The polyisocyanate residues are bonded to the polydiorganosiloxane units or organic polyamine residues via urea linkages. The end groups may be non-functional or functional, depending on the purpose of the polydiorganosiloxane urea segmented copolymer.

[0047] In some embodiments, polydiorganosiloxane urethane-containing copolymers useful as polymer processing additives contain at least two repeat units of formula II. [ka] In this formula II, each R 9 R is a moiety that is independently an alkyl group, a cycloalkyl group, an aryl group, a perfluoroalkyl group, or a perfluoroether group. 9 In some embodiments, alkyl has about 1 to 12 carbon atoms and is, for example, trifluoroalkyl, vinyl, a vinyl radical, or a group of the formula -R 10 (CH2) a CH=CH2 (wherein, R 10 is -(CH2) b -or-(CH2) cR may be substituted by a higher alkenyl represented by the formula: CH═CH—, a is 1, 2, or 3, b is 0, 3, or 6, and c is 3, 4, or 5. 9 In some embodiments of R, the cycloalkyl has about 6 to 12 carbon atoms and may be substituted with one or more alkyl, fluoroalkyl, or vinyl groups. 9 In some embodiments of R, the aryl has about 6 to 20 carbon atoms and may be substituted with, for example, alkyl, cycloalkyl, fluoroalkyl, and vinyl groups. 9 In some embodiments, the perfluoroalkyl groups are as described in U.S. Pat. No. 5,028,679, which is incorporated herein by reference, and the perfluoroether-containing groups are as described in U.S. Pat. Nos. 4,900,474 and 5,118,775, which are incorporated herein by reference. In some embodiments, R 9 is a fluorine-containing group as described in U.S. Pat. No. 5,236,997, which is incorporated herein by reference. In some embodiments, R 9At least 50% of the moieties are methyl radicals, and the remainder are monovalent alkyl or substituted alkyl, alkenylene, phenyl, or substituted phenyl radicals having 1 to 12 carbon atoms. In Formula II, each Z' is an arylene, arylalkylene, alkylene, or cycloalkylene. In some embodiments of Z', the arylene or arylalkylene has about 6 to 20 carbon atoms. In some embodiments of Z', the alkylene or cycloalkylene radical has about 6 to 20 carbon atoms. In some embodiments, Z' is 2,6-tolylene, 4,4'-methylenediphenylene, 3,3'-dimethoxy-4,4'-biphenylene, tetramethyl-m-xylylene, 4,4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclohexylene, 1,6-hexamethylene, 1,4-cyclohexylene, 2,2,4-trimethylhexylene, or a combination thereof. In Formula II, each Y' is independently alkylene, arylalkylene, alkylarylene, or arylene. In some embodiments of Y', the alkylene has 1 to 10 carbon atoms. In some embodiments of Y', the arylalkylene, alkylarylene, or arylene has 6 to 20 carbon atoms. In Formula II, each D is independently hydrogen, an alkyl radical having 1 to 10 carbon atoms, phenyl, or a radical that completes a cyclic structure with B' or Y' to form a heterocycle. In Formula II, B is a polyvalent radical selected from the group consisting of alkylene, arylalkylene, alkylarylene, cycloalkylene, phenylene, and polyalkylene oxide (e.g., polyethylene oxide, polypropylene oxide, polytetramethylene oxide, and copolymers and mixtures thereof). In Formula II, "s" is a number from 0 to about 1000, "r" is a number equal to or greater than 1, and "q" is a number from about 5 or greater, in some embodiments from about 15 to 2000, and in some embodiments, from about 30 to 1500.

[0048] In the use of polyisocyanates (where Z' is a radical with a functionality greater than 2) and polyamines (where B' is a radical with a functionality greater than 2), the structure of Formula II is modified to reflect the branching of the polymer backbone. In the use of end-capping agents, the structure of Formula II is modified to reflect the termination of the polydiorganosiloxane urea chain.

[0049] Linear block copolymers having repeating units of Formula I and polydiorganosiloxane urea-containing polymers of Formula II can be prepared, for example, as discussed in US Pat. No. 8,552,136 (Papp et al.).

[0050] Other examples of silicone-containing polymers include those formed from silanols, silicone hydrides, siloxanes, epoxides, and (meth)acrylates. When film-forming polymers are prepared from (meth)acrylate-functional siloxanes, the polymers are sometimes referred to as siloxane (meth)acrylates. Furthermore, other amphiphilic siloxy-containing polymers have been reported to be useful in gel compositions (U.S. Pat. No. 7,795,326 (Salamone et al.)), in which hydrophobic siloxylane monomers are copolymerized with hydrophilic nitrogen-containing monomers. Other siloxy-containing polymers include block copolymers of polydimethylsiloxane and polyurethane and block copolymers of polydimethylsiloxane and poly(ethylene glycol). Additionally, other potentially effective film-forming polymers include block copolymers of polystyrene and ethylene / butylene, block copolymers of polystyrene and polyisobutylene, block copolymers of polystyrene and polyisoprene, block copolymers of polystyrene and polybutadiene, block copolymers of polydimethylsiloxane and polyurethane, polymers of C4 to C18 acrylates and methacrylates, butyl rubber, polyisobutylene, and combinations thereof.

[0051] Another suitable siloxy-containing monomer for certain gel compositions is the siloxy monomer, 3-methacryloyloxypropyltris(trimethylsiloxy)silane (TRIS). TRIS can be used in combination with both hydrophilic comonomers, such as N-isopropylacrylamide (NIPAM), or hydrophobic comonomers, such as methyl methacrylate, so that the resulting copolymers are soluble in volatile solvents.

[0052] The film-forming polymer is typically present in an amount of at least 5% and up to 30% by weight, based on the total weight of the gel composition, or any amount within that range. In certain implementations, it may be preferred for the film-forming polymer to be present in a concentration of at least 5, 8, 10, or even 12% by weight, and up to 15, 20, 25, or even 30% by weight, based on the total weight of the gel composition.

[0053] In one embodiment, a dry film cast from the gel composition may comprise film-forming polymer in an amount of at least 30, 35, 40, 45, or even 50 wt. % and up to 55, 60, 65, 70, 75, 80, 85, or even 90 wt. % based on the total weight of the dry film.

[0054] Silicate tackifying resin

[0055] A silicate tackifying resin can be added to a film-forming polymer to provide or enhance the adhesive properties of the composition. The silicate tackifying resin can affect the physical properties of the resulting gel composition. For example, as the silicate tackifying resin content increases, the glassy to rubbery transition of the gel composition occurs at progressively higher temperatures. In some exemplary gel compositions, multiple silicate tackifying resins can be used to achieve the desired performance. Suitable silicate tackifying resins include those having the following structural unit M (i.e., monovalent R'SiO 1 / 2 units), D (i.e., divalent R'2SiO 2 / 2 units), T (i.e., trivalent R'SiO 3 / 2units) and Q (i.e., tetravalent SiO 4 / 2 units), and resins composed of combinations thereof. Typical exemplary silicate resins include MQ silicate tackifying resins, MQD silicate tackifying resins, and MQT silicate tackifying resins. These silicate tackifying resins typically have number average molecular weights in the range of 100 to 50,000, or 500 to 15,000, and generally have methyl R' groups.

[0056] Such resins are described, for example, in Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley & Sons, New York, (1989), pp. 265-270, as well as U.S. Pat. Nos. 2,676,182 (Daudt et al.), 3,627,851 (Brady), 3,772,247 (Flannigan), and 5,248,739 (Schmidt et al.). Other examples are disclosed in U.S. Pat. No. 5,082,706 (Tangney). The above resins are generally prepared in a solvent. Dry or solvent-free M silicone tackifying resins can be prepared as described in U.S. Pat. Nos. 5,319,040 (Wengrovius et al.), 5,302,685 (Tsumura et al.), and 4,935,484 (Wolfgruber et al.).

[0057] MQ silicate tackifying resins are particularly suitable for some gel compositions of the present disclosure. MQ silicate tackifying resins are R'SiO 1 / 2 Units ("M" units) and SiO 4 / 2 units ("Q" units), where M units are bonded to Q units, each of which is bonded to at least one other Q unit. 4 / 2 Some of the units ("Q" units) are bonded to hydroxyl radicals, forming HOSiO 3 / 2 Units ("T OH " units), which account for the silicon-bonded hydroxyl content of the silicate tackifying resin, some of which are other SiO4 / 2 It is only attached to the unit.

[0058] Certain MQ silicate tackifying resins can be prepared by the silica hydrosol capping process described in U.S. Pat. No. 2,676,182 (Daudt et al.) and modified by U.S. Pat. Nos. 3,627,851 (Brady) and 3,772,247 (Flannigan).

[0059] In one embodiment, the silicate tackifying resin is added to the composition in an amount of at least 1, 2, 3, 4, 5, 8, 10, or even 15% by weight, and up to 35, 30, 25, 20, or even 15% by weight, based on the total weight of the gel composition. In one embodiment, the silicate tackifying resin is added to the composition in an amount of at least 5, 8, 10, 15, or even 20% by weight, and up to 40, 35, 30, 25, or even 20% by weight, based on the total weight of the dry film.

[0060] additives

[0061] The present disclosure includes additives used with silicone-containing film-forming polymers to uniformly incorporate salicylic acid into gel compositions and achieve a dry film. Most useful additives also improve adhesion or do not result in a loss of adhesion. Additives include nonionic surfactants, aminosilicones, silicone polyquaterniums, or combinations thereof.

[0062] In one embodiment, the additive is a non-ionic surfactant having a hydrophilic-lipophilic balance (HLB) of at least 5, 6, or even 7, and up to 7.5, 8, 8.5, or even 9.

[0063] Any nonionic surfactant that meets the defined HLB range can be used, as long as it is suitable for topical (eg, cutaneous) application. Nonionic surfactants that may be particularly useful include polyglyceryl esters with a defined HLB, such as polyglyceryl-4-isostearate (available from Evonik, Essen, Germany under the trade name "ISOLAN GI 34"), methyl glucose isostearate (available from Evonik under the trade name "ISOLAN IS"), polyglyceryl-6-disterate, and polyglyceryl-4-stearate; polyoxyethylene oleyl ethers with a defined HLB, such as those available from Crodo, Plainsboro, NJ under the trade names "BRIJ O3-LQ" and "BRIJ O5-LQ"; fatty acid monoesters of glycerin and propylene glycol, such as glycerol monolaurate, glycerol monocaprylate, glycerol monocaprate, 2-ethylhexylglycerin ether (available from Schuelke Mayr, Norderstedt, Germany under the trade name "SENSIVA SC"); C8-C6 with glycerin and propylene glycol with defined HLB such as 50% 12 alkyl monoethers; polyethylene glycol ethers of lauryl alcohol, such as laureth-3 (2-[2-[2-(dodecyloxy)ethoxy]ethoxy]-ethanol); and 1,2-alkanediols having a chain length ranging from 5 to 10 carbon atoms and a defined HLB, such as 1,2-octanediol. An example of a suitable 1,2-octanediol composition is 3-[(2-ethylhexyl)oxy]-1,2-propanediol, sold by Schuelke & Mayr GmbH (Germany) as SENSIVA SC-10.

[0064] In one embodiment, the additive is an aminosilicone. As used herein, "aminosilicone" refers to any amine-functionalized silicone, i.e., silicone containing at least one primary amine group, secondary amine group, or tertiary amine group. Typically, these are silicones that have been chemically modified so that some of the pendant groups along the main chain are replaced with various alkylamine groups (-R-NH2). These amine groups can be positively charged in aqueous solution due to their electron-donating properties, resulting in inorganic cationic polymers. Useful aminosilicones are typically water-soluble or water-dispersible.

[0065] In one embodiment, aminosilicones with an amine number greater than 60, 80, 100, or even 150 appear to aid in solubilizing salicylic acid. In one embodiment, the aminosilicone has an amine number of 60 or less. In this disclosure, "amine number" refers to the number of milliliters of 0.1 N HCl required to neutralize 10 g of the amine-rich adhesion promoter. The amine number is preferably calculated according to the following formula: 1 / FGMW*×100,000 *FGMW = Functional group molecular weight of amine group

[0066] Without being bound by theory, the amine content of aminosilicone appears to be directly correlated with the improved dissolution of salicylic acid, among other parameters and properties.Therefore, the aminosilicone suitable for use in the gel composition of the present disclosure advantageously comprises a larger number of available amine groups and a correspondingly larger amine value.Ideally, the aminosilicone has a higher amine value for a given polymer chain length.In one embodiment, the aminosilicone has an amine number-to-viscosity ratio of less than 4, 2, 1, 0.5, 0.2, or even 0.1.

[0067] Exemplary aminosilicones for use in embodiments of the present disclosure can be linear polymers, branched polymers, copolymers, and mixtures thereof. In some embodiments, the copolymers are block copolymers. In some embodiments, including those of currently preferred compositions, the aminosilicones have one or more amine groups pendant from the polymer backbone. Examples of such embodiments are exemplified by compounds of Formula IV having a pendant monoamine and compounds of Formula VI having a pendant diamine, as shown hereinbelow. In some embodiments, the polymers have amine groups at one or more termini of the polymer. An example of such an embodiment is exemplified by compounds of Formula V, as shown hereinbelow. The aminosilicone may further be selected from the group including aminodimethicone, trimethylsilyl amodimethicone, aminoethylaminopropylsiloxane-dimethylsiloxane copolymer, and mixtures thereof.

[0068] In some embodiments, the aminosilicone has the structure of Formula IV: [ka] (wherein R is C1-12 (preferably C1-6) alkyl, blocks having subscripts x and y may be randomly mixed, the total value of x is 10 to 5,000, for example 58 or 100 or 118, and the total value of y is 2 to 20, preferably 2 to 11, for example 4 or 11) In some embodiments, x is 58 and y is 4, or x is 100 and y is 4, or x is 118 and y is 11. In some embodiments, R is a straight chain CH group.

[0069] In some embodiments, the one or more aminosilicones have the structure of Formula V, characterized by a terminal amine group: [ka] wherein x is 5 to 5,000, and R and R' may be the same or different and are each a saturated, straight-chain or branched-chain alkyl group of 1 to 12 carbon atoms (in currently preferred circumstances, 1 to 6 carbon atoms), e.g., a straight-chain CH group. It has.

[0070] In other embodiments, the aminosilicone has Formula VI: [ka] (wherein the blocks having subscripts x and y may be randomly mixed and have a total value of 5 to 5,000, the total value of y is 1 to 20, for example 8, and R and R' may be the same or different and each is a saturated, linear or branched alkyl group having 1 to 12 carbon atoms (preferably 1 to 6), for example, R is a linear CH group and R' is a linear CH group). branched diamino-functional polydimethylsiloxanes.

[0071] In some embodiments, the aminosilicone is selected from the group consisting of GP-4 (a compound of formula IV where R=(CH2)3, x=58, and y=4, available from, e.g., Genesee Polymers Corporation (“GPC”), Burton, Michigan, USA, and having an amine value of about 90); GP-581 (a compound of formula IV where R=(CH2)3, x=118, and y=11, available from, e.g., GPC, and having an amine value of about 110); GP-965 (a compound of formula V where R=R′=(CH2)3, x=10, available from, e.g., GPC, and having an amine value of about 200); KF-393 (a diamino-modified compound of formula IV with an amine value of about 286, available from Shin-Etsu Silicones); KF-8004 (a diamino-modified compound of formula IV with an amine value of about 67, available from Shin-Etsu Silicones), Siltech The compound of formula VI, where R=(CH2)3, R'=(CH2)2, has an amine value of about 230, and is available from Siltech Corporation, Toronto, Ontario, Canada, under the trade name "SILAMINE AO EDA"; the compound of formula VI, where R=(CH2)3, R'=(CH2)2, has an amine value of about 170, and is available from Siltech Corporation, Toronto, Ontario, Canada, under the trade name "SILAMINE D2 EDA"; and commercially available alternatives of these amine values ​​(amine silicones from other sources, as will be understood by those skilled in the art), and mixtures thereof. In one embodiment, the additive is a cationic silicone polyquaternium. As used herein, "silicone polyquaternium" includes any silicone containing one or more quaternary ammonium groups.Exemplary cationic silicone polyquaterniums include silicone quaternium-12 (e.g., available from Phoenix Chemical, Somerville, NJ under the tradename "PECOSIL CA-1240," which is the reaction product of cocamidopropyl dimethylamine and dimethicone PEG-7 acetyl chloride); silicone quaternium-8 (e.g., available from Phoenix Chemical, Somerville, NJ under the tradename "PECOSIL AD-3640"); silicone quaternium-19 (a functionalized cationic polymeric silicone polyester made from the reaction of a cationic dimethicone copolyol with a dimer acid, available from Zenitech, Toronto, Ontario under the tradename "ZENESTER Q"); silicone quaternium-22 (available from Evonik Industries AG, Essen, Germany under the tradename "ABIL T QUAT 60"); silicone quaternium-80 (available from Evonik Industries, Available from AG, and mixtures thereof.

[0072] In one embodiment, the additive is typically present in an amount of at least 0.05, 0.1, 0.5, 1, 1.25, 1.5, 1.75, 2, or even 2.25 wt.% based on the total weight of the gel composition. In one embodiment, the additive is present in an amount of up to 2, 2.5, 3, 3.5, 4, 4.5, 5, 7, or even 10 wt.% based on the total weight of the gel composition. The amount of additive present may be dictated by the amount of salicylic acid present; the more salicylic acid present, the more additive is present.

[0073] A dry film cast from the gel composition can include, for example, additives in an amount of at least 0.1, 0.5, 1, 1.5, 2, 2.25, 2.5, 3, 4, 5, 6, or even 8 wt. % and up to 10, 15, 20, 25, or even 30 wt. % based on the total weight of the dry film.

[0074] solvent

[0075] The composition in gel form comprises a volatile solvent. In one embodiment, the volatile solvent is selected from the group consisting of volatile linear and cyclic siloxanes, volatile polydimethylsiloxanes, isooctane, octane, and combinations thereof. The solvent typically comprises at least 40, 50, 55, or even 60% by weight of the total gel composition, and up to 65, 70, 75, or 80% by weight.

[0076] Because the composition may be applied to tissue, the solvent is desirably volatile and non-stinging. As used herein, "volatile" has its standard meaning, i.e., the ability to evaporate quickly at standard temperature and pressure. For example, a solvent may be volatile if a 1 meter drop (1 / 20 mL, 50 μL) of the solvent completely evaporates within 5 minutes, 4 minutes, 3 minutes, 2 minutes, 1 minute, 30 seconds, or 15 seconds at 20°C to 25°C. Exemplary volatile solvent systems include liquid carbon dioxide, as well as linear or cyclic siloxanes such as hexamethyldisiloxane (HMDSO), octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and octamethyltrisiloxane; or linear, branched, or cyclic alkanes such as propane, isobutane, liquid butane (e.g., under pressure), pentane, hexane, heptane, octane, petroleum distillates, cyclohexane, and the like; fluorocarbons such as trichloromonofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, tetrafluoroethane, heptafluoropropane, 1,1-difluoroethane, pentafluoropropane, perfluoroheptane, perfluoromethylcyclohexane, 1,1,1,2,-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, chlorofluorocarbons, and the like; and combinations thereof.

[0077] The use of non-polar, volatile solvents, alone or in combination, as the primary liquid phase of the gel composition can provide a desirable balance between dryness and reduced skin irritation during application. In a currently preferred implementation, the solvent is one of HMDSO and isooctane. If a non-stinging gel composition is not necessary or desired, other more polar solvents, such as ethanol, isopropanol, glycerin, N-methylpyrrolidone, and N,N-dimethylacetamide, can be used in other implementations. Many aprotic solvents are useful, such as acetates such as methyl acetate, ethyl acetate, and propylene glycol diacetate; volatile ketones such as acetone and methyl ethyl ketone; volatile ethers such as diethyl ether, ethyl propyl ether, dipropyl ether, and dipropylene glycol dimethyl ether; volatile fluorocarbons such as pentafluoropropane, perfluoroheptane, and perfluoromethylcyclohexane; or volatile gases such as carbon dioxide can also be used, each of which may cause varying degrees of discomfort to the user.

[0078] In some implementations, water may be included in the solvent system. In certain implementations, a relatively small amount of water, at least 0.1 or even 1 wt. % but not more than 5 or 10 wt. % based on the total weight of the composition, is present in the gel composition. Higher water contents can be used in the gel composition, but such compositions may require longer drying times.

[0079] Optional ingredients

[0080] In addition to the above components, optional ingredients can be added to the composition to improve its performance, including coagulants, fillers, clays, silicas, colorants, and / or fiber reinforcements, such as those disclosed in U.S. Patent No. 10,603,405, which is incorporated herein by reference.

[0081] In one embodiment, an antiseptic and / or antibiotic may be added to the composition. Such agents can be used to preserve the shelf life of the composition and / or to supplement the effectiveness of salicylic acid for various treatments. Such agents are described in U.S. Patent No. 10,603,405. Exemplary agents include benzethonium chloride, cetylpyridinium chloride, benzalkonium chloride, chlorhexidine, polyhexamethylene biguanide, chloroxylenol, methylparaben, and propylparaben.

[0082] Other solid biologically active substances, such as anti-itch agents such as chamomile, eucalyptus, camphor, menthol, zinc oxide, talc, and calamine, anti-inflammatory agents such as corticosteroids, antifungal agents such as terbinafine hydrochloride and miconazole nitrate, nonsteroidal anti-inflammatory agents such as ibuprofen, and antibiotics such as bacitracin, neomycin, and polymyxin, can be added in a similar manner. Essential oils can also be added as flavorings, fragrances, or antibacterial agents, including thymol, menthol, sandalwood, cinnamon, jasmine, lavender, pine, lemon, rose, eucalyptus, clove, orange, mint, spearmint, peppermint, lemongrass, bergamot, citronella, cypress, nutmeg, spruce, tea tree, oil of wintergreen, and vanilla.

[0083] In one embodiment, colorants such as dyes, pigments, or pigment dyes can be added to the composition to improve its aesthetic appearance, for example, to make the composition skin-toned.

[0084] Manufacturing method

[0085] Typically, compatible gel compositions containing film-forming polymers are prepared by adding all ingredients except the silicone-containing film-forming polymer together and mixing them uniformly, and then adding the silicone-containing film-forming polymer at the end of the preparation process to produce a viscous solution.As mentioned above, salicylic acid does not seem to dissolve easily in silicate tackifying resins and / or volatile solvents.Therefore, it has been discovered that the addition of certain additives and at least a portion of the silicone-containing film-forming polymer to salicylic acid can be used to solubilize salicylic acid while preventing the solution from becoming too viscous.As can be seen in the Examples section below, certain additives help solubilize salicylic acid.Generally, the resulting gel compositions and / or films contain only a small amount of salicylic acid microparticles (i.e., less than 20, 10, 5, 2, or even 1% by weight of the amount initially added), and more preferably no salicylic acid microparticles. When the gel composition contains a small amount of salicylic acid microparticles, the composition can be optimized (for example, by increasing the amount of additives, increasing the amount of silicone-containing film-forming polymer, and / or decreasing the amount of salicylic acid), and / or the composition can be gently heated to help dissolve salicylic acid.Other components of the composition (for example, silicate tackifying resin, additives, and any other components) can be added to this first mixture containing at least a portion of salicylic acid and silicone-containing film-forming polymer, or they can be added separately.Generally, the remaining silicone-containing film-forming polymer is added at the end of mixing the components due to its viscosity.

[0086] Generally, the salicylic acid and at least a portion of the silicone-containing film-forming polymer, and optional additives, are mixed at ambient conditions using techniques known in the art, such as an overhead mixer. The mixture may be heated slightly (e.g., to at least 40, 60, or even 80°C and below the boiling / flash point of the solvent or 200°C, whichever is lower) to more quickly solubilize the salicylic acid.

[0087] The compositions of the present disclosure may be useful in topical applications for the treatment of acne, warts, psoriasis, ringworm, ichthyosis, and / or thickened skin.

[0088] The treatment procedure may involve preparing the skin prior to application of the gel composition of the present disclosure. After the target site is preferably dried, for example, by blotting dry with absorbent paper, the gel composition is applied to form a lightly adherent polymeric film over the site.

[0089] A sufficient amount of the composition is used to cover (i.e., coat) the entire target area with a layer of the gel composition. Typically, it is preferred that the resulting dry film have a thickness of about 4 mils (101.2 micrometers) to about 15 mils (351 micrometers). The resulting film typically covers only the area to be treated (e.g., acne, warts, etc.). If necessary, excess gel can be removed with a wipe or tissue before drying. The gel composition can be applied as a single dose or multiple doses (applications).

[0090] As used herein, "film-forming" refers to a composition that, when dried on skin or mucosal tissue under ambient conditions (e.g., 23°C and 50% relative humidity (RH)), forms a continuous layer that does not peel off after simple flexion of the tissue.

[0091] A typical gel composition can include, based on the total weight of the gel composition, (a) 0.1% to 10% by weight of salicylic acid, (b) 5% to 30% by weight of a silicone-containing film-forming polymer, (c) 1% to 35% by weight of a silicate tackifying resin, (d) 0.1% to 5% by weight of an additive, and (e) 50% to 80% by weight of a volatile solvent.

[0092] The gel composition can be applied to tissue and the volatile solvent evaporates to form a continuous dry film. The dry film of the present disclosure may comprise, based on the total weight of the dry film, (a) 0.1% to 20% by weight of salicylic acid, (b) 30% to 90% by weight of a silicone-containing film-forming polymer, (c) 5% to 40% by weight of a silicate tackifying resin, and (d) 0.1% to 25% by weight of an additive.

[0093] As used herein, "ready to use" refers to a composition that is intended to be applied (e.g., to the skin) without dilution. It is understood that the amounts listed for all identified components (unless otherwise specified) are for the "ready to use" gel composition.

[0094] The gel compositions of the present disclosure typically have a viscosity of at least 20,000 centipoise (cps) and up to 1,100,000 cps, including all values ​​therebetween, as measured at 23° C. using a Brookfield LVT viscometer as described in U.S. Pat. No. 10,603,405.

[0095] In one embodiment, the film of the dried gel composition can have a thickness of at least 25, 50, 75, or even 100 micrometers, typically no more than 0.2, 0.25, 0.5, 1, and 1.3 mm. Although the gel compositions of the present disclosure can be coated in a manner to form a film having a uniform or substantially uniform thickness, variations in, for example, the pressure applied or the applicator used may result in varying thicknesses throughout the film layer.

[0096] In one embodiment, the dry film of the present disclosure adheres lightly to the skin, and in one embodiment, has adhesive properties similar to those described in U.S. Patent No. 10,603,405.

[0097] Advantageously, the dry films of the present disclosure are self-supporting after a single application of the gel composition, meaning that therapeutic levels of salicylic acid can be applied in a single layer without applying an additional layer of gel composition onto the outer surface of the dry film. Furthermore, "self-supporting" films do not require an additional flexible backing for continuous wear (i.e., continuous presence on the skin or other target tissue for at least 8 hours).

[0098] In one embodiment, the compositions of the present disclosure are useful in the treatment of acne. Propionibacterium acnes, now known as Cutibacterium acnes, is a bacterium often associated with acne skin conditions. In one embodiment of the present disclosure, the dry films of the present disclosure can achieve at least a 1, 3, 5, or even 6 log reduction using the Antimicrobial Efficacy Test described herein.

[0099] The dry films of the present disclosure should be capable of releasing an active agent, such as salicylic acid, during use. The films should not significantly irritate the skin when placed during application and use after drying. The dry films are substantially painless and can be removed as needed without substantial pain. The therapeutic films can be formed at standard room temperature and reasonable temperature variations when applied to a surface wetted with water, blood, or bodily fluids within a short period of time. [Example]

[0100] Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained or are available from general chemical suppliers, such as Sigma-Aldrich Company (Saint Louis, Missouri), or can be synthesized by conventional methods. [Table 1] [Table 2] [Table 3] [Table 4]

[0101] Gel Compositions Containing Nonionic Surfactant Additives

[0102] The ingredients listed in Table 5, HMDSO (11 g), MQ resin (1 g), SPOx (1 g), salicylic acid (0.075 g), and nonionic surfactant (0.4 g), were combined in a vial and mixed with stirring at 60°C until the SPOx ingredients were completely dissolved in the mixture. An additional 1.3 g of SPOx was added to the vial, and the resulting mixture was stirred at 60°C for 4 to 6 hours.

[0103] After the vial was cooled to room temperature, the gel composition was allowed to sit on the bench without stirring for a minimum of 24 hours. The gel composition was then inspected by visual inspection to determine whether the components of the composition were dissolved or uniformly dispersed throughout the gel and recorded accordingly.

[0104] The gel compositions were then individually coated onto the surface of LEXAN polycarbonate test sheets (5.1 cm x 12.7 cm) (a single composition was coated per test sheet). Approximately 2 mL to 3 mL of gel was applied to the test sheet using a syringe. A pull-down hand coater was used with a gap set at 50 mils (1.27 mm) using a feeler gauge. The coated sheets were allowed to air dry overnight and then observed for the presence of particulates. The nonionic surfactant used for each sample, as well as observations made on the gel and dried film, are reported in Table 5. [Table 5]

[0105] Gel compositions containing aminosilicone additives

[0106] The ingredients listed in the table below, HMDSO (11 g), MQ resin (1 g), SPOx (1 g), salicylic acid (0.075 g), and aminosilicone (0.4 g), were combined in a vial and mixed with stirring at 60°C until the SPOx component was completely dissolved in the mixture. An additional 2 g of SPOx was added to the vial, and the resulting mixture was stirred at 60°C for 4 to 6 hours. After the vial was cooled to room temperature, the gel composition was allowed to sit on the bench without stirring for a minimum of 24 hours. The gel composition was then inspected, and observations were recorded.

[0107] The gel compositions were individually coated onto the surface of LEXAN polycarbonate test sheets, which were then inspected and observations recorded. The aminosilicone additive used in each sample, as well as the observations made on the gel and dry film, are reported in Table 6. [Table 6]

[0108] Gel compositions containing cationic silicone polyquaternium additives - Patent Application 20070122997

[0109] The ingredients listed in the table below, HMDSO (11 g), MQ resin (1 g), SPOx (1 g), salicylic acid (0.075 g), and polyquaternium (0.4 g), were combined in a vial and mixed with stirring at 60°C until the SPOx component was completely dissolved in the mixture. An additional 2 g of SPOx was added to the vial, and the resulting mixture was stirred at 60°C for 4 to 6 hours. After the vial was cooled to room temperature, the gel composition was allowed to sit on the bench without stirring for a minimum of 24 hours. The gel composition was then inspected, and observations were recorded.

[0110] The gel compositions were individually coated onto the surface of LEXAN polycarbonate test sheets, which were then inspected and observations recorded. The cationic silicone polyquaternium additive used in each sample, as well as the observations made on the gels and dry films, are reported in Table 7. [Table 7]

[0111] Sample 37: Gel composition containing a nonionic surfactant additive and a cationic silicone polyquaternium additive

[0112] The components HMDSO (9 g), MQ resin (1 g), SPOx (2.4 g), salicylic acid (0.075 g), SENSIVA-SC10 (0.2 g), and PECOSIL AD-3640 (0.2 g) were combined in a vial and mixed with stirring at 60 °C until the SPOx components were completely dissolved in the mixture. An additional 2 g of SPOx was added to the vial, and the resulting mixture was stirred at 60 °C for 4 to 6 hours. After the vial was cooled to room temperature, the gel composition was allowed to stand on the bench without stirring for a minimum of 24 hours. The gel composition was then inspected, and observations were recorded.

[0113] The gel composition was coated onto the surface of a LEXAN polycarbonate test sheet, which was then inspected and observations recorded. No visible particulates were observed in either the gel composition or the dried film.

[0114] Sample 38. Gel composition containing a nonionic surfactant additive and a cationic silicone polyquaternium additive

[0115] The same procedure was followed as reported for Sample 37, except that 0.2 g of SENSIVA-SC10 was replaced with 0.2 g of SENSIVA-SC50 in the composition. No visible particulates were observed in either the gel composition or the dried film.

[0116] Sample 39. Gel composition containing a nonionic surfactant additive and a cationic silicone polyquaternium additive

[0117] The same procedure was followed as reported in Sample 37, except that 0.2 g of SENSIVA-SC10 was replaced with 0.1 g of SENSIVA-SC50 in the composition and a higher amount of PECOSIL AD-3640 (0.3 g) was used. No visible particulates were observed in either the gel composition or the dried film.

[0118] Sample 40. Gel composition containing two nonionic surfactant additives

[0119] The same procedure was followed as reported in Sample 37, except that SENSIVA-SC10 (0.2 g) was replaced with BRIJ O5-LQ (0.1 g) and PECOSIL AD-3640 (0.2 g) was replaced with polyglyceryl-4-stearate (0.3 g) in the composition. No visible particulates were observed in either the gel composition or the dry film.

[0120] Sample 41. Gel Composition Containing Two Nonionic Surfactant Additives

[0121] The same procedure was followed as reported for Sample 40, except that BRIJ O5-LQ (0.1 g) was replaced with BRIJ O3-LQ (0.1 g) in the composition. No visible particulates were observed in either the gel composition or the dried film.

[0122] Sample 42. Gel Composition Containing Two Nonionic Surfactant Additives

[0123] The same procedure was followed as reported in Sample 37, except that SENSIVA-SC10 (0.2 g) was replaced with SPAN 20 (0.1 g) and PECOSIL AD-3640 (0.3 g) was replaced with polyglyceryl-6-stearate (0.3 g) in the composition. No visible particulates were observed in either the gel composition or the dry film.

[0124] Sample 43. Gel Composition Containing Two Nonionic Surfactant Additives

[0125] The same procedure was followed as reported for Sample 42, except that 0.1 g of SPAN 20 was replaced with 0.1 g of Laureth-3 in the composition. No visible particulates were observed in either the gel composition or the dried film.

[0126] Sample 44.

[0127] Propionibacterium acnes (P. acnes) ATCC 6919 was obtained from ATCC (Manassas, VA). A single colony of P. acnes from a stock agar culture was inoculated into DIFCO anaerobic broth (Becton, Dickinson, Franklin Lakes, NJ) and incubated at 37°C for 18 hours to obtain 1 × 10 P. acnes . 9 cfu / mL (colony forming units per milliliter) cultures were provided.

[0128] Circular discs (1.2 cm diameter) were punched from the coated polycarbonate test sheets prepared for samples 16, 18, 27, 34, and 37–39. Three replicates of each disc type were prepared and tested (n=3). One disc was placed in a 100 × 15 mm sterile plastic Petri dish and oriented so that the uncoated surface of the disc was in contact with the bottom of the dish. An aliquot (40 microliters) of P. acnes sample was deposited onto the coated surface of each disc using a micropipette. Each disc was then covered with a sterile glass microscope slide cover slip. A control sample was also prepared by placing a 40 microliter aliquot of P. acnes sample directly onto the bottom of a Petri dish without a disc. The aliquot was then covered with a sterile glass microscope slide cover slip. Each Petri dish was placed in a room temperature incubator for 24 hours. After removal from the incubator, the coverslips and discs were separated from each other while still in the Petri dishes. An aliquot (10 mL) of phosphate-buffered saline (PBS) (1X, Thermo Fisher Scientific, Waltham, MA) was added to each Petri dish, and the Petri dishes were shaken at 100 rpm (revolutions per minute) for 20 minutes using a MAXQ Model 8000 orbital shaker (Thermo Fisher Scientific). The resulting PBS solution was serially diluted (10-fold with PBS), and 3 microliters of each diluted sample was pipetted onto DIFCO anaerobic agar plates (Becton Dickinson). The individually inoculated agar plates were incubated at 37°C for 16 hours. Colonies from each incubated plate were counted by visual inspection. The cfu counts for each individual plate (n = 3) were averaged, and the average counts were used to calculate the number of colony-forming units per milliliter (cfu / mL) recovered from each type of inoculated disc (based on the serial dilutions). For each sample disc, the log reduction value (LRV) was calculated according to Equation 1. The results are reported in Table 8. An LRV reported in Table 8 as >6 indicates that no colonies were observed in any of the diluted samples for that example disc. Equation 1:

number

[0129] Foreseeable modifications and variations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. The present invention is not limited to the embodiments set forth in this application for illustrative purposes. In the event of any inconsistency or discrepancy between the description in this specification and the disclosure in any document set forth in this specification or incorporated by reference, the description in this specification shall control.

Claims

1. 1. A composition for use as a therapeutic article, comprising: salicylic acid, a silicone-containing film-forming polymer; a silicate tackifying resin, and additives wherein the additive comprises: (i) a nonionic surfactant having an HLB of 5 to 9; (ii) an aminosilicone having an amine number greater than 60; (iii) a cationic silicone polyquaternium; or (iv) a combination thereof.

2. The composition of claim 1 , wherein the silicone-containing film-forming polymer comprises a linear polydiorganosiloxane.

3. 3. The composition of claim 1 or 2, wherein the silicate tackifying resin is an MQ silicate tackifying resin.

4. The composition of any one of claims 1 to 3, wherein the nonionic surfactant has an HLB of 6 to 8.

5. 5. The composition of claim 1, wherein the nonionic surfactant comprises at least one of glyceryl stearate, polyoxyethylene oleyl ether, glycerol monolaurate, 2-ethylhexylglycerin ether, 1,2-alkanediol, and combinations thereof.

6. The aminosilicone has the structure 【Chemistry 1】 (In the formula, R is an alkyl containing 1 to 12 carbons, and blocks having subscripts x and y may be randomly mixed, with the total value of x being 10 to 5,000 and the total value of y being 2 to 20. The composition according to any one of claims 1 to 5, having

7. The aminosilicone has the structure 【Chemistry 2】 (In the formula, The blocks having subscripts x and y may be randomly mixed, the total value of x being 5 to 5,000, the total value of y being 1 to 20, R and R' may be the same or different, and R and R' are each saturated, straight or branched chain alkyl groups having 1 to 12 carbon atoms. The composition according to any one of claims 1 to 6, having

8. 8. The composition of any one of claims 1 to 7, wherein the cationic silicone polyquaternium comprises at least one of silicone quaternium-12, silicone quaternium-8, silicone quaternium-19, silicone quaternium-22, and mixtures thereof.

9. The composition according to any one of claims 1 to 8, wherein the composition comprises at least 0.5% and at most 30% by weight of the salicylic acid.

10. The composition according to any one of claims 1 to 9, wherein the composition comprises at least 0.1 at% and at most 10 at% of the salicylic acid.

11. The composition of any one of claims 1 to 10, wherein the composition further comprises a volatile solvent, optionally wherein the volatile solvent is isooctane or hexamethyldisiloxane.

12. The composition of any one of claims 1 to 11, wherein the composition further comprises a filler.

13. The composition of any one of claims 1 to 12, wherein the composition further comprises a coagulant.

14. The composition of any one of claims 1 to 13, wherein the composition comprises at least 2 wt% of the additive.

15. The composition comprises: 0.1% to 10% by weight of salicylic acid, 5% to 30% by weight of a silicone-containing film-forming polymer; 1% to 35% by weight of a silicate tackifying resin; 0.1% to 5% by weight of an additive, and 50% to 80% by weight of a volatile solvent; The composition of any one of claims 1 to 14, each based on the total weight of the composition.

16. The film composition comprises: 0.1% to 20% by weight of salicylic acid, 30% to 90% by weight of a silicone-containing film-forming polymer; 5% to 40% by weight of a silicate tackifying resin, and 0.1% to 25% by weight of an additive; The composition of any one of claims 1 to 15, each based on the total weight of the composition.

17. A composition for use as a skin treatment, said composition being as defined in any one of claims 1 to 16.

18. 1. A method for producing a gel composition, the method comprising: and combining a first portion and a second portion to produce the gel composition, the gel composition comprising: salicylic acid, a silicone-containing film-forming polymer; silicate tackifying resin, volatile solvents, and additives the additive comprises: (i) a nonionic surfactant having an HLB of 5 to 9; (ii) an aminosilicone having an amine number greater than 60; (iii) a cationic silicone polyquaternium; or (iv) a combination thereof; The method of claim 1, wherein the first portion comprises the salicylic acid in a first portion of the silicone-containing film-forming polymer, and the second portion comprises a second portion of the silicone-containing film-forming polymer.

19. A method comprising exposing tissue containing Propionibacterium acnes to a composition, said composition comprising salicylic acid, a silicone-containing film-forming polymer; a silicate tackifying resin, and additives wherein the additive is (i) a nonionic surfactant having an HLB of 5 to 9, (ii) an aminosilicone having an amine ratio greater than 0.05, (iii) a cationic silicone polyquaternium, or (iv) a combination thereof.

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