Methods for forming aqueous dispersions of copolymers, adhesive compositions containing such copolymers, films or articles containing same, and methods for coating substrates

Abstract

A method for forming an aqueous dispersion of a copolymer includes preparing a copolymerizable composition in water. The copolymerizable composition includes 5 to 95 weight percent of an ethylenically functionalized silicone polymer or silane, based on the total weight of the copolymerizable composition, and 5 weight percent or more of an organic acrylic monomer, based on the total weight of the copolymerizable composition. The method also includes preparing 0.1 to 10 weight percent of a surfactant, based on the total weight of the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer. The ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized to form an aqueous dispersion of a copolymer. The copolymer exhibits a glass transition temperature (Tg) of 0 to -100°C. Tg is measured by differential scanning calorimetry in an open crucible at a heating rate of 10°K per minute according to DIN 53765.

Description

[Technical Field]

[0001] The present invention relates to aqueous dispersions of copolymers, adhesives containing such copolymers, and methods of coating substrates with such materials.

[0002] Adhesives, such as pressure sensitive adhesives (PSAs), adhere to a substrate when pressure is applied to bond the adhesive to the substrate.

[0003] Conventional PSAs contain organic solvents, but recently, due to considerations of the environment, resource conservation, and safety, water is used as the solvent.

[0004] Water-based PSAs primarily contain dispersions of acrylic polymers or copolymers. Acrylic-based PSAs offer advantages such as the ability to control the glass transition temperature (Tg), molecular structure, and crosslink density, as well as the competitive cost of such systems. Acrylic formulations can produce PSAs with excellent tack and peel strength, and these adhesive tapes have good environmental stability and oxidation resistance.

[0005] However, a drawback of acrylic PSAs is their difficulty adhering to low surface energy surfaces, such as silicone, polyethylene, and polypropylene. Over time, acrylic PSAs can build up adhesion to the applied surface, making them difficult to cleanly remove. Furthermore, when applied to the skin, acrylic PSAs can cause skin trauma during removal and have limited repositionability.

[0006] PSAs containing acrylate systems suffer from the same drawbacks and also generally have poor high and low temperature performance.

[0007] It would therefore be desirable to provide materials that can be utilized in adhesives that enable the adhesives to overcome the above-mentioned deficiencies, as well as processes for forming such materials, along with accompanying embodiments thereof. Summary of the Invention

[0008] An embodiment of a method for forming an aqueous dispersion of a copolymer is provided. In one embodiment, the process includes providing a copolymerizable composition in water. The copolymerizable composition includes 5 to 95 weight percent of an ethylenically functionalized silicone polymer or silane, based on the total weight of the copolymerizable composition. The copolymerizable composition also includes 5 weight percent or more of an organic acrylic monomer, based on the total weight of the copolymerizable composition. The method includes providing 0.1 to 10 weight percent of a surfactant, based on the total weight of the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer. The ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized to form an aqueous dispersion of a copolymer. The copolymer exhibits a glass transition temperature (Tg) of 0 to -100°C. Tg is measured by differential scanning calorimetry at a heating rate of 10°K per minute according to DIN 53765.

[0009] In certain embodiments, the method further comprises forming a miniemulsion comprising the ethylenically functionalized silicone polymer or silane, the organic acrylic monomer, and the surfactant. A radical initiator is further introduced. The organic acrylic monomer comprises one or more acrylate or acrylic acid monomers. The ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized in the presence of the surfactant and water.

[0010] In some embodiments, the miniemulsion comprises organic droplets comprising an ethylenically functionalized silicone polymer or silane and an organic acrylic monomer, the organic droplets being formed before the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized.

[0011] In another embodiment, the method further comprises the step of curing the aqueous dispersion of the copolymer by heating the aqueous dispersion to evaporate water therefrom.

[0012] Preferably, the aqueous dispersion of the copolymer has a solids content of 40 wt% or more, based on the total weight of the aqueous dispersion, and more preferably, the solids content of the aqueous dispersion of the copolymer is 40-70 wt% based on the total weight of the aqueous dispersion.

[0013] In one embodiment, the copolymer exhibits a Tg of −10 to −60° C. In another embodiment, the copolymer has a z-average particle size of 1000 nanometers or less as measured by dynamic light scattering.

[0014] In one embodiment, the aqueous dispersion of the copolymer exhibits a viscosity of 1 to 20,000 mPa·s at 25°C.

[0015] In another embodiment, an adhesive composition is provided. In one embodiment, the adhesive composition comprises a copolymer formed by a process of forming an aqueous dispersion of the copolymer.

[0016] In one embodiment, a film of the adhesive composition having a wet thickness of 381 microns exhibits a peak tack of 100 grams of force or greater after curing, as measured on a TA.XT Plus Texture Analyzer using a TA-57R probe and a TA-303 instrument. Preferably, the film exhibits a peak tack of 100 to 1000 grams of force.

[0017] In another embodiment, the adhesive composition further comprises an active compound capable of being released at a controlled rate from the matrix formed by the copolymer. In yet another embodiment, the adhesive composition is stable to phase separation at 25° C. as assessed by the absence of observable phase separation for 180 days.

[0018] Preferably, the adhesive composition has a volatile organic content of 2.5% or less according to EPA Test Method 24. In certain embodiments, the adhesive composition is stable to phase separation at 25° C. as assessed by not having more than a 20% variation in z-average particle size. In other embodiments, the adhesive composition is pressure-sensitive.

[0019] In yet another embodiment, there is provided a film comprising the adhesive composition, wherein the film exhibits no residual transfer upon contact.

[0020] Also provided are embodiments of articles. In one embodiment, the article comprises the adhesive composition described above on a substrate. The adhesive composition forms a film. The film has a wet thickness of 381 microns, and after curing at 60°C for 15 minutes, a stainless steel plate is attached to the outer surface of the film, allowed to stand for 30 minutes, and then the stainless steel plate is peeled off at a speed of 300 mm / min (12 in / min). The film has a 180-degree peel strength of 1.5 N / in or greater when measured at a speed of 12 in / min using an adhesion / peel tester.

[0021] Also provided are methods of coating a substrate, which in one embodiment include applying the adhesive composition to a substrate and curing the composition. In some embodiments, the adhesive composition is applied by spraying, knife coating, roller coating, casting, drum coating, dipping, and combinations thereof, or transfer coating.

[0022] These and other advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description when considered in light of the accompanying drawings: [Brief explanation of the drawings]

[0023] [Figure 1] 1 shows a release profile illustrating the release of an active over time from an adhesive composition according to the present invention. [Figure 2]1 shows a release profile illustrating the release of an active over time from an adhesive composition according to the present invention. Specific Description of the Invention

[0024] Detailed Description of the Preferred Embodiments It is to be understood that the present invention may contemplate various alternative directions and sequences of steps, unless expressly stated to the contrary. Also, it is to be understood that the specific processes, compositions, articles and methods described in the following specification are merely exemplary embodiments of the inventive concepts. Accordingly, specific characteristics, conditions or other physical characteristics related to the disclosed embodiments are not to be considered limiting, unless expressly stated otherwise.

[0025] Furthermore, as used herein, the terms "comprises," "comprising," "includes," "has," "having," or other variations thereof, are intended to cover a non-exclusive inclusion. For example, a method, article, or composition consisting of a list of features is not necessarily limited to only those features and may include other features not expressly listed or inherent in such method, article, or composition. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or. For example, condition A or B is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), or both A and B are true (or present).

[0026] Additionally, the use of "a" or "an" is employed to describe elements and components described herein. This is merely for convenience and to give a general sense of the scope of the invention. This specification should be read to include one or at least one, and the singular also includes the plural, and vice versa, unless otherwise clearly indicated. For example, where a single item is described herein, plural items may be used in place of the single item. Similarly, where multiple items are described herein, the single item may be substituted for the multiple items.

[0027] In certain embodiments, a method for forming an aqueous dispersion of the copolymer is provided. The copolymer is stable for use in adhesive compositions. For example, the copolymer can be utilized in pressure-sensitive adhesives. Such adhesives exhibit good tack, adhesion, and shear resistance and may be used on the skin and / or in medical applications such as surgical tapes, dressings, drapes, bandages, and wearable devices. However, the adhesive composition is not limited to medical applications and may be utilized in other applications where a tacky, cohesive, and low-trauma adhesive is desired. For example, the adhesive composition may be utilized in non-medical wearable device applications such as headset devices, as well as other applications such as industrial tapes, surface protection films for electronic devices, other appliances, and automotive parts.

[0028] In one embodiment, a method for forming an aqueous dispersion of a copolymer includes providing a copolymerizable composition in water. The copolymerizable composition includes 5 to 95 wt. % of an ethylenically functionalized silicone polymer or silane, based on the total weight of the copolymerizable composition, and 5 wt. % or more of an organic acrylic monomer, based on the total weight of the copolymerizable composition. The surfactant is provided in an amount of 0.1 to 10 wt. % based on the total weight of the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer. The ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized to form an aqueous dispersion of the copolymer. The copolymer exhibits a glass transition temperature (Tg) of 0 to -100°C, as measured by differential scanning calorimetry in an open crucible at a heating rate of 10°K per minute according to DIN 53765.

[0029] In some embodiments, the weight ratio of ethylenically functionalized silicone polymer or silane to ethylenically unsaturated organic acrylic monomer can vary from 0.05 to 99.

[0030] Organic acrylic monomers suitable for use in the copolymerizable composition are acrylic or methacrylic acid and esters. Suitable monomers forming the acrylic or methacrylic ester group are esters of unbranched or branched alcohols having 1 to 20 carbon atoms. Preferred methacrylic or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate, phenyl acrylate, and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and norbornyl acrylate. Preferably, the organic acrylic monomer comprises one or more acrylate, methacrylic, or acrylic monomers. In some embodiments, the organic acrylic monomer comprises one or more acrylate, one or more methacrylic, and / or one or more acrylic monomers.

[0031] Additional monomers are also suitably included in the copolymerizable composition. In some embodiments, such monomers are ethylenically unsaturated monomers, including vinyl esters (preferably of carboxylic acids having 1 to 15 carbon atoms). Preferred are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate, and vinyl esters of α-branched monocarboxylic acids having 9 to 11 carbon atoms (e.g., VeoVa9® or VeoVa10® (trade names of Resolution)). Particularly preferred is vinyl acetate.

[0032] Additional monomers may include vinyl aromatic compounds, vinyl halides, vinyl ethers, and olefins. Preferred vinyl aromatic compounds are styrene, α-methylstyrene, the isomeric vinyl toluenes and vinyl xylenes, and divinylbenzene. Styrene is particularly preferred. Preferred vinyl halides include vinyl chloride, vinylidene chloride, tetrafluoroethylene, difluoroethylene, hexylperfluoroethylene, 3,3,3-trifluoropropene, perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene, and vinyl fluoride. Vinyl chloride is particularly preferred. An example of a preferred vinyl ether is methyl vinyl ether. Preferred olefins are ethene, propene, 1-alkylethenes, and polyunsaturated alkenes. Preferred dienes are 1,3-10 butadiene and isoprene. Ethene and 1,3-butadiene are particularly preferred.

[0033] Optionally, 0.1 to 5 wt % of auxiliary monomers can be copolymerized, based on the total weight of the copolymerizable components. Preference is given to using 0.5 to 2.5 wt % of auxiliary monomers. Examples of auxiliary monomers include fumaric acid, maleic acid; ethylenically unsaturated carboxamides and carbonitriles, preferably acrylamides, such as N-methylacrylamide, N,N-dimethylacrylamide, t-octylacrylamide, diacetone acrylamide (DAAM), and acrylonitrile; monoesters and diesters of fumaric and maleic acid, such as diethyl esters and diisopropyl esters; maleic anhydride; ethylenically unsaturated sulfonic acids and their salts, preferably vinyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Further examples include pre-crosslinking comonomers, such as polyethylenically unsaturated comonomers, such as divinyl adipate, diallyl maleate, allyl methacrylate, or triallyl cyanurate, or post-crosslinking comonomers, such as alkyl ethers of acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME), N-methylol acrylamide (NMA), N-methylol methacrylamide, N-methylol allyl carbamate, isobutoxy ether, or esters of N-methylol acrylamide, N-methylol methacrylamide, and N-methylol allyl carbamate. Also suitable are vinyl amides having from 1 to about 8 carbon atoms, such as vinyl pyrrolidone. Also suitable are comonomers having epoxide functionality, such as glycidyl methacrylate and glycidyl acrylate. Mention may also be made of monomers containing hydroxyl or CO groups, examples being hydroxyalkyl esters of acrylic and methacrylic acid, such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate.

[0034] Particularly preferred copolymers are one or more members selected from the group consisting of vinyl acetate, vinyl esters of α-branched monocarboxylic acids having 9 to 11 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, and 1,3-butadiene. Also particularly preferred as copolymers are mixtures of vinyl acetate and ethylene; mixtures of vinyl acetate, ethylene, and a vinyl ester of an α-branched monocarboxylic acid having 9 to 11 carbon atoms; mixtures of n-butyl acrylate and 2-ethylhexyl acrylate and / or methyl methacrylate; mixtures of styrene and one or more monomers from the group methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; mixtures of vinyl acetate and one or more monomers from the group methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, optionally with ethylene; and mixtures of 1,3-butadiene and styrene and / or methyl methacrylate; the above mixtures may optionally further comprise one or more of the auxiliary monomers mentioned above.

[0035] In certain embodiments, the organic acrylic monomer may include a combination of acrylic monomers. One preferred combination of organic acrylic monomers includes a soft monomer and a hard monomer. As used herein, "soft monomer" refers to a monomer that, when homopolymerized, has a glass transition temperature below 0°C. Examples of acrylic soft monomers include alkyl acrylates (e.g., butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate), and the like. Other soft monomers, such as dialkyl fumarates, may also be present. As used herein, "hard monomer" refers to a monomer that, when homopolymerized, has a glass transition temperature above 0°C. Preferred hard monomers include methyl acrylate, ethyl acrylate, and alkyl methacrylates (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, and vinyl acetate), which serve to modify adhesive properties. The hard monomer may also be one or more unsaturated carboxylic acids containing from 3 to about 5, preferably from 3 to about 4, carbon atoms, such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, etc. These monomers serve to improve the cohesive strength of the resulting adhesive composition and promote adhesion.

[0036] The copolymerizable composition includes at least one ethylenically functionalized silicone polymer or silane. The use of the silicone polymer or silane in forming the copolymer improves certain properties, such as water resistance, skin-friendliness, breathability, and heat resistance, for example, when the copolymer is used in an adhesive.

[0037] The silicone polymer is preferably ethylenically unsaturated, has radically polymerizable groups, and contains siloxane units represented by the general formula: [ka] (In the ceremony R 1 are the same or different at each occurrence, and the group R * or E, where the group R *are the same or different at each occurrence and are a hydrogen atom or an optionally substituted hydrocarbon group (preferably a C1-C18 alkyl, C6-C18 cycloalkyl or C6-C18 aryl group) that does not contain aliphatic multiple C-C bonds and has 1 to 18 carbon atoms, and E is a group of the formula (CR 5 2) m -X or -(CH2)3-X (wherein m is an integer of 1 to 10 (preferably 3)), R 2 are the same or different at each occurrence and are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms (preferably a C1-C18 alkyl or C6-C18 cycloalkyl group), and R 5 is a hydrogen atom, a C1-C12 alkyl group, or a C6-C18 aryl group (preferably a hydrogen atom), and X is an ethylenically unsaturated organic group; R 1 is an ethylenically unsaturated group E in at least 1 mol % and at most 50 mol % of all siloxane units (I), p is 0, 1, 2 or 3; z is 0, 1, 2, 3, or 15; where the sum p+z has a value of 0, 1, 2, or 3; However, for at least 20 mol % of all siloxane units represented by formula (I) in the silicone polymer, the sum of p+z is 1 or 0 (p is 1 or 0, and z is 0). It is a silicone resin consisting of

[0038] The polymerizable silane is vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, Vinylmethyldiethoxysilane, Vinylmethyldipropoxysilane, γ-Methacryloxypropyltrimethoxysilane γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltripropoxysilane, 7-methacryloxydimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-Methacryloxypropylmethyldiethoxysilane γ-methacryloxypropylmethyldipropoxysilane, γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxymethyltriethoxysilane, (Methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, γ-methacryloxypropyltriacetoxysilane γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltripropoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-Acryloxypropylmethyldiethoxysilane, Acryloxypropylmethyldipropoxysilane, Methacryloxypropyltris(trimethylsiloxysilane) etc. Preferably, the silane is methacryloxypropyltris(trimethylsiloxysilane).

[0039] The method includes preparing a surfactant. Preferably, the surfactant is provided in an amount of 0.1 to 10 wt %, in each case based on the total weight of the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer. In some embodiments, the surfactant is an emulsifier. In some embodiments, the surfactant is a polymerizable surfactant, also known as a reactive surfactant or copolymerizable surfactant. These surfactants are preferred when the copolymer is intended for use in aqueous medical adhesives with minimal or no surfactant leaching. Preferred surfactant embodiments include allyl- or vinyl-substituted alkylphenol ethoxylates and their sulfates, block copolymers of polyethylene oxide, propylene oxide, or butylene oxide with polymerizable end groups, allyl- or vinyl-substituted ethoxylated alcohols and their sulfates, maleic acid half esters of fatty alcohols, monoethanolamide ethoxylates of unsaturated fatty acids capable of undergoing autoxidative polymerization, allyl- or vinyl-substituted polyalkylene glycol ethers, alkyl polyalkylene glycol ether sulfates, functionalized monomers and surfactants, and combinations thereof. Examples of polymerizable surfactants include those sold under the HITENOL trade name, such as the HITENOL AR series and HITENOL KH series, available from Montello Inc.

[0040] As mentioned above, organic acrylic monomers can also be used in combination. For example, the organic acrylic monomers can include one or more acrylic acid ester monomers and acrylic acid monomers. In one such embodiment, the copolymerizable composition includes, based on the total weight of the copolymerizable composition, 67 wt% methacryloxypropyltris(trimethylsiloxysilane), 19 wt% 2-ethylhexyl acrylate, 6.6 wt% methyl acrylate, 2.8 wt% acrylic acid, and 4.6 wt% polymerizable surfactant. In this embodiment, the polymerizable surfactant can be, for example, HITENOL KH-10.

[0041] In certain embodiments, the aqueous dispersion of the copolymer can be prepared in a heterogeneous process. In one embodiment, the heterogeneous process is a miniemulsion polymerization. In such embodiments, the miniemulsion can be radical initiated and includes the polymerization of an ethylenically functionalized silicone polymer or silane and 5% by weight or more of an organic acrylic monomer.

[0042] As those skilled in the art will appreciate, miniemulsion polymerization differs from emulsion polymerization in many respects. For example, in contrast to emulsion polymerization, in which the size of polymer latex particles is essentially determined by kinetic processes and lattice stability, miniemulsion polymerization is based on the complete presence of monomers within micelles prior to polymerization. Therefore, miniemulsion polymerization requires less time because it does not require additional time for the monomers to diffuse from the monomer droplets into the micelles during polymerization. In other words, the copolymer particles formed may be considered polymerized copies of the micelles or organic droplets present at the start of polymerization. As a result, the size of the copolymer particles is determined solely by the dispersion process and the stability of the micelles. Because there is no need to transport monomers, such as ethylenically functionalized silicone polymers, silanes, or organic acrylic monomers, into the continuous phase, this method allows the use of monomers that are completely insoluble in the continuous phase. To enhance the stability of the organic droplets, it is necessary to suppress possible Ostwald ripening. During miniemulsion polymerization, a hydrophobizing agent, or in the case of inverse miniemulsion, an oleophilizing agent, is added. Among the species that can act as hydrophobizing agents are optionally hydrophobic monomers suitable for that purpose, such as silicon-containing components, which in one such embodiment are ethylenically functionalized silicone polymers or silanes.

[0043] Miniemulsion polymerization differs from suspension polymerization in that the resulting copolymer particles are much smaller (50-500 nm) than those obtained in suspension polymerization (1 μm-1 mm), and the number of radicals per growing copolymer particle in suspension polymerization is 10, which is significantly higher than that in miniemulsion polymerization (statistically, there are 0.5 radicals per particle growing during the reaction).

[0044] To carry out radical miniemulsion polymerization, a miniemulsion of a vinyl monomer must first be constructed in a continuous phase that is immiscible with the monomer. In certain embodiments, the vinyl monomer may be an organic acrylic monomer. To this end, the monomer is dispersed in water with an emulsifier and a hydrophobizing agent by the input of energy, for example, using a high-pressure homogenizer or ultrasound. In certain embodiments, the combination of the emulsifier and the hydrophobizing agent retards the occurrence of Ostwald ripening and the coalescence of the organic droplets. In the second stage, the organic droplets thus formed are polymerized. This can be initiated by a water-soluble initiator added after the preparation of a stable miniemulsion, or by an oil-soluble initiator present in the monomer phase from the beginning, or a combination of both.

[0045] In certain embodiments, the organic droplets formed in the miniemulsion have a size of approximately 50 to 500 nm. As used herein and in certain embodiments, the organic droplets formed in the miniemulsion may also be referred to as particles. The size of the organic droplets is the result of homogenization of the miniemulsion, which is achieved by the input of a large amount of energy. Preferably, the migration of monomers between individual organic droplets is inhibited by a specific type of stabilizer.

[0046] Concurrently with the formation of small organic droplets, free micelles no longer exist in miniemulsions. Therefore, in contrast to conventional emulsion polymerization, nucleation (droplet nucleation) is primarily performed by the droplets. In miniemulsion polymerization, monomer diffusion is also minimal. Consequently, in miniemulsion polymerization, each dispersed organic droplet can be described as an individual reactor manipulated at the nanoscale. Consequently, the use of miniemulsion polymerization to form aqueous dispersions of copolymers, as opposed to conventional emulsion or suspension polymerization, offers numerous advantages, which are discussed below.

[0047] For example, because the monomers do not need to be transported through a continuous, usually aqueous, phase, it is possible to polymerize even monomers that are absolutely insoluble in water. Furthermore, the size of the copolymer particles can correspond to the size of the preformed organic droplets and can be adjusted with considerable precision by the nature and amount of emulsifier used. Furthermore, each organic droplet has a uniform composition. Therefore, specifically, in the case of copolymerization, the monomer ratio in each droplet is the same, and there is no difference in the diffusion of the monomers. Furthermore, because miniemulsions are stabilized only kinetically, not thermodynamically, less emulsifier is required.

[0048] To prepare the miniemulsion used to form the aqueous dispersion of the copolymer, the following steps are carried out:

[0049] In the first step, an ethylenically functionalized silicone polymer or silane is dissolved in one or more organic acrylic monomers described herein to form a silicone- or silane-in-monomer solution. It should be noted that the silicone polymer or silane must be soluble in the respective organic acrylic monomer. In certain embodiments, insoluble components are separated by filtration, if appropriate. Preferably, the silicone- or silane-in-monomer solution exhibits a viscosity of 2 to 20,000 mPa·s at 25°C, preferably 5 to 15,000 mPa·s at 25°C, and more preferably 7 to 10,000 mPa·s at 25°C.

[0050] The silicone or silane-containing monomer solution is optionally combined with a hydrophobic co-emulsifier, examples of which are known in the art and suitable for forming an aqueous dispersion of the copolymer.

[0051] In the second step, the silicone- or silane-containing monomer solution is emulsified, preferably under high shear, with water and at least one surfactant, and optionally with an auxiliary agent such as a polymerization inhibitor to prevent premature radical emulsion polymerization, to obtain an emulsion with a droplet size of 350 nm or less, known as a miniemulsion. High shear in this context may be generated by suitable emulsifying equipment, such as a conventional rotor-stator system, or by other methods known in the art, such as high-pressure homogenizers, dissolver disks, ultrasonic devices, or equivalent emulsifying techniques capable of exerting high shear forces that allow the generation of small particles of 200 nm or less, forming a miniemulsion with a droplet size of 350 nm or less. When using commercially available rotor-stator systems, rotation speeds of 4000 to 12,000 rpm, preferably 5000 to 11,000 rpm, and more particularly 6000 to 10,000 rpm, have proven particularly advantageous. Both continuous and discontinuous embodiments are suitable. When using a high-pressure homogenizer, pressures of preferably 300 bar to 1000 bar, more preferably 350 bar to 900 bar, and particularly preferably 400 bar to 800 bar have proven advantageous. Because the preparation is polymerizable, it is preferable to implement an effective temperature monitoring strategy. In some embodiments, it is preferred that the temperature of the miniemulsion does not exceed 60°C, preferably 55°C, and more preferably 50°C. In embodiments in which the temperature of the miniemulsion does not exceed 50-60°C, the method may include a step of rapidly cooling the miniemulsion to below the aforementioned temperature.

[0052] The miniemulsion comprises a continuous aqueous phase and a dispersed organic phase. The amount of water in the miniemulsion is 20 to 80 weight percent (wt%), preferably 20 to 75, and more particularly 25 to 70 wt%, in each case based on the total weight of the miniemulsion. Furthermore, the miniemulsion of the present invention has a viscosity of 2 to 5000 mPa·s at 25°C, particularly 3 to 4500 mPa·s at 25°C, and more particularly 5 to 4000 mPa·s at 25°C. Viscosities in the above ranges are desirable for processing advantages and ease of handling.

[0053] The organic phase of the miniemulsion is polymerized by the process of radical emulsion polymerization. In this case, in the third stage, the dispersed organic droplets are subjected to free radical polymerization. This radical emulsion polymerization is preferably carried out by metering the miniemulsion into an initial charge containing water and a portion of the catalyst. Further metered feeds may include a polymerization initiator, which may optionally include multiple components, each of which is metered separately into the initial charge or included in the initial charge according to their interaction and function in the polymerization procedure. Metering of the feeds can be carried out using commercially available equipment such as metering pumps and addition funnels.

[0054] Polymerization is initiated by a water-soluble initiator or a redox initiator combination, preferably the latter. Examples of initiators include sodium, potassium, and ammonium salts of peroxodisulfate, hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, potassium peroxodiphosphate, tert-butyl peroxopivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, and azobisisobutyronitrile. The initiators described are preferably used in amounts of 0.01 to 4.0 wt.% based on the total weight of the monomers. In redox initiator combinations, the initiators are used in combination with a reducing agent. Suitable reducing agents include sulfites and bisulfites of monovalent cations (e.g., sodium sulfite), derivatives of sulfoxylic acid (e.g., zinc or alkali metal formaldehyde sulfoxylates, e.g., sodium hydroxymethanesulfinate), and ascorbic acid. An example of a preferred reducing agent is a sulfinic acid compound such as 2-hydroxy-2-sulfinatoacetic acid disodium salt. Reducing agents of this preferred type are sold, for example, under the trade names Bruggolite® FF6 and Bruggolite® FF6 M. The amount of reducing agent is preferably 0.15 to 3 wt% of the amount of monomer used. Furthermore, a small amount of a metal compound soluble in the polymerization medium and whose metal component is redox-active under the polymerization conditions may be incorporated, such as a compound based on iron or vanadium. One particularly preferred initiator system containing the aforementioned components is tert-butyl hydroperoxide / sodium hydroxymethanesulfinate / Fe(EDTA). 2+ / 3+ It is a system of:

[0055] It is also possible to use mainly oil-soluble initiators such as cumene hydroperoxide, isopropylbenzene monohydroperoxide, dibenzoyl peroxide, azobisisobutyronitrile, etc. Preferred initiators for miniemulsion polymerization are potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and dibenzoyl peroxide.

[0056] After forming the miniemulsion containing the ethylenically functionalized silicone polymer or silane, the organoacrylic monomer and the surfactant, the initiator is introduced as described above.

[0057] After the addition of the initiator, the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized to form an aqueous dispersion of copolymer. Thus, the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized in the presence of a surfactant and water. The polymerization can be carried out batchwise or continuously, with all or individual components of the reaction mixture initially charged, with some of the individual components initially charged and then metered in, or with no initial charge. All metering is preferably carried out at the rate at which the components are consumed. The polymerization can be carried out at a predetermined temperature. In certain embodiments, the reaction temperature in miniemulsion polymerization is 0°C to 100°C. More preferably, the reaction temperature in miniemulsion polymerization is 5°C to 80°C, and in some embodiments, the reaction temperature is 30°C to 70°C.

[0058] Upon completion of the miniemulsion polymerization, the resulting aqueous dispersion of copolymer is adjusted to the desired pH, optionally filtered, and then used for its intended purpose. In certain embodiments, the pH of the dispersion medium is 2 to 9, preferably 4 to 8. In a preferred embodiment, the pH is 4.5 to 7.5. The pH can be adjusted by adding hydrochloric acid or aqueous sodium hydroxide to the dispersion medium before the start of the reaction.

[0059] Advantageously, this process forms an aqueous dispersion of the copolymer having a high solids content. For example, the aqueous dispersion of the copolymer may contain 40 wt% or more solids, based on the total weight of the aqueous dispersion. In some embodiments, the aqueous dispersion of the copolymer contains 40 to 70 wt% solids, based on the total weight of the aqueous dispersion. Preferably, the aqueous dispersion of the copolymer contains 40 to 65 wt% solids, based on the total weight of the aqueous dispersion.

[0060] In some embodiments, aqueous dispersions of the copolymers exhibit a viscosity of 1 to 20,000 mPa·s at 25° C. Preferably, aqueous dispersions of the copolymers exhibit a viscosity of 1 to 5,000 mPa·s at 25° C. The viscosities of aqueous dispersions of the copolymers reported herein can be determined by measurements using rotational viscosity according to DIN EN ISO 3219 using a Brookfield viscometer (spindle LV1, 10 rpm), in each case at 25° C. and atmospheric pressure of 1013 mbar.

[0061] Additionally, copolymers formed by polymerization may exhibit certain advantageous properties.

[0062] For example, the copolymer exhibits a desired glass transition temperature (Tg) suitable for use in a particular application. The Tg of the copolymer can be preselected by the selection of the monomers and / or the weight fraction of the monomers. In one embodiment, the copolymer exhibits a Tg of 0 to -100°C. In another embodiment, the copolymer exhibits a Tg of -10 to -60°C. In these embodiments, the Tg is determined by differential scanning calorimetry in accordance with DIN 53765, open crucible, at a heating rate of 10°K per minute. The Tg of a polymer can be measured in known manner by differential scanning calorimetry (DSC) in accordance with DIN 53765, open crucible, heating at 10°K / min. The Tg may be approximately calculated in advance using Fox's formula. According to Fox TG, Bull. Am. Physics Soc. 1, 3, 123 (1956), it is as follows:

number

[0063] The tack of an adhesive composition is a function of, among other things, the Tg of the copolymer. Therefore, the tack of an adhesive composition can be predetermined by selecting the Tg of the copolymer. In some embodiments, when a copolymer is included in the adhesive composition, the adhesive composition is provided as a film. Prior to curing, the film of the adhesive composition has a wet thickness. In some embodiments, the film has a wet thickness of 381 microns. After curing the film from this thickness, the film exhibits a peak tack of 100 grams of force (gf) or greater. Preferably, after curing at a wet thickness of 381 microns, the film exhibits a peak tack of 100 to 1,000 grams of force. The peak tack of the film can be measured with a TA.XT Plus Texture Analyzer using a TA-57R probe and a TA-303 instrument.

[0064] The resulting film may be cohesive and non-residue on contact, meaning that the film may be sticky but does not leave a residue on contact with and removal from it.

[0065] The copolymer also exhibits a desirable particle size. In some embodiments, the z-average particle size of the copolymer dispersion is 1000 nm or less, preferably 350 nm or less, more preferably 250 nm or less, and highly preferably 200 nm or less, and is at least 20 nm, preferably at least 30 nm, and more preferably at least 50 nm. Preferably, the z-average particle size of the copolymer dispersion is 50 to 300 nm. As described below, the z-average particle size can be measured by dynamic light scattering (DLS) using a Malvern Zetasizer Nano ZS particle size analyzer. The particle size polydispersity (PDI) indicates the width of the particle size distribution.

[0066] In some embodiments, the size of the silicone or silane domains in the copolymer after copolymerization preferably ranges from 5 nm to 150 nm, more particularly preferably from 10 nm to 140 nm, and especially preferably from 15 nm to 125 nm, and may be determined, for example, by scanning or transmission electron microscopy of dispersions or resulting films of the copolymer.

[0067] The aforementioned properties make the copolymer particularly suitable for certain applications. For example, in one embodiment, an adhesive composition comprising the copolymer is provided. The adhesive composition may be utilized to provide a PSA type adhesive. In these embodiments, the PSA comprises the copolymer.

[0068] Surprisingly, in some embodiments, aqueous dispersions of the copolymer have low viscosities (less than 100 mPa·s) even when the amount of water is fairly low (less than 50 wt %, based on the total weight of the aqueous dispersion of the copolymer). The low viscosity of the aqueous dispersion makes the dispersion suitable for application to a surface by spraying. In other embodiments, when the viscosity of the aqueous dispersion is high, a film applicator can be used to draw a film including the dispersion onto a surface.

[0069] After applying the aqueous copolymer dispersion to a substrate, or before applying it to a substrate, the copolymer dispersion can be cured. In this application, curing refers to the process of removing water from the copolymer dispersion, which may also be referred to herein as "drying." Preferably, the water is removed by evaporation, which can be achieved, for example, by heating the aqueous dispersion to evaporate the water therefrom. The copolymer is said to be cured when it can form a dry film or when the copolymer does not show a weight change of more than 2% when heated in an oven at 120°C for 1 hour.

[0070] The aqueous dispersion of the copolymer can be applied to a substrate using conventional equipment and techniques. Suitable substrates include commercially available substrates, such as high surface energy substrates and low surface energy substrates (metal substrates and polymer substrates, respectively). Substrates may include stainless steel, paper, cardboard, glass, polyolefins, PET, PVC, PMMA, PC, polyurethane, composites, wood, textiles, and various types of plastics and other materials. Coating can be achieved by spraying, knife coating, roller coating, casting, drum coating, dipping, and combinations thereof. Coating techniques include, but are not limited to, gravure coating, reverse roll coating, Mayer rod coating, Dahlgren coating, knife-over-roll coating, slot-die coating, dip coating, curtain coating, and the like. Indirect application to the substrate using a transfer process can also be used, in which the copolymer is first applied to a release liner instead of directly to the substrate (also called facestock). After drying, the substrate is laminated to an adhesive-coated liner. When the liner and facestock are separated, the adhesive is transferred from the release liner to the facestock.

[0071] Coated articles can be formed by applying an adhesive composition to a substrate. The coated article includes the adhesive composition and the substrate, which is preferably a polymeric substrate. The adhesive composition forms a film on the substrate. The film adheres well to the substrate. In fact, the film exhibits high peel strength. For example, in certain embodiments, a film having a wet thickness of 381 microns exhibits a 180-degree peel strength of 1.5 N / inch or greater after curing at 60°C for 15 minutes. In one such embodiment, a film having a wet thickness of 381 microns exhibits a 180-degree peel strength of 1.5 N / inch to 60 N / inch after curing at 60°C for 15 minutes. Peel strength can be measured using an adhesion / peel tester by attaching a stainless steel plate to the outer surface of the film, allowing it to stand for 30 minutes, and then peeling the stainless steel plate off at a rate of 300 mm / min (12 in / min). Suitable adhesion / peel testers for use in measuring peel strength include the Shimadzu AGS-X-10kNX tensile tester or the Cheminstruments AR-1000 adhesion / peel tester.

[0072] When the copolymer is used in a PSA adhesive composition, it has been discovered that the PSA retains many of its desirable properties under various conditions. For example, the PSA may retain its adhesive properties in a moist environment, meaning that the PSA can be used on or near sweaty or wet skin. In this embodiment, the PSA may be insoluble in water after curing.

[0073] In other embodiments, PSAs containing the copolymers exhibit improved properties. For example, PSAs may exhibit improved moisture vapor transmission rates (MVTR). MVTR can be controlled by varying the organic acrylic monomer. For example, according to WO 2001 / 042384, the use of hydroxyethyl acrylate (HEA) affects MVTR. Also, increasing the acrylic acid content in the copolymer can increase MVTR (Journal of Applied Polymer Science, Vol. 59, No. 8, pp. 1243-1247). In one embodiment, the adhesive compositions of various PSAs have a water vapor permeability of >300 g / m when measured according to the method described above using a fabric backing. 2 / day. In these embodiments, the MVTR may be measured according to ASTM D1653.

[0074] Adhesive compositions containing the copolymers may exhibit other advantageous properties. For example, the adhesive compositions exhibit excellent stability. In certain embodiments, when the adhesive composition is a PSA type, the composition is surprisingly highly storage stable. As used herein, storage stability refers to the degree of phase separation observed in the adhesive composition at room temperature over a period of time. In certain embodiments, the adhesive composition does not exhibit any phase separation at 25°C, as assessed by the absence of observable phase separation for 180 days. In certain embodiments, the adhesive composition does not exhibit any phase separation at 25°C, as assessed by the absence of observable phase separation for 720 days or more. Stability can also be measured by the consistency of z-average particle size. In certain embodiments, the adhesive composition is stable to phase separation at 25°C, as assessed by the absence of more than a 20% variation in z-average particle size. In some embodiments, the adhesive composition does not exhibit more than a 20% variation in z-average particle size over a period of at least 6 months. The Z-average particle size of these embodiments may be measured by the method of dynamic light scattering (DLS) using a Malvern Zetasizer Nano ZS particle size analyzer.

[0075] When the copolymer is utilized in an adhesive composition that is a PSA, the PSA may exhibit very low residual volatile organic carbon (VOC) or no VOC. For example, in one embodiment, the adhesive composition may exhibit 2.5% or less VOC. The VOC content of the adhesive composition may be measured according to EPA Test Method 24.

[0076] In other embodiments, the adhesive composition is biocompatible, meaning that it has no observable adverse effects when applied to the skin or in close proximity to the human body. In these embodiments, the residual monomer reaction components, such as residual organic acrylic monomers, should be very low, preferably less than 0.5 wt %, based on the total weight of the cured adhesive composition.

[0077] As described above, the adhesive compositions can be utilized in medical applications such as wound care and other healthcare applications, including medical tapes, adhesive patches, wound care dressings, ostomy care, drug delivery, cosmetic patches, and wearables. Such adhesive tapes can be of the PSA variety and include the copolymer formed by this process. This adhesive tape is useful for medical applications requiring low-trauma properties, meaning that the adhesive adheres to the skin but does not exhibit excessive adhesion buildup over time, which would result in difficult and therefore painful removal.

[0078] Because of the diversity of potential medical applications, it may be important for compositions containing the copolymers to be able to exhibit a wide range of physical properties. For example, compositions containing the copolymers may exhibit hydrophobicity / hydrophilicity that can be controlled by carefully selecting appropriate monomers or combinations thereof. For example, in certain embodiments, adhesive compositions, such as PSA types, may be provided with relatively hydrophilic properties by incorporating hydrophilic monomers during polymerization, such as 2-hydroxymethacrylate and acrylamide.

[0079] In certain embodiments, the adhesive composition may also contain a drug or active compound, an adhesive resin, a penetration enhancer, a water-absorbing material, an emollient, and / or a tackifier. Examples of suitable adhesive resins include polyacrylates, natural rubber, or synthetic rubber. Examples of suitable penetration enhancers include polar substances capable of forming strong hydrogen bonds, such as urea, which polarize the user's skin molecules and increase skin permeability through ionic forces. Another suitable polar agent for use in the adhesive composition is DMSO (dimethyl sulfoxide) solution. Other examples of suitable agents include nonionic surfactants or solvents with a hydrophilic-lipophilic balance (HLB) value of approximately 6 to 30. As used herein, the term "HLB" refers to a numerical representation of the ability to emulsify insoluble ingredients in oil and water. These may be selected from the chemical groups of glycerol esters, polyglycerol esters, alkyl fatty acid esters, ethoxylated sorbitan esters, alcohol ethoxylates, lanolin ethoxylates, ethoxylated fatty acid methyl esters, and alkanolamides. Preferably, in these embodiments, the agent has an HLB value of about 8 to 28. Examples of suitable agents with an HLB value of 8 to 10 include PEG 200 monolaurate, sorbitan monolaurate, polypropylene glycol myristyl ether, polypropylene glycol lauryl alcohol, polypropylene glycol lauryl ether, polypropylene glycol sorbitan monooleate, octyphenoxypoly(ethyleneoxy)ethanol, linear alcohol ethoxylates, polysorbate 80-containing mono- and diglycerides, nonylphenol ethoxylates, alkylaryl polyether ethanols, and N,N-dimethylamides. Examples of suitable agents having an HLB value of 11 to 14 include PEG 400 monooleate, polyoxyaryl ether, POE oleyl alcohol, PEG 600 monooleate, POE sorbitan monooleate, PEG 400 monolaurate, POG lauryl alcohol, and nonylphenoxypoly(ethyleneoxy)ethanol.Examples of suitable agents having an HLB value of 15 to 28 include nonylphenol ethoxylate, castor oil ethoxylate, ethoxylated coco monoglyceride, ethylene oxide condensed oleyl alcohol, modified oxyethylated linear alcohol, ethoxylated lanolin alcohol, nonylphenyl ethoxylate, polyethylene 100 stearyl ether, PEG 6000 monooleate, ethoxylated polyoxypropylene glycol, and ethoxylated polyoxypropylene glycol. Preferably, the agent is provided in an amount of about 1 to 50 wt. % based on the total weight of the adhesive composition before curing. Examples of water-absorbing materials may be selected from highly water-absorbent polymers, polyols, and water-absorbent inorganic materials. Examples of superabsorbent polymers include mucopolysaccharides such as hyaluronic acid, chondroitin sulfate, and dermatan sulfate; polymers with multiple hydrophilic groups in the molecule such as chitin, chitin derivatives, starch, and carboxymethylcellulose; and semi-synthetic and synthetic superabsorbent polymers such as polyacrylic acid, polyoxyethylene, polyvinyl alcohol, and polyacrylonitrile. Examples of water-absorbent inorganic materials that may be incorporated into the adhesive to adjust water absorption include powdered silica, zeolite, and powdered ceramic. Examples of polymers include propylene glycol, glycerin, and sorbitol. Suitable tackifiers may be selected from the group consisting of hydrocarbon resins, hydrogenated hydrocarbon resins, fully hydrogenated hydrocarbon resins, hydrogenated rosin esters, fully hydrogenated rosin esters, and combinations thereof. Examples of suitable emollients include alpha bisabolol, chamomile oil, allantoin, and d-panthenol.

[0080] Although the copolymer is prepared in water, adhesive compositions comprising the copolymer are preferably dry, meaning that they contain little or no residual water when used. Thus, in certain embodiments, it may be desirable for the copolymer to be hydrophobic, imparting hydrophobicity to the adhesive composition, which generally results in low water absorption and better adhesive properties.

[0081] The adhesive composition embodiments described herein should provide good adhesive properties. However, the adhesive composition may be blended with other adhesives to obtain optimal properties for a particular application. Tackifiers may also be added to the adhesive composition to tailor the properties exhibited. Other additives suitable for use in the adhesive composition may include wetting agents, defoamers, and / or coalescents.

[0082] Compositions containing the copolymers may also be utilized to provide a matrix for containing one or more active ingredients. Advantageously, such actives can be incorporated into such compositions and released therefrom at a controlled rate. Such compositions may also have the adhesive properties described above. Thus, in certain embodiments, the adhesive compositions described above may be used for the controlled release of one or more active substances. Active substances suitable for use in adhesive compositions may be referred to herein simply as "actives" or "actives."

[0083] Preferably, the active agent utilized is compatible with the aqueous dispersion. Water-soluble or partially water-soluble active agents are more preferred. Non-limiting examples of such active agents include melamine, niacinamide, Benadryl, vitamin C, and the like. Water-insoluble active agents may also be used, in which case the active agent may be added in an emulsified form to be compatible with the aqueous dispersion of the copolymer. For example, in some embodiments, the water-insoluble active agent may be encapsulated (e.g., encapsulated in a cyclodextrin cavity or other encapsulating agent) to be compatible with the aqueous dispersion.

[0084] The active substance is preferably incorporated into the adhesive composition, for example, PSA composition, before curing.The active substance may be, for example, a pharmacological active substance, such as cannabinoid.However, the active substance may also be suitable for use in cosmetics, wound care, wellness, or performance improvement applications.The active substance suitable for use can be delivered topically or transdermally.

[0085] In some embodiments, the active agent may be a cannabinoid. Pharmacological active agents suitable for use, in addition to cannabinoids, include oxymorphone, caffeine, zidovudine, pilocarpine, ranitidine, lazabemide, thiopental, scopolamine, butabarbital, digoxin, tiapride, pemoline, diclofenac, antipyrine, albuterol, oxycodone, terbutaline, ephedrine, pseudoephedrine, morphine, captopril, mescaline, naloxone, phenelzine, secobarbital, flumazenil, fluvastatin; sumatriptan, oxcarbazepine, modafinil , moclobemide, nadolol, aldosterone, pentaerythritol, prazosin, ramipril, guanfacine, physostigmine, phenobarbital, minoxidil, aprobarbital, naltrexone, leflunomide, terazosin, pindolol, fludrocortisone, mephobarbital, profentofylline, methysergide, transylcypromine, prednisone, hydromorphone, dantrolene, hydrocortisone, talipexole, lidocaine, metoprolol, betamethasone, timolol, resopitron, benzodiazepine Caine, clobazam, colchicine, butalbital, prilocalcin, atropine, mepivacaine, procaine, pentobarbital, amobarbital, clorazepate, yohimbine, temazepam, hydrocodone, phenytoin, trimethobenzamide, warfarin, carbamazepam, nedosiomil, buspirone, ketorolac, oxazepam, piribedil, pramipexole, secobarbital, hydrocortisone, lorazepam, chlordiazepoxide, quetiapine, enalapril, betamethasone acetate, tamsulosin, nifedipine, eltrombopag Gotamine, clonazepam, atorvastatin, tolmetin, bumetanide, piroxicam, perindopril, propranolol, mexilethene, chlorzoxazone, indapamide, diazepam, sithiopirox, ramipril, amphetamine, benztropine, methylphenidate, apomorphine, diltiazem alprenolol, clozapine, ropivacaine, valproic acid, norethindrone, ketoprofen, tramadol, tetracaine, etorphine, flurazepam, meperidine, ropinirole, carvedilol, bupranolol,Pravastatin, naproxen, diphenhydramine, ketamine, albendazole, idebenone, tacrine, finasteride, nabumetone, gestodene, testosterone, venlafaxine, estazolam, rimantadine, phentolamine, propafenone, levorphanol, bupivacaine, perindopril, droperidol, celecoxib, norgestrel, isradipine, risperidone, benazepril, loratidine, betamethasone, progesterone, butorphanol These include benzodiazepine, papaverine, quinapril, alprostadil, prostaglandins, citalopram, ibuprofen, flurbiprofen, chlorpheniramine, zolpidem, alprazolam, fentanyl, nisoldipine, benztropine, betamethasone, etodolac, tibolone, estradiol, adamantane, chlormadinine, oxybutynin, triazolam, doxepin, prazepam, capsaicin, granisetron, frovatriptan, and norethindrone acetate.

[0086] Other actives suitable for practicing the above methods include antioxidants, free radical scavengers, moisturizers, depigmenting agents, reflective agents, moisturizers, antimicrobials (e.g., antibacterial agents), allergy suppressants, anti-acne agents, anti-aging agents, anti-wrinkle agents, antiseptics, analgesics, antitussives, antipruritics, local anesthetics, hair loss prevention agents, hair growth promoters, hair growth inhibitors, antihistamines, keratolytic agents, anti-inflammatory agents, cooling agents, healing agents, anti-infective agents, anti-inflammatory agents, anticholinergics, vasoconstrictors, vasodilators, wound healing promoters, peptides, polypeptides and proteins, deodorants and antiperspirants, emollients and skin moisturizers, hair conditioners. , hair softeners, hair moisturizers, tanning agents, skin lightening agents, antifungals (such as antifungals for foot preparations), depilatories, topical analgesics, anti-irritants, hemorrhoidal agents, insecticides, poison ivy products, poison sumac products, burn products, diaper rash prevention agents, heat rash agents, cosmetics, vitamins, amino acids and derivatives thereof, herbal extracts, retinoids, fragrances, sensory markers (e.g., cooling agents, heating agents, etc.), skin conditioners, hair lighteners, chelating agents, cell turnover promoters, colorants, sunscreens, anesthetics, immunomodulators and nutrients, moisture absorbents, sebum absorbents, and the like, and mixtures thereof. Skin treatment methods may include topical anesthetics, topical antibiotics, antiseptics, antifungals, antihistamines, antipruritics, keratolytic and caustic agents, antivirals, antipsoriatics, steroids, and a variety of substances for the treatment of acne, psoriasis, photosensitivity, or precancerous stages.

[0087] In certain embodiments, intradermally administered active agents may be utilized. Active agents that can be applied via the intradermal route include, for example, steroidal and nonsteroidal anti-inflammatory agents, local anesthetics, substances that stimulate blood flow, vasoprotectants and vasoconstrictors for treating vascular disease, and active agents that affect processes within subcutaneous adipose tissue.

[0088] Additional active agents suitable for use include, for example, analgesics, antiarrhythmics, narcotics and their antagonists, neuroleptics, hormones or hormone replacements, antidepressants, tranquilizers, hypnotics, psychostimulants, antiparkinsonian agents, ganglionic blocking agents, sympathomimetics, alpha-sympathomimetics, beta-sympathomimetics, antisympathomimetics, antiasthmatics, antiparkinsonian agents, ganglionic blocking agents, sympathomimetics, alpha-sympathomimetics, beta-sympathomimetics, antisympathomimetics, antiasthmatics, antiemetics, appetite suppressants, diuretics, or active agents for weight loss.

[0089] In some embodiments, suitable active agents can provide an effect at very low concentrations. Examples of these active agents include estradiol, estriol, progesterone, norethisterone, norethindrone, levonorgestrel and its derivatives, estradiol diacetate, norgestamate, gestagens, desogestrel, delenegestrone, promegestrone, testosterone, hydrocortisone and its derivatives, nitro compounds such as amyl nitrate, nitroglycerin, isosorbide dinitrate, amine compounds such as nicotine, chlorpheniramine, terfenadine, triprolidine, oxicam derivatives such as piroxicam, mucopolysaccharidases such as thiomucase, opioid substances and their salts such as buprenorphine, morphine, fentanyl, Derivatives or analogs thereof include naloxone, codeine, dihydroergotamine, lysergic acid derivative pizotyline, salbutamol, terbutaline, prostaglandins such as PGA, PGB, and PGE, PGF series such as misoprostol and enprostil, benzamides such as omeprazole, imipramine, metoclopramine, and scopolamine, peptides and growth factors such as EGF, TGF, and PDGF, somatostatin, dihydropyridines such as clonidine, nifedipine, nitrendipine, verapamil, diltiazem, ephedrine, propanolol, metoprolol, and spironolactone, and thiazides such as hydrochlorothiazide and flunarizine. Active substances for irritation or wound cleansing such as enzymes, antiseptics, disinfectants, and antibiotics, analgesics, anesthetic active substances, and wound healing promoting active substances that stimulate granulation, induce angiogenesis, or promote epithelialization may also be used. In some embodiments, the active agent can be a steroid hormone, preferably estradiol, alone or in combination with other active agents.

[0090] Active ingredients derived from plant preparations, such as extracts and tinctures, are also suitable for topical skin treatment. Suitable extracts and tinctures include oak bark extract, walnut extract, arnica tincture, witch hazel extract, liposome extract, pansy extract, thyme or sage extract, St. John's wort tincture, cornflower tincture, chamomile flower extract, calendula flower tincture, birch leaf extract, nettle extract, coldfoot extract, comfrey tincture, horsetail extract, or aloe vera extract. Additional active ingredients suitable for use in transdermal treatment of diseases include horse chestnut and butcher's broom extracts for venous diseases, and arnica, calendula, and capsicum extracts and tinctures for bruising, strains, and bleeding. Suitable active ingredients derived from plant preparations may also be used in transdermal therapy, such as ginseng extract, valerian tincture, melissa and hop extract, kola and tea extract, and hawthorn extract.

[0091] Suitable effervescent actives can be used, including sodium bicarbonate and sodium carbonate.Suitable amino acid actives can be used, including the amino acids derived from the hydrolysis of various proteins, and their salts, esters, and acyl derivatives.Examples of such amino acids include amphoteric amino acids, such as alkylamidoalkylamines, stearyl acetylglutamic acid, capryloylsilk amino acids, caprylol collagen amino acids, capryloylkeratin amino acids, capryloylpea amino acids, cocodimonium hydroxypropylsilk amino acids, corn gluten amino acids, cysteine, glutamic acid, glycine, hair keratin amino acids, hair amino acids, such as aspartic acid, threonine, serine, glutamic acid, proline, glycine, alanine, half cystine, valine, methionine, isoleucine, leucine, tyrosine, phenylalanine, cysteic acid, lysine, histidine, arginine, cysteine, tryptophan, citrulline, lysine, silk amino acids, wheat amino acids, and mixtures thereof.

[0092] Suitable peptides, polypeptides, and proteins can be utilized as active ingredients, including those polymers formed by the self-condensation of amino acids, having long chains, such as at least about 10 carbon atoms, and high molecular weights, such as at least about 1000. Examples of such proteins include collagen, deoxyribonuclease, iodized corn protein, keratin, milk protein, protease, serum protein, silk, sweet almond protein, wheat germ protein, wheat protein, alpha and beta helices of keratin protein, hair protein (intermediate filament protein, high sulfur protein, ultra-high sulfur protein, intermediate filament-associated protein, tyrosine-rich protein, glycine-tyrosine-rich protein, trichohyalin), and mixtures thereof.

[0093] Vitamins may be utilized as active ingredients in the above methods. Examples of suitable vitamins that may be used include B vitamins (thiamine, nicotinic acid, biotin, pantothenic acid, choline, riboflavin, vitamin B6, vitamin B12, pyridoxine, inositol, carnitine), vitamins A, C, D, E, K and their derivatives (such as vitamin A palmitate), provitamins such as panthenol (provitamin B5) and panthenol triacetate, and mixtures thereof.

[0094] Antibacterial agents may be utilized as active ingredients. Examples of suitable antibacterial agents that may be used include bacitracin, erythromycin, neomycin, tetracycline, chlortetracycline, benzethonium chloride, phenol, and mixtures thereof.

[0095] Emollients and skin moisturizers may be utilized as actives. Examples of suitable emollients and skin moisturizers that may be used include mineral oil, lanolin, vegetable oil, isostearyl isostearate, glyceryl laurate, methyl gluceth 10, methyl gluceth 20 chitosan, and mixtures thereof.

[0096] Hair conditioners may be utilized as actives. Examples of suitable hair conditioner actives include quaternized compounds such as behenamidopropyl PG dimonium chloride, tricetyl ammonium chloride, dehydrogenated tallowamidoethyl hydroxyethylmonium methosulfate, and mixtures thereof, as well as lipophilic compounds such as cetyl alcohol, stearyl alcohol, hydrogenated polydecene, and mixtures thereof.

[0097] Sunscreens may be utilized as actives. Examples of suitable sunscreens that may be used as actives include butyl methoxydibenzoylmethane, octyl methoxycinnamate, oxybenzone, octocrylene, octyl salicylate, phenylbenzimidazole sulfonic acid, ethyl hydroxypropyl aminobenzoate, menthyl anthranilate, aminobenzoic acid, cinoxate, diethanolamine methoxycinnamate, glyceryl aminobenzoate, titanium dioxide, zinc oxide, oxybenzone, padimate, red petrolatum, and mixtures thereof.

[0098] Tanning agents and whitening agents can be used as active ingredients. Examples of suitable tanning agents that can be used as active ingredients include dihydroxyacetone. Examples of suitable whitening agents that can be used include hydroquinone, catechol and its derivatives, ascorbic acid and its derivatives, and mixtures thereof.

[0099] Insecticides may be used as the active ingredient. Examples of suitable insecticides include permethrin, pyrethrins, piperonyl butoxide, imidacloprid, and N,N-diethyltoluamide (referring primarily to materials containing the meta isomer).

[0100] Antifungal agents for foot preparations that may be used as actives include those with antifungal activity such as tolnaftate.

[0101] Depilatories may be utilized as actives. Examples of suitable depilatories include calcium thioglycolate, magnesium thioglycolate, potassium thioglycolate, strontium thioglycolate, and mixtures thereof.

[0102] Pain relievers and local anesthetics may be utilized as active agents. Examples of suitable pain relievers and local anesthetics that may be used as active agents include enzocaine, dibucaine, benzyl alcohol, camphor, capsaicin, capsicum, capsicum resin, juniper tar, menthol, methyl nicotinate, methyl salicylate, phenol, resorcinol, turpentine, and mixtures thereof.

[0103] Antiperspirants and deodorants may be utilized as actives. Examples of suitable antiperspirants and deodorants that may be used as actives include aluminum chlorohydrate, aluminum zirconium chlorohydrate, and mixtures thereof.

[0104] In some embodiments, the active agent may be an anti-irritant. Examples of suitable anti-irritants that may be used include camphor, menthol, methyl salicylate, peppermint and clove oil, ichthammol, and mixtures thereof.

[0105] In some embodiments, the active agent may be an anti-inflammatory agent, such as hydrocortisone. In other embodiments, the active agent may be an anti-hemorrhoid agent. Examples of suitable anti-hemorrhoid agents include anesthetics such as benzocaine, pramoxine hydrochloride, antiseptics such as benzethonium chloride, astringents such as zinc oxide, bismuth subgallate, balsam of Peru, and mixtures thereof, skin protectants such as cod liver oil, vegetable oils, and mixtures thereof.

[0106] Benefit agents are also suitable for use as active ingredients.Suitable benefit agents include therapeutic agents that are effective in treating dandruff, seborrheic dermatitis, psoriasis and the symptoms associated therewith.Examples of such suitable therapeutic agents include zinc pyrithione, shale oil and its derivatives (such as sulfonated shale oil), selenium sulfide, sulfur, salicylic acid, coal tar, povidone-iodine, imidazole, etc.

[0107] In some embodiments, the active agent may be an antimicrobial, antiseptic, or keratolytic agent. Antimicrobial agents that can be used for topical application include penicillin, cephalosporins, other beta-lactam compounds, aminoglycosides, tetracyclines, erythromycin, antifungals, and the like, and combinations thereof. Antiseptics that can be used as active agents for topical application to acneiform skin include triclosan (Irgasan DP 300), phenoxyisopropanol, resorcinol, chlorhexidine, and povidone-iodine. Keratolytic agents that can be used as active agents for topical application to acneiform skin include salicylic acid, benzoyl peroxide, sulfur, retinoic acid, and various fruit acids and alpha hydroxy acids.

[0108] In other embodiments, the active may be an anti-irritant. Suitable anti-irritants for topical application to acne-prone skin are alpha-bisabolol, famesol, chamomile extract, and glycyrrhetinic acid.

[0109] In some embodiments, the active agent may be an anti-inflammatory analgesic. Examples of anti-inflammatory analgesics suitable for use in the above methods include acetaminophen, methyl salicylate, monoglycol salicylate, aspirin, mefenamic acid, flufenamic acid, indomethacin, diclofenac, alclofenac, diclofenac sodium, ibuprofen, ketoprofen, naproxen, pranoprofen, fenoprofen, sulindac, fenclofenac, clidanac, flurbiprofen, fentiazac, bufexanac, piroxicam, phenylbutazone, oxyphenbutazone, clofezone, pentazocine, mepirizole, tiaramide hydrochloride, and the like.

[0110] In certain embodiments, the active agent may be a steroidal anti-inflammatory agent. Examples of steroidal anti-inflammatory agents that may be used in the above methods include hydrocortisone, prednisolone, dexamethasone, triamcinolone acetonide, fluocinolone acetonide, hydrocortisone acetate, prednisolone acetate, methylprednisolone, dexamethasone acetate, betamethasone, betamethasone valerate, flumethasone, fluorometholone, beclomethasone dipropionate, and the like.

[0111] Antihistamines are also suitable for use as actives. Examples of antihistamines include diphenhydramine hydrochloride, diphenhydramine salicylate, diphenhydramine, chlorpheniramine hydrochloride, chlorpheniramine maleate, isothipendyl hydrochloride, tripelennamine hydrochloride, promethazine hydrochloride, methdilazine hydrochloride, and the like.

[0112] In certain embodiments, the active agent may be a local anesthetic such as, for example, dibucaine hydrochloride, dibucaine, lidocaine hydrochloride, lidocaine, benzocaine, p-butylaminobenzoic acid 2-(diethylamino)ethyl ester hydrochloride, procaine hydrochloride, tetracaine, tetracaine hydrochloride, chloroprocaine hydrochloride, oxyprocaine hydrochloride, mepivacaine, cocaine hydrochloride, piperocaine hydrochloride, dyclonine, dyclonine hydrochloride, and the like.

[0113] In other embodiments, the active may be a disinfectant or antiseptic. Antiseptics and antiseptics that may be used include thimerosal, phenol, thymol, benzalkonium chloride, benzethonium chloride, chlorhexidine, povidone-iodine, cetylpyridinium chloride, eugenol, trimethylammonium bromide, and the like.

[0114] In other embodiments, the active agent may be a vasoconstrictor, a hemostatic agent, a chemotherapeutic agent, or an antibiotic. Suitable vasoconstrictors include naphazoline nitrate, tetrahydrozoline hydrochloride, oxymetazoline hydrochloride, phenylephrine hydrochloride, tramazoline hydrochloride, and the like. Suitable hemostatic agents include thrombin, phytonadione, protamine sulfate, aminocaproic acid, tranexamic acid, carbazochrome, carbaxochrome sodium sulfate, rutin, hesperidin, and the like. Examples of chemotherapeutic agents that may be used include sulfamine, sulfathiazole, sulfadiazine, homosulfamine, sulfisoxazole, sulfisomidine, sulfamethizole, nitrofurazone, and the like. Examples of antibiotics include penicillin, methicillin, oxacillin, cephalothin, cephalosin, erythromycin, lincomycin, tetracycline, chlortetracycline, oxytetracycline, methacycline, chloramphenicol, kanamycin, streptomycin, gentamicin, bacitracin, and cycloserine.

[0115] Suitable active agents include protease inhibitors, thymazine kinase inhibitors, sugar or glycoprotein synthesis inhibitors, structural protein synthesis inhibitors, attachment and adsorption inhibitors, antiviral agents such as nucleoside analogues such as acyclovir, penciclovir, valacyclovir, ganciclovir, etc.

[0116] Further suitable actives include alpha-hydroxy acids (AHAs), which can be used as exfoliants, moisturizers, and emollients, lactate salts such as sodium lactate, and salicylic acid, which can be used as peeling agents. The moisturizing activity of AHAs and their ability to exfoliate the skin and inhibit intercellular cohesion in the outer layer of the epidermis are well known. AHAs, unlike salicylic acid and other exfoliants, have been suggested to inhibit cohesion in the granular layer.

[0117] In certain embodiments, skin benefit actives may be used. Such actives may be of the cosmetic type, such as melatonin or niacinamide. Another suitable skin benefit active is vitamin C (ascorbic acid), which may be used in practicing the present methods. In some embodiments, vitamin C may be provided in a mixture containing vitamin E and other ingredients, such as moisturizers, collagen synthesis promoters, and exfoliants. In other embodiments, vitamin C may be provided with vitamin E and, optionally, alpha-hydroxy acids, such as lactic acid or glycolic acid, or other keratinolytics, for the treatment or prevention of wrinkles and dry skin.

[0118] Further examples of cosmetic actives include D-α-tocopherol, DL-α-tocopherol, D-α-tocopherol acetate, DL-α-tocopherol acetate, ascorbyl palmitate, vitamin F and vitamin F glycerides, vitamin D, retinol, retinol esters, retinyl palmitate, retinyl propionate, β-carotene, D-panthenol, farnesyl acetate, jojoba oil and blackcurrant oil rich in essential fatty acids, 5-n-octanoyl salicylic acid and its esters, salicylic acid and its esters, citric acid, These include alkyl esters of alpha-hydroxy acids such as lactic acid, glycolic acid, asiatic acid, madecassic acid, and asiaticoside, Centella asiatica whole extract, β-glycyrrhetinic acid, α-bisabolol, ceramides such as 2-oleoylamino 1,3-octadecane, phytantriol, marine-derived phospholipids rich in polyunsaturated essential fatty acids, ethoxyquin, rosemary extract, perfume oil extract, quercetin, dried microalgae extract, anti-inflammatory agents such as steroidal anti-inflammatory agents, and biostimulants such as hormones or compounds for lipid and / or protein synthesis.

[0119] Other examples of actives suitable for use include vitamin D3, iron in any form, zinc in any form (such as zinc citrate), folic acid, melatonin, niacinamide, green tea or green tea extract, ginseng, arnica, turmeric, curcumin, cannabinoids, tea tree oil, chlortrimazole, hyaluronic acid, alpha hydroxy acids, resveratrol, argan oil, and CoQ10.

[0120] In some embodiments, the actives may be delivered in free base or acid form, or in the form of a salt, ester, or any other acceptable derivative, or as a component of a molecular complex. It should be understood that, even if not specifically mentioned, the above actives may also be delivered as a mixture of actives. [Example]

[0121] The following examples are presented solely for the purpose of further illustrating and disclosing embodiments of methods of forming aqueous dispersions of copolymers and adhesive compositions containing such copolymers. Examples within the scope of the present invention include Examples 1-9, described below. Two comparative examples, which are not part of the present invention, are also described below.

[0122] Further in this section, the materials are characterized below by reporting data obtained by instrumental analysis. The underlying measurements were performed according to publicly available standards or determined using specially developed techniques. For clarity of the discussion, the methods used are specified below.

[0123] In all examples, all parts and percentages are by weight unless otherwise specified.

[0124] viscosity: Unless otherwise stated, the viscosity was determined by rotational viscosity measurements using a Brookfield viscometer (spindle LV 1, 10 rpm) according to DIN EN ISO 3219. All viscosity values ​​are for 25°C and atmospheric pressure of 1013 mbar unless otherwise stated.

[0125] Molecular composition: Molecular composition was determined by nuclear magnetic resonance spectroscopy (see ASTM E 386:35 High-Resolution Nuclear Magnetic Resonance Spectroscopy (NMR): Terminology and Symbols for terminology). 1 H nucleus and 29 Determined by measuring Si nuclei.

[0126] Description of 1H NMR measurements Solvent: CDCl3, 99.8%d Sample concentration: approx. 50 mg / 1 ml CDCl3 in a 5 mm NMR tube Measured without the addition of TMS, see spectrum of CHCl3 residue in CDCl3 (7.24 ppm 5) Spectrometer: Bruker Avance 400 Sample head: 5 mm BBO sample head or SMART sample head (Bruker) Measurement parameters: 10 Pulprog = zg30 TD = 64k NS = 64 or 128 (depending on sample head sensitivity) SW = 20.6 ppm AQ = 3.17 s 15 D1 = 5 s SFO1 = 500.13 MHz O1 = 6.175 ppm Processing parameters: SI = 32k 20 WDW = EM LB = 0.3 Hz

[0127] Depending on the type of spectrometer used, individual adjustment of measurement parameters may be required.

[0128] 29 Description of Si NMR measurements Solvent: C6D6 99.8%d / CCl4 1:1 v / v with 1 wt% Cr(acac)3 as relaxation agent Sample concentration: approximately 2 g / 1.5 ml solvent in a 10 mm NMR 30 tube Spectrometer: Bruker Avance 400 Sample head: 10 mm 1 H / 13 C / 15 N / 29 Si glass-free QNP sample head (manufactured by Bruker) Measurement parameters: Pulprog = zgig60 TD = 64k NS = 1024 (depending on the sensitivity of the sample head) SW = 200 ppm AQ = 2.75 s D1 = 4 s SFO1 = 300.13 MHz O1 = -50 ppm 5 Processing parameters: SI = 64k WDW = EM LB = 0.3 Hz

[0129] Depending on the type of spectrometer used, individual adjustment of measurement parameters may be required.

[0130] Molecular weight distribution: The molecular weight distribution is determined as weight average Mw and number average Mn by gel permeation chromatography (GPC or size exclusion chromatography (SEC)) using polystyrene standards and a refractive index detector (RI detector). Unless otherwise specified, THF is used as the eluent, and DIN 55672-1 is used. The polydispersity is the quotient Mw / Mn.

[0131] Glass transition temperature: The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, open crucible, heating rate 10 K / min.

[0132] Particle size determination: Particle size (z-average particle size) was measured by dynamic light scattering (DLS) using a Malvern Zetasizer Nano ZS Particle Size Analyzer. The polydispersity index (PDI) of particle size indicates the width of the particle size distribution.

[0133] Tack Measurement: Tack was measured on a 381 micron wet adhesive film stretched onto MYLA™ film. The MYLAR™ film was corona treated as needed. Probe tack was measured using a TA.XT plus Texture Analyzer equipped with a TA-57R probe and a TA-303 instrument for consistent placement of the substrate being tested. Peak tack was reported for each sample and is expressed in grams of force (gf). This is the force required for the probe head to contact the sample surface and then be pulled away from the sample. For each example, five samples were taken and tested. The final peak tack value is the arithmetic mean of the five corresponding peak tack results, unless otherwise noted.

[0134] 180° peel stress measurement The adhesive composition was coated onto MYLAR® film at a wet film thickness of 381 microns. The MYLAR® film was corona treated as needed. After coating, the film was cured in a 60°C oven for 15 minutes. The Mylar®-backed sample was cooled and applied to a polished stainless steel test plate. The sample was allowed to rest on the steel plate for either 30 minutes or 1 hour. Peel strength was measured using a Shimadzu AGS-X-10kNX tensile tester at a speed of 300 mm / min or a Cheminstruments AR-1000 adhesion and peel tester at a speed of 12 inches / min.

[0135] Measurement of static shear stress An appropriate thickness of adhesive composition was coated onto MYLAR® film. The film was dried in a 60°C oven for 15 minutes. The MYLAR®-backed sample was cooled and attached to a cut, polished stainless steel plate. A rubber roller loaded with a 5 lb. load applied four strokes (two sets of back and forth strokes) to the sample portion of the steel plate. The steel plate was placed in a vertical sample holder and a 1 kg weight was attached. The measured sample contact area was 1 inch x 0.5 inch. The time until the weight fell, i.e., failure of adhesion, was measured.

[0136] Volatile Organic Carbon (VOC) Measurement: Measurement of Volatile Organic Carbon (VOC) VOC was measured according to EPA Test Method 24.

[0137] Water contact angle measurement: Water contact angles were measured on dried adhesive films on aluminum Q panels using a KRUSS Mobile Surface Analyzer.

[0138] Water vapor transmission rate measurement: The adhesive composition was coated onto a nonwoven fabric at a wet film thickness of 203.2 microns. The film was dried in a 60°C oven for 15 minutes. The nonwoven-backed samples were cooled, cut into 5.6 cm diameter circles, and mounted in GARDCO® Perm cups pre-filled with 10.00±0.05 g of deionized water. Water vapor transmission rates were measured using the "Wet (Pain) Cup Method" of ASTM D1653.

[0139] Franz Cell: The examples provided below, which refer to the release of melatonin or niacinamide, were performed using Franz diffusion cells (Franz cells) through a disk of cellulose acetate membrane. The Franz cell described in the examples was a DHC-6AT Dry Heat Transdermal Diffusion Cell Transdermal Systems, available from Logan Instruments Corp. The molecular weight cutoff of the cellulose acetate membrane was 12-14. Prior to use in the study, each cellulose acetate membrane was soaked in a 20% EtOH solution in water for 1 hour to remove unbound chemicals.

[0140] To study the release of the active substances mentioned in Examples 7 and 8, gel samples were formed and cut into circular, 1.5 cm diameter sections. These sections were attached to cellulose acetate membranes, and the release of melatonin or niacinamide was measured. In these examples, a 20% EtOH solution in water was used as the receptor cell solution. The solution was stirred at a constant speed of approximately 600 rpm, and the receptor cell temperature of the Franz cell was set at 37°C. Solution samples were taken at various time points throughout the study. After each solution sample, a 1.00 mL aliquot was removed and replaced with a fresh volume of the same solution. In Examples 7 and 8, the concentrations of melatonin and niacinamide in the collected samples were measured by high-pressure liquid chromatography.

[0141] Preparation of Ethylenically Functionalized Silicone Resin B1 by Cocondensation of Ethoxy-Functionalized Silicone Resin with Methacryloxypropyltrimethoxysilane (CH3O)3Si(CH2)3OC(=O)C(CH3)=CH2

[0142] The methacryloxypropyl-functional silicone resin was prepared by condensing tetraethylsilicate oligomer with an average degree of oligomerization of 9, hexamethyldisiloxane, 3-methacryloxypropyltrimethoxysilane, and a low-viscosity OH-terminated polydimethylsiloxane with an average of 45 siloxane units. The condensation reaction is carried out in the presence of water and catalytic hydrochloric acid. The detailed procedure is described in U.S. Patent Application Publication No. 2018 / 0305576. The resin is diluted with 25% butyl acrylate. The following are the properties of the methacryloxypropyl-functional silicone resin: Molecular weight: M w = 4018 g / mol M n = 1557 g / mol PD = 2.58 1 H NMR and 29 Molecular composition from Si NMR Me3SiO 1 / 2 : 23.18 mol % Me2SiO 2 / 2 : 20.66 mol % ((CH2)3OC(=O)C(CH3)=CH2)SiO 3 / 2 : 0.72 mol % SiO 4 / 2 : 37.30 mol % EtO-Si: 3.68 mol % MeO-Si: 0.12 mol %

[0143] Example 1: Preparation of an aqueous dispersion of a copolymer from an ethylenically functionalized silicone resin B1 and an organic acrylic monomer (1:9 silicone:organic acrylic monomer)

[0144] Step 1: Preparation of miniemulsion The miniemulsion is prepared by dissolving the silicone resin B1, which is a mixture of (meth)acrylic monomers, followed by high-pressure homogenization. In this example, the miniemulsion was prepared using an IKA® HPH 2000 / 5 high-pressure homogenizer.

[0145] The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 1]

[0146] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 2]

[0147] The pre-emulsion was passed through a high-pressure homogenizer at a pressure of 400 to 800 bar to obtain a mini-emulsion with a z-average particle size of 233 nm (PDI = 0.32).

[0148] Step 2: Polymerization A 3-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 236.11 grams of deionized water and 68 grams of the miniemulsion prepared in step 1 as initial charges and heated to 50°C with stirring. One sealable vessel was charged with a 70 wt% strength aqueous solution of 6.26 grams of tert-butyl hydroperoxide (TBHP) diluted with 40.38 grams of deionized water (Feed 1). A second sealable vessel was charged with a solution of 2.19 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 42.42 grams of reverse osmosis water (Feed 2). A third vessel was charged with 855.7 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started at a rate of 220 μL / min, followed by Feed 3 at a rate of 5.0 mL / min. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 8 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 0.25g) was added and the product was filtered through a 100µm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.02; Glass transition temperature: -41.9℃; Solid content: 41.4 wt%; Residual free monomer: <300 ppm; Freshly prepared z-average particle size: 129 nm (PDI = 0.10); z-average particle size measured after 840 days of standing at 25°C: 117 nm (PDI = 0.02); Viscosity (Brookfield): 18.3 mPa.s Stability: The dispersion is stable with no observable phase separation for more than 720 days at 25°C. VOC: 1.1 wt%

[0149] When an aqueous dispersion of the copolymer was applied to a substrate and cured to form a film, the adhesive composition had the following properties: Peak Tack: 492 ± 36.6 gf 180° Peel Stress: 1299 ± 100.6 mN / mm (33.0 ± 2.6 N / in) Shear strength: 4.3 ± 1.1 min Water contact angle: 120.8±0.5°

[0150] The adhesive composition of Example 1 can be used as a PSA.

[0151] Example 2: Preparation of an aqueous dispersion of a copolymer from linear methacryloxypropyl-terminated polydimethylsiloxane (1:9 silicone:organic acrylic monomer)

[0152] Step 1: Preparation of miniemulsion The silicone component was a linear methacryloxypropyl-terminated polydimethylcycloane containing approximately 333 siloxane units.

[0153] The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 3]

[0154] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 4]

[0155] The pre-emulsion was passed through an IKA® HPH 2000 / 5 high-pressure homogenizer at a pressure of 400-800 bar, resulting in a mini-emulsion with a z-average particle size of 405 nm (PDI=0.5).

[0156] Step 2: Polymerization A 3-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 250 grams of reverse osmosis water and 72 grams of the miniemulsion prepared in step 1 as initial charges and heated to 50°C with stirring. One sealable vessel was charged with a 70 wt% strength aqueous solution of 6.61 grams of tert-butyl hydroperoxide (TBHP) diluted with 39.56 grams of deionized water (Feed 1). Another sealable vessel was charged with a solution of 2.32 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 44.93 grams of reverse osmosis water (Feed 2). A third vessel was charged with 828 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started at a rate of 220 μL / min, followed by Feed 3 at a rate of 5.0 mL / min. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 8 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 0.25g) was added and the product was filtered through a 100µm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.03; Glass transition temperature: -48.3℃; Solid content: 47.9 wt%; Residual free monomer: 3300 ppm; z-average particle size: 126 nm (PDI = 0.11); z-average particle size measured after 860 days of standing at 25°C: 114 nm (PDI = 0.13); Viscosity (Brookfield): 440 mPa.s Stability: The dispersion is stable with no observable phase separation for more than 720 days at 25°C. VOC: 1.6 wt%

[0157] When an aqueous dispersion of the copolymer was applied to a substrate and cured to form a film, the adhesive composition had the following properties: Peak Tack: 651 ± 254gf 180° Peel Stress: 522.8 ± 93.23 mN / mm (13.3 ± 2.4 N / in) Shear strength: 28.8 ± 6.1 min Water contact angle: 114.9±2.3°

[0158] The adhesive composition of Example 2 can be used as a PSA.

[0159] Example 3: Preparation of an aqueous dispersion of a copolymer of silicone resin B1 and organic acrylic monomers (1:9 silicone:organic acrylic monomers with a slightly higher amount of polymerized surfactant)

[0160] Step 1: Preparation of miniemulsion The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 5]

[0161] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 6]

[0162] The pre-emulsion was passed through an IKA® HPH 2000 / 5 high-pressure homogenizer at a pressure of 400-800 bar, resulting in a mini-emulsion with a z-average particle size of 272 nm (PDI=0.3).

[0163] Step 2: Polymerization A 3-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 250 grams of reverse osmosis water and 72 grams of the miniemulsion prepared in step 1 as initial charges and heated to 50°C with stirring. One sealable vessel was charged with a 70 wt% strength aqueous solution of 6.61 grams of tert-butyl hydroperoxide (TBHP) diluted with 39.54 grams of deionized water (Feed 1). A second sealable vessel was charged with a solution of 2.37 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 44.94 grams of reverse osmosis water (Feed 2). A third vessel was charged with 825 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started at a rate of 220 μL / min, followed by Feed 3 at a rate of 5.0 mL / min. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 8 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 0.24g) was added and the product was filtered through a 100µm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.02; Glass transition temperature: -42.2℃; Solid content: 46.5 wt%; Residual free monomer: 4050 ppm; z-average particle size: 132 nm (PDI = 0.11); Viscosity: 167 mPa.s Stability: The dispersion is stable with no observable phase separation for more than 720 days at 25°C. VOC: 1.9 wt%

[0164] When an aqueous dispersion of the copolymer was applied to a substrate and cured to form a film, the adhesive composition had the following properties: Peak Tack: 989 ± 23.7 gf 180° Peel Stress: 1646 ± 63.25 mN / mm (41.8 ± 1.6 N / in) Shear strength: 8.3 ± 2.5 min Water contact angle: 119.9±1.0° Water vapor transmission rate: 780 g / m 2 / day

[0165] The adhesive composition of Example 3 can be used as a PSA.

[0166] Example 4: Preparation of an aqueous dispersion of a copolymer of silicone resin B1 and organic acrylic monomer (1:1 silicone:organic acrylic monomer)

[0167] Step 1: Preparation of miniemulsion The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 7]

[0168] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 8]

[0169] The pre-emulsion was passed through an IKA® HPH 2000 / 5 high-pressure homogenizer at a pressure of 400-800 bar, resulting in a mini-emulsion with a z-average particle size of 227 nm (PDI=0.2).

[0170] Step 2: Polymerization A 3-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 241.3 grams of reverse osmosis water and 69.5 grams of the miniemulsion prepared in step 1 as initial charges and heated to 50°C with stirring. One sealable vessel was charged with a 70 wt% strength aqueous solution of 6.36 grams of tert-butyl hydroperoxide (TBHP) diluted with 38.16 grams of deionized water (Feed 1). A second sealable vessel was charged with a solution of 2.28 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 43.32 grams of reverse osmosis water (Feed 2). A third vessel was charged with 799 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started at a rate of 220 μL / min, followed by Feed 3 at a rate of 5.0 mL / min. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 8 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 0.24g) was added and the product was filtered through a 100µm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.04; Glass transition temperature: -40.3℃; Solid content: 45.9 wt%; Residual free monomer: 1381 ppm; z-average particle size: 182 nm (PDI = 0.19); Viscosity: 17 mPa.s VOC: 1.51 wt%

[0171] When an aqueous dispersion of the copolymer was applied to a substrate and cured to form a film, the adhesive composition had the following properties: Peak Tack (381 microns wet thickness): 289 ± 49 gf 180° Peel Stress: 815 mN / mm (20.7 N / inch) Water vapor transmission rate: 790 g / m 2 / day

[0172] The adhesive composition of Example 4 can be used as a PSA.

[0173] Example 5: Preparation of an aqueous dispersion of a copolymer of methacryloxypropyltris(trimethylsiloxysilane) and an organic acrylic monomer (7:3 silane:organic acrylic monomer)

[0174] Step 1: Preparation of miniemulsion The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 9]

[0175] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 10]

[0176] The pre-emulsion was passed through an IKA® HPH 2000 / 5 high-pressure homogenizer at a pressure of 400-800 bar, resulting in a mini-emulsion with a z-average particle size of 936.5 nm (PDI=0.3).

[0177] Step 2: Polymerization A 3-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 201.10 grams of reverse osmosis water and 57.90 grams of the miniemulsion prepared in step 1 as an initial charge and heated to 50°C with stirring. One of the sealable vessels was charged with a 70 wt% strength aqueous solution of 5.30 grams of tert-butyl hydroperoxide (TBHP) diluted with 31.80 grams of deionized water (Feed 1). A second sealable vessel was charged with a solution of 1.90 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 36.10 grams of reverse osmosis water (Feed 2). A third vessel was charged with 665.90 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started at a rate of 220 μL / min, followed by Feed 3 at a rate of 5.0 mL / min. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 8 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 0.20 g) was added and the product was filtered through a 100 μm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.00; Glass transition temperature: -47.6℃; Solid content: 49.8 wt%; Residual free monomer: 2961 ppm; z-average particle size: 269 nm (PDI = 0.04); Viscosity: 126 mPa.s VOC: 1.46 wt%

[0178] When an aqueous dispersion of the copolymer was applied to a substrate and cured to form a film, the adhesive composition had the following properties: Peak Tack: 809 ± 168.9 gf 180° Peel Stress: 886 mN / mm (22.5 N / inch) Water vapor transmission rate: 1160 g / m 2 / day

[0179] The adhesive composition of Example 5 can be used as a PSA.

[0180] Example 6: Preparation of an aqueous dispersion of silicone resin B1, a copolymer of methacryloxypropyltris(trimethylsiloxysilane) and organic acrylic monomers (14:1 (silicone + silane):organic acrylic monomers)

[0181] Step 1: Preparation of miniemulsion The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 11]

[0182] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 12]

[0183] The pre-emulsion was passed through an IKA® HPH 2000 / 5 high-pressure homogenizer at a pressure of 400-800 bar, resulting in a mini-emulsion with a z-average particle size of 296 nm (PDI=0.3).

[0184] Step 2: Polymerization A 1-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 152.81 grams of reverse osmosis water and 44.00 grams of the miniemulsion prepared in step 1 as an initial charge and heated to 50°C with stirring. One of the sealable vessels was charged with a 70 wt% strength aqueous solution of 1.35 grams of tert-butyl hydroperoxide (TBHP) diluted with 25.36 grams of deionized water (Feed 1). A second sealable vessel was charged with a solution of 0.47 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 26.23 grams of reverse osmosis water (Feed 2). A third vessel was charged with 665.90 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started at a rate of 220 μL / min, followed by Feed 3 at a rate of 5.0 mL / min. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 8 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 0.15g) was added and the product was filtered through a 100µm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.01; Glass transition temperature: -59.0℃; Solid content: 47.4 wt%; Residual free monomer: 2740 ppm; z-average particle size: 292 nm (PDI = 0.4); Viscosity: 50mPa.s VOC: 1.37 wt%

[0185] When an aqueous dispersion of the copolymer was applied to a substrate and cured to form a film, the adhesive composition had the following properties: Peak Tack (1 wt% of wetting agent WACKER® L067 was blended into the dispersion prior to film drawdown): 510±50 gf 180° Peel Stress (film drawdown with 1 wt% wetting agent L067): 91 mN / mm (2.3 N / in) Water vapor transmission rate: 820 g / m 2 / day

[0186] The adhesive composition of Example 6 can be used as a PSA.

[0187] Example 7: Melatonin release The controlled release of melatonin from the copolymer samples was measured as the inverse of time (min 1 / 2 ) versus cumulative flow rate Q (μg / cm 2 The viscosity is reported as % tack, and was determined by adding melatonin to a copolymer dispersion (Example 4, RH47). Samples were prepared by mixing 0.069 g of melatonin with 10,000 g of the copolymer dispersion (approximately 1.5 wt% melatonin solids content). A film was formed from the mixture. The film had a thickness of 381 microns after being drawn with a film applicator onto a corona-treated MYLART™ sheet and cured in an oven at 80°C for 10 minutes. After film formation, the film's tack was measured at 248 gf.

[0188] To measure the release of melatonin from the film, the sample was mounted in a Franz cell. As shown in Figure 1, the release of melatonin from the sample was 256.5 μg / cm after 24 hours. 2 The release profile shown in Figure 1 demonstrates a controlled release of melatonin, as evidenced by the positive correlation between release and the inverse of time.

[0189] Example 8: Niacinamide Release The controlled release of niacinamide from the copolymer samples was measured as the inverse of time (min 1 / 2 ) versus cumulative flow rate Q (μg / cm 2The viscosity is reported as % niacinamide (H2O), and was determined by adding niacinamide to a copolymer dispersion (Example 4, RH47). A sample was prepared by mixing 0.237 g of melatonin with 10.00 g of the copolymer dispersion (approximately 5.0 wt% melatonin solids content). A film was formed from the mixture. The film had a thickness of 381 microns after being drawn with a film applicator onto a corona-treated MYLART™ sheet and cured in an oven at 80°C for 10 minutes. After film formation, the tack of the film was measured at 825 gf.

[0190] To measure the release of niacinamide from the films, the samples were mounted in Franz cells. As shown in Figure 2, the release of melatonin from the samples was 79.2 μg / cm after 24 hours. 2 The release profile shown in Figure 2 demonstrates a controlled release of melatonin, as evidenced by the positive correlation between release and the inverse of time.

[0191] Example 9: Transfer coating of adhesive composition An aqueous dispersion of the copolymer from Example 5 was mixed with a wetting agent, WACKER Fluid L067 (1% by weight of the PSA dispersion). An adhesive film with a wet thickness of 127 microns was formed on a strip of 3M® Medical Release Liner 9955 (fluoropolymer-coated polypropylene) and cured in a 60°C oven for 15 minutes. The resulting adhesive-coated strip was applied to the target substrate (facestock) (stainless steel, aluminum, Mylar®, polyurethane) using four strokes (two sets of back and forth strokes) of a rubber roller loaded with a 5 lb. load, applying pressure. After a 5-minute dwell time, the adhesive-coated strip was peeled from the substrate. The adhesive film transferred to the substrate, resulting in a continuous adhesive film of approximately 25.4 to 38.1 microns in thickness on each substrate.

[0192] Comparative Example 1: Preparation of a solvent-based silicone-acrylic hybrid adhesive prepared from silicone resin B1 and an organic acrylic monomer

[0193] A 250 mL four-neck round bottom flask equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with the following ingredients: [Table 13]

[0194] The ingredients were stirred until uniform. 10 grams of initiator azobisisobutyronitrile was added with stirring. The mixture was heated to 70°C under nitrogen with continuous stirring. After 10 minutes of stirring, the reaction mixture turned into an inworkable gel.

[0195] Comparative Example 2: Water-boron silicone-acrylic hybrid without adhesive properties prepared according to US Patent Application Publication No. 2018 / 0305576

[0196] Step 1: Preparation of miniemulsion The following ingredients were added to a sealable container and mixed on an orbital shaker: [Table 14]

[0197] The resulting mixture was combined with a solution of the following ingredients and mixed on an orbital shaker for approximately 1 hour: [Table 15]

[0198] The pre-emulsion was passed through an IKA® HPH 2000 / 5 high-pressure homogenizer at a pressure of 400-800 bar, resulting in a mini-emulsion with a z-average particle size of 185.3 nm (PDI=0.2).

[0199] Step 2: Polymerization A 10-liter polymerization vessel equipped with an anchor stirrer, reflux condenser, thermometer, and nitrogen inlet was charged with 1278 grams of reverse osmosis water and 320 grams of the miniemulsion prepared in step 1 as initial charges and heated to 50°C with stirring. One of the sealable vessels was charged with a 70 wt% strength aqueous solution of 29.32 grams of tert-butyl hydroperoxide (TBHP) diluted with 96.56 grams of deionized water (Feed 1). A second sealable vessel was charged with a solution of 10.28 grams of formaldehyde-free reducing agent (Bruggolite® FF6 M) in 107.21 grams of reverse osmosis water (Feed 2). A third vessel was charged with 3976.3 grams of miniemulsion (Feed 3). Feeds 1 and 2 were started, followed by Feed 3. All three feeds were metered continuously over a period of 165 minutes. Feeds 1 and 2 were continued for an additional 30 minutes after the completion of Feed 3, and the reaction was then held at 50°C for an additional 60 minutes. After cooling to room temperature, the product was adjusted to pH 6.5 by the addition of aqueous ammonia. Biocide (Acticide BW 20, 1.11 g) was added and the product was filtered through a 100 μm filter to give an aqueous dispersion of copolymer with the following properties: Specific gravity: 1.05; Glass transition temperature: 13.7℃; Solid content: 45.8%; Residual free monomer: 1768 ppm; Z-average particle size: 119.5 nm (PDI = 0.19)

[0200] Films stretched from the copolymer dispersions showed no tack after curing.

[0201] It will be apparent from the foregoing detailed description that various modifications, additions, and other alternative embodiments are possible without departing from the true scope and spirit. The embodiments and examples discussed herein have been chosen and described to provide the best explanation of the principles of the invention and its practical application, thereby enabling those skilled in the art to use the invention in various embodiments and with various modifications suited to the particular uses contemplated. It is to be understood that all such modifications and variations are within the scope of the invention.

Claims

1. 1. A method for forming an aqueous dispersion of a copolymer, comprising:

1. A process for preparing a copolymerizable composition in water, the copolymerizable composition comprising: a) 5 to 95 weight percent of an ethylenically functionalized silicone polymer or silane, based on the total weight of the copolymerizable composition; and b) 5% by weight or more of an organic acrylic monomer, based on the total weight of the copolymerizable composition. a process comprising: providing 0.1 to 10 wt % of a surfactant, based on the total weight of the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer; polymerizing the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer to form an aqueous dispersion of a copolymer; Including, wherein the copolymer exhibits a glass transition temperature (Tg) of 0 to -100°C, Tg being determined by differential scanning calorimetry in an open crucible at a heating rate of 10°K per minute according to DIN 53765; method.

2. 10. The method of claim 1, further comprising forming a mini-emulsion comprising the ethylenically functionalized silicone polymer or silane, the organic acrylic monomer, and the surfactant, and introducing an initiator, wherein the organic acrylic monomer comprises one or more acrylate or acrylic acid monomers, and wherein the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized in the presence of the surfactant and water.

3. 10. The method of claim 1, further comprising forming a mini-emulsion comprising organic droplets, wherein the organic droplets comprise the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer before the ethylenically functionalized silicone polymer or silane and the organic acrylic monomer are polymerized.

4. 10. The method of claim 1, further comprising the step of curing the aqueous dispersion of copolymer by heating the aqueous dispersion to evaporate water therefrom.

5. 10. The method of claim 1, wherein the aqueous dispersion of the copolymer comprises a solids content of 40 wt% or greater, based on the total weight of the aqueous dispersion.

6. 10. The method of claim 1, wherein the aqueous dispersion of the copolymer comprises a solids content of 40 to 70 wt %, based on the total weight of the aqueous dispersion.

7. The method of claim 1, wherein the copolymer exhibits a Tg of from -10 to -60°C.

8. 10. The method of claim 1, wherein the copolymer has a z-average particle size of 1000 nanometers or less as measured by dynamic light scattering.

9. 10. The method of claim 1, wherein the aqueous dispersion of the copolymer exhibits a viscosity of 1 to 20,000 mPa·s at 25°C.

10. 10. An adhesive composition comprising the copolymer formed by the method of claim 1, An adhesive composition wherein a film of the adhesive composition having a wet thickness of 381 microns exhibits a peak tack of 100 grams of force or greater after curing as measured with a TA.XT Plus Texture Analyzer using a TA-57R probe and a TA-303 instrument.

11. 11. The adhesive composition of claim 10, further comprising an active compound capable of being released at a controlled rate from the matrix formed by said copolymer.

12. 11. The adhesive composition of claim 10, wherein the adhesive composition is stable to phase separation at 25°C as assessed by the absence of observable phase separation for 180 days.

13. 11. The adhesive composition of claim 10, wherein the adhesive composition has a volatile organic content of 2.5% or less according to EPA Test Method 24.

14. The adhesive composition of claim 10, wherein the film exhibits a peak tack of 100 to 1000 grams of force.

15. 11. The adhesive composition of claim 10, wherein the composition is stable to phase separation at 25°C as assessed by not having more than a 20% variation in z-average particle size.

16. The adhesive composition of claim 10, wherein the adhesive composition is a pressure sensitive adhesive.

17. 11. A film comprising the adhesive composition of claim 10, which exhibits no residual transfer upon contact.

18. The adhesive composition of claim 10; and a substrate having the adhesive composition disposed thereon; 1. An article comprising: said adhesive composition forming a film on a polymer substrate, said film having a wet thickness of 381 microns, and after curing at 60°C for 15 minutes, a stainless steel plate is applied to the outer surface of said film, allowed to stand for 30 minutes, and then the stainless steel plate is peeled off at a rate of 300 mm / min (12 in / min), and said film has a 180 degree peel strength of 1.5 N / in or more when measured at a rate of 12 in / min using an adhesion / peel tester.

19. applying the adhesive composition of claim 10 to a substrate; and curing the composition; A method of coating a substrate, comprising:

20. 20. The method of claim 19, wherein the adhesive composition is applied by spraying, knife coating, roller coating, casting, drum coating, dipping and combinations thereof, or transfer coating methods.

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