Polydiorganosiloxane compositions, articles and methods containing antimicrobial agents

Abstract

A composition is described comprising a polydiorganosiloxane; a silver material; and at least 1% by weight of an oxygen-containing metal filler of silicone, titanium, zirconium, or combinations thereof. The crosslinked composition may have a higher tensile strength than the same composition without the oxygen-containing metal filler. In some embodiments, the polydiorganosiloxane comprises a nonfunctional polydiorganosiloxane. In another embodiment, a method of manufacturing an adhesive article is described, comprising providing a layer of a polydiorganosiloxane composition on a substrate (e.g., a release liner), wherein the layer comprises a nonfunctionalized polydiorganosiloxane and a silver material; and subjecting the layer of the polydiorganosiloxane composition to radiation treatment, thereby crosslinking the layer of the polydiorganosiloxane composition.

Description

Summary of the Invention

[0001] In one embodiment, a composition is described comprising a polydiorganosiloxane; a silver material; and at least 1% by weight of an oxygen-containing metal filler of silicone, titanium, zirconium, or combinations thereof. (Electron beam crosslinking) The composition may have a higher tensile strength than the same composition without the oxygen-containing metal filler. In some embodiments, the polydiorganosiloxane comprises a nonfunctional polydiorganosiloxane.

[0002] In another embodiment, a method of manufacturing an adhesive article is described, the method comprising: a) providing a layer of a polydiorganosiloxane composition on a substrate, wherein the layer comprises a nonfunctionalized polydiorganosiloxane and a silver material; and b) subjecting the layer of the polydiorganosiloxane composition to radiation treatment, thereby crosslinking the layer of the polydiorganosiloxane composition. The substrate is typically a release liner. In one embodiment, a first layer of the polydiorganosiloxane composition having the silver material is disposed on the substrate, and a second layer of the polydiorganosiloxane composition not containing the silver material is disposed on the first layer. In another embodiment, the first layer comprises (e.g., a silicate) tackifying resin, and the second layer does not contain (e.g., a silicate) tackifying resin.

[0003] Adhesive articles comprising layers of crosslinked polydiorganosiloxane compositions as described herein are also described.

[0004] In some implementations, the adhesive product is a medical product, such as medical tape, bandage, dressing, or pressure bandage.

[0005] In some implementations, the adhesive articles described herein are suitable for use as medical articles.

[0006] A method for using an adhesive article is also described, the method comprising providing the adhesive article as described herein and bringing it (e.g., a first primary surface) into contact with skin or a wound. Attached Figure Description

[0007] Figure 1 This is a schematic side view of an adhesive article comprising a cross-linked polydiorganosiloxane layer on a release liner; Figure 2 This is a schematic side view of an adhesive article comprising a cross-linked multilayer polydiorganosiloxane layer on a release liner; Figures 3 to 5 This is a schematic side view of an adhesive article comprising a cross-linked polydiorganosiloxane layer and a porous substrate on a release liner. Detailed Implementation

[0008] Adhesive products

[0009] refer to Figure 1 In one embodiment, the adhesive article 10 includes a cross-linked polydiorganosiloxane layer (120A) adjacent to (e.g., a release liner) a substrate (140). Figure 2 In another embodiment depicted, the adhesive article 50 includes a first crosslinked polydiorganosiloxane layer (120A) adjacent to (e.g., a release liner) a substrate (140) and a second crosslinked polydiorganosiloxane layer (120B) disposed on the first crosslinked polydiorganosiloxane layer (120A). Reference Figures 3 to 5 The crosslinking agent polydiorganosiloxane composition may also include a porous substrate (180, 280, 380).

[0010] The polydiorganosiloxane composition has layers with a first primary surface (121, 221, 321) adjacent to the release liner carrier (140, 240, 340) and opposing second primary surfaces (123, 223, 323). The primary surfaces are generally parallel to each other. The thickness of one or more layers is the distance in a direction orthogonal to the primary surfaces. In some embodiments, the first primary surface is a pressure-sensitive adhesive, and the opposing second primary surface is a film backing.

[0011] In some implementations, the second peeling liner contacts the surface of the membrane backing.

[0012] In another embodiment, the adhesive (e.g., tape) article may comprise a cross-linked layer of a polydiorganosiloxane composition without a release liner. The adhesive (e.g., tape) article is wound in a roll such that the backing surface is in contact with the pressure-sensitive adhesive surface.

[0013] In some embodiments, the cross-linked layer of the polydiorganosiloxane composition is suitable for medical products such as medical tapes, bandages, wound dressings, IV site dressings, pressure bandages, surgical drapes, prostheses, ostomy or ostomy bags, oral patches, or transdermal patches. In some embodiments, the cross-linked layer of the polydiorganosiloxane composition can also be used in other products, including dentures and wigs.

[0014] In some embodiments, the cross-linked layer of the polydiorganosiloxane composition is suitable for contact with the skin or other tissues of humans and / or animals.

[0015] Polydiorganosiloxane Composition

[0016] Silicone gel materials have been used in medical therapies to promote scar tissue healing. Slightly cross-linked silicone gels are soft, tacky, and elastic materials with low to moderate adhesive strength compared to traditional tackifying silicone PSA. Silicone gels are generally softer than silicone PSA, resulting in less discomfort when adhering to and removing from the skin. This combination of relatively low adhesive strength and moderate tack makes silicone gels suitable for gentle adhesive applications on the skin.

[0017] The cross-linked siloxane network can be formed from functional or non-functional organosilicon materials. However, in some embodiments, non-functional polydiorganosiloxanes are preferred. When the siloxane network is formed from a functional organosilicon material, the functional groups can react or, in other words, cure, which can also be characterized as cross-linking. Due to the very low glass transition temperature (Tg) and modulus of the polysiloxane network, these gel adhesives exhibit excellent wetting properties.

[0018] Organosilicon materials are polydiorganosiloxanes, i.e., materials comprising a polysiloxane backbone. In some embodiments, nonfunctionalized organosilicon materials can be linear materials described by the following formula, which exemplifies a siloxane backbone having aliphatic and / or aromatic substituents:

[0019] R1, R2, R3, and R4 are independently selected from the group consisting of alkyl and aryl groups, each R5 is an alkyl group, and n and m are integers, with at least one of m or n being non-zero. In some embodiments, one or more of the alkyl or aryl groups may contain a halogen substituent, such as fluorine. For example, in some embodiments, one or more alkyl groups may be -CH2CH2C4F9.

[0020] In some embodiments, R5 is a methyl group, i.e., the nonfunctionalized polydiorganosiloxane material is end-capped with a trimethylsiloxy group. In some embodiments, R1 and R2 are alkyl groups, and n is zero, i.e., the material is poly(dialkylsiloxane). In some embodiments, the alkyl group is a methyl group, i.e., poly(dimethylsiloxane) (“PDMS”). In some embodiments, R1 is an alkyl group, R2 is an aryl group, and n is zero, i.e., the material is poly(alkylarylsiloxane). In some embodiments, R1 is a methyl group, and R2 is a phenyl group, i.e., the material is poly(methylphenylsiloxane). In some embodiments, R1 and R2 are alkyl groups, and R3 and R4 are aryl groups, i.e., the material is poly(dialkyldiarylsiloxane). In some embodiments, R1 and R2 are methyl groups, and R3 and R4 are phenyl groups, i.e., the material is poly(dimethyldiphenylsiloxane).

[0021] In some embodiments, the nonfunctionalized polydiorganosiloxane material may be branched. For example, one or more of the R1, R2, R3 and / or R4 groups may be linear or branched siloxanes having alkyl or aryl (including haloalkyl or aryl) substituents and a terminal R5 group.

[0022] As used herein, a “nonfunctional group” is an alkyl or aryl group consisting of carbon, hydrogen, and, in some embodiments, a halogen (e.g., fluorine) atom. As used herein, a “nonfunctionalized polydiorganosiloxane material” is a polydiorganosiloxane material in which the R1, R2, R3, R4, and R5 groups are nonfunctional groups.

[0023] Typically, functionalized organosilicon systems include specific reactive groups (e.g., hydrogen, hydroxyl, vinyl, allyl, or acrylic groups) attached to the polysiloxane backbone of the starting material. As used herein, a “functionalized polydiorganosiloxane material” is a material in which at least one of the R groups of Formula 2 is a functional group.

[0024]

[0025] In some embodiments, the functionalized polydiorganosiloxane material comprises at least two R-groups that are functional groups. Typically, the R-groups of Formula 2 can be chosen independently. In some embodiments, at least one functional group, such as a hydride group, hydroxyl group, alkoxy group, vinyl group, epoxy group, and acrylate group. When the polydiorganosiloxane is a nonfunctional polydiorganosiloxane, the polydiorganosiloxane does not contain such functional groups.

[0026] In addition to the functional R groups, some R groups can be non-functional groups, such as alkyl or aryl groups, including haloalkyl (e.g., fluorinated) and aryl groups. In some embodiments, the functionalized polydiorganosiloxane material can be branched. For example, one or more R groups can be linear or branched siloxanes having functional and / or non-functional substituents.

[0027] Polydiorganosiloxanes (such as polydimethylsiloxane PDMS) can be oils, fluids, gums, elastomers, or resins, such as brittle solid resins. Materials with lower molecular weights and lower viscosity are referred to as fluids or oils, while materials with higher molecular weights and higher viscosity are referred to as gums; however, there is no clear distinction between these terms. Silicone oils are commercially available (e.g., from Wacker) and have a viscosity of 0.65 mPa at 25°C. s to 1,000,000 mPa In typical embodiments, a high-viscosity (e.g., nonfunctional) liquid polydiorganosiloxane is preferred. In some embodiments, the liquid polydiorganosiloxane has a viscosity of at least 50,000 mPa at 25°C. s, 100,000 mPa s, 250,000 mPa s, 500,000 mPa s, 750,000 mPa s or 1,000,000 mPa When using polydiorganosiloxane adhesive, the viscosity at 25°C can exceed 1,000,000 mPa. s.

[0028] Skin-friendly adhesives are prepared by optionally combining one or more polydiorganosiloxane materials (e.g., silicone oils or fluids) with a suitable tackifying resin, coating the resulting combination, and crosslinking it using radiation (typically an electron beam (E-beam) or gamma radiation). Typically, any known additives that can be used in the adhesive formulation may also be included.

[0029] In some embodiments, silicate tackifying resins may be used. In some exemplary adhesive compositions, a variety of silicate tackifying resins may be used to achieve the desired properties.

[0030] Suitable silicate tackifying resins include those composed of the following structural units: M (i.e., monovalent R'3SiO) 1 / 2 unit), D (i.e., divalent R'2SiO), 2 / 2 Unit), T (i.e., trivalent R'SiO), 3 / 2 Unit) and Q (i.e., quaternary SiO) 4 / 2 (units) and combinations thereof. Typical exemplary silicate resins include MQ silicate tackifying resin, MQD silicate tackifying resin, and MQT silicate tackifying resin. These silicate tackifying resins typically have a number average molecular weight in the range of 100 gm / mol to 50,000 gm / mol, for example, 500 gm / mol to 15,000 gm / mol, and typically the R' group is a methyl group.

[0031] MQ silicate tackifying resin is a copolymer resin in which each M unit is bonded to a Q unit, and each Q unit is bonded to at least one other Q unit. Some Q units are bonded only to other Q units. However, some Q units are bonded to hydroxyl radicals, producing HOSiO 3 / 2 Unit (i.e., "T") OH (Unit), thereby obtaining the content of some silicon-bonded hydroxyl groups in the silicate tackifying resin.

[0032] Based on the weight of the silicate tackifying resin, the amount of silicon-bonded hydroxyl groups (i.e., silanols) on the MQ resin can be reduced to no more than 1.5 wt%, no more than 1.2 wt%, no more than 1.0 wt%, or no more than 0.8 wt%. This can be achieved, for example, by reacting hexamethyldisilazane with the silicate tackifying resin. This reaction can be catalyzed, for example, with trifluoroacetic acid. Alternatively, trimethylchlorosilane or trimethylsilylacetamide can be reacted with the silicate tackifying resin, in which case a catalyst is not necessary.

[0033] MQD silicone tackifying resin is a terpolymer having M, Q, and D units. In some embodiments, some methyl R' groups of the D unit can be replaced by vinyl (CH2=CH-) groups (“D…”). Vi (Unit) replacement. MQT silicate tackifying resin is a terpolymer having M, Q and T units.

[0034] Suitable silicate tackifying resins are commercially available from sources such as Dow Corning (e.g., DC 2-7066), Momentive Performance Materials (e.g., SR545 and SR1000), and Wacker Chemie AG (e.g., BELSIL TMS-803).

[0035] In some embodiments, the layer of the polydiorganosiloxane composition comprises at least 5%, 6%, 7%, 8%, 9%, or 10% by weight of a (e.g., silicate) tackifying resin. In some embodiments, the amount of (e.g., silicate) tackifying resin is no more than 20%, 25%, or 10% by weight. In some embodiments, the amount of (e.g., silicate) tackifying resin is less than 5%, 4%, 3%, 2%, or 1% by weight (e.g., zero).

[0036] In some embodiments, the polydiorganosiloxane composition comprises more than one layer. For example, a first layer may be disposed on a substrate (e.g., a release liner), and a second layer may be disposed on the first layer. In this embodiment, the first polydiorganosiloxane layer may contain a tackifying resin (e.g., silicate) in the described amount; while the second polydiorganosiloxane layer may not contain a tackifying resin (e.g., silicate) or may contain less tackifying resin (e.g., silicate) than the first polydiorganosiloxane layer.

[0037] In some embodiments, the polydiorganosiloxane composition may include any of a variety of other known fillers and additives, including but not limited to filler pigments, additives for improving adhesion, additives for improving moisture permeability, antimicrobial agents, pharmaceuticals, cosmetics, natural extracts, silicone waxes, silicone polyethers, hydrophilic polymers, and rheology modifiers. Additives for improving adhesion (particularly adhesion to wet surfaces) include polymers such as poly(ethylene oxide) polymers, poly(propylene oxide) polymers, and copolymers of poly(ethylene oxide) and poly(propylene oxide), acrylic polymers, hydroxyethyl cellulose polymers, silicone polyether copolymers, such as copolymers of poly(ethylene oxide) and polydiorganosiloxane, and copolymers of poly(propylene oxide) and polydiorganosiloxane, and blends thereof.

[0038] In some embodiments, the polydiorganosiloxane composition comprises up to 10%, 15%, 20%, 25%, or 30% by weight of other additives in the total polydiorganosiloxane composition. In other embodiments, the polydiorganosiloxane composition comprises less than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% by weight of other additives.

[0039] Polysiloxane materials, antimicrobial agents (e.g., silver materials), tackifying resins (if present), and any optional components can be combined using any of a variety of known methods prior to coating and crosslinking. For example, in some embodiments, the various components can be pre-blended using common equipment such as mixers, blenders, mills, extruders, etc.

[0040] In some embodiments, the material can be dissolved in a solvent, coated, and dried prior to crosslinking. In some embodiments, a solvent-free compounding and coating process can be used. In some embodiments, solvent-free coating can be performed at approximately room temperature. For example, in some embodiments, the material may have a kinematic viscosity of no more than 100,000 centistokes (cSt), such as no more than 50,000 cSt. However, in some embodiments, a hot-melt coating process such as extrusion can be used, for example, to reduce the viscosity of higher molecular weight materials to a value more suitable for coating. Various components can be added together in various combinations or individually through one or more separate ports of an extruder, blended (e.g., melt-mixed) within the extruder, and extruded to form a hot-melt coated composition.

[0041] silver compounds

[0042] The wound contact layer (e.g., the first primary surface) also includes a silver material, such as silver particles, ionic silver, and silver salts, to provide antimicrobial and / or bacteriostatic properties. The silver material may be distributed throughout the wound contact layer and on its surface. For example, in some embodiments, the silver material may include silver acetate, which may be added to a silicone composition. In some embodiments, the silver material may include other silver compounds, such as silver orthophosphate, silver sulfate, sodium zirconium hydrogen phosphate, silver lactate, silver-oxidized regenerated cellulose, and silver chloride.

[0043] In some embodiments, the silver material can be a slightly soluble silver compound, which provides a sustained release of silver ions over time, partly based on the limited solubility of silver ions and the inherent dissociation equilibrium constant. Silver compounds that can be used in this invention include silver oxide, silver sulfate, silver acetate, silver chloride, silver lactate, silver phosphate, silver sulfadiazine, silver stearate, silver thiocyanate, and silver carbonate.

[0044] In some implementations, higher valence silver oxide may be used, i.e., silver in the oxidation state of Ag(II) or Ag(III), as described in WO2005 / 056067.

[0045] Different combinations of silver-containing particles can be used.

[0046] Typically, the silver material is dispersed within the polydiorganosiloxane composition. In some embodiments, the polydiorganosiloxane composition contains at least 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% of silver material based on the total weight of the polydiorganosiloxane composition. The silver material typically does not exceed 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, or 5 wt%.

[0047] In another embodiment, the porous (e.g., mesh) substrate may be coated with a silver material, such as that described in WO2005 / 056067; which is incorporated herein by reference. In this embodiment, the porous substrate may contain no more than 10 mg / cm³ of silver. 2 Or 5mg / cm 2 Silver (e.g., compound) material. The amount of silver (e.g., compound) material can be 0.1 mg / cm³. 2 Up to 2 mg / cm 2 Within the specified range. A silver-coated porous (e.g., mesh) substrate is then bonded to a layer of the polydiorganosiloxane composition. In this embodiment, the polydiorganosiloxane composition may be silver-free.

[0048] Oxygen-containing metal fillers

[0049] In some embodiments, the polydiorganosiloxane composition comprises (e.g., biocompatible) oxygen-containing metal fillers. Typically, the metal is silicon, titanium, or zirconium. The covalently bonded oxygen-containing groups are typically oxides or hydroxyl groups.

[0050] In one embodiment, the oxygen-containing metal filler is silicic acid, which is a chemical compound containing elemental silicon attached to oxide (=O) and hydroxyl (-OH) groups, having the general formula... A representative formula is described below: .

[0051] Similarly, titanate is a substance with the general formula Chemical compounds.

[0052] In addition, zirconic acid, similar to silica, is known in its salt form (i.e., zirconate).

[0053] In some embodiments, oxygen-containing silica fillers are preferred. Other oxygen-containing silica fillers include, for example, precipitated silica (i.e., amorphous silica (silicon dioxide, SiO2)); and pyrolytic silica, also known as pyrolytic silica.

[0054] Oxygen-containing silica fillers are commercially available. Precipitated silica is available from Sigma Aldrich Chemie GmbH (Taufkirchen, Germany), and pyrolytic silica is available under the trade name HDK. ® Purchased from Wacker Chemie AG (Burghausen, Germany), and the pyrolytic silica can be traded under the name Aerosil. ® Purchased from Evonik Industries AG (Essen, Germany).

[0055] In some embodiments, the polydiorganosiloxane composition comprises at least 1 wt%, 2 wt%, 3 wt%, or 4 wt% of an oxygen-containing metal (e.g., silicon) filler, based on the total weight of the polydiorganosiloxane composition. The amount of the oxygen-containing metal (e.g., silicon) filler is typically no more than 30 wt%, 25 wt%, 20 wt%, 15 wt%, or 10 wt%.

[0056] hydrophilic components

[0057] In some embodiments, the polydiorganosiloxane composition comprises a hydrophilic component typically dispersed in an organosilicon gel. The hydrophilic component is a moisture-absorbing auxiliary agent.

[0058] In some embodiments, the hydrophilic component is a carbohydrate or a derivative thereof having at least three hydroxyl groups. Examples include sugars (e.g., monosaccharides, disaccharides, trisaccharides, polysaccharides) and naturally occurring polysaccharides (e.g., sodium carboxymethyl cellulose) and other modified cellulose derivatives (e.g., cellulose ethyl ether; cellulose ethyl hydroxyethyl ether; cellulose hydroxyethyl ether; cellulose methyl hydroxyethyl ether), alginate, sodium alginate, guar gum; amylopectin, pectin, gum arabic, and similar materials derived from carrageenan (from seaweed), pectin (from plant extracts), and xanthan gum (from microbial fermentation processes). Sodium alginate and carboxymethyl cellulose are generally preferred among ionic carbohydrate polymers.

[0059] Polydiorganosiloxane compositions may contain various combinations of hydrophilic components.

[0060] In some embodiments, the polydiorganosiloxane composition comprises at least 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% of a hydrophilic component (e.g., carboxymethyl cellulose) based on the total weight of the polydiorganosiloxane composition. The amount of the hydrophilic component is typically no more than 50 wt%, 40 wt%, or 30 wt%, and in some embodiments no more than 25 wt%, 20 wt%, 15 wt%, or 10 wt%.

[0061] Manufacturing method

[0062] Methods of manufacturing adhesive articles typically involve providing a layer of a polydiorganosiloxane composition (e.g., uncrosslinked or partially crosslinked) on a substrate. This layer has a first primary surface adjacent to the substrate and an opposing second primary surface. The method includes subjecting the opposing second primary surface of the polydiorganosiloxane composition layer to radiation treatment, thereby crosslinking the layer of the polydiorganosiloxane composition.

[0063] In some embodiments, the substrate is a support film, such as a polyester terephthalate support film. In typical embodiments, the substrate is (e.g., first) a release liner.

[0064] In some embodiments, an uncrosslinked polydiorganosiloxane composition may be applied to a release liner, with no substrate on the opposing surfaces (“open surfaces”). Generally, the chamber is inert (e.g., the oxygen-containing chamber air is replaced with an inert gas, such as nitrogen), while the sample is electron beam crosslinked, particularly when the open surfaces are crosslinked. However, the polydiorganosiloxane composition may be subjected to more than one radiation treatment from both sides or (e.g., radiation treatments of different intensities).

[0065] In some embodiments, the polydiorganosiloxane composition crosslinks upon contact with a first release liner. After crosslinking, the pressure-sensitive adhesive surface is brought into contact with a second release liner, and the first release liner is removed. In some embodiments, the method further includes winding the crosslinked layer of the polydiorganosiloxane composition into a roll (e.g., tape).

[0066] Various release liner types are known and commercially available. Release liner types may include a polyester terephthalate support film and a release coating. In some embodiments, the release coating may be a fluorosilicone material. Release coatings free of silicone and / or fluorinated materials have also been described for use with polydiorganosiloxane adhesives.

[0067] Release liners are typically characterized as having light, medium, or heavy peel strength based on the peel force required to remove the pressure-sensitive adhesive from the adhesive article. This can be measured according to EN ISO 29862, Annex B (Self-adhesive tapes – Peel adhesion measured from a surface at a 90° angle) using an SP-2100 peel tester from IMass, Inc., equipped with a 10 lbf force sensor and a peel rate of 30 cm / min. When heavy peel strength is required, the peel force required to remove the pressure-sensitive adhesive from the adhesive article from the release liner can be at least 40 g / in (2.54 nm) or greater. When light peel strength is required, the peel force required to remove the pressure-sensitive adhesive from the adhesive article from the release liner can be less than 10 g / in or 5 g / in (2.54 nm). When medium peel strength is required, the peel force required to remove the pressure-sensitive adhesive from the adhesive article from the release liner can be greater than 10 g / in and less than 40 g / in (2.54 nm).

[0068] Various release liner products are commercially available, including release liner products purchased under the trade name "SILFLU" from Siliconature Spa (Godega di Sant'Urbano, Italy); and release liner products purchased under the trade name Cerapeel. ™ The stripping liner was purchased from Toray; the POLYSILK was purchased from Loparex International BV (Apeldoorn, The Netherlands). ™ Silicone release liner; from 3M Company (St Paul, MN), Minnesota, USA. ™ Scotchpak ™9741 stripper gasket; and perfluorinated stripper chemicals as disclosed in US 4,472,480.

[0069] In a typical implementation, a thicker layer of the same polydiorganosiloxane composition is crosslinked from one side, thereby providing a crosslinking gradient, where one surface (i.e., the first primary surface in contact with the release liner) is a pressure-sensitive adhesive, and the opposite surface (i.e., the surface closest to the radiation source during curing) is a film backing. However, it is also contemplated that the polydiorganosiloxane layer can be formed by coating more than one layer of the same or different polydiorganosiloxane composition.

[0070] For example, in one embodiment, a first layer of a polydiorganosiloxane composition having a silver material is disposed on a substrate (e.g., a release liner), and a second layer of a polydiorganosiloxane composition not having a silver material is disposed on the first layer. In one embodiment, the first layer of the polydiorganosiloxane composition further comprises a tackifying resin; wherein the second layer comprises little or no tackifying resin. In yet another embodiment, the first layer comprises a silver material and a tackifying resin; while the second layer does not contain a silver material or a tackifying resin. In some embodiments, the first layer may have a thickness of at least 25 micrometers, 50 micrometers, or 100 micrometers. In some embodiments, the first layer may have a thickness of no more than 250 micrometers, 200 micrometers, 150 micrometers, 100 micrometers, or 50 micrometers.

[0071] The thickness and crosslinking conditions can be selected such that a pressure-sensitive adhesive forms on the first primary surface (closer to the substrate), and a membrane backing forms on the opposite second primary surface (closer to the radiation energy source). When the opposite surfaces of the crosslinked polydiorganosiloxane composition are membrane backings, the article may not contain other membrane backing materials, such as polyurethane membrane backings.

[0072] The total thickness of the polydiorganosiloxane layer is typically at least 250 micrometers. The thickness of the polydiorganosiloxane layer is typically no greater than 1000 micrometers, 900 micrometers, 800 micrometers, or 700 micrometers. In some embodiments, the thickness is no greater than 650 micrometers, 600 micrometers, 550 micrometers, 500 micrometers, 450 micrometers, 400 micrometers, 350 micrometers, 300 micrometers, or 250 micrometers.

[0073] In some embodiments, the polydiorganosiloxane composition can be crosslinked by treatment with electron beam irradiation. In some embodiments, the coating can be crosslinked by treatment with gamma radiation. In some embodiments, a combination of electron beam crosslinking and gamma-ray crosslinking can be used. For example, in some embodiments, the coating can be partially crosslinked by treatment with electron beam irradiation. Subsequently, the coating can be further crosslinked by gamma radiation.

[0074] Commercially available electron beam generating equipment is available, such as the CB-300 electron beam generator (available from Energy Sciences, Inc. (Wilmington, MA), also described in US 8,541,481). Commercially available gamma radiation equipment includes devices commonly used for gamma radiation sterilization of products intended for medical applications. In some embodiments, such equipment can be used to crosslink or partially crosslink the skin-friendly adhesives of this disclosure. In some embodiments, such crosslinking can occur simultaneously with the sterilization process of a semi-finished or finished product (e.g., tape or wound dressing).

[0075] In some embodiments, the polydiorganosiloxane material is subjected to electron beam radiation with a voltage of at least 200 kV, 250 kV, 280 kV, or 300 kV. The voltage of the electron beam radiation is typically no greater than 500 kV, 450 kV, 400 kV, 350 kV, or 300 kV. The total dose of the electron beam radiation is typically at least 8 MRad, 9 MRad, 10 MRad, 11 MRad, 12 MRad, 13 MRad, 14 MRad, or 15 MRad. In some embodiments, the total dose of the electron beam radiation is typically no greater than 25 MRad or 20 MRad. The intensity and total treatment dose are based on the electron beam generating device and the treatment time. It should be understood that in this invention, the first primary surface and the opposite second primary surface of the polydiorganosiloxane layer receive different doses of electron beam radiation.

[0076] Physical properties of cross-linked polydiorganosiloxane compositions

[0077] In some embodiments, the tack of the pressure-sensitive adhesive on the first main surface is at least 5 g / L, 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 70 g / L, 75 g / L, or 80 g / L. In some embodiments, the tack of the pressure-sensitive adhesive on the first main surface is not greater than 120 g / L, 110 g / L, or 100 g / L. In some embodiments, the tack of the pressure-sensitive adhesive on the first main surface is not greater than 75 g / L, 50 g / L, or 25 g / L. In some embodiments, the tack of the pressure-sensitive adhesive on the first main surface is not greater than 15 g / L, 10 g / L, or 5 g / L.

[0078] In some implementations, the adhesiveness of the membrane backing on the second primary surface is less than 30 g / L, 25 g / L, 20 g / L, 15 g / L, 10 g / L, or 5 g / L.

[0079] In some embodiments, the pressure-sensitive adhesive on the first main surface has greater tack than the membrane backing on the second main surface. The difference in tack can be at least 25 g / L, 50 g / L, 75 g / L, 100 g / L, 150 g / L, or greater. In other embodiments, the pressure-sensitive adhesive on the first main surface has substantially the same tack as the membrane backing on the second main surface (i.e., within 10% of the average tack value).

[0080] In some embodiments, the crosslinked polydiorganosiloxane layer has a maximum tensile strength of at least 1 N / inch, 2 N / inch, 3 N / inch, or 4 N / inch (2.54 cm). In some embodiments, the crosslinked polydiorganosiloxane layer has a maximum tensile strength of at least 5 N / inch, 6 N / inch, 7 N / inch, 8 N / inch, 9 N / inch, 10 N / inch, 11 N / inch, 12 N / inch, 13 N / inch, 14 N / inch, or 15 N / inch (2.54 cm). In some embodiments, the crosslinked polydiorganosiloxane layer has a maximum tensile strength of no more than 20 N / inch, 15 N / inch, 10 N / inch, or 5 N / inch. In some embodiments, the crosslinked polydiorganosiloxane layer has a maximum elongation of at least 100%, 150%, 200%, or 350%. In some embodiments, the crosslinked polydiorganosiloxane layer has a maximum elongation of no more than 700%, 600%, 500%, 400%, or 300%.

[0081] Peel adhesion to biological substrates such as human skin is known to be highly variable. Skin type, location on the body, and other factors can affect the results. Typically, the average peel adhesion to skin exhibits a large standard deviation. In some embodiments, the average peel adhesion to human skin can be less than 200 gm / 2.54 cm, and in some embodiments, less than 100 gm / 2.54 cm.

[0082] Additional components

[0083] (For example, medical) adhesive articles may include a variety of additional components known in the art. Such additional components are optional with respect to the most broad embodiments of the invention, but may be preferred for some medical articles.

[0084] In some embodiments, the adhesive article may also include a porous substrate. Various porous substrates can be used in the articles described herein. The porous substrate can be made of a variety of (e.g., thermoplastic) organic polymer materials, such as polyester, polyurethane, polyamide (e.g., nylon), polyimide, and polyolefin. In typical embodiments, the porous substrate is a fibrous web or an open-cell membrane. When the membrane is an open-cell membrane, the membrane may be opened before or after the crosslinking of the polydiorganosiloxane layer. Thus, although the article contains a porous substrate, in some embodiments, the method utilizes a non-porous organic polymer membrane substrate that has been imparted porosity during manufacturing.

[0085] Fiber webs can be made from the same organic polymer materials (e.g., thermoplastic) just described. Fiber webs can also be made from various organic fibers (such as cotton, wool, hemp, and flax). Although inorganic fibers (e.g., glass fiber, ceramics, and metals) are generally not used in medical products, porous substrates with inorganic fibers can be used in other adhesive products. In some embodiments, the fiber web comprises nylon, polyolefins, or cellulose acetate. Fiber webs come in many forms, including, for example, woven webs, nonwoven webs, knitted fabrics, loose fabrics, and mesh.

[0086] In other embodiments, the porous substrate is an open-cell organic polymer membrane. Pores can be formed in the organic polymer membrane using suitable techniques, such as die stamping as described, for example, in KR10-2251386. Pores can be formed before or after the layer of the polydiorganosiloxane composition is applied to the organic polymer membrane. Pores can contribute to the membrane's moisture permeability.

[0087] In some embodiments, the organic polymer membrane comprises a membrane material having high moisture permeability (non-porous). Suitable membranes include (e.g., thermoplastic) polyurethane membranes, such as those available under the trade names PELLETHANE or ESTANE from Lubrizol, Brecksville, Ohio; elastomeric polyesters, such as those available under the trade name HYTREL from El. duPont deNemours & Co., Wilmington, Del.; and polyether ester block amides, such as those available under the trade name PEBAX from Elf Altochem North America, Philadelphia, Pa. Other available membranes are those described in U.S. Patent No. 4,499,896 (Heinecke); U.S. Patent No. 4,598,004 (Heinecke); and U.S. Patent No. 5,849,325 (Heinecke et al.). Typically, the membrane has higher tensile strength and lower elongation than the crosslinked layer of the polydiorganosiloxane composition, and therefore provides reinforcement and improved web processing. In some embodiments, the membrane has a maximum tensile strength of at least 20 MPa, 30 MPa, or 40 MPa, and typically no greater than 60 MPa, 50 MPa, or 40 MPa (ASTM D 412). In some embodiments, the membrane has a maximum elongation of at least 100%, 200%, 300%, 400%, or 500%, and typically no greater than 1000%, 750%, or 500% (ASTM D 412). In some embodiments, the membrane thickness is at least 25 micrometers, 50 micrometers, or 75 micrometers. In some embodiments, the membrane thickness is no greater than 200 micrometers, 150 micrometers, or 100 micrometers. Perforated membranes can have lower tensile strength and higher elongation compared to the same membrane without pores.

[0088] (For example, fiber) porous substrates can have a density of at least 15 g / m³. 2 20g / m 2 25g / m 2 30g / m 2 35g / m 2 40g / m 2 45g / m 2 Or 50g / m 2 The basis weight. (e.g., fiber) porous substrates typically have a basis weight of no more than 200 g / m³. 2 150g / m 2 Or 100g / m 2The basis weight. In some embodiments, the open area (which may be determined by the basis weight and density of the material) is at least 10%, 20%, 30%, 40%, 50%, 60%, or 70%. The thickness of the porous substrate (e.g., fiber) is typically at least 0.05 mm (50 micrometers), 0.10 mm (100 micrometers), or 0.15 mm (150 micrometers). In some embodiments, the thickness of the substrate (e.g., fiber) is not greater than 0.5 mm (500 micrometers), 0.4 mm, 0.3 mm, or 0.2 mm. The number of strands in the porous fiber substrate is typically at least 5 strands / inch, 10 strands / inch, 15 strands / inch, 20 strands / inch, or 25 strands / inch (2.54 cm). In some embodiments, the number of strands in the porous fiber substrate is not greater than 150 strands / inch, 100 strands / inch, 75 strands / inch, or 50 strands / inch (2.54 cm). The porous fiber substrate may be compressed during manufacturing, resulting in a greater basis weight and a smaller thickness in the article.

[0089] Exemplary porous fiber substrates are commercially available from Industrial Netting (e.g., WN0100 and WN0200), Bedford Weaving Inc (ANCI), and Tessitura A. Ghiringhelli & CSpA, Azzate, Italy.

[0090] like Figures 3 to 5 As described, the porous substrate may be present near the first primary surface, near the opposing second primary surface, embedded within the cross-linked layer of the polydiorganosiloxane composition, or a combination thereof. The presence of the porous substrate can improve web processing, increase the strength of the cross-linked layer of the polydiorganosiloxane, and reduce tack or adhesion at one or both primary surfaces. In some embodiments, the porous substrate may contain silver material, rather than dispersing the silver material within the polydiorganosiloxane composition.

[0091] In some embodiments, when the adhesive article is a wound dressing, the article may also include an absorbent pad, such as that described in US2019 / 0231604; which is incorporated herein by reference.

[0092] Absorbent pads are typically positioned at the center of the surface of a pressure-sensitive adhesive, such that adhesive or pressure-sensitive adhesive is present on the opposite sides surrounding the absorbent pad.

[0093] The absorbent pad may be made of one or more layers, and each layer may be made of one or more absorbent materials. Preferably, the absorbent pad is relatively flexible. Flexibility allows the medical product incorporating the absorbent pad to be easily applied to flexible parts of the body, such as joints. The absorbent pad may be cut at one or more locations to provide additional flexibility. In some embodiments, the absorbent pad may be translucent or transparent, thus allowing visual inspection of the wound without removing the wound dressing.

[0094] Absorbent pads may be made of synthetic or natural materials and may include, but are not limited to, woven or nonwoven materials (e.g., woven or nonwoven cotton or rayon), hydrocolloids (e.g., pectin, gelatin, carboxymethyl cellulose (CMC), crosslinked carboxymethyl cellulose (X-link CMC), crosslinked polyacrylic acid (PAA), and hydrocolloids described in U.S. Patents 5,622,711 and 5,633,010), polymeric gels (e.g., hydrogels), foams, collagen, hydrocellulose, alginate, and combinations thereof. In some embodiments, the absorbent pad may comprise polymeric fabrics, polymeric foams, and combinations thereof. For example, the polymeric fabric may be a nonwoven fabric, and the polymeric foam may be a foam used in TEGADEM foam adhesive dressings, which are available from 3M Company, St. Paul, Minn. In some embodiments, the polymeric foam is a polyurethane foam. The absorbent pad may optionally include other components, including one or more active agents, such as pharmacologically active agents, as further described in US2019 / 0231604.

[0095] Example

[0096] Materials used in the examples

[0097] Using SpeedMixer ® The composition was prepared in 100g batches using the DAC600-P (Hausschild GmbH, Hamm, Germany). The silicone oil was placed in a suitable wide-mouth flask, MQ resin was added, and the composition was mixed at 2350 rpm and a vacuum of 200 mbar for 90 seconds to form a homogeneous mixture. For examples containing silicic acid, silicic acid was added, and the composition was mixed at 2350 rpm and a vacuum of 200 mbar for 90 seconds to form a homogeneous mixture. For examples containing CMC and / or silver compounds, those were added to the resulting composition, and the composition was mixed again at 2350 rpm and a vacuum of 200 mbar for at least 90 seconds until a homogeneous mixture was obtained.

[0098] The composition was applied to a release liner (a 50-micron polyethylene terephthalate film containing a release coating) using a doctor blade coater. The open side of the coated sheet was subjected to electron beam irradiation at an accelerating voltage of 280 kV using a CB-300 electron beam generator, available from Energy Sciences, Wilmington, Massachusetts, to provide the doses specified in Tables 1, 4, and 6, and then immediately laminated to the release liner after coating.

[0099] Strength and elongation : Tensile strength and elongation were measured according to EN ISO 527-3 using a ZwickRoell Z010 machine equipped with a 500N force sensor. Samples were cut to 80mm x 1-inch dimensions, with 1-inch protrusions on each side placed in the jaws for test run. Samples were measured in the coating direction. Machine settings: jaw spacing: 50mm, test speed: 100mm / min, preload: 0.1N. Tensile strength is reported as the maximum force, and elongation is reported as the elongation value at the maximum tensile force. Data represent the average and standard deviation of three measurements for each example.

[0100] Viscosity test : Adhesion (removal force) was measured using a TA-XT Plus texture analyzer equipped with a 5kg force sensor and a 7mm stainless steel cylindrical probe. Test samples were cut to 1-inch widths and laminated onto a brass rod with a 10mm diameter hole through it to allow the probe to reach the adhesive surface of the tape. The probe tip was cleaned with n-heptane after each measurement. Test parameters: pre-test speed: 1.0mm / s, test speed: 0.05mm / s, applied force: 5g, contact time: 5s, trigger force: 60g, and withdrawal distance: 12mm. Data represent the average of three measurements for each example.

[0101] Inhibition Zone Test : Overnight cultures of microorganisms were prepared by streaking on Mueller-Hinton agar and incubating for at least 16 hours. A suspension of approximately 10⁸ CFU / mL was prepared in PBW using McFarland 0.5 turbidity standard. This stock solution was then diluted 1:100 in PBW to form a working suspension. Mueller-Hinton agar plates were inoculated with 5 logs of bacteria by saturating swabs once in the working suspension, ensuring a uniform bacterial growth. The plates were then allowed to dry. Two discs (2 cm in diameter) were cut from the coated sheet, the two liners were carefully removed, and the discs were placed onto the plates using clamps. A single plate was used for each organism. The plates were incubated at 37°C, and the areas were observed separately after 24 hours.

[0102]

[0103] The results showed that the maximum tensile strength increased when silica was added to the composition.

[0104]

[0105] The results showed that the maximum tensile strength increased when silica was added to the composition.

Claims

1. A composition comprising: a polydiorganosiloxane; a silver material; and at least 1 weight percent of an oxygen-containing metal filler of silicon, titanium, zirconium, or a combination thereof.

2. The composition of claim 1, wherein the polydiorganosiloxane comprises a non- functional polydiorganosiloxane.

3. The composition of claims 1-2, wherein the composition further comprises a tackifying resin.

4. The composition of claims 1-3, wherein the composition further comprises a hydrophilic filler, including carboxymethyl cellulose.

5. The composition of claim 1, wherein the composition is crosslinked.

6. The composition of claim 5, wherein the crosslinked composition has a higher tensile strength than the same composition without the oxygen-containing metal filler.

7. A method of making an adhesive article, the method comprising: a) providing a layer of a polydiorganosiloxane composition on a substrate, wherein the layer comprises a non-functionalized polydiorganosiloxane and a silver material; b) subjecting the layer of polydiorganosiloxane composition to a radiation treatment, thereby crosslinking the layer of polydiorganosiloxane composition.

8. The method of claim 7, wherein the substrate is a first release liner.

9. The method of claims 7-8, wherein the layer of polydiorganosiloxane composition comprises a single layer or multiple layers of the same composition or different compositions.

10. The method of claim 9, wherein a first layer of polydiorganosiloxane composition with a silver material is disposed on the substrate and a second layer of polydiorganosiloxane composition without a silver material is disposed on the first layer.

11. The method of claims 1-10, wherein the polydiorganosiloxane composition has a viscosity of at least 50,000 mm 2 / s, 100,000 mm 2 / s, 250,000 mm 2 / s, 500,000 mm 2 / s, or 1,000,000 mm 2 / s prior to crosslinking.

12. The method of claims 1-11, wherein the polydiorganosiloxane composition further comprises i) a hydrophilic filler, including carboxymethyl cellulose; ii) an oxygen-containing metal filler of silicon, titanium, zirconium, or a combination thereof; or a combination thereof.

13. The method of claims 1-12, wherein the total thickness of one or more of the layers of polydiorganosiloxane composition is at least 250 micrometers, 300 micrometers, 350 micrometers, 400 micrometers, 450 micrometers, or 500 micrometers.

14. The method of claims 1-13, wherein the layer of polydiorganosiloxane composition comprises a first major surface proximate the substrate and an opposing second major surface, and the method further comprises providing a porous substrate proximate the substrate, proximate the opposing second surface, or embedded within the layer of polydiorganosiloxane composition.

15. The method of claims 1-14, wherein one or more of the layers of polydiorganosiloxane composition has a first major surface proximate the substrate and an opposing second major surface subjected to an electron beam radiation treatment of at least 8 MRad dosage, and the first major surface is subjected to a lower dosage of treatment.

16. The method of claims 1-15, wherein the first major surface is a pressure sensitive adhesive and the opposing second major surface is a film backing.

17. An adhesive article comprising a crosslinked layer of the polydiorganosiloxane composition of claims 1-16.

18. The adhesive article of claim 17, wherein the article is a medical article, medical tape, bandage, dressing, or compression wrap.

19. The adhesive article of claim 17 for use as a medical article.

20. A method for an adhesive article, the method comprising providing the adhesive article of claims 17-19 and contacting the first major surface to skin or a wound.

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