Breathable hot melt processable medical adhesive

Abstract

The article includes a substrate and a layer disposed on the substrate, the layer being at least one coated, photocrosslinked, hot-melt-processable pressure-sensitive adhesive. The adhesive is a (meth)acrylate-based copolymer that is the reaction product of a reaction mixture of a first (meth)acrylate monomer containing an alkyl, alkenyl, or aryl group having 4 to 20 carbon atoms, a second (meth)acrylate monomer containing an alkylene oxide group capped with an alkyl group, a copolymerizable reinforcing monomer, a copolymerizable photocrosslinker, and an initiator.

Description

[Technical Field]

[0001] Disclosed herein are adhesive compositions that are photocrosslinkable, hot-melt processable, pressure-sensitive adhesives. In particular, disclosed are articles containing the adhesive compositions.

[0002] In some embodiments, an article includes a substrate and a layer disposed on at least a portion of the substrate, the layer including at least one coated, photocrosslinked hot-melt processable pressure-sensitive adhesive having a general formula I: CH2=CR 1 -(CO)-OR 2 Formula I (In the formula, R 1 is hydrogen or a methyl group, and R 2 is an alkyl, alkenyl, or aryl group containing from 4 to 20 carbon atoms); and at least one first (meth)acrylate monomer of general formula II: CH2=CR 1 -(CO)-OR 3 Formula II (In the formula, R 1 is hydrogen or a methyl group, and R 3 is an alkylene oxide group capped with an alkyl group), at least one copolymerizable reinforcing monomer, at least one copolymerizable photocrosslinker, and at least one initiator. DETAILED DESCRIPTION OF THE INVENTION

[0003] The use of adhesive products in the medical industry has been widespread and is increasing. However, while adhesives and adhesive articles have proven themselves to be very useful in medical applications, their use also presents problems. In particular, the properties desired for adhesives are often contradictory. For example, it is desirable for adhesives to have high adhesion to many surfaces, including human skin, but it is also desirable for the adhesive to be removable without damaging the skin. In addition, medical articles are being worn for longer periods of time, and medical articles need to remain adhered and be removable without damaging the skin or leaving behind residue.

[0004] Another need in medical adhesives is to make them more hydrophilic to aid in moisture vapor transmission rate (MVTR) properties for extended wear. A wide variety of medical articles and devices are intended to remain attached to the skin for extended periods of time. Current adhesive systems have difficulty remaining on the skin for extended periods of time because they suffer from moisture load, i.e., moisture trapped between the skin and the adhesive layer due to an inadequate MVTR, which causes the adhesive to "float off." MVTR is a measure of the passage of water vapor through a substance or barrier. Because sweating naturally occurs on the skin, if a material or adhesive system has a low MVTR, this can lead to moisture accumulation between the skin and the adhesive, which can cause the adhesive to "float off" or peel, and can also promote other adverse effects such as bacterial growth and skin irritation. Therefore, much research has focused on developing adhesive systems with a high MVTR. Typically, adhesives are designed to be hydrophilic so that moisture from the skin can pass through the adhesive layer and not accumulate at the skin / adhesive interface. Because adhesives are typically hydrocarbon-rich and therefore non-polar and hydrophobic, one method used to make adhesives more hydrophilic is to add hydrophilic plasticizers. Typically, these plasticizers are polyalkylene oxide-based plasticizers. The drawback to this approach is that because plasticizers are free materials, they can migrate to the surface of the adhesive composition and leave behind residue when the adhesive is removed.

[0005] Another trend in adhesive technology is to prepare adhesives without the use of solvents. Although there are various environmental and other reasons for eliminating solvents in the preparation of adhesive articles, it can be difficult to produce adhesives, such as (meth)acrylate-based adhesives, without the use of solvents. Among the methods developed for preparing and coating adhesive systems are 100% solids systems, such as hot-melt processable pressure-sensitive adhesives. Difficulties have arisen when solvent processing has been replaced by hot-melt processing. It is often difficult to reproduce the properties of solvent-delivered adhesive layers with hot-melt delivery systems.

[0006] Thus, among the desirable, and often conflicting, characteristics desired for a medical adhesive include: high enough adhesion to adhere to skin without causing skin damage or leaving residue upon removal; high enough cohesive strength to be useful; high MVTR for long-term wear; and hot melt processable so that the use of solvents is not required.

[0007] The present specification discloses an adhesive composition and an article containing the adhesive composition, wherein the adhesive is (meth)acrylate-based and contains a monomer having an alkyl-capped polyalkylene oxide group. These groups help provide high MVTR, but because they are part of the polymer matrix, they do not migrate freely to the surface or migrate as residue, as is the case with added plasticizers. The adhesive is a desirable wet-tack adhesive in that it adheres to both wet and dry skin.

[0008] As used herein, the term "adhesive" refers to a polymeric composition that is useful for bonding two adherends together. An example of an adhesive is a pressure-sensitive adhesive.

[0009] Pressure-sensitive adhesive compositions are well known to those skilled in the art to have properties including: (1) strong and permanent tack, (2) adhesion with no more than finger pressure, (3) sufficient ability to hold on to an adherend, and (4) sufficient cohesive strength to remove cleanly from an adherend. Materials that have been found to perform well as pressure-sensitive adhesives are polymers designed and formulated to exhibit the necessary viscoelastic properties, resulting in the desired balance of tack, peel adhesion, and shear holding power. Obtaining the proper balance of properties is not an easy process.

[0010] As used herein, the term "wet stick adhesive" refers to a material that exhibits pressure sensitive adhesive properties when adhered to at least a wet surface, generally both wet and dry surfaces, particularly skin.

[0011] The term "(meth)acrylate" refers to a monomeric acrylic or methacrylic acid ester of an alcohol. Acrylate and methacrylate monomers or oligomers are collectively referred to herein as "(meth)acrylates." Materials referred to as "(meth)acrylate-based" are materials that contain a majority of one or more (meth)acrylates and may also contain additional copolymerized copolymerizable monomers.

[0012] The terms "room temperature" and "ambient temperature" are used interchangeably to mean a temperature in the range of 20°C to 25°C.

[0013] The terms "Tg" and "glass transition temperature" are used interchangeably. When measured, Tg values ​​are determined by Differential Scanning Calorimetry (DSC) at a scan rate of 10°C / min unless otherwise indicated. Typically, Tg values ​​of copolymers are not measured but are calculated using the well-known Fox equation using monomer Tg values ​​provided by the monomer supplier, as will be understood by those skilled in the art.

[0014] As used herein, the term "adjacent" when referring to two layers means that the two layers are close to each other with no intervening open space between them. They may be in direct contact with each other (e.g., laminated together) or there may be an intervening layer.

[0015] The terms "polymer" and "macromolecule" are used herein consistent with their common usage in chemistry. Polymers and macromolecules are composed of many repeating subunits. As used herein, the term "macromolecule" is used to describe a group attached to a monomer having multiple repeating units. The term "polymer" is used to describe the resulting material formed from a polymerization reaction.

[0016] The term "protein leather" is used herein in accordance with its commonly understood meaning. Protein leather, also known as synthetic leather (Pleather), is composed of protein powder and resins that form flexible sheets that resemble leather in appearance and durability.

[0017] The term "alkyl" refers to a monovalent group that is a radical of an alkane, which is a saturated hydrocarbon. Alkyl can be linear, branched, cyclic, or a combination thereof and typically has 1 to 20 carbon atoms. In some embodiments, an alkyl group contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.

[0018] The term "alkenyl" refers to a monovalent group that is a radical of an alkene, an unsaturated hydrocarbon. Alkenyl can be linear, branched, cyclic, or a combination thereof and typically has 3 to 20 carbon atoms. In some embodiments, alkenyl groups contain 3 to 18, 3 to 12, 3 to 10, 3 to 8, 3 to 6, or 3 to 4 carbon atoms.

[0019] The term "aryl" refers to a monovalent group that is aromatic and carbocyclic. An aryl can have 1 to 5 rings attached or fused to an aromatic ring. Other ring structures may be aromatic, non-aromatic, or combinations thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.

[0020] The term "alkylene" refers to a divalent group that is a radical of an alkane. Alkylene can be straight-chained, branched, cyclic, or a combination thereof. Alkylene often has 1 to 20 carbon atoms. In some embodiments, alkylene contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. The radical centers of the alkylene can be on the same carbon atom (i.e., alkylidene) or on different carbon atoms.

[0021] The term "heteroalkylene" refers to a divalent group containing at least two alkylene groups linked by thio, oxy, or -NR-, where R is alkyl. The heteroalkylene can be linear, branched, cyclic, or a combination thereof, substituted with alkyl groups. Some heteroalkylenes are, for example, -(CH2CH2O) n A polyoxyalkylene in which the heteroatom is oxygen, such as CH2CHO-. The terms "polyoxyalkylene" and "polyalkylene oxide" are used interchangeably. As used herein, the term "alkyl-capped alkylene oxide group" refers to a group of the type -(CH2CHO) n It refers to a monovalent group containing end-capped polyoxyalkylene groups of the formula CH2CH2OR, where R is an alkyl group.

[0022] The terms "free radically polymerizable" and "ethylenically unsaturated" are used interchangeably and refer to a reactive group containing a carbon-carbon double bond that can be polymerized via a free radical polymerization mechanism.

[0023] Disclosed herein are articles, particularly medical articles, that include a substrate and a layer disposed on at least a portion of the substrate, the layer comprising at least one hot-melt-processable pressure-sensitive adhesive that is coated and photocrosslinked. The at least one hot-melt-processable pressure-sensitive adhesive comprises a (meth)acrylate-based copolymer that is the reaction product of a reaction mixture. The reaction mixture includes a polymerizable component, at least one initiator, and an optional non-polymerizable component. The polymerizable component has the general formula I: CH2=CR 1 -(CO)-OR 2 Formula I (In the formula, R 1 is hydrogen or a methyl group, and R 2 is an alkyl, alkenyl, or aryl group containing from 4 to 20 carbon atoms), and at least one first (meth)acrylate monomer of general formula II: CH2=CR 1 -(CO)-OR 3 Formula II (In the formula, R 1 is hydrogen or a methyl group, and R 3 is an alkylene oxide group capped with an alkyl group), at least one copolymerizable reinforcing monomer, and at least one copolymerizable photocrosslinker. Each of the reactive components, initiators, and optional components is described in more detail below.

[0024] The adhesive composition is hot-melt processable. The term "hot-melt processable" is not a process description or limitation, but rather a material description, and means that the adhesive composition can be hot-melt processed, but does not mean that the composition necessarily has or needs to be hot-melt processed.

[0025] The articles of the present disclosure include a substrate. A wide variety of substrates are suitable for the articles of the present disclosure. In many embodiments, the substrate comprises a substrate suitable for use in medical articles. These articles may or may not be breathable, i.e., moisture-permeable. Examples of suitable substrates include medical substrates or release liners. Exemplary medical substrates include polymeric materials, plastics, natural polymeric materials (e.g., collagen, wood, cork, silk, and leather), paper, cloth, woven fabrics, nonwoven fabrics, composite materials, and combinations thereof. The medical substrate may also be a tape backing. Examples of suitable tape backings include breathable conformable backings on which an adhesive is disposed. A wide variety of breathable conformable backings are suitable for use in the articles of the present disclosure. Typically, breathable conformable backings include woven or knitted fabrics, nonwoven fabrics, or plastics.

[0026] In some embodiments, the breathable conformal backing comprises a highly moisture vapor permeable film backing. Examples of such backings, methods for making such films, and methods for testing their permeability are described, for example, in U.S. Patent Nos. 3,645,835 and 4,595,001. Typically, such backings are porous materials.

[0027] Generally, the backing conforms to the anatomical surface. Thus, when the backing is applied to an anatomical surface, the backing conforms to the surface even if the surface moves. Generally, the backing also conforms to the anatomical joint of an animal. When the joint is flexed and then returned to its unflexed position, the backing stretches to accommodate the flexion of the joint, but is sufficiently resilient to continue to conform to the joint when the joint is returned to its unflexed state.

[0028] Examples of particularly suitable backings can be found in U.S. Patent Nos. 5,088,483 and 5,160,315 and include elastomeric polyurethane, polyester, or polyether block amide films, which have a desirable combination of properties including resilience, high moisture vapor permeability, and transparency.

[0029] In some embodiments, the substrate can be a release liner. A release liner is a sheet material having a low-adhesion coating on at least one surface. The hot-melt-processable pressure-sensitive adhesive of the present disclosure can be disposed on a release liner to produce an article comprising a layer of pressure-sensitive adhesive on the release liner. This adhesive / release liner article can be used to prepare other adhesive / substrate articles by laminating the adhesive layer to a different substrate and then removing the release liner. This allows for the placement of the adhesive on substrates that are difficult to directly place a hot-melt-processable pressure-sensitive adhesive on, such as heat-sensitive substrates. The adhesive / release liner article can also be used to attach a pressure-sensitive adhesive layer to articles such as electrodes, ostomy appliances, and the like. The appliances do not need to be breathable.

[0030] Also disclosed herein is a hot-melt-processable pressure-sensitive adhesive composition. The composition is disposed on a substrate to form an adhesive layer, which is then photocrosslinked to form a photocrosslinked pressure-sensitive adhesive layer. Thus, the article also includes at least one coated, photocrosslinked layer of hot-melt-processable pressure-sensitive adhesive. "At least one" means that the layer may contain a single hot-melt-processable pressure-sensitive adhesive composition, or may contain two or more hot-melt-processable pressure-sensitive adhesive compositions, and different compositions may be blended or may exist in separate sublayers within the layer.

[0031] The hot-melt processable pressure-sensitive adhesive composition comprises a (meth)acrylate-based copolymer that is the reaction product of a reaction mixture. The reaction mixture comprises a polymerizable component, at least one initiator, and an optional non-polymerizable component. The polymerizable component comprises at least one first (meth)acrylate monomer, at least one second (meth)acrylate monomer, at least one copolymerizable reinforcing monomer, at least one copolymerizable photocrosslinker, and at least one initiator. The reaction mixture may also comprise optional components. Each of the reactive components, initiators, and optional components is described in more detail below.

[0032] As noted above, the reaction mixture comprises a compound of general formula I: CH2=CR 1 -(CO)-OR 2 Formula I (In the formula, R 1 is hydrogen or a methyl group, and R 2 is an alkyl, alkenyl, or aryl group containing 4 to 20 carbon atoms. 2 is an alkyl group containing 4 to 12 carbon atoms. In many embodiments, the first (meth)acrylate monomer comprises a mixture of (meth)acrylate monomers. Examples of suitable first (meth)acrylate monomers include BA (butyl acrylate), PA (propyl acrylate), HA (hexyl acrylate), 2-EHA (2-ethylhexyl acrylate), IOA (isooctyl acrylate), heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, and dodecyl acrylate. Examples of particularly suitable first (meth)acrylate monomers include BA (butyl acrylate), 2-EHA (2-ethylhexyl acrylate), IOA (isooctyl acrylate), and LA (lauryl acrylate).

[0033] The reaction mixture may also comprise a compound of general formula II: CH2=CR 1 -(CO)-OR 3 Formula II (In the formula, R 1 is hydrogen or a methyl group, and R 3 is an alkylene oxide group capped with an alkyl group). In some embodiments, R 3 is a polyethylene oxide group capped with an alkyl group. In some particularly preferred embodiments, R 3 is represented by general formula III: -(CH2-CH2-O) n -CH3 Formula III (wherein n is an integer from 8 to 230.) An example of a suitable second (meth)acrylate monomer is an acrylate formed from CARBOWAX 750 (methoxypolyethylene glycol having a molecular weight of 750) and MPEG500 (methoxypolyethylene glycol acrylate having a molecular weight of 550).

[0034] The reaction mixture also contains at least one reinforcing monomer. Copolymerizable reinforcing monomers are monoethylenically unsaturated monomers that increase the glass transition temperature and cohesive strength of the copolymer. Mixtures of reinforcing monomers can also be used. Generally, the reinforcing monomer has a homopolymer Tg of at least about 10°C. Typically, the reinforcing monomer is a reinforcing (meth)acrylic monomer containing acrylic acid, methacrylic acid, acrylamide, or a (meth)acrylate. Examples include, but are not limited to, acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-hydroxyethylacrylamide, diacetoneacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-ethyl-N-aminoethylacrylamide, N-ethyl-N-hydroxyethylacrylamide, N,N-dihydroxyethylacrylamide, t-butylacrylamide, N,N-dimethylaminoethylacrylamide, and N-octylacrylamide. Other examples of reinforcing monomers include itaconic acid, crotonic acid, maleic acid, fumaric acid, 2,2-(diethoxy)ethyl acrylate, 2-hydroxyethyl acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, methyl methacrylate, isobornyl acrylate, 2-(phenoxy)ethyl acrylate or methacrylate, biphenylyl acrylate, t-butylphenyl acrylate, cyclohexyl acrylate, dimethyl adamantyl acrylate, 2-naphthyl acrylate, phenyl acrylate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and N-vinylcaprolactam. Particularly suitable reinforcing monomers are acid-functional monomers. Acrylic acid is particularly useful because it is readily available.

[0035] The reaction mixture also contains at least one copolymerizable photocrosslinker. The copolymerizable photocrosslinker is a material containing free-radically polymerizable groups that copolymerize with the above-mentioned monomers. The copolymerizable photocrosslinker also contains photosensitive groups that, upon exposure to the appropriate wavelength of light, typically high-intensity ultraviolet (UV) radiation, form free radicals capable of forming crosslinks in the polymer. When the (meth)acrylate-based polymer is formed using a photoinitiator, the photocrosslinker is not activated by light of the same wavelength as the photoinitiator. In this way, the copolymerizable photocrosslinker is incorporated into the polymer, and the crosslinker can be heat-treated because it is thermally stable and remains intact until activated by light of the appropriate wavelength. This prevents the copolymerizable photocrosslinker from being activated until the polymer is hot-melt coated. In some embodiments, these crosslinkers are activated by UV light generated from an artificial light source, such as a medium-pressure mercury lamp or a UV black light.

[0036] Suitable photocrosslinkers include monoethylenically unsaturated aromatic ketone comonomers that do not contain orthoaromatic hydroxyl groups, such as those described in U.S. Patent No. 4,737,559 (Kellen et al.). Specific examples include para-acryloxybenzophenone (ABP), para-acryloxyethoxybenzophenone (AEBP), ketalized acryloxyethoxybenzophenone (KAEBP) as described in U.S. Patent No. 10,189,771 (Benson et al.), para-N-(methylacryloxyethyl)-carbamoylethoxybenzophenone, para-acryloxyacetophenone, ortho-acrylamidoacetophenone, and acrylated anthraquinone. Particularly suitable are ABP para-acryloxybenzophenone, also known as 4-acryloxybenzophenone, AEBP (para-acryloxyethoxybenzophenone), and KAEBP (ketalized acryloxyethoxybenzophenone).

[0037] The reactive mixture also includes at least one initiator. Typically, the initiator is a photoinitiator, meaning that the initiator is activated by light, typically ultraviolet (UV) light. As mentioned above, suitable photoinitiators are those activated by light different from the light that activates photocrosslinking. Photoinitiators are well understood by those skilled in the art of (meth)acrylate polymerization. Examples of suitable free radical photoinitiators include DAROCURE 1173, DAROCURE 4265, IRGACURE 184, IRGACURE 651, IRGACURE 1173, IRGACURE 819, LUCIRIN TPO, and LUCIRIN TPO-L, all commercially available from BASF, Charlotte, NC. The photoinitiator IRGACURE 1173 is particularly suitable.

[0038] The relative amounts of the components of the reaction mixture can be varied as desired. In some embodiments, the reaction mixture comprises: 50 parts by weight to 85 parts by weight of at least one first monomer; 10 parts by weight to 30 parts by weight of at least one second monomer; 3 parts by weight to 25 parts by weight of at least one copolymerizable reinforcing monomer; 0.05 parts by weight to 0.5 parts by weight of at least one copolymerizable photocrosslinker; and 0.01 to 1.0 parts by weight of an initiator.

[0039] The term "parts by weight" is used to describe the amount by weight of reactive material present in a mixture. This term is similar to, but should not be confused with, "wt. %" or "% by weight." Typically, the components total 100 parts by weight, and therefore parts by weight is the same as % by weight; however, in many embodiments, the reactive components do not total exactly 100 parts by weight. In these embodiments, the term parts by weight is close to, but not exactly the same as, % by weight. For example, a reactive mixture containing 70 parts by weight of a first monomer, 20 parts by weight of a second monomer, 10 parts by weight of a copolymerizable reinforcing monomer, and 0.1 parts by weight of a copolymerizable photocrosslinker has about 70% by weight of the first monomer, but the parts by weight of the monomers total more than 100, so it is incorrect to use that term.

[0040] The reaction mixture used to prepare at least one hot-melt processable pressure-sensitive adhesive may contain additional optional additives. The additives may be reactive or non-reactive with the reactive components described above. Reactive additives include covalent crosslinkers and chemical crosslinkers, also known as chain transfer agents. Non-reactive additives include antioxidants and plasticizers.

[0041] When used, the crosslinking agent is used in an effective amount, meaning an amount sufficient to cause crosslinking without interfering with the hot melt processability of the polymerized adhesive composition. Generally, when used, the crosslinking agent is used in an amount of less than 0.01 parts by weight.

[0042] One class of useful crosslinking agents is multifunctional (meth)acrylate species. Multifunctional (meth)acrylates include tri(meth)acrylates and di(meth)acrylates (i.e., compounds containing three or two (meth)acrylate groups). Typically, di(meth)acrylate crosslinkers (i.e., compounds containing two (meth)acrylate groups) are used. Useful di(meth)acrylates include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, alkoxylated 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol di(meth)acrylate, alkoxylated cyclohexanedimethanol diacrylate, ethoxylated bisphenol A di(meth)acrylate, neopentyl glycol diacrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and urethane di(meth)acrylate.Di(meth)acrylate HDDA (1,6-hexanediol diacrylate) is particularly suitable.

[0043] One particularly suitable additive is a chain transfer agent. Examples of useful chain transfer agents include, but are not limited to, those selected from the group consisting of carbon tetrabromide, mercaptans, alcohols, and mixtures thereof. A particularly suitable chain transfer agent is IOTG (isooctylthioglycolate). Chain transfer agents and their use are well understood in the adhesives art. When used, chain transfer agents are typically present in an amount of up to 0.30 parts by weight.

[0044] As mentioned above, the reaction mixture may contain non-reactive components that perform useful functions in the adhesive layer when formed, but do not participate in the polymerization reaction that forms the adhesive composition. Suitable additives are those that do not interfere with the polymerization reaction. Examples include plasticizers and antioxidants, with antioxidants being particularly preferred. Commercially available antioxidants include the IRGANOX series from BASF, such as IRGANOX 1076 and IRGANOX 1010. Typically, when used, antioxidants are present in an amount of up to 0.5 parts by weight.

[0045] The hot-melt processable adhesive composition is formed by polymerizing a reaction mixture containing the above-described components. An initiator is typically activated by light to initiate the polymerization. The polymerization can be carried out in a solvent or as a 100% solids mixture. Typically, 100% solids polymerization is more desirable. In some embodiments, the reactive components are mixed and polymerized in the absence of a solvent to form the hot-melt processable pressure-sensitive adhesive composition.

[0046] In many embodiments of the present disclosure, polymerization is carried out in a sealed package, as described in U.S. Patent No. 5,804,610 (Hamer et al.). In this method, the reaction mixture components described above are sealed in a package containing a thermoplastic material. These packages are then polymerized to form a hot-melt processable pressure-sensitive adhesive composition within the package.

[0047] In this method, two lengths of thermoplastic film are heat-sealed together across the bottom and at each of the side edges on a liquid form-fill-seal machine to form an open-ended pouch. Particularly suitable thermoplastic film materials are polyethylene and EVA (ethylene vinyl acetate). The reactive mixture is pumped through a hose to fill the pouch, which is then heat-sealed over the top to completely enclose the adhesive composition.

[0048] Typically, the reactive mixture is polymerized by activation of a photoinitiator with radiation of an appropriate wavelength, typically UV radiation. In many embodiments, the packaged pre-adhesive composition is immersed in a heat exchange medium to mitigate excess heat generation during polymerization. In many embodiments, the heat exchange medium is water maintained at room temperature.

[0049] Once polymerization is complete, a packaged adhesive composition is produced that can be used immediately, stored for later use, or shipped to a different location for hot melt processing.

[0050] The adhesive layer of the articles of the present disclosure is formed by disposing at least one of the hot-melt processable pressure-sensitive adhesive compositions described above on the surface of a substrate to form an adhesive layer, and then photocrosslinking the adhesive layer by exposing the adhesive layer to actinic radiation.

[0051] The adhesive composition can be applied to the surface by any conventional application method, including, but not limited to, extrusion coating, gravure coating, curtain coating, slot coating, spin coating, screen coating, transfer coating, brush or roller coating, etc. The adhesive composition can be applied to the microstructured surface as a hot melt composition, a solvent-based composition, or a 100% solids composition. The adhesive coating can be further processed to produce the adhesive layer. Processing can include drying the adhesive layer coating if solvent-based, or cooling the adhesive layer coating if hot melt coated.

[0052] In many embodiments, the hot-melt processable pressure-sensitive adhesive composition may be disposed on the surface of a substrate by hot-melt coating. Hot-melt coating is particularly suitable when the adhesive composition is prepared as a 100% solids composition. This eliminates the need to dry the coated adhesive composition and eliminates the need to use solvents. Optional ingredients, such as antioxidants, plasticizers, or tackifiers, can be added to the hot-melt processable pressure-sensitive adhesive composition. These optional additives can be added in addition to or instead of adding additives to the reaction mixture.

[0053] Various hot melt mixing techniques using various hot melt mixing equipment are suitable for processing hot melt processable pressure sensitive adhesive compositions. Both batch and continuous mixing equipment can be used. Examples of batch methods include those using a BRABENDER (e.g., BRABENDER PREP CENTER, commercially available from CW Brabender Instruments, Inc., South Hackensack, NJ) or a BANBURY internal mixing and roll milling device (e.g., equipment available from Farrel Co., Ansonia, CN). Examples of continuous methods include single screw extrusion, twin screw extrusion, disk extrusion, reciprocating single screw extrusion, and pin barrel single screw extrusion. Continuous methods can utilize dispersive elements such as distributive elements, pin mixing elements, static mixing elements, and Maddock mixing elements and Saxton mixing elements. A single hot melt mixing device or a combination of hot melt mixing devices can be used to process the packaged adhesive composition of the present disclosure.

[0054] The hot melt blend output is coated onto a substrate to form an adhesive layer. When using a batch device, the resulting hot melt blend can be removed from the device and placed in a hot melt coater or extruder to coat onto a substrate. When using an extruder to prepare the hot melt blend, the blend can be extruded directly onto a substrate to form an adhesive layer in a continuous forming process. In a continuous forming process, the adhesive can be drawn through a film die and subsequently contacted with the substrate surface.

[0055] In many embodiments of the present disclosure, the hot-melt processable pressure-sensitive adhesive composition comprises a hot-melt processable packaged adhesive composition. Methods for preparing the hot-melt processable packaged adhesive composition are described above. The hot-melt processable packaged adhesive composition is formed by enclosing the above-described reaction mixture components in a package containing a thermoplastic material and polymerizing the reactive components within the package. The package can then be added to an extruder, additional optional components added as needed, and the adhesive composition can be hot-melt coated onto the surface of a substrate.

[0056] The adhesive layer thus formed may be a continuous layer, a patterned layer, or a combination thereof. Additionally, the adhesive layer may include sublayers. The sublayers may be the same adhesive material or different adhesive materials. When the sublayers are different materials, the different materials are typically hot-melt-processable pressure-sensitive adhesive compositions of the type described above. The sublayers may also be continuous or patterned. In some embodiments, the adhesive layer includes two sublayers, with the first sublayer being continuous and the second sublayer being disposed on the first sublayer in a pattern.

[0057] After the hot-melt processable pressure-sensitive adhesive layer is placed on the surface of the substrate, the adhesive layer is subjected to a photocrosslinking process, thereby photocrosslinking the hot-melt processable pressure-sensitive adhesive layer.In this process, the photosensitive crosslinking agent is activated by exposure to a high-intensity UV lamp to cause crosslinking.Examples of suitable UV lamps include medium-pressure mercury lamps.

[0058] The thickness of the photocrosslinked adhesive layer can vary depending on many factors, such as the desired use of the adhesive article, whether the adhesive layer contains sublayers, etc. Typically, the thickness of the adhesive layer can range from about 0.05 micrometers to about 200 micrometers.

[0059] As noted above, the adhesive articles of the present disclosure have a variety of desirable properties. Many of these properties make the adhesive articles particularly suitable for medical applications. As noted above, one particularly desirable feature is high moisture vapor transmission (MVT). This property can be measured in a variety of ways. The MCT measurement method used in this disclosure and described in the Examples section uses an article comprising a polyurethane film substrate with an adhesive layer. Such articles have a tensile strength of 350 g / m 2 ~20,000g / m 2 It has a 24-hour inverted water vapor transmission rate (MVT) of

[0060] Also among the desirable properties of the articles of the present disclosure is adhesion to both wet and dry surfaces. This property makes the adhesive article suitable for use on wet or dry skin. The adhesion of the adhesive article to wet or dry skin can be modeled in various ways. In this disclosure, protein leather is used as a particularly suitable test surface. Protein leather refers to artificial leather (sometimes called synthetic leather) composed of protein powder and resin that forms a flexible sheet. These sheets resemble leather in appearance and durability. The use of protein leather in testing samples is described in detail in the Examples section. One particularly suitable protein leather is Protein Leather PBZ13001 KAKI manufactured by Ideatex Japan Co., Ltd.

[0061] In some embodiments, the adhesive article has an adhesion to dry protein leather of between 40 grams / inch and 400 grams / inch. In some embodiments, the adhesive article has an adhesion to wet protein leather of between 30 grams / inch and 300 grams / inch. [Example]

[0062] These examples are for illustrative purposes only and are not meant to limit the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the remainder of the specification are by weight unless otherwise noted. Solvents and other reagents used were obtained from Sigma-Aldrich Chemical Company; Milwaukee, Wisconsin, unless otherwise noted. The following abbreviations are used: m = meter, cm = centimeter, mm = millimeter, nm = nanometer, in = inch, RPM = revolutions per minute, oz = ounce, g = gram, kg = kilogram, lb = pound, mL = milliliter, dL = deciliter, Pa = pascal, h = hour, mW = milliwatt, mJ = millijoule, kGy = kilogray, PPM = parts per million.

[0063] [Table 1]

[0064] Preparation of "100% Solids" or "Bulk" Polymers Used in the Examples A monomer mixture was prepared by blending reactive acrylic monomer, photoinitiator, and antioxidant in a jar. A magnetic stir bar was added to the mixture, and the mixture was placed on a stir plate to form a curable composition. EVA film was heat-sealed to form open-ended containers, each 18 cm x 5 cm. Approximately 24 grams of curable composition was filled into each container. Air was forced out the open end, and the container was then sealed using a heat sealer (obtained from JJ Elemer Corp., St. Louis, MO, under the trade name "MIDWEST PACIFIC IMPULSE SEALER"). The sealed EVA film containers with the curable composition sealed within were immersed in a constant temperature water bath at 16°C and irradiated on both sides with ultraviolet light (365 nm, 4.5 mW / cm). 2 ) for 9 minutes to polymerize the curable composition.

[0065] Test Method Test Method 1A: Gel Content Measurement Approximately 24 g of rectangular polymer sample was placed in the center of a pre-weighed rectangular mesh. The mesh was a stainless steel type 304 square weave wire cloth (obtained from McMaster-Carr Co., Elmhurst, IL) with a 150-mesh woven construction using 0.0026-inch (66 micrometer) wires and 0.0041-inch (104 micrometer) openings (available under the trade name "MCMASTER-CARR"). The overhanging portion of the mesh was folded inward to cover and secure the sample inside the mesh. The folded mesh with the encapsulated polymer was weighed and then immersed in approximately 8 oz. (approximately 240 mL) of ethyl acetate in a glass jar placed on a mechanical roller for 24 hours. The mesh with the polymer was then removed from the jar, dried in an oven at 120°C for 30 minutes, and reweighed to calculate the sample mass. The gelled insoluble portion of the polymer was calculated as gel weight percent ("Gel wt%") using the following formula:

[0066]

number

[0067] Test Method 1B: Gel Content Measurement Samples were compounded in a Bonnot. The heated samples were pumped into a twin-screw extruder. The resulting hot melt was coated onto a silicone release liner using a rod coater die. The die and extruder extrusion temperature was maintained at 320°F (160°C). The extruded samples were coated at a thickness of 1.5 mils (38 micrometers). The samples were then coated at 40-50 mJ / cm using a UV melt lamp and H bulb. 2 The polymer sample was immediately cured with UV-C light. Approximately 1-2 g of polymer sample was placed in the center of a pre-weighed rectangular mesh. The mesh was stainless steel type 304 square weave wire cloth (obtained from McMaster-Carr Co., Elmhurst, IL, under the trade name "MCMASTER-CARR") with a 150-mesh woven construction using 0.0026-inch (66 micrometer) wire and 0.0041-inch (104 micrometer) openings. The overhanging portion of the mesh was folded inward to cover and secure the sample inside the mesh. The folded mesh with the encapsulated polymer was weighed and then immersed in approximately 2 oz. of ethyl acetate in a glass jar placed on a mechanical roller for 4 hours. The ethyl acetate containing the dissolved polymer was removed, and 2 oz. of fresh ethyl acetate was added to the jar. The sample was then rolled on the mechanical roller overnight. The mesh with the polymer was then removed from the jar, dried in an oven at 65°C for 16 hours, and reweighed to calculate the sample mass. The gelled insoluble portion of the polymer was calculated as gel weight percent ("Gel wt%") using the following formula:

[0068]

number

[0069] Intrinsic Viscosity ("IV") Measurement The intrinsic viscosities ("IV") reported herein were obtained by conventional methods known to those skilled in the art. IV was obtained using a single-bath dilute solution polymer viscometer (obtained under the trade designation "MINIPV-X" from Cannon Instrument Co., State College, PA) in a water bath controlled at 27°C to measure the flow time of 10 mL of polymer solution (0.25 g / dL polymer in ethyl acetate). The subsequent test procedures and the equipment used are described in detail in "Textbook of Polymer Science," F.W. Billmeyer, Wiley-Interscience, Second Edition, 1971, Pages 84 and 85.

[0070] Adhesion test to steel The bond was severed to a steel specimen measuring 1.27 cm x 12.7 cm. The liner was then removed from the adhesive, and the adhesive was placed on the test panel using two passes of a 2.0 kilogram steel roller in each direction. The test surface was #320 stainless steel. Peel tests were performed at room temperature using a Zwick tensile tester (Z005) equipped with a 50 kg load cell at a separation rate of 30.5 centimeters per minute. The average peel force was recorded and used to calculate the average peel adhesion strength (g / cm). Tests were performed in six replicates. Reported results are the average of three measurements as oz / inch or oz / 25 mm, converted to Newtons per decimeter (N / dm).

[0071] Shear Test A 1-inch x 3-inch (2.54 x 7.62 cm) shear specimen was cut. The 1-inch (2.54 cm) sample was left hanging from the edge of the panel and folded over the center of the adapter hood, ensuring that the ends were folded back at a right angle and that the doubled section was at least 1 inch (2.54 cm) long. The area between the panel and the hook was reinforced with orange tape and stapled. The plate was transferred to a shear stand, and a 500-gram weight was hung from the hook. The time until the weight fell was recorded.

[0072] MVTR test Moisture vapor transmission rate (MVTR) testing was completed using a method based on European Standard EN 13726-2-2002. Samples were pre-cut to a diameter of 55.6 mm. A foil ring with an inner diameter of 42 mm and an outer diameter of 62 mm was placed over the dressing sample.

[0073] To test the upright MVTR, 20 mL of deionized water was placed inside the cup, and then a pre-cut 55.6 mm diameter sample with a foil ring was placed over the opening of the cup with the adhesive facing down. The top plate was then placed on top of the sample and screwed down. The cup was weighed, and the mass of the cup, sample, and liquid was recorded as W1. The cup was placed in a chamber at a temperature of 37°C ± 1°C and a relative humidity of 19%, with the sample facing up and not in contact with the liquid. After 18 to 24 hours, the cup was removed from the chamber, and the cup, sample, and liquid were immediately reweighed, and the mass was recorded as W2. The time the cup was in the chamber was recorded as T1. The upright MVTR was measured as follows: X=(W1-W2)×1000×24 / T1 (In the formula: X is the upright MVTR (gm -2 24h -1 ), W1 is the mass of the cup, sample, and liquid before the test period; W2 is the mass of the cup, sample, and liquid after the test period; where T1 is the test duration in hours).

[0074] A new set of dressings and cups were used for the inverted MVTR measurement. 30 ml of deionized water was used for the inverted MVTR test. The cup was inverted and placed in the chamber with the sample facing downwards and in contact with the liquid. After 4 hours, the cup was removed from the chamber and the cup, sample, and liquid were immediately reweighed and the mass recorded as W3. The time the cup was in the chamber was recorded as T2. Inverted MVTR was calculated using the following formula: X=(W1-W3)×1000×24 / T2 (In the formula: X is the inverted MVTR (gm -2 24h -1 ), W1 is the mass of the cup, sample, and liquid before the test period (i.e., before inverting the cylinder) when the test solution is in contact with the dressing; W3 is the mass of the cup, sample and liquid after the test period when the test solution is in contact with the dressing. T2 is the test duration in hours).

[0075] The reverse MVTR of the test sample was 1000 gm after 4 hours. -2 24h -1 If it was less than 18 hours, the sample was placed back into the chamber for a total time of 18 hours to 24 hours and the results were recalculated.

[0076] Rheological Testing Rheological testing was performed on the transfer adhesive using an ARES G2 rheometer equipped with an 8 mm parallel plate fixture (top) and a 25 mm parallel plate fixture (bottom). Small amplitude oscillatory shear was applied at 10 rad / s while the temperature was increased from 25°C to 130°C at a rate of 0°C / min.

[0077] Adhesion to protein leather Test substrate: Protein Leather PBZ13001 KAKI (IDEATEX Japan Co. Ltd.). Protein leather is made from a special resin containing protein powder. Protein Leather PBZ has excellent tactile properties similar to human skin, and many cosmetic companies use it for cosmetic testing purposes.

[0078] Synthetic Sweat Dispersion: A synthetic sweat dispersion was used for the wet adhesion test and was prepared by mixing the following ingredients:

[0079] Synthetic sweat dispersion: 750ml of synthetic sweat + 0.75g of synthetic sebum

[0080] [Table 2]

[0081] Dry adhesion to protein leather A 25 mm × 125 mm tape sample was laminated onto a 30 mm × 125 mm PL using a 2 kg roller. The applied tape was removed by T-peel at a test speed of 150 mm / min using a peel tester SP-2100 (Imass), and the average peel adhesion was recorded.

[0082] Wet adhesion to protein leather The synthetic sweat dispersion was sprayed onto the protein leather and allowed to dwell for 10 to 40 minutes. After wiping the protein leather, the synthetic sweat dispersion was sprayed again (5 times). T-peel adhesion was measured using the same procedure as for dry adhesion.

[0083] Shrinkage test A 10 cm x 10 cm square of adhesive on a release liner was cut and folded parallel to the coating direction of the solvent-free adhesive. Gentle pressure was applied, and the release liner was removed from the top. Now, for the 10 cm x 5 cm adhesive sample, the adhesive was folded again parallel to the coating direction while gently applying pressure, resulting in a 10 cm x 2.5 cm sample. The folding and pressure process was repeated once more, resulting in a final sample dimension of 10 cm (length) x 1.25 cm (width), which was defined as the unrelaxed length. The adhesive sample was then placed on a bed of talc, and the adhesive in the talc was heated to 65°C for 3 minutes. The length of the sample was then measured to obtain the "relaxed" sample length. The shrinkage of the sample was defined as ("unrelaxed length" - "relaxed length") / "relaxed length."

[0084] Wet shear adhesion to protein leather DCT (double-coated tape - tape laminated to a Sontara backing) or ATT (adhesive transfer tape - tape laminated to two release liners) samples were cut to a size of 25 mm x 25 mm. After removing the liners, the first adhesive surface was laminated to a polycarbonate sheet (30 mm x 30 mm x 2 mm). The filament tape was laminated to the other surface of the polycarbonate sheet as a pull tab. The synthetic sweat dispersion was sprayed onto the protein leather and allowed to dwell for 10 to 40 minutes. After wiping the protein leather, the synthetic sweat dispersion was sprayed again (5 times). After removing the second liner, the test sample was placed on a wet test substrate, and a 275 g weight was then placed on it for 1 minute. The filament tab was pulled horizontally at a test speed of 90 inches / minute, and the peak adhesive force was measured in Newtons.

[0085] Example Example 1 (E-1A to E-1H) Samples of materials from Examples E-1A through E-1H in Table 1 (raw material RM is parts by weight) were compounded in a twin-screw extruder at 300°F (149°C) and 300 rpm for 3 minutes. The resulting hot melt was coated onto a silicone release liner using a drop die. The die and extruder extrusion temperature was maintained at 300°F (149°C). The extruded samples were coated to a thickness of 1.5 mils (38 micrometers). In a separate step, portions of the samples were then irradiated with 40 mJ / cm using a UV melt lamp and H bulb. 2 The samples were cured with UV-C radiation at 1000 W. The samples were then hand laminated onto polyurethane to create the final structure. The gel content was tested and is summarized below.

[0086] [Table 3]

[0087] Example 2 (E-2A to E-2D) and Comparative Example CE2 The solventless acrylate adhesives E-2A through E-2D and Comparative Example CE2 shown in Table 2 (raw material RM is parts by weight) were coated onto a double-sided silicone coated liner (Loparex, Hammond, WI) at a coating weight of 6 grains per 24 inches. 2 (6 grains / 155cm 2 ) and then pattern coated with 50 mJ / cm 2 The adhesive was UV cured (Hammer UV unit, H-Bulb) at a dose of 100 kJ / g. The adhesive was laminated with a polyurethane film (Lubrizol, Wickliffe, OH) and then gamma irradiated at approximately 30 kGy. The gel content, adhesion to steel, and shear performance tests are summarized in Table 2 below.

[0088] [Table 4]

[0089] Example 3 (E-3A to E-3C) and Comparative Example CE3 The solventless acrylate adhesives E-3A through E-3C and CE3 shown in Table 3 (raw material RM is parts by weight) were applied to a double-sided silicone coated liner (Loparex, Hammond, WI) at a coating weight of 5.5 grains per 24 inches. 2 (5.5 grains / 155cm 2 ) and then pattern coated with 40 mJ / cm 2 The adhesive was UV cured (Hammer UV unit, H-Bulb) at a dose of 100 kJ / cm. The adhesive was laminated with a polyurethane film (Lubrizol, Wickliffe, OH) and then gamma irradiated at approximately 30 kGy. Adhesion to steel was measured and is summarized in Table 3 below.

[0090] [Table 5]

[0091] Example 4 (E-4A to E-4I) Solventless acrylate adhesives E-4A through E-4I (raw material RM is parts by weight) shown in Table 4 were applied to a double-sided silicone coated liner (Loparex, Hammond, WI) at a coating weight of 5.5 grains per 24 inches. 2 (5.5 grains / 155cm 2 ) and then pattern coated with 50 mJ / cm 2 The adhesive was UV cured (Hammer UV unit, H-Bulb) at a dose of 100 kJ / cm². The adhesive was laminated with a polyurethane film (Lubrizol, Wickliffe, OH) and then gamma irradiated at approximately 30 kGy. Adhesion to steel and water vapor transmission rate data are summarized in Table 4 below.

[0092] [Table 6]

[0093] Example 5 (E-5A to E-5C and CE5A, CS5B) The solventless acrylate adhesives E-5A through E-5C and CE5A shown in Table 5 (raw material RM is parts by weight) were applied to a double-sided silicone coated liner (Loparex, Hammond, WI) at a coating weight of 5.5 grains per 24 inches. 2 (5.5 grains / 155cm 2 ) and then pattern coated with 50 mJ / cm 2 The adhesive was UV cured (Hammer UV unit, H-Bulb) at a dose of 1000 kJ / cm². The CE5B adhesive was continuously coated without UV. The adhesive was laminated with a polyurethane film (Lubrizol, Wickliffe, OH) and then gamma irradiated at approximately 30 kGy.

[0094] [Table 7]

[0095] The samples were evaluated in the clinical trial described below. A controlled, randomized, single-blind, in-house clinical trial was conducted. Three sets of samples were first cut into 3-inch (7.6 cm) strips. Samples prepared with 2% CHG (chlorhexidine gluconate) swabs (1.8%-2.2% CHG, 63%-77% alcohol) were then applied to the intact skin on the backs of healthy volunteers. The first set of samples was removed using the IMASS SP-2100 to obtain TO / pre-exercise skin adhesion data within 5-15 minutes of dwell time after the initial application. The subjects were then asked to exercise by either running or walking on a treadmill to induce sweating and simulate wet conditions. When the subjects reached their target heart rate, the heart rate was maintained for 30 minutes. TO / post-exercise samples were then removed using the IMASS SP-2100 to obtain skin adhesion data. After 24 hours, T24 / post-exercise samples were removed to obtain skin adhesion data. Edge lift on a 0% to 100% scale was also observed and recorded before removal of the T24 / post-exercise sample. The results are summarized in Table 6.

[0096] [Table 8] EM-05-014900 n=16.

[0097] Example 6 (E-6A to E-6D) The solventless acrylate adhesives E-6A to E-6D shown in Table 7 (Raw material RM is parts by weight) were applied to a double-sided silicone coated liner (Fujimori Kogyo, Filmbyna TSB / TSC) at a coating weight of 23.5 grains per 24 inches. 2 (23.5 grains / 155cm 2 ) and then 60 mJ / cm 2 The adhesive was UV cured (Heraeus UV unit, H-Bulb) at a dose of 1000 kJ / cm². The adhesive was laminated with Sontara and then tested for adhesion to protein leather. In Example E-6D, samples before and after lamination to Sontara (referred to as ATT for adhesive transfer tape) and Sontara (referred to as DCT for double-sided tape) were tested for wet shear on protein leather according to the test method described above. The results are shown in Table 7.

[0098] [Table 9]

[0099] Example 7 (E-7A to E-7F) Solventless acrylate adhesives E-7A through E-7E (raw material RM is parts by weight) shown in Table 8 were applied to a double-sided silicone coated liner (Loparex, Hammond, WI) at coating weights of 6 to 12 grains per 24 inches. 2 (6 grains / 155cm 2 ~12 grains / 155cm 2 ) either continuously or in a pattern, followed by 50 mJ / cm 2 ~60mJ / cm 2The adhesive was UV cured (Hammer UV unit, H-Bulb) at a dose of 100 kJ / cm. Two layers of adhesive were laminated together, which were then laminated onto either Sontara (Glatfelter, Charlotte, NC) or polyurethane film (BASF, Ludwigshafen, Germany), then gamma irradiated at approximately 30 kGy and tested for adhesion to protein leather (Table 9).

[0100] [Table 10]

[0101] [Table 11]

Claims

1. A substrate; a layer disposed on at least a portion of the substrate, the layer comprising at least one coated, photocrosslinked hot-melt processable pressure-sensitive adhesive, the at least one hot-melt processable pressure-sensitive adhesive comprising: General formula I: CH ２ =CR １ -(CO)-OR ２ Formula I (In the formula, R １ is hydrogen or a methyl group, R ２ is an alkyl, alkenyl, or aryl group containing from 4 to 20 carbon atoms; and General formula II: CH ２ =CR １ -(CO)-OR ３ Formula II (In the formula, R １ is hydrogen or a methyl group, R ３ is an alkylene oxide group capped with an alkyl group; and at least one copolymerizable reinforcing monomer; at least one copolymerizable photocrosslinker; and at least one initiator.

2. The article of claim 1 , wherein the substrate comprises a polymeric film, fabric, nonwoven, foam, paper, mesh, adhesive, or release liner.

3. General formula I: CH ２ =CR １ -(CO)-OR ２ Formula I (In the formula, R １ is hydrogen or a methyl group, R ２ is an alkyl group containing from 4 to 12 carbon atoms.

4. The at least one second (meth)acrylate monomer has the general formula II: CH ２ =CR １ -(CO)-OR ３ Formula II (In the formula, R １ is hydrogen or a methyl group, R ３ is a polyethylene oxide group capped with an alkyl group.

5. The at least one second (meth)acrylate monomer has the general formula II: CH ２ =CR １ -(CO)-OR ３ Formula II (In the formula, R １ is hydrogen or a methyl group, R ３ is of general formula III: -(CH) ２ -CH ２ -O) ｎ -CH ３ Formula III 10. The article of claim 1, wherein n is an integer from 8 to 230.

6. The article of claim 1 , wherein the at least one copolymerizable reinforcing monomer comprises an acid-functional monomer.

7. the reaction mixture 50 parts by weight to 85 parts by weight of at least one first monomer; 5 parts by weight to 30 parts by weight of at least one second monomer; 3 parts to 25 parts by weight of at least one copolymerizable reinforcing monomer; 0.05 parts by weight to 0.5 parts by weight of at least one copolymerizable photocrosslinker; 0.01 parts by weight to 1.0 parts by weight of at least one initiator.

8. The article of claim 1 , wherein the layer comprising at least one hot-melt processable pressure-sensitive adhesive comprises a continuous layer, a patterned layer, or a combination thereof.

9. 10. The article of claim 1, wherein the layer comprising at least one hot-melt processable pressure-sensitive adhesive comprises a layer of a first hot-melt processable pressure-sensitive adhesive composition comprising a continuous layer and a layer of a second hot-melt processable pressure-sensitive adhesive composition comprising a patterned layer.

10. The article comprises a polyurethane film substrate and has a thickness of 350 g / m ２ ~20,000g / m ２ 10. The article of claim 1, having a 24-hour inverted moisture vapor transmission rate (MVT) of

11. 10. The article of claim 1, wherein the article has a peel adhesion to dry protein leather of from 40 grams / inch to 400 grams / inch.

12. 10. The article of claim 1, wherein the article has a peel adhesion to wet protein leather of from 30 grams / inch to 300 grams / inch.

13. 10. The article of claim 1, wherein the layer comprising the hot-melt processable pressure-sensitive adhesive further comprises at least one additive selected from antioxidants, tackifiers, and plasticizers.

14. General formula I: CH ２ =CR １ -(CO)-OR ２ Formula I (In the formula, R １ is hydrogen or a methyl group, R ２ is an alkyl, alkenyl, or aryl group containing from 4 to 20 carbon atoms; and General formula II: CH ２ =CR １ -(CO)-OR ３ Formula II (In the formula, R １ is hydrogen or a methyl group, R ３ is an alkylene oxide group capped with an alkyl group; and at least one copolymerizable reinforcing monomer; at least one copolymerizable photocrosslinker; and at least one initiator.

15. The adhesive composition of claim 14 , wherein the reaction mixture further comprises a chain transfer agent.

16. General formula I: CH ２ =CR １ -(CO)-OR ２ Formula I (In the formula, R １ is hydrogen or a methyl group, R ２ is an alkyl group containing from 4 to 12 carbon atoms.

17. The at least one second (meth)acrylate monomer has the general formula II: CH ２ =CR １ -(CO)-OR ３ Formula II (In the formula, R １ is hydrogen or a methyl group, R ３ is a polyethylene oxide group capped with an alkyl group.

18. The at least one second (meth)acrylate monomer has the general formula II: CH ２ =CR １ -(CO)-OR ３ Formula II (In the formula, R １ is hydrogen or a methyl group, R ３ is of general formula III: -(CH) ２ -CH ２ -O) ｎ -CH ３ Formula III The adhesive composition of claim 14, wherein n is an integer of 8 to 230.

19. the reaction mixture 50 parts by weight to 85 parts by weight of at least one first monomer; 5 parts by weight to 30 parts by weight of at least one second monomer; 3 parts to 25 parts by weight of at least one copolymerizable reinforcing monomer; 0.05 parts by weight to 0.5 parts by weight of at least one copolymerizable photocrosslinker; 0.01 to 1.0 parts by weight of at least one initiator.

20. The adhesive composition of claim 14, wherein the hot-melt processable (meth)acrylate-based copolymer is photocrosslinkable.

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