Adhesive with thermal release properties

Abstract

Described herein is a polymer composition having a glass transition temperature below - 10°C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate. Also described herein is an adhesive comprising a backing and a polymer composition having a glass transition temperature is below -10 °C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate.

Description

[0001] Attorney Docket No. 205691-0067-00WO

[0002] TITLE

[0003] Adhesive with Thermal Release Properties

[0004] CROSS REFERENCE TO RELATED APPLICATIONS

[0005] The present application claims priority to U.S. Provisional Application No. 63 / 707,911, filed October 16, 2024, which is incorporated by reference herein in its entirety.

[0006] BACKGROUND OF THE INVENTION

[0007] Adhesives feature prominently in the healthcare industry for surgical procedures and appliance bonding, as well as in general wound care (e.g., band-aids, bandages, medical tape, etc.). These products may be used to help to cover traumatic wounds, surgical wounds, intravenous sites, and attach drains or other devices to the skin. Medical adhesives can be produced using a wide variety of materials, though they are typically composed of synthetic or biological materials. Different adhesives can be incorporated into medical devices; these adhesives can be disposable (e.g., one-time use), or can be used multiple times. Medical adhesives often have specific properties, such as pressure sensitivity, dissolvability, or electric conductivity. Unfortunately, there are over 1.5 million injuries annually in the US caused by medical adhesive removal. Skin burns, blisters, irritation, and the like, can render medical adhesive removal more difficult.

[0008] Pressure sensitive adhesives bond to a surface by being pressed onto the substrate and are most often used for skin bandages. The adhesives on these bandages can be made with different materials that include rubbers, acrylates, silicone formulations, acrylics, silicone, polyurethane, bioadhesives, and emulsion adhesives. Emulsion adhesives consist of a mixture of acrylic polymer, surfactants, and other additives that manage the performance. Acrylic adhesives are generally used for suturing wounds, but can also be used for pressure sensitive adhesives. These adhesives are peelable and are thus more easily removed due to the weaker adhesive nature, however they can still be difficult to remove, especially in patients with fragile skin (Tokumura et al., 2007, Skin Research and Technology, 13:211-216).

[0009] Providers in healthcare struggle with removing pressure sensitive adhesives from fragile skin, next to healing wounds, or from sites of frequent reapplication. With some patients, removal can cause a medical adhesive-related skin injury (MARSI), which can present as Attorney Docket No. 205691-0067-00WO persistent erythema, skin stripping, blisters, or bleeding. Skin tears become more common as people age, because the skin becomes drier and more delicate: the skin becomes thin due to sclerotic blood vessels that feed less moisture and nutrients to the skin tissue. The patient factors that can put someone at risk of MARSI include newborns, older adults, medications, malnutrition, and dehydration.

[0010] Thus, there is a need in the art for adhesives with improved release properties. The present invention satisfies this unmet need.

[0011] SUMMARY OF THE INVENTION

[0012] In one aspect, the current invention relates to a polymer composition having a glass transition temperature below -10 °C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate. In one embodiment, the acrylic acid in the polymer composition is selected from the group consisting of methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2- butylacrylic acid. In one embodiment, the acrylic acid in the polymer composition is methacrylic acid. In one embodiment, the alkyl acrylate in the polymer composition is a C2-4 alkyl acrylate. In one embodiment, the alkyl acrylate in the polymer composition is selected from the group consisting of methyl acrylate, methyl methacrylate, branched alkyl acrylates, isooctyl acrylate, 4- methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, sulfoethyl methacrylate, tert-butyl acrylate, isobornyl acrylate, butyl methacrylate, vinyl acetate, lauryl acrylate, octadecyl acrylate, acrylonitrile, and mixtures thereof. In one embodiment, the alkyl acrylate in the polymer composition is butyl acrylate.

[0013] In one embodiment, the polymer composition comprises acrylic acid at a concentration between 1% and 5% (w / w). In one embodiment, the polymer composition comprises acrylic acid at a concentration between 1% and 3% (w / w). In one embodiment, the polymer composition has a glass transition temperature below -20 °C. In one embodiment, the polymer composition has a glass transition temperature between -18 °C and -28 °C. In one embodiment, the polymer composition is noncrystalline. In one embodiment, the polymer composition further comprises an adhesion enhancer. In one embodiment, the polymer composition further comprises a surfactant. In one embodiment, the polymer composition further comprises a plasticizer. Attorney Docket No. 205691-0067-00WO

[0014] In one aspect, the current invention relates to an adhesive comprising a backing and a polymer composition having a glass transition temperature is below -10 °C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate. In one embodiment, the acrylic acid in the adhesive is methacrylic acid. In one embodiment, the alkyl acrylate in the adhesive is butyl acrylate. In one embodiment, the glass transition temperature of the adhesive is between -18 °C and -28 °C. In one embodiment, the backing is selected from the group consisting of a woven fabric, a non-woven fabric, a net, a knit, a gauze, a fdm, an electrode, a surgical dressing, a transdermal drug delivery patch, a synthetic film, an adhesive tape, and a pad. In one embodiment, the adhesive is a medical adhesive.

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The following detailed description of various embodiments of the invention will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings illustrative embodiments. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities of the embodiments shown in the drawings.

[0017] Figure 1 depicts a graph with results from a heat lamp thermoregulated 180-degree peel experiment of standard Consumer Value Store (CVS) adhesives.

[0018] Figure 2 depicts a graph with results from a heat lamp thermoregulated 180-degree peel experiment of novel adhesives.

[0019] Figure 3 depicts a graph with results from a water bath thermoregulated 180-degree peel experiment of standard CVS adhesives.

[0020] DETAILED DESCRIPTION

[0021] The invention is in part based on the benefit of using an adhesive comprising a polymer composition with thermal release properties at lower temperatures, which require less force for removal.

[0022] It is to be understood that the Drawings and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clear understanding of the present invention, while eliminating, for the purpose of clarity, many other elements found in polymer Attorney Docket No. 205691-0067-00WO composites and methods of making. Those of ordinary skill in the art may recognize that other elements and / or steps are desirable and / or required in implementing the present invention. However, because such elements and steps are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements and steps is not provided herein. The disclosure herein is directed to all such variations and modifications to such elements and methods known to those skilled in the art.

[0023] As used herein, each of the following terms has the meaning associated with it in this section. Unless defined otherwise, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0024] The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.

[0025] As used herein, the term “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending on the context in which it is used. As used herein when referring to a measurable value such as an amount, a temporal duration, and the like, the term “about” is meant to encompass variations of ±20%, ±10%, ±5%, ±1 %, or ±0.1 % from the specified value, as such variations are appropriate to perform the disclosed methods.

[0026] Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.

[0027] As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does Attorney Docket No. 205691-0067-00WO not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety.

[0028] As used herein, the term “alkyl,” by itself or as part of another substituent means, unless otherwise stated, a straight or branched chain hydrocarbon having the number of carbon atoms designated (i.e. Ci-6 means one to six carbon atoms) and including straight, branched chain, or cyclic substituent groups. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and cyclopropylmethyl.

[0029] As used herein, the term “substituted alkyl” means alkyl as defined above, substituted by one, two or three substituents selected from the group consisting of halogen, -OH, alkoxy, -NH2, amino, azido, -N(CHs)2, -C(=O)OH, trifluoromethyl, -C=N, -C(=O)O(Ci-C4)alkyl, -C(=O)NH2, - SO2NH2, -C(=NH)NH2, and -NO2. Examples of substituted alkyls include, but are not limited to, 2,2-difluoropropyl, 2-carboxycyclopentyl and 3 -chloropropyl.

[0030] As used herein, the term “olefin” encompasses compounds having a C=C bond.

[0031] The term "olefin-based polymer," as used herein, refers to a polymer that contains at least a majority weight percent, based on the weight of the polymer, polymerized olefin (for example, ethylene or propylene), and, optionally, one or more additional comonomers.

[0032] As used herein, the term “heteroalkyl” by itself or in combination with another term means, unless otherwise stated, a stable straight or branched chain alkyl group consisting of the stated number of carbon atoms and one or two heteroatoms selected from the group consisting of O, N, and S, and wherein the nitrogen and sulfur atoms may be optionally oxidized and the nitrogen heteroatom may be optionally quatemized. The heteroatom(s) may be placed at any position of the heteroalkyl group, including between the rest of the heteroalkyl group and the fragment to which it is attached, as well as attached to the most distal carbon atom in the heteroalkyl group. Examples include -O-CH2-CH2-CH3, -CH2-CH2-CH2-OH, -CH2-CH2-NH-CH3, -CH2-S-CH2-CH3, and -CH2CH2-S(=O)-CH3. Up to two heteroatoms may be consecutive, such as, for example, -CH2-NH-OCH3, or -CH2-CH2-S-S-CH3.

[0033] As used herein, the term “alkoxy” employed alone or in combination with other terms means, unless otherwise stated, an alkyl group having the designated number of carbon atoms, as Attorney Docket No. 205691-0067-00WO defined above, connected to the rest of the molecule via an oxygen atom, such as, for example, methoxy, ethoxy, 1 -propoxy, 2-propoxy (isopropoxy) and the higher homologs and isomers.

[0034] As used herein, the term “halo” or “halogen” alone or as part of another substituent means, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0035] As used herein, the term “cycloalkyl” refers to a mono cyclic or polycyclic non-aromatic radical, wherein each of the atoms forming the ring (i.e. skeletal atoms) is a carbon atom. In one embodiment, the cycloalkyl group is saturated or partially unsaturated. In another embodiment, the cycloalkyl group is fused with an aromatic ring. Cycloalkyl groups include groups having from 3 to 10 ring atoms. Illustrative examples of cycloalkyl groups include, but are not limited to, the following moi eties:

[0036] Monocyclic cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Dicyclic cycloalkyls include, but are not limited to, tetrahydronaphthyl, indanyl, and tetrahydropentalene. Polycyclic cycloalkyls include adamantine and norbornane. The term cycloalkyl includes “unsaturated nonaromatic carbocyclyl” or “nonaromatic unsaturated carbocyclyl” groups, both of which refer to a nonaromatic carbocycle as defined herein, which contains at least one carbon double bond or one carbon triple bond.

[0037] As used herein, the term “heterocycloalkyl” or “heterocyclyl” or “heterocyclic” refers to a cyclic group containing one to four ring heteroatoms each selected from O, S, and N. In one embodiment, each heterocycloalkyl group has from 4 to 10 atoms in its ring system, with the proviso that the ring of said group does not contain two adjacent O atoms. In another embodiment, the heterocycloalkyl group is fused with an aromatic ring. In one embodiment, the nitrogen and sulfur heteroatoms may be optionally oxidized, and the nitrogen atom may be optionally quaternized. The heterocyclic system may be attached, unless otherwise stated, at any Attorney Docket No. 205691-0067-00WO heteroatom or carbon atom that affords a stable structure. A heterocycle may be aromatic or nonaromatic in nature. In one embodiment, the heterocycle is a heteroaryl.

[0038] An example of a 3-membered heterocycloalkyl group includes, and is not limited to, aziridine. Examples of 4-membered heterocycloalkyl groups include, and are not limited to, azetidine and a beta lactam. Examples of 5-membered heterocycloalkyl groups include, and are not limited to, pyrrolidine, oxazolidine and thiazolidinedione. Examples of 6-membered heterocycloalkyl groups include, and are not limited to, piperidine, morpholine and piperazine.

[0039] Examples of non-aromatic heterocycles include monocyclic groups such as aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, imidazoline, dioxolane, sulfolane, 2,3 -dihydrofuran, 2, 5 -dihydrofuran, tetrahydrofuran, thiophane, piperidine, 1,2,3,6-tetrahydropyridine, 1,4-dihydropyridine, piperazine, morpholine, thiomorpholine, pyran,

[0040] 2.3-dihydropyran, tetrahydropyran, 1,4-dioxane, 1,3-dioxane, homopiperazine, homopiperidine,

[0041] 1.3-dioxepane, 4,7-dihydro-l,3-dioxepin, and hexamethyleneoxide.

[0042] As used herein, the term “aromatic” refers to a carbocycle or heterocycle with one or more polyunsaturated rings and having aromatic character, i.e. having (4n + 2) delocalized it (pi) electrons, where n is an integer.

[0043] As used herein, the term “aryl,” employed alone or in combination with other terms, means, unless otherwise stated, a carbocyclic aromatic system containing one or more rings (typically one, two or three rings), wherein such rings may be attached together in a pendent manner, such as a biphenyl, or may be fused, such as naphthalene. Examples of aryl groups include phenyl, anthracyl, and naphthyl.

[0044] As used herein, the term “aryl-(Ci-C3)alkyl” means a functional group wherein a one- to three-carbon alkylene chain is attached to an aryl group, e.g., -CH2CH2- phenyl, -CHz-phenyl (benzyl), aryl-CHz- and aryl-CH(CH3)-. The term “substituted aryl-(Ci-C3)alkyl” means an aryl-(Ci-C3)alkyl functional group in which the aryl group is substituted. Similarly, the term “heteroaryl-(Ci-C3)alkyl” means a functional group wherein a one to three carbon alkylene chain is attached to a heteroaryl group, e.g., -CEECHz-pyridyl. The term “substituted heteroaryl-(Ci-C3)alkyl” means a heteroaryl-(Ci-C3)alkyl functional group in which the heteroaryl group is substituted.

[0045] As used herein, the term “heteroaryl” or “heteroaromatic” refers to aryl groups which contain at least one heteroatom selected from N, O, Si, P, and S; wherein the nitrogen and sulfur Attorney Docket No. 205691-0067-00WO atoms may be optionally oxidized, and the nitrogen atom(s) may be optionally quaternized. Heteroaryl groups may be substituted or unsubstituted. A heteroaryl group may be attached to the remainder of the molecule through a heteroatom. A polycyclic heteroaryl may include one or more rings that are partially saturated. Examples include tetrahydroquinoline,

[0046] 2.3-dihydrobenzofuryl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4- imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4- isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3- thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2- benzimidazolyl, 5-indolyl, 1 -isoquinolyl, 5 -isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3- quinolyl, and 6-quinolyl.

[0047] Examples of non-aromatic heterocycles include monocyclic groups such as aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazoline, pyrazolidine, dioxolane, sulfolane, 2, 3 -dihydrofuran, 2, 5 -dihydrofuran, tetrahydrofuran, thiophane, piperidine, 1,2,3,6-tetrahydropyridine, 1,4-dihydropyridine, piperazine, morpholine, thiomorpholine, pyran,

[0048] 2.3-dihydropyran, tetrahydropyran, 1,4-dioxane, 1,3-dioxane, homopiperazine, homopiperidine,

[0049] 1.3-dioxepane, 4,7-dihydro-l,3-dioxepin and hexamethyleneoxide.

[0050] Examples of heteroaryl groups also include pyridyl, pyrazinyl, pyrimidinyl (particularly 2- and 4-pyrimidinyl), pyridazinyl, thienyl, furyl, pyrrolyl (particularly 2-pyrrolyl), imidazolyl, thiazolyl, oxazolyl, pyrazolyl (particularly 3- and 5-pyrazolyl), isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, tetrazolyl, 1,2,3-thiadiazolyl, 1,2,3-oxadiazolyl, 1,3,4-thiadiazolyl and 1,3,4-oxadiazolyl.

[0051] Examples of polycyclic heterocycles and heteroaryls include indolyl (particularly 3-, 4-, 5-, 6- and 7-indolyl), indolinyl, quinolyl, tetrahydroquinolyl, isoquinolyl (particularly 1- and 5 -isoquinolyl), 1,2,3,4-tetrahydroisoquinolyl, cinnolinyl, quinoxalinyl (particularly 2- and 5-quinoxalinyl), quinazolinyl, phthalazinyl, 1,8-naphthyridinyl, 1,4-benzodioxanyl, coumarin, dihydrocoumarin, 1,5-naphthyridinyl, benzofuryl (particularly 3-, 4-, 5-, 6- and 7-benzofuryl),

[0052] 2.3-dihydrobenzofuryl, 1,2-benzisoxazolyl, benzothienyl (particularly 3-, 4-, 5-, 6-, and 7-benzothienyl), benzoxazolyl, benzothiazolyl (particularly 2-benzothiazolyl and 5-benzothiazolyl), purinyl, benzimidazolyl (particularly 2-benzimidazolyl), benzotri azolyl, thioxanthinyl, carbazolyl, carbolinyl, acridinyl, pyrrolizidinyl, and quinolizidinyl. Attorney Docket No. 205691-0067-00WO

[0053] As used herein, the term “substituted” means that an atom or group of atoms has replaced hydrogen as the substituent attached to another group. The term “substituted” further refers to any level of substitution, namely mono-, di-, tri-, tetra-, or penta-substitution, where such substitution is permitted. The substituents are independently selected, and substitution may be at any chemically accessible position. In one embodiment, the substituents vary in number between one and four. In another embodiment, the substituents vary in number between one and three. In yet another embodiment, the substituents vary in number between one and two.

[0054] As used herein, the term “optionally substituted” means that the referenced group may be substituted or un substituted. In one embodiment, the referenced group is optionally substituted with zero substituents, i.e., the referenced group is unsubstituted. In another embodiment, the referenced group is optionally substituted with one or more additional group(s) individually and independently selected from groups described herein.

[0055] In one embodiment, the substituents are independently selected from the group consisting of oxo, halogen, -CN, -NHz, -OH, -NH(CH3), -N(CH3)2, alkyl (including straight chain, branched and / or unsaturated alkyl), substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, fluoro alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkoxy, fluoroalkoxy, -S-alkyl, S(=0)2alkyl, S(=O)2N[H, alkyl, or aryl], - C(=O)NH[substituted or unsubstituted alkyl, or substituted or unsubstituted phenyl], -C(=O)N[H or substituted or unsubstituted alkyl or aryl]2, -OC(=O)N[substituted or unsubstituted alkyl]2, -NHC(=O)NH[substituted or unsubstituted alkyl, or substituted or unsubstituted phenyl], -NHC(=O)alkyl, -N[substituted or unsubstituted alkyl]C(=O)[substituted or unsubstituted alkyl], -NHC(=0) [substituted or unsubstituted alkyl], -C(OH)[substituted or unsubstituted alkyl]2, and - C(NH2)[substituted or unsubstituted alkyl]2. In another embodiment, by way of example, an optional substituent is selected from oxo, fluorine, chlorine, bromine, iodine, -CN, -NH2, -OH, - NH(CH3), -N(CH3)2, -CH3, -CH2CH3, -CH(CH3)2, -CF3, -CH2CF3, -OCH3, -OCH2CH3, - OCH(CH3)2, -0CF3, - OCH2CF3, -S(=O)2-CH3, -C(=0)NH2, -C(=0)-NHCH3, - NHC(=0)NHCH3, -C(=O)CH3, -ON(O)2, and -C(=0)0H. In yet one embodiment, the substituents are independently selected from the group consisting of C1-6 alkyl, -OH, C1-6 alkoxy, halo, amino, acetamido, oxo and nitro. As used herein, where a substituent is an alkyl or alkoxy group, the carbon chain may be branched, straight or cyclic. Attorney Docket No. 205691-0067-00WO

[0056] The term “derivative” refers to a small molecule that differs in structure from the reference molecule but retains the essential properties of the reference molecule. A derivative may change its interaction with certain other molecules relative to the reference molecule. A derivative molecule may also include a salt, an adduct, tautomer, isomer, or other variant of the reference molecule.

[0057] The term “tautomers” are constitutional isomers of organic compounds that readily interconvert by a chemical process (tautomerization).

[0058] The term “isomers” or “stereoisomers” refer to compounds, which have identical chemical constitution, but differ with regard to the arrangement of the atoms or groups in space.

[0059] As used herein, the term “polymer” refers to a molecule composed of repeating structural units typically connected by covalent chemical bonds. The term “polymer” is also meant to include the terms copolymer and oligomers.

[0060] As used herein, the term “polymerization” refers to at least one reaction that consumes at least one functional group in a monomeric molecule (or monomer), oligomeric molecule (or oligomer) or polymeric molecule (or polymer), to create at least one chemical linkage between at least two distinct molecules (e.g., intermolecular bond), at least one chemical linkage within the same molecule (e.g., intramolecular bond), or any combination thereof. A polymerization reaction may consume between about 0% and about 100% of the at least one functional group available in the system. In one embodiment, polymerization of at least one functional group results in about 100% consumption of the at least one functional group. In another embodiment, polymerization of at least one functional group results in less than about 100% consumption of the at least one functional group.

[0061] As used herein, the term “polymer segment” means and includes a grouping of multiple monomer units of a single type (i.e., a homopolymer segment) or multiple types (i.e., a copolymer segment) of constitutional units into a continuous region of a polymer block that are of a length that is insufficient for microphase separation to inherently occur with other segments in the same block type.

[0062] As used herein, the term “block copolymer” means and includes a polymer composed of chains where each chain contains two or more polymer blocks as defined above and at least two of the blocks are of sufficient segregation strength (e.g., / N>10) for those blocks to phase separate. A wide variety of block polymers are contemplated herein including diblock Attorney Docket No. 205691-0067-00WO copolymers (i.e., polymers including two polymer blocks), triblock copolymers (i.e., polymers including three polymer blocks), multiblock copolymers (i.e., polymers including more than three polymer blocks), and combinations thereof.

[0063] In some examples, the present invention relates to a polymer composition having a glass transition temperature below -10 °C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate. In some examples, the polymer composition is in the form of a gel. In some examples, the polymer composition is in the form of a water-soluble hydrogel. In some examples, the polymer composition is in the form of a powder. In some examples, the polymer composition is in the form of a paste. In some examples, the polymer composition is in the form of a liquid. In some examples, the composition loses its adhesiveness upon cooling.

[0064] In some examples, the polymer composition comprises one or more poly(acrylates). In some examples, the composition comprises alkyl acrylates containing alkyl groups with between 2-20 carbon atoms (C2-20 alkyl acrylate). In some examples, the composition comprises alkyl methacrylates containing alkyl groups with between 2-20 carbon atoms (C2-20 alkyl methacrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-10 carbon atoms (C2-10 alkyl acrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-9 carbon atoms (C2-9 alkyl acrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-8 carbon atoms (C2-8 alkyl acrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-7 carbon atoms (C2-7 alkyl acrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-6 carbon atoms (C2-6 alkyl acrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-5 carbon atoms (C2-5 alkyl acrylate). In some examples, the alkyl acrylate contains alkyl groups with between 2-4 carbon atoms (C2-4 alkyl acrylate).

[0065] In some examples, the alkyl acrylates and alkyl methacrylates include, but are not limited to, methyl acrylate, methyl methacrylate, branched alkyl acrylates, isooctyl acrylate, 4-methyl-2- pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, sulfoethyl Attorney Docket No. 205691-0067-00WO methacrylate, tert-butyl acrylate, isobomyl acrylate, butyl methacrylate, vinyl acetate, lauryl acrylate, octadecyl acrylate, acrylonitrile, and mixtures thereof.

[0066] In one embodiment, the polymer composition further comprises one or more polar monomers. Polar monomers include, but are not limited to, acrylic acids, acrylic acids containing 1 to 20 carbon atoms, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2- butylacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, sodium methacrylate, ammonium acrylate, sodium acrylate, trimethylamine p-vinyl benzimide, 4.4.9-trimethyl-4- azonia-7-oxo-8-oxa-dec-9-ene-l -sulphonate, N,N-dimethyl-N-(beta methacryloxy-ethyl) ammonium propionate betaine, trimethylamine methacrylimide, 1,1 -dimethyl- 1 -(2,3- dihydroxypropyl)amine methacrylimide, N-vinyl pyrrollidone, N-Vinyl caprolactam, acrylamide, t-butyl acrylamide, dimethyl amino ethyl acrylamide, N-octyl acrylamide, monoolefinic mono carboxylic acids, monoolefinic dicarboxylic acids, acrylamides, N-substituted acrylamides, acrylic acid, methacrylic acid, N-Vinyl pyrrolidone, salts thereof, and mixtures thereof.

[0067] In one embodiment, the monomers described herein further comprise a substituent including, but not limited to, halogen, -CN, -NH2, -OH, -NH(CH3), -N(CH3)2, aryl group, heteroaryl group, alkyl (including straight chain, branched and / or unsaturated alkyl), substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, fluoro alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkoxy, fluoroalkoxy, -S- alkyl, S(=O)2alkyl, S(=O)2N[H, alkyl, or aryl], -C(=O)NH[substituted or unsubstituted alkyl, or substituted or unsubstituted phenyl], -C(=O)N[H or substituted or unsubstituted alkyl or aryl]2, - OC(=O)N[substituted or unsubstituted alkyl]2, -NHC(=O)NH[substituted or unsubstituted alkyl, or substituted or unsubstituted phenyl], -NHC(=O)alkyl, -Nfsubstituted or unsubstituted alkyl]C(=O)[substituted or unsubstituted alkyl], -NHC(=O)[substituted or unsubstituted alkyl], - C(OH) [substituted or unsubstituted alkyl]2, and -C(NH2)[substituted or unsubstituted alkyl]2. In another embodiment, by way of example, an optional substituent is selected from oxo, fluorine, chlorine, bromine, iodine, -CN, -NH2, -OH, -NH(CH3), -N(CH3)2, -CH3, -CH2CH3, -CH(CH3)2, - CF3, -CH2CF3, -OCH3, -OCH2CH3, -OCH(CH3)2, -OCF3, - OCH2CF3, -S(=O)2-CH3, - C(=O)NH2, -C(=O)-NHCH3, -NHC(=O)NHCH3, -C(=O)CH3, -ON(O)2, and -C(=O)OH. In yet one embodiment, the substituents are independently selected from the group consisting of C1-6 alkyl, -OH, C1-6 alkoxy, halo, amino, acetamido, oxo and nitro. As used herein, where a substituent is an alkyl or alkoxy group, the carbon chain may be branched, straight or cyclic. Attorney Docket No. 205691-0067-00WO

[0068] In one embodiment, the polymer composition further comprises a polyacrylate based pressure sensitive adhesives commercially available, e.g. under the trademarks DuroTAK® and EUDRAGIT®, including, but not limited to EUDRAGIT® E PO, Duro-Tak® 87-202A, Duro- Tak® 87-208A, Duro-Tak® 87-502A, Duro-Tak® 87-503 A, Duro-Tak® 87-2051, Duro-Tak® 87-2054, Duro-Tak® 87-2287, Duro-Tak® 87-2353, Duro-Tak® 87-2510, Duro-Tak® 87-2516, Duro-Tak® 87-4098, Duro-Tak® 87-4287, Duro-Tak® 87-9088, and Duro-Tak® 87-9301, or Duro-Tak® 387-2516.

[0069] In some examples, the composition comprises methyl acrylate at a concentration of at least 1% (w / w), at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 25% (w / w), at least 30% (w / w), at least 35% (w / w), at least 40% (w / w), at least 45% (w / w), at least 50% (w / w), at least 55% (w / w), at least 60% (w / w), and at least 65% (w / w). In some examples, the composition comprises methyl arylate at a concentration of less than 99% (w / w), less than 85% (w / w), less than 75% (w / w), less than 70% (w / w), less than 65% (w / w), and less than 60% (w / w).

[0070] In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 25% and 75% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 30% and 70% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 35% and 65% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 40% and 60% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 43% and 53% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 45% and 52% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 47% and 51% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration between 48% and 50% (w / w).

[0071] In one embodiment, the polymer composition comprises methyl acrylate at a concentration of about 46% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration of about 47% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration of about 48% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration of about 49% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a Attorney Docket No. 205691-0067-00WO concentration of about 50% (w / w). Tn one embodiment, the polymer composition comprises methyl acrylate at a concentration of about 51% (w / w). In one embodiment, the polymer composition comprises methyl acrylate at a concentration of about 52% (w / w).

[0072] In some examples, the polymer composition comprises a C2-20 alkyl acrylate described herein at a concentration of at least 1.0% (w / w), at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 25% (w / w), at least 30% (w / w), at least 35% (w / w), at least 40% (w / w), at least 45% (w / w), at least 50% (w / w), at least 55% (w / w), at least 60% (w / w), and at least 65% (w / w). In some examples, the composition comprises a C2-20 alkyl acrylate described herein at a concentration of less than 99% (w / w), less than 85% (w / w), less than 75% (w / w), less than 70% (w / w), less than 65% (w / w), and less than 60% (w / w).

[0073] In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 25% and 75% (w / w). In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 30% and 70% (w / w). In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 35% and 65% (w / w). In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 40% and 60% (w / w). In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 45% and 55% (w / w). In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 47% and 53% (w / w). In one embodiment, the polymer composition comprises a C2-20 alkyl acrylate at a concentration between 48% and 52% (w / w).

[0074] In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 25% and 75% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 30% and 70% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 35% and 65% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 40% and 60% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 45% and 55% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 47% and 53% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration between 48% and 52% (w / w). Attorney Docket No. 205691-0067-00WO

[0075] In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 25% and 75% (w / w). In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 30% and 70% (w / w). In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 35% and 65% (w / w). In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 40% and 60% (w / w). In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 45% and 55% (w / w). In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 47% and 53% (w / w). In one embodiment, the polymer composition comprises a C2-6 alkyl acrylate at a concentration between 48% and 52% (w / w).

[0076] In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 25% and 75% (w / w). In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 30% and 70% (w / w). In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 35% and 65% (w / w). In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 40% and 60% (w / w). In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 45% and 55% (w / w). In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 47% and 53% (w / w). In one embodiment, the polymer composition comprises a C2-4 alkyl acrylate at a concentration between 48% and 52% (w / w).

[0077] In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 46% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 47% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 48% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 49% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 50% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 51% (w / w). In one embodiment, the polymer composition comprises a C2-10 alkyl acrylate at a concentration of about 52% (w / w).

[0078] In some examples, the polymer composition comprises an acrylic acid at a concentration of at least 0.1% (w / w), at least 0.5% (w / w), at least 0.7% (w / w), at least 1.0% (w / w), at least Attorney Docket No. 205691-0067-00WO

[0079] 1 .2% (w / w), at least 1 .5% (w / w), at least 2.0% (w / w), at least 2.5% (w / w), at least 3.0% (w / w), at least 5.0% (w / w), at least 10.0% (w / w), at least 15.0% (w / w), and at least 20.0% (w / w). In some examples, the polymer composition comprises an acrylic acid at a concentration of less than 40.0% (w / w), less than 30.0% (w / w), less than 20.0% (w / w), less than 10.0% (w / w), less than 5.0% (w / w), less than 4.0% (w / w), less than 3.0% (w / w), less than 2.0% (w / w), and less than 1.9% (w / w).

[0080] In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 0.1% and 10% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 0.5% and 8% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 1% and 5% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 1% and 4% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 1% and 3% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 1% and 2% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration between 1.5% and 2% (w / w).

[0081] In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 0.5%. In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 1% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 1.5% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 2% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 2.5% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 3% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 3.5% (w / w). In one embodiment, the polymer composition comprises an acrylic acid at a concentration of about 4% (w / w).

[0082] In one embodiment, the polymer composition further comprises one or more vinyl ester monomers. Vinyl esters monomers include but are not limited to vinyl 2-ethyl hexanoate, vinyl caprate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, vinyl octanoate, and other monofunctional unsaturated vinyl esters of linear or branched carboxylic acids having about 1-14 carbon atoms. Attorney Docket No. 205691-0067-00WO

[0083] In one embodiment, the polymer composition further comprises an ingredient selected from the list consisting of a pH adjusting agent, a crosslinking agent, a plasticizer, a moisturizer, a thickener, a moisture adjuster, an absorption enhancer, a surfactant, a preservative, an antioxidant, a perfume, and combinations thereof.

[0084] Examples of pH adjusting agents include, but are not limited to, citric acid, malic acid, tartaric acid, oxalic acid, benzoic acid, glycolic acid, acetic acid, propionic acid, succinic acid, malonic acid, and the like.

[0085] Examples of thickeners include, but are not limited to, a powder, powdered acacia, dextrin, powdered tragacanth, pectin, a xanthan gum, glycerin, talc, and the like.

[0086] Examples of surfactants include, but are not limited to, polysorbate, a polyoxyethylene hydrogenated castor oil, a polyether, sucrose esters fatty acids, sodium lauryl sulfate, sodium lauryl alcohol ethoxy sulfate, stearyl alcohol, diethyl sebacate, polyethylene glycol monostearate, oleic acid, sunflower oil, lecithin, phosphatidylcholine, isopropyl myristate, stearic acid, medium and long chain triglycerides, capric acid, caprylic acid, a polysorbate, polysorbate 20, polysorbate 60, polysorbate 80, Calfoam® ES-701, ethoxylated surfactants, sorbitan trioleate, and the like.

[0087] Examples of plasticizers include, but are not limited to, phthalates, esters of polycarboxylic acids, acetylated monoglycerides, alkyl citrates, triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), trioctyl citrate (TOC), acetyl trioctyl citrate (ATOC), trihexyl citrate (THC), acetyl trihexyl citrate (ATHC), butyryl trihexyl citrate (BTHC, trihexyl o-butyryl citrate), trimethyl citrate (TMC), methyl laurate, lauric acid, lauryl lactate, lauryl alcohol, alkyl sulphonic acid phenyl ester, diethylene glycol monoethyl ether, bis(2-ethylhexyl) phthalate (DEHP), diisooctyl phthalate (DIOP), bis(n- butyl)phthalate (DnBP, DBP), diisobutyl phthalate (DIBP), bis(2-ethylhexyl)adipate (DEHA), dimethyl adipate (DMAD), monomethyl adipate (MMAD), dioctyl adipate (DOA), ethyl oleate, sorbitan monooleate, glycerol monooleate, dibutyl sebacate (DBS), dibutyl maleate (DBM), diisobutyl maleate (DIBM), benzoates, epoxidized vegetable oils, tri s(trom ethamine), N-ethyl toluene sulfonamide (o / p ETSA), N-(2-hydroxypropyl)benzene sulfonamide (HP BSA), N-(n- butyl)benzene sulfonamide (BBSA-NBBS), tri cresyl phosphate (TCP), tributyl phosphate (TBP), tri ethylene glycol dihexanoate (3G6, 3GH), tetraethylene glycol diheptanoate (4G7), 1,3- butyleneglycol, dipropylene glycol, PEG400, Span 80, and polyvinylpyrrolidone. Attorney Docket No. 205691-0067-00WO

[0088] In one embodiment, the polymer composition further comprises one or more crosslinking agents. In one embodiment, the polymer composition does not comprise a cross-linking agent. Cross-linking agents include but are not limited to multifunctional crosslinking agents, water-soluble crosslinking polymers, polymeric multifunctional (meth)acrylates, e.g., poly(ethylene oxide) diacrylate or poly (ethylene) oxide dimethacrylate, polyvinylic crosslinking agents, substituted and unsubstituted divinylbenzene, difunctional urethane acrylates, acrylic or methacrylic esters of diols, hexanediol, triols, glycerol, tetrols, pentaerythritol, and mixtures thereof.

[0089] In one embodiment, the polymer composition further comprises a solubilizer. Examples of solubilizers include, but are not limited to, polyhydric alcohols, polyvalent alcohols, glycols, polyethyleneglycol, propyleneglycol, glycerin, diglycerin, sorbitol, dipropyleneglycol, polypropyleneglycol. 1,3-butyleneglycol, 1,4-butyleneglycol, isobutyleneglycol, triacetin, triethylcitrate, ethyl oleate, ethyl caprylate, dimethylacetamide, N-methylpyrrolidone, N- hydroxyethylpyrrolidone, polyvinylpyrrolidone, hydroxypropylmethyl cellulose, hydroxypropyl cyclodextrins, ethanol, glycofurol, transcutol, (2-(2-Ethoxyethoxy)ethanol), and mixtures thereof.

[0090] In one embodiment, the polymer composition further comprises an adhesion enhancer. Adhesion enhancers include, but are not limited to, starch acrylate, polyvinyl alcohol, a carboxyvinyl polymer, hydroxypropyl cellulose, carboxymethyl cellulose, casein Sodium, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, polyvinyl pyrrolidone, sodium alginate, a methylvinylether-maleic anhydride copolymer, and combinations thereof.

[0091] In one embodiment, initiators are used to enhance the rate of polymerization and / or crosslinking. Suitable free radical initiators include thermally activated initiators such as azo compounds, hydroperoxides, peroxides, sulfates, ammonium persulfate, and photoinitiators. Photoinitiators can be organic, organometallic, or inorganic compounds, benzoin and its derivatives, benzil ketals, acetophenone, acetophenone derivatives, benzophenone, and benzophenone derivatives.

[0092] In embodiment, the polymer composition is crystalline. In one embodiment, the polymer composition is non-crystalline. In one embodiment, the polymer composition further comprises a crystalline polymer. In one embodiment, the polymer composition does not comprise a Attorney Docket No. 205691-0067-00WO crystalline polymer. In one embodiment, the polymer composition of amorphous. In one embodiment, the polymer composition is semi-crystalline.

[0093] In one embodiment, the polymer composition is a block copolymer. Other exemplary copolymers which may describe the present invention include, but are not limited to, random copolymers, statistical copolymers, alternating copolymers, stereoblock copolymers, gradient copolymers, graft copolymers, star copolymers, and combinations thereof.

[0094] In one embodiment, the polymer composition forms higher order assemblies. In one embodiment, the polymer composition forms secondary structures. In one embodiment, the polymer composition comprises exposed hydrophilic pockets. In one embodiment, the polymer composition comprises exposed hydrophobic pockets. In one embodiment, the polymer composition forms nanoassemblies. In one embodiment, the polymer composition participates in intramolecular hydrogen bonding. In one embodiment, the polymer composition participates in intermolecular hydrogen bonding.

[0095] In one embodiment, the polymer composition has a glass transition temperature below -10 °C. In one embodiment, the polymer composition has a glass transition temperature below -20 °C. In one embodiment, the polymer composition has a glass transition temperature between -10 °C and -40 °C. In one embodiment, the polymer composition has a glass transition temperature between -15 °C and -35 °C. In one embodiment, the polymer composition has a glass transition temperature between -16 °C and -33 °C. In one embodiment, the polymer composition has a glass transition temperature between -18 °C and -28 °C.

[0096] Adhesive Materials

[0097] In some examples, the present invention relates to an adhesive material and / or medical adhesive comprising the composition described elsewhere herein. In some examples, the adhesive comprises a backing; and a polymer composition having a glass transition temperature below -10°C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate.

[0098] In some examples, the present invention relates to a medical adhesive having thermal release properties, the medical adhesive comprising: a backing; and a polymer composition having a glass transition temperature is below -10 °C, wherein the polymer composition Attorney Docket No. 205691-0067-00WO comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate.

[0099] In some examples, the polymer composition is coated onto the backing comprised in the adhesive and / or medical adhesive. The polymer composition may be coated onto the backing in any number of ways, e.g., by spray deposition, painting, dipping, gravure printing, rolling, or the like. In one embodiment, the backing includes, but is not limited to, a woven fabric, a non-woven fabric, a net, a knit, a gauze, a fdm, paper, wood, metal, glass, an electrode, a surgical dressing, a transdermal drug delivery patch, a stoma appliance, a synthetic film, a tape, a pad, and similar skin contact applications.

[0100] In some examples, the adhesive and / or medical adhesive comprises a release liner comprising a material including, but not limited to, polyethylene terephthalate, polyethylene, polypropylene, glassine paper, or a laminated composite thereof. The release liner material may be coated on at least one side with a release agent such as a silicone-based compound, a fluoropolymer, or an acrylate-based low surface energy material. In some examples, the release liner includes a fdm or sheet material comprising polyethylene terephthalate, BOPP (biaxially oriented polypropylene), or high density polypropylene, which may be further treated with a release coating to facilitate clean removal from the adhesive surface. The coating may include, but is not limited to, crosslinked silicone, perfluoropolyether, or UV-cured silicone formulations.

[0101] Examples of materials to support the backing include, but are not limited to, staple fiber muslin, a vinylchloride film, a polyethylene film, a polyurethane-vinylchloride copolymer film, a polyurethane film, a polypropylene film, a polyester film, a polyethylenetelephthalate separator (PET), cellulose acetate, ethylcellulose, a plastic vinyl acetate-vinylchloride copolymer, nylon, an ethylene-vinyl acetate copolymer, a plastic polyvinylchloride, polyvinylidene chloride, aluminum, and the like.

[0102] In some examples, the polymer composition has a glass transition temperature below -10 °C. In some examples, the polymer composition has a glass transition temperature below -20 °C. In some examples, the polymer composition has a glass transition temperature between -10 °C and -40°C. In some examples, the polymer composition has a glass transition temperature between -15 °C and -35 °C. In some examples, the polymer composition has a glass transition temperature between -16 °C and -33 °C. In some examples, the polymer composition has a glass transition temperature between -18 °C and -28 °C. Attorney Docket No. 205691-0067-00WO

[0103] In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.01 N and 1.0 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.02 N and 0.9 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.03 N and 0.8 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.04 N and 0.7 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.05 N and 0.6 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.06 N and 0.6 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.05 N and 0.08 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.1 N and 0.2 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.4 N and 0.5 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is between 0.5 N and 0.65 N.

[0104] In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.02 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.03 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.04 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.05 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34- 37 °C is about 0.06 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.07 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.08 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.09 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34- 37 °C is about 0.1 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.13 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.16 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.2 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 Attorney Docket No. 205691-0067-00WO

[0105] °C is about 0.25 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.3 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.35 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.4 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.45 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.5 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.55 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.6 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.65 N. In some examples, the maximum amount of force required to peel the adhesive from skin at 34-37 °C is about 0.7 N.

[0106] EXPERIMENTAL EXAMPLES

[0107] The invention is now described with reference to the following Examples. These Examples are provided for the purpose of illustration only, and the invention is not limited to these Examples, but rather encompasses all variations that are evident as a result of the teachings provided herein.

[0108] Example 1 : Testing of Thermally Reversible Adhesives on Skin Analogs

[0109] The investigation of new adhesives was conducted with relation to interest of the glass transition temperature of the polymer composition. Glass transition temperature is the temperature at which a material alters its state, going from a glass-like rigid solid to a more flexible, rubbery compound. This was an important measurement to assess how the bonded joint of the adhesive would operate within a specific temperature range, as well as its impact on other materials it is bonding to. Typically, adhesives work well above their glass transition temperature, rendering them flexible for application to permit patient movement when applicable. Upon exposure to lower temperatures, such as freezing conditions, thermally sensitive adhesives become more brittle, causing them to break instead of flex, further making them less sticky. Attorney Docket No. 205691-0067-00WO

[0110] The exploration of adhesives was conducted using standard marketed adhesives and inlab created novel polymer adhesives. The focus was to investigate how each type of adhesive peeled from a liquid latex skin analog. This was first done on Heat Lamp Thermoregulated latex skin and then on Water Bath Thermoregulated latex skin. The amount of force needed to peel each type of adhesive from the latex skin was measured.

[0111] The experiments were conducted on liquid latex skin analogs. The latex skin analogs were prepared by dipping a brush into liquid latex and applying an even coat of the latex onto a tin tray. Once the latex coat had dried, three more coats of liquid latex were applied, and the latex was allowed to dry overnight. Two tin trays with latex skin were prepared, one for each type of experiment. These skin analogs were then modified for each experiment as described below.

[0112] To prepare the standard adhesives for testing, 3 inches of adhesive were measured and cut. With the end of the cut adhesive, the sticky side was folded back onto itself creating a pull tab and leaving 2 inches of sticky side exposed. Using a hole puncher, a hole was punched out of the center of the pull tab. To prepare the novel adhesives for testing, a piece of CVS Health Durable Hold Cloth was stuck onto the end of the novel polymer adhesive to create a pull tab, and 2 inches of adhesive were left open for testing. A hole was then punched out in the center of the pull tabs.

[0113] For the Heat Lamp Thermoregulated latex skin experiments, the set-up comprised of one of the tin trays with the latex skin facing a heat lamp. A Vernier force gauge reader, a Vernier Labpro transfer device, and a Field Piece Hs36 with a top adaptor for a Field Piece ATH4 thermometer were used. LoggerPro was used, and the force gauge was set to ±50N. The skin analog reached a temperature between 34-37°C through use of the heat lamp and the temperature was measured using the Field Piece Hs36. The first standard adhesive was slid onto the force gauge hook with use of the pull tab. The adhesive was then attached to the latex skin analog. The force gauge was zeroed before beginning collection. The 0-degree angle was first tested while not exceeding the force gauge measurement by 20%. Once the adhesive had been peeled off from the skin analog or 20% force was exceeded, collection was stopped. The steps were repeated at various angles of 0, 45, 90, 135, and 180 degrees.

[0114] The following standard adhesives were first tested to provide a baseline analysis: CVS Health Durable Hold Cloth Tape 1” x 10YD, CVS Health Sensitive Skin Paper Tape 1” x 10YD, Attorney Docket No. 205691-0067-00WO

[0115] CVS Health Waterproof Adhesive Tape l / 2in x 5YD, and CVS Health Foam Adhesive Pads 4in x 4in. With the use of the Heat Lamp Thermoregulated skin latex it was seen that the waterproof tape, cloth tape, and paper tape caused skin tearing. The paper tape had broken off from the force gauge, splitting into two pieces. The adhesive pad did not cause skin tearing.

[0116] The max force applied with the cloth tape was 12.3627 N. The max force applied with the paper tape was 26.4792 N. The max force applied with the waterproof tape was 15.6688 N. The max force applied with the adhesive pad tape was 0.46236 N. The adhesive peel comparison of the standard tapes is shown in Figure 1 and Table 1. Figure 1 depicts the amount of force applied to peel off the various CVS standard adhesives from the latex skin analog over time in seconds. The orange small dash line denotes the paper tape, the gray dash line denotes the waterproof tape, the solid blue line denotes the cloth tape, the staggered yellow line denotes the pad adhesive.

[0117] The following novel polymer adhesives were then tested in comparison to the standard adhesives: JS01 Cut 2, JS01 Cut 3, J0S4 Cut 1, and LAA Cut 1. The JS01 composition comprised 42.8% (w / w) butyl acrylate, 55.4% (w / w) methyl acrylate, and 1.8% (w / w) methacrylic acid. The JS04 composition comprised 34.5% (w / w) butyl acrylate, 63.5% (w / w) methyl acrylate, and 2.0% (w / w) methacrylic acid. The LAA composition comprised 58.3% (w / w) butyl acrylate, 39.8% (w / w) methyl acrylate, and 1.9% (w / w) methacrylic acid.

[0118] With the use of the Heat Lamp Thermoregulated skin setup it was seen that none of the novel adhesives caused skin tearing. The max force applied with the JS01 Cut 2 adhesive was 0.46236 N. The max force applied with the JS01 Cut 3 adhesive was 0.13032 N. The max force applied with the JS04 Cut 1 was 0.06921 N. The max force applied with the LAA Cut 1 was 0.58672 N. The novel adhesive comparisons are shown in Figure 2 and Table 1. Figure 2 depicts the amount of force applied to peel off the various Novel polymer emulsion adhesives from the latex skin analog over time in seconds. The solid blue line denotes JS01 Cut 2, the dotted yellow line denotes LAA Cut 1, the small dash red line denotes JS01 Cut 3, the dashed gray line denotes JS04 Cut 1.

[0119] Table 1: Max Applied Force For Adhesive 180 Degree Peel Heat Lamp Thermoregulated Attorney Docket No. 205691-0067-00WO

[0120] For the Water Bath Thermoregulated latex skin: a Water Bath Thermoregulated skin analog, a Kedsum Aquarium Water Pump, a water bath thermoregulator, the prepared adhesives strips, a Vernier force gauge reader, a Vernier LabPro transfer device, and a Field Piece Hs36 with top adaptor of Field Piece ATH4 thermometer were obtained. To prepare the Water Bath Thermoregulated skin analog, the liquid latex skin analog was initially applied to the convex portion of the tin tray. Silicone tubing was attached to the other side of the tin tray and the tubing was connected to the water pump. The water pump was placed in the water bath thermoregulator and the water bath was filled until the water pump was submerged. The other end of the silicone tubing was placed into the water bath thermoregulator. The temperature of the thermoregulator was set to 40 °C. The water pump was then turned on and water circulated across the tin try until the latex skin temperature read between 35-37 °C. The force gauge was set to ±50 N. The standard adhesive was slid onto the force gauge hook and the tape was placed onto the skin analog. The 0-degree angle was first tested while not exceeding the force gauge measurement by 20%. Once tape was peeled off from the skin analog or 20% force was exceeded, collection was stopped. The above steps were repeated for all prepped adhesives (standard and novel) and at the various angles of 0, 45, 90, 135, and 180 degrees.

[0121] The same standard and novel adhesives were used with the water bath thermoregulated skin analog. It was seen that the cloth tape and paper tape had caused skin tearing. The waterproof tape and adhesive pad did not cause skin tearing. The paper tape had broken off from the force gauge, splitting into two pieces. The max force applied with the cloth tape was 15.351 N. The max force applied with the paper tape was 28.522 N. The max force applied with the waterproof tape was 7.8833 N. The max force applied with the adhesive pad tape was 1.263 N. The adhesive peel comparison of the standard tapes is shown in Figru 3. The same novel polymer adhesives were then tested. With the use of the Water Bath Thermoregulated skin analog, it was seen that none of novel adhesives caused skin tearing. The max force applied with Attorney Docket No. 205691-0067-00WO the LAA Cut 1 was 0.161N. The JS01 Cut 2, JS01 Cut 3, and JS04 Cut 1 adhesives did not stick to the skin. These results are shown in Figure 3 and Table 2. Figure 3 depicts the amount of force applied to peel off the various CVS standard adhesives from the latex skin analog over time in seconds. The solid orange line denotes the paper tape, the dotted blue line denotes the cloth tape, the small dash gray line denotes the waterproof tape, the dashed yellow line denotes the adhesive pad.

[0122] Table 2: Max Applied Force For Adhesive 180 Degree Peel Water Bath Thermoregulated

[0123] Methods for the novel adhesives composition: A 3-neck round bottom glass flask was charged with 95 ml of deionized water. The flask was placed on a heating mantle with magnetic stirring. A reflux condenser, a pressure equalizing addition funnel, and a double-hole rubber stopper holding a thermometer and a glass pipette nozzle were attached. The water was sparged with N2 for 10 minutes. The temperature was raised to and controlled at 80 ± 5°C.

[0124] To make the monomer solution, 153.6 g Butyl Acrylate (1.1982 moles), 101.0 g Methyl Acrylate (1.172 moles), 3.9 g Methacrylic Acid (0.0450 moles), and 3.5g surfactant (Pilot Cal Foam ES-701) monomer were added to 95 ml of deionized water. The solution was mixed while sparging with N2 for 10 min. To make the initiator solution, 1.12 g of ammonium persulfate were added to 49 ml of deionized water.

[0125] One quarter of the initiator solution and 2% of the monomer solution were added to the initial charge using the addition funnel, at a rate of about 2 ml / min. After the initial addition, the reaction ran at 80 °C for 15 minutes then the reaction temperature was raised to 85 °C. The remaining initiator and monomer solution were added through the addition funnel at a rate of about 2 ml / min. The reaction was maintained at 85 °C for the entire addition and the reaction ran for a net 3 hours. The reaction was removed from heat and allowed to cool. The reaction was fdtered if necessary and transferred. Attorney Docket No. 205691-0067-00WO

[0126] The experiments were conducted to compare adhesives and their effects on thin skin to see which ones may cause tearing. The overall purpose was to test the designed novel polymer emulsion adhesives created in the lab to see which mixtures provided the best outcomes regarding adhesion to the skin and less force applied when being peeled off, thus lower the odds of skin tearing. With the standard adhesives that are currently on the market, 3 out of the 4 had caused skin tearing and had a high yield of force applied to the peel when being removed. The novel adhesives were then tested and did not cause skin tearing.

[0127] Another area of applicability will be stoma appliances that need to adhere firmly, but can be difficult to remove, which also offer a risk of tearing the skin where another appliance has to be replaced immediately.

[0128] The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations.

Claims

Attorney Docket No. 205691-0067-00WOCLAIMSWe claim:

1. A polymer composition having a glass transition temperature below -10°C; wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid,(ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate.

2. The polymer composition of claim 1, wherein the acrylic acid is selected from the group consisting of methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-butylacrylic acid.

3. The polymer composition of claim 1, wherein the acrylic acid is methacrylic acid.

4. The polymer composition of claim 1, wherein the alkyl acrylate is a C2-4 alkyl acrylate5. The polymer composition of claim 1, wherein the alkyl acrylate is selected from the group consisting of methyl acrylate, methyl methacrylate, branched alkyl acrylates, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, sulfoethyl methacrylate, tert-butyl acrylate, isobornyl acrylate, butyl methacrylate, vinyl acetate, lauryl acrylate, octadecyl acrylate, acrylonitrile, and mixtures thereof.

6. The polymer composition of claim 1, wherein the alkyl acrylate is butyl acrylate.

7. The polymer composition of claim 1, wherein the polymer composition comprises acrylic acid at a concentration between 1% and 5% (w / w).

8. The polymer composition of claim 1, wherein the polymer composition comprises acrylic acid at a concentration between 1% and 3% (w / w).Attorney Docket No. 205691-0067-00WO9. The polymer composition of claim 1, wherein the polymer composition has a glass transition temperature below -20 °C.

10. The polymer composition of claim 1, wherein the polymer composition has a glass transition temperature between -18 °C and -28 °C.

11. The polymer composition of claim 1, wherein the polymer composition is noncrystalline.

12. The polymer composition of claim 1, wherein the polymer composition further comprises an adhesion enhancer.

13. The polymer composition of claim 1, wherein the polymer composition further comprises a surfactant.

14. The polymer composition of claim 1, wherein the polymer composition further comprises a plasticizer.

15. An adhesive comprising: a backing; and a polymer composition having a glass transition temperature is below -10 °C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate.

16. The adhesive of claim 15, wherein the acrylic acid is methacrylic acid.

17. The adhesive of claim 15, wherein the alkyl acrylate is butyl acrylate.

18. The adhesive of claim 15, wherein the glass transition temperature is between -18°C and -28 °C.Attorney Docket No. 205691-0067-00WO19. The adhesive of claim 15, wherein the backing is selected from the group consisting of a woven fabric, a non-woven fabric, a net, a knit, a gauze, a film, an electrode, a surgical dressing, a transdermal drug delivery patch, a synthetic film, an adhesive tape, and a pad.

20. A medical adhesive having thermal release properties, the medical adhesive comprising: a backing; and a polymer composition having a glass transition temperature is below -10 °C, wherein the polymer composition comprises (i) 0.1% to 10% (w / w) acrylic acid, (ii) 43% to 53% (w / w) methyl acrylate, and (iii) 45% to 55% (w / w) C2-6 alkyl acrylate.

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