Pressure-sensitive adhesive including acrylic copolymer and polyoxyalkylene polymer and related article

Abstract

A pressure-sensitive adhesive includes a polyoxyalkylene polymer having no fluorinated carbon atoms and an acrylic copolymer. The acrylic copolymer includes at least 60 weight percent of linear or branched alkyl (meth)acrylate monomer units, based on the weight of the acrylic copolymer, and from 12.5 weight percent to 40 weight percent of (meth)acrylic acid monomer units, based on the weight of the acrylic copolymer. An article includes the pressure-sensitive adhesive disposed on a backing. The article can be water vapor permeable. A process for making the pressure-sensitive adhesive is also disclosed.

Description

[0001] PRESSURE-SENSITIVE ADHESIVE INCLUDING ACRYLIC COPOLYMER AND POLYOXYALKYLENE POLYMER AND RELATED ARTICLE

[0002] Cross-Reference to Related Application

[0003] This application claims priority to U.S. Provisional Application Nos. 63 / 635,815 and 63 / 635,837, fded April 18, 2024, the disclosures of which are incorporated by reference in their entirety herein.

[0004] Background

[0005] Water-vapor-permeable air and water barrier articles are disclosed in U.S. Pat. Nos. 10,704,254 (Seabaugh et al.), 11,105,089 (Widenbrant et al.), 11,365,328 (Seabaugh et al.), 11,512,463 (Widenbrant et al.), and 11,731,394 (Seabaugh et al.), and U.S. Pat. Appl. Pub. Nos. 2017 / 0173916 (Widenbrant et al.), 2021 / 0207005 (Seabaugh et al.), and 2022 / 0282476 (Widenbrant et al.). Self-adhesive permeable membrane sheets for use in buildings are disclosed in U.S. Pat. Nos. 10,899,107 (Bess) and 9,562,174 (Russell).

[0006] Summary

[0007] In one aspect, the present disclosure provides a pressure -sensitive adhesive including a polyoxyalkylene polymer having no fluorinated carbon atoms and an acrylic copolymer. The acrylic copolymer includes at least 60 weight percent of linear or branched alkyl (meth)acrylate monomer units, based on the weight of the acrylic copolymer, and from 12.5 weight percent to 40 weight percent of (meth)acrylic acid monomer units, based on the weight of the acrylic copolymer. Typically, and advantageously, the pressure-sensitive adhesive is water vapor permeable.

[0008] In another aspect, the present disclosure provides an article, which includes the pressure -sensitive adhesive disposed on a backing. Typically, and advantageously, the article is water vapor permeable.

[0009] In another aspect, the present disclosure provides a process for making the pressure sensitive adhesive. The process includes partially polymerizing a first polymerizable composition that comprises a linear or branched alkyl (meth)acrylate and (meth)acrylic acid to form a syrup composition. The process further includes combining the syrup composition with the polyoxyalkylene polymer and, optionally, a crosslinking agent to provide a second polymerizable composition and polymerizing the second polymerizable composition to form the pressure sensitive adhesive.

[0010] In this application, terms such as "a", "an" and "the" are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terms "a", "an", and "the" are used interchangeably with the term "at least one". The phrases "at least one of and "comprises at least one of followed by a list including the conjunction “or” refers to any one of the items in the list and any combination of two or more items in the list. All numerical ranges are inclusive of their endpoints and non-integral values between the endpoints unless otherwise stated (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5, and the like).

[0011] The term “water vapor permeable” as used herein means an article having a permeance of more than 1 perm (inch-pounds units) (57.2135 nanograms per second per meter squared per Pascal (ng s m2Pa)) according to ASTM E 96 Procedure A (Desiccant Method).

[0012] The term “continuous” as used herein means a coating having an uninterrupted extension along a two-dimensional surface. For example, in some embodiments, in an article having a continuous pressuresensitive adhesive layer, the pressure-sensitive adhesive covers a major surface of the backing.

[0013] The term “discontinuous” as used herein means a coating having an interrupted extension along a two-dimensional surface. For example, in some embodiments, in an article having a discontinuous coating of pressure sensitive adhesive, the pressure-sensitive adhesive does not cover a major surface of the backing.

[0014] The term "polymer" refers to a molecule having a structure which includes the multiple repetition of units derived, actually or conceptually, from one or more monomers. The term “monomer” refers to a molecule of low relative molecular mass that can combine with others to form a polymer. The term “polymer” includes homopolymers and copolymers, as well as homopolymers or copolymers that may be formed in a miscible blend, e.g., by coextrusion or by reaction. The term “polymer” includes random, block, graft, and star polymers. The term “polymer” encompasses oligomers.

[0015] A “monomer unit” of a polymer or oligomer is a segment of a polymer or oligomer derived from a single monomer. As an example, the monomeric unit of acrylic acid (H2C=CH-(C=0)-0H) is where the asterisks (*) indicate the attachment site to another group such as another monomeric unit in the polymer.

[0016] The term “acrylic” refers to both acrylic and methacrylic polymers, oligomers, and monomers.

[0017] The term "(meth)acryl" refers to acryl (also referred to in the art as acryloyl and acrylyl) and / or methacryl (also referred to in the art as methacryloyl and methacrylyl).

[0018] "Alkyl group" and the prefix "alk-" are inclusive of both straight chain and branched chain groups and of cyclic groups having up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons) unless otherwise specified. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms.

[0019] "Alkylene" is the multivalent (e.g., divalent or trivalent) form of the "alkyl" groups defined above.

[0020] Pressure-sensitive adhesives (PSAs) are well known to those of ordinary skill in the art to possess properties including the following: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be cleanly removable from the adherend. Materials that have been found to function well as PSAs are polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power. One useful method for identifying pressure sensitive adhesives is the Dahlquist criterion. This criterion defines a pressure-sensitive adhesive as an adhesive having a creep compliance of greater than 3 x 10’6cm2 / dyne as described in Handbook of Pressure Sensitive Adhesive Technology, Donatas Safas (Ed.), 2nd Edition, p. 172, Van Nostrand Reinhold, New York, NY, 1989. Alternatively, since modulus is, to a first approximation, the inverse of creep compliance, pressure sensitive adhesives may be defined as adhesives having a storage modulus of less than about 3 x 105N / m2.

[0021] Brief Description of the Drawings

[0022] FIG. 1 is a side view of an embodiment of the article of the present disclosure including a pressure-sensitive adhesive disposed on a backing.

[0023] FIG. 2 is a side view of another embodiment of the article of the present disclosure including a pressure-sensitive adhesive disposed on a backing and a release liner on the pressure-sensitive adhesive.

[0024] FIG. 3 is a side view of yet another embodiment of the article of the present disclosure including a pressure-sensitive adhesive disposed on a multilayer backing and a release liner on the pressuresensitive adhesive.

[0025] FIG. 4 is a perspective view of another embodiment of an article of the present disclosure, applied to a window frame.

[0026] Detailed Description

[0027] The pressure-sensitive adhesive (PSA) of the present disclosure and / or useful in the article of the present disclosure includes an acrylic copolymer and a polyoxyalkylene polymer. The acrylic copolymer comprises at least 60 weight percent (wt.%), 65 wt.%, or 70 wt.% of linear or branched alkyl (meth)acrylate monomer units, based on the weight of the acrylic copolymer. In some embodiments, the acrylic copolymer comprises less than 85 wt.% or up to 84 wt.%, 83 wt.%, 82 wt.%, 81 wt.%, or 80 wt.% of linear or branched alkyl (meth)acrylate monomer units, based on the weight of the acrylic copolymer. The acrylic copolymer comprises from 12.5 wt.% to 40 wt.% of (meth)acrylic acid monomer units, based on the weight of the acrylic copolymer. In some embodiments, the acrylic copolymer comprises (meth)acrylic acid monomer units in an amount of at least 12.5 wt.%, greater than 12.5 wt.%, at least 15 wt.%, greater than 15 wt.%, at least 16 wt.%, or at least 17 wt.%, based on the weight of the acrylic copolymer. In some embodiments, the acrylic copolymer comprises from 15.5 to 40 wt.%, 16 to 40 wt.%, from 16 to 35 wt.%, from 16 to 30 wt.%, from 16 to 25 wt.%, from 17 to 25 wt.%, from 17 to 23 wt.%, from 17 to 20 wt.%, or from 17 to 19.5 wt.% of (meth)acrylic acid monomer units, based on the weight of the acrylic copolymer. In some embodiments, the linear or branched alkyl (meth)acrylate monomer units are C1-C32 (meth)acrylic acid ester monomer units, C1-C24 (meth)acrylic acid ester monomer units, or Ci-Cis (meth)acrylic acid ester monomer units. Examples of suitable alkyl (meth)acrylates useful for providing these monomer units include those represented by Formula CH2=C(R)COOR’, wherein R is hydrogen or a methyl group and R’ is an alkyl group having 1 to 30, 4 to 30, 6 to 30, 8 to 30, 6 to 24, 6 to 20, 6 to 18, 8 to 24, 8 to 20, or 8 to 20 carbon atoms and may be linear or branched. Examples of suitable monomers represented by this formula include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, iso-pentyl (meth)acrylate, n-hexyl (meth)acrylate, iso-hexyl (meth)acrylate, octyl (meth)acrylate, iso-octyl (meth)acrylate, 2-octyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl acrylate, undecyl (meth)acrylate, n-dodecyl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 2-propylheptyl (meth)acrylate, stearyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.

[0028] Suitable linear or branched alkyl (meth)acrylate monomer units also include mixtures of at least two or at least three structural isomers of a secondary alkyl (meth)acrylate of Formula (I): wherein R1and R2are each independently a Ci to C30 saturated linear alkyl group, in which the sum of the number of carbons in R1and R2is 7 to 31, and R3is H or CH3. The sum of the number of carbons in R1and R2can be, in some embodiments, 7 to 27, 7 to 25, 7 to 21, 7 to 17, 7 to 11, or 7. Methods for making and using such monomers and monomer mixtures are described in U.S. Pat. No. 9,102,774 (Clapper et al.).

[0029] In some embodiments, the linear or branched alkyl (meth)acrylate monomer units are low Tgmonomer units. A low Tgmonomer is one that provides a homopolymer with a glass transition temperature (Tg) no greater than 20 °C, as reported in Thermal Transitions of Homopolymers: Glass Transition & Melting Point (sigmaaldrich.com). Tables of glass transition temperatures for homopolymers are also available from various suppliers of monomer such as Polyscience and BASF. Examples of low Tgmonomers include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylbutyl acrylate, 4-methyl-2 -pentyl acrylate, 2-methylhexyl acrylate, n- octyl acrylate, 2-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate, isotridecyl acrylate, isostearyl acrylate, and octadecyl acrylate. In some embodiments, the linear or branched alkyl (meth)acrylate monomer units are units of n-butyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, or isononyl acrylate.

[0030] Examples of (meth)acrylic acid monomer units include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, beta-carboxy ethyl acrylate, and 2-methacrylolyloxyethyl succinate. In some embodiments, the (meth)acrylic acid monomer units are acrylic acid monomer units or methacrylic acid monomer units. (Meth)acrylic acid monomer units encompass salts of these acids, such as alkali metal salts and ammonium salts.

[0031] In some embodiments, the acrylic copolymer useful in PSA of the present disclosure further comprises monomer units of a “high Tg” monomer that when polymerized provides a homopolymer having a glass transition temperature (Tg) of at least 50 °C, 60 °C, or 70 °C (i.e., a homopolymer formed from the monomer has a Tg at least 50 °C, 60 °C, or 70 °C). In some embodiments, the acrylic copolymer further comprises at least 5 wt.% (in some embodiments, at least 7.5 wt.%, 10 wt.%, 12.5 wt.% or 15 wt.%) monomer units of a “high Tg” monomer. Some suitable high Tg monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth)acrylate, cyclohexyl methacrylate, isobomyl (meth)acrylate, stearyl (meth)acrylate, phenyl acrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl (meth)acrylate, tert-butyl cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, N- octyl (meth)acrylamide, tetrahydrofurfuryl methacrylate, and mixtures thereof. Other suitable high Tg monomers have a single vinyl group that is not a (meth)acryloyl group such as various vinyl ethers (e.g., vinyl methyl ether), vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrene (e.g., alpha-methyl styrene), vinyl halide, and mixtures thereof. The Tg of many homopolymers are reported in Thermal Transitions of Homopolymers: Glass Transition & Melting Point (sigmaaldrich.com). Tables of glass transition temperatures for homopolymers are also available from various suppliers of monomer such as Polyscience and BASF.

[0032] Other optional monomers useful in some embodiments of the acrylic copolymer of the PSA of the present disclosure include a (meth)acrylamide (e.g., acrylamide, methacrylamide, N-ethyl acrylamide, N- hydroxyethyl acrylamide, N-octyl acrylamide, N-t-butyl acrylamide, N,N-dimethyl acrylamide, N,N- diethyl acrylamide, N-ethyl-N-dihydroxyethyl acrylamide, and methacrylamides of the foregoing acrylamides), a hydroxy-functional (meth)acrylate (e.g., 2-hydroxyethyl acrylate or methacrylate), N- vinyl pyrrolidone, N-vinyl caprolactam, an alpha-olefin, a vinyl ether, an allyl ether, or a maleate.

[0033] In some embodiments, the acrylic copolymer useful in the PSA of the present disclosure is crosslinked. Acrylic copolymers can be crosslinked by including crosslinking agents in the formulation. Examples of crosslinking agents include copolymerizable polyfunctional ethylenically unsaturated monomers such as those described below; ethylenically unsaturated compounds which in the excited state are capable of abstracting hydrogen (e.g., acrylated benzophenones such as described in U.S. Pat. No. 4,737,559 (Kellen et al.), p-acryloxy-benzophenone, which is available from Sartomer Company, Exton, PA, monomers described in U.S. Pat. No. 5,073,611 (Rehmer et al.) including p-N-(methacryloyl-4- oxapentamethylene)-carbamoyloxybenzophenone, N-(benzoyl-p-phenylene)-N’- (methacryloxymethylene)-carbodiimide, and p-acryloxy-benzophenone); nonionic crosslinking agents which are essentially free of olefinic unsaturation and capable of reacting with carboxylic acid groups, for example, in the second monomer described above (e.g., l,4-bis(ethyleneiminocarbonylamino)benzene; 4,4-bis(ethyleneiminocarbonylamino)diphenyhnethane; l,8-bis(ethyleneiminocarbonylamino)octane; 1,4- tolylene diisocyanate; 1,6-hexamethylene diisocyanate, N,N’-bis-l,2-propyleneisophthalamide, diepoxides, dianhydrides, bis(amides), and bis(imides)); and nonionic crosslinking agents which are essentially free of olefinic unsaturation, are noncopolymerizable with the first and second monomers, and, in the excited state, are capable of abstracting hydrogen (e.g., 2,4-bis(trichloromethyl)-6-(4- methoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(3,4-dimethoxy)phenyl)-s-triazine; 2,4- bis(trichloromethyl)-6-(3,4,5-trimethoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(2,4- dimethoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(3-methoxy)phenyl)-s-triazine as described in U.S. Pat. No. 4,330,590 (Vesley); 2,4-bis(trichloromethyl)-6-naphthenyl-s-triazine and 2,4- bis(trichloromethyl)-6-(4-methoxy)naphthenyl-s-triazine as described in U.S. Pat. No. 4,329,384 (Vesley)). In some embodiments, the acrylic copolymer is crosslinked with a triazine, in some embodiments, with any of the aforementioned triazines. If a photocrosslinking agent is used, the coated adhesive can be exposed to ultraviolet (UV) radiation having a wavelength of about 250 nm to about 400 nm. The radiant energy in this range of wavelength required to crosslink the adhesive is about 100 millijoules / cm2to about 1,500 millijoules / cm2, or in some embodiments, about 200 millijoules / cm2to about 800 millijoules / cm2.

[0034] Suitable copolymerizable polyfimctional ethylenically unsaturated monomers include diacrylate esters of diols, such as ethylene glycol diacrylate, diethylene glycol diacrylate, propanediol diacrylate, butanediol diacrylate, butane- 1,3-diyl diacrylate, pentanediol diacrylate, hexanediol diacrylate (including 1,6-hexanediol diacrylate), heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, and dimethacrylates of any of the foregoing diacrylates. Further suitable polyfunctional monomers include polyacrylate esters of polyols, such as glycerol triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, dipentaerythritol pentaacrylate, methacrylates of the foregoing acrylates, and combinations thereof. Further suitable polyfunctional crosslinking monomers include divinyl benzene, allyl methacrylate, diallyl maleate, diallyl phthalate, and combinations thereof. Further suitable polyfimctional crosslinking monomers include polyfimctional acrylate oligomers comprising two or more acrylate groups. The polyfimctional acrylate oligomer may be a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, a polyether acrylate, a polyacrylic acrylate, a methacrylate of any of the foregoing acrylates, or a combination thereof. Combinations of any of these crosslinking agents may be useful.

[0035] The crosslinking agent, including any of those described above, can be used in an amount of 0.005 wt.% to 4 wt.% based on the combined weight of the monomers, for example from about 0.01 wt.% to about 2 wt.% or from about 0.05 wt.% to 1 wt.%. In some embodiments, the crosslinking agent is used in an amount of up to 4.0 wt.%, 3.0 wt.%, 2.0 wt.%, or 1.0 wt.% based on the total weight of monomer units in the acrylic copolymer. In some embodiments, the crosslinking agent is used in an amount of at least 0.10 wt.%, 0.15 wt.%, 0.20 wt.%, 0.25 wt.%, 0.30 wt.%, 0.40 wt.%, 0.50 wt.%, 0.60 wt.%, or 0.70 wt.%, based on the total weight of monomer units in the acrylic copolymer.

[0036] In some embodiments of the PSA of the present disclosure, the acrylic copolymer has a Tgin a range from 2°C and 100°C, between 2°C and 80°C, between 2°C and 60°C, between 2°C and 50°C, between 2°C and 45°C, between 5°C and 45°C, between 5°C and 40°C, between 5°C and 35°C, or between 10°C and 30°C.

[0037] Mixtures of acrylic copolymers can be useful in the PSA of the present disclosure. However, in some embodiments, the PSA of the present disclosure comprises not more than 5 wt.%, 4 wt.%, 3 wt.%, 2 wt.%, 1 wt.%, or 0 wt.% of a further acrylic copolymer having from 0. 1 wt.% to 15 wt.% (in some embodiments, 0.1 to 14.5 wt.%, 0.1 to 12 wt.%, 0.1 to 11 wt.%, from 0.1 to 10 wt.%, from 0.2 to 10 wt.%, from 0.2 to 9 wt.%, from 0.2 to 8 wt.%, from 0.3 to 8 wt.%, from 0.5 to 8 wt.%, from 0.5 to 6 wt.%, from 1 to 6 wt.%, or from 1 to 5 wt.%) of (meth)acrylic acid monomer units, based on the weight of the further (meth)acrylate copolymer. Such a further (meth)acrylate copolymer in the PSA of the present disclosure would tend to lower the Tg, cohesive strength, and / or the storage modulus of the PSA.

[0038] An acrylic polymer can be analyzed by nuclear magnetic resonance spectroscopy (1H or13C NMR) to identify the monomer units in the polymer. Solid state or solution NMR may be useful depending on the level of crosslinking in the polymer. For solid state NMR the acrylic polymer can be swelled in an appropriate solvent for analysis.

[0039] Acrylic copolymers useful for PSAs in the article the present disclosure can be prepared, for example, by any conventional free radical polymerization method, including solution, radiation, bulk, dispersion, emulsion, solventless, and suspension processes. In some embodiments, the acrylic copolymer is prepared in a solvent or by a solvent free, bulk, free-radical polymerization process (e.g., using heat, electron-beam radiation, or UV radiation). Such polymerizations are typically facilitated by a polymerization initiator (e.g., a photoinitiator or a thermal initiator). The polymerization initiator is used in an amount effective to facilitate polymerization of the monomers (e.g., 0. 1 part to about 5.0 parts or 0.2 part to about 1.0 part by weight, based on 100 parts of the total monomer content). The resulting copolymers may be random or block copolymers.

[0040] A typical solution polymerization method is carried out by adding the monomers, a suitable solvent, and an optional chain transfer agent to a reaction vessel, adding a free radical initiator, purging with nitrogen, and maintaining the reaction vessel at an elevated temperature, typically in the range of about 40 °C to 100 °C until the reaction is completed, typically in about 1 to 24 hours, depending upon the batch size and temperature. Examples of the solvent are methanol, tetrahydrofuran, ethanol, isopropanol, tert-butanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and an ethylene glycol alkyl ether. Those solvents can be used alone or as mixtures thereof. In a typical thermal polymerization method, a monomer mixture may be subjected to thermal energy in the presence of a thermal polymerization initiator (i.e., thermal initiators). Examples of suitable thermal initiators are those available under the trade designations “VAZO” from DuPont.

[0041] A syrup polymer technique comprises partially polymerizing monomers to produce a syrup polymer comprising an acrylic copolymer and unpolymerized monomers. The syrup polymer composition is polymerized to a useful coating viscosity, which may be coated onto a substrate (such as a tape backing) and further polymerized. In some embodiments, the polymerization is conducted in the absence of a solvent such as ethyl acetate, toluene, or tetrahydrofuran which are unreactive with the functional groups of the components of the syrup polymer. Polymerization to achieve a coatable viscosity may be conducted such that the conversion of monomers to polymer is up to about 20%, 15%, or 10%. Polymerization can be accomplished by exposing the syrup polymer composition to light energy in the presence of a photoinitiator. Polymerization can be terminated when the desired conversion and viscosity have been achieved by removing the light source and by bubbling air (oxygen) into the solution to quench propagating free radicals. Energy activated initiators may be unnecessary where, for example, ionizing radiation is used to initiate polymerization.

[0042] In some embodiments, a free-radical photoinitiator is useful in the polymerization to make an acrylic copolymer. In some embodiments, the free radical photoinitiator is a type I (cleavage-type) photoinitiator. Cleavage-type photoinitiators include acetophenones, alpha-aminoalkylphenones, benzoin ethers, benzoyl oximes, acyl (e.g., benzoyl) phosphine oxides, acyl (e.g., benzoyl) phosphinates, and mixtures thereof. Examples of useful benzoin ethers include benzoin methyl ether and benzoin butyl ether. Examples of suitable acetophenone compounds include 4-diethylaminoacetophenone, 1- hydroxycyclohexyl phenyl ketone, 2-benzyl-2 dimethylamino-4'-morpholinobutyrophenone, 2-hydroxy- 2-methyl-l-phenylpropan-l one, 2,2-dimethoxyacetophenone, and 2,2-dimethoxy-l,2-diphenylethan-l- one. Example of suitable acyl phosphine oxide, acyl phosphinate, and acyl phosphonate compounds include bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, phenylbis(2,4,6- trimethylbenzoyl) phosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, (2,4,6- trimethylbenzoyl)diphenylphosphine oxide, dimethyl pivaloylphosphonate, and poly(oxy-l,2-ethanediyl), a,a',a"-l,2,3-propanetriyltris[co-[[phenyl(2,4,6-trimethylbenzoyl)phosphinyl]oxy]. Further suitable photoinitiators include substituted alpha-ketols such as 2- methyl-2-hydroxy propiophenone; aromatic sulfonyl chlorides such as 2-naphthalene-sulfonyl chloride; and photoactive oximes such as 1 -phenyl- 1,2- propanedione-2-(O-ethoxy-carbonyl)oxime. Many photoinitiators are available, for example, IGM Resins, Waalwijk, Netherlands, under the trade designations “OMNIRAD” and “ESACURE”. Two or more of any of these photoinitiators may also be used together in any combination. Additional photoinitiator can be added to a mixture to be coated after the copolymer has been formed, (i.e., photoinitiator can be added to the syrup polymer mixture).

[0043] The degree of conversion (of monomers to copolymer) can be monitored during the irradiation by measuring the index of refraction of the polymerizing mixture. If desired, a chain transfer agent may be added to the monomer mixture to prepare the acrylic copolymer useful for the PSA of the present disclosure. Examples of useful chain transfer agents include carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. In some embodiments, the chain transfer agent comprises at least one of isooctylthioglycolate or carbon tetrabromide.

[0044] A useful solvent-free polymerization method is disclosed in U.S. Pat. No. 4,379,201 (Heilmann et al.). Initially, a mixture of first and second monomers can be polymerized with a portion of a photoinitiator by exposing the mixture to UV radiation in an inert environment for a time sufficient to form a coatable base syrup, and subsequently a crosslinking agent and the remainder of the photoinitiator may be added. This final syrup containing a crosslinking agent (e.g., which may have a Brookfield viscosity of about 100 centipoises to about 6000 centipoises at 23 °C, as measured with a No. 4 LTV spindle, at 60 revolutions per minute) can then be coated onto a substrate, for example, a polymeric film substrate. Once the syrup is coated onto the substrate, for example, the polymeric film substrate, further polymerization and crosslinking can be carried out in an inert environment (e.g., nitrogen, carbon dioxide, helium, and argon, which exclude oxygen). A sufficiently inert atmosphere can be achieved by covering a layer of the photoactive syrup with a polymeric film, such as silicone-treated PET film, that is transparent to UV radiation or e-beam and irradiating through the film in air.

[0045] The PSA of the present disclosure and useful in the article of the present disclosure includes a polyoxyalkylene polymer. It should be understood that the polyoxyalkylene polymer is a separate polymer from the acrylic copolymer in the PSA. In other words, the acrylic copolymer and the polyoxyalkylene polymer are not covalently attached. In some embodiments, suitable polyoxylalkylene polymers include ethyleneoxy (e.g., -CH2CH2O-), propyleneoxy (e.g., -CH(CH3)CH2O-, -CH2CH2CH2O-, -CH2CH(CH3)O-), or butyleneoxy (e g., -CH2CH2CH2CH2O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, and -CH2C(CH3)2O-) groups or combinations of any of these. The polyoxyalkylene polymer may have a wide variety of terminal groups including alkyl (e.g., having up to 30 carbon atoms), hydroxyl (i.e., -OH), amino (i.e., -N(R4)2), and silane (i.e., -Si(Y)3.x(R5)x) terminal groups. Each R4is independently hydrogen, an alkyl group having up to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, or n-octyl), a phenyl group, or a polyoxyalkylene group such as any of those described above. In some embodiments, each R4is hydrogen. R5is an alkyl group having up to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, or n- octyl) or a phenyl group. In some embodiments, R5is an alkyl group having up to 4 carbon atoms. In some embodiments, R5is methyl or ethyl. Each Y is independently a hydrolyzable group, e.g., halogen (i.e., fluoride, chloride, bromide, or iodide), alkoxy (i.e., -O-alkyl), acyloxy (i.e., -OC(O)alkyl), or aryloxy (i.e., -O-aryl), and x is 0, 1, or 2. The Y groups are generally capable of hydrolyzing, for example, in the presence of water under acidic conditions to produce groups capable of undergoing a condensation reaction, for example silanol groups. In these embodiments, alkyl (e.g., in alkoxy and acyloxy) is optionally substituted with one or more halogen atoms. In some embodiments, alkoxy and acyloxy have up to 8, 6, 4, 3, or 2 carbon atoms. In some embodiments, aryloxy has 6 to 12 (or 6 to 10) carbon atoms which may be unsubstituted or substituted by halogen, alkyl (e.g., having up to 4 carbon atoms), and haloalkyl. The polyoxyalkylene polymer can also include functional groups other than ethers in the backbone, for example, secondary and tertiary amines, esters, amides, ureas, and carbamates.

[0046] In some embodiments, the polyoxyalkylene polymer comprises at least one of an alkoxylated alcohol, diol, or polyol, an alkoxyated amine, diamine, or polyamine, an alkoxylate ester, an alkoxylated amide, or an alkoxylated urethane. Mono- or multi-functional alcohols and amines can be alkoxylated using methods known in the art. Carboxylic acids and amides can be alkoxylated to provide alkoxylate esters and amides using methods known in the art. Polyoxyalkylene alcohols can be reacted with isocyanates to provide urethanes using known methods.

[0047] In some embodiments, the polyoxyalkylene polymer is a polyether represented by formula R7O-(EO)p-(R6O)q-(EO)p-R7or R7O-(R6O)q-(EO)p-(R6O)q-R7. In these formulas, each R7is independently hydrogen or alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl), wherein alkyl is unsubstituted or substituted by hydroxyl (i.e., -OH), amino (i.e., -N(R4)2), or silane (i.e., -Si(Y)3.x(R5)x), wherein R4, R5, and x are as described above in any of their embodiments. In some embodiments, each R7is hydrogen. In some embodiments, each R7is methyl. EO represents -CH2CH2O-. Each R6O is independently -CH(CH3)CH2O-, -CH2CH2CH2O-, -CH2CH(CH3)O- -CH2CH2CH2CH2O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, or -CH2C(CH3)2O-. In some embodiments, each R6O independently represents -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH2CH2CH2CH2O-. Each p is independently a value from 0 to 150 (in some embodiments, from 7 to about 130, or from 14 to about 130); and each q is independently a value from 0 to 150 (in some embodiments, from about 20 to about 100, 1 to 55, or from about 9 to about 25). The sum p + q is at least 3 (in some embodiments, at least 5, 10, 15, 20, or at least 25.) In some embodiments, the ratio p / q has a value from at least 0.5, 0.75, 1 or 1.5 to 2.5, 2.7, 3, 4, 5, or more. For example, the percentage of the repeating EO groups in the polyoxyalkylene polymer can be in a range from 10 to 90, 10 to 75, or 20 to 50, based on the total number of EO and R6O groups in the polyoxyalkylene polymer. Useful polyoxyalkylene polymers include those available from Dow Chemical Company, Midland, MI, under the trade designations "CARBOWAX" and “UCON” and block copolymers of ethylene oxide and propylene oxide having a molecular weight of about 500 to 15000 grams per mole (g / mol) (e.g., those available from BASF Corporation, Ludwigshafen, Germany, under the trade designation "PLURONIC"). In some embodiments, the polyoxyalkylene polymer has a number average molecular weight in a range from 200 to 15,000, 1000 to 15,000, 1000 to 10,000, or 1000 to 5000 g / mol.

[0048] In some embodiments, the polyoxyalkylene polymer contains ethylene glycol repeating units and hydroxyl terminal groups. Examples of polyols with ethylene glycol repeat units include polyethylene glycol, polyethylene glycol-block-propylene glycol, polyethylene glycol-random-propylene glycol), poly(diethylene glycol)adipate, bisphenol A ethoxylate, and combinations of these polyols. In some embodiments, the polyoxyalkylene polymer is polyethylene glycol diol. In some embodiments, the number average molecular weight of the polyethylene glycol diol is at least 500 g / mol, 800 g / mol, or 1000 g / mol. In some embodiments, the molecular weight of the polyethylene glycol diol is not more than 4000 g / mol, 3000 g / mol, 2500 g / mol, or 1000 g / mol.

[0049] In some embodiments, the polyoxyalkylene polymer is a monoamine, diamine, or triamine having one, two, or three primary amino groups, respectively. Polyether amines typically have a number average molecular weight of at least 200 g / mol and can have a molecular weight up to 2500, 2000, 1500, 1000, or 500 g / mol. Useful polyether amines are commercially available, for example, under the trade designation “JEFF AMINE” from Huntsman Chemical, The Woodlands, Texas, and from BASF, Florham Park, New Jersey.

[0050] In some embodiments, the polyoxyalkylene polymer is a fatty acid ester or a fatty amine ethoxylate. In some embodiments, the poly oxyalkylene polymer is a tallowalkyl amine ethoxylate. In some embodiments, the polyoxyalkylene polymer is tris polyoxyethylene (15)-N-tallowalkyl-l,3- diaminopropane. Some fatty amines are commercially available, for example, under the trade designations “ETHOMEEN T / 25” and “ETHODUOMEEN T / 25” from Nouryon, Amsterdam, The Netherlands. Fatty acid esters can be made, for example, by ethoxylating fatty acids.

[0051] Useful commercially available polyoxyalkylenes having silane terminal groups can be obtained, for example, from Kaneka under the trade designation “MS” and “SILYL” in various grades, for example, "MS S203", "MS S303", "SILYL SAT10", and "SILYL SAT30". In some embodiments, the main chain of the polyoxyalkylene polymer may contain other functional groups such as a group represented by formula -NR8-C(O)-W-, wherein W is -O-, -S-, or -NR8-, and wherein R8represents a hydrogen atom or a monovalent organic group, such as a substituted or unsubstituted monovalent C1-20 hydrocarbon group or a substituted or unsubstituted monovalent Cus hydrocarbon group. Poly oxyalkylene polymers having -NR8-C(O)-W- groups may be produced, for example, by the reaction of an isocyanato group and a hydroxy group; by the reaction of an isocyanato group and an amino group; or by the reaction of an isocyanato group and a mercapto group. Examples of methods for producing a poly oxyalkylene polymer having a group represented by formula -NR8-C(O)-W- and groups represented by formula -Si(Y)3-x(R5)xinclude those described in U.S. Pat. Nos. 3,632,557 (Brode); 3,711,445 (Chu); 4,067,844 (Barron); 4,345,053 (Rizk); 4,374,237 (Berger); 4,645,816 (Pohl); 5,068,304 (Higuchi); 5,364,955 (Zwiener); 5,756,751 (Schmalstieg); 5,990,257 (Johnston); 6,001,946 (Waldman); 6,046,270 (Roesler); 6,197,912 (Huang); and 7,060,750 (Jansen) and European Patent Publication EP 0676403, published October 11, 1995. Examples of suitable commercially available polymers having silane terminal groups include the “GENIOSIL STP-E” series products from Wacker Chemical such as “GENIOSIL STP-E10”, “GENIOSIL STP-E 35” trimethoxysilylpropyl-carbamate-terminated polyether, and “GENIOSIL STP-E 30” silane-terminated polyether with dimethoxy(methyl)silylmethylcarbamate terminal groups.

[0052] In some embodiments of the PSA of the present disclosure, the PSA comprises from 55 to 80 wt.%, from 55 to 75 wt.%, from 55 to 70 wt.%, from 60 to 75 wt.%, or from 60 to 70 wt.%, of the acrylic copolymer, wherein the weight percentages are based on the total weight of the PSA. In some embodiments, the PSA comprises from 20 to 45 wt.%, from 21 to 45 wt.%, from 22 to 45 wt.%, from 25 to 45 wt.%, from 30 to 45 wt.%, from 25 to 40 wt.%, or from 30 to 40 wt.% of the polyoxyalkylene polymer, wherein the weight percentages are based on the total weight of the PSA. Amounts of the polyoxyalkylene polymer in these ranges is typically sufficient to make the PSA tacky.

[0053] In some embodiments, the PSA of the present disclosure has a moisture vapor transmission rate of at least 3 perms, at least 4 perms, at least 5 perms, at least 10 perms, or at least 15 perms, for example, when the PSA is present in a layer having a thickness in a range from 25 micrometers to 1000, 500, 250, or 100 micrometers. Despite the high amount of (meth)acrylic acid monomer units in the PSA, the PSA is tacky at room temperature. It has been taught, for example, in U.S. Pat. No. 4,415,615 (Esmay et al.) that PSAs having more than 15 wt.% (meth) acrylic acid monomer units are not tacky at room temperature. The polyoxyalkylene polymer is typically present in the PSA in an amount sufficient to make it tacky.

[0054] In some embodiments, the PSA of the present disclosure comprises a tackifying resin. Tackifying resins generally refer to materials that increase the tack of the PSA and have a number average molecular weight of up to 10,000 g / mol. Useful tackifying resins can have a softening point of at least 70 °C as determined using a ring and ball apparatus and a glass transition temperature of at least -30 °C as measured by differential scanning calorimetry. In some embodiments, the tackifying resin comprises at least one of rosin, a polyterpene (e.g., those based on a-pinene, P-pinene, or limonene), an aliphatic hydrocarbon resin (e.g., those based on cis- or trans-piperylene, isoprene, 2-methyl-but-2-ene, cyclopentadiene, dicyclopentadiene, or combinations thereof), an aromatic resin (e.g. those based on styrene, a-methyl styrene, methyl indene, indene, coumarone, or combinations thereof), or a mixed aliphatic -aromatic hydrocarbon resin. Any of these tackifying resins may be hydrogenated (e.g., partially or completely). In some embodiments, the PSA includes at least about one wt.% and up to about 50 wt.% of the tackifying resin, based on the total weight of the PSA. In some embodiments, the tackifying resin is present in a range from 1 to 25, 2 to 20, 2 to 15, 1 to 10, or 3 to 10 wt.%, based on the total weight of the PSA. In some embodiments, the PSA does not include a tackifier or includes less than 1, 0.5, 0. 1, or 0.05 wt.% of a tackifier, based on the total weight of the PSA.

[0055] Other additives can be added to the PSA in the article of the present disclosure, in any of its embodiments described above, if desired. For example, leveling agents, ultraviolet light absorbers, hindered amine light stabilizers (HAUS), oxygen inhibitors, wetting agents, rheology modifiers, defoamers, biocides, flame retardants, dyes, and particulate fillers can be included. Natural and petroleum waxes, oil, and bitumen may also be useful as additives to the PSA.

[0056] In some embodiments, the PSA of the present disclosure takes the form of a foam. A foam comprises voids, which may be open or closed cells. In some embodiments, the voids are present in the foam in an amount of at least 5% by volume, from 10% to 55% by volume, from 10% to 45% by volume, from 15% to 45% by volume, or from 20% to 45% by volume. The voids or cells in the foam can be created in any of the known methods described in the art and include the use of a gas or blowing agent and / or including hollow particles into the composition for the foam. For example, according to one method to create a foam described in U.S. Pat. No. 4,415,615 (Esmay et al.), an acrylic foam can be obtained by frothing a composition containing acrylate monomers and optional comonomers, coating the froth on a backing, and polymerizing the frothed composition. It is also possible to coat the unfrothed composition of the acrylate monomers and optional comonomers to the backing and to then simultaneously foam and polymerize that composition. Frothing of the composition may be accomplished by whipping a gas into the polymerizable composition optionally in the presence of a surfactant (e.g., hydrocarbon or fluorochemical surfactant) or surface-modified nanoparticles to stabilize the foam. Inert gases such as nitrogen, argon, and carbon dioxide may be useful, particularly if the polymerization is photoinitiated. In some embodiments, the PSA useful in the article of the present disclosure is not frothed or foamed. In some embodiments, the PSA is free of a fluorinated surfactant.

[0057] In some embodiments, the PSA of the present disclosure incorporates hollow fillers, such as hollow polymeric particles, hollow glass microspheres, and hollow ceramic microspheres. Hollow polymeric microspheres include elastomeric particles available, for example, from Akzo Nobel, Amsterdam, The Netherlands, under the trade designation "EXPANCEL". Examples of hollow ceramic microspheres include alumina / silica microspheres having particle sizes in the range of 5 to 300 microns and a specific gravity of 0.7 (“FILLITE”, Pluess-Stauffer International), aluminum silicate microspheres having a specific gravity of from about 0.45 to about 0.7 (“Z -LIGHT”), calcium carbonate-coated polyvinylidene copolymer microspheres having a specific gravity of 0.13 (“DUALITE 6001AE”, Pierce & Stevens Corp.), and glass bubbles marketed by 3M Company, Saint Paul, Minnesota, as “3M GLASS BUBBLES” in grades KI, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S38XHS, S42HS, S42XHS, S60, S60HS, iM30K, iM16K, XLD3000, XLD6000, and G-65, and any of the HGS series of “3M GLASS BUBBLES”. Foams that include hollow microspheres are referred to as syntactic foams. In some embodiments, the PSA is free of hollow microspheres or includes not more than 1, 0.5, 0.1, 0.05, or 0.01 wt.% hollow microspheres.

[0058] In some embodiments, the PSA of the present disclosure is free of transition metal complexes or includes less than 0.01 wt.%, 0.010 wt.%, 0.005 wt.%, or 0.001 wt.% of a transition metal complex, based on the total weight of the PSA. Such transition metal complexes include copper complexes such as copper (II) 2-ethylhexanoate, copper (II) acetate, copper (II) acetylacetonate, copper (II) trifluoroacetate, and combinations thereof.

[0059] The PSA useful in article of the present disclosure may be prepared by simple blending of the acrylic copolymer, in some embodiments, the polyoxyalkylene polymer, and in some embodiments, the optional ingredients such as the fdler material and the tackifying resin. The components can be blended using several conventional methods, such as melt blending, solvent blending, or any suitable physical blending device.

[0060] The present disclosure provides a process for making the PSA of the present disclosure. The process includes forming a syrup composition by partially polymerizing a first polymerizable composition that comprises a linear or branched alkyl (meth)acrylate and (meth)acrylic acid. The syrup composition contains 1 to 20 wt.% of the acrylic copolymer and 80 to 99 wt.% monomers based on a total weight of the syrup composition, wherein the monomers comprise the linear or branched alkyl (meth)acrylate and (meth)acrylic acid. The composition is a solution of acrylic copolymer in the monomers and can be, for example, about 3 wt.% to 15 wt.% or 5 wt.% to 10 wt.% of the acrylic copolymer and 85 wt.% to 97 wt.% or 90 wt.% to 95 wt.% of the monomers. The process further includes combining the syrup composition with the polyoxyalkylene polymer and, optionally, a crosslinking agent to provide a second polymerizable composition and polymerizing the second polymerizable composition to form the PSA.

[0061] The present disclosure provides an article comprising the PSA as described above in any of its embodiments disposed on a backing. As shown in FIG. 1, article 10 includes a backing 20 having a first surface 24 and a second surface 22. In the illustrated embodiment, the PSA 50 of the present disclosure is disposed on the first surface 24 of the backing 20.

[0062] In some embodiments, the article is water vapor permeable. By selecting the composition of the PSA and the backing, thickness of the PSA and the backing, and coverage (e.g., continuous or discontinuous) of the pressure sensitive adhesive, the article of the present disclosure can advantageously have a moisture vapor transmission rate of at least 3 perms, at least 4 perms, at least 5 perms, at least 10 perms, or at least 15 perms.

[0063] In embodiments in which the article is water vapor permeable, the backing is water vapor permeable. In some embodiments, the backing can be a continuous film. The water vapor permeability of the backing can be influenced by the hydrophilic nature of at least a portion of the polymer that makes up the continuous film. A higher degree of swelling in water may be useful to enhance the water vapor permeability of a continuous polymeric film. In some embodiments, at least a portion of the polymer in the polymeric film backing includes polyether segments (e.g., polytetrahydrofuran, polypropylene oxide, polyethylene oxide, or combinations thereof).

[0064] In some embodiments, the polymeric film backing comprises at least one of a polyurethane, polyamide, polylactic acid, an acrylic block copolymer, or an amorphous polyester. In some embodiments, the polymeric film backing is not covalently crosslinked, but in some embodiments, the second polymeric film is a thermoplastic elastomer having physical crosslinks.

[0065] In some embodiments, the polymeric film backing, which may be a continuous polymeric film backing, in the article of the present disclosure is a polyurethane. Polyurethanes may be formed using any suitable reactants and any suitable process. Polyurethanes are typically formed from starting materials that include one or more isocyanates, one or more polyols, and optionally one or more additional reactants (e.g., having one or more active hydrogen groups). In some cases, a stoichiometric excess of isocyanate is reacted with the polyol. For example, a ratio of isocyanate groups to hydroxyl groups can range from about 1.1: 1 to 3: 1 (NCO:OH), from about 1.2: 1 to 2.5: 1, or from about 1.3: 1 to 2: 1. The polyurethane may have any suitable molecular weight, for example, a number average molecular weight from about 1,000 g / mol to about 10,000 g / mol or from about 2,500 g / mol to about 7,500 g / mol.

[0066] Suitable isocyanates include those having one, two, three, or four isocyanate groups and mixtures thereof. Suitable diisocyanates include isophoronediisocyanate (i.e., 5 -isocyanato- 1-isocyanatomethyl- 1 ,3 ,3 -trimethylcyclohexane); 5 -isocyanato- 1 -(2-isocyanatoeth- 1 -yl)- 1 ,3 ,3 -trimethylcyclohexane; 5 - isocyanato- 1 -(3 -isocyanatoprop- 1 -yl)- 1 ,3 ,3 -trimethylcyclohexane; 5 -isocyanato-(4-isocyanatobut- 1 -yl)- 1 ,3 ,3 -trimethylcyclohexane; 1 -isocyanato-2-(3 -isocyanatoprop- 1 -yl)cyclohexane ; 1 -isocyanato-2-(3 - isocyanatoeth- 1 -yl)cyclohexane; 1 -isocyanato-2-(4-isocyanatobut- 1 -yl)cyclohexane ; 1 ,2- diisocyanatocyclohexane; l,3-diisocyanatocyclohexane;l,4-diisocyanatocyclohexane; dicyclohexylmethane 2,4'-diisocyanate; trimethylene diisocyanate; tetramethylene diisocyanate; pentamethylenediisocyanate; hexamethylene diisocyanate; ethylethylene diisocyanate;trimethylhexane diisocyanate; heptamethylene diisocyanate;2-heptyl-3,4-bis(9-isocyanatononyl)-l-pentyl-cyclohexane; 1,2-, 1,4-, andl,3-bis(isocyanatomethyl)cyclohexane; 1,2-, 1,4-, and l,3-bis(2-isocyanatoeth-l- yl)cyclohexane; l,3-bis(3-isocyanatoprop-l-yl)cyclohexane; 1,2-, 1,4- or l,3-bis(4-isocyanatobuty-l- yl)cyclohexane; liquid bis(4-isocyanatocyclohexyl)-methane; and derivatives or mixtures thereof. In some embodiments, the isocyanate or mixture of isocyanates is non-aromatic (e.g., aliphatic). In some embodiments, the isocyanate comprises at least one of isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HMDI). In some embodiments, HMDI is the predominant isocyanate used to prepare the polyurethane, in other words, more HMDI units are present than any other isocyanate units.

[0067] In some embodiments, the polyurethane of the polymeric fdm backing is formed using aliphatic isocyanates, which may provide improved stability to UV exposure compared to aromatic isocyanates. In some embodiments, the isocyanate is dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'- diisocyanate, or liquid bis(4-isocyanatocyclohexyl)-methane.

[0068] Suitable polyols for preparing polyurethanes include monomers, oligomers, polymers, and mixtures thereof and include diols, triols, polyols having 4 or more hydroxyl groups, and mixtures thereof. Examples of polyols for use as reactants or as starting materials for oligomer or polymer polyols include ethylene glycol, propylene glycol, 1,3 -propanediol, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, trimethylolpropane, trimethylolethane, tripropyleneglycol, neopentyl glycol, pentaerythritol, 1,4-butanediol, hexyleneglycol, 1,6-hexanediol, cyclohexanedimethanol, a polyethylene or polypropylene glycol, isopropylidene bis(p-phenylene-oxypropanol-2), and mixtures thereof. Examples of suitable oligomer and / or polymer polyols include polyether polyols, polyester polyols, polyether-ester polyols, polyureapolyols, polyamide polyols, polycarbonate polyols, saturated or unsaturated polyolefin polyols, and combinations thereof. In some embodiments, the soft segments in the polyurethane of the polymeric film backing include polyethers (e.g., polytetrahydrofuran, polypropylene oxide, polyethylene oxide, or combinations thereof). The polyether segments may be incorporated into the polyurethane by reaction of a polyoxyalkylene polymer having hydroxyl terminal groups as described above in any of the embodiments of the polyoxyalkylene polymer. In some embodiments, the polyether has number average molecular weight in a range from 600 g / mol to 6000 g / mol, for example.

[0069] In some embodiments, the polyurethane of the polymeric fdm backing is formed using polyols that provide high water vapor permeability. In some embodiments, the polyol contains ethylene glycol repeat units. Examples of polyols with ethylene glycol repeat units include polyethylene glycol, poly(ethylene glycol-block-propylene glycol, polyethylene glycol-random-propylene glycol), poly(diethylene glycol)adipate, bisphenol A ethoxylate, and combinations of these polyols. In some embodiments, the polyol is polyethylene glycol diol. In some embodiments, the number average molecular weight of the polyethylene glycol diol is at least 500 g / mol, 800 g / mol, or 1000 g / mol. In some embodiments, the molecular weight of the polyethylene glycol diol is not more than 4000 g / mol, 3000 g / mol, 2500 g / mol, or 1000 g / mol.

[0070] In some embodiments, the polyurethane is a reaction product of components comprising polyethylene glycol, a chain extender, and an aliphatic isocyanate. The polyethylene glycol and aliphatic isocyanate can be any of those described above in any of their embodiments. A chain extender is a diol having a molecular weight of not more than 250 g / mol and can be any of those described above.

[0071] In some embodiments, the polyurethane of the polymeric fdm backing is formed using at least one polyol having a functionality of greater than two, in some embodiments, a functionality of about three. Examples of polyols with a functionality of three include glycerol, polycaprolactone triol, polypropylene oxide triol, poly(ethylene-co-propylene oxide) triol, and trimethylol propane. In some embodiments, the hydroxyl groups from the triol comprise at least or more than 1 mole percent (mol %), 2 mol %, or 3 mol % of the total number of hydroxyl groups in the formulation to make the polyurethane. In some embodiments, the hydroxyl groups from the triol comprise not more than or less than 10 mol %, 6 mol %, or 4 mol % of the total number of hydroxyl groups in the formulation to make the polyurethane. Including at least one polyol having a functionality of greater than two in the preparation of the polyurethane can be useful, for example, to increase the melt viscosity of polyurethanes of the polymeric fdm backing.

[0072] In some embodiments, the polyurethane is a TPU, composed of molecules that are substantially linear and have some physical crosslinking, usually through the interaction between urethane groups in the molecules. Commercially available polyurethanes that can be useful in the polymeric fdm backings in the article of the present disclosure include those obtained from BASF Company, Ludwigshafen, Germany, under the trade designation “ELASTOLLAN”, from Covestro Company under the trade designation “DESMOPAN”, and under the trade designation “ESTANE” from Lubrizol, Wickliffe, OH.

[0073] In some embodiments, the polymeric fdm backing includes an acrylic block copolymer having hard segments and soft segments. In some embodiments, the acrylic block copolymer includes poly(methyl methacrylate) (PMMA) hard segments, and the soft segments of the acrylic block copolymer can be formed from monomers of an acrylate or methacrylate having a C4-C9 alkyl sidechain or mixtures thereof, for example. Examples of monomers useful for forming the second block include n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, n- octyl acrylate, n-nonyl acrylate, methacrylates of the foregoing acrylates, and mixtures thereof. In some embodiments, monomers useful for forming soft segments include a C2-4 hydroxyalkyl acrylate or methacrylate such as 2-hydroxyethyl acrylate, 3 -hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 3 -hydroxypropyl methacrylate. In some embodiments, the acrylic block copolymer is a poly(methyl methacrylate)-poly(n-butylacrylate)-poly(methyl methacrylate) triblock copolymer. In some embodiments, the block copolymer contains about 70% PMMA and 30% poly(n-butyl acrylate). The block copolymer may have a number average molecular weight of up to about 120,000 g / mol. Suitable commercially available materials useful for the block copolymer include those obtained under the trade designation “KURARITY” from Kuraray, Chiyoda City, Japan (e.g., grades LA2330 and LA 3320), and those obtained under the trade designation “NANOSTRENGTH” from Arkema, King of Prussia, PA.

[0074] In some embodiments, the polymeric film backing comprises a polyamide. In some embodiments, the polyamide is a thermoplastic polyamide elastomer, and the soft segment is a polyether polyol segment such as any of these described above. Certain useful thermoplastic polyamides are commercially available, for example, under the trade designation “PEBAX” from Arkema. In some embodiments, the polymeric film backing comprises an amorphous polyester. In some embodiments, the amorphous polyester has polyether polyol segments such as any of those described above. Useful amorphous polyesters include those obtained from BASF, Florham Park, NJ, under the trade designation “ARNITEL”. In some embodiments, the polymeric film backing comprises polylactic acid (PLA). PLA is typically prepared from renewable resources (e.g., com starch, tapioca, or sugarcane) and is commercially available, for example, from NatureWorks, LLC (Plymouth, MN).

[0075] Continuous polymeric film backings can be provided by techniques known in the art, such as hot melt extrusion of an extrudable composition comprising the components of the continuous polymeric film. Examples of methods for making extrudable continuous layers are described, for example, in Progelhof, R. C., and Throne, J. L., “Polymer Engineering Principles,” Hanser / Gardner Publications, Inc., Cincinnati, OH, 1993.

[0076] In some embodiments, the backing for the article of the present disclosure comprises a fibrous layer. The fibrous layer may comprise a variety of suitable materials including woven fabrics, nonwoven webs, knitted fabrics (e.g., made by warp knitting, weft insertion knitting, and circular knitting), netting, scrim, and combinations thereof. In some embodiments, the fibrous layer comprises a woven, nonwoven, or knit material. Useful fibrous layers may be made of natural fibers (e.g., natural cellulosic fibers such as wood, cotton, flax, hemp, jute, and ramie), synthetic fibers (e.g., thermoplastic fibers), or a combination of natural and synthetic fibers. Examples of suitable materials for forming thermoplastic fibers include polyolefins (e.g., polyethylene, polypropylene, polybutylene, ethylene copolymers, propylene copolymers, butylene copolymers, and copolymers and blends of these polymers), polyesters, rayon, polyamides, and polylactic acid. The fibers may also be multi-component fibers, for example, having a core of one thermoplastic material and a sheath of another thermoplastic material. A fiber can be defined as an elongated material having a substantially uniform transverse cross- sectional diameter or thickness, and an aspect ratio, defined as the ratio of fiber length to fiber cross- sectional diameter or thickness, greater than about 100. “Substantially uniform” means that the cross- sectional dimension does not vary by more than 10 percent. Typically, the diameter or thickness of a fiber is less than 250 pm.

[0077] The term “nonwoven” refers to a material having a structure of individual fibers or threads that are interlaid but not in an identifiable manner such as in a knitted fabric. Examples of nonwoven webs include spunbond webs, spunlaced webs, airlaid webs, wetlaid webs, meltblown webs, and bonded carded webs. In some embodiments, the fibrous layer comprises multiple layers of nonwoven materials with, for example, at least one layer of a meltblown nonwoven and at least one layer of a spunbonded nonwoven, or any other suitable combination of nonwoven materials. For example, the fibrous layer may be a spunbond-meltblown-spunbond, spunbond-spunbond, or spunbond-spunbond-spunbond multilayer material. In some embodiments, the fibrous layer is a nonwoven comprising fibers selected from polyester, polylactic acid, polyolefin, polyamide, rayon, and combinations thereof.

[0078] In some embodiments, the backing for the article of the present disclosure comprises a polymeric film layer comprising a porous random network of strands and connective regions. In some embodiments, the strands are elongated strands. In some embodiments, the random network has a first optical density, and the connective regions have a second optical density, wherein the first optical density is greater than the second optical density. Optical density can be visually determined. A person skilled in the art can determine if the first optical density is greater than the second optical density if the random network of strands appears to have higher opacity than the connective regions. There are openings (i.e., through holes) in at least some of the connective regions. In some embodiments there are no openings (i.e., no through holes) in some of the connective regions. In some embodiments, there are at least 2, 3, 4, 5, 6, or 7 polymeric layers exhibiting a random network of strands and connective regions. In some embodiments, some of the layers are adjacent another layer exhibiting a random network of strands and connective regions. In some embodiments, at least one of the first or second (in some embodiments each of the first and second) major surfaces of a polymeric multilayer film exhibits a random network of strands and connective regions. A polymeric film layer comprising a porous random network of strands and connective regions is distinguished from a fibrous layer in that it does not include fibers as defined above. Thus, the layer comprising a porous random network of strands and connective regions is not a nonwoven, woven, or knitted fabric layer.

[0079] In some embodiments, the backing that includes a polymeric layer that comprises a porous random network of strands and connective regions comprises at least one of a polyolefinic material (e.g., polypropylene and / or polyethylene), modified polyolefinic material, polyvinyl chloride, polycarbonate, polystyrene, polyester (including co-polyester), polylactide, polyvinylidene fluoride, (meth)acrylic (e.g., polymethyl methacrylate), thermoplastic polyurethane (TPU), acrylic urethane, ethylene vinyl acetate copolymer, acrylate-modified ethylene vinyl acetate polymer, ethylene acrylic acid copolymers, nylon, engineering polymer (e.g., a polyketone and / or polymethylpentane), or elastomer (e.g., natural rubber; synthetic rubber; styrene block copolymer containing isoprene, butadiene, or ethylene (butylene) blocks; metallocene-catalyzed polyolefin, polyurethanes; or polydiorganosiloxane). A TPU is a thermoplastic block copolymer composed of a soft segment and a hard segment alternately connected, wherein the hard segment is an isocyanate segment (e.g., including an aliphatic isocyanate segment, an aromatic isocyanate segment, or a combination thereof), and the soft segment is a polyether polyol segment or a polyester polyol segment, described in detail above. The soft segments and uncrystallized hard segments form an amorphous phase, and a portion of the hard segment crystallizes to form crystalline microdomains, which can function as physical crosslinking domains. Useful TPUs for a polymeric layer that comprises a porous random network of strands and connective regions can have a high percentage of hard segments. In some embodiments, each polymeric layer that comprises a porous random network of strands and connective regions comprises a vapor impermeable resin. In some embodiments, each polymeric layer that comprises a porous random network of strands and connective regions comprises a polyolefin. In some embodiments, each polymeric layer that comprises a porous random network of strands and connective regions comprises at least one of polyethylene or polypropylene. In some embodiments, the polymeric layer that comprises a porous random network of strands and connective regions comprises low density polyethylene, high density polyethylene, an ethylene -containing copolymer, or a combination thereof. In some embodiments, the polymeric layer that comprises a porous random network of strands and connective regions comprises a thermoplastic polyolefin resin available under the trade designation “ADFLEX KS 021 P” from LyondellBasell, Houston, TX.

[0080] In some embodiments, the polymeric layer that comprises a porous random network of strands and connective regions comprises an ethylene-containing copolymer. The copolymer can include a polar comonomer. Examples of ethylene-containing copolymers including a polar comonomer include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer. In some embodiments, the ethylene -containing copolymer of the polymeric layer that comprises a porous random network of strands and connective regions includes at least 70 wt.%, at least 75 wt.%, or at least 80 wt.%, of ethylene. In some embodiments, the ethylene-containing copolymer of the polymeric layer includes up to 99 wt.%, up to 95 wt.%, up to 90 wt.%, or up to 85 wt.% of ethylene. In some embodiments, the ethylene-containing copolymer includes at least 1 wt.%, at least 5 wt.%, at least 10 wt.%, or at least 15 wt.% of one or more polar comonomers. In some embodiments, the ethylenecontaining copolymer includes up to 30 wt.%, up to 25 wt.%, or up to 20 wt.%, of one or more polar comonomers. Ethylene -vinyl acetate copolymers are commercially available from various suppliers including DuPont Packaging and Industrial Polymers under the trade designations “ELVAX”, for example, grades 750, 550, and 350. Ethylene-acrylic acid copolymers are available from various suppliers such as Dow Chemical Company under the trade designation “PRIMACOR”, for example, grade 1410 or 3460. Ethylene-methacrylic acid copolymers are available from various suppliers such as DuPont Packaging and Industrial Polymers under the trade designations “NUCREL”, for example, grades 0403 and 0903. Useful ethylene-containing copolymers can also contain two or more polar comonomers. Examples of such ethylene-containing copolymers include carbon monoxide-modified ethylene-vinyl acetate or anhydride modified ethylene-vinyl acetate. Such ethylene-containing copolymers are commercially available from various suppliers including DuPont Packaging and Industrial Polymers under the trade designations “BYNEL E418” and “ELVALOY 741”. Mixtures of at least two different ethylene-containing copolymers (e.g., each having different polar comonomers or each having the same polar comonomer but in different amounts) can also be useful.

[0081] A polymeric layer that comprises a porous random network of strands and connective regions can be foamed or overfoamed, for example, by introducing a gas into the molten polymer inside an extruder. The gas is readily absorbed into the polymer under the heat and pressure of the extrusion process. When the molten polymer exits the extrusion die, the absorbed, pressurized gas rapidly expands and forms voids. The proper process conditions can be adjusted so that when the polymer solidifies, the void structure is “locked in” resulting in a foam structure in the polymeric film.

[0082] Foaming of a polymer layer can be facilitated, for example, by including or injecting a foaming agent in the resin for that layer(s). Foaming agents are known in the art and include injecting gases (e.g., nitrogen or carbon dioxide); a blend of alkaline earth metal carbonates and alkaline metal acid salts that are described in U.S. Pat. No. 8,563,621 (Lapierre), the disclosure of which is incorporated herein by reference; hydrazine; hydrazide; and azodicarbonamide materials (e.g., 4,4’-oxybis (benzene sulfonyl hydrazide) (OBSH) (available, for example, in a masterbatch form under the trade designation “CELOGEN OT” from ChemPoint, Bellevue, WA). Further examples of commercially available blowing agents include those under the trade designation “ECOCELL H” from Polyfd Corp., Rockaway, NJ, an endothermic foaming agent, available as a masterbatch under the trade designation “FCX111263” from RTP Company, Winona, MN, and “HYDROCEROL CF 40 E”, from Avient, Avon Lake, OH.

[0083] In some embodiments, the foaming agent is added to the resins that are fed into the extruder. The foaming agent and other processing conditions are selected or adjusted to provide a desired or acceptable polymeric layer exhibiting a random network of strands and connective regions.

[0084] Referring now to FIG. 2, article 10 includes a backing 20 having a first surface 24 and a second surface 22 as described in FIG. 1. In the illustrated embodiment, the PSA 50 of the present disclosure is disposed on the first surface 24 of the backing 20. Article 10 includes release liner 25 disposed on the PSA 50 opposite the backing 20. The release liner can be useful, for example, when the article is wound into a roll. In some embodiments, the release liner 25 is coated on at least one of the major surfaces with a release coating. In some embodiments both major surfaces of the release liner 25 are coated with a release coating. In this case, the release coating may the same or different on each of the major surfaces of the release liner 50. Examples of materials useful as release coatings for the liners disclosed herein include acrylics, silicones, siloxanes, fluoropolymers, and urethanes. In some embodiments, a silicone coating is useful for facilitating release of the PSA. Various release liners may be useful. In some embodiments, the release liner comprises at least one of a polyester film, polyethylene film, polypropylene film, polyolefin coated polymer film, polyolefin coated paper, acrylic coated polymer film, and polymer coated kraft paper. The polyolefin coated film or paper may be polyethylene coated film or paper. Examples of suitable commercially available liners include those available under the trade designations “2.0 CL PET U4162 / U4162”, “48# CL PET H / H UE 1095 / 000”, and “4 BU DHP UE1094B / 000” from Loparex, Hammond, Wisconsin, a red pigmented, multilayer, thermoplastic olefin film containing a proprietary blend of high density polyethylene and low density polyethylene, having a thickness of about 63 micrometers (0.0025 inches), commercially available from Iso Poly Films, Incorporated, Gray Court, South Carolina, and a clear, polyester release liner available under the designation “2PAKN” from Mitsubishi Polyester Film, Inc., Greer, SC.

[0085] The release liner may be produced using a variety of processing techniques. For example, liner processing techniques such as those disclosed in U.S. Pat. Appl. No. 2013 / 0059105 (Wright et al.) may be useful to produce a liner suitable for practicing the present disclosure. A suitable liner processing technique may include applying a layer comprising a (meth)acrylate-functional siloxane to a major surface of a substrate and irradiating that layer in a substantially inert atmosphere comprising no greater than 500 ppm oxygen with a short wavelength polychromatic ultraviolet light source having at least one peak intensity at a wavelength of from about 160 nanometers to about 240 nanometers. Irradiating can at least partially cure the layer. In some embodiments, the layer is cured at a curing temperature greater than 25 °C. The layer may be at a temperature of at least 50 °C, 60 °C 70 °C, 80 °C, 90 °C, 100 °C, 125 °C, or at least 150 °C, in some embodiments, no more than 250 °C, 225 °C, 200 °C, 190 °C, 180 °C, 170 °C, 160 °C, or 155 °C.

[0086] Alternatively, referring again to FIG. 1, the second surface 22 of the backing 20 may include an overlaid or overcoated low surface energy release layer or low adhesion backsize (LAB), which may be useful for making a linerless article.

[0087] FIG. 3 illustrates another embodiment of an article 100 according to the present disclosure in which the backing includes multiple layers. Certain porous layers described above are not considered barrier materials on their own in that they do not provide a barrier to air or liquid water. The article 100 includes a water-vapor permeable polymeric material 130 disposed on a first major surface 122 of a porous layer 120. Together the polymeric material 130 and the porous layer 120 form the backing of the article 100, which can provide an air and water barrier. The polymeric material 130 may at least one of completely cover or impregnate the porous layer 120. PSA 150 of the present disclosure is disposed on a second major surface 124 of the porous layer 120 opposite the first major surface 122. In the illustrated embodiment, a surface 152 of the PSA 150 is attached to a release liner 125, which may be any of the release liners described above in any of their embodiments.

[0088] In some embodiments a peel adhesion between one major surface of the liner 125 and the adhesive surface 152 is less than or equal to a peel adhesion between the other major surface of the liner 125 and the surface 132 of the polymeric material 130. In some embodiments, liner can be surface treated (e.g., at least on one major surface) to increase tack or adhesion between the liner and the polymeric materials 130. Examples of materials or surface treatments useful for increase tack or adhesion between the polymeric coating and the surface of the liner include any chemical or physical surface modifications to any of the polymeric material 130, the surface of the liner, or both. For example, a chemical surface modifier or chemical coating can be used. In some embodiments, adhesion modification can be accomplished by selecting a specific liner surface morphology to increase surface area and physical interlocking of the polymeric coating. In these embodiments, the release liner 125 may adhere to the surface 132 when the article is unwound from a roll, for example, providing a reverse-wound roll with the PSA 150 on the outside of the roll.

[0089] Backings having multiple layers can be made, for example, by extruding a continuous polymeric film described above in any of its embodiments onto a porous layer as described above in any of its embodiments, for example, the polymeric layer that comprises a porous random network of strands and connective regions. Alternatively, the continuous polymeric film may be extruded as a separate sheet and laminated together with another layer, for example, the polymeric layer that comprises a porous random network of strands and connective regions or the fibrous layer as described above in any of their embodiments.

[0090] In some embodiments, the water vapor permeable polymeric material 130 is a crosslinked polymeric layer. In some embodiments, the polymeric layer comprises a polyoxyalkylene polymer having at least one crosslink site derived from a silane having hydrolyzable groups. Crosslinking can occur when hydrolyzable groups of a silane hydrolyze to silanol groups, which then condense to form siloxane bonds. The polyoxyalkylene having silicon atoms bearing hydrolyzable groups can be any of those described above in connection with the PSA, in any of their embodiments. A crosslinkable composition including a polyoxyalkylene having silicon atoms bearing hydrolyzable groups typically includes one or more catalysts. The catalyst may be present in the polymeric material in an amount of from about 0.05 wt% to about 5 wt%, in some embodiments from about 0.1 wt% to about 2 wt%, and in some embodiments, from about 0.1 wt% to about 1 wt%. Useful catalysts include organometallic compounds and amines that are known as silanol condensation catalysts. Examples of suitable silanol condensation catalysts include titanate esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibuytltin maleate, dibutyltin diacetate, stannous octylate, stannous napthenate, reaction products from dibutyltin oxide and phthalate esters, and dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum tris(ethylacetoacetate) and diisopropocyaluminum ethyl acetoacetate; reaction products from bismuth salts and organic carboxylic acids, such as bismuth tris(2 -ethylhexonate) and bismuth tris(neodecanoate); chelate compounds such as zirconium tetra-acetylacetonate and titanium tetra-acetylactonate; organolead compounds such as lead octylate; organovanadium compounds; amines such as butylamine, octylamine, dibutylamine, monoethanolamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6- tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole with carboxylic or other acids; low-molecular-weight polyamide resins derived from excess polyamines and polybasics acids; and reaction products from excess polyamines and epoxy compounds. Any of these may be used individually or in combination.

[0091] Compositions including a polyoxyalkylene having silicon atoms bearing hydrolyzable groups may optionally include various additives such as dehydrating agents, fdlers, rheology additives, compatibilizers, tackifiers, storage stability improving agents, adhesion promoters, ultraviolet absorbers, metal deactivators, antiozonants, antioxidants, light stabilizers, lubricants, amine type radical chain inhibitors, phosphorus-containing peroxide decomposers, pigments, foaming agents, solvents, flame retardants, antifungal agents, blowing agents, and antistatic agents, each in any adequate amount and in any combination. Specific examples of these additives are disclosed in U.S. Pat. Nos. 10,704,254 (Seabaugh et al.), 11,105,089 (Widenbrant et al.), 11,365,328 (Seabaugh et al.), 11,512,463 (Widenbrant et al.), and 11,731,394 (Seabaugh et al.), and U.S. Pat. Appl. Pub. Nos. 2017 / 0173916 (Widenbrant et al.), 2021 / 0207005 (Seabaugh et al.), and 2022 / 0282476 (Widenbrant et al.).

[0092] Any suitable method may be useful for applying the crosslinkable polymeric composition to the porous layer. Examples of such methods include knife coating, slot coating, die coating, flood coating, rod coating, curtain coating, cast coating, spray coating, brush coating, dip coating, kiss coating, gravure coating, and print coating operations such as flexographic, inkjet, or screen print coating. The composition may then be heated at an elevated temperature (e.g., at least 50 °C, 60 °C 70 °C, 80 °C, or 90 °C, in some embodiments, no more than 250 °C, 225 °C, 200 °C, 190 °C, 180 °C, 170 °C, 160 °C, or 150 °C) to crosslink the composition thus forming a polymeric layer comprising a poly oxyalkylene polymer having at least one crosslink site derived from a silane having hydrolyzable groups on a porous layer.

[0093] In some embodiments of a backing comprising multiple layers useful in the article of the present disclosure, a polymeric layer that comprises a porous random network of strands and connective regions is coextruded with a continuous polymeric film layer as described above in any of its embodiments. Coextrusion means, for the purposes of the present disclosure, the simultaneous melt processing of multiple molten streams and combination of such molten streams into a single unified structure, or coextruded film, for example, from a single extrusion die. The backing in some embodiments of the article of the present disclosure can be coextruded using any suitable type of coextrusion die and any suitable method of film making such as blown film extrusion or cast film extrusion. In some embodiments, a multilayer melt stream can be formed by a multilayer feedblock, such as that shown in U.S. Pat. No. 4,839,131 (Cloeren) or other specialized feedblock or a specialized die such as those made by Cloeren Co., Orange, TX. The feed block and die used are typically heated to facilitate polymer flow and layer adhesion, with the temperature of the die depending on the polymers used. Techniques of coextrusion are found in many polymer processing references, including Progelhof, R. C., and Throne, J. E., "Polymer Engineering Principles", Hanser / Gardner Publications, Inc., Cincinnati, Ohio, 1993. In some embodiments of a backing useful in the article of the present disclosure, a polymeric layer that comprises a porous random network of strands and connective regions is coextruded with a continuous polymeric film layer as described above in any of its embodiments by foaming a layer in a blown film process that uses an annular die to form a molten tube of film oriented radially via air pressure in a “bubble” and also pulled lengthwise in the molten area to thin the film to the final desired thickness. A suitable annular die and apparatus is illustrated and described, for example, in U.S. Pat. Nos. 10,953,573 (Emslander et al.), 10,953,574 (Young et al.), 10,953,623 (Young et al.), 10,987,894 (Emslander et al.). The number of layers in the coextruded film can be adjusted by the number of stacking die plates in the annular die. A polymeric layer that comprises a porous random network of strands and connective regions can be coextruded with a continuous polymeric film layer in a blown film apparatus, for example, by not including or injecting a foaming agent in the resin for the continuous layer in the annular stacked die. To facilitate coextrusion, in some embodiments, the melt viscosity of the polymer in the continuous polymeric film layer is similar to the melt viscosity of the polymer in the polymer layer that comprises a porous random network of strands and connective regions.

[0094] In some embodiments, the backing useful in the article of the present disclosure is a polymeric multilayer film including a polymeric layer that comprises a porous random network of strands and connective regions and a continuous polymeric film layer as described above in any of its embodiments. In some embodiments of the backing useful in the article of the present disclosure, there are at least 2, 3, 4, 5, 6, or 7 polymeric film layers comprising a porous random network of strands and connective regions and at least 2, 3, 4, 5, 6, or 7 continuous polymeric film layers as described above in any of their embodiments. In some embodiments with more than one polymeric film layer comprising a porous random network of strands and connective regions, at least two such layers exhibit different random networks of strands and connective regions. In some embodiments with more than one continuous polymeric film layer, at least two such layers have a different polymeric composition. In some embodiments, the polymeric film layers comprising a porous random network of strands and connective regions at least partially alternate with the continuous polymeric film layers. In some embodiments only one polymeric film layer comprising a porous random network of strands and connective regions is in direct contact with a continuous polymeric film layer. In some embodiments, at least one polymeric film layer comprising a porous random network of strands and connective regions is disposed between two continuous polymeric film layers. In some embodiments, a continuous polymeric film layer is disposed between two polymeric film layers comprising a porous random network of strands and connective regions. In some embodiments, the first major surface of the backing comprises the polymeric film layer comprising a porous random network of strands and connective regions. In some embodiments, the second major surface of the backing comprises the continuous polymeric film layer. Further information about multilayer films including a polymeric layer that comprises a porous random network of strands and connective regions and a continuous polymeric film layer useful in the article of the present disclosure can be found in co-pending U.S. Pat. Appl. Serial No. 63 / 635,837, fded on the same day as the present application, which is incorporated by reference in its entirety herein.

[0095] In some embodiments, at least one layer of polymeric multilayer fdm described above comprises a release agent. Examples of suitable release agents include at least one of an alkyl dimethicone, a polyvinyl octadecyl carbamate, or an ethylene bis-stearamide. Alkyl dimethicones, are described, for example, in U.S. Pat. No. 9,187,678 (Boardman et al.). A polyvinyl octadecyl carbamate is commercially available, for example, under the trade designation “ESCOAT P-77” (a polyvinyl octadecyl carbamate in a linear, low density carrier resin) from Mayzo, Inc., Suwanee, GA. An ethylene bis-stearamide is available, for example, under the trade designation “AMPACET 100666” from Ampacet Corporation, Tarrytown, NY. The layer comprising the release agent may exhibit a random network of strands and connective regions, or it may be a continuous film.

[0096] In some embodiments, at least one layer of a polymeric multilayer film described above comprises at least one of a dye or pigment (e.g., imparting a color such as white, yellow, green, blue, red, orange, brown, black, etc.). Examples of suitable dyes include those commercially available, for example, under the trade designation “CLARIANT REMAFIN PE63421213-ZN” (a green dye masterbatch) from Clariant International AG, Muttenz, Switzerland. Examples of suitable pigments include titanium dioxide, zinc oxide, and zirconium dioxide. In some embodiments, polymeric multilayer film described above comprises a layer that is separable from the first polymeric layer and the second polymeric layer.

[0097] In some embodiments of the polymeric multilayer film useful as a backing in the article of the present disclosure, there is a tie layer between the polymeric film layer comprising a porous random network of strands and connective regions and the continuous polymeric film layer. In some embodiments, the tie layer comprises an ethylene -containing copolymer, for example, including a polar comonomer, as described above in any of its embodiments. Examples of ethylene-containing copolymers including a polar comonomer include ethylene -vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene -methacrylic acid copolymer. In some embodiments, the ethylene-containing copolymer of the tie layer includes at least 70 wt.%, at least 75 wt.%, or at least 80 wt.%, of ethylene. In some embodiments, the ethylene-containing copolymer of the first polymeric layer includes up to 99 wt.%, up to 95 wt.%, up to 90 wt.%, or up to 85 wt.% of ethylene. The tie layer can comprise a porous random network of strands and connective regions as described above in any of its embodiments. In some embodiments, the tie layer is a continuous layer.

[0098] In some embodiments, the polymeric multilayer film useful as a backing in the article of the present disclosure is water-vapor permeable. In some embodiments, the polymeric multilayer film has a moisture vapor transmission rate of at least 5 perms, at least 10 perms, at least 15 perms, or at least 20 perms. In some embodiments, polymeric multilayer films described herein have a thickness in a range from 1 micrometer to 1000 micrometers (in some embodiments, in a range from 25 micrometers to 500 micrometers, 50 micrometers to 250 micrometers, or even 2 micrometers to 10 micrometers). The number of open pores (e.g., in the first polymeric film layer), the thickness, and materials (e.g., in the first and second polymeric film layers) influences the permeability. A person skilled in the art can select materials (e.g., in the first and second polymeric film layers) and porosity (e.g., in the first polymeric film layer) depending on the desired permeability.

[0099] In some embodiments, to retain a desired level of water vapor permeance in the article, the pressure sensitive adhesive layer is discontinuous in order to leave portions of a major surface of the backing. For discontinuous layers, typically in the range of about 10% to 90%, more typically about 30% to 80%, most typically 40% to 70%, of the area of a major surface of the backing is covered with adhesive. In other words, at least 10% to 90%, in some embodiments 20% to 70% or 30% to 60%, of the area of a major surface of the backing can be adhesive-free.

[0100] Discontinuous layers of pressure sensitive adhesive may be applied in a random fashion or in a specific pattern. Some examples of discontinuous coatings of adhesive are described, for example, in U.S. Pat. Nos. 3,039,893 (Banigan, Jr.), 3,426,754 (Bierenbaum), 5,374,477 (Lawless), 5,593,771 (Lawless), 5,895,301 (Porter), 6,495,229 (Carte), 6,901,712 (Lionel), and 10,704,254 (Seabaugh et al.) and U.S. Pat. Appl. Pub. No. US 2017 / 0072430 (Maier et al.).

[0101] To prevent the lateral movement of air between the article of the present disclosure and a substrate to which it is bonded and through lap joints of the article, the adhesive coated areas of the article can be made to intersect to isolate the uncoated areas, thereby eliminating channels through which air can laterally move. This can be achieved by any number of patterns, such as intersecting circles with adhesive free centers, intersecting squares or rectangles of adhesive, and intersecting strips in a checkered pattern. In some embodiments of the article of the present disclosure, the PSA is present in a continuous layer.

[0102] The PSA useful in the article of the present disclosure can have a variety of thicknesses depending on the desired application. In some embodiments, the PSA has a thickness in a range from 50 to 6000 micrometers, from 100 to 4000 micrometers, from 100 to 2000 micrometers, or from 100 to 1500 micrometers. In some embodiments, the PSA has a thickness of at least 100 micrometers.

[0103] In some embodiments, the article of the present disclosure and / or made by the methods disclosed herein is applied to a substrate. The substrate can be made from a variety of materials such as wood, vinyl, metal, or concrete. In some embodiments, the article of the present disclosure may be simultaneously adhered to two different substrates (e.g., side-by-side substrates). Useful substrates can include at least one of an air and water barrier film, a subfloor, a window frame, a door frame, and wall sheathing materials (e.g., oriented strand board (OSB), foam insulation sheathing, exterior grade gypsum sheathing board, concrete, concrete masonry units (CMUs)). The substrate, in some cases, can be compacted soil or gravel. The substrate may be horizontal or vertical. In some embodiments, the article of the present disclosure and / or made by the methods disclosed herein is at least a portion of an interior wall, an exterior wall, a floor, a ceiling, or a roof. A method of the present disclosure includes applying the article disclosed herein to the substrate using the pressure sensitive adhesive layer. The substrates can be any of those described above. The article of the present disclosure may be in the form of a tape, for example, useful as seaming tape or flashing tape.

[0104] The present disclosure also provides a method of installing a window or door. FIG. 4 is a perspective, exploded view of an embodiment of an article of the present disclosure, in the form of a tape, applied to a window frame. FIG. 4 illustrates a window opening 434 in wall sheathing 432 that is optionally covered with building wrap 436. Suitable materials for wall sheathing include plywood, oriented strand board (OSB), foam insulation sheathing, exterior grade gypsum sheathing board, concrete, concrete masonry units (CMUs), and other conventional sheathing materials commonly used in the construction industry. As shown in FIG. 4, tape 405, which is an article as described in any of the above embodiments, is applied on building wrap 436 or wall sheathing 432 level with the bottom edge of the rough opening frame 434 to form a sill flashing. Windowsill pans may be installed in the opening and the first layer 405 can overlap the sill pan. Window 446 is inserted into opening 434. Typically, the window frame fits within the opening and flanges extend from the window frame and over the wall sheathing. The window flanges are secured to the wall. Tape 415 and 425 of the present disclosure can also be applied on the window jambs extending from the window flange and onto the building wrap 436 or wall sheathing 432. Tape 435 of the present disclosure can also be applied at the top flange on the window and the sheathing. Cutting a flap of building wrap 436 to expose the wall sheathing 432 can allow clearance for the tape 435 at the top of the window.

[0105] In some embodiments, the article of the present disclosure and / or made according to the method of the present disclosure is an air and water barrier film. The air and water barrier film can be, for example, a building wrap as described above or a membrane used under a concrete floor or on an interior wall. An air and water barrier film can be useful, for example, for preventing external liquid water from infiltrating through the sheet yet venting water in vapor form. In some embodiments in which the article of the present disclosure is a tape, the tape of the present disclosure can be useful as seaming tape or flashing tape, for example, in connection with an air and water barrier film. The air and water barrier film can be an article according to the present disclosure as described above in any of its embodiments. Another example of a suitable air and water barrier film is commercially available under the trade designation “TYVEK” from E. I. Du Pont de Nemours and Company, Wilmington, Delaware USA, which is obtained by thermo-compressing a three-dimensionally-meshed fiber of high-density polyethylene.

[0106] The article of the present disclosure can have a wide variety of widths. Useful widths for a flashing tape or a sealing tape can include between 2 inches (5.1 cm) and 18 inches (45.7 cm) in width. In some embodiments, the width of the tape is at least 1 inch (2.5 cm). In some embodiments, the width of the tape is at least 5 cm. In some embodiments, the width of the article (in some embodiments, the tape) is at most 75 cm (29.5 inches), 45 cm (17.7 inches), 30.5 cm (12 inches), or 10 cm (3.9 inches). In some embodiments, the width of the article is up to 75 cm (29.5 inches), up to 150 cm (59. 1 inches), or up to 160 cm (63.0 inches).

[0107] In a first embodiment, the present disclosure provides a pressure-sensitive adhesive comprising a polyoxyalkylene polymer having no fluorinated carbon atoms and an acrylic copolymer, the acrylic copolymer comprising: at least 60 weight percent of linear or branched alkyl (meth)acrylate monomer units, based on the weight of the acrylic copolymer; and from 12.5 weight percent to 40 weight percent of (meth)acrylic acid monomer units, based on the weight of the acrylic copolymer. In a second embodiment, the present disclosure provides the pressure-sensitive adhesive of the first embodiment, wherein the polyoxyalkylene polymer is present in an amount of 20 weight percent to 45 weight percent, based on the total weight of the pressure -sensitive adhesive. In a third embodiment, the present disclosure provides the pressure-sensitive adhesive of the first or second embodiment, wherein the acrylic copolymer is crosslinked. In a fourth embodiment, the present disclosure provides the pressure-sensitive adhesive of any one of the first to third embodiments, wherein the acrylic copolymer is crosslinked with a triazine. In a fifth embodiment, the present disclosure provides the pressure -sensitive adhesive of any one of the first to fourth embodiments, wherein the pressure-sensitive adhesive is free of a fluorinated surfactant and / or is free of transition metal complexes or includes less than 0.01 wt.%, 0.010 wt.%, 0.005 wt.%, or 0.001 wt.% of a transition metal complex, based on the total weight of the pressure-sensitive adhesive. In a sixth embodiment, the present disclosure provides the pressure-sensitive adhesive of any one of the first to fifth embodiments, wherein the pressure-sensitive adhesive is not frothed. In a seventh embodiment, the present disclosure provides the pressure-sensitive adhesive of any one of the first to sixth embodiments, wherein the polyoxyalkylene polymer comprises at least one of an alkoxylated alcohol, diol, or polyol, an alkoxyated amine, diamine, or polyamine, an alkoxylate ester, an alkoxylated amide, or an alkoxylated urethane. In an eighth embodiment, the present disclosure provides the pressure-sensitive adhesive of any one of the first to seventh embodiments, wherein the polyoxyalkylene polymer is divalent or multivalent and comprises a plurality of at least one of ethoxy, propoxy, or butoxy groups and terminal groups comprising at least one of alkyl, hydroxyl, amino, or silane. In a ninth embodiment, the present disclosure provides the pressure-sensitive adhesive of any one of the first to eighth embodiments, wherein the polyoxyalkylene polymer is represented by formula R7O-(EO)p-(R6O)q-(EO)p-R7or R7O-(R6O)q-(EO)p-(R6O)q-R7, wherein each R7is independently hydrogen or alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl), wherein alkyl is unsubstituted or substituted by hydroxyl, -N(R4)2, or -Si(Y)3-x(R5)x; each R4is independently hydrogen, an alkyl group having up to 8 carbon atoms, a phenyl group, or a polyoxyalkylene group; each R5is independently an alkyl group having up to 8 carbon atoms or a phenyl group; each Y is independently a hydrolysable group; x is 0, 1, or 2; EO represents -CH2CH2O-; each R6O is independently selected from the group consisting of-CH(CH3)CH2O-, -CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH2CH2CH2O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, and -CFhC CFb^O-; each p is independently 1 to 150; and each q is independently 0 to 150, wherein p+q is at least 3. In a tenth embodiment, the present disclosure provides the pressure-sensitive adhesive of any one of the first to ninth embodiments, wherein the linear or branched alkyl (meth)acrylate monomer units comprise units of at least one of n-butyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, or isononyl acrylate; and the (meth)acrylic acid monomer units are acrylic acid monomer units.

[0108] In an eleventh embodiment, the present disclosure provides a process for making the pressuresensitive adhesive of any one of the first to tenth embodiments, the process comprising partially polymerizing a first polymerizable composition that comprises a linear or branched alkyl (meth)acrylate and (meth)acrylic acid to form a syrup composition; combining the syrup composition with the polyoxyalkylene polymer and, optionally, a crosslinking agent to provide a second polymerizable composition; and polymerizing the second polymerizable composition to form the pressure sensitive adhesive. In a twelfth embodiment, the present disclosure provides the process of the eleventh embodiment, wherein the syrup composition comprises 1 weight percent to 20 weight of the acrylic copolymer and 80 weight percent to 99 weight percent monomers based on a total weight of the syrup composition, wherein the monomers comprise the linear or branched alkyl (meth)acrylate and (meth)acrylic acid.

[0109] In a thirteenth embodiment, the present disclosure provides an article comprising the pressuresensitive adhesive of any one of the first to tenth embodiments or made by the process of the eleventh or twelfth embodiment disposed on a backing. In a fourteenth embodiment, the present disclosure provides the article of the thirteenth embodiment, wherein the pressure-sensitive adhesive is present in a discontinuous pattern. In a fifteenth embodiment, the present disclosure provides the article of the thirteenth embodiment, wherein the pressure-sensitive adhesive is present in a continuous layer. In a sixteenth embodiment, the present disclosure provides the article of any one of the thirteenth to fifteenth embodiments, wherein the article is water vapor permeable. In a seventeenth embodiment, the present disclosure provides the article of any one of the thirteenth to sixteenth embodiments, wherein the article has a water vapor permeability of at least 5 US Perms. In an eighteenth embodiment, the present disclosure provides the article of any one of the thirteenth to sixteenth embodiments, wherein a release liner is disposed on the pressure-sensitive adhesive opposite the backing.

[0110] In a nineteenth embodiment, the present disclosure provides the article of any one of the thirteenth to eighteenth embodiments, wherein the backing comprises at least one of a polyurethane, a polyamide, polylactic acid, an acrylic block copolymer, or an amorphous polyester. In a twentieth embodiment, the present disclosure provides the article of any one of the thirteenth to nineteenth embodiments, wherein the backing comprises a porous layer having first and second major surfaces and a polymeric layer disposed on at least the first major surface of the porous layer. In a twenty-first embodiment, the present disclosure provides the article of the twentieth embodiment, wherein the polymeric layer comprises a crosslinked polyoxyalkylene polymer having at least one crosslink site comprising at least one siloxane bond. In a twenty-second embodiment, the present disclosure provides the article of the twentieth or twenty-first embodiment, wherein the porous layer is fibrous. In a twenty- third embodiment, the present disclosure provides the article of any one of the twentieth to twenty-second embodiments, wherein the porous layer comprises a nonwoven.

[0111] In a twenty-fourth embodiment, the present disclosure provides the article of any one of the eighteenth to twenty-third embodiments, wherein the backing comprises a porous random network of strands and connective regions. In a twenty-fifth embodiment, the present disclosure provides the article of the twenty-fourth embodiment, wherein the random network of strands has a first optical density, and the connective regions have a second optical density, wherein the first optical density is greater than the second optical density. In a twenty-sixth embodiment, the present disclosure provides the article of the twenty-fourth or twenty-fifth embodiments, wherein a portion of the connective regions includes through holes, and portion of the connective regions does not include through holes. In a twenty-seventh embodiment, the present disclosure provides the article of any one of the twenty-fourth to twenty-sixth embodiments, wherein the porous random network of strands and connective regions comprises a polyolefin. In a twenty-eighth embodiment, the present disclosure provides the article of any one of the twenty-fourth to twenty-seventh embodiments, wherein the backing comprises a polymeric multilayer film comprising a first polymeric layer and a second polymeric layer, wherein the first polymeric layer comprises the porous random network of strands and connective regions, and wherein the second polymeric layer is a continuous polymeric film layer. In a twenty-ninth embodiment, the present disclosure provides the article of the twenty-eighth embodiment, wherein the second polymeric layer comprises at least one of a polyurethane, a polyamide, polylactic acid, an acrylic block copolymer, or an amorphous polyester. In a thirtieth embodiment, the present disclosure provides the article of the nineteenth or twenty-ninth embodiment, wherein the polyurethane is a reaction product of components comprising polyethylene glycol, a chain extender, and an aliphatic isocyanate. In a thirty-first embodiment, the present disclosure provides the article of the thirtieth embodiment, wherein the polyethylene glycol has a number average molecular weight in a range from 500 grams per mole and 2500 grams per mole, and wherein the aliphatic isocyanate comprises dicyclohexylmethane-4,4'- diisocyanate. In a thirty-second embodiment, the present disclosure provides the article of the thirtieth or thirty-first embodiment, wherein the components further comprise a triol, and wherein the triol contributes hydroxyl groups in a range from 2 mole percent to 10 mole percent, based on the total moles of hydroxyl groups in the polyethylene glycol, the chain extender, and the triol. In a thirty-third embodiment, the present disclosure provides the article of any one of the twenty-eighth to thirty-second embodiments, further comprising a tie layer between the first polymeric layer and the second polymeric layer. In a thirty-fourth embodiment, the present disclosure provides the article of the thirty-third embodiment, wherein the tie layer comprises an ethylene -containing copolymer. In a thirty-fifth embodiment, the present disclosure provides the article of any one of the twenty-eighth to thirty-fourth embodiments, wherein the first polymeric layer is one of a plurality of layers comprising a porous random network of strands and connective regions, and wherein the second polymeric layer is one of a plurality of continuous polymeric fdm layers.

[0112] Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated.

[0113] EXAMPLES

[0114] Table 1. Materials

[0115] Example 1: Pressure-Sensitive Adhesive

[0116] A pressure sensitive adhesive precursor composition was prepared by mixing 84 parts by weight (pbw) isooctyl acrylate (IOA), 16 pbw acrylic acid (AA) and 0.04 pbw of 2,2-dimethoxy-l,2- diphenylethan-l-one. This mixture was partially polymerized under a nitrogen atmosphere by exposure to low intensity ultraviolet radiation to provide a coatable syrup. An additional 0.272 pbw of 2,2- dimethoxy-l,2-diphenylethan-l-one, 0.467 pbw of 2,4-bis-trichoromethyl-6-(4-methoxyphenyl)-s- triazine, and 56 pbw of a monobutyl ether of a linear polymer of ethylene oxide: propylene oxide (1: 1) polyglycolwere added to the syrup and mixed until all the components had completely dissolved to give a pressure sensitive adhesive precursor composition.

[0117] The adhesive precursor composition was then coated onto a siliconized polyethylene coated Kraft paper liner using a notch bar with a 0.130-millimeter (mm) (0.005 inches) gap setting greater than the thickness of the liner. The adhesive precursor was then exposed to a total energy of 850 milliJoules / square centimeter from an ultraviolet radiation source having a maximum at 351 nanometers in a nitrogen-rich environment. The result was a pressure sensitive adhesive coated release liner.

[0118] Example 2: Article

[0119] A seven-layer film was produced using a seven-layer annular stack die (obtained under the trade designation “COEX 7-LAYER” (Type LF-400) from Labtech Engineering, Samut Prakan, Thailand) except there were only seven stacked die plates. Airflow to the die was manually controlled to achieve a blow-up ratio of about 2: 1. The bubble was subsequently collapsed about 3 meters (10 feet) above the die and rolled up. The feed materials were supplied by 7 independent 20-mm diameter extruders with about a 30: 1 length to diameter ratio.

[0120] A first extruder was used to melt and feed a blend containing 91.0 weight percent (wt.%) of Polyurethane 1 and 9 wt.% of the anti-blocking agent into an inside channel of the annular stack die at a rate of 15 revolutions per minute (rpm). The extrusion temperature was maintained at 180°C. Second, third, fourth, and fifth extruders were used to melt and feed Polyurethane 1 on subsequent outer layers of the first resin at a rate of 15 rpm. A sixth extruder was used to feed a blend containing 46.5 wt.% of the Thermoplastic Polyolefin , 46.5 wt.% of EMA, 5 wt.% of CBA, and 2 wt.% of carbon black at a rate of 60 rpm. An extrusion temperature of 215°C was maintained in layer 6. A seventh extruder was used to feed a blend containing 93.0 wt.% of the Thermoplastic Polyolefin, 5 wt.% of CBA, and 2 wt.% of carbon black at a rate of 60 rpm. The 7-layer coextruded blown film bubble was collected at a 3.7 feet per minute (fpm) line speed and was slit producing a single film. The Example 1 vapor permeable pressure sensitive adhesive on release liner was hand laminated to the first extruder feed side of the film resulting in an overall vapor permeable construction with a removable release liner.

[0121] Example 3: Article

[0122] Example 3 was carried out using the method of Example 2 with the following modifications. The sixth and seventh extruders were both fed at a rate of 90 rpm, and the blown film bubble was collected at a line speed of 4. 1 fpm.

[0123] Example 4: Article

[0124] Example 4 was carried out using the method of Example 2 with the following modifications. The blown film bubble was collected at a line speed of 4.1 fpm.

[0125] Example 5: Article

[0126] Example 4 was carried out using the method of Example 2 with the following modifications. The blown film bubble was collected at a line speed of 4.1 fpm. The fourth and fifth extruders were both fed at a rate of 20 rpm.

[0127] Example 6: Article

[0128] The seven-layer annular stack die described for Example 2 was used. First and second extruders were used to melt and feed LDPE into the inside channels of the annular stack die at a rate of 60 rpm. Third, fourth, and fifth extruders were used to melt and extrude Polyurethane 1 on subsequent outer layers of the first resin at a rate of 15 rpm. A sixth extruder was used to feed a blend containing 46.5 wt.% of the Thermoplastic Polyolefin, 46.5 wt.% of EMA, 5 wt.% of CBA, and 2 wt.% of carbon black at a rate of 60 rpm. An extrusion temperature of 215°C was maintained in layer 6. A seventh extruder was used to feed a blend containing 93.0 wt.% of the Thermoplastic Polyolefin, 5 wt.% of CBA, and 2 wt.% of carbon black at a rate of 60 rpm. The 7-layer coextruded blown film bubble was collected at a line speed of 4. 1 fpm and was slit producing a single film. The inner two LDPE layers were stripped from the film creating an overall 5-layer coextruded blown film. The Example 1 vapor permeable pressure sensitive adhesive on release liner was hand laminated to the polyurethane side of the film creating an overall vapor permeable construction with a removable release liner. Example 7: Article

[0129] Example 7 was carried out using the method of Example 6 with the following modifications. The sixth and seventh extruders were both fed at a rate of 90 rpm.

[0130] Water Vapor Transmission Evaluation

[0131] The water vapor transmission rates of Examples 1 to 6 were evaluated generally as described in ASTM E96 / E96M: “Standard Test Methods for Water Vapor Transmission of Materials” using Paragraph 11: Desiccant Method at (23 °C (73 °F)) and 50% relative humidity, with the following modifications. Six data points were obtained and used to calculate a permeance value. The six individual values were used to determine an average permeance value which was reported in units of Perms. Two samples were evaluated for permeance per condition and are both reported. The results are shown in Table 2, below.

[0132] Tensile Strength

[0133] The tensile strength of samples was evaluated according to ASTM D412, Method A, Die C, using an elongation rate of 508 mm / minute (20 inches / minute). Tensile strength was measured in both the machine direction (MD) and cross machine direction (CD). Three measurements were taken per condition and the average tensile strength was reported in pounds per square inch (lb / in2).

[0134] Peel Adhesion

[0135] Peel adhesion measurements were evaluated at a 90-degree angle according to ASTM D3330, Method F, on stainless steel after a 24-hour dwell time. Two measurements were taken per condition and the average peel adhesive was reported in pounds per inch (lb / in).

[0136] Table 2. Evaluations of Examples 1 to 6

[0137] Example 8: Article

[0138] A pressure-sensitive adhesive coated liner was prepared as described above in Example 1.

[0139] Polyurethane 2 was hotmelt extruded using a twin-screw extruder through a casting die onto a polyethylene coated Kraft paper liner at a thickness of 0.102 mm (0.004 inch). The pressure-sensitive adhesive was hand laminated to the film of Polyurethane 2. The Water Vapor Transmission Evaluation was carried out as described above, and the results were 13.71 US Perms and 14.57 US Perms.

[0140] Example 9: Article

[0141] Example 9 was prepared as described in Example 8 expect that Polyurethane 1 was used instead of Polyurethane 2. The Water Vapor Transmission Evaluation was carried out as described above, and the results were 18.52 US Perms and 16.65 US Perms.

[0142] Example 10: Article

[0143] Example 10 was prepared as described in Example 8 expect that Polyurethane 3 was used instead of Polyurethane 2. The Water Vapor Transmission Evaluation was carried out as described above, and the results were 14.31 US Perms and 13.91 US Perms.

[0144] Preparation of Aliphatic Thermoplastic Polyurethane

[0145] Pellets of an aliphatic thermoplastic polyurethane were prepared through a reactive extrusion process using a twin-screw extruder, Model ZSK25, available from Coperion Corp., Stuttgart Germany, having 12 barrel sections with each barrel having a length of 100 mm. The first barrel was closest to the extruder drive mechanism and twelfth barrel was nearest the exit of the extruder. Polyethylene glycol diol (addition rate of 75 grams per minute (g / min)) was added to the first barrel section via a heated ZENITH B-9000 gear pump, available from Circor International, Inc., Burlington, MA. 1,4-Butanediol (addition rate of 15.4 g / min) was added to the second barrel section by a Flow Meter Controlled Pump, sold as from the Mini-Cori series from Bronkhorst (Ruurlo, The Netherlands). Dibutyltin dilaurate (addition rate of 0. 15 g / min) was added to the second barrel section via a syringe pump, available from Harvard Apparatus, Holliston, MA. Polycaprolactone triol (addition rate of 1.2 g / min) was added to the second barrel section via a syringe pump. A blend of 3 parts-by-weight UV Absorber and 2 parts-by- weight HALS was added to the fourth barrel section via syringe pump (addition rate of 2.25 g / min). H12MDI (addition rate of 59.6 g / min) was added to the third barrel section via a second ZENITH B-9000 gear pump. The molten polyurethane was discharged from the extruder into a ZENITH PEP II gear pump, available from Circor International, Inc. The polyurethane was pumped into an underwater pelletizer, model number EUP10, available from ECON Inc., Monroe, MI.

[0146] Example 11: Article

[0147] The seven-layer annular stack die described for Example 2 was used. First, second, and third extruders were used to melt and feed LDPE into the inside channels of the annular stack die at a rate of 40 rpm. The fourth extruder was used to melt and extrude the Aliphatic Thermoplastic Polyurethane described above on subsequent outer layers of the first resin at a rate of 20 rpm. A fifth extruder was used to melt and feed a blend containing 70.0 wt.% of EVA 1, 23.0 wt% of EVA 2, 5.0 wt.% CBA, and 2 wt.% of TiO2at a rate of 20 rpm. A sixth and seventh extruder were used to melt and feed a blend containing 70.0 wt.% of the Thermoplastic Polyolefin, 23.0 wt.% of EMA, 5 wt.% of CBA, and 2 wt.% of TiO2at a rate of 20 and 60 rpm, respectively. The 7-layer coextruded blown film bubble was collected at a line speed of 4. 1 fpm and was slit producing a single film. The inner three LDPE layers were stripped from the film creating an overall 4-layer coextruded blown film. A vapor permeable pressure sensitive adhesive on release liner prepared as described in Example 1 was hand laminated to the layer 4, polyurethane, side of the film creating an overall vapor permeable construction with a removable release liner. The Water Vapor Transmission Evaluation was carried out as described above, and the results were 5.50 US Perms and 5.58 US Perms.

[0148] Examples 12 and 13 and Control Example A: Pressure-Sensitive Adhesives

[0149] A pressure sensitive adhesive precursor composition was prepared by mixing 90 pbw IO A, 10 pbw AA, 0.19 pbw of 2,2-dimethoxy-l,2-diphenylethan-l-one, and 0.1 pbw 2,4-bis(trichloromethyl)-6- (4-methoxyphenyl)-triazine. This mixture was partially polymerized under a nitrogen atmosphere by exposure to low intensity ultraviolet radiation to provide a coatable syrup. An additional 6.8 pbw AA, 0.13 pbw of 2,2-dimethoxy-l,2-diphenylethan-l-one, and the amounts of 2,4-bis(trichloromethyl)-6-(4- methoxyphenyl)-triazine, isooctyl thioglycolate (IOTG), tallow amine ethoxylate, and tris (15- hydroxyethyl)-N-tallowalkyl-l,3-diaminopropane shown in Table 3, below, were added to the syrup and mixed until all the components had completely dissolved to give a pressure sensitive adhesive precursor composition. The adhesive precursor composition was then coated onto a release liner and cured as described in Example 1.

[0150] The pressure sensitive adhesive was transferred to a paper towel for the measurement of Water Vapor Transmission as described above. Also, Peel Adhesion was measured according to the test method described above using a 50.8-micrometer (2 -mil) aluminum foil backing. The results are shown in Table 3, below.

[0151] Table 3. Pressure-Sensitive Adhesives Control Example A (C.E. A) and Examples (Ex. 12 and 13)

[0152] Foreseeable modifications and alterations of this disclosure will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes.

Claims

What is claimed is:

1. A pressure-sensitive adhesive comprising a polyoxyalkylene polymer having no fluorinated carbon atoms and an acrylic copolymer, the acrylic copolymer comprising: at least 60 weight percent of linear or branched alkyl (meth)acrylate monomer units, based on the weight of the acrylic copolymer; and from 12.5 weight percent to 40 weight percent of (meth)acrylic acid monomer units, based on the weight of the acrylic copolymer.

2. The pressure-sensitive adhesive of claim 1, wherein the acrylic copolymer is crosslinked.

3. The pressure-sensitive adhesive of claim 1 or 2, wherein the acrylic copolymer is crosslinked with a triazine.

4. The pressure-sensitive adhesive of any one of claims 1 to 3, wherein the pressure-sensitive adhesive is not frothed.

5. The pressure-sensitive adhesive of any one of claims 1 to 4, wherein the polyoxyalkylene polymer is present in an amount of 20 weight percent to 45 weight percent, based on the total weight of the pressure-sensitive adhesive.

6. The pressure-sensitive adhesive of any one of claims 1 to 5, wherein the polyoxyalkylene polymer is divalent or multivalent and comprises: a plurality of at least one of ethoxy, propoxy, or butoxy groups; and terminal groups comprising at least one of alkyl, hydroxyl, amino, or silane.

7. The pressure-sensitive adhesive of any one of claims 1 to 6, wherein the polyoxyalkylene polymer comprises at least one of an alkoxylated alcohol, diol, or polyol, an alkoxyated amine, diamine, or polyamine, an alkoxylate ester, an alkoxylated amide, or an alkoxylated urethane.

8. An article comprising the pressure -sensitive adhesive of any one of claims 1 to 7 disposed on a backing.

9. The article of claim 8, wherein the backing comprises at least one of a polyurethane, a polyamide, polylactic acid, an acrylic block copolymer, or an amorphous polyester.

10. The article of claim 8 or 9, wherein the backing comprises a porous layer having first and second major surfaces and a polymeric layer disposed on at least the first major surface of the porous layer.

11. The article of claim 10, wherein the polymeric layer comprises a crosslinked poly oxyalkylene polymer having at least one crosslink site comprising at least one siloxane bond.

12. The article of any one of claims 8 to 10, wherein the backing comprises a polymeric layer comprising a polyurethane, and wherein the polyurethane is a reaction product of polyethylene glycol, and chain extender, and an aliphatic isocyanate.

13. The article of any one of claims 8 to 12, wherein the pressure-sensitive adhesive is a continuous layer on the backing.

14. The article of any one of claims 8 to 13, wherein the article has a water vapor permeability of more than 1 US Perm or at least 5 US Perms.

15. The article of any one of claims 8 to 14, wherein a release liner is disposed on the pressuresensitive adhesive opposite the backing.

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