Compositions including polymerizable ionic liquids and pressure sensitive adhesive articles

Abstract

A polymerizable composition includes a C1-C30 alkyl (meth)acrylate ester monomer and a polymerizable ionic liquid. The anion of the ionic liquid includes a polymerizable functional group. Additionally, an at least partially polymerized reaction product of the polymerizable composition and a pressure sensitive adhesive article are provided. Further, another polymerizable composition includes specific polymerizable ionic liquid(s). Also, numerous polymerizable ionic liquids are provided.

Description

PA104211W002COMPOSITIONS INCLUDING POLYMERIZABLE IONIC LIQUIDS AND PRESSURE SENSITIVE ADHESIVE ARTICLESField

[0001] The present disclosure generally relates to the field of adhesives containing polymerizable ionic liquids.Background

[0002] New adhesives are needed for use in the preparation of electronic devices and in various industrial applications. For example, in electronic devices, particularly mobile electronic devices (e.g., hand-held, or wearable electronic devices), various adhesives such as pressure sensitive adhesives are used to bond the cover glass (or lens) to the underlying display module, bond the touch sensor to the cover glass and display, or bond the lower components of the display to the housing. The selected adhesive typically should have sufficiently high adhesive strength to properly maintain good adhesion to those components, not only when the mobile electronic devices are operating under normal conditions, but also when they are subjected to traumatic forces (e.g., when impacted and / or dropped onto a hard surface).

[0003] Further, new adhesives are needed for electronic devices that can perform well during the lifetime of the devices but that can be removed (e.g., debonded) from the electronic components after the useful lifetime of the device or to repair the device to extend its useful lifetime. The removal of the adhesives is preferably clean so that the electronic components can be reused or recycled, or so that the electronic device can be repaired. Additionally, debonding enables reworking of mistakes made during manufacturing before a device is fully assembled using the adhesives.Brief Description of Drawings

[0004] FIG. 1 A is a schematic cross-sectional view of an exemplary tape, according to some embodiments of the present disclosure.

[0005] FIG. 1B is a schematic cross-sectional view of an exemplary tape including two liners, according to some embodiments of the present disclosure.

[0006] FIG. 2 is a representation of the experimental setup for the Tensile Pushout Test Method.

[0007] FIG. 3 shows a bonded assembly to which DC voltage is applied, resulting in a debonded assembly.

[0008] FIG. 4 shows a bonded assembly to which a series of applied currents in opposite polarity is applied according to the present disclosure, resulting in a strengthened assembly according to the present disclosure, to which a DC voltage is then applied, resulting in a debonded assembly.

[0009] FIG. 5 shows a graphical depiction of an applied voltage sawtooth wave.

[0010] FIG. 6 shows a graphical depiction of an applied voltage multi-frequency wave, being a sum of multiple sinusoidal voltage waves each with different frequency and amplitude.

[0011] FIG. 7 shows a graphical depiction of an applied voltage frequency sweep, where frequency of the wave is continuously ramped from a starting low frequency to and ending high frequency, then stepped back to the initial low frequency.

[0012] FIG. 8 shows a graphical depiction of an applied voltage amplitude-modulated wave, being a square wave function amplitude-modulated by a triangle wave.

[0013] Repeated use of reference characters in the specification and drawings is intended to represent the same or analogous features or elements of the disclosure. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the disclosure. The figures may not be drawn to scale.Summary

[0014] In a first aspect, a polymerizable composition is provided. The polymerizable composition comprises a) a C1-C30 alkyl (meth)acrylate ester monomer; and b) a polymerizable ionic liquid, wherein the anion of the ionic liquid comprises a polymerizable functional group.

[0015] In a second aspect, an at least partially polymerized reaction product is provided. The at least partially polymerized reaction product is of the polymerizable composition according to any embodiment of the first aspect.

[0016] In a third aspect, a pressure sensitive adhesive article is provided. The pressure sensitive adhesive article comprises an adhesive composition comprising the at least partially polymerized reaction product of the second aspect. The adhesive composition is disposed on at least a portion of a substrate.

[0017] In a fourth aspect, another polymerizable composition is provided. The polymerizable composition comprises an adhesive precursor and at least one polymerizable ionic liquid selected from the group consisting of octyldimethyl-2-hydroxyethylammonium 3-sulfopropyl acrylate, tributylmethylammonium 3-sulfopropyl acrylate, tetrabutylphosphonium 3-sulfopropyl acrylate, tetrabutylphosphonium acrylamido-2-methyl-1-propanesulfonate, trimethylammonium ethyl acrylate 3-sulfopropyl acrylate, trimethylammonium ethyl acrylate acrylamido-2-methyl-1-propanesulfonate, octyldimethyl-2 -hydroxyethylammonium acrylamido-2-methyl-l-propanesulfonate, tributylmethylammonium acrylamido-2-methyl-1-propanesulfonate, tributylmethylammonium acryloxy-succiny 1- 1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-1-propanesulfonate, 1-octyl-3-methylimidazolium acryloxy-succinyl-1-propanesulfonate, 1 -butyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, trimethylammonium ethyl acrylate acryloxy-succinyl-1 -propanesulfonate, 1 -octy 1-3 -methylimidazolium acryloxy-succinate, l-octyl-3 -methylimidazolium acryloxy-succinate, and 1-octyl-3-methylimidazolium 3-sulfopropyl acrylate.

[0018] In a fifth aspect, a polymerizable ionic liquid is provided. The polymerizable ionic liquid is selected from the group consisting of tributylmethylammonium acryloxy-succinyl-1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-1-propanesulfonate, 1-octyl-3-methylimidazolium acryloxy-succinyl-1-propanesulfonate, 1-butyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate,trimethylammonium ethyl acrylate acryloxy-succinyl-1-propanesulfonate, and 1-octyl-3-methylimidazolium acryloxy-succinate.

[0019] In a sixth aspect, an article is provided. The article comprises a polymerizable composition according to any embodiment of the first aspect. The polymerizable composition is disposed on at least a portion of a substrate.

[0020] The above summary is not intended to describe each embodiment. The details of one or more embodiments are also set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims.Detailed Description

[0021] The terms “a”, “an”, “the”, “at least one”, and “one or more” are used interchangeably.

[0022] The term “and / or” means one or both such as in the expression A and / or B refers to A alone, B alone, or to both A and B.

[0023] The term “essentially free of’ means 10 parts per hundred parts resin (phr) or less, 7 phr, 5 phr, 3 phr, 2 phr, or 1 phr or less.

[0024] The term “alkyl” refers to a monovalent radical of an alkane. Suitable alkyl groups can have up to 50 carbon atoms, up to 40 carbon atoms, up to 30 carbon atoms, up to 20 carbon atoms, up to 16 carbon atoms, up to 12 carbon atoms, up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, up to 4 carbon atoms, or up to 3 carbon atoms. The alkyl groups can be linear, branched, cyclic, or a combination thereof. Linear alkyl groups often have 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Branched alkyl groups often have 3 to 50 carbon atoms, 3 to 40 carbon atoms, 4 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms. Cyclic alkyl groups often have 3 to 50 carbon atoms, 5 to 40 carbon atoms, 6 to 20 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms.

[0025] The term “alkylene” refers to a divalent group that is a radical of an alkane. The alkylene can be straight-chained, branched, cyclic, or combinations thereof. The alkylene typically has 1 to 20 carbon atoms. In some embodiments, the alkylene contains 4 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. The radical centers of the alkylene can be on the same carbon atom (i.e., an alkylidene) or on different carbon atoms. In certain embodiments, the alkylene can be substituted with an OH group.

[0026] The term "hydroxyl group” means a monovalent group of formula -OH.

[0027] The term "aryl” refers to a monovalent group that is radical of an arene, which is a carbocyclic, aromatic compound. The aryl can have one to five rings that are connected to or fused to the aromatic ring. The other ring structures can be aromatic, non-aromatic, or combinations thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.

[0028] The term “aralkyl” refers to a monovalent group of formula -R-Ar where R is an alkylene and Ar is an ary 1 group. That is, the aralkyl is an alky 1 substituted with an aryl.

[0029] The term “aralkylene” refers to a divalent group of formula -R-Ara- where R is an alkylene and Arais an arylene (i.e., an alkylene is bonded to an arylene).

[0030] The term “arylene” refers to a divalent group that is carbocyclic and aromatic. The group has one to five rings that are connected, fused, or combinations thereof. The other rings can be aromatic, non-aromatic, or combinations thereof. In some embodiments, the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromatic ring. For example, the arylene group can be phenylene. The term “alkarylene” refers to a divalent group that is an arylene group substituted with an alkyl group or an arylene group attached to an alkylene group. Unless otherw ise indicated, the alkarylene group typically has from 1 to 20 carbon atoms, 4 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Unless otherwise indicated, for both groups, the alkyl or alkylene portion typically has from 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Unless otherwise indicated, for both groups, the aryl or arylene portion typically has from 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. In certain embodiments, the arylene group or the alkarylene group has 4 to 14 carbon atoms.

[0031] The term “(meth)acrylate” means acry late or methacry late.

[0032] The term “(meth)acryloyf’ refers to a group of formula CH2=CR-(C=O)- where R is hydrogen (for an acryloyl group) or methyl (for a methacry loyl group).

[0033] As used herein, the term “macromer” refers to a monomer having a poly meric group. A macromer is a subset of the term “monomer”.

[0034] The term “monomeric unit” refers to the reaction product of a polymerizable component (i.e., a monomer (including a macromer)) within the (meth)acrylate copolymer. As an example, the monomeric unit of acrylic acidH HH2C=CH *–C–C–*|=O H |=OOH isOHwhere the asterisks (*) indicate the attachment site to another group such as another monomeric unit or terminal group in the (meth)acrylate copolymer.

[0035] The term “(meth)acrylate macromer” refers to a monomer having a single (mctli)acry loy loxy group (i.e.. a group of formula CH2=CR-(CO)-O- where R is hydrogen or methyl) plus a polyethylene oxide) group, polypropylene oxide) group, poly(ethylene oxide-co-propylene oxide) group, poly (ethylene oxide-block-propylene oxide) group, polypropy lene-co-butylene oxide) group, poly(tetrahydrofuran) group, or poly(ester) group.

[0036] The term “polyethylene oxide) group” refers to a group that contains at least 3 ethylene oxide (-(C2H4O)-) groups and the term “polypropylene oxide) group” refers to a group that contains at least 3 propylene oxide (-(CsHgO)-) groups. The term "poly tbuty lene oxide) group” refers to a group that contains at least 3 butylene oxide (-(C4H8O)-) groups.

[0037] The term “poly (ethylene oxide-co-propylene oxide) group” contains at least 3 monomer units of some combination of ethylene oxide groups and propylene oxide groups. The polyethylene oxide-co-propylene oxide) group is a copolymeric group.

[0038] The term “poly(tetrahydrofuran) (meth)acrylate macromer” refers to a monomer having a single (meth)acryloyloxy group (i.e.. a group of formula CH2=CR-(CO)-O- where R is hydrogen or methyl) plus a poly(tetrahydrofuran) group that contains at least three -(C4H8O)- groups. The term “poly(tetrahydrofuran)” can be used interchangeably with the terms “poly(tetramethylene oxide)” and “poly (tetramethylene glycol)”.

[0039] The term “polyester” refers to repeating difunctional polymer wherein the repeat units are joined by ester linkages. Ester groups have the general formula -R — C(O) — OR’. The term “polyether” refers to repeating difunctional alkoxy radicals having the general formula -O-R-. Preferred R and R’ groups have the general formula -CntE,- and include, for example, methylene, ethylene, propylene (including n-propylene and i-propylene) and butylene, or a combination thereof. Combinations of R and R’ groups may be provided, for example, as random or block type copolymers.

[0040] The term “ambient temperature” refers to a temperature in the range of 20 degrees Celsius to 25 degrees Celsius, inclusive.

[0041] The terms “cure” and “curable” refer to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably. A cured or crosslinked polymer is generally characterized by insolubility, but may be swellable in the presence of an appropriate solvent.

[0042] The term “polymerizable component” refers to any material (e.g.. monomers, crosslinkers, oligomers, macromers. prepolymers, polymers, etc.) that participates in a curing or crosslinking reaction in forming a polymer and / or crosslinked polymer.

[0043] The term “resin” with respect to “parts per hundred parts resin” refers to 100 parts of the total polymerizable components.

[0044] The term “backbone” refers to the main continuous chain of a polymer.

[0045] The term “substantially”, unless otherwise specifically defined, means to a high degree of approximation (e.g., within + / - 10% for quantifiable properties) but again without requiring absolute precision or a perfect match. Terms such as same, equal, uniform, constant, strictly, and the like, are understood to be within the usual tolerances or measuring error applicable to the specific circumstance rather than requiring absolute precision or a perfect match.

[0046] By definition, the total weight percentages of all ingredients in a composition equals 100 weight percent.

[0047] The term “film” or “layer” refers to a single stratum within a multilayer film or article.

[0048] The term “substrate” encompasses fihns, layers, and articles.

[0049] The term “perimeter” refers to a continuous line forming the exterior boundary of an object, e.g., a layer.

[0050] As used herein, “thickness” refers to the smallest dimension of a film or layer, e.g., in a z-axis while a major surface of the film or layer is in the x- and y-axes. Thickness may be determined using a micrometer gauge or doing a microscopic analysis of a cross-sectional sample of a layer or an article.

[0051] The term “electrical potential” refers to a voltage difference between two surfaces separated by an intermediate, with the intermediate having some electrical resistance.

[0052] The terms “alternating current voltage” or “AC voltage” refer to an applied voltage in which the magnitude and direction of the voltage vary continuously in time as a sinusoidal wave. The voltage value assigned to the AC voltage (“V AC”) indicates the amplitude of the sine wave (height between midpoint of the curve and the peak). As an example, as used herein, 50 V AC refers to an applied sinusoidal voltage with a midpoint at zero volts where the amplitude of the sine wave is 50 V.

[0053] The term “series of applied currents in opposite polarity” refers to electrical current being applied in which the polarity or direction of the current switches between negative and positive with time, where the amplitudes, durations, frequencies, and profiles of the applied negative and positive voltages can be the same or different and may vary in time. As examples, alternating current (sine waves), square waves, triangle waves, a series of DC voltages in opposite directions, combinations of the above, and other arbitrary waveform patterns where the applied voltage switches between positive and negative with time can all be classified as series of applied currents in opposite polarity.

[0054] The term “strengthened assembly” refers to a bonded assembly that has been exposed to a series of applied currents in opposite polarity to increase the work required to separate the assembly.

[0055] The term “debonded assembly” refers to a bonded assembly or strengthened assembly that has been exposed to DC voltage to reduce the work required to separate the assembly.

[0056] Electronics bonding customers desire the ability to debond pressure sensitive adhesives (“PSAs”) by applying an electrical current to the substrates in contact with the PSA. Applying a voltage to the substrates in contact with the adhesive should significantly lower the adhesion force and result in clean separation (i.e., no cohesive failure) from the substrates such that they can be recovered rapidly.

[0057] Polymerizable Compositions

[0058] In a first aspect, a polymerizable composition is provided. The polymerizable composition comprises:

[0059] a) a C1-C30 alkyl (meth)acrylate ester monomer; and

[0060] b) a polymerizable ionic liquid, wherein the anion of the ionic liquid comprises a polymerizable functional group.

[0061] Additionally, one or more optional components may also be included in a polymerizable composition, for instance and without limitation, a second monomer that is different than the C1-C30 alkyl (meth)acrylate ester monomer, an ethoxy group-containing (meth)acrylate monomer, at least one additive, a filler, a carboxylic acid-containing (meth)acrylate monomer, a (meth)acrylate macromer. a crosslinker, or any combinations thereof.

[0062] The various components of such polymerizable compositions are described below.

[0063] In some cases, an article comprises a polymerizable composition according to any embodiment of this first aspect, wherein the polymerizable composition is disposed on at least a portion of a substrate. Suitable substrates are described in detail below.

[0064] C1-C30 Alkyl (Meth) acrylate Ester Monomer

[0065] Polymerizable compositions according to the present disclosure include a C1-C30 alkyl (meth)acrylate ester monomer. The Cl -C30 alkyl (meth)acrylate ester monomer is a polymerizable component.

[0066] Suitable exemplary’ alkyl (meth)acrylate ester monomers include for instance and without limitation, methyl acr late, ethyl acr late, iso-octy l acrylate, 2-octyl acrylate, 2-ethylhexyl acry late, isodecyl acry late, n-butyl acrylate, 2-methylbutyl acrylate, n-hexyl acrylate, dodecyl acry late, strearyl acrylate, heptadecyl acry late or 6-methylheptyl acrylate, isopropyl acry late, isoamyl acry late, sec-butyl acrylate, n-butyl acrylate, 2-methylbutyl acry late, 4-methyl-2 -pentyl acry late, 2-ethylhexyl acry late, isooctyl acry late, 2-ethylhexy l methacry late, n-hexyl acry late, 6-methylheptyl acry late and mixtures thereof. In certain embodiments, the C1-C30 alkyl (mcth)acrylatc ester monomer comprises at least one of 2-ethylhexyl acrylate, n-buty l acrylate, 2-methylbutyl aery late, or n-hexyl acry late.

[0067] Often, the C1-C30 alkyl (meth)acrylate ester monomer is present in an amount of 15 wt.% or greater, based on a total weight of polymerizable components, such as 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, or 70 wt.% or greater, based on a total weight of polymerizable components; and 90 wt.% or less, based on a total weight of polymerizable components, such as 85 wt.%, 80 wt.%, 75 wt.%, 70 wt.%, 65 wt.%, 60 wt.%. 55 wt.%, 50 wt.%. 45 wt.%, 40 wt.%, 35 wt.%, or 30 wt.% or less, based on a total weight of polymerizable components.

[0068] In some embodiments, the C1-C30 alkyl (meth)acrylate ester monomer comprises a C8 acrylate in an amount of 30 wt.% or greater, based on a total weight of polymerizable components, such as 35 wt.%, 40 wt.%, 45 wt.%. 50 wt.%, 55 wt.%. 60 wt.%, 65 wt.%. 70 wt.%, 75 wt.%, 80 wt.%, or 85 wt.% or greater, based on a total weight of polymerizable components; and 90 wt.% or less, based on a total weight of polymerizable components. In certain cases, the C1-C30 alkyl (meth)acrylate ester monomer comprises a C8 acrylate in an amount of 30 wt.% to 90 wt.%, based on a total weight of polymerizable components.

[0069] In some embodiments, the C1-C30 alkyl (meth)acrylate ester monomer comprises a C6-C30 (meth)acry late ester monomer present in an amount of 30 wt.% or greater, based on a total weight of polymerizable components, such as 35 wt.%. 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, or 85 wt.% or greater, based on a total weight of polymerizable components; and 90 wt.% or less, based on a total weight of polymerizable components. In certain cases, the C1-C30 alky 1 (meth)acrylate ester monomer comprises a C6-C30 (meth)acrylate ester monomer present in an amount of 30 wt.% to 90 wt.%, based on a total weight of polymerizable components.

[0070] Ionic Liquid

[0071] Poly merizable compositions according to the present disclosure include a poly merizable ionic liquid. Curing of the polymerizable compositions results in formation of a covalent bond between thethen-polymerized ionic liquid and the polymer(s) formed from the C1-C30 alkyl (meth)acrylate ester monomer and any other optional polymerizable components (e.g., the reaction product of the polymerizable composition). Such a chemical bond tethers the polymerized ionic liquid to the polymer, minimizing the ability of the ionic liquid to migrate within an article, e.g., to a surface of the reaction product of the polymerizable composition or even migrating out of the article. It is not expected that a significant amount of the polymerizable ionic liquid homopolymerizes instead of co-polymerizing with the other polymerizable components of the polymerizable composition.

[0072] The presence of an ionic liquid may be useful in easing die peeling (or peel-ability) of the adhesive when reworking or recycling an article. An ionic liquid is a unique salt, which is in a liquid state at about 100 °C or less, has negligible vapor pressure, and high thermal stability. The ionic liquid is composed of a cation and an anion and has a melting point of no more than 100 °C, (i.e., being a liquid at about 100 °C or less), about 95 °C or less, or even about 80 °C or less. Certain ionic liquids exist in a molten state even at ambient temperature since their melting points are less than room temperature, and therefore they arc sometimes referred to as ambient temperature molten salts. The cation and / or anion of the ionic liquid are relatively sterically bulky, and typically one and / or both of these ions are an organic ion. Further, the cation and / or anion of a polymerized ionic liquid is non-protonated. The ionic liquid can be synthesized by known methods, for example, by a process such as anion exchange or metathesis process, or via an acid-base or neutralization process.

[0073] The cation of the ionic liquid of the present disclosure may be a nitrogen-containing cation (e.g., an ammonium ion), a phosphonium ion, a sulfonium ion, an imidazolium ion, a pyridinium ion, an iodonium ion, or the like, including various delocalized heteroaromatic cations, but is not limited thereto. The cation portion advantageously has an easily tunable side group, which makes the ionic liquid more soluble in a variety of different monomers. The nitrogen-containing cation includes ions such as, alkylammonium, imidazolium, pyridinium, pyrrolidinium, pyrrolinium, pyrazinium, pyrimidinium, triazonium, triazinium, quinolinium, isoquinolinium. indolinium, quinoxalinium, piperidinium, oxazolinium, thiazolinium, morpholinium, or piperazinium. Examples of the phosphonium ion include tetraalkylphosphonium, arylphosphonium, or alkylarylphosphonium. Examples of the sulfonium ion include alkylsulfonium, arylsulfonium, thiophenium, or tetrahydrothiophenium. The alkyl group directly bonded to a nitrogen atom, a phosphorus atom, or a sulfur atom may be a linear, branched or cyclic alkyl group having a carbon number of at least 1, 2, or even 4 and not more than 8, 10, 12, 15, or even 20. The alky l group may optionally contain heteroatoms such as O, N. and / or S in the chain or at the end of the chain (e.g.. a terminal -OH group). The aryl group directly bonded to a nitrogen atom, a phosphorus atom, or a sulfur atom may be a monocyclic or condensed cyclic aryl group having at least 5, 6. or even 8 carbon atoms and not more than 12, 15, or even 20 carbon atoms. An arbitrary site in the structure constituting such a cation may be further substituted by an alky 1 group, an alkenyl group, an alky ny 1 group, a cycloalkyl group, an ary l group, an aralkyl group, an arylalkyl group, an alkoxy group, an aryloxy group, a hydroxy l group, a carbonyl group, a carboxy l group, an ester group, an acyl group, an amino group, a dialky lamino group, an amide group, an imino group, an imide group, a nitro group, anitrile group, a sulfide group, a sulfoxide group, a sulfone group, a halogen atom or the like. A heteroatom such as oxygen atom, nitrogen atom, sulfur atom, and / or silicon atom may be contained in the main chain or ring of the structure constituting the cation.

[0074] In select embodiments, the polymerizable functional group of the anion of the ionic liquid comprises at least one of a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an alcohol group, an epoxy group, a primary or secondary amino group, or a thiol group.

[0075] Specific examples of the cation include N-ethyl-N'-methylimidazolium, N-methyl-N'-buty limidazolium, N-methyl-N-propylpiperidinium, N,N,N-trimethyl-N-propylammonium, N-methyl-N,N,N-tripropylammonium, N,N,N-trimethyl-N-butylammonium, N,N,N-trimethyl-N-methoxyethylammonium, N-methyl-N,N,N-tris(methoxyethyl)ammonium, N,N-dimethyl-N-butyl-N-methoxyethylammonium, N,N-dimethyl-N,N-dibutylammonium, N-methyl-N,N-dibutyl-N-methoxyethylammonium, N-methyl-N,N,N-tributylammonium, N,N,N-trimethyl-N-hexylammonium, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium, 1-propyl-tetrahydrothiophenium, 1-butyl-tetrahydrothiophenium, 1-pentyl-tetrahydrothiophenium, 1-hexyl-tetrahydrothiophenium, glycidyltrimethylammonium, N-ethylacryloyl-N, N, N-trimethylammonium, N-ethyl-N-methylmorphonium, N, N, N-triocty lamm onium, N-methyl-N, N, N-trioctylammonium, N, N-dimethyl-N-octyl-N-(2-hydroxyethyl)animonium, triethylsulfonium, or mixtures thereof.

[0076] The anion of the ionic liquid of the present disclosure may be, for example, a sulfate (R-OSO3); a sulfonate (R-SO3); a carboxylate (R-CO2 ); a phosphate ((RO)2P(=O)O); a borate represented by the formula: BRT, such as tetrafluoroborate (BF4 ), tetraalkylborate, and tetraphenylborate; an oxalato borate, such as lithium difluoro(oxalato)borate; a phosphate represented by the formula: PR.,. such as (PFe ) and hexaalkylphosphate; an imide (R2N ); a bis(sulfonyl)imide (either symmetrical or asymmetrical, e.g., a bis(fluorosulfonyl)imide, a bis(fluoroalkylsulfonyl)imide); a sulfidoimide; an imide; a methide (R3C); a nitrate ion (NO3 ); a nitrite ion (NO2 ); a dicyanamide ((CN)2N‘); a tricyanomethanide; a phosphorus-containing ion; or a halide such as iodide. In certain embodiments, the ionic liquid comprises at least one anion having a polymerizable group which comprises a sulfonate. In the formulas listed above, each R may be independently a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, iodine), a substituted or unsubstituted alkyl, alkenyl, alkynyl. cycloalkyl, aryl, aralkyl, arylalkyl, acyl or sulfonyl group, or the like. A heteroatom such as an oxygen atom, a nitrogen atom or a sulfur atom may be contained in the main chain or ring of the group R, and a part or all of hydrogen atoms on the carbon atom of the group R may be replaced with fluorine atoms. In the case where a plurality of R's are present in the anion, these R's may be tire same or different.

[0077] In select cases, the anion of a polymerizable ionic liquid is a carboxylate, e.g., a deprotonated acrylic acid-type monomer having a coordinating cation. One such example cation is 1 -octyl 3-methyl imidazolium.

[0078] In some embodiments, it is advantageous to use a perfluorinated ion, such as a perfluorinated anion to achieve excellent corrosion resistance and electro-debonding. However, the use of fluorinated ions should be balanced with the environmental impact of the finished good, as some fluorinatedchemicals may have restricted use due to environmental concerns. Examples of an anion containing a perfluoroalkyl group, which can be used, include a bis(perfluoroalkylsulfonyl)imide ((RfSO2)2N–), a perfluoroalkylsulfonate (RfSO3–) and a tris(perfluoroalkylsulfonyl)methide ((RfSO2)3C–) (wherein Rf represents a perfluoroalkyl group). The perfluoroalkyl group may comprise, for example, from at least 1, 2, 3 or even 4 to at most 8, 10, 12, 15, or even 20 carbon atoms. Specific examples of the bis(perfluoroalkylsulfonyl)imide include: bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, bis(heptafluoropropanesulfonyl)imide. or bis(nonafluorobutanesulfonyl)imide. Specific examples of the perfluoroalkylsulfonate include: trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate. or nonafluorobutane sulfonate. Specific examples of the tris(perfluoroalkylsulfonyl)methide include: tris(trifluoromethanesulfonyl)methide, tris(pentafluoroethanesulfonyl)methide, tris(heptafluoropropanesulfonyl)methide, or tris(nonafluorobutanesulfonyl)methide. Examples of fluorinated anions not comprising a C-F bond are hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, difluoroiodide, and bis(fluorosulfonyl)imide.

[0079] Enough ionic liquid should be added to enable electro-debondmg, while too much ionic liquid may negatively impact the physical properties of the adhesive, such as shear, peel adhesion, and / or ability to survive the random free fall test. For example, if the ionic liquid can be polymerized into (meth)acrylate matrix, for example, the ionic liquid comprises at least one (or even at least two) acrylate, methacrylate, or styrene functional group or combinations thereof, more ionic liquid may be incorporated into the adhesive. It is noted that use of an ionic liquid that contains at least two functional groups may be less preferable for applications in which there is a substantial delay between polymerization and final use of the adhesive because the presence of multiple functional groups could result in disadvantageous early gelation of the adhesive.

[0080] Exemplary suitable polymerizable ionic liquids include for instance and without limitation. octyldimethyl-2 -hydroxyethylammonium 3-sulfopropyl acrylate, tributylmethylammonium 3-sulfopropyl acrylate, tetrabutylphosphonium 3-sulfopropyl acrylate, tetrabutylphosphonium aery lamido-2 -methyl- 1-propanesulfonate, trimethylammonium ethyl acrylate 3-sulfopropyl acrylate, trimethylammonium ethyl acry late acrylamido-2-methyl-l-propanesulfonate, octyldimethyl-2-hydroxyethylammonium acrylamido-2-methyl-1-propanesulfonate, tributylmethylammonium aery lamido-2 -methyl- 1 -propane sulfonate, tributy lmethylammonium acryloxy-succinyl-1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl- 1 -propanesulfonate, 1 -octy 1-3 -methy limidazolium acryloxy-succinyl-1 -propanesulfonate, 1 -butyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, trimethylammonium ethyl acrylate acryloxy-succinyl-1 -propanesulfonate, l-octyl-3-methylimidazolium 3-sulfopropyl acrylate, 3-sulfopropyl acrylate n-butylpyridinium salt, 1-buty 1-3 -methy limidazolium 3-sulfopropyl acry late. 1-octyl- 3 -methy limidazolium acryloxy-succinate, (CsHi7N(CH3)2CH2CH2OH+ -O3S(CH2)3OC(O)CH=CH2), tributylmethylammonium 3-sulfopropyl acrylate ((C4H9)3N(CHs)+ -OsS(CH2)3OC(O)CH=CH2), tetrabutylphosphonium 3-sulfopropyl acrylate ((C4H9)4P+-O3S(CH2)3OC(O)CH=CH2), tetrabutylphosphonium acrylamido-2-methyl-1-propanesulfonate ((C4H9)4P+-O3SCH2C(CH3)2NHC(O)CH=CH2). trimethylammonium ethyl acrylate 3-sulfopropyl acrylate ((CH3)3NCH2CH2OC(O)CH=CH2+- O3S(CH2)3OC(O)CH=CH2). trimethylammonium ethyl acrylate acrylamido-2-methyl-l-propanesulfonate ((CH )3NCH2CH2OC(O)CH=CH2+ -O3SCH2C(CH3)2NHC(O)CH=CH2), octyldimethyl-2-hydroxyethylammonium acrylamido-2-methyl-l-propanesulfonate (C8H17N(CH3)2CH2CH2OH+ -O3SCH2C(CH3)2NHC(O)CH=CH2), tributylmethylammonium acrylamido-2-methyl- 1 -propanesulfonate ((C4H9)3N(CH3)+ -O SCH2C(CH3)2NHC(O)CH=CH2), tributylmethylammonium acryloxy-succinyl-l-propanesulfonate ( (C4H9)3N(CH3)+-O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2), tetrabutylphosphonium aery loxy-succiny 1-1 -propanesulfonate, (C4H9)4P+- O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2), 1 -octyl-3-methylimidazolium (OMI) aery loxy-succiny 1-1 -propanesulfonate (OMI+-O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2), l-butyl-3-methylimidazolium (BMI) aery loxy-succiny 1-1 -propanesulfonate (BMI+ -O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2), trimethylammonium ethyl acrylate acryloxy-succinyl- 1 -propancsulfonatc ((CH3)3NCH2CH2OC(O)CH=CH2+-O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2), l-octyl-3-methylimidazoliuin (OMI) 3-sulfopropyl acrylate (OMI+- O3S(CH2)3OC(O)CH=CH2), l-butyl-3-methylimidazolium (BMI) 3-sulfopropyl acrylate (BMI+- O3S(CH2)3OC(O)CH=CH2), l-octyl-3-methylimidazolium acryloxy-succinate (OMI+ -OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2),]N, N, N-trimethyl ammonium ethyl acrylate bis(fluorosulfonyl)imide, N, N, N-trimethyl ammonium ethyl acrylate iodide, N, N, N-trimethyl ammonium ethyl acrylamide bis(fluorosulfonyl)imide, N. N, N-trimethyl ammonium ethyl acrylate bis(trifluoromethane sulfonyl)imide, N-hexyl-N, N-dimethyl ammonium ethyl acrylate bis(fhiorosulfonyl)imide. N-hexyl-N, N-dimethyl-ammonium ethyl acrylamide tricyanomethanide or N, N, N-trimethyl ammonium ethyl acrylate tricyanomethanide. N-butyl-imidazolium-N'-ethyl acrylate bis(fluorosulfonyl)imide. N-butyl-imidazolium-N'-ethyl acrylate tricyanomethanide. dibutyl-sulfonium-ethyl acrylate bis(fluorosulfonyl)imide, dibutyl-phosphonium ethyl acrylate bis(fluorosulfonyl)imide. 3-sulfopropyl acrylate N-octyl-N-methyl-imidazolium or 3-sulfopropyl acrylate N-butyl-N-methyl-imidazolium, N-vinyl-imidazolium bis(fluorosulfonyl)imide, sulfopropyl acrylamide N-butyl-N'-methyl imidazolium. sulfopropyl acrylamide N-octyl-N'-methyl imidazolium. styrene sulfonate N-butyl-N'-methyl imidazolium, and styrene sulfonate N-octyl-N'-methyl imidazolium.

[0081] Some ionic liquids comprising higher molecular weight anions such as acryloxy-succinyl-1-propanesulfonate, (-O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2), can provide advantages in use in some adhesive compositions. One advantage is improved solubility’ of the ionic liquid, which can allow higher loadings ionic liquid into the adhesive, leading to better debonding or strengthening with applied voltages, and maintenance of optical clarity. Another advantage is to lower the glass transition of the adhesive to control its rheological properties and allow greater flexibility and / or foldability of an adhesive.

[0082] A polymerizable ionic liquid may be present in an amount of 1 wt.% or greater, based on a total weight of polymerizable components (e.g., adhesive precursor), such as 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%,6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%. 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 18 wt.%. or 20 wt.% or greater, based on a total weight of polymerizable components; and 50 wt.% or less, based on a total weight of polymerizable components, such as 45 wt.%, 40 wt.%, 35 wt.%, 30 wt.%, 28 wt.%, 26 wt.%. 24 wt.%, 22 wt.%, 20 wt.%, 18 wt.%, 16 wt.%. 15 wt.%, 14 wt.%. 12 wt.%, or 10 wt.% or less, based on a total weight of polymerizable components.

[0083] The choice of the ionic liquid used in the adhesive can impact electro-debonding. For example, it may be advantageous to choose ionic liquids that have a high conductivity or ionic mobility. High conductivity (e.g., having sheet resistance less than 1x103ohms per square) of the ionic liquid in the adhesive matrix could help enable electro-debonding in thicker adhesives. In some embodiments the adhesive thickness could be 10, 25, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 400, or even up to 500 microns thick. Alternatively, or additionally, it may be advantageous to choose ionic liquids that have electrochemically unstable cations or anions. While not wanting to be limited by theory, it is believed that more electrochemically unstable cations or anions could produce an increased electro-debonding response. As such, it may be beneficial to choose cations comprised of imidazolium or pyridinium derivatives over quaternary ammonium derivatives.

[0084] In one embodiment, it may be beneficial for environmental reasons to choose ionic liquids that do not contain carbon-fluorine bonds. As such, it may be beneficial to choose ionic liquids containing inorganic fluorine such as the hexafluorophosphate or tetrafluoroborate ion in lieu of organic fluorine such as bis(trifluoromethylsulfonyl)imide.

[0085] In one or more embodiments, the polymerizable anion has a sulfonate group and has a structure such as, for example:

[0086] In one or more embodiments, the polymerizable anion can be combined with non-polymerizable cations, including but not limited to structures such as, for example:

[0087] imidazolium cations having the structure:

[0088] phosphonium cations having the structure:R4

[0089] pyridinium cations having the structure:Ri

[0090] ammonium cations having the structure:R Ri’N-R2R4

[0091] of sulfonium cations having the structure:1rR''3S'Rr'2orheterocycles thereof.

[0092] Suitable R groups (e.g.. R, Ri, Rc, Rs, and R4) may independently be selected from an alkyl moiety, an alicyclic moiety, an aryl moiety, an alkalicyclic moiety, an alkaryl moiety, an alicyclicalkyl moiety, and an aralicyclic moiety, wherein such moiety may comprise one or more oxygen atoms, nitrogen atoms, or other functional groups.

[0093] In some embodiments, a suitable polymerizable ionic liquid is of Formula 1 and / or of Formula II:

[0094] In each of Formula I and Formula II, Ri is independently H or methyl, and R2 and R3 are each independently linear or branched alkyl groups and / or ethoxy groups.

[0095] In some embodiments, a suitable polymerizable ionic liquid is of Formula III:o

[0096] In some embodiments, a suitable polymerizable ionic liquid is of Formula IV:

[0097] In some embodiments, a suitable polymerizable ionic liquid is of Formula V:

[0098] In some embodiments, a suitable polymerizable ionic liquid is of Formula VI:

[0099] In some embodiments, a suitable polymerizable ionic liquid is of Formula VII:(VII).

[0100] In some embodiments, a suitable polymerizable ionic liquid is of Formula VIII:1(IX).

[0102] In some embodiments, a suitable polymerizable ionic liquid is of Formula X:

[0103] In some embodiments, a suitable polymerizable ionic liquid is of Formula XI:

[0104] In some embodiments, a suitable polymerizable ionic liquid is of Formula XII:

[0106] In some embodiments, a suitable polymerizable ionic liquid is of Formula XIV:o H17C8(XIV).

[0107] In a fifth aspect, a polymerizable ionic liquid is provided. The polymerizable ionic liquid is selected from the group consisting of tributylmethylammonium acryloxy-succinyl-1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-1 -propanesulfonate, l-octyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, l-butyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, trimethylammonium ethyl acrylate acryloxy-succinyl-l-propanesulfonate, and 1-octyl-3-methylimidazolium acryloxy-succinate. These polymerizable ionic liquids may provide at least some of the advantages described above with respect to the inclusion of higher molecular weight anions.

[0108] Second Monomer

[0109] Polymerizable compositions according to the present disclosure optionally further comprise a second monomer that is different than the C1-C30 alkyl (meth)acrylate ester monomer. In some cases, such a second monomer comprises a C1-C30 alkyl (meth)acrylate ester monomer that is different from component a), a nitrogen-containing monomer, a hydroxy-containing monomer, an ethoxy containing monomer, an epoxy-containing monomer, an acid-containing monomer, or a nonpolar monomer having a glass transition temperature (Tg) of greater than 10°C to 200°C. In select embodiments, the second monomer comprises a nitrogen-containing monomer or a hydroxy containing monomer. In cases where more than one different second monomer is included, the additional monomer(s) will be considered a third monomer, a fourth monomer, etc.

[0110] Suitable C 1 -C30 alkyl (meth)acrylate ester monomers are described in detail above.

[0111] Suitable nitrogen-containing monomer include for instance and without limitation, (meth)acrylamide, N-alkyl (meth)acrylamides or N-alkoxyalkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, or N-octyl (meth)acrylamide. N-(3-methoxypropyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-vinyl carbazole, N-vinyl caprolactam, N-vinyl-2 -pyrrolidone, N-vinyl azlactone, 4-(meth)acryloylmorpholine, N-vinylimidazole, ureido (meth)acrylate, and N, N-dialkyl (meth)acrylamides such as N, N-dimethyl (meth)acrylamide, N, N-diethyl (meth)acrylamide, N. N-dipropyl (meth)acrylamide, N. N-dibuty I (mcth)acrylamidc, various N, N-dialkylaminoalkyl (meth)acrylates and N, N-dialkylaminoalkyl (meth)acrylamides (e.g., N, N-dimethylaminoethyl (meth)acrylate, N, N-dimethylaminoethyl (meth)acrylamide, N, N-dimethylaminopropyl (meth)acrylate. N, N-dimethylaminopropyl (meth)acrylamide, N, N -diethylaminoethyl (meth)acrylate, N, N-diethylaminoethyl (meth)acrylamide, N, N-diethylaminopropyl (meth)acrylate, and N, N-diethylaminopropyl (meth)acrylamide), or combinations thereof.

[0112] In some embodiments, a suitable nitrogen-containing monomer is an acrylamide monomer. Examples of acrylamide monomers include for instance and without limitation, N, N-dimethylacrylamide(NNDMA), N. N -diethylacrylamide (NNDEA), N. N -dimethylaminopropyl acrylamide (DMAPACM), N-tert-octyl-acrylamide (NTOA), N-octyl-acrylamide (NOA), acrylamide (Acm), 4-acryloylmorpholine (ACMO), N-isopropylacrylamide, (NIP AM), N-hydroxyethyl acrylamide (NHEA), N-(isobutoxymethyl)acrylamide (NIBMA), N-tert-butylacrylamide (NTBA), N-(3-methoxypropyl)acrylamide (NMPA), a combinations thereof.

[0113] In some embodiments, a suitable nitrogen-containing monomer has a nitrogen atom directly attached to a vinyl group. Examples of nitrogen-containing monomers having a nitrogen atom directly attached to a vinyl group include for instance and without limitation, N-vinyl pyrrolidone, vinyl methyl oxazolidinone, or N-vinyl caprolactam, N-vinyl imidazole, N-vinyl carbazole, N-vinyl formamide, N-methyl-N-vinyl acetamide, N-vinyl piperidone, and combinations thereof.

[0114] In some embodiments, the second monomer is a first nitrogen-containing monomer that is an acrylamide monomer and the polymerizable composition further comprises a third monomer that is a second nitrogen-containing monomer that has a nitrogen atom directly attached to a vinyl group.

[0115] In embodiments including a second nitrogen-containing monomer, typically the first nitrogen-containing monomer is present in an amount of 5 wt.% to 30 wt.% based on a total weight of polymerizable components, and the second nitrogen-containing monomer is present in an amount of 5 wt.% to 30 wt.% based on a total weight of polymerizable components, wherein a total amount of a combination of the first nitrogen-containing monomer and the second nitrogen-containing monomer is at most 40 wt.% based on a total weight of polymerizable components.

[0116] In some cases, the combined amount of the first nitrogen-containing monomer to the second nitrogen-containing monomer is 10 wt.% or greater, based on a total weight of polymerizable components, such as 12 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 28 wt.%, 30 wt.%, 32 wt.%, 34 wt.%, or 35 wt.% or greater, based on a total weight of polymerizable components; and 40 wt.% or less, based on a total weight of polymerizable components, such as 38 wt.%, 36 wt.%, 35 wt.%. 34 wt.%, 32 wt.%, 30 wt.%, 28 wt.%, 26 wt.%, 25 wt.%, 24 wt.%, 22 wt.%, or 20 wt.% or less, based on a total weight of polymerizable components. Stated another way, in some cases the combined amount of the first nitrogen-containing monomer and the second nitrogen-containing monomer ranges from 10 wt.% to 40 wt.%, based on a total weight of polymerizable components.

[0117] In some embodiments, a weight ratio the first nitrogen-containing monomer to the second nitrogen-containing monomer is 1: 1 or greater, such as 2: 1. 3: 1, 4: 1, 5: 1. or 6: 1. Stated another way. in certain embodiments, a weight ratio of the first nitrogen-containing monomer to the second nitrogen-containing monomer is between 1 and 6. As such, the first nitrogen-containing monomer may be present in a larger amount than the second nitrogen-containing monomer, including a significantly larger amount.

[0118] The nitrogen-containing monomer is optionally present in an amount of 5 wt.% or greater, based on a total weight of polymerizable components, such as 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, or 20 wt.%, based on atotal weight of polymerizable components; and 40 wt.% or less, based on a total weight of polymerizable components. 38 wt.%, 36 wt.%, 35 wt.%, 34 wt.%, 32 wt.%, 30 wt.%, 28 wt.%. 26 wt.%, 25 wt.%. 24 wt.%, 22 wt.%, 20 wt.%, 18 wt.%, 16 wt.%, 15 wt.%, 14 wt.%, 12 wt.%. or 10 wt.% or less, based on a total weight of polymerizable components.

[0119] Examples of suitable hydroxy-functional monomers include for instance and without limitation.2-hydroxyethyl (meth)acrylate, 2-hydroxy-propyl (meth)acrylate. 4-hydroxybutyl (meth)acry late. and the like. In some embodiments, the polymerizable composition includes between about 0 and about 40 parts by weight of the hydroxy-functional monomer, particularly between about 5 and about 35 parts, and more particularly between about 10 and about 30 parts.

[0120] Examples of suitable ethoxy group-containing (meth) aery late monomers include for instance and without limitation, 2-ethoxy ethyl (meth)acrylate, 2-methoxy ethyl acrylate. 2-(2-ethoxyethoxy)ethyl acrylate, and 2-[2-(2-methoxyethoxy)ethoxy]. When included in a polymerizable composition, an ethyl acry late ethoxy group-containing (meth)acrylate monomer may be present in an amount of 5 wt.% or greater, based on a total weight of polymerizable components, such as 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.% or greater, based on a total weight of polymerizable components; and 50 wt.% or less, based on a total weight of polymerizable components, such as 45 wt.%, 40 wt.%, 35 wt.%, 30 wt.%, 25 wt.%, 20 wt.%, 15 wt.%, or 10 wt.% or less, based on a total weight of polymerizable components.

[0121] Suitable exemplary polyether components include at least one of a polyethylene oxide), a polypropylene oxide), a polyethylene glycol), poly (propylene glycol), or a poly(tetrahydrofuran).

[0122] The polyether component may be present in an amount of 0.1 wt.% or greater, based on a total weight of polymerizable components. 0.25 wt.%, 0.5 wt.%, 0.75 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, or 15 wt.% or greater; and 20 wt.% or less, 19 wt.%. 18 wt.%, 17 wt.%, 16 wt.%, 15 wt.%, 14 wt.%, 13 wt.%, 12 wt.%.11 wt.%, 10 wt.%. 9 wt.%, 8 wt.%, 7 wt.%, 6 wt.%, 5 wt.%, 4 wt.%, 3 wt.%, or 2 wt.% or less, based on a total weight of polymerizable components.

[0123] Polymerizable compositions according to the present disclosure optionally include a acid-containing (meth)acrylate monomer, e.g., a carboxylic acid-containing monomer. Exemplary suitable carboxylic acid-containing (meth)acry late monomers include for instance and without limitation, acrylic acid, methacrylic acid, and carboxyethyl b-acrylate.

[0124] While a very’ small amount of acid-containing (meth)acry late monomer, namely an amount of less than 2 phr of the polymerizable composition may be used, including even 2 phr, may have a significantly’ negative impact on the ability to electro-debond an adhesive when measured using a tensile pushout test.

[0125] Nonpolar monomers lack polar groups, including: a hydroxyl group, an acidic group, a basic group (such as a primary’ amido group, a secondary’ amido group, a tertiary’ amido group, or an amino group). Some suitable nonpolar monomers include high Tg nonpolar monomeric units derived from monomers such as styrene, substituted styrene (e.g., methyl styrene), isobornyl acrylate, methyl(meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, and combinations thereof. Optional nonpolar monomers may be included in an amount of 5 wt.% or greater, 10 wt.%, 15 wt.%, or 20 wt.% or greater; and 30 wt.% or less, 25 wt.%, 20 wt.%, 15 wt.%, or 10 wt.% or less.

[0126] Crosslinker

[0127] Polymerizable compositions according to the present disclosure optionally include a crosslinker. Nonlimiting examples of suitable crosslinkers include multifunctional (meth)acrylate(s), e.g.. butanediol diacrylate or hexanediol diacrylate, or other multifunctional crosslinkers such as divinylbenzene and mixtures thereof. In some embodiments, at least 0.005, 0.01, 0.02, 0.05, or even 0.08 wt.% of the crosslinker is used based on the total weight of polymerizable components. In some embodiments, at most 0.1, 0.2, 0.5, 1, 2, or even 5 wt.% of the crosslinker is used based on the total weight of polymerizable components.

[0128] (Meth)acrylate Macromer

[0129] Polymerizable compositions according to the present disclosure optionally include a (meth)acrylate macromer. Typically, the addition of the (meth)acrylate macromer is thought to decrease the shear storage modulus and Tgof the resulting composition, enabling the resulting adhesive to have improved resistance to tensile debonding as demonstrated by improved performance in random free fall testing.

[0130] The (meth)acrylate macromer typically has a (meth)acryloyloxy group plus (i) a polyethylene oxide) group, (ii) polypropylene oxide) group, (iii) poly(ethylene oxide-co-propylene oxide) group, which can also be referred to as a polyethylene glycol), polypropylene glycol), or polyethylene glycol-co-propylene glycol) groups respectively, (iv) a poly(tetrahydrofuran) group, or (v) combinations thereof. If the macromer contains a poly (ethylene oxide) group, it can be referred to as a poly (ethylene oxide) (meth)acrylate. If the macromer contains a polypropylene oxide) group, it can be referred to as a polypropylene oxide) (meth)acrylate. If the macromer contains a polyethylene oxide-co-propylene oxide) group, it can be referred to as a polyethylene oxide-co-propylene oxide) (meth)acrylate, which is a copolymer. If the macromer contains a poly(tetrahydrofuran) group, it can be referred to as a poly(tetrahydrofuran) (meth) aery late.

[0131] The (meth)acrylate macromer typically has a number average molecular weight in a range of 300 to 10,000 Daltons. For example, the (meth)acrylate macromer has a number average molecular weight no greater than 10,000, 8000, 6000, 4000. 2000. 1000. 800, 650, or even 500 Daltons. The number average can be determined by gel permeation chromatography using techniques known in the art.

[0132] The (meth)acrylate macromer often has a Tg(as measured using a homopolymer of the macromer) that is no greater than -10 °C. For example, the glass transition temperature can be no greater than -10, -20, -30, or even -40 °C. In one embodiment, the Tgis less than -70 or even -80 °C. Such a low macromer Tgimparts compliance and flexibility’ to the (meth)acrylate copolymer and to the adhesive composition.

[0133] Examples of such commercially available (meth)acrylate macromers include polyethylene glycol) methyl ether acrylate, such as that having a reported number average molecular weight (Mn) of 480 Daltons (available from Sigma-Aldrich) and polypropylene glycol) acrylate, such as that having a reported number average molecular weight of 475 Daltons (available from Sigma-Aldrich). Other suitable macromers are available under the trade designation BISOMER from Geo Specialty Chemicals. Ambler, PA, such as BISOMER PPA6 polypropylene glycol) acrylate reported to have a number average molecular weight of 420 Daltons). BISOMER PEM63P HD (a mixture of polyethylene glycol) methacrylate and polypropylene glycol) reported to have a number average molecular weight of 524 Daltons), BISOMER PPM5 LI (polypropylene glycol) methacrylate reported to have a number average molecular weight of 376 Daltons), BISOMER PEM6 LD (polyethylene glycol) methacrylate reported to have a number average molecular weight of 350 Daltons), BISOMER MPEG350MA (methoxy poly(ethylene glycol) methacrylate) reported to have a number average molecular weight of 430 Daltons), and BISOMER MPEG550MA (methoxy poly(ethylene glycol) methacrylate reported to have a number average molecular weight of 628 Daltons). Other suitable macromers are available under the trade designation MIRAMER from Miwon Specialty Chemical Company, Gyeonggi-do, Korea, such as MIRAMER M193 MPEG600MA (methoxy poly(ethylene glycol) methacrylate reported to have a number average molecular weight of 668 Daltons, MIRAMER M164 (nonyl phenol polyethylene glycol) acrylate reported to have a number average molecular weight of 450 Daltons), MIRAMER M1602 (nonyl phenol poly(ethylene glycol) acrylate reported to have a number average molecular weight of 390 Daltons), and MIRAMER Ml 66 (nonyl phenol poly (ethylene glycol) acrylate reported to have a number average molecular weight of 626 Daltons. Still other suitable macromers are available from San Esters Corporation. New York, NY such as MPEG-A400 (methoxy poly (ethylene glycol) acrylate reported to have a number average molecular weight of 400 Daltons), and MPEG-A550 (methoxy poly (ethylene glycol) acrylate reported to have a number average molecular weight of 550 Daltons. Examples of commercially available polyester macromers include the PLACCEL F SERIES from Daicel Corporation Osaka Japan, which are epsilon-caprolactone-modified hydroxyalkyl(meth)acrylates, i.e., FM2D reported to have a molecular weight of 358 Daltons, FA2D reported to have a molecular weight of 344 Daltons, or FA10L reported to have a molecular weight of 1256 Daltons. Other such commercial sources include polyester macromers from BASF, such as hydroxy ethyl caprolactone acrylate, or HECLA, which is reported to have a molecular weight of 436 Daltons. Various combinations of such macromers may be used if desired.

[0134] The macromer having the poly(tetrahydrofuran) group can be prepared, for example, by polymerizing tetrahydrofuran using cationic polymerization. For instance, such a polymerization is described in detail in PCT Application Publication No. WO 2023 / 175421 (Maher et al.), incorporated herein by reference in its entirety. The weight average molecular weight of the poly(tetrahydrofuran) (meth)acrylate macromer is typically in a range of 300 to 10,000 Daltons, which can be determined using known methods such as gel permeation chromatography with polystyrene standards. If the molecular weight is higher, it may not be miscible with the other components in the polymerizable compositionand / or it may crystallize before, during, or after polymerization of the matrix. In many embodiments, the poly(tetrahydrofuran) (meth) aery late macromer has a weight average molecular weight of at least 500, 600, 800, 1,000, 2,000 or even 3,000 Daltons and up to 10,000, 8,000, 6,000, 5,000, or even 3,000 Daltons.

[0135] In some embodiments, the (meth)acrylate macromers include one or more of the following: a polyethylene oxide) group, a polypropylene oxide) group, a poly(ethylene oxide-co-propylene oxide) group, a poly(tetrahydrofuran) group; or a poly(ester) group or combinations thereof.

[0136] Additive

[0137] Polymerizable compositions according to the present disclosure optionally include at least one additive. Typically, each additive that is included may be present (independently) in an amount of 1 phr or greater, 2 phr, 3 phr. 5 phr, 7 phr, or 10 phr or greater; and 20 phr or less, 18 phr, 16 phr, 15 phr. 14 phr, 12 phr, 10 phr, or 8 phr or less.

[0138] In certain embodiments, at least one additive includes a tackifier (e.g., C5-resins, terpene phenol resins, (poly)tcrpcncs and rosin esters, hydrogenated hydrocarbons, and non-hydrogenated hydrocarbon resins), a plasticizer, an adhesion promoter (e.g., glycidyl propyl trimethoxy silane), a stabilization agent (e.g., calcium carbonate), a corrosion inhibitor (e.g., benzotriazole or 2-(methacryloyloxy)ethyl acetoacetate), a conducting salt (e.g., lithium bis(fluorosulfonyl)imide or sodium hexafluorophosphate), a colorant (e.g., titania or carbon black), an antioxidant, a UV absorber, a polymer having a glass transition temperature of at least 40 degrees Celsius (e.g., polyvinyl butyral), or a filler.

[0139] Some suitable antioxidants include hindered phenol compounds, phosphoric esters, or derivatives thereof. Exemplary antioxidants include those available from Ciba Specialty Chemicals Incorporated, Tarrytown, New York.

[0140] Some suitable ultraviolet (“UV”) absorbers include benzotriazole, substituted triazine, oxazolic acid amide, benzophenone, or derivatives thereof, such as 2-(2H-Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1, 1, 3, 3-tetramethylbutyl) phenol (commercially available as TINUVIN 928 from BASF, Florham Park, New Jersey).

[0141] In certain embodiments, a filler comprises a plurality of hollow glass microspheres, a plurality of polymeric microparticles, a plurality of polymeric nanoparticles each comprising an interior region comprising a polymer having a glass transition temperature below room temperature and an outer shell comprising a polymer having a glass transition temperature of at least 50°C, an organo-phosphinate, a plurality of alumina particles, a plurality of pre-expanded hollow polymeric microspheres, a plurality of conductive particles (e.g.. nickel coated graphite or carbon black), or combinations thereof.

[0142] Suitable hollow microspheres include for instance and without limitation, hollow glass microspheres. Hollow glass microspheres can be made by techniques known in the art (see, e.g., U. S. Pat. Nos. 2,978,340 (Veatch et al.); 3,030,215 (Veatch et al.); 3,129,086 (Veatch et al.); and 3,230,064 (Veatch et al.); 3,365,315 (Beck et al.); 4,391,646 (Howell); and 4,767,726 (Marshall); and U. S. Pat. App. Pub. No. 2006 / 0122049 (Marshall et. al).

[0143] Exemplary polymeric microparticles include for instance, the polymeric microspheres described in detail in PCT Publication No. WO 2023 / 175424 (Maher et al.). Exemplary suitable polymeric nanoparticles include, for instance, the polymeric nanoparticles described in detail in PCT Publication No. WO 2023 / 228050 (Moughton et al.).

[0144] Suitable organo-phosphinate fillers include for instance and without limitation, those commercially available under the trade designations “EXOLIT OP 930”, “EXOLIT OP 935”. and “EXOLIT OP 1230”, all from Clariant Ltd (Louisville, KY), which are each white, fine-grained powders of aluminum diethyl phosphinate flame retardant particles. Advantageously, the use of organo-phosphinate fillers tends to improve drop resistance of an adhesive even in the absence of other additives that have also been used to increase shear modulus.

[0145] Expanded microspheres are obtained by exposing expandable microspheres to heat. A wide range of expandable microspheres are suitable. Suitable expandable microspheres are ones with low density, high elasticity, and low moisture absorption such as those commercially available from Nouryon under the trade name “EXPANCEL” such as “EXPANCEL 920DU20”. In some embodiments, the expandable microspheres have a maximum expansion ratio of 6.4.

[0146] Initiators

[0147] An initiator is preferably added to aid in polymerization of the polymerizable composition. The type of initiator used depends on the polymerization process. In a preferred embodiment, photoinitiators are used to initiate the polymerization. Useful photoinitiators include benzoin ethers such as benzoin methyl ether or benzoin isopropyl ether, substituted benzoin ethers such as 2-methyl-2-hydroxypropiophenone, or photoactive oxides such as 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime. An example of a commercially available photoinitiator is “OMNIRAS 651” available from IGM resins, having a formula of 2,2-dimethoxy-1.2-diphenylethane-l-one. Generally, the photoinitiator is present in an amount of about 0.01 phr to 0.10 phr. The polymerization may be carried out in the presence of at least one free-radical initiator. Useful free-radical UV initiators include, for example, benzophenones. In another embodiment, a thermal initiator may be used, such as for example, AIBN (azobisisobutyronitrile) and / or peroxides.

[0148] At Least Partially Polymerized Reaction Product of Polymerizable Compositions

[0149] In a second aspect, an at least partially polymerized reaction product of the polymerizable composition is provided. The polymerizable composition is according to any embodiment of the first aspect described in detail above.

[0150] The polymerizable composition may be at least partially polymerized by techniques known in the art, including, for example, the conventional techniques of solventless polymerization. A ‘ substantially solvent free” polymerization refers to less than 5%, 2%, 1% or even 0.5% by weight of solvent being used, based on the weight of the polymerizable components, and more preferably no additional solvent is added during the polymerization. The term “solvent” refers both to water and to conventional organic solvents used in the industry’ which arc volatilized in the process.

[0151] As noted above, the polymerizable composition optionally includes an initiator for photoinitiation or thermal initiation of polymerization of polymerizable components of the polymerizable composition. By only partially polymerizing the composition, the partially polymerized reaction product may be easier to handle during use in an adhesive application.

[0152] Pressure Sensitive Adhesive Articles

[0153] In a third aspect, a pressure sensitive adhesive article is provided. The pressure sensitive adhesive article comprises an adhesive composition comprising the at least partially polymerized reaction product according to the second aspect, wherein the adhesive composition is disposed on at least a portion of a substrate. Pressure sensitive adhesives (PSAs) are well known to one of ordinary skill in the art to possess certain 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 removable from an adherend. PSAs commonly provides overlap shear strength not exceeding 1, or 2, or at most 4 mcgaPascals (MPa) when bonding substrates at room temperature.

[0154] Referring to FIG. 1A, a pressure sensitive adhesive article 100a comprises a substrate 110 having a first major surface 112 and a layer of an adhesive composition 120 disposed on at least a portion of die first major surface 112 of the substrate 110. A second major surface 114 of the substrate 110 is also indicated in FIG. 1A. In some embodiments, the substrate is one of the following: a liner comprising a release agent, a backing, or a carrier.

[0155] Referring to FIG. IB, a pressure sensitive adhesive article 100b comprises a substrate 110 having a first major surface 112 and a layer of an adhesive composition 120 disposed on at least a portion of the first major surface 112 of the substrate 110. The pressure sensitive adhesive article 100b further comprises an optional second adhesive layer 130 disposed on at least a portion of the second major surface 114 of the substrate 110. In such an embodiment, the substrate 110 is a carrier and the substrate 110 is disposed between the adhesive composition 120 and the second adhesive layer 130.

[0156] “ Debond-on-demand” adhesives, also referred to herein as "debondable” adhesives, are known and are described in PCT International Publication Number WO 2022 / 254267 (Hedegaard et al.). In some embodiments, a suitable adhesive has a glass transition temperature (Tg) of -35 degrees Celsius or lower. As shown in FIG. 3. for example, a bonded assembly 60 including a first component 10 having an electrically conductive surface and a second component 20 having an electrically conductive surface and an adhesive composition 50 comprising an ionic liquid (i.e.. a debondable adhesive) disposed between the first component 10 and the second component 20 can be subjected to a DC voltage, resulting in a debonded assembly 70. Typically, the substrate that is attached to the positive electrode will retain the adhesive and the adhesive will be debonded / separated from the substrate attached to the negative terminal, though examples of both anodic and cathodic disbondment are known (see. e.g., Progress in Organic Coatings, vol. 105 (2017), pp. 163-175).

[0157] In some applications, however, it may be further desirable to reposition an adhesive during placement by having the adhesive initially bond loosely to a substrate until it is positioned correctly andthen strengthening the bond to its ultimate holding power. In this instance, for example, it may be useful to have a PSA of modest adhesive strength initially while providing a triggering mechanism (e.g., electricity) to increase the adhesive bond strength after placement.

[0158] In other applications, it may be desirable to have an adhesive that can adaptively change its bonding strength depending on the external forces on the bonded assembly. For example, it may be beneficial to have a compliant adhesive under ordinary circumstances to improve energy dissipation and retain low stiffness in applications where the adhesive is expected to fold or bend, such as when bonding curved or folding parts, but then be able to transition the adhesive to a high stiffness, strongly bonded material before a high stress impact on the adhesive is expected.

[0159] To address and solve at least these problems, provided herein are articles including adhesives such that the bonding strength of the adhesive may be reversibly strengthened via application of an electric current, either operated in alternating current (“AC”) mode or as a series of applied currents in opposite polarity, through the adhesive.

[0160] Foldable optically clear adhesives (OCAs) and PSAs arc used to bond display components together in foldable phones / tablets. To ensure they are foldable over a broad temperature range they need to have a low glass transition temperature (Tg), which then means that the adhesion strength at room temperature tends to be quite low. It has unexpectedly been discovered that certain polymerizable ionic liquids can copolymerize into foldable OCA formulations to make foldable OCAs that have low optical haze, low modulus and Tg, and good foldable mechanics (e.g., high strain when under fixed stress). When these formulations are subjected to AC potentials at low frequencies their adhesion strength can be greatly increased over the initial adhesion strength. This could enable foldable OCAs / PSAs to have much higher adhesion strength than their rheology allows them whilst still ensuring good folding mechanics. Such properties can be measured, for instance using one or more of the test methods described in detail in the Examples below, including the Optical Testing methods (e.g.. for transmission / haze / clarity), Creep Compliance by Dynamic Mechanical Analysis (DMA) Testing, Rheology Test Method, or Rheometer Adhesion Strengthening Test Method.

[0161] In a flexible assembly, the OCA will also serve as an assembly layer, which in addition to the typical OCA functions, may also absorb most of the folding induced stress to prevent damage to the fragile components of the display panel and protect the electronic components from breaking rmder the stress of folding. The OCA layer may also be used to position and retain the neutral bending axis at. or at least near, the fragile components of the display, such as for example the barrier layers, the driving electrodes, or the thin film transistors of an organic light emitting display (OLED).

[0162] The OCA is soft, is predominantly elastic with good adhesion to plastic films or other flexible substrates like glass, and has high tolerance for dynamic shear loading. In addition, the OCA has relatively low modulus, high percent compliance at moderate stress, a low glass transition temperature, generation of minimal peak stress during folding, and good strain recovery after applying and removing stress, making it suitable for use in a flexible assembly because of its ability to withstand repeated folding and unfolding. Under repeated flexing or rolling of a multi-layered construction, the shear loading on theadhesive layers becomes very significant and any form of stress can cause not only mechanical defects (delamination, buckling of one or more layers, cavitation bubbles in the adhesive, etc.) but also optical defects or Mura. Unlike traditional adhesives that are mainly visco-elastic in character, the OCA of the present disclosure is predominantly elastic at use conditions, yet maintains sufficient adhesion to pass a range of durability requirements. In one embodiment, an OCA assembly layer is optically clear and exhibits low haze, high visible light transparency, and environmental durability.

[0163] As shown in FIG. 4, a bonded assembly 60 including a first component 10 having an electrically conductive surface and a second component 20 having an electrically conductive surface and an adhesive composition 50 comprising an ionic liquid disposed between the first component 10 and the second component 20 may be subjected to a voltage of switching polarity to provide a strengthened assembly 100. In some embodiments, the strengthened assembly 100 may be subjected to a DC voltage to provide a debonded assembly 70.

[0164] In some embodiments, the strengthening of the adhesive bond is reversible by application of a DC voltage of at least 5 V, at least 10 V, at least 20 V, at least 50 V, at least 100 V, or at least 200 V across the adhesive composition. In some embodiments, application of the DC voltage is for at least 10 seconds, optionally at least 20 seconds, optionally at least 30 seconds, optionally at least 45 seconds, optionally at least 60 seconds, optionally at least 2 minutes, optionally at least 3 minutes, optionally at least 5 minutes, optionally at least 10 minutes, optionally at least 15 minutes, or optionally at least 20 minutes.

[0165] In some cases, an adhesive bond may be strengthened by application of a series of electric potentials in opposite polarity across the pressure sensitive adhesive article, e.g.. for a duration of from one second to four hours. For instance, following strengthening, the pressure sensitive adhesive article may exhibit a maximum strain of 300% or greater and a recovery of 50% or greater, as determined by the Creep Test Method, and / or the pressure sensitive adhesive article may exhibit an increase in adhesion strength of at least 20% following subjection to an alternating current, as determined by the Rheometer Adhesion Strengthening Test Method.

[0166] In certain embodiments, the series of electric potentials in opposite polarity has a voltage amplitude of 1 V to 1000 V, optionally 5 V to 1000 V, optionally 9 V to 1000 V. or optionally 10 V to 100 V. The series of electric potentials in opposite polarity optionally comprises an AC electric potential. The frequency of the AC electric potential may be less than 1000 Hz, optionally less than 500 Hz. optionally less than 100 Hz. optionally less than 75 Hz. optionally less than 60 Hz. or optionally less than 50 Hz. e.g., 0.01 Hz to 50 Hz.

[0167] In certain embodiments, the series of electric potentials in opposite polarity comprises a series of applied currents in opposite polarity, e.g., selected from the group consisting of polarity -switched DC voltages, sinusoidal waves, square waves, sawtooth waves, triangle waves, random noise, positive interference waves, and combinations thereof. In select cases, the series of applied currents are frequency -modulated waves and / or amplitude-modulated waves.

[0168] Methods for strengthening an adhesive bond and determining the extent of strengthening are described in detail in co-owned application Docket No. PA102224US01, incorporated herein by reference in its entirety.

[0169] It is contemplated that such debonded assemblies may be subsequently rebonded to provide a restrengthened assembly, that such restrengthened assembly may again be subjected to a DC voltage to provide a debonded assembly, and that such process may be repeated multiple times.

[0170] Alternately, a non-strengthened assembly may be subjected to a DC voltage to provide a debonded assembly 70. It is contemplated that such debonded assemblies may be subsequently rebonded to provide a restrengthened assembly, that such restrengthened assembly may again be subjected to a DC voltage to provide a debonded assembly, and that such process may be repeated multiple times.

[0171] FIG. 5 shows a graphical depiction of an applied voltage sawtooth wave. FIG. 6 shows a graphical depiction of an applied voltage multi-frequency wave, being a sum of multiple sinusoidal voltage waves each with different frequency and amplitude. FIG. 7 shows a graphical depiction of an applied voltage frequency sweep, where frequency of the wave is continuously ramped from a starting low frequency to and ending high frequency, then stepped back to the initial low frequency. FIG. 8 shows a graphical depiction of an applied voltage amplitude -modulated wave, being a square wave function amplitude-modulated by a triangle wave.

[0172] The first component and / or the second component of the bonded assembly may comprise a conductive metal such as, for example, stainless steel, aluminum, or copper. In some embodiments, the first component and / or the second component may comprise a conductive coating or conductive ink on a non-conductive substrate such as a plastic substrate (e.g.. polypropylene, polyester, polyethylene) glass, epoxy-molded substrate or anodized aluminum. In some embodiments, the first component and / or the second component may comprise a conductive coating on a conductive substrate. In some embodiments, the first component and / or the second component may comprise an electrically conductive filler dispersed in a polymeric matrix. In some embodiments, the second component is different from the first component.

[0173] In certain embodiments, adhesive compositions disclosed herein comprising a polymerized ionic liquid can undergo electrically induced adhesive debonding, wherein the adhesive composition can be debonded on demand with the application of a voltage across certain portions of the pressure sensitive adhesive article. Although not wanting to be limited by theory, it is believed that when a voltage is applied to the adhesive composition comprising an ionic liquid, electrolysis of the ionic liquid occurs, wherein the cations migrate toward the cathode side and the anions migrate toward the anode side, thereby weakening the adhesive interface.

[0174] Advantageously, in at least certain embodiments according to the present disclosure, an adhesive composition exhibits a tensile pushout strength of greater than 0.2 megaPascals (MPa), as determined by the Tensile Pushout Test Method. The Tensile Pushout Test Method is described in detail in the Examples below. In some cases, an adhesive composition exhibits a tensile pushout strength of greater than 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa. 1.8 MPa, 1.9 MPa, or even greater than 2.0. MPa. as determined by the Tensile Pushout Test Method.

[0175] In at least certain embodiments according to the present disclosure, an adhesive composition exhibits a decrease in tensile pushout strength of at least 50% following subjection to 9 volts (V), 10 V, 20 V, 30 V, 40 V. or 50 V for one minute, as determined by the Tensile Pushout Test Method. In some cases, an adhesive composition exhibits a decrease in tensile pushout strength of at least 55%, 60%. 65%, 70%, 75%. 80%, 85%, 90%, or at least 95%. as determined by the Tensile Pushout Test Method. The decrease in tensile pushout strength following subjection to the voltage is a measure of the extent of electro-debonding capability of an adhesive composition, with a larger decrease indicating greater debonding.

[0176] In at least certain embodiments according to the present disclosure, an adhesive composition exhibits a decrease in peel strength of at least 50% following subjection to 50 volts (V) for one minute or following subjection to 10 V for 5 seconds, 10 seconds, 20 seconds, 30 seconds, 45 seconds, or 60 seconds, as determined by the Peel Adhesion Test Method. In some cases, an adhesive composition exhibits a decrease in peel strength of at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or at least 95%, as determined by the Peel Adhesion Test Method. The decrease in peel strength following subjection to the voltage is a measure of the extent of electro-debonding capability of an adhesive composition, with a larger decrease indicating greater debonding.

[0177] The thickness of a layer of an adhesive composition may vary, such each independently having as an average thickness of 10 micrometers or greater, 20 micrometers, 30, 50, 75, 100, 125. 150, 175, 200.225. 250, 275, 300, 325, 350, 375, 400, 425. 450, 475, 500, 525, 550, 575, 600, 625. 650, 675, 700. 725, 750. 775, 800, 825, 850, 875. 900, 925, 950. 975, 1000, 1025, 1050, 1075, 1100, 1125, 1150. 1175. 1200.1225, 1250, 1275, or 1300 micrometers or greater; and 1500 micrometers or less, 1475, 1450, 1425, 1400, 1375, 1350, 1325, 1300, 1275, 1250, 1225, 1200, 1175, 1150, 1125, 1100, 1075, 1050, 1025. 1000.975. 950, 925. 900, 875, 850. 825, 800, 775. 750, 725, 700, 675, 650. 625, 600, 575. 550, 525, 500. 475, 450. 425, 400. 375, 350, 325. 300, 275, 250. 225, 200. 175, 150, 125. or 100 micrometers or less.Coating techniques known in the art for applying a layer of a pressure sensitive adhesive may be used such as spray coating, flood coating, knife coating, Meyer bar coating, gravure coating, and double roll coating.

[0178] In some embodiments, suitable electrically conductive substrates comprise a metal, a mixed metal, an alloy, a metal oxide, a composite metal, a conductive plastic, a conductive polymer, a polymer matrix containing an electrically conductive material dispersed in the matrix (e.g., as described in further detail above with respect to the electrically conductive composite layer), or combinations thereof. Such an electrically conductive layer 140 can be formed, for example, by plating, chemical vapor deposition, vacuum deposition, or sputtering. Polymer coatings may also be coated from solvent or aqueous solutions. The thickness of the electrically conductive layer 140 is not particularly limited. In some embodiments, the thickness of the electrically conductive layer 140 is 0.001 micrometers or larger, 0.01 micrometers or larger, 0.03 micrometers or larger, or 0.05 micrometers or larger. In some embodiments,the thickness of the electrically conductive layer 140 is 1,000 micrometers or less. 500 micrometers or less. 300 micrometers or less. 50 micrometers or less, or 10 micrometers or less. In some embodiments, the carrier is a polymeric film with a vapor-deposited aluminum film formed thereon.

[0179] Liners

[0180] Suitable (e.g.. release) liners may comprise flexible paper and polymeric films having sufficient dimensional stability to hold layers formed thereon in position without excessive stretching. Suitable paper liners include, but are not limited to. densified Kraft paper (commercially available from, for example. Loparex North America. Willowbrook. IL), poly -coated paper such as polyethylene coated Kraft paper, and the like. Suitable polymeric film / liners include, but are not limited to. thermoplastic polymer films including polyalkydenes, e.g., polyethylene and polypropylene; polybutadiene, polyisoprene; polyalkydene oxides, e.g., polyethylene oxide; polyesters, e.g.. PET and PBT; polyamides; polycarbonates, polystyrenes, block copolymers of any of the preceding polymers, and combinations thereof. Other suitable polymeric materials include polyimide, polysilicone, polytetrafluoroethylene, polyethylenephthalate, polyvinylchloride, or combinations thereof. Polymer blends of any of the above may also be employed, and nonwoven or woven liners may also be used.

[0181] In some embodiments, any or all of the major surfaces of a release liner may include a release coating, which may be the same or different, to tune or otherwise modify their release values. In various embodiments, which are not intended to be limiting, the release coatings applied to tire major surfaces of the release liners may be selected from a fluorine-containing material, a silicone-containing material, a fluoropolymer, a silicone polymer, or a poly(meth)acrylate ester derived from a monomer including an alkyl (methjacrylate having an alkyl group with 12 to 30 carbon atoms. In one embodiment, the alkyl group on the alkyl (meth)acrylate can be branched. Illustrative examples of useful fluoropolymers and silicone polymers can be found in U. S. Patent No. 4.472.480 (Olson). U. S. Patent No. 4,567.073 and U. S. Patent No. 4,614,667 (both Larson et al), incorporated herein by reference in their entireties. Illustrative examples of useful poly(meth)acrylate esters can be found in U. S. Patent Appl. Publ. No. 2005 / 0118352 (Suwa). incorporated herein by reference in its entirety.

[0182] Carriers

[0183] The carrier film may be a flexible or inflexible backing material, a release liner, or a conductive carrier. Exemplary materials useful as the carrier film for the pressure sensitive adhesive articles of the disclosure include, but are not limited to, polyolefins such as polyethylene, polypropylene (including isotactic polypropylene and high impact polypropylene), polystyrene, polyester, including poly(ethylene terephthalate), polyvinyl chloride, poly(butylene terephthalate), poly(caprolactam), polyvinyl alcohol, polyurethane, poly(vinylidene fluoride), cellulose and cellulose derivatives, such as cellulose acetate and cellophane, and wovens and nonwovens. Commercially available carrier film include kraft paper (available from Monadnock Paper, Inc.); spun-bond poly(ethylene) and polypropylene), such as those available under the trade designations “TYVEK” and “TYPAR” (available from The Chemours Co.); and porous films obtained from poly(ethylene) and polypropylene), such as those available under the trade designations “TESLIN” (available from PPG Industries, Inc.), and “CELLGUARD” (available fromHoechst-Celanese). Exemplary conductive materials include for instance and without limitation, a layer of (e.g.. metal) foil, a metal-coated polymeric film, a layer of a conductive primer coated onto or transferred onto the adhesive, a conductive primer deposited on a carrier layer, a conductive woven fabric, a conductive nonwoven fabric, a conductive mesh fabric (metal-coated insulative fibers), a conductive foam, a conductive elastomer, a conductive polymer film (e.g., poly(3,4-ethylenedioxythiophene), PEDOT) or coating on another film or polymer layer, and a conductive ceramic / alloy and / or oxides (e g., Indium Tin Oxide, ITO) with or without a carrier layer. In certain embodiments, the conductive material comprises a carbon-based material, e.g., conductive carbon black, carbon nanotubes, carbon fibers, carbon nanofibers, carbon nanotubes, graphite, and / or graphene.

[0184] In some embodiments, the carrier comprises a transparent conductive material. Some exemplary transparent conductive carriers include transparent conductive electrodes and transparent conductive substrates, which are commonly known to those of ordinary skill in the art. Transparent conductive electrodes can be made of, for example, transparent conducting oxides (TCO) such as indium tin oxide, antimony tin oxide, fluorine doped tin oxide, doped zinc oxide; conducting polymers such as polyacetylenes, polyanilines, polypyrroles, polythiophenes, poly (3,4-ethylenedioxythiphene) [PEDOT]: poly(styrene sulfonate) [PSS], doped poly(4,4-dioctylcyclopentadithiophene); metal mesh; metal nanowires (e.g., silver, copper, and nickel); graphene; carbon nanotubes; and combinations thereof. Techniques for providing transparent conductive electrodes are known in the art, including roll coating, slot die coating, sputtering, evaporation, flexographic printing, screen-printing, gravure printing, offset printing, inkjet printing, photolithography, chemical etching, and laser-scribing as may be applicable to the particular material comprising the layer. Criteria for selecting the particular material for the transparent conductive electrode include the desired electrical transport characteristics (described quantitatively primarily by electrical sheet resistance, Rs, measured in units of ohms per square by techniques such as four-point probe or eddy current testing) and optical characteristics (described quantitatively primarily by the light transmittance. % T, measured in units of percentage, for example for photopically weighted visible light). The sheet resistance of exemplary transparent electrodes may be between, for example. 0.1 and 1000 ohms per square, in some embodiments between 1 and 100 ohms per square. The light transmittance of exemplary transparent electrodes, for example the visible light transmittance, may be betw een, for example. 25% and less than 100%. in some embodiments between 50% and 99.75%, in other embodiments between 75% and 99.5%. and in yet other embodiments between 80% and 99%.

[0185] The carrier film delivers the adhesive of the present disclosure to the desired substrate. The carrier film may comprise on the surface opposite the adhesive, a pigment, indicia, text, design, etc., which is then fixedly attached to the surface of the substrate or the carrier film may be free of such pigments and / or markings.

[0186] Backings

[0187] Adhesive compositions disclosed herein may advantageously be used to prepare a wide range of adhesive tapes and articles. Many of these tapes and articles contain backings or release liners used tosupport the layer of adhesive. As used herein a backing is a permanent support intended for final use of the adhesive article. A liner, on the other hand, is a temporary support that is not intended for final use of the adhesive article and is used during the manufacture or storage to support and / or protect the adhesive article. A liner is removed from the adhesive article prior to final use. To facilitate easy removal from the adhesive layer, the liner is typically coated with a release coating comprising a release agent. Such release agents are known in the art and are described, for example in " Handbook of Pressure Sensitive Adhesive Technology," D. Satas, editor. Van Nostrand Reinhold. New York, N. Y., 1989, pp. 585-600. In one embodiment, the release agent migrates to the surface (on the liner or release coating) to provide the appropriate release properties. Examples of release agents include carbamates, silicones and fluorocarbons. Illustrative examples of surface applied (i.e., topical) release agents include polyvinyl carbamates such as disclosed in U. S. Pat. No. 2,532,011 (Dahlquist et al.), reactive silicones, fluorochemical polymers, epoxysilicones such as are disclosed in U. S. Pat. Nos. 4,313.988 (Bany et al.) and 4,482,687 (Kessel et al.), polyorganosiloxane-polyurea block copolymers such as are disclosed in EP Pat. No. 0250248 Bl (Loir et al.), etc.

[0188] The backing layer may be a film, a non-woven web, paper, or a foam as further described below. The double-sided tape may comprise one or tw o release liners protecting the adhesive surface not in contact with the backing layer. In one embodiment, the adhesive layer is disposed between two release liners, which may be the same or different. In another embodiment, the adhesive layer is disposed on a backing and the opposing side of the backing comprises a release agent. The adhesive article is wound upon itself such that the exposed surface of the adhesive layer (opposite the backing) contacts the release-coated backing forming, for example, a roll of tape. In yet another embodiment, the adhesive is disposed between a backing and release liner. In some embodiments, the adhesive tapes and articles do not contain a backing and therefore are freestanding adhesive layers. Transfer adhesive tapes are an example of such an adhesive article. Transfer adhesive tapes, also called transfer tapes, have an adhesive layer delivered on one or more release liners. The adhesive layer has no backing within it, so once delivered to the target substrate and the liner is removed, there is only adhesive. Some transfer tapes are multi-layer transfer tapes with at least two adhesive layers that may be the same or different. Transfer tapes are widely used in the printing and paper making industries for making flying splices, as well as being used for a variety of bonding, mounting, and matting applications both by industry and by consumers.

[0189] Select Embodiments of the Disclosure

[0190] In a first embodiment, the present disclosure provides a polymerizable composition comprising: a) a C1-C30 alkyl (meth) aery late ester monomer; andb) a polymerizable ionic liquid, wherein the anion of the ionic liquid comprises a polymerizable functional group.

[0191] In a second embodiment, the present disclosure provides a polymerizable composition according to the first embodiment, wherein the C1-C30 alkyl (me th) aery late ester monomer comprises methyl acrylate, iso-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, iso-decyl acrylate, n-butyl acrylate,2-methylbutyl acrylate, n-hexyl acrylate, dodecyl acrylate, strearyl acrylate, heptadecyl acrylate or 6-methylheptyl acrylate.

[0192] In a third embodiment, the present disclosure provides a polymerizable composition according to the first embodiment or the second embodiment, wherein the C1-C30 alkyl (meth)acrylate ester monomer is present in an amount of 30 wt.% to 95 wt.%. based on a total weight of polymerizable components.

[0193] In a fourth embodiment, the present disclosure provides a polymerizable composition according to any of the first through third embodiments, further comprising a crosslinker.

[0194] In a fifth embodiment, the present disclosure provides a polymerizable composition according to any of the first through fourth embodiments, further comprising an ethoxy group-containing (meth)acrylate monomer.

[0195] In a sixth embodiment, the present disclosure provides a polymerizable composition according to any of the first through fifth embodiments, further comprising a carboxylic acid-containing (meth)acrylate monomer in an amount of less than 2 parts per hundred parts resin (phr) of the polymerizable composition.

[0196] In a seventh embodiment, the present disclosure provides a polymerizable composition according to any of the first through sixth embodiments, further comprising a (meth)acry late macromer comprising one or more of a polyethylene oxide) group, a polypropylene oxide) group, a polyethylene oxide-co-propylene oxide) group, a poly(tetrahydrofuran) group, a poly(ester) group, or combinations thereof.

[0197] In an eighth embodiment, the present disclosure provides a polymerizable composition according to any of the first through seventh embodiments, further comprising an additive comprising at least one of a filler, a tackifier, a plasticizer, an adhesion promoter, a stabilization agent, a corrosion inhibitor, a colorant, an antioxidant, a UV absorber, or a polymer having a glass transition temperature of at least 40 degrees Celsius.

[0198] In a ninth embodiment, the present disclosure provides a polymerizable composition according to any of the first through eighth embodiments, wherein the polymerizable functional group of the anion of the ionic liquid comprises at least one of a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an alcohol group, an epoxy group, a primary or secondary amino group, or a thiol group.

[0199] In a tenth embodiment, the present disclosure provides a polymerizable composition according to any of the first through ninth embodiments, wherein the ionic liquid comprises at least one of an imidazolium. an ammonium, a pyridinium, a phosphonium, a sulfonium, or an iodonium ion.

[0200] In an eleventh embodiment, the present disclosure provides a polymerizable composition according to any of the first through tenth embodiments, wherein the ionic liquid comprises at least one anion having a polymerizable group which comprises a sulfate, a sulfonate, a carboxylate, a phosphate, a phosphonate, a phosphorus-containing ion, a borate, a phenyl borate, an oxalato borate, a nitrate, an imide, or a bis(sulfonyl)imide.

[0201] In a twelfth embodiment, the present disclosure provides a polymerizable composition according to any of the first through eleventh embodiments, wherein the ionic liquid comprises at least one anion having a polymerizable group which comprises a sulfonate.

[0202] In a thirteenth embodiment, the present disclosure provides a polymerizable composition according to any of the first through twelfth embodiments, further comprising a second monomer that is different than the C1-C30 alkyl (meth)acrylate ester monomer.

[0203] In a fourteenth embodiment, the present disclosure provides a polymerizable composition according to the thirteenth embodiment, wherein the second monomer comprises a C1-C30 alkyl (meth)acrylate ester monomer that is different from component a), a nitrogen-containing monomer, a hydroxy-containing monomer, an ethoxy containing monomer, an epoxy -containing monomer, an acid-containing monomer, or a nonpolar monomer having a glass transition temperature (Tg) of greater than 10°C to 200°C.

[0204] In a fifteenth embodiment, the present disclosure provides a polymerizable composition according to the fourteenth embodiment, wherein the second monomer comprises a nitrogen-containing monomer or a hydroxy-containing monomer.

[0205] In a sixteenth embodiment, the present disclosure provides a polymerizable composition according to the fifteenth embodiment, wherein the second monomer is a first nitrogen-containing monomer that is an acrylamide monomer and the polymerizable composition further comprises a third monomer that is a second nitrogen-containing monomer that has a nitrogen atom directly attached to a vinyl group.

[0206] In a seventeenth embodiment, the present disclosure provides a polymerizable composition according to the fourteenth embodiment, wherein the second monomer comprises a C1-C30 alkyl (meth)acrylate ester monomer that is different from component a).

[0207] In an eighteenth embodiment, the present disclosure provides an at least partially polymerized reaction product of the polymerizable composition according to any of the first through seventeenth embodiments, the thirty-second embodiment, or the thirty -third embodiment.

[0208] In a nineteenth embodiment, the present disclosure provides a pressure sensitive adhesive article comprising an adhesive composition comprising the at least partially polymerized reaction product according to the eighteenth embodiment, wherein the adhesive composition is disposed on at least a portion of a substrate.

[0209] In a twentieth embodiment, the present disclosure provides an adhesive article according to the nineteenth embodiment, wherein the substrate is a liner comprising a release agent, a backing, or a carrier.

[0210] In a twenty-first embodiment, the present disclosure provides an adhesive article according to the nineteenth embodiment or the twentieth embodiment, further comprising a second adhesive layer, wherein the substrate is a carrier and the substrate is disposed between the adhesive composition and the second adhesive layer.

[0211] In a twenty-second embodiment, the present disclosure provides an adhesive article according to the twentieth embodiment or the twenty-first embodiment, wherein the carrier comprises a conductive material.

[0212] In a twenty -third embodiment, the present disclosure provides an adhesive article according to the twenty-second embodiment, wherein the conductive material is transparent.

[0213] In a twenty-fourth embodiment, the present disclosure provides an adhesive article according to any of the nineteenth through twenty -third embodiments, wherein the adhesive composition exhibits a tensile pushout strength of greater than 0.2 megapascals (MPa), as determined by the Tensile Pushout Test Method.

[0214] In a twenty -fifth embodiment, the present disclosure provides an adhesive article according to any of the nineteenth through twenty -fourth embodiments, wherein the adhesive composition exhibits a decrease in tensile pushout strength of at least 50% following subjection to 9 volts (V), 10 V, 20 V, 30 V, 40 V, or 50 V, for one minute, as determined by the Tensile Pushout Test Method.

[0215] In a twenty-sixth embodiment, the present disclosure provides an adhesive article according to any of the nineteenth through twenty-fifth embodiments, wherein the adhesive composition exhibits a decrease in peel strength of at least 50% following subjection to 50 volts (V) for one minute, as determined by the Peel Adhesion Test Method.

[0216] In a twenty-seventh embodiment, the present disclosure provides an adhesive article according to any of the nineteenth through twenty-sixth embodiments, wherein the adhesive composition has a glass transition temperature (Tg) of -35 degrees Celsius or lower.

[0217] In a twenty-eighth embodiment, the present disclosure provides an adhesive article according to any of the nineteenth through twenty-seventh embodiments, wherein the adhesive composition exhibits a maximum strain of 300% or greater and a recovery of 50% or greater, as determined by the Creep Test Method.

[0218] In a twenty-ninth embodiment, the present disclosure provides an adhesive article according to any of the nineteenth through twenty-eighth embodiments, wherein the adhesive composition exhibits an increase in adhesion strength of at least 20% following subjection to an alternating current, as determined by the Rheometer Adhesion Strengthening Test Method.

[0219] In a thirtieth embodiment, the present disclosure provides a polymerizable composition. The polymerizable composition comprises an adhesive precursor and at least one polymerizable ionic liquid selected from the group consisting of tributylmethylammonium acryloxy-succinyl-1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-1-propanesulfonate, 1-octyl-3-methylimidazolium acryloxy-succinyl-1-propanesulfonate, 1-butyl-3-methylimidazoliumacryloxy-succinyl-1-propanesulfonate, trimethylammonium ethyl acrylateacryloxy-succinyl-1-propanesulfonate, 3-sulfopropyl acrylate 1-butyl-3-methylimidazolium salt, 3-sulfopropyl acrylate n-butylpyridinium salt, 1-octyl-3-methylimidazolium 3-sulfopropyl acrylate, octyldimethyl-2-hydroxyethylammonium 3-sulfopropyl acrylate, octyldimethyl-2-hydroxyethylammonium acrylamido-2-methyl-1-propanesulfonate, tetrabutylphosphonium 3-sulfopropylacrylate, tetrabutylphosphonium acrylamido-2-methyl-1-propanesulfonate, trimethylammonium ethyl acrylate 3 -sulfopropyl acrylate, trimethylammonium ethyl acrylate acrylamido-2-methyl-1-propanesulfonate, tributylmethylammonium 3-sulfopropyl acrylate tributylmethylammonium acrylamido-2-methyl-1-propanesulfonate, and l-octyl-3-methylimidazolium acryloxy-succinate.

[0220] In a thirty -first embodiment, the present disclosure provides a polymerizable ionic liquid. The polymerizable ionic liquid is selected from the group consisting of tributylmethylammonium acryloxy-succinyl-1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-1-propanesulfonate, 1-octyl-3-methylimidazolium acryloxy-succinyl-1-propanesulfonate, l-butyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, trimethylammonium ethyl acrylate acryloxy-succinyl-1-propanesulfonate, and l-octyl-3-methylimidazolium acryloxy-succinate.

[0221] In a thirty -second embodiment, the present disclosure provides a polymerizable composition according to any of the thirteenth through sixteenth embodiments, wherein the second monomer is a polymerizable anion ionic liquid.

[0222] In a thirty -third embodiment, the present disclosure provides a polymerizable composition according to the thirty -second embodiment, wherein the second monomer comprises 2-acrylamido-2-methyl-1 -propanesulfonate N-octyl-N'-methyl imidazolium or N-vinyl-N'-alkylimidazolium bis(fluorosulfonyl)imide.

[0223] In a thirty -fourth embodiment, the present disclosure provides an article. The article comprises a polymerizable composition according to any of the first through seventeenth embodiments, the thirty-second embodiment, or the thirty-third embodiment, the polymerizable composition disposed on at least a portion of a substrate.EXAMPLES

[0224] Unless otherwise noted or readily apparent from the context, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight. Table 1 (below) lists materials used in the examples and their sources:Table 1. Materials used in the examples.Abbreviation Description2-EHA 2-ethyl hexyl acrylate, obtained from BASF, Florham Park, New Jersey, USABA n-butyl acrylate, obtained from BASF, Florham Park, New Jersey, USANNDMA N, N-dimethylacrylamide, obtained from TCI America, Portland, Oregon, USANVP N-vinyl-pvrrolidone, obtained from TCI America, Portland, Oregon, USAHBA 4-hydroxybutyl acrylate, obtained from BASF, Florham Park, New Jersey, USAHA n-hexvl acrylate, obtained from Osaka Organic Chemical Industry Ltd., Osaka, Japan THFA Tetrahydrofurfuryl acrylate, obtained from Osaka Organic Chemical Industry Ltd, Osaka, Japan AA Acrylic acid, obtained from BASF, Florham Park, New Jersey, USAACM Acrylamide, obtained from TCI America, Portland, Oregon, USAVMOX Vinyl methyl oxazolidinone, obtained from BASF, Florham Park, New Jersey, USA TOACM Tert-octylacrylamide, obtained from Nouryon, Amsterdam, NetherlandsNVC N-vinyl-caprolactam, obtained from TCI America, Portland, Oregon, USAHDDMA Hexanediol dimethacrylate obtained from TCI America, Portland, Oregon, USAHDDA Hexanediol diacrylate, obtained as SR 238 from Sartomer Americas, Arkema, Exton, PA, USA Methoxypolyethyleneglycol acrylate having a molecular weight of 550 Da obtained from Osaka MPEGAOrganic Chemical Industry Ltd., Osaka, JapanSPA BMI 3-Sulfopropyl acrylate l-butyl-3-methylimidazolium salt, synthesized as described herein SPA OMI 3-Sulfopropyl acrylate l-octyl-3-methylimidazolium salt, synthesized as described herein l-butyl-3-methylimidazolium acrylamido-2-methylpropane sulfonate, synthesized as described AMPS BMIhereinSPA TBMA Tributylmethylammonium 3-sulfopropyl acrylate, synthesized as described hereinl-[Dimethyl(2-{[2-(vinylcarbonyloxy)ethyl](aminocarbonyloxy)}ethyl)ammonio]octane methyl IEA QMSsulfonate, synthesized as described hereinSPA BPY 3-Sulfopropyl acrylate n-butylpyridinium salt, synthesized as described herein1 -Ethyl-3-methylimidazolium tosylate, obtained from EMD Millipore Corporation, Burlington, EMI TosMA, USAOleyl Ethylimidazolinium Ethosulfate, obtained from Colonial Chemical, South Pittsburg, TN, OEI ES USAl-Ethyl-3-methylimidazolium ethyl sulfate, obtained from EMD Millipore Corporation, EMI ESBurlington, MA, USAl-octyl-3-methylimidazolium (OMI ) acryloxy-succinyl-1 -propanesulfonate (OMI+- SPAMAC OMIO3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2)l-butyl-3-methylimidazolium (BMI ) acryloxy- succinyl- 1 -propanesulfonate (BMI+ - SPAMAC BMIO3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2)tetrabutylphosphonium acryloxy-succinyl-1-propanesulfonate (C4H9)4P+- SPAMAC Bu4PO3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2)SPA Bu4P tetrabutylphosphonium 3-sulfopropyl acrylate ( (C4H9)4P+ -O3S(CH2)3OC(O)CH=CH2)N,N,N-Trimethylammonium ethyl acrylate bis(fluorosulfonyl)imide, synthesized as described by TMAEA FSIMoughton et al in W02023228050 Al2,2-Dimethoxy-2-phenylacetophenone, obtained as Omnirad BDK from IGM Resins, Charlotte, IRG 651NC, USA.1 -Hydroxycyclohexyl-phenyl ketone, obtained as Omnirad 184 from IGM Resins, Charlotte, NC, IRG 184USA.EB-230 Ebecryl 230, obtained from Allnex, Frankfurt am Main, GermanyKBM 403 (3-Glycidvloxypropyl)trimethoxysilane, obtained from Shin-Etsu Chemical, Tokyo, Japan A methylmethacrylate-butadiene-styrene (MBS) core-shell tougheningnanoparticle with an average particle size of less than 200 nm, obtainedXT100under the trade designation '‘CLEARSTRENGTH XT100” from Arkema,Paris, FranceHollow soda-lime borosilicate glass microsphere, D95 of < 40 microns, density of 0.46 g / cm3 and S4630 a crush strength of 16,000 psi, obtained under the trade designation “3M GLASS BUBBLES S4630”, from 3M Company, St Paul, MN, USAOrganic phosphorus salt CAS#: 225789-38-8, obtained from Clariant Plastics & Coatings OP930(Germany)Low-density, polymeric microspheres coated with inorganic metal salts,MFL SEVEN obtained under the trade designation “MFL SEVEN” from MatsumotoYashi Seiyaku, JPBMI Cl 1-butyl-3-methylimidazolium chloride, obtained from TCI America, Portland, OR, USA OMI Cl 1-Methyl-3-octylimidazolium chloride, obtained from MillaporeSigma, Burlington, MA, USA SPAMACK Nominally K+-O3S(CH2)3OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2, CAS 2252168-19-5:This material was prepared by a procedure like that found in European Polymer Journal 107 (2018) 218-228, in the sections of the paper labeled 2.2. land 2.22, substituting CN147 for the methacrylate acid CH2=C(CH3)C(O)OCH2CH2OC(O)CH2CH2C(O)OH.MAC K Nominally K+-OC(O)CH2CH2C(O)OCH2CH2OC(O)CH=CH2; This material was prepared by a procedure like that found in European Polymer Journal 107 (2018) 218-228, in the sections of the paper labeled 2.2.1., substituting CN147 for the methacrylate acid CH2=C(CH3)C(O)OCH2CH2OC(O)CH2CH2C(O)OHCN147 Acidic acrylate oligomer obtained from Arkema, Colombes, France which is believed to have CH2=CH2C(O)OCH2CH2OC(O)CH2CH2C(O)OH as a major componentAMPS Na 2-acrylamido-2-methyl-propanesulfonic acid sodium salt, CAS number 15214-89-8, 50% solidsin water, obtained from Millipore Sigma, Burlington, MA, USAPelstat 1128 Octyldimethyl-2-hydroxyethylammonium methanesulfonate, C8H17N(CH3)2CH2CH2OH+ - O3SCH3, ~87% in water, obtained from Ele Chemical, McCook, IL.IEA 2-isocyanatoethyl acrylate, CAS 13641-96-8, obtained as Karenz AOI from Resonac New York, NYMolecular sieves Molecular sieves, 3 Angstrom, obtained from MilliporeSigma, Burlington, MA., USA EtOAc Ethyl acetate, obtained from MilliporeSigma, Burlington, MA., USABuPy Cl N-Butylpyridinium chloride, obtained from MilliporeSigma, Burlington, MA, USABu4P Cl Tetrabutylphosphonium chloride, 80% solids in water, obtained from TCI America, Portland, OR. TBMA C1 Tributylmethylammonium chloride, 75% solids in water, obtained from TCI America, Portland,OR.SPA K 3-Sulfopropyl acrylate potassium salt, obtained from TCI America, Portland, OR, USA MEK Methyl ethyl ketone, obtained from MilliporeSigma, Burlington, MA, USAAcetone Acetone, obtained from MilliporeSigma, Burlington, MA, USADBTDL Dibutyltin diacrylate, obtained from MilliporeSigma, Burlington, MA, USATEMPO-OH 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, obtained from Oakwood Chemical,Estill, SC.RF12N 2 mil thick PET release liner, obtained under product name RF12N from SKC, Seoul, KoreaRF02N 2 mil thick PET release liner, obtained under product name RF02N from SKC, Seoul, Korea

[0225] Preparation of SPA BMI

[0226] A round bottom flask was equipped with a TEFLON-coated stir bar and charged with 3-sulfopropyl acrylate potassium salt (10 g), l-butyl-3-methylimidazolium chloride (7.52g), and deionized water (10 g). The solution was stirred for 15.5 hours and then was precipitated into 900 mL of acetone. The solvent was filtered through a bed of celite. The solvent was removed by rotary evaporation under reduced pressure to yield SPA BMI as a clear liquid, which was further dried under a stream of air. 'H-NMR (500 MHz; DMSO-d6): δ 9.24 (s, 1H), 7.81 (t, J= 1.8 Hz, 1H), 7.74 (t, J = 1.7 Hz, 1H), 6.30 (dd, J = 17.3, 1.6 Hz, 1H), 6.16 (dd, J= 17.3, 10.3 Hz, 1H), 5.93 (dd, J= 10.3, 1.6 Hz, 1H), 4.19-4.16 (m, 4H), 3.86 (s, 3H), 2.50 (dd, J= 8.3, 6.8 Hz, 2H), 1.94-1.88 (m, 2H), 1.79-1.73 (m, 2H), 1.24 (dq, J= 15.0, 7.5 Hz, 2H), 0.88 (t, J= 7.4 Hz, 3H). 13-C NMR (126 MHz; DMSO): δ 165.6, 136.7, 131.4, 128.4, 123.7, 122.3, 63.6, 48.5, 47.9, 35.7, 31.5, 24.9, 18.8, 13.3.

[0227] Preparation of SPA OMI

[0228] A round bottom flask was equipped with a TEFLON-coated stir bar and charged with 3-sulfopropyl acrylate potassium salt (10 g), l-octyl-3-methylimidazolium chloride (9.93g), and deionized water (15 g). The solution was stirred for 48hours and then was precipitated into 900 mL of acetone. The solution was filtered through filter paper and removed by rotary evaporation under reduced pressure to yield SPA OMI (14.25 g, 85% yield) as a clear liquid. ’H-NMR (500 MHz; DMSO-d6): δ 9.22 (s, 1H), 7.81 (t, J= 1.8 Hz, 1H), 7.74 (t, J= 1.7 Hz, 1H), 6.31 (dd, J= 17.3, 1.6 Hz, 1H), 6.17 (dd, J= 17.3, 10.3 Hz, 1H), 5.94 (dd, J= 10.3, 1.6 Hz, 1H), 4.17 (td, J= 7.0, 3.8 Hz, 4H), 3.87 (s, 3H), 2.52-2.49 (m, 2H), 1.94-1.89 (m, 2H), 1.78 (quintet, J= 7.2 Hz, 2H), 1.29-1.20 (m, 10H), 0.85 (t, J= 7.0 Hz, 3H). 13-C NMR (126 MHz; DMSO): δ 165.5, 136.7, 131.4, 128.4, 123.6, 122.3, 63.6, 48.8, 47.9, 35.7, 31.2, 29.5, 28.55, 28.41, 25.6, 24.9, 22.1, 14.0.

[0229] Preparation of SPACM BMI

[0230] A round bottom flask was equipped with a TEFLON -coated stir bar and charged with 2-acrylamido-2-methyl-l -propane sulfonic acid sodium salt solution (30 g of a 50 wt.% solution in water) and l-butyl-3-methylimidazolium chloride (11.42 g). The solution was stirred for 48 hours and then was precipitated into 900 mL of acetone. The solution was filtered and removed by rotary evaporation under reduced pressure to yield SPACM BMI (21.2 g, 96% yield) as a clear liquid. ’H-NMR (500 MHz; DMSO-d6): δ 9.20 (s, 1H). 8.37 (s, 1H), 7.80 (t. J = 1.7 Hz, 1H). 7.73 (t, J = 1.7 Hz. 1H), 6.07 (dd. J = 17.1, 10.0 Hz, 1H), 5.96 (dd, J= 17.1, 2.2 Hz. 1H), 5.50 (dd. J= 10.0, 2.2 Hz. 1H), 4.18 (t, J = 7.2 Hz, 2H), 3.87 (s, 3H), 2.78 (s, 2H), 1.79-1.73 (m, 2H), 1.44 (s, 6H). 1.25 (dd, J= 15.1, 7.5 Hz, 2H), 0.89 (t, J = 7.4 Hz, 3H). 13-C NMR (126 MHz; DMSO): δ 163.8, 136.7, 133.4, 124.0, 123.7, 122.3, 60.0, 51.7, 48.5. 35.8, 31.5, 26.1. 18.8, 13.3.

[0231] Synthesis of SPA BPY

[0232] A round bottom flask was charged with 10 g of 1-butylpyridinium chloride, 13.53 g of 3-sulfopropyl acrylate potassium salt, and 15 g of water. The solution was stirred with a TEFLON-coated magnetic stir bar for 24 hrs. Then, the solution was poured in 950 mL of acetone. The white precipitate was filtered off, and the solvent was removed by rotary evaporation. Subsequent drying under high vacuum yield 18.3 g of a colorless oil. ’H-NMR (500 MHz; DMSO-d6): δ 9.14 (dd. J = 6.7, 1.2 Hz, 2H).8.62 (tt, J= 7.8, 1.3 Hz, 1H), 8.17 (dd, J= 7.6, 6.8 Hz, 2H), 6.31 (dd, J= 17.3, 1.6 Hz, 1H), 6.16 (dd, J = 17.3. 10.3 Hz, 1H). 5.93 (dd, J= 10.3. 1.6 Hz, 1H). 4.63 (t, J= 7.5 Hz, 2H), 4.17 (t, J= 6.7 Hz. 2H), 2.52-2.49 (m. 2H), 1.94-1.87 (m, 4H), 1.28 (dd, J= 15.2, 7.5 Hz, 2H). 0.90 (t, J= 7.4 Hz. 3H). 13-C NMR (126 MHz; DMSO): δ 165.6, 145.6, 144.9. 131.5, 128.4, 128.2, 63.6, 60.6. 47.9, 32.8, 24.9. 18.8, 13.4.

[0233] Synthesis of IEA QMS

[0234] Pelstat 1128 was dried on a rotary evaporator at 80 °C at aspirator pressure for 1 hr, then further dried at 80C at 73 Pa for 1.5 hrs. The resulting molten liquid was then diluted to 50% solids in EtOAc and dried overnight over molecular sieves. Pelstat 1128, 20 g solution, 10 g solids (MW297, 0.03367 mol) was charged into a 100 mL round bottom flask equipped with stirbar along with IEA (4.75g. 0.03367 mol) and 7.3 mg of 10% DBTDL in EtOAc and heated for 20 hrs at 65 °C. The material was concentrated at 60 °C at aspirator pressure to provide the product as a colorless oil.

[0235] Synthesis of SPA TBMA

[0236] To a 250 mL round bottom flask equipped with a stirbar was added 18.47 g (0.0795 mol) potassium 3-sulfopropyl acrylate, followed by 9.29g water, and the mixture was stirred to provide a clearsolution. Next was added to the reaction 25.0 g of 75% solids in water tributylmethylammonium chloride (MW 235.84, 0.0795 mol) to provide a cloudy mixture (potassium chloride precipitating from the acetone). After 10 min the reaction was added to a 1 L flask charged with 200 mL of acetone with stirring and the 250 mL round bottom was rinsed with acetone aliquots totaling 50 mL. which was also added to the 1 L flask, resulting in a cloudy dispersion which was stirred for 10 minutes. A 150 mL C porosity fritted Buchner funnel was prepared with an acetone washed Celite (Sigma -Aldrich) pad. The cloudy dispersion was vacuum filtered through the Celite pad, with additional acetone washing to provide a slightly cloudy filtrate to which was added 16.4 mg of TEMPO-OH. The filtrate was concentrated on a rotary evaporator at 60 °C for 30 min under aspirator pressure and then at 60 °C at 48 Pa for 40 min resulting in a slightly hazy yellow oil, which was characterized by proton NMR as being consistent with the product.

[0237] Synthesis of SPA Bu4P

[0238] In a manner like that for TBMA-SPA, 20.53 g SPA K (MW 232.3, 0.0884 mol) dissolved in 10.27 g water was reacted with 32.57 g 80% aqueous Bu4P Cl (EW 368.61, 0.0884 mol) and added into 500 g acetone to provide after isolation, with TEMPO-OH addition, the clear liquid title product.

[0239] Synthesis of SPAMAC BMI

[0240] A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 9.87 g of BMI Cl (MW 174.67. 0.0565 mol) and 9 g of water. Then, SPAMAC K (22.80 g. EW 403.5, 0.0565 mol) was dissolved in 9.0 g of water and added to the round bottom flask. After mixing, the solution was poured into 500 g of acetone. After filtering the solids, the solvent was removed via rotary evaporation to yield SPAMAC BMI as a slightly cloudy yellow oil. TEMPO-OH was added for stabilization.

[0241] Synthesis of SPAMAC OMI

[0242] A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 13.16 g of OMI Cl (MW 230.78, 0.0570 mol) and dissolved in 11 g water. Then. SPAMAC K (23.01g, 0.0570 mol) was dissolved in 11.26 g of water and added to the solution of OMI Cl. After mixing, the solution was poured into 500 g of acetone. After filtering off the solids, the solvent was removed via rotary evaporation to yield SPAMAC OMI as a slightly cloudy yellow liquid. TEMPO-OH was added for stabilization.

[0243] Synthesis of SPAMAC Bu4P

[0244] In a manner like that for TBMA-SPA, 15.04 g 80% solids aqueous Bu4P Cl (EW 368.61. 0.0408 mol) was reacted with SPAMAC K, 16.46 g (EW 403.5, 0.0408 mol) dissolved 7.72 g water and added into 500 g acetone to provide after isolation, with TEMPO-OH addition, the slightly yellow oil title product.

[0245] Synthesis of MAC OMI° U N*° H17C8

[0246] In a manner like that for TBMA-SPA, 4.57 g OMI Cl (MW 230.78, 0.0198 mol) and MAC K, 5.09 g (MW 257.15, 0.0198 mol) were dissolved in 2.37 g water and added into 125 g acetone to provide after isolation, with TEMPO-OH addition, the clear light-yellow oil title product.

[0247] Peel Adhesion Testing

[0248] For all peel adhesion testing, the easy side, RF02N release liner (SKC Haas Display Films LLC, Seoul KR) was removed, and the exposed side of the tacky adhesive transfer tape was rolled by hand lamination using a 6 inch (15 cm) rubberized hand roller. (Polymag Tek, NY) onto a 6 inch (15 cm) wide primed polyester (PET) film backing (3M Company. St. Paul, MN). The treated PET film backing was 2-mil / 50 μm thick biaxially oriented PET film with plasma treatment conditions described in U. S. Pat. No.10,134,566, David et al. The film backing was laminated to the adhesive ensuring no air bubbles were trapped between the adhesive and the plasma treated side of the PET film. Peel adhesion was measured at an angle of 180 degrees. Peel adhesion testing was performed on annealed 18-gauge. 304 stainless steel (" SS") or glass panels (from Chem. Instruments, Fairfield, OH). The RF12N release liner (SKC Haas Display Films LLC, Seoul KR) was removed from the tapes on PET backings and the adhesives were laminated directly to the 2- inch x 6-inch (5.08 cm x 15.24 cm) substrate using a weighted rubberized (4.5 lb. 2.04 kg) hand roller with four repetitions of 3-second roll downs. This method followed ASTM D3330, test method E, liner side. All samples and substrates w ere conditioned in a controlled temperature and humidity (" CTH") room (set at 23°C, 50% RH (relative humidity)) prior to peel testing. SS test panels were cleaned w ith methyl ethyl ketone before and after testing. Peel testing was done using an SP-2300 iMass (iMass Inc., Accord, MA USA) at a rate of 12 inches / min (0.3 m / min) after a dwell time of 1 day.

[0249] Rheometer Adhesion Strengthening Test Method

[0250] Adhesive strength was measured in a tensile debond mode using a strain-controlled rheometer (ARES G2, from TA Instruments, New Castle, Delaware, United States) equipped with an electrorheological accessory (TA Instruments). The 25-mm diameter stainless steel lower plate was attached to a water-cooled Advanced Peltier System (APS, from TA Instruments, New Castle, Delaware, United States) for temperature control. Temperature was regulated at 25 °C for all adhesion tests. For the electric potential, an arbitrary waveform generator (33210A, from Keysight Technologies, Santa Rosa, California, United States) was connected to a high voltage amplifier (Trek Model 609E-6, from Trek Inc., Lockport, New York, United States), which was connected to the 25-mm diameter stainless steel upper plate geometry. The upper geometry was electrically isolated from the transducer electronics via a ceramic connection. The lower geometry was grounded. This allowed for an electric potential in the range of 0 to 4000 V to be applied across a test specimen between the rheometer plates, in AC, DC, or arbitrary wave modes. For each test, the 25-mm diameter plates were attached to the rheometer and the gap between them was zeroed. A 4-mm diameter disk was punched from the cured adhesive sheet (between 100 and 200 um thick). The first release liner was removed, and the adhesive side was placed at the center of the lower plate fixture. Then the second release liner was removed. The temperature was equilibrated at 25 °C for one minute. Then the upper plate was lowered to contact and compress the adhesive with a compressive load of 5 N for 300 seconds. During the final 60 seconds of the compression step, optionally, an AC voltage (sinusoidal) of 50 V AC was applied across the sample. The frequency of the AC voltage w as 0.1 Hz. For the control tests, no AC voltage w as applied. At the end of the 300 seconds of compression, the plates w ere separated at a rate of 0.001 cm / s, and the tensile force required to separate the plates was measured as a function of plate separation distance. The adhesion energy per unit surface area is expressed in New tons per square centimeter of bonded surface multiplied by the travelled distance between plates in centimeters (with final units of N / cm). This w as analyzed by integrating the area underthe curve of the tensile force in Newtons (N) plotted against the change in gap between the bonded surfaces in centimeters (cm) and then dividing that value by the initial contact area in square centimeters (cm2) of the bonded test surfaces. The percentage (%) increase in the energy per unit surface area was calculated by subtracting the average value of energy in the control test (no AC) from the average value of energy with the 50 V AC applied potential and then dividing that difference by the work computed for the control test (no AC). A positive value for the % increase indicates that the adhesion energy was higher after application of AC voltage.

[0251] Optical Testing

[0252] Transmittance, haze, and color (THC) measurements were performed using a HunterLab Ultrascan Pro. The adhesive transfer tape was cut to approximately 5 cm width by 10 cm length. The RF02N liner was removed, and the adhesive with the second liner was laminated to an optically clear piece of 1 mm thick glass (Eagle Glass, Corning Glass, Coming, NY). The second liner was then removed, and the sample was placed in the instrument to measure transmittance / haze / color through the PSA / glass assembly using D65 as a standard daylight illuminant. Typically, samples acceptable for optically clear applications will have haze values of less than 5 percent, or 2 percent, or more ideally less than 1 percent for certain applications. Typically samples acceptable for optically clear applications will also have a b* of less than 1.5 and a transmittance of greater than 85%.

[0253] Creep Compliance by Dynamic Mechanical Analysis (DMA) Testing

[0254] The adhesives were evaluated for creep compliance using a DHR-3 rheometer (TA Instruments) that was fitted with a Peltier stage using an 8-mm parallel plate geometry. The sample temperature was maintained at 25 °C while a stress of 95 kPa was applied to the sample for a period of 5 sec at which time the applied stress was returned to 0 kPa. The maximum strain during the time-period of applied stress (after 5 sec) was recorded for each sample to provide a measure of extensibility of the adhesive (max% strain in Table 7). The % strain recovered at 60 sec after the stress was reduced to 0 kPa was then recorded to calculate the % elastic recoverability of the adhesive during this time. This is noted as the % strain recovery after 60 sec in Table 7. This was calculated as follows: ((max. strain % after 5 sec - strain % at 60 sec) / (max strain % after 5 sec)* 100).

[0255] Rheology Test Method

[0256] Both the RF02N and RF 12N liners were removed from the transfer tape samples and the adhesive was tested on a TA Instruments discovery hybrid rheometer III (DHR-3). (New Castle DE). The sample was heated from room temperature up to 40° C. at a rate of 3° C. / min then cooled to -50° C. at a rate of 3° C. / min, warming up to 20° C. and then heating the sample from 20° C. to 140° C. at a rate of 3° C. / min. The data was collected during the second heating cycle at oscillatory frequencies of 1 Hz with strain values in the linear viscoelastic regime (typically 1-5%). The glass transition temperature (at 1 Hz) was determined as the peak of the tan(5) curve from the rheology plot of G' and G" (y axis-1) versustemperature (° C.). (x axis) and tan(5) (y axis-2). The peak (i.e., highest value) in tan(δ) was selected from y axis-2, and the corresponding temperature on the x axis was selected as the glass transition temperature. Tan(5) is an abbreviation for the tangent of the phase angle between the stress and strain oscillation waves in the shear rheology oscillation plot.

[0257] Tensile Pushout Method

[0258] A tensile pushout setup (represented in FIG. 2) was used comprising a stainless steel coupon (40 mm×40 mm×3 mm) containing a circular hole (diameter=24 mm) in the center and a circular stainless steel puck (diameter=33 mm, 3 mm thick). The designated transfer tapes were die cut into a ring having an outer diameter of 31 mm and an inner diameter of 26 mm. The RF02N liner was removed and the exposed adhesive side of the transfer tape ring was laminated around the circular hole on the stainless steel coupon. Then the RF12N liner was removed from the transfer tape bonded to the coupon and the exposed adhesive was bonded to the stainless steel puck such that the puck covered the hole in the coupon. The test specimens were weighed down with an 8 kg weight for 30 seconds at 23° C. and then removed. The test specimens then were dwelled at 23° C. / 50% RH for at least 2 days before testing. Then, a power source (1685B series available from B& K Precision, Yorba Linda. CA) was connected to the pushout setup, with the positive electrode connected to puck and the negative electrode connect to the coupon. A voltage of 50 volts was applied across the coupon and puck for 60 seconds unless otherwise indicated. Immediately following the 60 seconds of applied voltage, the electrodes w ere disconnected from the test specimen and the test specimen was loaded onto an electromechanical tester (MTS Criterion Model C43, Eden Prairie, MN). The stainless steel coupon was held in place while a 0.75 inch (19 millimeter)-diameter rod from the electromechanical tester was positioned through the circular hole of the stainless steel coupon, contacting the circular stainless steel puck. The electromechanical tester w as used to push the puck away from the coupon in the direction shown in FIG. 2 at a rate of 10 mm / min under ambient conditions. The peak stress required to remove the puck from the coupon was recorded in MPa (mega Pascals). Test specimens where no voltage was applied were also tested in this way. Initial push out peak stress (i.e., when no voltage was applied prior to testing) and the % reduction in the push out peak stress after applying 50 volts across the test specimen for 1 minute is reported.

[0259] Electrical Debonding Peel Testing

[0260] This method followed a modified version of ASTM D3330. test method E. liner side. For peel adhesion testing, the easy side, RF02N release liner (SKC Haas Display Films LLC, Seoul KR) was removed, and the exposed side of the tacky adhesive transfer tape was rolled by hand lamination using a 6 inch (15 cm) rubberized hand roller. (Polymag Tek, NY) onto a 6 inch (15 cm) wide Mylar fdm (HFS, Azusa, CA USA). The conductive side of the mylar film was laminated to be in contact with the adhesive, ensuring no air bubbles were trapped between the adhesive and the primed polyester film. Samples were cut into 0.5” x 6” (1.27 cm x 15.24 cm) strips where at least 3” (7.62 cm) of adhesive free, Mylar backing was exposed for attaching a positive electrode during later clcctro-dcbonding experiments Initial peeladhesion was measured at an angle of 180 degrees. Peel adhesion testing was performed on annealed 18-gauge, 304 stainless steel (" SS") from Chem. Instruments, Fairfield, OH). The RF12N release liner (SKC Haas Display Films LLC, Seoul KR) was removed from the tapes, and the adhesive side were laminated directly to the 2-inch x 6-inch (5.08 cm x 15.24 cm) substrate using a weighted rubberized (4.5 lb, 2.04 kg) hand roller with four repetitions of 3-second roll downs. All samples and substrates were conditioned in a controlled temperature and humidity (" CTH") room (set at 23°C, 50% RH (relative humidity)) prior to peel testing for 24 hours. SS test panels were cleaned with methyl ethyl ketone before and after testing. Peel testing was done using an SP-2300 iMass (iMass Inc., Accord, MA USA) at a rate of 12 inches / min (0.3 m / min) after a dwell time of 30 minutes. For electro-debonded peel adhesion testing, samples were prepared in the same way. The adhesive / Mylar construction bonded to the stainless steel panel was loaded onto an iMass peel tester using an SP-2300 iMass (iMass Inc., Accord, MA USA). To electrically debond the peel adhesion samples, a BK Precision 1685 B power source was connected to the conductive side of the Mylar backing and the SS panel via a positive and negative electrode, respectively. For 60 seconds, a voltage of 50 V was applied across the Mylar backing and the SS substrate.Immediately after this time, the samples were disconnected from the power source electrodes. Then the sample was tested forl80-degree peel adhesion at a rate of 12 inches / min (0.3 m / min).

[0261] Sample Preparation

[0262] Monomer-polymer mixtures (MP-X) were prepared by adding the monomers (as specified in either Table 2 or Table 3) together at the appropriate loadings and exposing the monomer solution to 0.3 mW / cm2UV-LED irradiation (365 nm) until the mixture had a higher viscosity (about 1,000 cP). Curable compositions were made by combining the components listed in Tables 4-6. The designated monomer-polymer mixture, i.e. MP-X from Tables 2-3 was used at 100 wt.% or 100 parts and the rest of the components listed in Tables 4-6 were added at the amounts listed by calculating the parts per hundred (ppr or phr) based on 100 parts of the MP-X. Each curable composition from Tables 5-7 was coated between two release liners (RF12N and RF02N). The samples were then cured under 365 nm UV-LED lights with a total dosage of 3.1 J / cm2as measured with a radiometer equipped with a high-power sensing head (available under the trade designation “POWER PUCK II” from EIT Incorporated, Sterling, VA), resulting in adhesive transfer tapes, which had an adhesive layer thicknesses noted in Tables 7-8.Table 2. Monomer-Polymer mixture (MP-X) curable compositions.Composition (phr)MP-X2-EHA BA NNDMA NVP HBA HA THFA HDDMA Irg651A 50 15 25 10 002 0.025B 80 20 0.025C 50 20 15 20 002 0.025D 80 5 15 0.025E 55 15 30 0.025F 20 80 0.025G 45 15 20 20 0.025Table 3. Additional monomer-Polymer mixture (MP-X) curable compositions.Composition (phr)MP-X2-EHA BA NNDMA NVP AA ACM VMOX TOACM NVC HDD MA Irg 651 H 90 10 0.025 I 50 20 25 5 002 0.025 J 70 30 0.025 K 70 25 5 0.025 L 45 15 30 10 0.02 0.04Table 4. Adhesive compositions.Adhesive Compositions (phr)ID MP-X Ionic LiquidMPEGA S4630 TMAEA FSI XT100 HDDMA HDDA IRG 651Type phr Type phrEl A 100 SPABMI 20 20 10 0.1 0.2 E2 A 100 SPA OMI 20 5 0.075 0.2 E3 A 100 SPA OMI 10 10 10 0.075 0.2 E4 A 100 AMPS BMI 10 10 0.075 0.2 E5 B 100 SPABMI 10 10 10 0.1 0.5 E6 B 100 AMPS BMI 10 20 0.075 0.2 E7 B 100 SPA TBMA 10 0.1 0.2 CE1 B 100 IEA QMS 20 10 10 0.1 0.5 E8 C 100 SPA BPY 20 15 0 1 02 E9 C 100 SPA BPY 25 15 0.1 0.2 E10 D 100 SPA BPY 20 15 0.1 0.2 Ell E 100 SPA OMI 10 10 0.05 0.2 E12 G 100 SPA OMI 10 5 0.05 0.2 CE2 H 100 SPA OMI 10 5 0.05 0.2 E13 I 100 AMPS BMI 20 0.075 0.2 CE3 J 100 EMI Tos 5 5 10 0.125 0.5 CE4 J 100 OEIES 10 5 10 0.1 0.5 CE5 K 100 EMI ES 5 10 10 0.05 0.5E28 A 100 MAC OMI 15 20 0.1 0.2Table 5. Additional adhesive compositionsAdhesive Compositions (phr)ID MP-X Ionic Liquid MFLMPEGA XT100 OP930 HDDMA IRG 651 Type phr Type phr SEVENE24 L 100 SPAMAC OMI 15 20 0.1 0.2 E25 L 100 SPAMAC BMI 15 20 0.1 0.2 E26 L 100 SPAMAC Bu4P 20 35 20 32 1 0.1 0.2E27 L 100 SPA Bu4P 20 35 20 32 1 0.1 0.2Table 6. Additional adhesive compositionsAdhesive Compositions (phr)ID MP-X Ionic LiquidMPEGA IRG 184 EB-230 KBM 403 Type phr Type phrCE6 F 100 None 0.25 0.75 0.1 E14 F 100 SPA TBMA 10 10 0.25 0.75 0.1 E15 F 100 SPA BMI 15 10 0.25 0.75 0.1 E16 F 100 SPA OMI 15 10 0.25 0.75 0.1 E17 F 100 AMPS OMI 15 10 0.25 0.75 0.1 E18 F 100 SPA BMI 5 0.25 0.75 0.1 E19 F 100 SPA BMI 10 0.25 0.75 0.1 E20 F 100 SPA BMI 10 10 0.25 0.75 0.1 E21 F 100 SPA OMI 5 0.25 0.75 0.1 E22 F 100 SPA OMI 10 0.25 0.75 0.1 E23 F 100 SPA OMI 10 10 0.25 0.75 0.1E29 F 100 SPA OMI 15 10 0.25 0.75 0.1Table 7. Data for the adhesive compositions.Rheology Tensile Push Out Temperature Ramp 1 day, CTH Peel(1Hz) SS to SS Adhesion, 1 circleID Caliper day CTH on(microns) SS, 12’7minG’ Initial Peak stress (N / mm) Peak after % 25 °C 50 V,Stre Stress (°C) (kPa) ss 1 min(MPa) (MPa) Reduction E1 200 -16 107 0.76 0.49 0.09 81% E2 200 -2 151 0.78 0.80 009 89% E3 200 -1 316 0.85 1.34 0 19 86% E4 200 -4 171 0.78 1.06 034 68% E5 200 -19 264 0.79 1.29 055 58% E6 200 -19 132 0.62 0.70 020 72% E7 100 -7 117 0.99 1.26 046 63% CE1 200 -7 317 0.45 0.65 0.65* 0%E8 100 -13 80 0.66 0.54 0.01** 99%E9 100 -15 72 0.62 0.55 0.03** 95% E10 100 -28 65 0.43 0.53 0.16** 70% Ell 100 -39 46 0.57 0.47 004 91% E12 50 -30 52 0.45 0.83 024 72% CE2 50 -30 64 0.75 1.26 1.76 0% E13 25 -7 344 0.48 0.33 007 77% CE3 200 -3 267 0.75 0.91 092 0% CE4 200 -11 257 0.01 0 N / A N / A CE5 200 -11 244 0.35 0.46 037 19% CE6 100 -45 57 0.33 0.39 029 26% E14 100 -42 28 0.56 0.39 0 13 67% E15 100 -43 53 0.38 0.30 000 100% E16 100 -43 45 0.37 0.21 003 83% E17 100 -38 45 0.36 0.42 0 11 72% E18 100 -42 36 0.39 N / T N / T N / T E19 100 -42 64 0.43 0.51 020 61% E20 100 -42 47 0.35 0.25 002 92% E21 100 -42 55 0.42 N / T N / T N / T E22 100 -42 55 0.45 N / T N / T N / T E23 100 -41 64 0.34 N / T N / T N / T E24 100 -10 74 0.87 0.50 007 85% E25 100 -10 85 0.96 0.59 001 98% E26 200 -29 182 0.39 0.87 0.194 78% E27 200 -29 153 022 061 0012 98% E28 200 -22 56 NTT N / T N / T N / TE29 100 -43 45 0.37 0.21 003 83% *3 minute data**5 minute dataN / T = not testedN / A= unable to testTable 8. Optical clarity and creep test data.Creep Test95 kPa, 25 °CID Transmittance b* Haze (%)Max % RecoveryStrain (%)7E16 92.4% 0.18 0.61 636% 97%E17 92.3% 0.19 0.38 779% 74%E18 92.3% 0.18 0.66 839% 63%E20 92.3% 0.20 1.10 937% 79%E21 92.4% 0.17 0.24 451% 96%E22 92.4% 0.19 0.46 416% 99%E23 92.4% 0.17 0.33 733% 89%E29 92.4% 0.18 0.61 651% 98%Table 9. Rheometer Adhesion Strengthening Test Method.Rheometer Adhesion StrengtheningIDInitial Energy Final Energy PerPer Unit Area Unit Area after %Change afterbefore Voltage Voltage: (0.1 Hz,50V, 1 min) Voltage(N / cm) (N / cm)CE6 0.65 0.65 0%E15 1.12 2.50 123%E16 1.05 1.72 64%E17 1.15 2.34 199%E18 1.31 3.04 131%E19 1.06 4.02 280%E20 0.83 2.35 184%E21 0.83 1.52 83%E22 1.26 2.76 119%E23 0.63 1.48 136%E28 2.53 3.26 27%Table 10. Electrical Debonding Peel Test ResultsPeel Force afterID after 50 V, 1 min(N / cm)E11 0.2E16 0.2E29 0.1

[0263] Other modifications and variations to the present disclosure may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present disclosure, which is more particularly set forth in the appended claims. It is understood that aspects of the various embodiments may be interchanged in whole or part or combined with other aspects of the various embodiments. All cited references, patents, or patent applications in the above application for letters patent are herein incorporated by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. The preceding description, given in order to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, w hich is defined by the claims and all equivalents thereto.

Claims

What is claimed is:

1. A polymerizable composition comprising:a) a C1-C30 alkyl (meth)acrylate ester monomer; andb) a polymerizable ionic liquid, wherein the anion of the ionic liquid comprises a polymerizable functional group.

2. The polymerizable composition of claim 1, wherein the C1-C30 alkyl (meth)acrylate ester monomer comprises methyl acrylate, iso-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, iso-decyl acrylate, n-butyl acrylate. 2-methy Ibuty 1 acrylate, n-hexyl acrylate, dodecyl acrylate, strearyl acry late, heptadecyl acry late or 6-methylheptyl acrylate.

3. The polymerizable composition of claim 1 or claim 2, wherein the C1-C30 alkyl (rneth)acrylate ester monomer is present in an amount of 30 wt.% to 95 wt.%, based on a total weight of polymerizable components.

4. The polymerizable composition of any of claims 1 to 3, further comprising a crosslinker.

5. The polymerizable composition of any of claims 1 to 4. further comprising an ethoxy group-containing (meth)acrylate monomer.

6. The polymerizable composition of any of claims 1 to 5. further comprising a carboxylic acidcontaining (meth)acrylate monomer in an amount of less than 2 parts per hundred parts resin (phr) of the polymerizable composition.

7. The polymerizable composition of any of claims 1 to 6. further comprising a (meth)acrylate macromer comprising one or more of a polyethylene oxide) group, a polypropylene oxide) group, a poly(ethylene oxide-co-propylene oxide) group, a poly(tetrahydrofuran) group; a poly(ester) group, or combinations thereof.

8. The polymerizable composition of any of claims 1 to 7. further comprising an additive comprising at least one of a filler, a tackifier, a plasticizer, an adhesion promoter, a stabilization agent, a corrosion inhibitor, a colorant, an antioxidant, a UV absorber, or a polymer having a glass transition temperature of at least 40 degrees Celsius.

9. The polymerizable composition of any of claims 1 to 8. wherein the polymerizable functional group of the anion of the ionic liquid comprises at least one of a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an alcohol group, an epoxy group, a primary or secondary’ amino group, or a thiol group.

10. The polymerizable composition of any of claims 1 to 9, wherein the ionic liquid comprises at least one of an imidazolium, an ammonium, a pyridinium, a phosphonium, a sulfonium, or an iodonium ion.

11. The polymerizable composition of any of claims 1 to 10, wherein the ionic liquid comprises at least one anion having a polymerizable group which comprises a sulfate, a sulfonate, a carboxylate, a phosphate, a phosphonate, a phosphorus-containing ion, a borate, a phenyl borate, an oxalato borate, a nitrate, an imide, or a bis(sulfonyl)imide.

12. The polymerizable composition of any of claims 1 to 11, wherein the ionic liquid comprises at least one anion having a polymerizable group which comprises a sulfonate.

13. The polymerizable composition of any of claims 1 to 12, further comprising a second monomer that is different than the C1-C30 alkyl (meth)acrylate ester monomer.

14. The polymerizable composition of claim 13, wherein the second monomer comprises a Cl -C30 alkyl (meth)acrylate ester monomer that is different from component a), a nitrogen-containing monomer, a hydroxy-containing monomer, an ethoxy containing monomer, an epoxy-containing monomer, an acidcontaining monomer, or a nonpolar monomer having a glass transition temperature (Tg) of greater than 10°C to 200°C.

15. The polymerizable composition of claim 14, wherein the second monomer comprises a nitrogencontaining monomer and / or a hydroxy-containing monomer.

16. The polymerizable composition of claim 15, wherein the second monomer is a first nitrogencontaining monomer that is an acrylamide monomer and the polymerizable composition further comprises a third monomer that is a second nitrogen-containing monomer that has a nitrogen atom directly attached to a vinyl group.

17. The polymerizable composition of any of claims 13 to 16. wherein the second monomer is a polymerizable anion ionic liquid.

18. The polymerizable composition of claim 17, wherein the second monomer comprises 2-acrylamido-2-methyl-1-propanesulfonate N-octyl-N'-methylimidazolium or N-vinyl-N’-alky limidazolium bis(fluorosulfonyl)imide.

19. The polymerizable composition of claim 14, wherein the second monomer comprises a C1-C30 alkyl (meth)acrylate ester monomer that is different from component a).

20. An at least partially polymerized reaction product of the polymerizable composition of any of claims 1 to 19.

21. A pressure sensitive adhesive article comprising an adhesive composition comprising the at least partially polymerized reaction product of claim 20, wherein the adhesive composition is disposed on at least a portion of a substrate.

22. The adhesive article of claim 21, wherein the substrate is a liner comprising a release agent, a backing, or a carrier.

23. The adhesive article of claim 21 or claim 22, further comprising a second adhesive layer, wherein the substrate is a carrier and the substrate is disposed between the adhesive composition and the second adhesive layer.

24. The adhesive article of claim 22 or claim 23, wherein the carrier comprises a conductive material.

25. The adhesive article of claim 24, wherein the conductive material is transparent.

26. The adhesive article of any of claims 21 to 25, wherein the adhesive composition exhibits a tensile pushout strength of greater than 0.2 megaPascals (MPa), as determined by the Tensile Pushout Test Method.

27. The adhesive article of any of claims 21 to 26, wherein the adhesive composition exhibits a decrease in tensile pushout strength of at least 50% following subjection to 9 volts (V), 10 V, 20 V, 30 V, 40 V, or 50 V, for one minute, as determined by the Tensile Pushout Test Method.

28. The adhesive article of any of claims 21 to 27, wherein the adhesive composition exhibits a decrease in peel strength of at least 50% following subjection to 50 volts (V) for one minute, as determined by the Peel Adhesion Test Method.

29. The adhesive article of any of claims 21 to 28, wherein the adhesive composition has a glass transition temperature (T ) of -35 degrees Celsius or lower.

30. The adhesive article of any of claims 21 to 29, wherein the adhesive composition exhibits a maximum strain of 300% or greater and a recovery of 50% or greater, as determined by the Creep Test Method.

31. The adhesive article of any of claims 21 to 30, wherein the adhesive composition exhibits an increase in adhesion strength of at least 20% following subjection to an alternating current, as determined by the Rheometer Adhesion Strengthening Test Method.

32. A polymerizable composition comprising an adhesive precursor and at least one polymerizable ionic liquid selected from the group consisting of tributylmethylammonium aery loxy -succinyl- 1-propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-1 -propanesulfonate, l-octyl-3-metliy limidazolium aery loxy -succinyl- 1 -propanesulfonate, 1 -buty 1-3 -methy limidazolium aery loxy -succinyl- 1 -propanesulfonate, trimethylammonium ethyl acrylate acryloxy-succinyl-l-propanesulfonate, 1-octy 1-3 -methy limidazolium 3-sulfopropyl acrylate, octyldimethyl-2-hydroxyethylammonium 3-sulfopropyl acrylate, octyldimethyl-2-hydroxyethylammonium acrylamido-2-methyl-l-propanesulfonate. tetrabutylphosphonium 3-sulfopropyl acrylate, tetrabutylphosphonium acrylamido-2-methyl-1-propanesulfonate, trimethylammonium ethyl acrylate 3-sulfopropyl acrylate, trimethylammonium ethyl acry late acrylamido-2-methyl-l-propanesulfonate, tributylmethylammonium 3-sulfopropyl acrylate tributy lmethylammonium acrylamido-2-methyl-l-propanesulfonate. and l-octyl-3-methylimidazolium acryloxy-succinate.

33. A polymerizable ionic liquid selected from the group consisting of tributylmethylammonium acryloxy-succinyl-1 -propanesulfonate, tetrabutylphosphonium acryloxy-succinyl-l-propanesulfonate. 1-octyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, l-butyl-3-methylimidazolium acryloxy-succinyl-1 -propanesulfonate, trimethylammonium ethyl acrylate acryloxy-succinyl-1 -propanesulfonate, and l-octyl-3-methylimidazolium acryloxy-succinate.

34. An article comprising a polymerizable composition of any of claims 1 to 19 disposed on at least a portion of a substrate.

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