FOR USE IN HIGH AND LOW HUMIDITY ENVIRONMENTS

Inventors: Yufen Hu, Stanislaw Rachwal, Jie Cai, Eduardo Aguirre, Hongxi Zhang, and Peng

Wang

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of United States Provisional Application Nos. 62/749,478, filed October 23, 2018, and 62/876,394, filed July 19, 2019, both of which are incorporated by reference in their entireties.

FIELD

The present disclosure relates to compounds and compositions for use as corrosion resistant coatings and adhesives that may be de-bonded from a surface to which they are bonded without harm to that surface upon the application of an electromotive force. Some embodiments include methods for de-bonding adhesives and coatings from substrate surfaces in high and low humidity environments. In some embodiments, the adhesive may comprise ionic liquid salt compositions.

BACKGROUND

In the electronic arts there is a need for securing and removing device wafers to a metal carrier for processing and assembly of processed components for final assembly. Typically, pressure sensitive adhesives are widely incorporated for securing and removing of the device wafers from metal carriers and processed components for final assembly. These pressure sensitive adhesives leave an adhesive residue on the metal carriers, requiring an expensive and time-consuming cleaning process.

In recent years there have been reports involving commercial applications of adhesives containing ionic compositions. More specifically there are reports of l-ethyl-3- methylimidazolium bis(fluorosulfonyl)imide for use as an electrochemically de-bondable adhesive. Re-workable adhesives containing ionic compositions offer a cost effective alternative to the present pressure sensitive adhesives with the added advantage of producing no adhesive residue on a metalized substrate. However, adhesive containing ionic compositions are relatively corrosive to metallic surfaces. It has also been observed that certain adhesive compositions containing ionic compositions do not de-bond when exposed to low humidity/arid conditions.

Thus, there remains need for new adhesive coatings that can be de-bonded from a metal surface in a variety of environmental conditions while providing resistance to metal corrosion on the electrically conductive surfaces to which they are applied.

The present disclosure discloses a low-cost adhesive with strong adhesive qualities while providing resista nce to metal corrosion and low humidity/arid environment de-bonding without leaving adhesive residue on a metal substrate.

SUMMARY

The present disclosure generally relates to electrochemical adhesive compositions capable of strong substrate bonding or coating, that are capable of electrochemically de bonding adherents which are bound together. These adhesives can de-bond adherents in both low and high humidity environments with the application of an electromotive force. Some embodiments include an electrochemically de-bondable adhesive composition comprising: a polymer matrix; an ionic compound dispersed in the polymer matrix; and a conductivity agent that is soluble with the ionic compound in the polymer matrix at room temperature; wherein, upon application of an electromotive force, the adhesive composition is de-bondable from an adherent surface in a high humidity or low humidity environment. Some embodiments include an adhesive sheet comprising an electrochemically de- bondable ad hesive composition described herein, wherein the sheet is bonded to two electrically conductive substrates such that the substrates stay in fixed relation to one another in the absence of an electromotive force, and wherein the sheet is de-bonded from the two electrically conductive substrates in the presence of an electromotive force. These and other embodiments are described in greater detail below. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of a device incorporating an embodiment of a compound described herein.

FIG. 2 is a schematic of a device incorporating an embodiment of a compound described herein.

FIG. 3 is a schematic of a device used in testing the adhesion properties of the compositions described herein.

FIG. 4 is a schematic of a device used in testing the ionic conductivity of the embodiments of compounds described herein.

FIG. 5 is an illustrative representation of the equivalent circuit of the device used for the calculation of ionic conductivity of embodiments of compounds described herein.

DETAILED DESCRIPTION

Some embodiments include an electrochemically de-bondable adhesive composition comprising a polymer matrix. In some embodiments, the electrochemically de-bondable adhesive composition may comprise an ionic compound. The ionic compound may comprise a high molecular weight compound. In some embodiments, the electrochemically de- bondable adhesive composition may comprise a conductivity agent. The conductivity agent may comprise an ammonium cation and a low molecular weight anion, and when the conductivity agent is mixed with the ionic compound and the polymer matrix to form a composition, the composition is soluble at room temperature. In some embodiments, the electrochemically de-bondable adhesive composition may further comprise a water retention agent. In some embodiments, the electrochemically de-bondable composition described above may further comprise an anti-corrosion compound. In some embodiments, the electrochemically de-bondable adhesive composition may further comprise a cross-linker.

In some embodiments, the polymer matrix may comprise an acrylic polymer. In some embodiments, the polymer matrix may comprise a butyl acrylate monomer, an acrylic acid monomer, or a combination thereof. In some embodiments, the ionic compound may comprise a cation of the following formula: Formula 1.

With respect to Formula 1, in some embodiments, R ¹ may be C ₁ -C ₃ alkyl. In some embodiments, R ³ may be C ₁ -C ₃ al kyl.

In some embodiments, the ionic compound may contain an imide-containing anion. In some embodiments, the imide-containing anion may comprise a sulfonylimide anion.

In some embodiments, the electrochemically de-bondable adhesive may form an adhesive sheet. In some examples, the adhesive sheet can be capable of de-bonding adherents in high humidity environments. In other embodiments, the adhesive sheet may be capable of de-bonding adherents in low humidity environments.

As used herein, the term "electrochemically de-bondable adhesive composition" refers to adhesive compositions that may be de-bonded, or have no adhesion or reduced adhesion, when an electromotive force (electrical current) is applied across the composition. The electrochemically de-bondable adhesive composition of the present disclosure may be de-bonded from the substrates to which they are adhered by the application of an electrical current passing through the composition.

As used herein the term "low humidity" refers to environments where the amount of water vapor present in the air is less than 50% of the amount needed for saturation at the given temperature.

As used herein the term "high humidity" refers to environments where the amount of water vapor present in the air is 50% or more of the amount needed for saturation at the given temperature.

At 100% humidity, the air is saturated with water.

As used herein, the term "high molecular weight" refers to compounds with a molecular weight greater than 290 g/mol. As used herein, the term "low molecular weight" refers to compounds with a molecular weight that is 290 g/mol or less.

The current disclosure describes an electrochemically de-bondable adhesive composition capable of separating from an adherent in a high humidity and/or a low humidity environment which may comprise a polymer matrix, an ionic compound, and a conductivity agent, wherein the ionic compound may comprise a high molecular weight compound and a conductivity agent may comprise an ammonium cation and a low molecular weight anion and when the ammonium cation and low molecular weight anion is mixed with the ionic compound and the polymer matrix to form a composition, the composition is soluble and homogenous at room temperature. In some embodiments, the electrochemically de- bondable adhesive composition may further comprise a water retention agent. In some embodiments, the electrochemically de-bondable adhesive composition may further comprise an anti-corrosion compound. In some embodiments, the electrochemically de- bondable adhesive composition may include a polymer matrix, the polymer matrix may comprise an acrylic polymer. I n some embodiments, the electrochemically de-bondable adhesive composition may be separated from an adherent in a high humidity environment. In other embodiments, the electrochemically de-bondable adhesive composition may be separated from an adherent in a low humidity environment.

In some embodiments, the electrochemically de-bondable adhesive composition may comprise a polymer matrix. I n some embodiments, the electrochemically de-bondable adhesive composition may comprise an ionic compound. The ionic compound may comprise a high molecular weight compound. In some embodiments, the electrochemically de- bondable adhesive composition may comprise a conductivity agent. The conductivity agent may comprise a low molecular weight ionic compound. In some embodiments, the electrochemically de-bondable adhesive composition may further comprise a water retention agent. In some embodiments, the electrochemically de-bondable adhesive composition described above may further comprise an anti-corrosion compound. In some embodiments, the electrochemically de-bondable adhesive composition may further comprise a cross-linker. In some embodiments, the electrochemically de-bondable adhesive composition may be capable of separating adherents in high humidity environments (e.g., within a range of 50- 100% humidity). I n still other embodiments, the electrochemically de-bondable adhesive composition may be capable of separating adherents in low humidity environments (e.g., within a range of 0-50% humidity). In some embodiments, the electrochemically de-bondable adhesive composition may have a reduced corrosion effect on the adherent substrates.

Polymer Matrix (acrylic polymer)

In some embodiments, the electrochemically de-bondable adhesive composition may comprise a polymer matrix. I n some embodiments, the polymer matrix may comprise an acrylic polymer. In some embodiments, the acrylic polymer may contain a monomer unit derived from an alkyl acrylate ester containing a CI-CM alkyl group, an alkyl methacrylate ester containing a CI-CM alkyl group, and/or a carboxyl-containing unsaturated monomer such as acrylic acid. In some embodiments, the acrylic polymer may contain a monomer unit derived from a CI-CM alkyl, or an C ₁ -C ₃ alkoxy alkyl group. I n some embodiments, the alkyl (meth)acrylate ester is butyl acrylate. I n some embodiments, the carboxyl-containing unsaturated monomer may comprise a (meth)acrylic acid (e.g. acrylic acid or methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. The acrylic polymer may be composed of (i) butyl acrylate, and (ii) acrylic acid as raw material monomers. The acrylic polymers may be used alone or in combinations of two or more.

The butyl acrylate may be used as the main monomer component in the composition. By taking advantage of its basic characteristic, its tackiness, butyl acrylate plays a major role in the electrochemically de-bondable adhesive composition's adhesion properties. The carboxyl-containing unsaturated monomer (acrylic acid) helps improve the mechanical stability of the acrylic polymer.

In some embodiments, the amount of butyl acrylate may be 80 wt% to 100 wt% by weight, 80 wt% to 97 wt% by weight, or 90-95 wt% by weight in the total amount (100% by weight) of the raw material monomers constituting the polymer matrix of the present disclosure. I n some embodiments, the amount of butyl acrylate may be about 80-82 wt%, about 82-84 wt%, about 84-86 wt%, about 86-88 wt%, about 88-90 wt%, about 90-92 wt%, about 92-94 wt%, about 94-96 wt%, about 96-98 wt%, about 98-99.5 wt%, or about 85 wt%, about 90 wt%, about 95 wt%, or any wt% in a range bounded by any of these values. In some embodiments, the amount of acrylic acid may be about 0 wt% to 20 wt% by weight of the total amount (100% by weight) of the raw material monomers constituting the polymer matrix in the present disclosure. In some embodiments, the amount of acrylic acid may be about 0 wt% to 20 wt%, about 0.5-10 wt% about 1-7.5 wt%, about 3-5 wt%, about 3- 3.5 wt%, about 3.5-4 wt%, about 4-4.5 wt%, about 4.5-5 wt%, about 4.2-4.4 wt%, about 4.4-

4.6 wt%, about 4.6-4.8 wt%, about 4.8-5 wt%, about 4.4-4.5 wt%, about 4.5-4.6 wt%, about 4.6-4.7 wt%, or about 0.5 wt%, about 3 wt%, about 5 wt%, about 7.5 wt% or about 10 wt%, or any wt% in a range bounded by any of these values.

In some embodiments, the polymer matrix may have a glass transition temperature T _g of 0 °C or lower.

It is believed that the electrochemical peeling rate of an adhesive is directly related to the capacitance of the adhesive. Capacitance may be shown by the following equation:

where C _adh is the capacitance of the adhesive; e ₀ equals a constant, permittivity of vacuum; e _r is the relative dielectric constant and d is the thickness of the adhesive. It is further believed that when an adhesive is bound to a metal substrate, a metal oxide layer is formed between the adhesive and metal substrate interface. When an electromotive force or a current is passed between the bound metal substrate and the adhesive, electrons flow through the adhesive and to the metal oxide layer. Once the electrons localize to the metal oxide layer a redox reaction occurs on the cathode side, resulting in the reduction of the metal oxide layer and weakening of the adhesive's adhesion. By increasing the capacitance of the adhesive, the electron flow rate will increase and allow for faster adhesive peel (de-bonding) times.

Ionic Compound

As used herein the term "imidazolium" refers to the general chemical group:

As used herein the term "amino" refers to the uncharged chemical group:

As used herein the term "ammonium" refers to the overall charged or net charged chemical compound: N R ₄ ⁺ . Salts containing NR ₄ ⁺ groups are termed "ammonium salts."

As used herein the term "onium" refers to the overall charged or net charged cation formed by the protonation or alkylation of a pnictogen, chalcogen, or halogen group. The oldest known onium cation is the ammonium cation, NH ₄ ⁺ .

As used herein the term bis(fluorosulfonyl)imide and/or "sulfonylimide" refers to the charged or net uncharged chemical group:

The electrochemically de-bondable adhesive composition of the present disclosure includes an ionic compound. I n some embodiments, an ionic compound may comprise an ionic liquid. An ionic liquid refers to molten salt which may exhibit a liquid state at room temperature (about 25 °C). In some embodiments, an ionic compound may comprise a nitrogen containing onium salt. Since electrochemical de-bondability is preferred in the current disclosure, a nitrogen-containing onium salt comprising an organic cation component and an anion component is preferably used. In some embodiments, the onium cation may comprise an imidazolium cation. I n some embodiments, the ionic compound may comprise a cation represented by Formula 2: Formula 2.

In some embodiments, R ¹ of Formula 2 may be C1-C3 alkyl, R ² , R ⁴ , and R ⁵ may be hydrogen or C1-3 alkyl, and R ³ may represent a C1-C3 alkyl.

In some embodiments, R ¹ and R ³ of Formula 1 or Formula 2 may be independently Ci- alkyl, such as methyl (also depicted as -CH ₃ , or ), ethyl (also depicted as -CH ₂ CH ₃ , or propyl (also depicted as -CH ₂ CH ₂ CH ₃ or or combinations and/or mixtures thereof.

In some embodiments, the imidazolium cation is l-ethyl-3-methylimidazolium:

In some embodiments, an ionic compound described above, comprises an anion, such as a sulfonylimide anion. In some embodiments, the sulfonylimide anion may be:

In some embodiments, the electrochemically de-bondable adhesive composition may comprise an ionic compound having a reduced Lewis acidity. In some embodiments, the cation of the ionic compound may have a reduced size, e.g., less than 160 g/mole. In some embodiments, the amount of the ionic compound may be about 0 to 10 wt% by weight of the % of total weight (100%) of the raw material monomers constituting the polymer matrix. I n some embodiments, the amount of the ionic compound may be about 2.5 wt% to 5.5 wt%. In some embodiments, the amount of the ionic compound may be about 0.01 wt% to about 10 wt%, about 0.01-0.1 wt%, about 0.1-0.5 wt%, about 0.5-1 wt%, about 1-2.5 wt%, about

9

5UB5TITUTE SHEET (RULE 26) 2.5-5 wt%, about 5-7.5 wt%, about 7.5-10 wt%, %, about 3-3.5 wt%, about 3.5-4 wt%, about 4-4.5 wt%, about 4.5-5 wt%, about 4.2-4.4 wt%, about 4.4-4.6 wt%, about 4.6-4.8 wt%, about 4.8-5 wt%, about 4.4-4.5 wt%, a bout 4.5-4.6 wt%, about 4.6-4.7 wt%, or about 2.5 wt%, about 4 wt%, about 5.5 wt%, about 7 wt% or about 8.5 wt%, or any wt% in a range bounded by any of these values.

As for the aforementioned ionic compound, a commercially available ionic compound may be used, e.g., EMIM-FSI, or it may be synthesized as described in the United States Patent No. 7,901,812. However, the ionic compound may be synthesized by any suitable method.

Conductivity Agent The electrochemically de-bondable adhesive composition may include a conductivity agent (conductivity salt). The conductivity agent may increase the conductivity across the adhesive, thus al lowing for increased electron flow through the adhesive. The conductivity agent may comprise a high molecular weight ionic compound, wherein the high molecular weight compound may comprise an ammonium cation a nd a low molecular weight anion. The conductivity agent may comprise a low molecular weight ionic compound, wherein the low molecular weight compound may comprise an ammonium cation and a low molecular weight anion. When the conductivity agent, comprising a low molecular weight ionic compound, is mixed with the ionic compound and the polymer matrix to form a composition, the composition is soluble and homogenous at room temperature. In some embodiments the conductivity agent may comprise a nitrogen-containing onium salt. Since electrochemical de bonding is preferred in the current disclosure, an onium salt comprising an organic ammonium cation component and a low molecular weight anion component is preferably used to help increase the conductivity of the adhesive and help retain water molecules with in the electrochemically de-bondable adhesive. It is believed that the addition of the conductivity agent's cation and anion help preserve water within the adhesive by hydrogen bonding.

In some embodiments, the nitrogen-containing onium salt may comprise quaternary ammonium salts. Not wanting to be limited, some examples of quaternary ammonium salts include tetraalkylammonium salts, dialkyldimethylammonium salts, alkyltrimethylammonium salts, where the alkyl groups are one or more groups containing two (2) to fourteen (14) carbon atoms (C2-C14 alkyl groups) including linear, branched, and cyclic alkyl groups. The quaternary ammonium salt may comprise an hydroxyalkyl ammonium salt of carboxylic acids (including high molecular weight carboxylic acids and unsaturated carboxylic acids. Examples include EFKA 50701, an hydroxyalkyl ammonium salt of high molecular weight carboxylic acid (BASF SE, Ludwigshafen, Germany) and BYK-ES80 (BYK USA, Wallingford, Conn. USA), an hydroxyalkyl ammonium salt of an unsaturated acidic carboxylic acid ester.

In some embodiments, the quaternary ammonium salts may comprise a hydroxyalkyl ammonium salt of an ethyl sulfate. In some embodiments the hydroxyalkyl ammonium salt of ethyl sulfate may further comprise a bivalent alcohol. Examples include Deuteron LE-80, Deuteron LE-100LV, Deuteron LE-151, Deuteron LE-512, Deuteron LE-829 and Deuteron LE- 947 (Deuteron GmbH, Achim Germany).

In some embodiments, the quaternary ammonium salt may comprise a tributylethylammonium salt of ethyl sulfate, such as EFKA 10-6782 (BASF).

In some embodiments, the quaternary ammonium salt may comprise a tris(2- hydroxyethyl)methylammonium salt of methyl sulfate, such as EFKA 10-6783 (BASF).

In some embodiments, the nitrogen-containing onium salt may comprise an imidazolium salt of ethyl sulfate, such as, EFKA 10-6785 (BASF). In some embodiments the nitrogen-containing onium salt may comprise an imidazolium salt of chloride and dicyanamide, such as, EFKA 10-6786 (BASF). In some embodiments, the nitrogen-containing onium salt may comprise an imidazolium salt of nitrate, such as l-ethyl-3-methylimidazolium nitrate (Lolitec, I nc., Tuscaloosa, AL, USA). In some embodiments, the nitrogen-containing onium salt may comprise an imidazolium salt of sulfonate, such as l-ethyl-3- methylimidazolium methanesulfonate (MilliporeSigma, Burlington, MA, USA).

In some embodiments, the conductivity agent may comprise a quaternary ammonium salt, an imidazolium salt, a conductive metal oxide, and/or combinations thereof. In some embodiments, the conductivity agent may comprise an imidazolium cation of the general structure of Formula 1. In some embodiments, the conductivity agent is the imidazolium cation of structure:

In some embodiments, the conductivity agent may include a low molecular weight anion. I n some embodiments, the low molecular weight anion may comprise an ethyl sulfate anion. In some embodiments, the low molecular weight ethyl sulfate anion has the structure:

In some embodiments the low molecular weight a nion may comprise a chloride anion: Cl .

In some embodiments, the low molecular weight anion may comprise a dicyanamide anion of structure:

In some embodiments, the low molecular weight anion may comprise a nitrate anion of structure:

In some embodiments, the low molecular weight anion may comprise a sulfate anion of structure:

In some embodiments, the low molecular weight anion may comprise an ethyl sulfate anion, a chloride anion, a dicyanamide anion, a nitrate anion, a sulfonate anion, and/or a combination thereof. For electrochemically de-bondable adhesive compositions comprise a conductivity agent, any suitable amount of the conductivity agent may be used, such about 0.01 wt% to about 8 wt% by weight of the % of total weight (100%) of the raw material monomers constituting the polymer matrix. I n some embodiments, the amount of the conductivity agent may be about 1.5 wt% to about 5.5 wt%. In some embodiments, the amount of the conductivity agent may be about 0.01 wt% to about 1 wt%, about 0.1-5.5 wt%, about 1-2 wt%, about 2-3 wt%, about 3-4 wt%, about 4-5 wt%, about 5-6 wt%, about 6-7 wt%, about 7-8 wt%, about 0.1-1.5 wt%, about 1.5-2.5 wt%, about 2.5-4 wt%, about 4-5.5 wt%, about 5.5-8 wt%, or about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, or about 4 wt%, about 5 wt%, about 5.5 wt%, or any wt% in a range bounded by any of these values. Water Retention Agent

As used herein the term "water retention agent" refers to an agent which maintains the water content of the adhesive composition within appropriate limits without depleting or enriching the water content.

It is believed that the electrochemical de-bonding rate of an adhesive in a low humidity/arid environment is directly related to the percentage of water contained within the adhesive layer (see aforedescribed formula). This is due to the fact that the relative dielectric constant _r is directly proportional to the % of water in the adhesive, since _r is a measurement of the % of polymer, ionic liquid and the water within the adhesive (e^ e,- polymer* V% _poly m _e r + ionic liquid* V% ionic liquid + £ _/ - water* V% water, wherein Er polymer, £ _/ - ionic liquid 3 nd Er water 3 re COnSta ntS for the polymer, ionic liquid and water, respectively). So small changes in the % of water within the adhesive may be observed in the final e _G value. It is further theorized that when the adhesive composition is contacted to a metalized substrate, that a metal oxide layer forms between and in physical communication with the metal substrate and the adhesive composition. It is believed that water is needed to speed dissolving of the metal oxide layer during de-bonding.

In some embodiments, the electrochemically de-bondable adhesive composition may comprise a water retention agent. In some embodiments, the water retention agent may comprise an anionic polyacrylamide resin. In some examples, the water retention agent may be, for example, Somarex-530 (Somar Corp., Tokyo, Japan).

In some embodiments, the amount of water retention agent may be about 0.01 wt% to about 2.5 wt% by weight of the % of total weight (100%) of the raw material monomers constituting the polymer matrix. In some embodiments, the amount of water retention agent may be about 0.01 wt% to about 0.5 wt%. I n some embodiments, the amount of water retention agent may be about 0.01-0.1 wt%, about 0.1-0.5 wt%, about 0.1-0.2 wt%, about 0.2-0.3 wt%, about 0.3-0.4 wt%, about 0.4-0.5 wt%, about 0.5-1.5 wt%, about 1.5-2.5 wt%, about 0.35-0.36 wt%, about 0.36-0.37 wt%, about 0.37-0.38 wt%, or about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, or about 0.45 wt%, or any wt% in a range bounded by any of these values.

Anti-corrosive compound

In some embodiments, the electrochemically de-bondable adhesive composition may comprise an anti-corrosion compound. The anti-corrosion compound (also known as a "metal deactivator" in the art) may be any single compound or a mixture of compounds that inhibits oxidation of metallic surfaces.

As used herein the term "corrosion" refers to an electrochemical process leading to the oxidation of the metallic substrate, usually with the help of an electrolyte, typically accompanied by the reduction of atmospheric oxygen or water. An anti-corrosion compound is one that inhibits or hinders active corrosion process, i.e., metal oxidation, which would otherwise have occurred in the absence of the compound.

In some embodiments, the anti-corrosive compound may comprise one or more thiazoles, triazoles, benzodiazoles, benzotriazoles, thiodiazoles and/or combination or mixtures thereof. In some embodiments, an anti-corrosive compound may comprise a liquid tolutriazole derivative. I n some embodiments, an anticorrosive compound may comprise an imidazoline derivative. In some embodiments, an anti-corrosive compound may comprise an aminosuccinic acid. In some embodiments, the aminosuccinic acid may comprise a n- acylamino acid. In some embodiments, the n-acylamino acid may comprise an amphiphilic oleic acid derivative. In some embodiments, the amphiphilic oleic acid derivative may comprise n-oleylsarcosine.

The anti-corrosion compound may be any conventional material so long as it meets solubility requirements for the current disclosure. By way of example, the anti-corrosion compounds may include, but are not limited to, lrgamet™30 (liquid triazole derivative, BASF), lrgamet™39 (tolutriazole), Irgamet™ SBT (tetrahydrobenzotriazole, BASF), Irgamet™ 42 (tolutriazole, BASF), lrgamet™L190 (polycarboxylic acid), lrgalube™349, Irgamet™ NPA (4- nonyl phenoxy acetic acid), Ingamet™ BTZ (benzotriazole), Irgacor™ DSSG (n-oleyl sarcosine, BASF), Sarkosykl O (amphiphilic oleic acid, BASF), Amine O (BASF), M-138, M-415, M-238, and M-5365 (Cortec Corporation, St. Paul, MN, USA).

In some embodiments, the amount of the anti-corrosion compound(s) may be about 0 wt% to about 5 wt% by weight of the % of total weight (100%) of the raw material monomers constituting the polymer matrix. In some embodiments, the amount of the anti-corrosion compound may be about 0.01 wt% to about 5 wt%. In some embodiments, the amount of the anti-corrosion compound may be about 0.01-0.05 wt%, 0.05-0.1 wt%, 0.1-0.2 wt%, about 0.2-0.3 wt%, about 0.3-0.4 wt%, about 0.4-0.5 wt%, about 0.5-0.6 wt%, about 0.6-0.7 wt%, about 0.7-0.8 wt%, about 0.8-0.9 wt%, about 0.9-1 wt%, about 1-1.2 wt%, about 1.2-1.4 wt%, about 1.4-1.6 wt%, about 1.6-1.8 wt%, about 1.8-2 wt%, about 2-2.2 wt%, about 2.2-2.4 wt%, about 2.4-2.6 wt%, about 2.6-2.8 wt%, about 2.8-3 wt%, about 3-3.2 wt%, about 3.2-3.4 wt%, about 3.4-3.6 wt%, about 3.6-3.8 wt%, about 3.8-4 wt%, about 4-4.2 wt%, about 4.2-4.4 wt%, about 4.4-4.6 wt%, about 4.6-4.8 wt%, about 4.8-5 wt%, or about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, or about 0.7 wt%, or about 0.8 wt%, or about 0.9 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 3.5 wt%, or about 3.7 wt%, or any wt% in a range bounded by any of these values. Cross-linker

In some embodiments, the electrochemically de-bondable adhesive composition may include a cross-linker. In some embodiments, the electrochemically de-bondable adhesive composition may comprise a cross-linker, such as a high molecular weight polycarbodiimide cross-linker. The polycarbodiimide cross-linker reacts with and is coupled to the hydroxyl group and/or a carboxyl group of the acrylate copolymer matrix thereby forming a cross- linked structure. In another embodiment, the cross-linker may comprise an isocyanate. I n still another embodiment, the cross-linker may comprise an epoxy-based cross-linker.

The polycarbodiimide cross-linker may include any suitable carbodiimide cross-linking agent. For example, a compound having at least two carbodiimide groups (-N=C=N-) may be used and any suitable polycarbodiimide may be used.

The method or means of producing the polycarbodiimide is not limited to the current disclosure. For example, a high molecular weight polycarbodiimide may be prepared by decarbonation condensation reactions of a diisocyanate in the presence of a carbodiimide catalyst. Some examples of diisocyanates include but are not limited to 4,4'- diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 4,4'- diphenylether diisocyanate, 3.3'-dimethyl-4,4'-diphenylether diisocyanate, 2,4-toylene diisocyanate, 2,6-toylene diisocyanate, l-methoxyphenyl-2, 4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and tetramethyl xylene diisocyanate, which may be used alone or in mixtures of two or more.

The carbodiimide catalyst may include phospholene oxides, such as, l-phenyl-2- phospholene-l-oxide, 3-methyl-2-phospholene-l-oxide, l-ethyl-3-methyl-2-phospholene-l- oxide, l-ethyl-2-phospholene-l-oxide, 3-phospholene, and isomers thereof.

In addition, high molecular weight polycarbodiimides may be a commercial product including CARBODILITE ^® (Nisshinbo Chemical Inc., Tokyo, Japan), specifically CARBODILITE V- 01, V-03, V-05., V-07, and V-09, which have excellent compatibility with organic solvents.

In some embodiments, the electrochemically de-bondable adhesive composition may further comprise an epoxy-based cross-linker. The term "epoxy-based cross-linker" refers to a polyfunctional epoxy compound having two or more epoxy groups per molecule. The epoxy- based cross-linker may include glycidylamino cased cross-linkers.

Some examples of an epoxy-based cross-linker may include N,N,N',N'-tetraglycidyl-m- xylenediamine, diglycidy laniline, l,3-bis(N,N-digclycidylaminomethyl)cyclohexane, 1,6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, sorbitol trimethylolpropane, polyglycidyl ethers, diglycidyl adipate, o- diglycidyl phthalate, triglycidyl tris(2-hydroxyethyl)isocyanurate, resorcinol diglycidyl ether, and bis phenol-S diglycidyl ether; as well as epoxy-based resins having two or more epoxy groups per molecule. The cross-linking agents may be used alone or in a combination of two or more.

In addition, epoxy-based cross-linkers may be commercial products including, "TETRAD-C™" (l,3-bis(N,N-digclycidylaminomethyl)cyclohexane) and/or "TETRAD-X™" (N,N,N',N'-tetraglycidyl-m-xylenediamine,) (Mitsubishi Gas Chemical Company, Inc., Tokyo, Japan).

In some embodiments, the amount of cross-linker may be about 0.25 wt% to about 1.25 wt% by weight of the % of total weight (100%) of the raw material monomers constituting the polymer matrix. In some embodiments, the amount of high molecular weight cross-linker may be about 0.25 wt% to about 0.4 wt%, about 0.4-0.55 wt%, about 0.55-0.7 wt%, about 0.7-0.85 wt%, about 0.85-1 wt%, about 1-1.15 wt%, about 1.15-1.25 wt%, about 0.8-0.9 wt%, or about 0.25 wt%, about 0.35 wt%, about 0.5 wt%, about 0.75 wt%, about 1 wt%, about 1.25 wt%, or any wt% in a range bounded by any of these values.

Adhesive Sheets

The electrochemically de-bondable adhesive composition of the present disclosure may comprise adhesive sheets, films, or layers. A method for forming an adhesive sheet, film or layer with the present disclosure is not limited and a ny conventional method, or any other suitable method, may be employed. In some embodiments, the thickness of the electrically conductive layer may vary. In some embodiments, the electrically conductive layer has a thickness from about 2 nm to about 200 miti.

The electrochemically de-bondable adhesive composition of the present disclosure may contain various kinds of additives other than those described above. Examples of the various kinds of additives include a pigment, a filler, a leveling agent a dispersant, a n antioxidant, an ultraviolet absorber, a light stabilizer, a de-foaming agent, an antioxidant, a preserver, and the like.

In some embodiments, the selectively adhesive compositions described herein may be formulated to minimize corrosion of the above described electrically conductive substrates under conditions of prolonged high humidity and high temperature. The adhesive composition is capable of maintaining two such electrically conductive substrates in fixed relation to each other during and after being subjected to Accelerated Aging Test Method I I (preferably after exposure to 60°C/90% RH for a period of time described above). Selective adhesive separating layers comprising the compounds disclosed herein may be fabricated using known techniques, as informed by the guidance provided herein.

It is contemplated that the electrochemically de-bondable adhesive compositions described herein could be utilized for a number of different applications.

Referring to FIGs. 1 and 2, additional details regarding the bonding and de-bonding of adherents using the electrical ly de-bondable adhesive compositions described herein are provided. An apparatus, such as apparatus 200, consists of an adhesive material, such as adhesive material 203, which includes an electrochemically de-bondable adhesive composition described herein, providing a layer or coating interposed between an electrically conductive surface 206 of substrate 202 and an electrically conductive surface 207 of substrate 201. I n one form, one or both substrates may be formed of an electrically conductive material such that one or both of electrically conductive surfaces is/are formed of the same material as the remainder of the substrate. However, it is possible in other forms to use one or more electrically conductive materials for electrically conductive surfaces which are different from the material(s) forming the substrate(s). Similarly, it should be appreciated that one or both substrates could be formed of one or more materials which are not electrically conductive provided that the surfaces are electrically conductive. I n these forms, electrically conductive surfaces may be provided as a coating or layer on the substrates.

In the illustrated form, electrically conductive surfaces are electrically coupled to or in electrical communication with a power source 204 in a closeable electrical circuit that includes an intervening switch 205. I n one form, power source may be a direct current power supply that provides a DC voltage in the range of about 3V to 100V, although other variations are contemplated. When the intervening switch is closed (e.g. as depicted in FIG. 2), the electrical potential is applied between the electrically conductive surfaces in order to de-bond the adhesive material from one or both of electrically conductive surfaces and, as a result, allow substrates to be physically separated from one another.

In one form, one or both of the substrates may include an electrically conductive carbonaceous material or an electrically conductive metal. As suggested above, one or both of the substrates may also include an electrically conductive layer which may be formed of a metallic material such as, but not limited to, aluminum. The electrically conductive layer may include a conventional material such as a metal, mixed metal, alloy, metal oxide, and/or composite metal oxide, or it may include a conductive polymer. Examples of suitable metals for the electrically conductive layer include the Group 1 metals, the metals in Groups 4, 5, 6, and the Group 8-10 transition metals. Further examples of suitable metals for the electrically conductive layer include stainless steel, Al, Ag, Mg, Ca, Cu, Mg/Ag, LiF/AI, CsF, and/or CsF/AI and/or alloys thereof.

If an electrically conductive layer is present, it may have a thickness in the range of about 1 nm to about 1000 pm, about 1-10 nm, about 10-20 nm, about 20-30 nm, about 30- 40 nm, about 40-50 nm, about 50-60 nm, about 60-70 nm, about 70-80 nm, about 80-90 nm, about 90-100 nm, about 100-110 nm, about 110-120 nm, about 120-130 nm, about 130-140 nm, about 140-150 nm, about 150-160 nm, about 160-170 nm, about 170-180 nm, about 180- 190 nm, about 190-200 nm, about 200-300 nm, about 300-400 nm, about 400-500 nm, about 500-600 nm, about 600-700 nm, about 700-800 nm, about 800-900 nm, about 900-1000 nm, about 1-10 pm, about 10-20 pm, about 20-30 pm, about 30-40 pm, about 40-50 pm, about 50-60 pm, about 60-70 pm, about 70-80 pm, about 80-90 pm, about 90-100 pm, about 100- 110 miti, about 110-120 miti, about 120-130 miti, about 130-140 miti, about 140-150 miti, about 150-160 miti, about 160-170 miti, about 170-180 miti, about 180-190 miti, about 190-200 miti, about 200-300 miti, about 300-400 miti, about 400-500 miti, about 500-600 miti, about 600-700 miti, about 700-800 miti, about 800-900 miti, about 900-1000 miti, about 20 nm to about 200 miti, about 20 nm to about 200 nm, or about any thickness bound by any of these ranges.

While not previously discussed, it should be appreciated that the electrochemically de-bonda ble adhesive compositions described herein may provide various properties which are desirable for certain applications. For example, in some forms, the compositions disclosed herein may eliminate or reduce corrosion of the electrically conductive surfaces on which they are positioned. In one embodiment, for example, the compositions disclosed herein include components which have lower acidity with respect to the environment immediately adjacent to the electrically conductive surfaces. In one aspect, an adhesive material may include one or more materials, in addition to the cationic and anionic compounds themselves, which may be used to reduce the corrosiveness of the ionic cations and/or anions immediately adjacent the electrically conductive surfaces. The corrosive effect of an adhesive material may be assessed pursuant to the procedures described in ASTM G69-12 (Standard Test Method for Measurement of Corrosion Potentials of Aluminum Alloys). Additional procedures for assessing the corrosive effect of an adhesive material on the electrically conductive surfaces are described in the Examples of the subject application.

In one form, an adhesive material including an electrochemically de-bondable adhesive composition disclosed herein may be chemically inert relative to an electrically conductive electrode or an electrically conductive material; i.e., there is a lack of (or minimal presence of) undesired reactions between a metal electrode and the adhesive material. Undesired reactions may include, for example, corrosive degradation of the metal electrode, dissolution of the metal in the selectively adherent adhesive and/or pitting of the metal electrode. An adhesive material including an electrochemically de-bondable adhesive composition disclosed herein may be chemically inert relative to aluminum, copper, bronze, zinc, lead, stainless steel, carbonaceous material, and/or mixtures thereof, just to provide a few examples. In one form, contact of an adhesive material including an electrochemically de-bonda ble adhesive composition disclosed herein upon an electrically conductive surface may result in the absence of, or minimize, any corrosive degradation of the surface for a period of at least or greater than 15 minutes, 30 minutes, 1 hour, 3 hours, 5 hours, 7 hours, 24 hours, 50 hours, 100 hours, 125 hours, 200 hours, 300 hours, 400 hours, 500 hours, 600 hours, 700 hours, 800 hours, 900 hours, or any amount of time in a range bounded by any of these values. In some forms, direct contact of an adhesive material including an electrochemically de-bondable adhesive composition disclosed herein upon an electrically conductive surface may have reduced and/or essentially no corrosive degradation of the surface for one of the time periods identified above in an environment of 60° to 85° C and 85% to 90% relative humidity. In one form, the absence of any corrosive degradation may be demonstrated by a lack of total penetration of an electrically conductive 50 nm thick sheet of aluminum foil for one of the time periods identified above and/or at the environmental conditions identified above.

In one form, an adhesive material including an electrochemically de-bondable adhesive composition described herein may be formulated to minimize corrosion of an electrically conductive surface under conditions of prolonged high humidity and high temperature. For example, an adhesive composition may be capable of maintaining two substrates in fixed relation to each other during and after being subjected to Accelerated Aging Test Method II (preferably after exposure to 60 °C and 85% relative humidity for one of the periods of time identified above). Also, while not previously discussed, it should be appreciated that the ionic compositions disclosed herein may have a molar mass that is less than or equal to about 160 grams per mole.

In some embodiments, the electrochemically de-bondable adhesive compositions described herein may show excellent de-bonding in low humidity environments. In some forms, the electrochemically de-bondable adhesive compositions of the present disclosure leave little or no residue on the substrates to which they have been secured upon de-bonding. Similarly, the electrochemically de-bondable adhesive compositions of the present disclosure leave little or no residue on the substrates to which they have been secured upon de-bonding in high humidity and/or high temperature environments.

EMBODIMENTS: The following specific embodiments are specifically contemplated:

Embodiment 1 An electrochemically de-bondable adhesive composition capable of separating from an adherent in a high humidity and/or a low humidity environment comprising:

a polymer matrix;

an ionic compound, wherein the ionic compound has a high molecular weight; and a conductivity agent, the conductivity agent comprises a small anion containing low molecular weight ionic compound that when combined with the ionic compound within the polymer matrix is soluble at room temperature.

Embodiment 2 The electrochemically de-bondable adhesive composition of embodiment 1, further comprising a water retention agent.

Embodiment 3 The electrochemically de-bondable adhesive composition according to embodiments 1 or 2, further comprising an anti-corrosion compound.

Embodiment 4 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the polymer matrix comprises an acrylic polymer.

Embodiment 5 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the polymer matrix comprises butyl acrylate, acrylic acid and/or combinations or mixtures thereof.

Embodiment 6 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the ionic compound is present in an amount ranging from about 2 wt% to about 20 wt%, or about 2.5 wt% to about 5.5 wt %, per weight of the polymer matrix.

Embodiment 7 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the ionic compound comprises an ionic liquid.

Embodiment 8 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the ionic compound comprises a cation represented by the general formula;

wherein R ¹ is a C ₁ -C ₃ alkyl;

wherein R ² , R ⁴ and R ⁵ are hydrogen; and

wherein R ³ is a C1-C3 alkyl.

Embodiment 9 The electrochemically de-bondable adhesive composition of embodiment 8, wherein the R ¹ and R ³ may be independently selected from one of the following:

3

or combinations or mixtures thereof. Embodiment 10 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the ionic compound cation is:

Embodiment 11 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the ionic compound comprises a sulfonylimide anion.

Embodiment 12 The electrochemically de-bondable adhesive composition of embodiment 8, wherein the sulfonylimide anion is:

Embodiment 13 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the conductivity agent comprises one or more l-ethyl-3- methylimidazolium based ionic liquid selected from l-ethyl-3-methylimidazolium nitrate, l-ethyl-3-methylimidazolium methanesulfonate, l-ethyl-3-methylimidazolium ethyl sulfate, and or combinations thereof. Embodiment 14 The electrochemically de-bondable adhesive composition of embodiment 1, wherein the conductivity agent is present in an amount ranging from about 0.5 wt% to about 5 wt%, or about 1.5 wt% to about 5.5 wt%, per weight of the polymer matrix.

Embodiment 15 The electrochemically de-bondable adhesive composition of embodiment 2, wherein the water retention agent is present in an amount ranging from about 0.01 wt% to about 0.5 wt% per weight of the polymer matrix.

Embodiment 16 The electrochemically de-bondable adhesive composition of embodiment 2, wherein the water retention agent comprises an anionic polyacrylamide resin.

Embodiment 17 The electrochemically de-bondable adhesive composition of embodiment 3, wherein the anti-corrosive compound is present in an amount ranging from about 0 wt% to about 4 wt%, or about 0 wt% to about 2 wt%, per weight of the polymer matrix.

Embodiment 18 The electrochemically de-bondable adhesive composition of embodiment 3, wherein the anti-corrosive compound comprises thiazoles, triazoles, benzodiazoles, benzotriazoles, thiodiazoles, or any combination or mixture thereof.

Embodiment 19 The electrochemically de-bondable adhesive composition of embodiment 1, further comprising a high-molecular weight polycarbodiimide cross-linker.

EXAMPLES

It should be appreciated that the following Examples are for illustration purposes and are not intended to be construed as limiting the subject matter disclosed in this document to only the embodiments disclosed in these examples.

It has been discovered that embodiments of composite ionic compositions and elements described herein reduce the deterioration and/or corrosion of the conductive metal layers described herein. These benefits are further shown by the following examples, which are intended to be illustrative of the embodiments of the disclosure but are not intended to limit the scope or underlying principles in any way. Synthesis of Ionic Liquid Solution:

Example 1. Ionic liquid solution AS110: _ l-Ethyl-3-methyl-imidazolium bis(fluorosulfonyl)imide l-Ethyl-3-methyl-imidazolium bis(fluorosulfonyl)imide (EMIM-FSI) may be made as described in U nited States Patent Nos. 7,901,812.

Preparation of Acryl-Based Polymer Solution

Example 1.2

95 mass parts n-butyl acrylate, 5 mass parts acrylic acid and 125 mass parts ethyl acetate were introduced into a stirring flask attached to a condenser that was equipped with a nitrogen gas inlet. The mixture was stirred at room temperature while introducing the nitrogen gas, for about 1 hour to remove oxygen from the reaction system. 0.2 mass parts azobisisobutyronitrile (AI BN) as an initiator were added, which increased the temperature of the resulting mixture to about 63° ± 2°C, and the mixture was mixed/stirred for about 5-6 hours for polymerization. After stopping the reaction, an acrylic polymer-containing solution resulted, having a solid content of about 30%. The apparent molecular weight of the polymer solution (PI) was determined to be about 800,000, with a glass transition temperature of about -50°C.

Preparation of Stock Solutions:

Example 2.1 Conductivity Solution 1:

Conductivity Compound solution was prepared as follows: 1 g of Efka 10-6785 was added to 4 g of dimethylformamide and vortexed until the Efka 10-6785 was completely dissolved forming a homogenous solution.

Example 2.2 Conductivity Solution 2:

Conductivity Compound Solution was prepared as follows: 1 g of Efka 10-6782 was added to 4 g of dimethylformamide and vortexed until Efka 10-6582 was completely dissolved forming a homogenous solution.

Example 2.3 Conductivity Solution 3: Conductivity Compound Solution was prepared as follows: 1 g of Efka 10-6786 was added to 4 g of dimethylformamide and vortexed until Efka 10-6582 was completely dissolved forming a homogenous solution.

Example 2.4 Conductivity Solution 4:

Conductivity Compound Solution 4 was prepared as follows: 1 g of l-ethyl-3- methylimidazolium nitrate (EMI nitrate) was added to 4 g of dimethylformamide and vortexed until EMI nitrate completely dissolved forming homogenous solution.

Example 2.5 Conductivity Solution 5:

Conductivity Compound Solution was prepared as follows: 1 g of l-ethyl-3- methylimidazolium methanesulfonate was added to 4 g of dimethylformamide and vortexed until the l-ethyl-3-methylimidazolium methanesulfonate was completely dissolved forming a homogenous solution.

Example 2.6 Water Retention Solution:

Water retention agent Somarex™ 530 solution was prepared as follows: 1 g of Somarex™ 530 was added to 19 g of acetonitrile and vortexed until the Somarex™ 530 was completely dispersed and a homogenous suspension was obtained.

Example 2.7 Anti-Corrosion Solution 1:

Anti-corrosion compound Irgacor™ DSS-G solution was prepared as follows: 1 g of Irgacor™ DSS-G was added to 19 g of 2-methyltetrahydrofuran and vortexed until the Irgacor™ DSS-G was completely dissolved and a homogenous solution was obtained.

Example 2.8.1 Anti-Corrosion Solution 2:

Anti-corrosion compound I rgamet™ 30 solution was prepared as follows: 1 g of Irgamet™ 30 was added to 19 g of ethyl acetate and vortexed until the Irgacor™ 30 was completely dissolved and a homogenous solution was obtained. Example 2.8.2 Anti-Corrosion Solution 3:

Anti-corrosion compound Amine O™ solution was prepared as follows: 1 g of Amine O™ was added to 5 g of ethyl acetate and vortexed until the Amine O™ was completely dissolved and a homogenous solution was obtained. Example 2.9 Cross-linker Solution 1:

Cross-linker Carbodilite™ V-05 solution was prepared as follows: 1 g of Carbodilite™ V-05 was added to 9 g of ethyl acetate and vortexed until the Carbodilite™ V-05 was completely dissolved and a homogenous solution was obtained. Example 2.10 Cross-linker Solution 2:

Cross-linker Coronate L™ solution was prepared as follows: 1 g of Coronate™ L was added to 20 g of ethyl acetate and vortexed until the Coronate™ V-05 was completely dissolved and a homogenous solution was obtained.

Composition of Adhesive Solutions:

Example 3.1 Comparative Solution (CS-1)

A 20 mL glass vial was placed on a scale and the scale was tared to 0.00 g. Next, add 0.14 g of the ionic liquid solution, 10 g of P-1 polymer solution, 0.21 g of cross-linker solution and 0.31 g of ethyl acetate to the tared 20 mL glass vial and vortex until the solution is homogenous. Example 3.2 Adhesive Solutions:

S-2 Adhesive solution:

A 20 mL glass vial was placed on a scale and the scale was tared to 0.00 g. To the tared 20 mL glass vial, 0.14 g of Ionic Liquid Solution, 0.112 g of water retention solution and 0.28 g of conductivity solution 1 where added and vortexed until a homogenous solution was obtained. Next 10 g of P-1 polymer solution, 0.21 g of cross-linker solution, and 0.31 g of ethyl acetate was added and vortexed until a homogenous solution was obtained.

S-l and S-3-S-31 Adhesive solutions:

Adhesive solutions where prepared as in Example 3.1, except that in the preparation of the adhesive solutions the amount of each component was changed as shown in Table 1.

Table 1.

Preparation of Adhesive Sheet

An adhesive sheet was prepared by mixing the adhesive solutions as described in experimental section 3.1 and according to mixtures described in Table 1. The prepared compositions were coated/deposited upon a surface treated PET separator (release liner) [MRF38, made by Mitsubishi Chemical Corp., Japan], forming an adhesive composite layer at a thickness of about 150 pm (microns). The coated film was then heat dried initially at 40 °C for 5 minutes and then at 130 °C for about 3 minutes for cross-linking. A second PET separator (release liner) was then aligned over the exposed adhesive coating to obtain a layered sheet (PET separator/adhesive coating/PET separator) which was then aged/dried at 50° C for about 20-24 hours and then stored under ambient conditions until needed.

Corrosive Testing Method

Sample preparation 1:

Just prior to the application of the adhesive sheet to the nano-AI coated layer, the aforementioned release liner was removed. The adhesive sheet, as previously described above was applied to the metallic surface of the aluminum film (50 nm-thick aluminum coated PET film [Toray Advanced Film, Tokyo, Japan]). Next the second PET separator (release liner) was removed from the adhesive sheet and placed on a solid transparent support (e.g., glass, transparent plastic, etc.) so the adhesive side is in physical contact with the solid transparent support. Sample preparation 1 was used for preparation of samples S-l through S-ll.

Sample preparation 2:

Specimen preparation is the same as in low humidity testing below. Just prior to the application of the adhesive sheet to the nano-AI coated layer, the aforementioned release liner was removed. The adhesive sheet, as previously described above was applied to the metallic surface of the aluminum film (50 nm-thick aluminum coated PET film [Toray Advanced Film, Tokyo Japan]). Next the second PET separator (release liner) was removed from the adhesive sheet and laminated upon another conductive aluminum substrate 301, of 20 mm wide and 100 mm long by the application of rolling pressure, by 2 kg roller and roll pressed. Sample preparation 2 was used for preparation of samples S-12 through S-31. The prepared samples were placed in a Temperature & Humidity Benchtop chamber, set at 60°C/90% RH (ESPEC North America, [Hudsonville, Ml, USA], Criterion Temperature & Humidity Benchtop Model BTL-433) and the samples were tested at 150 Hr., 500 Hr. and 1000 Hr. (results are shown in Table 2). The samples were placed on a light box (Hall Productions Model No. BL1012/500K, Grover Beach, CA, USA) and a back light was applied, so that the samples could be visually examined for an indication of corrosive degradation and/or pitting of the aluminum foil. If no corrosiveness described herein was visually observed, the sample was indicated as © ["No Corrosion"]. If any of the corrosiveness described herein was observed and was as extensive as (>20% total surface area) the corrosiveness visually observed for CE-1, the sample is indicated as X ["Excessive Corrosion"]. If very little of the corrosiveness (<5% of total surface area) described herein was visually observed and was significantly less corrosive than that was visually observed for CE-1, the sample was indicated as O ["Slight Corrosion"]. If there was moderate corrosiveness (5-20% of total surface area) as described herein was visually observed the sample was indicated as D ["Moderately Corrosive"]. The results are summarized in Table 2a and 2b, below.

Table 2a.

Low Humidity Peeling/De-bonding Testing

The testing for peeling/ de-bonding was performed in the manner as described in JP 2015- 228951 and/or JP 2015-204998 and shown in FIG. 3. As shown in FIG. 3, the adhesive material 303 was coated upon a conductive substrate

301 of 25 mm wide and 100 mm long and laminated upon another flexible conductive layer 302 (such as aluminum foil and / or metalized plastic film such as PET), which is 10 mm to 25 mm wide and 100 mm longer than substrate 301 and by the application of rolling pressure, by 2 kg roller and roll pressed. Samples were then placed in a Temperature & Humidity Benchtop chamber, set at room temperature at 20%, 15%, or 10% RH (ESPEC North America, [Hudsonville, Ml, USA], Criterion Temperature & Humidity Benchtop Model BTL-433) for three (3) days and then tested.

The bonding/de-bonding tester (Mark-10, Copiague, New York, USA, model ESM303 motorized tension / compression stand) was equipped with a Mark-10 force gauge (Series 7- 1000) and had lower and upper clamps. The conductive substrate 301 in FIG. 3, was fixed onto the lower clamp and then electrically connected to the positive pole of a power supply 304 (Protek DC Power Supply 3006B). The top layer 302 in FIG. 3 was fixed to the upper clamp which is connected with the negative pole of the same DC power supply. The power supply had an output range from 0 to 100 VDC. The moving/peeling speed was set at 300 mm/min. If the sample showed peeling strength of ~0.1 N/cm after applying 10 VDC for 10 seconds then it was rated as having excellent (©) peeling/de-bonding, if the sample exhibited a peeling strength of ~ 0.5 N/cm after applying 10 VDC for 10 seconds, it was rated as having good (o) peeling-de- bonding, if the sample exhibited a peeling strength of ~1 N/cm after applying 10 VDC for 10 seconds it was rated as fair (D), and finally if the sample exhibited a peeling strength of ~l-2 N/cm after applying 10 VDC for 10 seconds it was rated as poor (X) peeling/de-bonding if the sample exhibited a peeling strength > 2 N/cm. Results are presented in Tables 2a and 2b.

Damp Heat Peeling/De-bonding Test:

For the damp heat peeling/de-bonding testing, the samples were placed in a Temperature

& Humidity Benchtop chamber, set at 60°C at 90% RH (ESPEC North America, [Hudsonville, Ml, USA], Criterion Temperature & Humidity Benchtop Model BTL-433) and the samples were tested at 150 Hr., 500 Hr. and 1000 Hr, or alternatively 265 Hr, 625 Hr, and 1000 Hr.

In the static de-bonding tests, the sample was fixed on to the tester and connected to the power supply as described above. The initial 180 deg. peeling was measured at the same peeling speed. Then peeling was stopped. A DC voltage (10 VDC for example) was applied for some time (10 seconds, for example) and then the peeling strength was measured at the same peeling speed, of 300 mm/min, for all samples (see Tables 2a and 2b for results). If the sample showed peeling strength of ~0.1 N/cm after applying 10 VDC for 10 seconds then it was rated as having excellent (©) peeling/de-bonding, if the sample exhibited a peeling strength of ~ 0.5 N/cm after applying 10 VDC for 10 seconds, it was rated as having good (o) peeling-de-bonding, if the sample exhibited a peeling strength of ~1 N/cm after applying 10 VDC for 10 seconds it was rated as fair (D), and finally if the sample exhibited a peeling strength of ~l-2 N/cm after applying 10 VDC for 10 seconds it was rated as poor (X) peeling/de-bonding if the sample exhibited a peeling strength > 2 N/cm.

Aging Test:

For the aging test, the samples were placed in a vacuum control oven (Cascade Technical Solutions, Inc. Cornelius, OR, USA. Model No. TVO-5) set at 60 °C for three (3) days. The peeling strength of the samples were then tested using the abovementioned static de-bonding test. Sample grading was the same as previously described. The results are shown in Tables 2a and 2b.

Ionic Conductivity Measurements: Ionic conductivity measurements were performed on adhesive samples subjected to high (50%) relative humidity (RH) and low (20%) RH at room temperature. The results are presented in Table 3 below.

Impedance measurements were conducted using an LCR meter (model IM3533, HIOKI E.E. Corporation, Nagano Japan). Impedance measurements were conducted on a device 20, containing a 30 pm thick adhesive sheet, 21, as described above, interposed between an aluminum plate 22, and the metallic surface PET film 23 (PET film, Toray Advanced Film, Tokyo, Japan), as shown in FIG. 4. The aluminum plate, diode 25, and the metallic surface, anode 24, of the aluminum film connected to an LCR meter via wires. An alternating voltage, with a magnitude of 0.5V with a starting frequency of 0.5Hz and end frequency of 200kHz, was swept over the device. Impedance (ohms, W) and phase (degree, Q) where recorded at predetermined frequencies.

To determine ionic conductivity, an equivalent circuit for the device was assumed, see FIG. 5, wherein R ₀ 30, is the wiring resistance, Cicp 31, is the adhesive capacitance. Ionic conductivity of the adhesive device, 32, was calculated from the resistivity. First determine the resistivity of the device using the formula: wherein Z is the impedance, R ₀ is the wiring resistance, R _ICP is the adhesive resistance, Qo is the constant phase element (interface), CICP, is the adhesive capacitance, w is the angular frequency and a is constant (describing how the constant phase element (Qo) deviates from ideal capacitance.

Once you determine the resistivity of the device you can then calculate the ionic conductivity of the device by using the formula for resistivity:

1 l

R

s A , where R is resistivity, s is conductivity, / is the thickness of the adhesive, and A is the area cross section area of the device.

TABLE 3.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. For the processes and/or methods disclosed, the functions performed in the processes and methods may be implemented in differing order, as may be indicated by context. Furthermore, the outlined steps and operations are only provided as examples, and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations. This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely exemplary, and many other architectures may be implemented which achieve the same or similar functionality.

The terms used in this disclosure, and in the appended embodiments (e.g., bodies of the appended embodiments) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes, but not limited to," etc.). In addition, if a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). As used in this disclosure, any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the term, or both terms. For example, the phrase, "A or B: will be understood to include the possibilities of "A" or "B" or "A and B." The terms "a," "an," "the" and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. All methods described herein may be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiment. No language in the specification should be construed as indicating any non- embodied element essential to the practice of the present disclosure.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to embodiments precisely as shown and described.