Thermally separable two-layer adhesive system and adhesive separation method using said adhesive system

Abstract

The present invention relates to a thermally separable two-layer adhesive system, a method for adhesive separation using the adhesive system, and a thermally separable bonded composite. In particular, the present invention relates to a thermally separable two-layer adhesive system comprising an adhesive layer containing electrically conductive particles.

Description

[Technical Field]

[0001] The present invention relates to a thermally separable two-layer adhesive system, a method for adhesive separation using the adhesive system, and a thermally separable bonded composite. In particular, the present invention relates to a thermally separable two-layer adhesive system comprising an adhesive layer containing conductive particles. [Background technology]

[0002] Adhesive bonds are commonly used in product assembly and finishing. They replace mechanical fasteners such as screws, bolts, and rivets, providing a bond with reduced machining costs and greater adaptability in manufacturing processes. Adhesive bonds distribute stress evenly, reducing the potential for fatigue and insulating the joint from corrosive species.

[0003] However, the ease with which adhesive bonds can be separated offers many advantages. Separation, or debonding (peeling), of adhesive bonds may be desirable when temporary structures or already bonded article assemblies need to be disassembled, for example, to allow for repair, refurbishment, replacement, or restoration work. Simplified separation procedures also facilitate end-of-life recycling of materials and components from adhesively bonded products and structures. Reversible bonds also lend themselves to use in packaging or securing articles during transport.

[0004] Existing separation strategies typically involve time-consuming chemical procedures that require high temperatures and aggressive chemicals. Examples of such techniques are described in U.S. Patent No. 4,171,240 to Wong, U.S. Patent No. 7,407,704 to Kirsten, and U.S. Patent No. 4,729,797 to Linde, among others. While generally effective, these techniques are too harsh and can damage the objects being separated, making them unsuitable for many applications.

[0005] To provide materials that are more easily removed from substrates, the prior art describes adhesives formed from reactive monomers containing bonds susceptible to chemical degradation, such as curable resins containing thermally unstable bonds or thermally reversible crosslinks. While these specially formulated materials are more easily separated from the substrate, harsh conditions are still required for delicate substrates or adjacent adhesive bonds.

[0006] Electrically separable adhesives containing ionic components are known, as are various ionic liquids that can generate electrical conductivity in solids. For example, DE 102012 203 794 A1 describes a polyamide-based hot melt adhesive containing an ionic, electrically conductive component that can be separated by applying a voltage. EP 3262132 A1 describes a reactive hot melt adhesive composition comprising an isocyanate-functional polyurethane polymer and an organic or inorganic salt, which at least partially loses its adhesive properties when a voltage is applied, allowing substrates joined using the adhesive to be separated. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 4,171,240 [Patent Document 2] U.S. Patent No. 7,407,704 [Patent Document 3] U.S. Patent No. 4,729,797 [Patent Document 4] DE 102012 203 794 A1 [Patent Document 5] EP 3262132 A1 Summary of the Invention [Problem to be solved by the invention]

[0008] Thus, there remains a need in the art for improved adhesive systems, particularly those that can be used to separate a variety of adhesives, such as polyurethanes, epoxies, and acrylates, and that can be selectively and accurately separated under mild conditions. Such adhesive systems would provide adhesive bonds that can be used in a variety of applications where easy adhesive removal is desired, yet still provide all the benefits of adhesives. [Means for solving the problem]

[0009] Surprisingly, the inventors have found that this need is met by a thermally separable two-layer adhesive system comprising a layer of adhesive having conductive particles, which is all the more surprising since the adhesive system is made thermally separable by applying a relatively low power for heating.

[0010] In one embodiment, the present invention relates to a heat-separable two-layer adhesive system comprising a first adhesive layer and a second adhesive layer bonded to the first adhesive layer, wherein the first adhesive layer comprises conductive particles selected from the group consisting of silver, gold, palladium, platinum, carbon black, carbon fiber, graphite, indium tin oxide, silver-plated nickel, silver-plated copper, silver-plated graphite, silver-plated aluminum, silver-plated fiber, silver-plated glass, silver-plated polymers, antimony-doped tin oxide, and combinations thereof.

[0011] In another embodiment, the present invention relates to a method of adhesive separation comprising providing a thermally separable two-layer adhesive system of the present invention and subjecting a first adhesive layer to resistive heating, which locally heats the first adhesive layer, thereby rendering the adhesive system separable.

[0012] In yet another embodiment, the present invention relates to a heat-separable bonded composite comprising a first substrate, the heat-separable two-layer adhesive system of the present invention, and a second substrate.

[0013] Further preferred embodiments of the invention are set forth in the claims. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows a continuous corrugated polycarbonate substrate with a conductive adhesive layer used to test the separation performance in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] As used herein, the terms "a," "an," and "at least one" are equivalent to the term "one or more" and can be used interchangeably.

[0016] As used herein, "one or more" relates to "at least one" and includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or more of the referenced species. Similarly, "at least 1" means "one or more," i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. "At least 1," as used herein with respect to any moiety, refers to the number of chemically distinct molecules, i.e., the number of different types of the referenced species, and not the total number of molecules.

[0017] When referring to the molecular weight of a polymer or its components herein, this refers to the number average molecular weight Mn unless otherwise specified. The number average molecular weight Mn can be calculated based on end groups or can be measured by gel permeation chromatography using THF as an eluent. Unless otherwise specified, all molecular weights listed are measured by end group analysis. The weight average molecular weight Mw can be measured by GPC as described for Mn.

[0018] All percentages stated herein with respect to compositions or preparations relate to % by weight based on the total weight of the respective composition or preparation, unless otherwise stated.

[0019] In the present invention, a heat-separable two-layer adhesive system comprises a first adhesive layer and a second adhesive layer bonded to the first adhesive layer, wherein the first adhesive layer comprises conductive particles selected from the group consisting of silver, gold, palladium, platinum, carbon black, carbon fiber, graphite, indium tin oxide, silver-plated nickel, silver-plated copper, silver-plated graphite, silver-plated aluminum, silver-plated fiber, silver-plated glass, silver-plated polymers, antimony-doped tin oxide, and combinations thereof.

[0020] When a low voltage, such as 1-40 V, is applied to the first adhesive layer, the conductive particles heat up and loosen the interface between the first and second adhesive layers, thereby allowing the adhesive system to be easily separated.

[0021] In a preferred embodiment, the conductive particles in the first adhesive layer are selected from the group consisting of silver, silver-plated nickel, silver-plated copper, silver-plated graphite, silver-plated aluminum, silver-plated fiber, silver-plated glass, silver-plated polymer, and combinations thereof. The conductive particles in the first adhesive layer can have any shape. For example, the particles can be cubic, substantially spherical, or ovoid or flaky. The particle surface can be smooth, rough, or angled, and the particles can be polyhedral or have a single continuous curved surface. The particles can be porous or non-porous. In one or more preferred embodiments, the conductive particles are flaky silver (silver flakes).

[0022] In the present invention, the first adhesive is the cured product of an adhesive composition comprising a resin binder and conductive particles. A solvent is added, if necessary, in preparing the composition to achieve a viscosity that can be used for mixing and dispensing. The weight percentages of the components for the adhesive composition do not include the solvent.

[0023] Suitable binder resins for the first adhesive are thermoplastic resins selected to achieve the required conductivity, flexibility, and appropriate impact or scratch resistance for the intended end use. Suitable thermoplastic polymers include, but are not limited to, polyesters, phenoxy resins, phenolic resins, acrylic polymers, acrylic block copolymers, acrylic polymers with tertiary alkylamide functionality, polysiloxane polymers, polystyrene copolymers, polyvinyl polymers, divinylbenzene copolymers, polyetheramides, polyvinyl acetal, polyvinyl butyral, polyvinyl acetol, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, methylene polyvinyl ether, cellulose acetate, styrene-acrylonitrile, amorphous polyolefins, thermoplastic urethanes, polyacrylonitrile, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate terpolymers, functionalized ethylene-vinyl acetate, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene-butadiene copolymers and / or block copolymers, and styrene-butadiene block copolymers.

[0024] Suitable commercially available binder resins include thermoplastic polyurethanes available from The Lubrizol Corporation (Cleveland, Ohio, USA) sold under the product name ESTANE 5715P; polyester-type thermoplastic resins from Bostik Findley, Inc. sold under the product name VITEL 220B; and phenoxy resins available from Inchem (South Carolina, USA) sold under the product names PKHB, PKHC, PKHH, PKHJ, and PKFE.

[0025] The total resin binder content ranges from 1 to 60% by weight of the total dry composition; in another embodiment, the total resin binder content ranges from 5 to 30% by weight of the total dry composition.

[0026] In one embodiment, the conductive particles have a thickness of 0.01 m to improve the flexibility of the adhesive layer.2 / g~10m 2 / g, preferably 0.05m 2 / g~5m 2 The conductive particles have a surface area of ​​0.01g / g as measured by the Brunauer-Emmett-Teller (BET) method. The conductive particles are not limited to bulk metal or conductive particles (i.e., those without a core), but also include metal-plated core particles. The conductive particles are present in an amount ranging from 40 to 99% by weight of the total dry composition, preferably from 70 to 95% by weight of the total dry composition. The average particle size of the conductive particles is preferably in the range of 1 to 100 μm, more preferably in the range of 5 to 20 μm.

[0027] The viscosity of the adhesive composition can be adjusted with solvents as needed to allow efficient dispensing. Viscosities in the range of 50 to 150,000 mPa·s are suitable for most dispensing methods. For gravure or flexographic printing, suitable viscosities are in the range of 500 to 4,000 mPa·s; for stencil or screen printing, suitable viscosities are in the range of 4,000 to 50,000 mPa·s. The total amount of solvent is not critical and can be adjusted to obtain a useful viscosity.

[0028] Solvents may be used alone or in combination, examples of which include 1,4-butanediol diglycidyl ether, p-tert-butyl-phenyl glycidyl ether, allyl glycidyl ether, glycerol diglycidyl ether, butyl diglycol, 2-(2-butoxyethoxy)-ethyl ester, butyl glycol acetate, acetic acid, 2-butoxyethyl ester, butyl glycol, 2-butoxyethanol, isophorone, 3,3,5-trimethyl-2-cyclohexen-1-one, dimethyl succinate, dimethyl glutarate, dimethyl adipate, acetic acid, dipropylene glycol (mono)methyl ether, propyl acetate, glycidyl ethers of alkylphenols (commercially available from Cardolite Corporation as Cardolite NC513), and purified dimethyl esters of adipic, glutaric, and succinic acids (commercially available from Invista as DPE dibasic esters).

[0029] Preferred solvents have flash points above 70°C, including butyl glycol acetate (bp 192.3°C, fp 87°C), carbitol acetate (bp 217.4°C, fp 109°C), glycol ethers (DOWANOL DPM, bp 190°C, fp 75°C), dibasic esters such as the dimethyl esters of adipic, glutaric, and succinic acids (DPE, bp 196-225°C, fp 94°C), dibasic esters (DBE-9, bp 196-215°C, fp 94°C), and ethyl glycol (CARBITOL, bp 201.9°C, fp 83°C), where bp is the boiling point and fp is the flash point.

[0030] Additional organic additives may be included in the composition for the first adhesive to provide desired properties. Typical additives include catalysts, surfactants, surface-active substances, wetting agents, antioxidants, thixotropes, reinforcing fibers, silane-functional perfluoroethers, phosphate-functional perfluoroethers, titanates, waxes, phenol-formaldehyde, degassing agents, flow additives, adhesion promoters, and rheology modifiers. These optional components are specifically selected to achieve the desired properties for the selected end use. When used, additives may be included in amounts up to about 10% by weight of the total dry composition.

[0031] In the present invention, the second adhesive is a cured product of an adhesive composition comprising a resin binder. The choice of the resin binder is not particularly limited. Surprisingly, the inventors have found that the heat-separable adhesive system of the present invention is suitable for separating a wide variety of adhesives, including thermoplastic resin adhesives and thermosetting resin adhesives.

[0032] In one embodiment, the resin binder for the second adhesive is a thermoplastic resin. A wide variety of known thermoplastic resins can be used in the present invention. The thermoplastic resin can be any thermoplastic resin, preferably a block copolymer. Examples of thermoplastic resins suitable for use in the present invention include phenoxy resins, polyesters, thermoplastic urethanes, phenolic resins, acrylic polymers, acrylic block copolymers, acrylic polymers with tertiary alkylamide functionality, polysiloxane polymers, polystyrene copolymers, polyvinyl polymers, divinylbenzene copolymers, polyetheramides, polyvinyl acetals, polyvinyl butyrals, polyvinyl acetols, polyvinyl alcohols, polyvinyl acetates, polyvinyl chlorides, methylene polyvinyl ethers, cellulose acetate, styrene-acrylonitrile, amorphous polyolefins, polyacrylonitriles, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate terpolymers, functionalized ethylene-vinyl acetates, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene-butadiene copolymers and / or block copolymers, styrene-butadiene block copolymers, or combinations thereof.

[0033] In the present invention, when the second adhesive layer comprises a thermoplastic resin, the adhesive layer has a boundary layer that contacts the first adhesive layer, and when the boundary layer is heated via the first adhesive layer to a temperature higher than the softening point of the thermoplastic resin, the adhesive layers loosen and become separable.

[0034] In another embodiment, the resin binder for the second adhesive is a thermosetting resin. A wide variety of known thermosetting resins can be used in the present invention. Examples of thermosetting resins suitable for use in the present invention include vinyl resins, acrylic resins, phenolic resins, epoxy resins, maleimide resins, bismaleimide resins, polyimide resins, silicon-containing resins, and mixtures thereof. Preferably, the thermosetting resin is selected from epoxy resins, acrylic resins, and mixtures thereof.

[0035] Thermosetting resins suitable for use in the present invention have a molecular weight Mw greater than 10,000.

[0036] When the second adhesive layer comprises a thermosetting resin, the adhesive layer has a boundary layer in contact with the first adhesive layer, and when the boundary layer is heated through the first adhesive layer to a temperature at which the cross-linked thermosetting structure is destroyed, the adhesive layers become loose and separable.

[0037] The second adhesive composition may contain conductive particles, as used in the first adhesive composition, depending on the end use. In a preferred embodiment, the second adhesive composition does not contain conductive particles. In another preferred embodiment, the second adhesive composition contains conductive particles, such as carbon black, to improve the adhesive performance of the second adhesive.

[0038] Additional organic additives may be included in the second adhesive composition to provide desired properties. Typical additives include solvents, catalysts, surfactants, surface-active substances, wetting agents, antioxidants, thixotropes, reinforcing fibers, silane-functional perfluoroethers, phosphate-functional perfluoroethers, titanates, waxes, phenol-formaldehyde, degassing agents, flow additives, adhesion promoters, and rheology modifiers. These optional components are specifically selected to achieve the desired properties for the selected end use. When used, additives may be present in amounts up to about 30% by weight of the total dry composition.

[0039] Another subject of the present invention is a thermally separable bonded composite comprising a first substrate, the above-described thermally separable two-layer adhesive system, and a second substrate. The thermally separable bonded composite may further comprise one or more substrates and one or more adhesives. In a preferred embodiment, the thermally separable bonded composite is in the form of a laminate. In another preferred embodiment, the first substrate and the second substrate are bonded by the thermally separable two-layer adhesive system.

[0040] The thickness of the two adhesive layers used in the composite is not limited. The first adhesive layer may have a thickness of 1 μm to 10 mm, particularly 10 μm to 1 mm. The second adhesive layer may have a thickness of 1 μm to 10 mm, particularly 10 μm to 1 mm. In one embodiment, the first adhesive layer is thinner than the second adhesive layer.

[0041] The substrate used in the present invention is not limited. Examples of substrates suitable for use as the first or second substrate include wood, paper, cardboard, plastics such as polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polyester, or polyamide, organic polymers such as cellophane, polyolefins such as polyethylene (LDPE, LLDPE, metallocene-catalyzed PE, HDPE) or polypropylene (PP, CPP, OPP), polyvinyl chloride (PVC), ethylene copolymers such as ethylene vinyl acetate (EVA), ethylene acrylate copolymer (EMA), EMMA, EAA, polyester, ionomers or polyamides such as PLA, ethylene / acrylic acid copolymer, glass, concrete, ceramic, and stone.

[0042] The thermally separable bonded composite may include one or more adhesive layers other than the first adhesive layer and the second adhesive layer, and / or one or more substrates other than the first substrate and the second substrate, so long as the intended purpose of separating the composite can be achieved.

[0043] The thermally separable bonded composites of the present invention can be widely used in electronic devices, integrated circuits, semiconductor devices, solar cells and / or solar cell modules, and other devices including energy production, personal computers, control systems, telephone networks, automotive electronics, devices, displays, semiconductor packages, passive components, and handheld devices.

[0044] Another subject of the present invention relates to a method for adhesive separation, comprising providing a thermally separable two-layer adhesive system as described above and subjecting the first adhesive layer to resistive heating, thereby locally heating the first adhesive layer and rendering the adhesive system thermally separable. The two-layer adhesive system becomes thermally separable at temperatures between 60°C and 110°C, preferably between 60 and 90°C, more preferably between 60 and 75°C.

[0045] This heating of the first adhesive layer is used to separate the adhesive system or composite. Conductive particles are used as fillers with "signal-receiving" properties to transfer the energy resulting from the resistive heating into the first adhesive layer. The introduction of energy into the layer results in a large local increase in temperature, which promotes loosening of the adhesive system or composite. In the case of a non-reactive thermoplastic adhesive used as the second adhesive, this energy introduction into the first adhesive leads to melting of the adjacent adhesive polymers. In the case of a reactive, i.e., cross-linked, thermosetting, adhesive used as the second adhesive, the temperature increase causes thermal degradation of the polymer boundary layer, resulting in failure of the adhesive joint. In this regard, particularly preferred adhesives are those that are themselves thermally unstable or whose polymer backbone contains several thermally unstable groups. Modification of adhesives with thermally unstable additives that can be activated as a result of an increase in temperature and thus initiate adhesion loss can also be successfully used in the heat-separable adhesive systems or composites of the present invention.

[0046] Compared to conventional heating methods, the method of the present invention is characterized by the fact that heat generation is locally defined at the boundary layer between the heated adhesive layer and the adjacent adhesive layer in the adhesive system, and thermal stress on the bonded substrate materials and the second adhesive matrix itself is avoided or minimized. Because heat does not need to be introduced into the adhesive system by a diffusion process through the bonded substrates, the method of the present invention is time-saving and effective. The method of the present invention also significantly reduces heat loss due to heat dissipation or radiation through the substrates or the second adhesive matrix. This makes the method of the present invention particularly economical. As a result of the locally defined temperature increase within the first adhesive layer, the second adhesive is selectively broken down exclusively at the first adhesive / second adhesive interface, thereby facilitating "pseudo-adhesive" separation of the substrates.

[0047] Because only a low-power device for resistive heating, such as a lithium battery, is required and the adhesive system is resistively heat separable, the heating device requirements and costs in the present invention are much smaller than those of conventional heating methods using alternating electric, magnetic or electromagnetic fields.

[0048] In one embodiment, the power of the resistive heating applied to the first adhesive layer is 40 Watts or less, preferably 30 Watts or less. Preferably, the applied voltage of the resistive heating is 30 V or less, preferably 20 V or less, more preferably 15 V or less.

[0049] The present disclosure may be further understood with reference to the following examples, which are intended to be representative of certain embodiments of the disclosure and are not intended to limit the scope of the disclosure. [Example]

[0050] Example Preparation of the conductive adhesive composition Conductive adhesive composition 1 (CAC-1) 1.78 g of commercial polyurethane resin, 11.11 g of 0.7 to 1.35 m 2An adhesive composition was prepared by mechanically mixing silver flakes having a surface area of ​​1.5 g / g, 5.37 g of diethylene glycol monobutyl ether, and 1.74 g of dipropylene glycol methyl ether to produce a uniform paste.

[0051] Conductive adhesive composition 2 (CAC-2) 1.78 g of commercial polyurethane resin, 11.11 g of 1.2 m 2 An adhesive composition was prepared by mechanically mixing silver flakes having a surface area of ​​1.5 g / g, 5.37 g of diethylene glycol monobutyl ether, and 1.74 g of dipropylene glycol methyl ether to produce a uniform paste.

[0052] Conductive adhesive composition 3 (CAC-3) 0.43 g of commercial bisphenol F epichlorohydrin resin, 0.03 g of phenol formaldehyde resin, 18.27 g of 0.71 m 2 An adhesive composition was prepared by mechanically mixing silver flakes having a surface area of ​​0.95 g / g, 0.95 g of diethylene glycol monoethyl ether, and 0.28 g of hexahydrophthalic acid diglycidyl ester to produce a uniform paste.

[0053] Conductive adhesive composition 4 (CAC-4) 0.33 g of commercial bisphenol F epichlorohydrin resin, 0.55 g of phenol formaldehyde resin, 8.19 g of 0.71 m 2 An adhesive composition was prepared by mechanically mixing silver flakes having a surface area of ​​0.03 g / g, 0.03 g of polypropylene carbonate, and 0.87 g of carbitol acetate to produce a uniform paste.

[0054] Fabrication of thermoseparable composites The conductive adhesive composition was applied to the continuous corrugated polycarbonate substrate using a Henkel Loctite RB40 400 dispensing robot system. The needle to target distance was 0.5 mm. The application pressure was 1.6 bar. The application temperature was 26°C. The applied conductive adhesive composition was cured at 120°C for 1.5-2 hours.

[0055] As shown in Figure 1, the continuous corrugated polycarbonate substrate contains 28 loops and 29 lines. Each line on the substrate is 0.45 mm thick, 30 mm long, and has a 2.5 mm gap. The thickness of the cured conductive adhesive layer on the substrate is 0.37-0.4 mm, and the cured area is 30 mm x 86 mm. The resistor length is 95.4 cm.

[0056] A second adhesive was then applied on top of the conductive adhesive layer, and a polyester substrate having a thickness of approximately 100 μm was placed on top of the commercial adhesive. These substrates were briefly pressed together by hand. The second adhesive was cured and reached a thickness of 100 μm.

[0057] Example 1 In the above manufacturing method, CAC-1 was used as the conductive adhesive composition, and a commercially available two-component polyurethane adhesive composition was used as the second adhesive composition. The adhesive layer was cured to a thickness of 50 μm to obtain a composite.

[0058] Example 2 In the above manufacturing method, CAC-2 was used as the conductive adhesive composition, and a commercially available one-component epoxy adhesive composition was used as the second adhesive composition. The adhesive layer was cured to a thickness of 50 μm to obtain a composite.

[0059] Example 3 In the above manufacturing method, CAC-2 was used as the conductive adhesive composition, and a commercially available acrylate-based pressure-sensitive adhesive composition was used as the second adhesive composition, which was cured to form an adhesive layer with a thickness of 30 μm to obtain a composite.

[0060] Example 4 In the above manufacturing method, CAC-2 was used as the conductive adhesive composition, and a commercially available acrylate-based pressure-sensitive adhesive composition was used as the second adhesive composition, which was cured to form an adhesive layer with a thickness of 60 μm to obtain a composite.

[0061] Separation performance test method After the conductive adhesive layer was cured on the continuous corrugated substrate, two wires from a DC generator were connected to both ends of the substrate with the conductive adhesive layer. A voltage was applied to the conductive adhesive layer for 20 seconds until the average temperature of the adhesive layer on lines 3, 14, and 25, measured with a non-contact thermometer gun, reached 60-70°C. The test results are shown in Table 1.

[0062] TIFF0007810656000001.tif31139

[0063] After the second adhesive layer was cured on the second substrate, two wires from a DC generator were connected to both ends of the substrate with the conductive adhesive layer. A voltage was applied to the conductive adhesive layer for 20 seconds, and the temperature of the adhesive layer on lines 3, 14, and 25 was measured with a non-contact thermometer gun. A spring scale was also hooked onto the reinforcement hole on one side of the second substrate. The peel force was determined by the maximum value measured by the spring scale when the substrate was pulled up evenly vertically, and this was evaluated as "good." The test results are shown in Table 2.

[0064] TIFF0007810656000002.tif41140

[0065] As can be seen from these tables, composites consisting of polycarbonate and polyester substrates bonded with two-layer adhesive systems based on various types of thermoplastic or thermosetting resins used in both adhesives were able to reach a temperature between the interface of the two adhesive layers high enough to cause the bond to fail when low-power resistive heating was applied to the conductive adhesive layer for 20 seconds, allowing the composites of the examples to be easily peeled off with a relatively low force. Preferred aspects of the present invention include the following. [1] A thermally separable two-layer adhesive system comprising a first adhesive layer and a second adhesive layer bonded to the first adhesive layer, wherein the first adhesive layer comprises conductive particles selected from the group consisting of silver, gold, palladium, platinum, carbon black, carbon fiber, graphite, indium tin oxide, silver-plated nickel, silver-plated copper, silver-plated graphite, silver-plated aluminum, silver-plated fiber, silver-plated glass, silver-plated polymers, antimony-doped tin oxide, and combinations thereof. [2] The thermally separable two-layer adhesive system according to [1], wherein the first adhesive is a cured product of an adhesive composition comprising a resin binder and conductive particles. [3] Conductive particles are 0.01 m 2 / g~10m 2 1. A heat-separable two-layer adhesive system according to claim 1, having a surface area of ​​1000 ppm by weight measured by the BET method. [4] The thermally separable two-layer adhesive system according to [2], wherein the adhesive composition further comprises a solvent. [5] The heat-separable two-layer adhesive system of [2], wherein the solvent is selected from the group consisting of butyl glycol acetate, 1,4-butanediol diglycidyl ether, p-tert-butyl-phenyl glycidyl ether, allyl glycidyl ether, glycerol diglycidyl ether, butyl diglycol, 2-(2-butoxyethoxy)-ethyl ester, acetic acid, 2-butoxyethyl ester, butyl glycol, 2-butoxyethanol, isophorone, 3,3,5-trimethyl-2-cyclohexen-1-one, dimethyl succinate, dimethyl glutarate, dimethyl adipate, acetic acid, dipropylene glycol (mono)methyl ether, propyl acetate, glycidyl ethers of alkylphenols, and dimethyl esters of adipic acid, glutaric acid, succinic acid, and combinations thereof. [6] The thermally separable two-layer adhesive system of [1], wherein the second adhesive is a cured product of an adhesive composition comprising a resin binder. [7] Resin binders include phenoxy resins, polyesters, thermoplastic urethanes, phenolic resins, thermoplastic acrylic polymers, acrylic block copolymers, acrylic polymers with tertiary alkylamide functionality, polysiloxane polymers, polystyrene copolymers, polyvinyl polymers, divinylbenzene copolymers, polyether amides, polyvinyl acetal, polyvinyl butyral, polyvinyl acetol, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, methylene polyvinyl ether, cellulose acetate, styrene acrylonitrile, amorphous polyolefins, and polyacrylonite. ethylene vinyl acetate copolymers, ethylene vinyl acetate terpolymers, functionalized ethylene vinyl acetate, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene butadiene copolymers and / or block copolymers, styrene butadiene block copolymers, vinyl resins, acrylic resins, phenolic resins, epoxy resins, maleimide resins, bismaleimide resins, polyimide resins, silicon-containing resins, and mixtures thereof. [8] A thermally separable two-layer adhesive system according to any one of [1] to [7], wherein the adhesive system becomes thermally separable by subjecting it to resistive heating. [9] The thermally separable two-layer adhesive system according to [8], wherein the power of the resistive heating is 40 watts or less, preferably 30 watts or less.

[10] A thermally separable bonded composite comprising a first substrate, the thermally separable two-layer adhesive system according to [1], and a second substrate.

[11] The thermally separable bonded composite according to

[10] , wherein the first substrate and the second substrate are non-conductive materials, preferably each independently selected from wood, paper, cardboard, plastic, glass, concrete, ceramic, and stone.

[12] A method of adhesive separation comprising providing a thermally separable two-layer adhesive system according to [1] and subjecting a first adhesive layer to resistive heating, thereby locally heating the first adhesive layer and thereby rendering the adhesive system thermally separable.

[13] The adhesion separation method according to

[12] , wherein the second adhesive layer comprises a thermoplastic resin, the adhesive layer has a boundary layer in contact with the first adhesive layer, and the boundary layer is heated via the first adhesive layer to a temperature higher than the softening point of the thermoplastic resin, thereby making the adhesive layers thermally separable.

[14] The adhesive separation method described in

[12] , wherein the second adhesive layer comprises a thermosetting resin, the adhesive layer has a boundary layer in contact with the first adhesive layer, and the boundary layer is heated via the first adhesive layer to a temperature at which the cross-linked thermosetting structure is destroyed, thereby making the adhesive layers thermally separable.

[15] The adhesion / separation method according to any one of

[12] to

[14] , wherein the power of the resistance heating is 40 watts or less, preferably 30 watts or less.

Claims

1. A heat-separable two-layer adhesive system comprising a first adhesive layer and a second adhesive layer bonded to the first adhesive layer, wherein the first adhesive is a cured product of an adhesive composition comprising a resin binder and conductive particles, the resin binder content being in the range of 5 to 30 wt % of the total dry composition; 1. A thermally separable two-layer adhesive system, wherein the conductive particle content ranges from 70 to 95 weight percent of the total dry composition, and the first adhesive layer comprises conductive particles selected from the group consisting of silver, gold, palladium, platinum, carbon black, carbon fiber, graphite, indium tin oxide, silver-plated nickel, silver-plated copper, silver-plated graphite, silver-plated aluminum, silver-plated fiber, silver-plated glass, silver-plated polymer, antimony-doped tin oxide, and combinations thereof.

2. The conductive particles are 0.01 m ２ / g to 10m ２ 10. The heat-separable two-layer adhesive system of claim 1 having a surface area as measured by the BET method of 100 / g.

3. 10. The heat-separable two-layer adhesive system of claim 1, wherein the adhesive composition further comprises a solvent.

4. 2. The heat-separable two-layer adhesive system of claim 1, wherein the solvent is selected from the group consisting of butyl glycol acetate, 1,4-butanediol diglycidyl ether, p-tert-butyl-phenyl glycidyl ether, allyl glycidyl ether, glycerol diglycidyl ether, butyl diglycol, 2-(2-butoxyethoxy)-ethyl ester, acetic acid, 2-butoxyethyl ester, butyl glycol, 2-butoxyethanol, isophorone, 3,3,5-trimethyl-2-cyclohexen-1-one, dimethyl succinate, dimethyl glutarate, dimethyl adipate, acetic acid, dipropylene glycol (mono)methyl ether, propyl acetate, glycidyl ethers of alkylphenols, and dimethyl esters of adipic acid, glutaric acid, succinic acid, and combinations thereof.

5. 10. The heat-separable two-layer adhesive system of claim 1, wherein the second adhesive is a cured product of an adhesive composition comprising a resinous binder.

6. Resin binders include phenoxy resins, polyesters, thermoplastic urethanes, phenolic resins, thermoplastic acrylic polymers, acrylic block copolymers, acrylic polymers with tertiary alkylamide functional groups, polysiloxane polymers, polystyrene copolymers, polyvinyl polymers, divinylbenzene copolymers, polyether amides, polyvinyl acetal, polyvinyl butyral, polyvinyl acetol, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, methylene polyvinyl ether, cellulose acetate, styrene acrylonitrile, amorphous polyolefins, and polyacrylonitriles.

4. The heat-separable two-layer adhesive system of claim 1, wherein the thermoplastic or thermosetting resin binder is selected from the group consisting of ethylene vinyl acetate copolymers, ethylene vinyl acetate terpolymers, functionalized ethylene vinyl acetate, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene butadiene copolymers and / or block copolymers, styrene butadiene block copolymers, vinyl resins, acrylic resins, phenolic resins, epoxy resins, maleimide resins, bismaleimide resins, polyimide resins, silicon-containing resins, and mixtures thereof.

7. A heat-separable two-layer adhesive system according to any of claims 1 to 6, wherein the adhesive system is made heat-separable by subjecting it to resistive heating.

8. 8. The heat-separable two-layer adhesive system of claim 7, wherein the resistive heating power is 40 watts or less.

9. A heat-separable bonded composite comprising a first substrate, the heat-separable two-layer adhesive system of claim 1, and a second substrate.

10. The thermally separable bonded composite of claim 9 , wherein the first substrate and the second substrate are non-conductive materials.

11. 10. A method of adhesive separation comprising providing the heat-separable two-layer adhesive system of claim 1 and subjecting the first adhesive layer to resistive heating, whereby the first adhesive layer is locally heated, thereby rendering the adhesive system heat-separable.

12. 12. The adhesive separation method according to claim 11, wherein the second adhesive layer comprises a thermoplastic resin, the adhesive layer has a boundary layer in contact with the first adhesive layer, and the boundary layer is heated via the first adhesive layer to a temperature higher than the softening point of the thermoplastic resin, thereby making the adhesive layers thermally separable.

13. 12. The adhesive separation method according to claim 11, wherein the second adhesive layer comprises a thermosetting resin, the adhesive layer has a boundary layer in contact with the first adhesive layer, and the boundary layer is heated via the first adhesive layer to a temperature at which the cross-linked thermosetting structure is destroyed, thereby making the adhesive layers thermally separable.

14. The adhesion / separation method according to any one of claims 11 to 13, wherein the power of the resistance heating is 40 watts or less.

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