WO2024261670A1 - Articles comprising heat initiated debondable layers - Google Patents
Articles comprising heat initiated debondable layers Download PDFInfo
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- WO2024261670A1 WO2024261670A1 PCT/IB2024/056001 IB2024056001W WO2024261670A1 WO 2024261670 A1 WO2024261670 A1 WO 2024261670A1 IB 2024056001 W IB2024056001 W IB 2024056001W WO 2024261670 A1 WO2024261670 A1 WO 2024261670A1
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- Prior art keywords
- debondable
- layer
- adhesive
- heat
- initiated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
- F16B11/00—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding
- F16B11/006—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding by gluing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/542—Shear strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/737—Dimensions, e.g. volume or area
- B32B2307/7375—Linear, e.g. length, distance or width
- B32B2307/7376—Thickness
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Definitions
- the disclosure relates to heat-debondable attachment articles. Further, the present disclosure further relates to a die-cut and a part assembly comprising the heat-debondable attachment article. The present disclosure also relates to a method for bonding and debonding an assembly. Moreover, the present disclosure further relates to a use of the heat-debondable article in the manufacture of recyclable articles, in particular of vehicle parts or battery parts.
- Adhesives have been used in many structural applications. Such structural applications have included vehicles assembly like automobile and aircraft assembly. For example, epoxy-based adhesives are well stablished in those applications. This also applies in increasing extent in the manufacture of the presently quick-growing technical field of manufacturing batteries for the mobile electrification such as the automotive electrification. As common with these adhesive, very strong bonds between substrates, i.e. permanent bonds are generally desired and achieved.
- the present disclosure provides a heat-initiated debondable attachment article, comprising
- a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer
- a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer
- the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive
- the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive
- at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
- first debondable layer and the second debondable layer are in contact with each other through the porous support layer.
- the present disclosure further provides a die-cut, comprising the heat-debondable attachment article.
- the present disclosure relates to a method for bonding and debonding a part assembly, the method comprising the following steps:
- Figure 6 shows a picture of a die-cut manufacturing according to a comparative process.
- porous support layer refers to a support layer with orifices, where such orifices can be present, for example, due to the support layer being a woven, non woven, mesh, or other similar materials.
- polymer will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend.
- Polymers include those polymerized in-situ from monomers as well as those materials that exist in a polymeric form independent of the processes used to create them.
- adjacent refers to the relative position of two elements, such as, for example, two layers, that are close to each other and may or may not be necessarily in contact with each other or that may have one or more layers separating the two elements as understood by the context in which “adjacent” appears.
- immediately adjacent refers to the relative position of two elements, such as, for example, two layers, that are next to each other and in contact with each other and have no intermediate layers separating the two elements.
- adheresive refers to polymeric compositions useful to adhere together two components (adherents).
- room temperature and “ambient temperature” are used interchangeably and refer to a temperature of 23 °C at ambient pressure condition of about 101 kPa.
- the first aspect of the present disclosure is a heat-initiated debondable attachment article, comprising
- the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive
- the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive
- at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
- This article may be attached to surfaces by means of pressure and/or heat, thereby providing ample adhesive bonds between surfaces, i.e. different parts or articles.
- the at least one thermoplastic polymer in the at least one first debondable layer and/or the at least one second debondable layer may be caused to at least partially melt. This has the effect of weaken the bond sufficiently to be released, usually with the application of certain physical means such as wedges or simply moving the parts in different directions.
- the heat-initiated debondable article according to the present disclosure comprises a porous support layer between the first surface of the first debondable layer the first surface of the second debondable layer.
- this support structure facilitates the manufacture of diecuts, which is particularly desirable for a great variety of applications, the transportability of the article, as well as of ease of application of the article.
- the article may easily be attached onto a surface of a first substrate such as by means of heat and/or pressure. Then, this assembly may be further processed, stored and/or shipped, until a second substrate is attached to the assembly, e.g. by means of an adhesive.
- the porous support layer comprises at least one material selected from tissue, mesh, non-woven cloth, veils, woven cloth, scrim, and any combinations thereof, preferably non-woven cloth, mesh, veils, and any combinations thereof.
- the porous support layer comprises at least one material selected from natural and synthetic fibers, preferably from synthetic fibers, more preferably from polyethylene fibers. Also, it is advantageous when the porous support layer exhibits an area weight in the range of from 1 to 30 g/square meter, preferably from 2 to 25 g/square meter, and more preferably from 3 to 20 g/square meter. Preferably, the porous support layer exhibits a thickness in the range of from 20 to 200 micrometers, preferably from 40 to 180 micrometers, and more preferably from 50 to 120 micrometers. In a preferred exemplary embodiment of the present disclosure, the porous support layer is a mesh.
- At least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
- One of those at least two different polymers preferably exhibits a glass transition temperature in the range of from 20°C to 55 °C, preferably from 25°C to 55 °C, and more preferably from 35°C to 50 °C, and even more preferably from 35 to 45 °C.
- the other polymers forming the blend of at least two different polymers preferably exhibits a glass transition temperature in the range of from greater than 55 °C to 100°C, preferably from 55°C to 80 °C, and more preferably from 55°C to 75 °C, and even more preferably from 55°C to 70 °C.
- the inventors have found that the use of at least these two types of polymers has the effect that the blend of polymers at least partially melts upon application of heat, and therefore the article loses at least some of its stability, i.e. its bonding properties. This enables the desirable debonding as described herein.
- each of the at least two different polymers is advantageously independently selected from polyesters, poly(meth)acrylates, acrylonitrile butadiene styrenes, polyamides, polybenzimidazoles, polycarbonates, polyether sulfones, polyoxymethylenes, polyether ether ketones, polyetherimides, polyethylenes, polyphenylene oxides, polyphenylene sulfides, polypropylenes, polystyrenes, polyvinyl chlorides, and any combinations thereof, preferably polyesters.
- the each of the at least two different polymers independently exhibits a number average molecular weight determined by means of GPC in the range of from 5,000 to 50,000 g/mol, preferably from 7,000 to 40,000 g/mol, and more preferably from 8,000 to 30,000 g/mol.
- the at least one first debondable layer and/or the at least one second debondable layer comprises at least one toughener.
- the inventors have found that the presence of the toughener improves adhesive performance such as improved overlap shear strength and/or tensile strength at room temperature without compromising the performance at the maximum service temperature. Furthermore, this will have the effect of a reduced brittleness of the first and/or second debondable layer.
- the at least one toughener is selected from butadiene rubbers, nitrile rubbers, and core-shell rubbers, more preferably from core-shell rubbers.
- Exemplary compounds which may be advantageously used as butadiene rubbers or nitrile rubbers are carboxyl-, amine-, epoxy-, hydroxyl- or methacrylate-terminated butadiene, butadiene styrene or butadiene acrylonitrile copolymers, preferably amine terminated butadiene styrene or butadiene acrylonitrile copolymers.
- Such tougheners are commercially available, for example, under the trade designations Hypro CTBN, ATBN, ETBN, HTB or VTBNX from CVC Thermoset Specialities and Hycar ATBN from Amerald Materials, or of the MX Series from Kaneka such as MX 257.
- the core-shell rubber toughener is a composite material configured by materials where the core portion on the inside and the shell portion on the outside are mutually different.
- the term "different materials” refers to materials where the composition and/or properties are mutually different, and therefore includes materials where the same type of resins are used but the molecular weights are mutually different, and the like.
- the Tg of the shell portion is preferably higher than the Tg of the core portion.
- the shell portion suppresses unwanted agglomeration of the core-shell rubber, and thus the core-shell toughener can be uniformly dispersed in the compositions as described herein.
- Examples of the core-shell rubber toughener include methyl methacrylate - butadiene copolymer, methyl methacrylate - butadiene - styrene copolymer, methyl methacrylate - acrylonitrile - butadiene - styrene copolymer, methyl methacrylate - acrylic rubber copolymer, methyl methacrylate - acrylic rubber - styrene copolymer, methyl methacrylate - acrylic butadiene rubber copolymer, methyl methacrylate - acrylic butadiene rubber - styrene copolymer, methyl methacrylate - (acrylic silicone IPN rubber) copolymer, and the like, but are not restricted thereto.
- Methyl methacrylate - butadiene copolymer, methyl methacrylate - butadiene - styrene copolymer, and methyl methacrylate - acrylic butadiene rubber - styrene copolymer can be advantageously used as the core-shell toughening agent.
- the core-shell toughener is normally in the form of fine particles, and the average value (weight average particle diameter) of the primary particle diameter thereof is generally approximately 0.05 micrometers or higher or approximately 0.1 micrometers or higher to approximately 5 micrometers or lower or approximately 1 micrometer or lower.
- the core-shell rubber can be used in a state dispersed in a matrix.
- the matrix is an epoxy resin.
- a matrix with favourable affinity to either first or second epoxy resin as described herein is particularly preferable from the perspective of favourable dispersion of the core-shell rubber in the composition as described herein.
- the matrix can include epoxy resins (such as bisphenol A and the like).
- the core-shell toughener can be a commercial product that is provided as a resin modifying agent or the like, and examples include BTA 751 (commercially available from Dow Chemical) as a methyl methacrylate-butadiene-styrene (MBS) type core-shell resin, MX-153 (commercially available from Kaneka) as a resin where methyl methacrylate-butadiene-styrene (MBS) dispersed in bisphenol A diglycidyl ether), and MC-257 (commercially available from Kaneka) as a butadiene core-shell resin, dispersed in epoxy, and F351 (commercially available from Aika Industries) as the acrylic core-shell resin, Paraloid 2650A (butadiene rubber), Hycar ATBN (CVC Chemicals, liquid butadiene rubber), and the like.
- BTA 751 commercially available from Dow Chemical
- MX-153 commercially available from Kaneka
- MX-153 commercially available from Kaneka
- the at least one toughener is contained in the at least one first debondable layer in an amount in the range of from 1 to 25 wt.-%, preferably from 2.5 to 20 wt.-%, and more preferably from 5 to 15 wt.-%, based on the total weight of the at least one first debondable layer.
- the at least one toughener is contained in the at least one second debondable layer in an amount in the range of from 1 to 25 wt.-%, preferably from 2.5 to 20 wt.-%, and more preferably from 5 to 15 wt.-%, based on the total weight of the at least one second debondable layer.
- the at least one first debondable layer exhibits a thickness in the range of from 1 to 300 micrometers, preferably from 3 to 250 micrometers, and more preferably from 5 to 200 micrometers.
- the at least one second debondable layer exhibits a thickness in the range of from 1 to 300 micrometers, preferably from 3 to 250 micrometers, and more preferably from 5 to 200 micrometers.
- the complete article may advantageously exhibit a total thickness in the range of from 40 to 500 micrometers, preferably from 70 to 450 micrometers, and more preferably from 90 to 400 micrometers.
- the complete article may advantageously exhibit a total thickness in the range of from 40 to 500 micrometers, preferably from 70 to 450 micrometers, and more preferably from 90 to 400 micrometers.
- the heat-debondable attachment article according to the present disclosure may further comprise a first adhesive layer disposed on at least part of the second major surface of the first debondable layer. This may add to ease of application and/or enhancing the adhesive properties of the article.
- the heat-debondable attachment article according to the present disclosure may further comprise a second adhesive layer covering the second major surface of the second debondable layer.
- the first adhesive layer and/or the second adhesive layer comprises at least one adhesive selected from structural adhesives, semi-structural adhesives, and pressure sensitive adhesives, preferably pressure sensitive adhesives.
- the attachment article as described herein comprises perforations.
- first and second debondable layer comprise perforations. This may have the effect of effectively encapsulate the heat-initiated debondable layer, which enhances the bonding and debonding capabilities of the article as described herein.
- the perforations may extend through the complete thickness of the article from the first major surface to the second major surface. It is further preferred that at least a portion of the article comprises perforations. Thereby, adhesive bonding and debonding properties may be distributed as desired over the length or over certain areas of the article as described herein.
- the article provides an overlap shear strength for the debondable portion of the article at a temperature range from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and less than 5 MPa, preferably less than 3 MPa, and more preferably less than 1 .5 MPa at a temperature in the range of from 80 to 100 °C.
- Cleavage Strength was determined according to ASTM D1062 using an Instron 5500R tensile tester.
- Table 1 Used materials, their function and supplier.
- a particular advantage of the supported design is the ability to manufacture Die-Cuts. 10 out of 10 Die-Cuts were manufactured successfully. No Die-Cuts were successfully manufactured via the unsupported product design.
- Table 3 Used materials, their function and supplier.
- OLS Overlap Shear strength
- Tensile strength was tested.
- the specimens were manufactured according to figure 4. As substrates e-coated Steel was used and the gap size between the assembled substrates was 1.00 mm in all cases (table 4).
- Table 4 Result of Example 2 and Comparison Example 3 using 3M DP 610 and 3M DP 6330.
- CSR core-shell rubber
- Table 5 Used materials, their function and supplier.
- a HotMelt foil comprising a blend (50:50 wt%) of Marnex AH441 and Marnex AH645 was extruded on a siliconized PET liner.
- the thickness of the functional layer can be adjusted as desired between e.g. 10 - 200 m.
- two 80 pm thick functional layers were used in combination with a support layer (OptiveilTM, fine polyester veil, 8 g/m 2 ).
- the final supported functional layer was assembled by means of heat (105°C) and pressure for 5 minutes according to Example 1.
- thermocouple was positioned in the center of the supported functional layer strip.
- 3M Structural Adhesive 9860 was applied to the tubes and 1mm glass beads were added to adjust the bondline thickness.
- the second primed tube was as well covered with a SA 9860 bead and finally pressed on top of the first tube.
- the supported functional layer can be used as well in small patches only, allowing an easy first opening process of an assembly.
- a further variation would be the use of a perforated supported functional layer (figure 10).
- a HotMelt layer comprising a blend (45:45:10 wt%) of Marnex AH 441 :Marnex AH 645:Paraloid EXL-2650J was manufactured in such a way that a OptiveilTM, fine polyester veil was embedded in between a layer of the hot melt. The thickness of this functional layer was ⁇ 200 pm in total.
- Lap shear specimens were made using 2024-T3 phosphoric acid anodized and primed (corrosion inhibiting primer BR 127) panels in all cases (10 x 2.5 x 1.55 cm). Bond area was 12.5 mm x 25 mm per sample. Glass beads with 90 - 150 pm diameter within the DP6330 PUR based room temperature curable adhesive were used to control the bondline thickness in all cases.
- the curable adhesive was applied to one edge of each of the two panels (i.e., adherents) using a scraper.
- the HotMelt foil according to this invention was put between both adhesive layers before closing the samples. The specimens were fixed by means of clamps and allowed to cure for seven days at ambient temperature.
- the HotMelt foil according to this invention was laminated to one edge of an adherent by means of heat (130°C) and pressure (10 kPa) for 1 minute. After allowing the adherent to reach room temperature again, the curable adhesive was applied to the surface of the laminated HotMelt foil and the edge of the other adherent by means of a scrapper. The samples were closed and fixed with clamps and allowed to cure for seven days at ambient temperatures.
- the HotMelt foil according to this invention was put between the edges of both adherents. The bond was closed by applying heat (130°C) and pressure (10 kPa) for 1 minute.
- the curable adhesive was applied to one edge of each of the two panels using a scrapper.
- Example 4 The bond was closed and the samples were cured for seven days at room temperature. All excesses of e.g. cured adhesive at the edges of the specimens, were removed by means of sandpaper. Two samples were tested for Example 4 and Comparison Example 5-7 and the average value, incl. standard deviation (in MPa) was reported. The test was conducted at a rate of 5 mm/minute at -40°C, RT, 60°C and 100°C.
- Example 4 The methods of EN2243-2 2006 were followed.
- the specimen manufacturing for Example 4 and Comparison Example 5-7 are described in the following:
- Floating Roller Peel specimens were made using 2024-T3 phosphoric acid anodized and primed (corrosion inhibiting primer BR 127) panels, measuring 25 x 2.5 x 0.16 cm and 30 x 2.5 x 0.05 cm, in all cases. Bond area was 20 cm x 2.5 cm per sample. Glass beads with 90 - 150 pm diameter within the DP6330 PUR based room temperature curable adhesive were used to control the bondline thickness in all cases.
- the curable adhesive was applied to the bond areas of both panels (i.e., adherents) using a scraper.
- the HotMelt foil according to this invention was put between both adhesive layers before closing the samples. The specimens were fixed by means of clamps and allowed to cure for seven days at ambient temperature.
- the HotMelt foil according to this invention was laminated to the bond area of the adherent measuring 25 cm x 2.5 cm x 0.16 cm by means of heat (130°C) and pressure (10 kPa) for 1 minute. After allowing the adherent to reach room temperature again, the curable adhesive was applied to the surface of the laminated HotMelt foil and the bond area of the other adherent measuring 30 cm x 2.5 cm x 0.05 cm by means of a scrapper. The samples were closed and fixed with clamps and allowed to cure for seven days at ambient temperatures. For Comparison Example 6, the HotMelt foil according to this invention was put between the bond areas of both adherents.
- the bond was closed by applying heat (130°C) and pressure (10 kPa) for 1 minute.
- the curable adhesive was applied to the bond areas of both panels using a scrapper.
- the bond was closed and the samples were cured for seven days at room temperature. All excesses of e.g. cured adhesive at the edges of the specimens, were removed by means of sandpaper.
- Two samples were tested for Example 4 and Comparison Example 5-7 and the average value, incl. standard deviation (in N/25 mm) was reported.
- the test was conducted at a rate of 140 mm/minute at -40°C, RT, 60°C and 100°C. In each test, the thinner substrate was peeled from the thicker one, and the results normalized to a width of 25 mm.
- Table 8 Heat-Initiated Debondable Layer.
- Example 4 showed an excellent performance for Lap Shear (OLS) and Floating Roller Peel (FRP) from -40°C - 60°C, always fulfilling the above mentioned thresholds.
- OLS Lap Shear
- FRP Floating Roller Peel
- a clear cohesive failure mode (CF) was obtained for all test methods, which is a clear benefit of the herein disclosed invention.
- Comparison Example 5 and 6 especially showed drawbacks regarding their Peel properties, resulting in unsatisfactory results or even chipping (AF) of the panels at the start of the measurement. Therefore, no values were measurable.
- the targeted heat initiated debonding capability of Example 4 is obvious as the performance dropped 96% (OLS) and 43% (FRP) compared to Comparison Example 7 tested at 100°C.
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Abstract
The present disclosure provides a heat-initiated debondable attachment article, comprising (i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer; (ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer; (iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer; (iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer; (v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer; (vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and (vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
Description
ARTICLES COMPRISING HEAT INITIATED DEBONDABLE LAYERS
Technical Field
The disclosure relates to heat-debondable attachment articles. Further, the present disclosure further relates to a die-cut and a part assembly comprising the heat-debondable attachment article. The present disclosure also relates to a method for bonding and debonding an assembly. Moreover, the present disclosure further relates to a use of the heat-debondable article in the manufacture of recyclable articles, in particular of vehicle parts or battery parts.
Background
Adhesives have been used in many structural applications. Such structural applications have included vehicles assembly like automobile and aircraft assembly. For example, epoxy-based adhesives are well stablished in those applications. This also applies in increasing extent in the manufacture of the presently quick-growing technical field of manufacturing batteries for the mobile electrification such as the automotive electrification. As common with these adhesive, very strong bonds between substrates, i.e. permanent bonds are generally desired and achieved.
However, it may become desirable in numerous applications to release the bond between different parts in devices or in certain assemblies. This is in particular true when there is a desire to dissemble said parts or assemblies for in order to recycle at least parts thereof.
Therefore, there exist an increasing desire in the art for adhesive or bonding technologies which provide not only good bonds between parts, but also enable the debonding of parts at a point when desired.
Summary
The present disclosure provides a heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
In a preferred embodiment, the first debondable layer and the second debondable layer are in contact with each other through the porous support layer.
The present disclosure further provides a die-cut, comprising the heat-debondable attachment article.
Also, the present disclosure relates to a method for bonding and debonding a part assembly, the method comprising the following steps:
(I) Attaching an article as described herein onto at least part of the surface of a first part;
(II) Optionally, applying at least one adhesive onto a first major surface of a second part;
(III) Attaching the second part onto the article attached to the first part such that the article connects the first and second part, thereby forming a part assembly;
(IV) Optionally, allowing the at least one adhesive to cure;
(V) Heating the part assembly so as to soften and/or at least partially melt the thermoplastic resin comprised in the first debondable layer and/or second debondable layer;
(VI) Disconnecting the second part from the first part.
Furthermore, the present disclosure relates to a use of the heat-debondable article in the manufacture of recyclable articles, in particular of vehicle parts or battery parts.
Brief Description of the Figures
Figure 1 shows a representative a heat-initiated debondable attachment article according to the present disclosure.
Figure 2 shows a comparative process to produce a heat-initiated debondable attachment article.
Figure 3 shows a first process to produce a heat-initiated debondable attachment article according to this disclosure.
Figure 4 shows a second process to produce a heat-initiated debondable attachment article according to this disclosure.
Figure 5 shows a picture of a die-cut manufacturing according to this disclosure.
Figure 6 shows a picture of a die-cut manufacturing according to a comparative process.
Figure 7 shows a schematic description of a test specimen using the supported functional layer.
Figure 8 shows a picture of a test specimen using a supported functional layer.
Figure 9 shows a picture of a test specimen clamped into a test machine.
Figure 10 shows a schematic drawing of a perforated supported functional layer.
Detailed Description
Before any embodiments of this disclosure are explained in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and the arrangement of components set forth in the following description. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. As used herein, the term “a”, “an”, and “the” are used interchangeably and mean one or more; and “and/or” is used to indicate one or both stated cases may occur, for example A and/or B includes, (A and B) and (A or B). Also herein, recitation of ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.). Also herein, recitation of “at least one” includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.). Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. Contrary to the use of “consisting”, which is meant to be limiting, the use of “including,” “containing”, “comprising,” or “having” and variations thereof is meant to be not limiting and to encompass the items listed thereafter as well as additional items. Furthermore, it is understood that the term “comprise” as used herein may also embrace the term “consists of’ in the sense of “consists only of”, but in general is used according to its meaning generally used in the art. Hence, limiting down “comprise” to “consists of” or “comprising” to “consisting of” is fully embraced in the present disclosure.
Amounts of ingredients of a composition may be indicated by % by weight (or “% wt”. or “wt.-%”) unless specified otherwise. The amounts of all ingredients gives 100 % wt unless specified otherwise. If the amounts of ingredients is identified by % mole the amount of all ingredients gives 100% mole unless specified otherwise.
In the context of the present disclosure, the term “porous” support layer refers to a support layer with orifices, where such orifices can be present, for example, due to the support layer being a woven, non woven, mesh, or other similar materials.
The term “polymer” will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend. Polymers include those polymerized in-situ from monomers as well as those materials that exist in a polymeric form independent of the processes used to create them.
The term “adjacent” refers to the relative position of two elements, such as, for example, two layers, that are close to each other and may or may not be necessarily in contact with each other or that may have one or more layers separating the two elements as understood by the context in which “adjacent” appears.
The term “immediately adjacent” refers to the relative position of two elements, such as, for example, two layers, that are next to each other and in contact with each other and have no intermediate layers separating the two elements.
The term "adhesive" as used herein refers to polymeric compositions useful to adhere together two components (adherents).
In the context of the present disclosure, the terms “room temperature” and “ambient temperature” are used interchangeably and refer to a temperature of 23 °C at ambient pressure condition of about 101 kPa.
Unless explicitly stated otherwise, all embodiments and optional features of the present disclosure can be combined freely.
The first aspect of the present disclosure is a heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
This article may be attached to surfaces by means of pressure and/or heat, thereby providing ample adhesive bonds between surfaces, i.e. different parts or articles. However, upon application of heat, the at least one thermoplastic polymer in the at least one first debondable layer and/or the at least one second debondable layer may be caused to at least partially melt. This has the effect of weaken the bond sufficiently to be released, usually with the application of certain physical means such as wedges or simply moving the parts in different directions. By this means, a reliable bonding and debonding of parts and articles has surprisingly been achieved. Moreover, the heat-initiated debondable article according to the present disclosure comprises a porous support layer between the first surface of the first debondable layer the first surface of the second debondable layer. The use of this support structure facilitates the manufacture of diecuts, which is particularly desirable for a great variety of applications, the transportability of the article, as well as of ease of application of the article. In addition, the article may easily be attached onto a surface of a first substrate such as by means of heat and/or pressure. Then, this assembly may be further processed, stored and/or shipped, until a second substrate is attached to the assembly, e.g. by means of an adhesive. This is highly advantageous in a number of applications in industrial manufacturing processes.
In this regard, it is preferred that the porous support layer comprises at least one material selected from tissue, mesh, non-woven cloth, veils, woven cloth, scrim, and any combinations thereof, preferably non-woven cloth, mesh, veils, and any combinations thereof. Preferably, the porous support layer comprises at least one material selected from natural and synthetic fibers, preferably from synthetic fibers, more preferably from polyethylene fibers. Also, it is advantageous when the porous support layer exhibits an area weight in the range of from 1 to 30 g/square meter, preferably from 2 to 25 g/square meter, and more preferably from 3 to 20 g/square meter. Preferably, the porous support layer exhibits a thickness in the range of from 20 to 200 micrometers, preferably from 40 to 180 micrometers, and more preferably from 50 to 120 micrometers. In a preferred exemplary embodiment of the present disclosure, the porous support layer is a mesh.
At least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers. One of those at least two different polymers preferably exhibits a glass transition temperature in the range of from 20°C to 55 °C, preferably from 25°C to 55 °C, and more preferably from 35°C to 50 °C, and even more preferably from 35 to 45 °C. The other polymers forming the blend of at least two different polymers preferably exhibits a glass transition temperature in the range of from greater than 55 °C to 100°C, preferably from 55°C to 80 °C, and more preferably from 55°C to 75 °C, and even more preferably from 55°C to 70 °C. The inventors have found that the use of at least these two types of polymers has the effect that the blend of polymers at least partially melts upon application of heat, and therefore the article loses at least some of its stability, i.e. its bonding properties. This enables the desirable debonding as described herein. Provided the polymers meet the restrictions on glass transition temperature above, each of the at least two different polymers is advantageously independently selected from polyesters, poly(meth)acrylates, acrylonitrile butadiene styrenes, polyamides, polybenzimidazoles, polycarbonates, polyether sulfones, polyoxymethylenes, polyether ether ketones, polyetherimides, polyethylenes, polyphenylene oxides, polyphenylene sulfides, polypropylenes, polystyrenes, polyvinyl chlorides, and any combinations thereof, preferably polyesters. In this regard, it is preferred that the each of the at least two different polymers independently exhibits a number average molecular weight determined by means of GPC in the range of from 5,000 to 50,000 g/mol, preferably from 7,000 to 40,000 g/mol, and more preferably from 8,000 to 30,000 g/mol.
It is further preferred that the at least one first debondable layer and/or the at least one second debondable layer comprises at least one toughener. The inventors have found that the presence of the toughener improves adhesive performance such as improved overlap shear strength and/or tensile strength at room temperature without compromising the performance at the maximum service temperature. Furthermore, this will have the effect of a reduced brittleness of
the first and/or second debondable layer. Preferably, the at least one toughener is selected from butadiene rubbers, nitrile rubbers, and core-shell rubbers, more preferably from core-shell rubbers. Exemplary compounds which may be advantageously used as butadiene rubbers or nitrile rubbers are carboxyl-, amine-, epoxy-, hydroxyl- or methacrylate-terminated butadiene, butadiene styrene or butadiene acrylonitrile copolymers, preferably amine terminated butadiene styrene or butadiene acrylonitrile copolymers. Such tougheners are commercially available, for example, under the trade designations Hypro CTBN, ATBN, ETBN, HTB or VTBNX from CVC Thermoset Specialities and Hycar ATBN from Amerald Materials, or of the MX Series from Kaneka such as MX 257.
With regard to the core-shell rubber as toughener, any core-shell rubber toughener commonly known in the art may be used in the context of the present disclosure. In a typical embodiment, the core-shell rubber toughener is a composite material configured by materials where the core portion on the inside and the shell portion on the outside are mutually different. Herein, the term "different materials" refers to materials where the composition and/or properties are mutually different, and therefore includes materials where the same type of resins are used but the molecular weights are mutually different, and the like.
From the perspective of favourably achieving a toughening effect on the compositions as described herein, the Tg of the shell portion is preferably higher than the Tg of the core portion. In this case, while flexibility is provided to the cured epoxy adhesive because the core portion which has a relatively low Tg functions as a centralized point of stress, the shell portion suppresses unwanted agglomeration of the core-shell rubber, and thus the core-shell toughener can be uniformly dispersed in the compositions as described herein.
Examples of the core-shell rubber toughener include methyl methacrylate - butadiene copolymer, methyl methacrylate - butadiene - styrene copolymer, methyl methacrylate - acrylonitrile - butadiene - styrene copolymer, methyl methacrylate - acrylic rubber copolymer, methyl methacrylate - acrylic rubber - styrene copolymer, methyl methacrylate - acrylic butadiene rubber copolymer, methyl methacrylate - acrylic butadiene rubber - styrene copolymer, methyl methacrylate - (acrylic silicone IPN rubber) copolymer, and the like, but are not restricted thereto. Methyl methacrylate - butadiene copolymer, methyl methacrylate - butadiene - styrene copolymer, and methyl methacrylate - acrylic butadiene rubber - styrene copolymer can be advantageously used as the core-shell toughening agent.
The core-shell toughener is normally in the form of fine particles, and the average value (weight average particle diameter) of the primary particle diameter thereof is generally approximately
0.05 micrometers or higher or approximately 0.1 micrometers or higher to approximately 5 micrometers or lower or approximately 1 micrometer or lower.
Preferably, the core-shell rubber can be used in a state dispersed in a matrix. It is preferred that the matrix is an epoxy resin. A matrix with favourable affinity to either first or second epoxy resin as described herein is particularly preferable from the perspective of favourable dispersion of the core-shell rubber in the composition as described herein. Examples of the matrix can include epoxy resins (such as bisphenol A and the like).
The core-shell toughener can be a commercial product that is provided as a resin modifying agent or the like, and examples include BTA 751 (commercially available from Dow Chemical) as a methyl methacrylate-butadiene-styrene (MBS) type core-shell resin, MX-153 (commercially available from Kaneka) as a resin where methyl methacrylate-butadiene-styrene (MBS) dispersed in bisphenol A diglycidyl ether), and MC-257 (commercially available from Kaneka) as a butadiene core-shell resin, dispersed in epoxy, and F351 (commercially available from Aika Industries) as the acrylic core-shell resin, Paraloid 2650A (butadiene rubber), Hycar ATBN (CVC Chemicals, liquid butadiene rubber), and the like.
With regard to the effects brought about the presence of the at least one first toughener in the compositions as described herein, it is preferred that the at least one toughener is contained in the at least one first debondable layer in an amount in the range of from 1 to 25 wt.-%, preferably from 2.5 to 20 wt.-%, and more preferably from 5 to 15 wt.-%, based on the total weight of the at least one first debondable layer. Similarly, it is preferred that the at least one toughener is contained in the at least one second debondable layer in an amount in the range of from 1 to 25 wt.-%, preferably from 2.5 to 20 wt.-%, and more preferably from 5 to 15 wt.-%, based on the total weight of the at least one second debondable layer. Moreover, with regard to the effects described herein, it is preferred that the at least one first debondable layer exhibits a thickness in the range of from 1 to 300 micrometers, preferably from 3 to 250 micrometers, and more preferably from 5 to 200 micrometers. Similarly, it is preferred that the at least one second debondable layer exhibits a thickness in the range of from 1 to 300 micrometers, preferably from 3 to 250 micrometers, and more preferably from 5 to 200 micrometers.
The complete article may advantageously exhibit a total thickness in the range of from 40 to 500 micrometers, preferably from 70 to 450 micrometers, and more preferably from 90 to 400 micrometers. Alternatively, the complete article may advantageously exhibit a total thickness in the range of from 40 to 500 micrometers, preferably from 70 to 450 micrometers, and more preferably from 90 to 400 micrometers.
The heat-debondable attachment article according to the present disclosure may further comprise a first adhesive layer disposed on at least part of the second major surface of the first debondable layer. This may add to ease of application and/or enhancing the adhesive properties of the article. Similarly, the heat-debondable attachment article according to the present disclosure may further comprise a second adhesive layer covering the second major surface of the second debondable layer. Preferably, the first adhesive layer and/or the second adhesive layer comprises at least one adhesive selected from structural adhesives, semi-structural adhesives, and pressure sensitive adhesives, preferably pressure sensitive adhesives.
It is further preferred that the attachment article as described herein comprises perforations. In this regard, it is preferred that either or both first and second debondable layer comprise perforations. This may have the effect of effectively encapsulate the heat-initiated debondable layer, which enhances the bonding and debonding capabilities of the article as described herein. Alternatively, the perforations may extend through the complete thickness of the article from the first major surface to the second major surface. It is further preferred that at least a portion of the article comprises perforations. Thereby, adhesive bonding and debonding properties may be distributed as desired over the length or over certain areas of the article as described herein.
Preferably, the article provides an overlap shear strength for the debondable portion of the article at a temperature range from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and less than 5 MPa, preferably less than 3 MPa, and more preferably less than 1 .5 MPa at a temperature in the range of from 80 to 100 °C.
Preferably, the article provides Floating Roller Peel at a temperature range between -40°C to 65 °C in the range of from 80 N/2.5 cm to 250 N/2.5 cm and less than 55 N/2.5 cm, preferably less than 50 N/2.5 cm, and more preferably less than 45 N/2.5 cm and even more preferably less than 35 N/2.5 cm at a temperature in the range of from 80 to 100 °C.
The present disclosure further provides die-cut, comprising the article as described herein. Diecuts provide numerous advantages with regard to transportability, application, and very desirably the precise fit for various shapes and applications.
The present disclosure further provides a part assembly having a first end and a second end, comprising a first part, a second part, and the heat- initiated debondable attachment article as described herein between the first and the second part. The first and the second part may be selected from a great variety of shapes and materials. For instance, they may be selected from metal or composite panels as used in vehicle bodies or in aerospace interior or exterior parts. Also, in an advantageous embodiment of the present disclosure, they may be selected from
battery casing parts, i.e. one of first and second parts may be a battery casing, and the other part may be a battery lid or the like. This contributes advantageously to the recyclability of a battery system. It is further preferred that the part assembly further comprises at least one adhesive disposed between the attachment article and the at least one first part and/or the at least one second part. The at least one adhesive is preferably selected from structural adhesives and semistructural adhesives, such as from two-components structural adhesives. Advantageously, the heat-initiated debondable attachment article bonds the first panel and second parts together. The part assembly may comprise the attachment article in the complete length between the first end and the second end. Alternatively, the attachment article may be disposed only close to the first end and/or close to the second end. This may bring the advantage that only in this position a first cleavage between first and second part may be achieved, which then compromises the bond between the first and second part on the complete length. Thus, an easy debonding may be achieved, with strong or even very strong bonds on the major length of the bond between first and second part where, for example, a strong structural adhesive may be employed. For example, the attachment article may be disposed at a length in the range of from 0.1 to 30 cm, preferably from 0.2 to 20, more preferably from 0.3 to 15 cm starting from the first end and/or from the second end of the part assembly.
Another aspect of the present disclosure is a method for bonding and debonding a part assembly, the method comprising the following steps:
(I) Attaching an article as described herein onto at least part of the surface of a first part;
(II) Optionally, applying at least one adhesive onto a first major surface of a second part;
(III) Attaching the second part onto the article attached to the first part such that the article connects the first and second part, thereby forming a part assembly;
(IV) Optionally, allowing the at least one adhesive to cure;
(V) Heating the part assembly so as to soften and/or at least partially melt the thermoplastic resin comprised in the first debondable layer and/or second debondable layer;
(VI) Disconnecting the second part from the first part.
Attaching in step (I) may comprise the application of pressure and/or heat. Pressure and/or heat is selected such that the at least one thermoplastic resin comprised in the at least one first heat debondable layer and the at least one second heat debondable layer is caused to at least partially soften and/or at least partially melt, thereby effectuating a certain bonding or lamination of the article to the part. Preferably, the material of the first part and/or the material of the second part
is selected from metals, polymers, compound materials, carbon fiber materials, and ceramic materials. It is also preferred that the method as described herein is a method of manufacturing and recycling of automotive panel assemblies or battery assemblies.
Yet another aspect of the present disclosure is the use of the heat-initiated debondable article as described herein or the die-cut as described herein in the manufacture of recyclable articles. Preferably, the article is selected from panels, vehicle body parts, battery parts, interior parts, exterior parts. It is further preferred that the manufacture takes place in the automotive industry, the commercial transportation industry, the civil engineering industry, the aerospace industry, or the shipbuilding industry. It is particularly preferred that the recyclable article is a part of a battery, and the battery is part of a car, a truck, a train, an aircraft, a spacecraft, a watergoing vessel such as a ship or a boat, a tool, a household applicance or an electricity system or a photovoltaic system of a building.
Exemplary Embodiments
1 . A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C, wherein the at least one first debondable layer and/or the at least one second debondable layer optionally comprises at least one toughener. A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C, wherein the article has an overlap shear strength at a temperature from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and lower than 5 MPa, preferably less than 3 MPa, and more preferably less than 1.5 MPa at a temperature in the range of from 80 to 100 °C, wherein the at least one first debondable layer and/or the at least one second debondable layer optionally comprises at least one toughener. A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C, wherein the article has an overlap shear strength at a temperature from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and lower than 5 MPa, preferably less than 3 MPa, and more preferably less than 1.5 MPa at a temperature in the range of from 80 to 100 °C, wherein the article has a Floating Roller Peel at a temperature range between -40°C to 65 °C in the range of from 80 N/2.5 cm to 250 N/2.5 cm and less than 55 N/2.5 cm, preferably less than 50 N/2.5 cm, and more preferably less than 45 N/2.5 cm and even more preferably less than 35 N/2.5 cm at a temperature in the range of from 80 to 100 °C, wherein the at least one first debondable layer and/or the at least one second debondable layer optionally comprises at least one toughener. A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers. wherein the article has a Floating Roller Peel at a temperature range between -40°C to 65 °C in the range of from 80 N/2.5 cm to 250 N/2.5 cm and less than 55 N/2.5 cm, preferably less than 50 N/2.5 cm, and more preferably less than 45 N/2.5 cm and even more preferably less than 35 N/2.5 cm at a temperature in the range of from 80 to 100 °C, wherein the at least one first debondable layer and/or the at least one second debondable layer optionally comprises at least one toughener.
6. A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive,
wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers, wherein the first debondable layer and the second debondable layer are in contact with each other through the porous support layer, wherein the at least one first debondable layer and/or the at least one second debondable layer comprises at least one toughener. A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers,
wherein the first debondable layer and the second debondable layer are in contact with each other through the porous support layer, wherein the at least one first debondable layer and/or the at least one second debondable layer comprises at least one toughener, wherein the article has an overlap shear strength at a temperature from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and lower than 5 MPa, preferably less than 3 MPa, and more preferably less than 1.5 MPa at a temperature in the range of from 80 to 100 °C, wherein the article has a Floating Roller Peel at a temperature range between -40°C to 65 °C in the range of from 80 N/2.5 cm to 250 N/2.5 cm and less than 55 N/2.5 cm, preferably less than 50 N/2.5 cm, and more preferably less than 45 N/2.5 cm and even more preferably less than 35 N/2.5 cm at a temperature in the range of from 80 to 100 °C.
8. The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C.
9. The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the article has an overlap shear strength at a temperature from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and lower than 5 MPa, preferably less than 3 MPa, and more preferably less than 1.5 MPa at a temperature in the range of from 80 to
100 °C.
10. The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the article has a Floating Roller Peel at a temperature range between -40°C to 65 °C in the range of from 80 N/2.5 cm to 250 N/2.5 cm and less than 55 N/2.5 cm, preferably less than 50 N/2.5 cm, and more preferably less than 45 N/2.5 cm and even more preferably less than 35 N/2.5 cm at a temperature in the range of from 80 to 100 °C
11. The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the first debondable layer and the second debondable layer are in contact with each other through the porous support layer.
12. The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the porous support layer comprises at least one material selected from tissue, mesh, non-woven cloth, veils, woven cloth, scrim, and any combinations thereof, preferably non-woven cloth, mesh, veils, and any combinations thereof.
13. The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the porous support layer comprises at least one material selected from natural and synthetic fibers, preferably from synthetic fibers, more preferably from polyethylene fibers.
14. The heat-initiated debondable attachment article according to any one of the preceding embodiments, wherein the porous support layer exhibits an area weight in the range of from 1 to 30 g/square meter, preferably from 2 to 25 g/square meter, and more preferably from 3 to 20 g/square meter.
15. The heat-initiated debondable attachment article according to any one of the preceding embodiments, wherein the porous support layer exhibits a thickness in the range of from 20 to 200 micrometers, preferably from 40 to 180 micrometers, and more preferably from 50 to 120 micrometers.
16. The heat-initiated debondable attachment article according to any one of the preceding embodiments, wherein the at least one thermoplastic polymer exhibits a glass transition temperature in the range of from 20 to 100 °C, preferably from 25 to 80 °C, and more preferably from 35 to 75 °C.
17. The heat-initiated debondable attachment article according to any one of the preceding embodiments, wherein the at least one thermoplastic polymer is selected from polyesters, poly(meth)acrylates, acrylonitrile butadiene styrenes, polyamides, polybenzimidazoles, polycarbonates, polyether sulfones, polyoxymethylenes, polyether ether ketones, polyetherimides, polyethylenes, polyphenylene oxides, polyphenylene sulfides, polypropylenes, polystyrenes, polyvinyl chlorides, and any combinations thereof, preferably polyesters,.
18. The heat-initiated debondable attachment article according to any one of the preceding embodiments, wherein the at least one thermoplastic resin exhibits a number average molecular weight in the range of from 5,000 to 50,000 g/mol, preferably from 7,000 to 40,000 g/mol, and more preferably from 8,000 to 30,000 g/mol.
The heat-initiated debondable attachment article according to any of the preceding embodiments, wherein the at least one first debondable layer and/or the at least one second debondable layer comprises at least one toughener, and wherein the at least one toughener is selected from butadiene rubbers, nitrile rubbers, and core-shell rubbers, more preferably from core-shell rubbers. The heat-initiated debondable attachment article according to any one of the preceding embodiments, wherein the article comprises perforations. A die-cut, comprising the article according to any one of the preceding embodiments. A part assembly having a first end and a second end, comprising a first part, a second part, and the heat-initiated debondable attachment article according to any one of embodiments 1 to 20 disposed between the first and the second part. A method for bonding and debonding a part assembly, the method comprising the following steps:
(I) Attaching an article according to any one of embodiments 1 to 20 onto at least part of the surface of a first part;
(II) Optionally, applying at least one adhesive onto a first major surface of a second part;
(III) Attaching the second part onto the article attached to the first part such that the article connects the first and second part, thereby forming a part assembly;
(IV) Optionally, allowing the at least one adhesive to cure;
(V) Heating the part assembly so as to soften and/or at least partially melt the thermoplastic resin comprised in the first debondable layer and/or second debondable layer;
(VI) Disconnecting the second part from the first part. A recyclable article comprising a heat-initiated debondable attachment article according to any one of embodiments 1 to 20 or the die-cut according to embodiment 21.
Examples
The present disclosure is further described without however wanting to limit the disclosure thereto. The following examples are provided to illustrate certain embodiments but are not meant to be limited in any way. Prior to that some test methods used to characterize materials and their properties will be described. All parts and percentages are by weight unless otherwise indicated.
Test Methods
Overlap Shear Strength
Overlap Shear Strength was determined according to DIN EN 1465 (issued 2009). Testing details are described within the Example section.
Tensile Strength
Tensile strength was determined according to the LWF-KS-2 method [Patent DE 19522247 A1 ].
Cleavage Strength
Cleavage Strength was determined according to ASTM D1062 using an Instron 5500R tensile tester.
Floating Roller Peel (FRP) Strength Test
The methods of EN2243-2 2006 were followed.
Example 1 and Comparative Examples 1 & 2:
A HotMelt foil comprising a blend (50:50 wt%) of Marnex AH441 and Marnex AH645 was extruded on a siliconized PET liner. The thickness of the functional layer can be adjusted as desired between e.g. 10 -200 pm. For the mechanical analysis (OLS) of the comparison example 1 , a 50 pm thick functional layer was used, which was laminated to the given substrate by means of heat (105°C) and pressure for 5 minutes (process according to figure 2). For Example 1 , two 50 pm thick functional layers (same as in comparison example 1) were used in combination with a support layer (Optiveil™, fine polyester veil, 8 g/m2). The final functional layer was assembled by means of heat (105°C) and pressure for 5 minutes and was the starting material (supported functional layer) for the process shown in figures 3 and 4.
The OLS samples for Example 1 were assembled according to the process visualized in figure 4. As substrates pairs of e-coated Steel or AlClad 2024+PSA+BR127 were used. The gap size between the assembled substrates was 1.0 mm in all cases and was adjusted by means of PTFE spacers. PUR based DP6330 from 3M was used as adhesive in all cases. For the mechanical analysis (OLS) of the comparison example 2, DP6330 was used alone without any functional layer. To proof the ability to manufacture Die-Cuts a hydraulic press comprising a “dog-bone shaped” Die-Cut mold was used. The supported functional layer from example 1 was compared to the unsupported design (50, 80, 170 pm). 10 specimens were tried to be manufactured in all cases.
Table 2: Result of Example 1 and Comparison Example 1 and 2. Failure modes: AF
Adhesive Failure; CF Cohesive Failure; SCF Mixed Failure Mode.
As can be seen in table 2, the described new process according to figure 4) shows significantly better strength compared to the process according to figure 2 between RT - 60°C. Sufficiently low values were obtained for Example 1 and the Comparison Example 1 at 90°C, which allows easy de-bonding of the specimens. Significant differences can be also seen regarding the obtained failure modes. Cohesive failures were observed in all cases for Example 1. Adhesive failures are most likely in case of the Comparison example 1. DP6330 alone without any functional layer shows superior bond strength between RT - 60°C (Comparison Example 2.). No significant performance drop was found in this case at 90°C.
A particular advantage of the supported design is the ability to manufacture Die-Cuts. 10 out of 10 Die-Cuts were manufactured successfully. No Die-Cuts were successfully manufactured via the unsupported product design.
Example 2 and Comparative Example 3:
HotMelt foils comprising a blend (45:45:10 wt%) of Marnex AH 441 :Marnex AH 645:Paraloid EXL- 2650J (Example 2) and a blend (50:50 wt%) of Marnex AH 441 :Marnex AH 645 (Comparative Example 3) were manufactured the way, that a Optiveil, fine polyester veil was embedded. The thickness of the supported functional layer was ~ 320 pm in both cases.
For the mechanical analysis Overlap Shear strength (OLS) and Tensile strength was tested. The specimens were manufactured according to figure 4. As substrates e-coated Steel was used and the gap size between the assembled substrates was 1.00 mm in all cases (table 4).
As can be seen in table 4, the incorporation of a core-shell rubber (CSR) based toughener results in improved OLS/tensile strength of the assembly tested at room temperature.
Example 3 and Comparative Example 4
A HotMelt foil comprising a blend (50:50 wt%) of Marnex AH441 and Marnex AH645 was extruded on a siliconized PET liner. The thickness of the functional layer can be adjusted as
desired between e.g. 10 - 200 m. For patent Example 3, two 80 pm thick functional layers were used in combination with a support layer (Optiveil™, fine polyester veil, 8 g/m2). The final supported functional layer was assembled by means of heat (105°C) and pressure for 5 minutes according to Example 1.
As substrates for cleavage testing aluminium square tubes, 6063 T6, 10SWG, 25 mm width and height, 200mm length were used. The bonding surface were grit blasted to 2Ra and subsequently coated using EW5000AS cured in a preheated oven at 140°C for 1 hour. For patent example 3, the primed tubes were heated to 120°C, and the supported functional layer (5mm x 50 mm) was tacked on to surface (applied 2mm from tube end, see figures 7 and 8.)) then left in oven for 5mins to ensure wet out then cooled to room temperature (acc. to fire 1 , new process, path 1). In the next step, a 10mm wide strip was marked out on all tubes using Scotch ® 3434 masking tape. A thermocouple was positioned in the center of the supported functional layer strip. 3M Structural Adhesive 9860 was applied to the tubes and 1mm glass beads were added to adjust the bondline thickness. For assembly, the second primed tube was as well covered with a SA 9860 bead and finally pressed on top of the first tube. For comparison Example 4, the same steps were conducted despite that no supported functional layer was used. All specimens were allowed to cure for 7 days at room temperature. For testing, the samples were clamped in the test machine and heated up to 90°C using a hot air gun (figure 9)). All specimens (n = 3, per group) were allowed to dwell 30 seconds at 90°C before the test was started (test speed: 300 kgf/min).
As can be seen on table 6, the use of a patch of the supported functional layer results in a decrease of the heat induced cleavage force (90°C) of about 44% compared to the comparison example 3 which didn’t comprise the supported functional layer.
Based on the results of Example 3, the supported functional layer can be used as well in small patches only, allowing an easy first opening process of an assembly. Next to the use of small patches a further variation would be the use of a perforated supported functional layer (figure 10).
Example 4 and Comparative Examples 5-7
A HotMelt layer comprising a blend (45:45:10 wt%) of Marnex AH 441 :Marnex AH 645:Paraloid EXL-2650J was manufactured in such a way that a Optiveil™, fine polyester veil was embedded in between a layer of the hot melt. The thickness of this functional layer was ~ 200 pm in total.
Overlap Shear Strength was determined according to DIN EN 1465 (issued 2009). The specimen manufacturing for Example 4 and Comparison Example 5-7 are described in the following:
Lap shear specimens were made using 2024-T3 phosphoric acid anodized and primed (corrosion inhibiting primer BR 127) panels in all cases (10 x 2.5 x 1.55 cm). Bond area was 12.5 mm x 25 mm per sample. Glass beads with 90 - 150 pm diameter within the DP6330 PUR based room temperature curable adhesive were used to control the bondline thickness in all cases. For Example 4 the curable adhesive was applied to one edge of each of the two panels (i.e., adherents) using a scraper. The HotMelt foil according to this invention was put between both adhesive layers before closing the samples. The specimens were fixed by means of clamps and allowed to cure for seven days at ambient temperature. For Comparison Example 5, the HotMelt foil according to this invention was laminated to one edge of an adherent by means of heat (130°C) and pressure (10 kPa) for 1 minute. After allowing the adherent to reach room temperature again, the curable adhesive was applied to the surface of the laminated HotMelt foil and the edge of the other adherent by means of a scrapper. The samples were closed and fixed with clamps and allowed to cure for seven days at ambient temperatures. For Comparison Example 6, the HotMelt foil according to this invention was put between the edges of both adherents. The bond was closed by applying heat (130°C) and pressure (10 kPa) for 1 minute. For Comparison Example 3, the curable adhesive was applied to one edge of each of the two panels using a scrapper. The bond was closed and the samples were cured for seven days at room temperature. All excesses of e.g. cured adhesive at the edges of the specimens, were removed by means of sandpaper. Two samples were tested for Example 4 and Comparison Example 5-7 and the average value, incl. standard deviation (in MPa) was reported. The test was conducted at a rate of 5 mm/minute at -40°C, RT, 60°C and 100°C.
Floating Roller Peel (FRP) Strength Test
The methods of EN2243-2 2006 were followed. The specimen manufacturing for Example 4 and Comparison Example 5-7 are described in the following:
Floating Roller Peel specimens were made using 2024-T3 phosphoric acid anodized and primed (corrosion inhibiting primer BR 127) panels, measuring 25 x 2.5 x 0.16 cm and 30 x 2.5 x 0.05 cm, in all cases. Bond area was 20 cm x 2.5 cm per sample. Glass beads with 90 - 150 pm
diameter within the DP6330 PUR based room temperature curable adhesive were used to control the bondline thickness in all cases. For Example 4 the curable adhesive was applied to the bond areas of both panels (i.e., adherents) using a scraper. The HotMelt foil according to this invention was put between both adhesive layers before closing the samples. The specimens were fixed by means of clamps and allowed to cure for seven days at ambient temperature. For Comparison Example 5, the HotMelt foil according to this invention was laminated to the bond area of the adherent measuring 25 cm x 2.5 cm x 0.16 cm by means of heat (130°C) and pressure (10 kPa) for 1 minute. After allowing the adherent to reach room temperature again, the curable adhesive was applied to the surface of the laminated HotMelt foil and the bond area of the other adherent measuring 30 cm x 2.5 cm x 0.05 cm by means of a scrapper. The samples were closed and fixed with clamps and allowed to cure for seven days at ambient temperatures. For Comparison Example 6, the HotMelt foil according to this invention was put between the bond areas of both adherents. The bond was closed by applying heat (130°C) and pressure (10 kPa) for 1 minute. For Comparison Example 3, the curable adhesive was applied to the bond areas of both panels using a scrapper. The bond was closed and the samples were cured for seven days at room temperature. All excesses of e.g. cured adhesive at the edges of the specimens, were removed by means of sandpaper. Two samples were tested for Example 4 and Comparison Example 5-7 and the average value, incl. standard deviation (in N/25 mm) was reported. The test was conducted at a rate of 140 mm/minute at -40°C, RT, 60°C and 100°C. In each test, the thinner substrate was peeled from the thicker one, and the results normalized to a width of 25 mm.
Evaluation:
To evaluate the composition (Example 4) and its application according to the herein disclosed invention the mechanical performance was tested against Comparison Example 5-7. Overlap Shear Strength and Floating Roller Pell Strength were selected as test methods. The skilled person will understand that the performance of a bonded joint needs to be reliably strong at all temperatures the assembly could potentially be exposed to. For e.g. EV power batteries -40°C - 60°C can be regarded as suitable service temperatures over lifetime. For Overlap Shear Strength at least 6.5 MPa and for Floating Roller Peel 80 N/2.5 cm are needed to ensure a strong and reliable bond at all given temperatures. To ensure a heat induced debonding, the mechanical performance of the assembly needs to drop significantly when reaching the targeted temperature e.g. 80 - 100°C. Beside the mechanical results as well the obtained failure modes were evaluated
(Table below), whereby a cohesive failure (CF) is preferred. The results are summarized in table 9.
Table 9: Result of Example 4 and Comparison Example 5-7.
MF: Mixed failure mode; CF: Cohesive Failure, AF: Adhesion Failure
As can be seen in table 9 the composition according to Example 4 showed an excellent performance for Lap Shear (OLS) and Floating Roller Peel (FRP) from -40°C - 60°C, always fulfilling the above mentioned thresholds. A clear cohesive failure mode (CF) was obtained for all test methods, which is a clear benefit of the herein disclosed invention. Comparison Example 5 and 6 especially showed drawbacks regarding their Peel properties, resulting in unsatisfactory results or even chipping (AF) of the panels at the start of the measurement. Therefore, no values were measurable. The targeted heat initiated debonding capability of Example 4 is obvious as the performance dropped 96% (OLS) and 43% (FRP) compared to Comparison Example 7 tested at 100°C.
Claims
1. A heat-initiated debondable attachment article, comprising
(i) a first debondable layer having a first major surface and a second major surface and comprising at least one first thermoplastic polymer;
(ii) a second debondable layer having a first major surface and a second major surface and comprising at least one second thermoplastic polymer;
(iii) a porous support layer immediately adjacent the first surface of the first debondable layer and immediately adjacent the first surface of the second debondable layer;
(iv) a first adhesive layer immediately adjacent the second major surface of the first debondable layer;
(v) optionally, a second adhesive layer immediately adjacent the second major surface of the second debondable layer;
(vi) optionally, a first liner adjacent or immediately adjacent the outer surface of the first adhesive layer; and
(vii) optionally, a second liner adjacent or immediately adjacent the outer surface of the second adhesive layer or adjacent or immediately adjacent the second debondable layer, wherein the first adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein the optional second adhesive layer comprises a curable adhesive, preferably a 2-part adhesive, wherein at least one of the first thermoplastic polymer and the second thermoplastic polymer comprise a blend of at least two different polymers.
2. The heat-initiated debondable attachment article according to any of the preceding claims, wherein the blend of at least two different polymers comprises a first polymer having a glass transition temperature from 20°C to 55°C and a second polymer having a glass transition temperature from greater than 55°C to 100°C.
3. The heat-initiated debondable attachment article according to any of the preceding claims, wherein the article has an overlap shear strength at a temperature from -40°C to 65 °C higher than 6.5 MPa, for example in the range of from 6.5 to 25 MPa or from 6.5 to 10 MPa and lower than 5 MPa, preferably less than 3 MPa, and more preferably less than 1.5 MPa at a temperature in the range of from 80 to 100 °C.
4. The heat-initiated debondable attachment article according to any of the preceding claims, wherein the article has a Floating Roller Peel at a temperature range between -40°C to
65 °C in the range of from 80 N/2.5 cm to 250 N/2.5 cm and less than 55 N/2.5 cm, preferably less than 50 N/2.5 cm, and more preferably less than 45 N/2.5 cm and even more preferably less than 35 N/2.5 cm at a temperature in the range of from 80 to 100 °C.
5. The heat-initiated debondable attachment article according to any of the preceding claims, wherein the first debondable layer and the second debondable layer are in contact with each other through the porous support layer.
6. The heat-initiated debondable attachment article according to any of the preceding claims, wherein the porous support layer comprises at least one material selected from tissue, mesh, non-woven cloth, veils, woven cloth, scrim, and any combinations thereof, preferably non-woven cloth, mesh, veils, and any combinations thereof.
7. The heat-initiated debondable attachment article according to any one of the preceding claims, wherein the porous support layer exhibits a thickness in the range of from 20 to 200 micrometers, preferably from 40 to 180 micrometers, and more preferably from 50 to
120 micrometers.
8. The heat-initiated debondable attachment article according to any one of the preceding claims, wherein the at least one thermoplastic polymer exhibits a glass transition temperature in the range of from 20 to 100 °C, preferably from 25 to 80 °C, and more preferably from 35 to 75 °C.
9. The heat-initiated debondable attachment article according to any one of the preceding claims, wherein the at least one thermoplastic polymer is selected from polyesters, poly(meth)acrylates, acrylonitrile butadiene styrenes, polyamides, polybenzimidazoles, polycarbonates, polyether sulfones, polyoxymethylenes, polyether ether ketones, polyetherimides, polyethylenes, polyphenylene oxides, polyphenylene sulfides, polypropylenes, polystyrenes, polyvinyl chlorides, and any combinations thereof, preferably polyesters,.
10. The heat-initiated debondable attachment article according to any one of the preceding claims, wherein the at least one thermoplastic resin exhibits a number average molecular weight in the range of from 5,000 to 50,000 g/mol, preferably from 7,000 to 40,000 g/mol, and more preferably from 8,000 to 30,000 g/mol.
11. The heat-initiated debondable attachment article according to any of the preceding claims, wherein the at least one first debondable layer and/or the at least one second debondable
layer comprises at least one toughener, and wherein the at least one toughener is selected from butadiene rubbers, nitrile rubbers, and core-shell rubbers, more preferably from coreshell rubbers.
12. The heat-initiated debondable attachment article according to any one of the preceding claims, wherein the article comprises perforations.
13. A die-cut, comprising the article according to any one of the preceding claims.
14. A part assembly having a first end and a second end, comprising a first part, a second part, and the heat-initiated debondable attachment article according to any one of claims 1 to 20 disposed between the first and the second part.
15. A method for bonding and debonding a part assembly, the method comprising the following steps:
(I) Attaching an article according to any one of claims 1 to 20 onto at least part of the surface of a first part;
(II) Optionally, applying at least one adhesive onto a first major surface of a second part;
(III) Attaching the second part onto the article attached to the first part such that the article connects the first and second part, thereby forming a part assembly;
(IV) Optionally, allowing the at least one adhesive to cure;
(V) Heating the part assembly so as to soften and/or at least partially melt the thermoplastic resin comprised in the first debondable layer and/or second debondable layer;
(VI) Disconnecting the second part from the first part.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP24165471.4A EP4480678A1 (en) | 2023-06-19 | 2023-06-19 | Supported heat initiated debondable layer for power battery applications |
| EP23179911.5 | 2023-06-19 | ||
| EP24165471.4 | 2023-06-19 | ||
| EP23179911.5 | 2023-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024261670A1 true WO2024261670A1 (en) | 2024-12-26 |
Family
ID=91617171
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2024/055999 Pending WO2024261669A1 (en) | 2023-06-19 | 2024-06-19 | Supported heat initiated debondable layer for power battery applications |
| PCT/IB2024/056001 Pending WO2024261670A1 (en) | 2023-06-19 | 2024-06-19 | Articles comprising heat initiated debondable layers |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2024/055999 Pending WO2024261669A1 (en) | 2023-06-19 | 2024-06-19 | Supported heat initiated debondable layer for power battery applications |
Country Status (1)
| Country | Link |
|---|---|
| WO (2) | WO2024261669A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19522247A1 (en) | 1995-03-22 | 1997-01-02 | Hahn Ortwin | Sample for testing of strength of spot welds or riveted joints |
| DE202006010886U1 (en) * | 2005-03-15 | 2006-09-07 | Henkel Kgaa | Double-sided, multilayer adhesive tape for sticking two objects together so that the joint can be broken by twisting when required, for use e.g. on removable self-adhesive hooks, has a break point in at least one place |
| KR20140014824A (en) * | 2012-07-26 | 2014-02-06 | 도레이첨단소재 주식회사 | Thermally releasable double-sided adhesive sheet and processing method of a product using the same |
| US20150299521A1 (en) * | 2012-11-02 | 2015-10-22 | Nitto Denko Corporation | Thermally debondable tape |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262479A (en) * | 1992-11-24 | 1993-11-16 | National Starch And Chemical Investment Holding Corporation | Plasticizer resisant hot melt pressure sensitive adhesive |
| US7087539B2 (en) * | 2001-09-25 | 2006-08-08 | Michael Carbonare | Stitchless seam adhesive tape |
| DE102009006935A1 (en) * | 2009-01-30 | 2010-08-05 | Tesa Se | Carrier reinforced heat-activated adhesives |
| EP3548273B1 (en) * | 2016-12-02 | 2020-12-23 | 3M Innovative Properties Company | Multilayer adhesive article |
| CN111040711B (en) * | 2019-12-05 | 2022-02-01 | 广东盈通新材料有限公司 | TPU adhesive, hot melt adhesive film and application |
-
2024
- 2024-06-19 WO PCT/IB2024/055999 patent/WO2024261669A1/en active Pending
- 2024-06-19 WO PCT/IB2024/056001 patent/WO2024261670A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19522247A1 (en) | 1995-03-22 | 1997-01-02 | Hahn Ortwin | Sample for testing of strength of spot welds or riveted joints |
| DE202006010886U1 (en) * | 2005-03-15 | 2006-09-07 | Henkel Kgaa | Double-sided, multilayer adhesive tape for sticking two objects together so that the joint can be broken by twisting when required, for use e.g. on removable self-adhesive hooks, has a break point in at least one place |
| KR20140014824A (en) * | 2012-07-26 | 2014-02-06 | 도레이첨단소재 주식회사 | Thermally releasable double-sided adhesive sheet and processing method of a product using the same |
| US20150299521A1 (en) * | 2012-11-02 | 2015-10-22 | Nitto Denko Corporation | Thermally debondable tape |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024261669A1 (en) | 2024-12-26 |
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