JP6900593B2 - Adhesive structure, its manufacturing method and peeling method - Google Patents

Description

The present invention provides an adhesion technique and adhesion capable of softening or melting a thermoplastic hot melt adhesive layer by heating a metal layer by electromagnetic induction heating to quickly and firmly bond an adherend having a thickness of 1 mm or more. Provides an easy way to disassemble a structure.

The hot-melt adhesive structure is a structure in which a solvent-free pressure-sensitive adhesive is used, and the pressure-sensitive adhesive is applied to a base material to be bonded in a heated and melted state, and exerts a pressure-sensitive action after solidification. Due to various advantages such as no need for drying, the adhesives used in hot melt adhesive structures are economical and environmentally friendly alternatives to conventional solvent-based adhesives, especially labels, packaging, furniture and textile materials. And footwear are being used more and more industrially.
For example, in the field of packaging foods such as pudding, jelly, honey beans, yogurt, lactic acid drinks, and tofu, blow molding, injection molding, and injection blow molding methods for hard to semi-hard resins such as polyethylene, polypropylene, polystyrene, and polyester. A single-layer sheet such as these resins or polyvinyl chloride resin, or a laminated sheet by a co-extrusion method using these resins as one layer, is appropriately used for secondary molding such as vacuum molding and pressure molding. Containers such as cups and trays molded by the method are used, and adhesive structures such as a sealing layer for the lid material of these containers have been obtained. (Patent Document 1) However, in the adhesive structure, only a resin film or a sheet-like material having an adherend with a thickness of less than 1 mm is available.

On the other hand, when the thickness of the adherend of the adhesive structure is 1 mm or more, it also exists in fields such as construction, remodeling, and woodworking.
Conventionally, as a method of joining interior and exterior materials such as plywood, gypsum board, calcium silicate board, ceramic tile, and metal plate to the outer surface, inner wall, partition wall, etc. of buildings and structures, nails, bolts, etc. have been used. The method of using joint parts has been used for a long time. This joining method is relatively easy to work with, but because it is a point joining, stress is concentrated on that one point, and in order to disperse this, it is necessary to drive nails and bolts over a wide area, and it is workable. It also becomes complicated. In addition, protrusions and overlays appear at the joints, spoiling the aesthetic appearance. Instead of these methods, a bonding method using a solvent-based, water-based, or liquid adhesive such as an epoxy resin has come to be used. In this bonding method using an adhesive, since surface bonding is performed, the stress becomes uniform over the entire bonded portion, and the durability is improved. Moreover, the surface of the joint portion becomes smooth, which is preferable from the viewpoint of aesthetics. However, the joining method using these liquid adhesives requires a certain amount of time after the adhesive is applied until the adhesive force is developed, and requires a predetermined time of curing after the adhesive is applied. For this reason, there is a problem that continuous joining work cannot be performed when a large amount of work is performed. As a joining method for improving such a problem, a method using double-sided adhesive tape has come to be used. However, in this joining method, adhesiveness is exhibited at the same time as the double-sided adhesive tape is attached, so that it is difficult to correct when the position deviates from a desired position. Furthermore, when the surface of the adherend is rough, the contact area with the adhesive surface is not sufficient, and the stress due to the weight of the material and the expansion and contraction of the building material due to climate change such as temperature and humidity after adhesion may occur. There is a problem that the adhered adhesive tape is easily peeled off over time due to the stress generated by the warp. Therefore, even in the bonding method using the double-sided adhesive tape, there is a problem that reliability cannot be obtained for a long-time bonding force.

As a method for improving the above problems, a conductive material and a thermoplastic resin adhesive layer are provided on the building base material in advance, or a tape or film-like adhesive and a conductive sheet are used as the building base material. Recently, a joining method by electromagnetic induction heating has been performed by sandwiching it between the inner and outer materials. In this method, the conductive material generates heat due to the eddy current generated by electromagnetic induction, and the heat generated melts the thermoplastic resin adhesive and adheres to the adherend. According to this method, if a thermoplastic resin is interposed between the building substrate surface and the interior / exterior material surface and a high-frequency transmitter is brought into contact with the high-frequency transmitter from above, the thermoplastic resin is heated and melted, and the transmitter is removed. Since it is immediately solidified and bonded, the joining is completed in a short time, and not only the work is simple, but also the used material can be reused even in the case of dismantling.

An adhesive melting device (Patent Document 2) using an electromagnetic induction heating method has been developed. However, the method proposed in Patent Document 2 does not have sufficient joint strength between members, and has problems in terms of excellent workability and reattachability. It is also reported that when the adhesive structure was disassembled, the adhesive layer was heated again using an electromagnetic induction device, and the adherends could be peeled off before the hot melt adhesive layer solidified (patented). Document 3) uses an adhesive containing a heat-expandable fine-grained hollow body, which comprises an aqueous emulsion-based adhesive, and the type of the adhesive is also limited.

JP-A-2009-190745 Japanese Unexamined Patent Publication No. 2000-20288 Japanese Patent No. 2006-200279

An object of the present invention is to have excellent workability and reattachability by laminating an adherend having a thickness of 1 mm or more, a thermoplastic hot melt adhesive layer, and a metal layer in this order, and to make the adherend. To provide an adhesive structure capable of imparting sufficient adhesive force. It is also to provide a method of disassembling the adhesive structure.

As a result of intensive research, the present inventors have found a hot melt adhesive sheet that solves the problem and an adhesive structure using the hot melt adhesive sheet.

That is, the present invention relates to an adhesive structure in which an adherend having a thickness of 1 mm or more, a thermoplastic hot melt adhesive layer, and a metal layer are laminated in this order.

The present invention also relates to the above-mentioned adhesive structure in which an adherend having a thickness of 1 mm or more, a thermoplastic hot-melt adhesive layer, a thermosetting adhesive layer, and a metal layer are laminated in this order.

Further, the present invention is the above-mentioned adhesive structure in which an insulating layer and a patterned conductive layer are further laminated on the outside of the metal layer in this order from the metal layer side.

The present invention also relates to the above-mentioned adhesive structure, wherein the thickness of the thermoplastic hot-melt adhesive layer is 10 μm or more and 500 μm or less.

The present invention also relates to the above-mentioned adhesive structure, wherein the thickness of the metal layer is 1 μm or more and 1000 μm or less.

Further, from the outside of the metal layer, a laminate formed by heating with an electromagnetic induction heating device and laminating the thermoplastic hot melt adhesive layer and the metal layer in this order and an adherend having a thickness of 1 mm or more are adhered to each other. The present invention relates to a method for producing an adhesive structure.

Further, the adhesive structure is heated by an electromagnetic induction heating device to soften or melt the thermoplastic hot melt adhesive layer in a solid state, and the adherend and the thermoplastic hot melt adhesive layer are peeled off. Regarding the method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an adhesive structure having excellent workability and reattachability and capable of imparting sufficient adhesive force to an adherend.

FIG. 1 represents a typical embodiment of the present invention. FIG. 2 represents another typical embodiment of the present invention. FIG. 3 represents another typical embodiment of the present invention.

Hereinafter, the adhesive structure of the present invention will be described in more detail.

<Thermoplastic hot melt layer>
The thermoplastic hot melt adhesives that can be used to make the thermoplastic hot melt adhesive layer of the present invention are ABS, polyamide, polyester, polyurethane, acrylic, polycarbonate, polystyrene, polyethylene, polypropylene, poly-1-butene, Polyisobutylene, polymethylpentene, propylene-ethylene copolymer, ethylene-propylene-diene copolymer, ethylene / butene-1 copolymer, polyolefins such as ethylene / octene copolymer, cyclopentadiene and ethylene and / or propylene Cyclic polyolefin such as copolymer with, ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA), polyolefin with polar groups introduced such as isobutylene / maleic anhydride copolymer , Maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, acrylic acid-modified polypropylene, styrene-based elastomer, acid-modified polypropylene such as rubber, and the like. Polyamide is preferred.

A tackifier or the like may be added to the thermoplastic hot melt adhesive of the present invention in order to improve the adhesiveness. The main tackifier is not particularly limited, but petroleum such as phenol resin, modified phenol resin, terpene phenol resin, xylenephenol resin, cyclopentadiene-phenol resin, xylene resin, aliphatic, alicyclic, aromatic, etc. Resins, hydrogenated aliphatic, alicyclic, aromatic and other petroleum resins, phenol-modified petroleum resins, rosin ester resins, hydrogenated rosin ester resins, low molecular weight polystyrene resins, terpene resins, It is preferable that a tackifier resin such as hydrogenated terpene resin is contained. The tackifier resin may be used alone or in combination of two or more.

The thermoplastic hot melt adhesive of the present invention may be added with wax or the like for the purpose of reducing the viscosity. The main wax is not particularly limited, but is carnauba wax, canderia wax, montan wax, paraffin wax, microwax, Fishertropch wax, polyethylene wax, polypropylene wax, oxides of these waxes, ethylene-acrylic acid copolymer. , Polyethylene-methacrylic acid copolymer and the like. The wax can be used alone or in combination of two or more.

The surface of the thermoplastic hot-melt adhesive layer of the present invention is preferably corona-treated, and polyethylene, polypropylene, etc., which have low polarity, are heat-cured by applying a thermosetting adhesive to the corona-treated surface. , Adhere more firmly. The corona treatment may be performed immediately before the application of the thermosetting adhesive or the corona treatment may be performed in advance.

As the thermoplastic hot melt adhesive layer of the present invention, a film-like one can be preferably used. The thickness of the thermoplastic hot-melt adhesive layer of the present invention is preferably 10 μm or more and 500 μm or less. More preferably, it is 20 μm or more and 300 μm or less. If the thickness of the thermoplastic hot melt adhesive layer is less than 10 μm or thicker than 500 μm, poor adhesion may occur. Various types of additives can be used as an additive for the thermoplastic hot melt adhesive layer, if necessary. For example, colorants, antiblocking agents, inorganic fillers, antioxidants, fillers, flame retardants, plasticizers, antistatic agents, light stabilizers, UV absorbers and heavy metal inactivating agents.

As the colorant, commonly known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. For example, monoazo, dizuazo, azolake, and benzimidazolone. There are pigments, perylenes, diketopyrrolopyrroles, condensed azos, anthraquinones, quinacridones, phthalocyanines, and anthraquinones, and pigments are pigments, perylenes, monoazos, condensed azos, isoindolinones, and oxidations. Examples include titanium and carbon.
Examples of the blocking inhibitor include silicones, unsaturated fatty acid amides such as erucic acid amides and oleic acid amides, and saturated fatty acid amides such as stearic acid amides and behenic acid amides.

Examples of the inorganic filler include particles such as metals, metal oxides and metal hydroxides, and fibrous materials. Specifically, glass fiber, carbon fiber, calcium silicate, calcium titanate, aluminum borate fiber, flaky glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, monohydrogen phosphate. Calcium, Wallastonite, Silica, Zeolite, Alumina, Boehmite, Aluminum Hydroxide, Titanium Oxide, Silicon Oxide, Magnesium Oxide, Calcium Silica, Sodium Alumina Silica, Magnesium Silica, Carbon Nanochieve, Graphite, Copper, Silver, Aluminum, Nickel , Iron, calcium fluoride, mica, montmorillonite, apatite and the like.

Antioxidants include high molecular weight hindered polyhydric phenol, triazine derivative, high molecular weight hindered phenol, dialkyl phenol sulfide, 2,2-methylene-bis- (4-methyl-6-tri-butylphenol), 4 , 4-Methyl-bis- (2,6-di-3-butylphenol), 2,6-di-3-butylphenol-p-cresol, 2,5-di-3-butylhydroquinone, 2,2 , 4-trimethyl-1,2-dihydroquinone, 2,2,4-trimethyl-1,2-dihydroquinone, nickel dibutyl dithiocarbamate, 1-oxy-3-methyl-4-isopropylbenzene, 4,4- Butylidenebis- (3-methyl-6-3-butylphenol), 2-mercaptobenzoimidazole and the like can be mentioned.

Examples of the filler include wet silica, aluminum hydroxide, aluminum oxide, magnesium oxide, montmorillonite, mica, smectite, organic montmorillonite, organic mica, and organic smectite.
Examples of the flame retardant include a phosphorus-containing compound-based flame retardant, a halogen-containing compound-based flame retardant, a sulfonic acid metal salt-based flame retardant, and a silicon-containing compound-based flame retardant.
Examples of plasticizers include phthalate ester plasticizers, polyester plasticizers, aliphatic dibasic acid ester plasticizers, aliphatic monobasic acid ester plasticizers, phosphoric acid ester plasticizers, and citric acid ester plasticizers. , Epoxy plasticizers, trimellitic acid ester plasticizers, tetrahydrophthalate ester plasticizers, glycol plasticizers, bisphenol A alkylene oxide derivatives and the like.
The antistatic agent may be a general-purpose antistatic agent for plastics, and specifically, a nonionic surfactant (for example, a fatty acid ester of a polyhydric alcohol, an ethylene oxide adduct of an alkylamine, and an alkyl). Amine ethylene oxide adduct fatty acid esters, etc.), anionic surfactants (eg, alkylbenzene sulfonates, higher alcohol sulfates, etc.), cationic surfactants (eg, aliphatic amine salts, quaternary ammonium salts) Etc.), amphoteric surfactants (eg, imidazoline type, betaine type, etc.).
Examples of the light stabilizer include hindered amine compounds and benzoate compounds.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzotriazole-based ultraviolet absorber.
Examples of the heavy metal inactivating agent include salicylic acid derivatives, hydrazide derivatives, oxalic acid amide derivatives and the like.

The above additives may be used alone or in admixture of two or more at any ratio as required.

In addition to the inflation method, T-die method, solution casting method, calendar method, etc., the above-mentioned thermoplastic hot-melt adhesive is slit-coated on a release paper or film, and the thermoplastic hot-melt layer obtained is made of metal. Obtained by laminating in layers.

<Metal layer>
The metal layer of the present invention is for inducing an eddy current by a high-frequency magnetic flux generated by an electromagnetic induction heating device and heating the metal layer with Joule to melt the thermoplastic hot-melt adhesive layer and bond it to concrete. Any metal material of this metal layer magnetic material or non-magnetic material can be used, and for example, conductivity selected from iron, copper, silver, gold, aluminum, nickel, stainless steel, zinc, lead, magnesium and their alloys. It is preferably a metal, more preferably aluminum, copper, iron and stainless steel, and particularly preferably aluminum and copper.
As these metals, those in the form of a film can be preferably used. The thickness of the metal layer is 1
It is preferably μm or more and 1000 μm or less, more preferably 10 μm or more and 500 μm or less, and further preferably 20 μm or more and 100 μm or less. Especially in the above range, quick heat generation and optimum heat generation temperature are achieved.

<Thermosetting adhesive layer>
In the adhesive structure of the present invention, a thermosetting adhesive layer can be provided, if necessary.
An example of an adhesive that can be used in the construction of the thermosetting adhesive layer of the present invention will be described. Examples of the thermosetting adhesive include a thermosetting adhesive using a main agent having a functional group such as a polyester resin, a polyurethane resin, an acrylic resin, and an epoxy resin and a curing agent as a base resin.
As the polyester resin, as the acid component of the monomer composition, for example, aromatic dibasic acids such as dimethyl terephthalic acid, terephthalic acid, isophthalic acid, and phthalic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, Pimelic acid, 1,6-hexanedicarboxylic acid,
Aliper dibasic acids such as azelaic acid, sebatic acid, nonandicarboxylic acid, decandicarboxylic acid, and hexadecanedicarboxylic acid, and glycol components such as ethylene glycol, 1,2-propanediol, and 1,3-propanediol. 1,3 butanediol, 1,4-butanediol, 1,2-pentadiol, 1,5-pentadiol, 3-methylpentadiol, 1,3-hexanediol, 1,6-hexanediol, 1,4 -Glycol such as cyclohexanediol, hydrogenated bisphenol A, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol or its residue-forming derivative or α, ω-oxyic acid such as caprolactone or its It can be obtained by appropriately selecting a saturated difunctional monomer composed of a residue-forming derivative and copolymerizing it by a conventional method.

The polyurethane resin is obtained by reacting a polyol such as a polyether polyol, a polyester-based polyol, or a polymer polyol with an isocyanate compound composed of a polyisocyanate in excess of the above-mentioned polyol. Low molecular weight having 2 or more active hydrogens consisting of diols such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and amines such as ethylenediamine and butylene diamine. Examples thereof include polymers obtained by ring-opening polymerization of one or more alkylene oxides such as propylene oxide, ethylene oxide, and tetrahydrofuran in the presence of one or more active hydrogen compounds.
Examples of the polyester-based polyol include polybasic acids such as adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid and succinic acid, and bisphenol A, ethylene glycol, 1,2-propylene glycol and 1,4. Polymers obtained by dehydration condensation with polyhydric alcohols such as -butanediol, diethylene glycol, 1,6-hexanediol and neopentyl glycol, and lactones such as ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include polymers and condensates of hydroxycarboxylic acids such as castor oil and reaction products of castor oil and ethylene glycol and the above-mentioned polyhydric alcohols.
Examples of the polymer polyol include those obtained by graft-polymerizing the above-mentioned polyether-based polyol or polyester-based polyol with an ethylenically unsaturated compound such as acrylonitrile, styrene, or methyl (meth) acrylate, or 1,2- or 1,4-. Examples thereof include polybutadiene polyols or hydrogenated products thereof.
Examples of the polyisocyanate include diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate, trimerics of the diisocyanates, and triisocyanates such as triphenylmethane triisocyanate. Further, crude MDI which is a mixture of diphenylmethane diisocyanate, triphenylmethane triisocyanate and the like can be mentioned. These polyisocyanates may be used alone or in combination of two or more. It is blended with hydroxyl groups 1 of the hydroxyl-terminated polyurethane polymer so as to form isocyanate groups 2 to 8 of the isocyanate compound, and is used as the adhesive.

The epoxy resin may have two or more epoxy groups in one molecule, and specifically, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolac type epoxy resin. , Alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hidden in type epoxy resin, isocyanurate epoxy resin, acrylic acid modified epoxy resin (epoxy acrylate), phosphorus-containing epoxy resin and these halogen resins (bromination) (Epoxy resin, etc.) and hydrogen additives. These epoxy resins may be used alone or in combination of two or more. Brominated epoxy resin and the like are particularly effective when flame retardancy is required for the adhesive. Since acrylic acid-modified epoxy (epoxy acrylate) has photosensitivity, it is effective for imparting photocurability to an epoxy resin composition.
The curing agent can be used without particular limitation as long as it can be used for curing an epoxy resin. For example, an aliphatic amine-based curing agent, an alicyclic amine-based curing agent, and an aromatic amine-based curing agent can be used. Examples thereof include a curing agent, an acid anhydride curing agent, dicyandiamide, a boron trifluoride amine complex salt, and an imidazole compound. These may be used alone or in combination of two or more. The blending amount of the curing agent can be determined according to the epoxy resin.

Examples of the additive for the thermosetting adhesive layer include a silane coupling agent and an antioxidant. Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy). ) Silane, vinyl triacetylsilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptoethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloro Examples thereof include propyltriethoxysilane and vinyltrichlorosilane.
As the antioxidant, the antioxidant used for the thermoplastic hot melt adhesive layer described above is used.
The thermosetting adhesive of the present invention may contain various solvents. For example, ketone compounds such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone, cyclic ether compounds such as tetrahydrofuran (THF) and dioxolane, ester compounds such as ethyl acetate, ethyl acetate and butyl acetate, toluene, xylene and the like. Examples include aromatic compounds, alcohol compounds such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene coal monomethyl ether. These may be used alone or in combination of two or more.
As a device for applying the epoxy adhesive to the metal layer or the thermoplastic hot melt layer, a comma coater, a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a blade coater, and a gravure coater. , Micro gravure coater and the like. The amount of the thermosetting adhesive applied is preferably about 1 to 50 μm in terms of dry film thickness. More preferably, it is 2 to 25 μm. More preferably, it is 2 to 10 μm.

A thermosetting adhesive is applied to either the thermoplastic hot-melt adhesive layer or the metal layer, dried, and then the metal film is bonded so that the outermost surface becomes the thermoplastic hot-melt adhesive layer, and then the thermosetting is performed. It is necessary to perform aging to cure the sex adhesive. Thermosetting adhesives have a slow curing rate and are therefore aged.
Specifically, the thermoplastic hot melt and the adhesive film are bonded to each other via a thermosetting adhesive, and then stored in a greenhouse at 35 to 80 ° C. for about 3 to 5 days for aging. To cure. At this time, if the storage temperature is too high, for example, the thermoplastic hot-melt adhesive layers in contact with each other when rolled may cause blocking, so care must be taken in the winding pressure and the storage temperature. In addition, since the degree of curing of the thermosetting adhesive changes depending on the aging conditions, it may affect the adhesive strength between the thermoplastic hot-melt adhesive layer and the metal layer of the hot-melt adhesive sheet, resulting in insufficient aging. In this case, delamination (layer peeling) may occur due to poor curing of the adhesive.
In order to prevent blocking, it is effective to emboss the surface of the thermoplastic hot-melt adhesive sheet or put a release paper or release film on it. The surface roughness of the thermoplastic hot melt adhesive sheet is preferably 0.01 μm or more and 100 μm or less. When the surface roughness Ra of the thermoplastic hot melt adhesive sheet is less than 0.01 μm The thermoplastic hot melt adhesive sheet may block and become unusable, and when the surface roughness of the thermoplastic hot melt adhesive sheet is larger than 100 μm The strength of the thermoplastic hot melt adhesive sheet becomes low, which may cause problems such as the thermoplastic hot melt adhesive sheet being cut off during coating.
It is effective to perform corona treatment on the surface of the thermoplastic hot melt adhesive layer in order to increase the adhesive strength between the thermoplastic hot melt adhesive layer and the thermosetting adhesive layer. In particular, it is effective for adhering a film having low polarity such as a polyethylene film or a polypropylene film to a metal single layer film. However, since it is also possible to cure the thermosetting adhesive layer, it is not always necessary to age the thermosetting adhesive layer before electromagnetic induction heating.

Examples of the adherend include plastic, paper, a composite of paper and plastic, concrete, tile, paving material, wood, cloth, leather, rubber, glass and the like.
The thickness of the adherend of the present invention is preferably 1 mm or more.

<Insulation layer>
The insulating layer can be formed between the metal layer and the conductive layer by a method of adhering a PET film, a vinyl chloride film, a PEN film or the like to the metal layer with an adhesive or the like. It can also be formed by applying an insulating paint, and the insulating paint is generally a resin dissolved in a solvent.
Further, when a PET film or the like is formed as an insulating layer on the thermoplastic hot melt adhesive layer (C2), it can also be formed by thermal laminating.
The dry film thickness of the insulating layer is preferably about 1 to 1,000 μm, more preferably 10 to 500 μm, and even more preferably 10 to 200 μm.

<Patterned conductive layer>
Examples of the method for forming the patterned conductive layer include a method of photolithography of a conductive paint, a patterning method by various printing, and a method of pasting a conductive material.
As the conductive coating material, a composition in which a conductive filler is dispersed in a resin or the like is used, and examples of the conductive filler include silver-based, silver-copper composite-based, nickel-based, carbon-based, and copper-based.
As a patterning method by printing, a method such as screen printing, slot coating, or inkjet can be adopted.
The dry film thickness of the conductive layer is preferably about 1 to 1,000 μm, more preferably 5 to 500 μm, and even more preferably 50 to 200 μm.
Further, it is preferable to have a protective layer on the outside of the conductive layer.

The laminate is obtained by adhering a thermoplastic hot-melt adhesive obtained by slit-coating a plastic hot-melt adhesive on a release paper or a film to a metal layer, and has a sheet shape. And tape-like.

Manufacturing method of adhesive structure:
(1) Thermoplastic hot melt adhesive obtained by slit-coating the above thermoplastic hot melt adhesive on a release paper or film in addition to the inflation method, T-die method, solution casting method, calendar method, etc. The agent is adhered to the metal layer to obtain a laminate.
(2) A support is placed on the outside of the metal layer, and the above laminate and the adherend are heated in this order from the outside of the support by an electromagnetic induction heating device having an input voltage of 100 V and a power consumption of 550 W. By softening the plastic hot-melt adhesive and terminating the heating, the thermoplastic hot-melt adhesive is solidified and the adherend and the above-mentioned laminate are brought into close contact with each other to obtain an adhesive structure. (Structure of adhesive structure: adherend / thermoplastic hot melt adhesive / metal layer)
Examples of the support include plastic, paper, a composite of paper and plastic, concrete, tile, paving material, wood, cloth, leather, rubber, glass and the like.
If necessary, it is preferable to use an adhesive that can be thermoset. In the production of the adhesive structure in this case, either the thermoplastic hot melt adhesive layer or the metal layer is coated with a thermosetting adhesive, and after drying, the outermost surface becomes the thermoplastic hot melt adhesive layer. Since the heat-curable adhesive has a slow curing rate after the metal layers are bonded together, it is necessary to perform aging for the purpose of curing the thermosetting adhesive.
Specifically, after the thermoplastic hot melt layer and the thermosetting adhesive layer are bonded to each other via a thermosetting adhesive, they are stored in a greenhouse at 35 to 80 ° C. for about 3 to 5 days for aging. This cures the adhesive in the thermosetting adhesive layer. At this time, if the storage temperature is too high, for example, the thermoplastic hot-melt adhesive layers in contact with each other when rolled may cause blocking, so care must be taken in the winding pressure and the storage temperature. In addition, since the degree of curing of the thermosetting adhesive changes depending on the aging conditions, it may affect the adhesive strength between the thermoplastic hot-melt adhesive layer and the metal layer, and if aging is insufficient, , May cause delamination (layer peeling) due to poor curing of the adhesive.
It is effective to perform corona treatment on the surface of the thermoplastic hot melt adhesive layer in order to increase the adhesive strength between the thermoplastic hot melt adhesive layer and the thermosetting adhesive layer. In particular, it is effective for adhering a film having low polarity such as a polyethylene film or a polypropylene film to a metal layer.

How to disassemble the adhesive structure:
The adhesive structure is heated from the outside of the adherend and / or the outside of the support by an electromagnetic induction heating device to soften or melt the thermoplastic hot-melt adhesive layer in a solid state, and the adherend is formed with the adherend. Peel off the thermoplastic hot melt adhesive layer.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the present invention, unless otherwise specified, parts represent parts by weight and% represents% by weight.

The thermoplastic hot melt layer used in Examples 1 and 2 is as follows.
・ LDPE single layer film (with corona treatment) Film thickness: 50 μm manufactured by Hokuetsu Kasei Co., Ltd. ・ LDPE single layer film (with corona treatment) Film thickness: 100 μm manufactured by Hokuetsu Kasei Co., Ltd.

The thermoplastic hot melt layer used in Examples 3 to 24 was obtained by forming a film of the following polymer.
-Polyamide (nylon base): Platamide M1276 manufactured by Arkema Co., Ltd.
-Polyamide (dimeric acid base): Macromelt 6239 manufactured by Henkel Co., Ltd.
-Crystalline polyester: Byron GA6300 manufactured by Toyobo Co., Ltd.
-Amorphous polyester: Byron 600 manufactured by Toyobo Co., Ltd.
-Polyurethane (polyether type): Elastran ET-370 manufactured by BASF Ltd.
-Acrylic (methyl methacrylate): Sumipex EX manufactured by Sumitomo Chemical Co., Ltd.
-Ethylene-vinyl acetate copolymer: Ultrasen 540 manufactured by Tosoh Corporation
-Modified polyolefin: Admer SE810 manufactured by Mitsui Chemicals, Inc.

The thermosetting adhesive used in the present invention is as follows.
Main agent TM-585-60: (polyester) non-volatile content 60% Toyo Morton Co., Ltd. TM-K55: (polyester) non-volatile content 30% Toyo Morton Co., Ltd. TM-K76: (polyester) Non-volatile content 51% Toyo Morton Co., Ltd. Hardener CAT-10L: (Aromatic) Non-volatile content 52.5% Toyo Morton Co., Ltd. CAT-RT85: (Aliphatic) Non-volatile content 70% Made by Toyo Morton Co., Ltd.

The supports used in the present invention are as follows.
-Adhesive layer: Oliveine BPS8170 (manufactured by Toyochem Co., Ltd.)
-Base material: wood (thickness: 10 mm), leather (thickness: 3 mm), hard PVC (thickness: 3 mm), glass (thickness: 3 mm)

Method for producing thermosetting adhesive (adhesive A)
The main agent TM-K55 of the thermosetting adhesive and the curing agent CAT-10L were blended at a weight ratio of 100/7 and diluted with ethyl acetate so that the solid content was 30%.
(Adhesive B)
The main agent TM-585-60 of the thermosetting adhesive and the curing agent CAT-10L were mixed at a weight ratio of 100/7 and diluted with ethyl acetate so that the solid content was 30%.
(Adhesive C)
The main agent TM-K76 of the thermosetting adhesive and the curing agent CAT-10L were blended at a weight ratio of 100/7 and diluted with ethyl acetate so that the solid content was 30%.
(Adhesive D)
The main agent TM-K76 of the thermosetting adhesive and the curing agent CAT-RT85 were blended at a weight ratio of 100/7 and diluted with ethyl acetate so that the solid content was 30%.

The types and thicknesses of the metal layers are shown in Tables 1 and 2.

(Adjustment of conductive paint)
Conductive paint (1): REXALPHA RAFS045 manufactured by Toyochem Co., Ltd. (silver paste manufactured by Toyochem Co., Ltd.)
(Adjustment of insulation layer)
Insulation layer (1): PET film with a thickness of 188 μm

(Examples 1 to 22)
The corona-treated surface of the thermoplastic hot-melt layer and the aluminum foil were bonded together using a pressure-bonding roll whose surface temperature was heated to 120 ° C. to obtain a laminate.
When a thermosetting adhesive was used, the thermosetting adhesive was applied to the aluminum layer using a hand applicator so as to have a coating amount of Dry (after drying) of 3 to 10 g / m2. The drying conditions were 80 ° C. for 1 minute. Next, crimping was performed using a thermoplastic hot melt adhesive film and a crimping roll (the crimping roll was heated to 60 ° C.). Then, aging was carried out in an environment of 40 ° C. for 4 days to obtain a hot melt adhesive sheet. When a corona-treated thermoplastic hot-melt adhesive film was used, the corona-treated surface was brought into contact with a thermosetting adhesive surface.
The above laminate is pressed against an adherend and / or a support using an electromagnetic induction heating device (all-over adhesive device manufactured by Achilles Corporation) and heated for 1 to 10 seconds. The applicator portion (coil) of the electromagnetic induction heating device was kept pressed for about 5 seconds until the plastic hot-melt adhesive layer cooled, and the adhesive was adhered.

(Example 23)
The thermosetting adhesive C was applied to the corona-treated surface of the thermoplastic hot-melt layer and the aluminum layer using a hand applicator so that the amount of application Dry (after drying) was 4 g / m2. The drying conditions were 80 ° C. for 1 minute. Next, crimping was performed using a thermoplastic hot melt adhesive film and a crimping roll (the crimping roll was heated to 60 ° C.). Then, aging was carried out in an environment of 40 ° C. for 4 days to obtain a hot melt adhesive sheet. When a corona-treated thermoplastic hot-melt adhesive film was used, the corona-treated surface was brought into contact with a thermosetting adhesive surface.
The above laminate is pressed against the adherend using an electromagnetic induction heating device (all-over adhesive device manufactured by Achilles Corporation) and heated for 2 seconds. Even after the heating is completed, the thermoplastic hot melt adhesive layer is used. The applicator part (coil) of the electromagnetic induction heating device was kept pressed for about 5 seconds until it cooled down, and the adhesive was adhered.
A 188 μm-thick PET film, which is an insulating layer (1), was adhered onto the aluminum layer with a thermal lamina heated to 120 ° C., and the conductive paint (1) was printed on the aluminum layer by screen printing. Further, as a protective layer, a PET film having a thickness of 188 μm was adhered with a thermosetting agent C.

The types and thicknesses of the materials used in each of the layers of Examples 1 to 23 and Comparative Examples 1 and 2 are shown in Tables 1 and 2.

(Measuring method of adhesive strength)
For the adhesive strength, the shear strength was measured at a peeling speed of 300 mm / min using a tensile tester (manufactured by A & A Co., Ltd., trade name RTA-100) (measurement temperature: 23 ° C., humidity 50%). .. The peeling force was “◯” for 10 N / 25 mm or more (including substrate destruction) and “x” for less than 10 N / 25 mm. The evaluation results are shown in Tables 1 and 2.

(Peeling test)
When each of the adhesive structures of Examples 1 to 23 was heated under the same electromagnetic induction heating conditions as in the adhesive step, all of them could be easily peeled off from the adherend, and the adhesive structure could be disassembled. The evaluation results are shown in Tables 1 and 2.

(Comparative Example 1)
As Comparative Example 1, a commercially available line tape E-SD (manufactured by Nitto Denko) for indoor smooth floors was attached to concrete, and the physical properties of the adhesive structure were evaluated by the same evaluation method as in Examples 1 to 23. It was compared with the results of 1 to 23.
Evaluation: Compared with Examples 1 to 23, the adhesive strength between the concrete and the laminate of the thermoplastic hot melt adhesive layer and the metal layer was weak, and the evaluation result was “x”.

(Comparative Example 2)
As Comparative Example 2, a PE sheet having a thickness of 0.5 mm was used as an adherend, and the physical characteristics of the adhesive structure were compared with the results of Examples 1 to 23 by the same evaluation method as in Examples 1 to 23.
Evaluation: Compared with Examples 1 to 23, the adhesive strength between the PE sheet having a thickness of 0.5 mm and the laminate of the thermoplastic hot melt adhesive layer and the metal layer was weak, and the evaluation result was “x”.

Claims (6)

An adhesive structure in which an adherend having a thickness of 1 mm or more, a thermoplastic hot-melt adhesive layer, a heat-cured adhesive layer, and a metal layer are laminated in this order (however, an adherend having a thickness of 1 mm or more (D1). ), A hot melt adhesive sheet for electromagnetic induction heating, and a second adherend (D2) having a thickness of 1 mm or more, which is an adhesive structure formed by adhering the hot melt adhesive sheet for electromagnetic induction heating. However, the thermoplastic hot-melt adhesive layer (C1), the thermo-cured adhesive layer (B1), the metal layer (A), the second thermo-cured adhesive layer (B2), and the second thermoplastic hot-melt adhesive (Excluding the adhesive structure, which is a hot melt adhesive sheet for electromagnetic induction heating, which is laminated in the order of the agent layer (C2)) . The adhesive structure according to claim 1, further comprising an insulating layer and a patterned conductive layer laminated on the outside of the metal layer in this order from the metal layer side. The adhesive structure according to claim 1 or 2, wherein the thickness of the thermoplastic hot melt adhesive layer is 10 μm or more and 500 μm or less. The adhesive structure according to any one of claims 1 to 3 , wherein the thickness of the metal layer is 1 μm or more and 1000 μm or less. The method for manufacturing an adhesive structure according to any one of claims 1 to 4.
A laminate having a thickness of 1 mm or more, which is heated from the outside of the metal layer by an electromagnetic induction heating device and is laminated in the order of a thermoplastic hot melt adhesive layer, a heat-cured adhesive layer, and a metal layer. A method for manufacturing an adhesive structure, which comprises adhering a body to an adhesive structure. The adhesive structure according to any one of claims 1 to 4 is heated by an electromagnetic induction heating device to soften or melt the thermoplastic hot melt adhesive layer in a solid state, and the thermoplastic hot melt adhesive is bonded to the adherend. A method of peeling off the agent layer.

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