JP6900592B2 - Adhesive structures, methods of manufacturing and peeling adhesive structures - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention relates to an adhesive structure in which a concrete having a primer-treated layer and an adhesive sheet in which a thermoplastic hot-melt adhesive layer is provided in a metal layer are bonded, and a method for producing an adhesive structure to be bonded by electromagnetic induction heating. And the method of peeling by electromagnetic induction heating.

Since the high growth era, concrete has been used in many industries such as construction and civil engineering. Nails, bolts, etc. were used to bond concrete to other members. These methods
The work is relatively easy, but since it is necessary to bond at points, the force is concentrated on one point, and it was desirable to bond on the surface in order to disperse the force. In addition, there is a problem that the aesthetic appearance is spoiled because protrusions and build-ups appear at the joints. In order to solve these problems, an epoxy adhesive is used for bonding to concrete (Patent Documents 1 and 2). However, since it takes time for the adhesive to cure, the epoxy adhesive must be fixed for a long time after being attached to concrete with another base material, or it will come off if it is not fixed. I had a problem such as.

Adhesive tape has been developed as a method that does not require time to cure the adhesive (Reference 3). Adhesive tape has the advantage of shortening the curing time, but its adhesive strength is weak, and it is difficult to put it into practical use because the adhesive strength decreases when it is exposed to water or heat.
On the other hand, in recent years, an adhesive melting device using an electromagnetic induction heating method, an electromagnetic induction heating adhesive sheet, and the like have been developed. Electromagnetic induction heating is the generation of an alternating current by passing a high-frequency alternating current through the coil of an electromagnetic induction heating device to generate an eddy current in the metal of a conductive material in the magnetic field, and Joule based on this eddy current. This is a heating method in which a conductive material is heated by heat. The higher the frequency of the alternating current flowing through the coil, the faster the change in the magnetic field, the larger the eddy current based on it, and the shorter the heating time. The bonding method by electromagnetic induction heating has a short curing time, and it is possible to suppress a decrease in bonding strength due to water or heat.
Also in the case of bonding with concrete, a method of bonding and disassembling using electromagnetic induction heating has been proposed (Patent Document 4). However, the method proposed in the patent document has a problem that the adhesive strength to concrete is not sufficient and the range of use is limited.

Japanese Patent Application Laid-Open No. 2001-172597 Special fair 6-13689 Japanese Patent Application Laid-Open No. 8-3-19462 Japanese Patent Application Laid-Open No. 1015-136811

The problem to be solved by the present invention is an adhesive structure in which a thermoplastic hot melt adhesive is firmly adhered to concrete, a polyester member, a vinyl chloride member, an epoxy member, a wood member, and gypsum board. Alternatively, to provide an adhesive structure in which various members such as glass are firmly adhered, a method for manufacturing them by using an electromagnetic induction heating method, and a peeling method that can be easily peeled and disassembled by using an electromagnetic induction heating method. It is in.

That is, the present invention provides a primer layer (D) surface of a laminate (X) having a concrete layer (E) and a primer layer (D), a metal layer (A), and a thermoplastic hot melt adhesive layer (C1). The present invention relates to an adhesive structure in which a thermoplastic hot-melt adhesive layer (C1) surface of a laminate (Y) having an adhesive is bonded to the surface.

Further, the present invention relates to the above-mentioned adhesive structure having a thermosetting adhesive layer (B1) between the metal layer (A) and the thermoplastic hot-melt adhesive layer (C1) in the laminated body (Y). Regarding.

The present invention also relates to the above-mentioned adhesive structure having a second thermoplastic hot melt adhesive layer (C2) on the metal layer (A) side of the laminated body (Y).

Further, according to the present invention, in the laminated body (Y), a second thermosetting adhesive layer (B2) is formed between the metal layer (A) and the second thermoplastic hot melt adhesive layer (C2). The present invention relates to the above-mentioned adhesive structure having.

The present invention also relates to the above-mentioned adhesive structure having an insulating layer and a patterned conductive layer on the outside of the surface of the laminated body (Y) facing the thermoplastic hot-melt adhesive layer (C1).

Further, the present invention provides a primer layer (D) surface of a laminate (X) having a concrete layer (E) and a primer layer (D), a metal layer (A), and a thermoplastic hot melt adhesive layer (C1). The present invention relates to a method for producing an adhesive structure, which comprises bonding the thermoplastic hot melt adhesive layer (C1) surface of the laminated body (Y) to the surface of the laminated body (Y) by electromagnetic induction heating.

Further, in the present invention, the primer layer (D) surface of the laminate (X) having the concrete layer (E) and the primer layer (D) and the adherend (F) having a thickness of 0.3 mm or more are made of metal. Through a laminate (Y) having a thermoplastic hot-melt adhesive layer (C1) on one side of the layer (A) and a second thermoplastic hot-melt adhesive layer (C2) on the other side, The present invention relates to a method for producing an adhesive structure, which comprises bonding from the outside of a concrete layer (E) and / or the outside of an adherend (F) having a thickness of 0.3 mm or more by electromagnetic induction heating.

Further, in the present invention, the primer layer (D) surface of the laminate (X) having the concrete layer (E) and the primer layer (D) and the adherend (F) having a thickness of 0.3 mm or more are made of metal. Adhesion is provided via a laminate (Y) having a thermoplastic hot-melt adhesive layer (C1) on one side of the layer (A) and a second thermoplastic hot-melt adhesive layer (C2) on the other side. A thermoplastic hot-melt adhesive that is in a solid state by heating the bonded structure from the outside of the concrete layer (E) and / or the outside of the adherend (F) having a thickness of 0.3 mm or more by electromagnetic induction heating. A method of softening or melting the layer (C1) and / or the second thermoplastic hot-melt adhesive layer (C2) to peel off the concrete layer (E) and the adherend (F) having a thickness of 0.3 mm or more. Regarding.

According to the present invention, by providing a primer layer on a concrete layer, it is possible to provide an adhesive structure in which concrete and a thermoplastic hot melt adhesive are firmly adhered to each other. Further, it is possible to provide an adhesive structure in which concrete and various base materials such as polyester-based member, vinyl chloride-based member, epoxy-based member, wood member, gypsum board, and glass are firmly adhered to each other. Further, by using the electromagnetic induction heating method, it is possible to provide a manufacturing method capable of manufacturing these adhesive structures in a short time without aging and a method of peeling concrete without damaging it.

Represents a typical embodiment of the present invention. Represents a typical embodiment of the present invention. Represents a typical embodiment of the present invention.

<Adhesive structure>
The adhesive structure of the present invention is a laminate (X) having a concrete layer (E) and a primer layer (D), and a laminate (X) having at least a metal layer (A) and a thermoplastic hot melt adhesive layer (C1). Y) and are bonded together. Hereinafter, the laminates (X) and (Y) and the components constituting them will be described.

<Laminated body (X)>
[Concrete layer (E)]
The concrete layer of the present invention is a lump of a paste obtained by adding water to cement and mixing it over time, and even if it contains fine aggregate such as sand and coarse aggregate such as gravel as aggregate. Good. Concrete is hardened by the dissolution and precipitation reaction of cement. Cement is composed of elements such as calcium, silicon, aluminum and iron. When in contact with water, calcium ions dissolve and the amount of calcium ions in the aqueous solution increases. The main components, silicic acid (SiO2) and alumina (AL ₂ O ₃ ), exist as stable substances (polymers) in which their ions are polymerized with each other, and do not react with calcium ions. However, in cement, silicate ions and aluminum ions (alumina-ions) are relatively easy to react and exist as monomers, and when the surrounding calcium ions are leached out, they dissolve into the solution and calcium ions. Cement hydrate (CSH: ettringite) that is difficult to dissolve in water is produced by reacting with water molecules and excess calcium ions are precipitated as calcium hydroxide. The hydrate particles bind to each other and begin to cure.
Bonds between particles are considered to be retained by intermolecular attractive force or hydrogen bonds, and unlike calcium hydroxide, CSH is a fine bond of 0.1 μm or less, and particles per unit volume. Since the bonding area between them is extremely large, it exerts a high bonding force and exhibits the strength of the cured product.
The concrete layer of the present invention includes cement hardened by mixing cement and water, mortar hardened by mixing cement, water and fine aggregate (sand), and cement, water and aggregate (fine aggregate (sand)). It is possible to use concrete or the like mixed with coarse aggregate (sand) and hardened.

[Primer layer (D)]
The primer layer of the present invention exists between the concrete layer and the thermoplastic hot melt adhesive layer, and (1) when there is a crack on the concrete, the primer enters the crack to increase the strength of the base material. However, (2) the presence of the primer layer greatly improves the adhesiveness between the concrete layer and the thermoplastic hot melt adhesive layer.
Examples of the resin forming the primer layer include polyurethane, epoxy, acrylic acid ester copolymer, styrene-butadiene rubber, ethylene vinyl acetate copolymer, polyamide, polyester and other emulsions, and latex, but polyurethane resin, Epoxy resin or acrylic resin is preferable, epoxy resin or acrylic resin is more preferable, and acrylic resin is particularly preferable. These primer layer forming resins are used alone or in combination of two or more. The thickness of the primer layer is preferably about 0.1 mm to 4 mm.

The primer used for the primer layer of concrete is preferably a two-component mixed type. It cures several hours after coating, more preferably tens of minutes. In order to shorten the curing time, if it is a thermosetting resin, it may be heated, or if it has an anaerobic effect, a film may be adhered to the coated surface and the film may be peeled off for use.

The laminate (X) can be obtained by applying a primer resin to a concrete layer with a brush or a roll and sufficiently drying and curing the concrete layer, but the method is not limited to this method. The amount of primer resin applied depends on the type of concrete or thermoplastic hot melt adhesive, but is 10 g / m ² or more and 1,000 g / m ² or less, preferably 50 g / m ² or more and 500 g / m ² or less. preferable.

<Laminated body (Y)>
[Metal layer A]
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 the concrete layer. The metal layer is preferably a conductive metal selected from iron, aluminum, nickel, stainless steel, zinc, lead, magnesium and alloys thereof, more preferably aluminum, iron and stainless steel, and particularly preferably aluminum.

As these metals, those in the form of a film can be preferably used. The thickness of the metal layer is preferably 1 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.

[Thermoplastic hot melt adhesive layer (C1) (C2)]
The thermoplastic hot melt adhesive layer of the present invention comprises ABS, polyamide, polyester, polyurethane, acrylic, polycarbonate, polystyrene, polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene copolymer, Polypropylene-propylene-diene copolymers, ethylene / butene-1 copolymers, polyolefins such as ethylene / octene copolymers, cyclic polyolefins such as cyclopentadiene and ethylene and / or propylene copolymers, ethylene / vinyl acetate Polypropylene with polar groups such as copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA), isobutylene / maleic anhydride copolymer, maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, acrylic acid Examples thereof include modified polypropylene, styrene-based elastomer, and acid-modified polypropylene such as rubber. 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.

[Thermosetting adhesive layers (B1), (B2)]
The adhesive structure of the present invention is formed between the metal layer (A) and the thermoplastic hot melt adhesive layer (C1), or between the metal layer (A) and the thermoplastic hot melt adhesive layer (C2). The adhesive layer may have a thermosetting adhesive layer independently of each other in terms of film thickness, composition, and the like. By having the thermosetting adhesive layer, the laminate (Y) can be produced without wrinkling in the metal layer (A), and olefins and the like that could not be directly adhered to the metal layer (A) and the like. Is preferable because it can be used as a thermoplastic hot melt adhesive layer (C1) or (C2). The thermosetting adhesive layer of the present invention is formed by, for example, a main agent having a functional group such as a polyester resin, a polyurethane resin, an acrylic resin, and an epoxy resin, and a thermosetting adhesive using the curing agent as a base resin. Is preferable.

(Main agent)
As a polyester resin, examples of the acid component of the monomer composition include aromatic dibasic acids such as dimethylterephthalic acid, terephthalic acid, isophthalic acid, and phthalic acid, succinic acid, glutaric acid, adipic acid, and β-methyladipic acid. An aliphatic dibasic acid such as pimelic acid, 1,6-hexanedicarboxylic acid, adipic acid, sebatic acid, nonandicarboxylic acid, decandicarboxylic acid, and hexadecanedicarboxylic acid, and ethyleneglycol as a glycol component, 1,2. -Propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentadiol, 1,5-pentadiol, 3-methylpentadiol, 1,3-hexane Glycols such as diols, 1,6-hexanediols, 1,4-cyclohexanediols, hydrogenated bisphenol A, diethylene glycols, triethylene glycols, polyethylene glycols, dipropylene glycols, polypropylene glycols, polytetramethylene glycols or residue-forming derivatives thereof. Alternatively, a saturated difunctional monomer composed of α, ω-oxyic acid such as caprolactone or a residue-forming derivative thereof can be appropriately selected and copolymerized 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 a polymer of the above, and a condensate of hydroxycarboxylic acid such as adipic acid, a reaction product of adipic acid and ethylene glycol, and the above-mentioned polyhydric alcohol.

Examples of the polymer polyol include those obtained by graft-polymerizing the above-mentioned polyether 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 the acrylic acid-modified epoxy (epoxy acrylate) has photosensitivity, it is effective in imparting photocurability to the epoxy resin composition.

(Hardener)
The curing agent can be used without particular limitation as long as it can be used for curing the main agent. For example, an isocyanate-based curing agent, an aliphatic amine-based curing agent, an alicyclic amine-based curing agent, and the like. Examples thereof include aromatic amine-based curing agents, acid anhydride curing agents, dicyandiamides, boron trifluoride amine complex salts, and imidazole compounds. 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 main agent.

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 and butyl acetate, and aromatic compounds such as toluene and xylene. Examples thereof include compounds, alcohol-based 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 method for forming the thermosetting adhesive layer, a thermosetting adhesive may be applied to a film-shaped metal layer (A) or a film-shaped thermoplastic hot-melt adhesive layer, and dried and heat-cured. preferable. Further, from the viewpoint of preventing wrinkles from being generated in the metal layer (A), the thermosetting adhesive is preferably formed by coating on a thermoplastic hot melt adhesive film.
Devices for applying the heat-curable adhesive include comma coaters, roll knife coaters, die coaters, roll coaters, bar coaters, gravure roll coaters, reverse roll coaters, blade coaters, gravure coaters, micro gravure coaters, etc. Can be mentioned. The amount of the thermosetting adhesive applied is preferably about 1 to 50 μm in terms of dry film thickness, more preferably 2 to 25 μm, and even more preferably 2 to 10 μm.

As the thermosetting adhesive layer, it is preferable to use a polyester resin and a urethane resin as main agents from the viewpoints of adhesion to the metal layer (A) and the thermoplastic hot melt adhesive layer, heat resistance, and water resistance. Polyester resin is preferred. Further, it is more preferable to use an aromatic polyisocyanate curing agent as the curing agent.

<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.

<Subject (F)>
The adherend of the present invention is not particularly limited as long as it has a thickness of 0.3 mm or more, and is concrete, plastic, paper, a composite of paper and plastic, a metal plate, a tile, a paving material, wood, cloth, leather, and rubber. , Glass and the like can be used as appropriate.
Examples of the plastic of the adherend (F) include polyethylene terephthalate, polyester, vinyl chloride, polyethylene, ABS, polyamide, polyurethane, acrylic, polycarbonate, polystyrene, polypropylene and the like.
Materials for the tiles of the adherend include ceramics, concrete, plastic, and marble. If the tile of the adherend is ceramic, plastic, or marble, priming is not required, but if it is concrete, priming is required. Concrete is synonymous with the description of the concrete layer described above. Ceramic tiles are used for the exterior of buildings and interiors of bathrooms and washrooms, concrete tiles are used for pavement of sidewalks, and plastic tiles are called P tiles, which are used for floors of offices and the like.

The thickness of the adherend of the present invention is 0.3 mm or more, but more preferably 1 mm or more. Further, in order to effectively heat the metal layer and sufficiently melt the thermoplastic hot melt adhesive layer, the thickness of the adherend on the side heated by electromagnetic induction heating is preferably thinner than 500 mm, preferably 150 mm. The following is more preferable. If the thickness of the adherend is less than 0.3 mm, heat from the metal layer may be transferred when heated and the adherend may melt. When the thickness of the adherend is thicker than 500 mm, the metal layer may not be heated even if it is heated by the electromagnetic induction heating device.

The laminate (Y) is produced by (1) a method of adhering a metal layer and a plastic hot melt adhesive layer by thermal lamination or electromagnetic induction heating, and (2) after heating the thermoplastic hot melt adhesive. A method of directly coating a metal layer by a die method, a spray method, a roll coater method, etc., (3) A thermoplastic hot melt adhesive is applied to a ketone solvent such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, tetrahydrofuran ( THF), cyclic ether compounds such as dioxofuran, ester compounds such as ethyl acetate, methyl acetate and butyl acetate, aromatic compounds such as toluene and xylene, alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene. It can be obtained by a method of coating on a metal layer after dissolving in an organic solvent such as a compound.
If a thermosetting adhesive layer is provided between the metal layer and the thermoplastic hot-melt adhesive layer, the thermosetting hot-melt adhesive layer or the metal layer is coated with the above-mentioned thermosetting adhesive. If the thermosetting adhesive contains a solvent, the solvent is sufficiently dried, a metal layer or a thermoplastic hot melt resin layer is bonded, and then the thermosetting adhesive is thermally cured to obtain a laminate (Y). Can be done.

<Manufacturing method and peeling method of adhesive structure>
In the adhesive structure of the present invention, the above-mentioned laminated body (X) and laminated body (Y), or the laminated body (X), laminated body (Y) and adherend (F) are subjected to thermal lamination and electromagnetic induction. It can be obtained by bonding by a known bonding method such as a heating method. The bonding method can be appropriately selected depending on the presence or absence of an adherend and the thickness of the adherend. Since the adhesive structure of the present invention has a metal layer, it is particularly suitable for adhesion by an electromagnetic induction heating method. There is.
Further, the concrete layer and the adherend can be peeled off by using the electromagnetic induction heating method from the outside of the concrete layer or the adherend in the same manner as in the case of bonding.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

<Making concrete>
(Preparation of concrete 1: cement paste)
After mixing 70 wt% of cement and 30 wt% of tap water well, they were placed in a wooden frame and allowed to stand for 30 days or more to prepare concrete 1.

(Making concrete 2: mortar)
After mixing 30 wt% of cement and 50 wt% of fine aggregate (sand) well, 20 wt% of tap water was mixed and stirred, and then placed in a wooden frame and allowed to stand for 30 days or more to prepare concrete 2.

(Preparation of concrete 3: concrete)
After mixing 15% of cement, 30% of fine aggregate (sand) and 45 wt% of coarse aggregate (gravel), mix with 10 wt% of tap water, stir, put in a wooden frame and leave to stand for 30 days or more to concrete. 3 was prepared.

<Primer adjustment>
(Adjustment of primer 1: acrylic type)
Agent A Hard Rock IIDK550-003RA (methacrylic ester, manufactured by Denka Co., Ltd.) and Agent B Hard Rock IIDK550-003RB (methacrylic acid ester, manufactured by Denka Co., Ltd.) are mixed in a mass ratio of 1/1. Mixing was used to prepare Primer 1.

(Adjustment of primer 2: epoxy type)
RatioM-CS primer (S) main agent (epoxy resin solid content 100% manufactured by KFC Co., Ltd.) and RatioM-CS primer (S) curing agent (epoxy resin solid content 100% KFC Co., Ltd.) (Manufactured by Sea Co., Ltd.) and was prepared by blending at a ratio of 1/1 by weight.

<Manufacturing of laminated body (X)>
(Manufacturing of laminated bodies X1 to X7)
Using the concrete and primer shown in Table 1, the surface of the concrete is sufficiently polished with a sander, dust and concrete residue on the surface are removed with a vacuum cleaner, and then the primer is applied on the concrete with a brush and laminated. Body X1-X4 was obtained. Primer 1 (acrylic) is coated, then a PET film that has been demolded is attached, and the anaerobic reaction is promoted by blocking air, and the mixture is allowed to stand for 1 week or more to be sufficiently cured to prepare a laminate. did. Primer 2 (epoxy type) was applied and then allowed to stand at room temperature to be cured. In the laminated bodies X5 to X7, the surface of the concrete was sufficiently polished with a sander, but the primer was not applied.

<Manufacturing of thermoplastic hot melt film>
Using an extruded laminator, the thermoplastic hot-melt adhesive resin shown in Table 2 was laminated on a PET film (thickness: 25 μm) that had been demolded at different film thicknesses, and wound up at the winding section. ~ 6 was prepared. The processing conditions are shown below.
Extruded laminator: 400M / M test made by Musashinokikai Resin temperature directly under the EXT laminator die: 140 to 240 ° C (adjusted appropriately by resin MFR, etc.)
Machining speed: 30m / min T-die width: 400mm
Cooling roll surface temperature: 20 ° C

<Adjustment of thermosetting adhesive>
(Adjustment of thermosetting adhesive 1)
The main agent TM-76 and the curing agent CAT-RT85 were mixed at a mass ratio of 100/7 and diluted with ethyl acetate so that the solid content was 30%.
・ Main agent TM-K76 (polyester resin non-volatile content 51% manufactured by Toyo Morton Co., Ltd.) ・ Curing agent: CAT-RT85 (polyisocyanate non-volatile content 70% manufactured by Toyo Morton Co., Ltd.)

(Adjustment of thermosetting adhesive 2)
The main agent LIS-073-50U and the curing agent CR-001 were mixed at a mass ratio of 17/3 and diluted with ethyl acetate so that the solid content was 30%.
・ Main agent LIS-073-50U (urethane resin, non-volatile content 30%, manufactured by Toyo Morton Co., Ltd.)
-Curing agent: CR-001 (aliphatic polyisocyanate non-volatile content 70% manufactured by Toyo Morton Co., Ltd.)
(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

<Manufacturing of laminated body (Y)>
(Manufacturing of laminated body Y1)
The HM film 1 and the aluminum foil having a thickness of 20 μm were bonded together using a pressure-bonding roll whose surface temperature was heated to 120 ° C. to obtain a single-sided hot melt sheet (laminated body 1).

(Manufacturing of laminated body Y2)
The HM film 1, the aluminum foil having a thickness of 20 μm, and the HM film 1 were bonded together using a pressure-bonding roll heated to 120 ° C. to obtain a double-sided hot melt sheet (laminated body 2).

(Manufacturing of laminated body Y3)
The thermosetting adhesive 1 was applied to the HM film 4 with a ^{gravure coater so that the coating amount was 3 to 10 g / m 2} (Dry), and dried to obtain a laminate 3a. At this time, the temperature of the adhesive was heated to about 30 to 45 ° C., and the drying time was set to 80 ° C. for 1 minute.
Further, the HM film 1 and the aluminum foil having a thickness of 20 μm were bonded together using a pressure-bonding roll having a surface temperature of 120 ° C. to obtain a laminated body 3b.
The adhesive layer of the laminated body 3a and the aluminum foil of the laminated body 3b were crimped with a crimping roll having a surface temperature of 70 ° C. Then, aging was carried out in an environment of 40 ° C. for 4 days to cure the adhesive 1 to obtain a double-sided hot melt sheet (laminated body 3).

(Manufacturing of laminated body Y4)
The thermosetting adhesive 1 was applied to the HM film 1 with a ^{gravure coater so that the coating amount was 3 to 10 g / m 2} (Dry), and dried to obtain a laminate 4a. At this time, the temperature of the adhesive was heated to about 30 to 45 ° C., and the drying time was set to 80 ° C. for 1 minute. Adhesive layer of laminate 4a and thickness 20
The μm aluminum foil was crimped with a crimping roll having a surface temperature of 70 ° C. to obtain a laminated body 4b.
Similarly, the thermosetting adhesive 2 was applied to the corona-treated surface of the HM film 1 and dried to obtain a laminate 4c.
The aluminum foil surface of the laminated body 4a and the adhesive layer of the laminated body 4c were crimped with a crimping roll having a surface temperature of 70 ° C. Then, aging was carried out in an environment of 40 ° C. for 4 days to cure the adhesives 1 and 2 to obtain a double-sided hot melt sheet (laminated body 4).

(Manufacturing of laminated bodies Y5 to Y11)
Laminated bodies Y5 to 11 were manufactured in the same manner as the laminated body 4 except that the configurations and materials shown in Table 2 were changed.

(Manufacturing of laminated body Y12)
A 188 μm-thick PET film of the insulating layer (1) was adhered onto the thermoplastic hot-melt adhesive layer (C2) of the laminate Y4 shown in Table 3 with a thermal lamina heated to 120 ° C., and conductive on the PET film. The paint was printed by screen printing. Further, a PET film having a size of 188 μm as a protective layer was adhered with a thermosetting heat-adhesive agent 1 to produce a laminate Y12.

<Subject>
Adhesion F1: Primer 1 (acrylic) is applied to a mortar with a thickness of 2 mm, and then a PET film that has been demolded is attached to block air to promote an anaerobic reaction and allow it to stand for 1 week or longer. Then, it was sufficiently cured to prepare an adherend F1.
Adhesion F2: Wood adherend F3 with a thickness of 10 mm: Acrylic plate with a thickness of 3 mm Adhesion F4: Tile with a thickness of 5 mm (earthenware)
Adhesion F5: Primer 1 (acrylic) is applied to a tile (concrete) with a thickness of 5 mm, and then a PET film that has been demolded is attached to block air to promote an anaerobic reaction for one week. The adherend F5 was prepared by allowing it to stand as described above and sufficiently curing it.
Adhesive body F6: PE film with a thickness of 0.5 mm Adhesive body F7: Non-woven fabric with a thickness of 0.5 mm (polyester)

<Manufacturing of adhesive structures>
[Example 1]
(Manufacturing of structure 1)
The laminate Y1 is sandwiched between the laminate X1 and a wooden board having a thickness of 5 mm so that the primer layer of the laminate X1 and the HM film layer (C1) of the laminate Y1 are in contact with each other, and an electromagnetic induction heating device (Achilles) is used. An all-over adhesive device manufactured by the company was pressed against a wooden board and heated at 37 kHz for 3 seconds. After the heating was completed, the mixture was left to stand for 24 hours until it returned to room temperature.

[Example 2]
(Manufacturing of structure 2)
The laminate Y2 is placed in contact with the primer layer of the laminate X1 and the HM film layer (C1) of the laminate Y2, and the HM film layer (C2) of the laminate Y2 and the adherend F1. It was sandwiched between X1 and the adherend F1, and an electromagnetic induction heating device (all-over bonding device manufactured by Achilles Co., Ltd.) was pressed against the adherend F and heated at 37 kHz for 3 seconds. After the heating was completed, the mixture was left to stand for 24 hours until it returned to room temperature.

[Examples 3 to 18, 21 and Comparative Examples 1 to 3]
(Manufacturing of structures 3-18, 21-23)
Structures 3 to 18 and 21 to 24 were obtained in the same manner as in structure 2 except that the materials were changed to those shown in Table 5.

[Examples 19 and 20]
(Manufacturing of structures 19 and 20)
Structures 19 and 20 were obtained in the same manner as in structure 2 except that the material was changed to the material shown in Table 5 and the electromagnetic induction heating time was changed from 3 seconds to 1 second.

<Evaluation of adhesive structure>
For the obtained structure, the adhesive strength between the concrete layer and the adherend was evaluated by the following method. For the structure without the adherend F, the adhesive strength between the concrete layer and the metal layer was evaluated. The results are shown in Table 5.
[Adhesive strength (normal test) (JIS K6859 compliant)]
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 5).
0%), evaluated according to the following criteria. If the evaluation is other than "D", there is no particular problem in actual use.
"A": 15 N / cm ² or more (including substrate destruction)
"B": 10 N / cm ² or more and less than to 15 / cm ² "C": 5N / cm ² or more 10 N / cm less than ² "D": 5N / cm less than ²

[Peeling test]
When each of the structures 1 to 21 obtained in the examples was heated under the same electromagnetic induction heating conditions as in the bonding step, all of them could be easily peeled off from the adherend.

As shown in Table 5, the adhesive structure of the present invention showed excellent adhesive strength. In particular, when laminates X1, 3 and 4 using an acrylic primer were used for the primer layer and polyamide (nylon base and dimer acid base) was used for the HM adhesive layer, particularly excellent adhesiveness was exhibited. (Examples 2-9, 11, 13-21).

Claims (7)

The primer layer (D) surface of the laminate (X) having the concrete layer (E) and the primer layer (D), the metal layer (A) , the heat-cured adhesive layer (B1), and the thermoplastic hot-melt adhesive layer. An adhesive structure in which a thermoplastic hot-melt adhesive layer (C1) surface of a laminate (Y) having (C1) is bonded. The adhesive structure according to claim 1, further comprising a second thermoplastic hot melt adhesive layer (C2) on the metal layer (A) side of the laminate (Y). In the laminate (Y), the metal layer (A), between the second thermoplastic hot melt adhesive layer (C2), in claim 2 having a second thermosetting adhesive layer (B2) The described adhesive structure. The adhesive structure according to any one of claims 1 to 3 , further comprising an insulating layer and a patterned conductive layer on the outside of the surface of the laminated body (Y) facing the thermoplastic hot melt adhesive layer (C1). The primer layer (D) surface of the laminate (X) having the concrete layer (E) and the primer layer (D), the metal layer (A) , the heat-cured adhesive layer (B1), and the thermoplastic hot-melt adhesive layer. A method for producing an adhesive structure, which comprises bonding a thermoplastic hot-melt adhesive layer (C1) surface of a laminate (Y) having (C1) to an adhesive layer (C1) surface by electromagnetic induction heating. The primer layer (D) surface of the laminate (X) having the concrete layer (E) and the primer layer (D) and the adherend (F) having a thickness of 0.3 mm or more are formed.
The metal layer (A) has a thermosetting adhesive layer (B1) and a thermoplastic hot melt adhesive layer (C1) on one side, and a second thermoplastic hot melt adhesive layer (C2) on the other side. ) Through the laminate (Y)
A method for producing an adhesive structure, which comprises bonding from the outside of a concrete layer (E) and / or the outside of an adherend (F) having a thickness of 0.3 mm or more by electromagnetic induction heating. The primer layer (D) surface of the laminate (X) having the concrete layer (E) and the primer layer (D) and the adherend (F) having a thickness of 0.3 mm or more are on one side of the metal layer (A). Laminated body (Y) having a heat-cured adhesive layer (B1) and a thermoplastic hot-melt adhesive layer (C1) on the other side, and a second thermoplastic hot-melt adhesive layer (C2) on the other side. The adhesive structure adhered through the adhesive is heated by electromagnetic induction heating from the outside of the concrete layer (E) and / or the outside of the adherend (F) having a thickness of 0.3 mm or more, and is in a solid state. The hot melt adhesive layer (C1) and / or the second thermoplastic hot melt adhesive layer (C2) is softened or melted, and the concrete layer (E) and the adherend (F) having a thickness of 0.3 mm or more are formed. How to peel off.

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