WO2021215404A1 - Matériau équipé d'une couche d'apprêt et corps assemblé - Google Patents

Matériau équipé d'une couche d'apprêt et corps assemblé Download PDF

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WO2021215404A1
WO2021215404A1 PCT/JP2021/015900 JP2021015900W WO2021215404A1 WO 2021215404 A1 WO2021215404 A1 WO 2021215404A1 JP 2021015900 W JP2021015900 W JP 2021015900W WO 2021215404 A1 WO2021215404 A1 WO 2021215404A1
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bifunctional
compound
resin
primer
group
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PCT/JP2021/015900
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English (en)
Japanese (ja)
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大谷　和男
浩志 前川
臣二 沼尾
高橋　信行
良太 新林
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昭和電工株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/04—Dielectric heating, e.g. high-frequency welding, i.e. radio frequency welding of plastic materials having dielectric properties, e.g. PVC
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to a material with a primer and a method for producing the same, which is suitable for use in firmly welding materials such as metal, glass, ceramic, fiber reinforced plastic, resin, and rubber, and a bonded body using the material with a primer and a method for producing the same. Regarding.
  • Patent Documents 1 and 2 describe a thermoplastic sheet material having a functional group between a molded product obtained by molding a thermoplastic resin composition and a thermoplastic resin different from the thermoplastic resin of the molded product. And a technique for ultrasonic welding with a reinforcing fiber bundle interposed therebetween is disclosed. Further, Patent Document 3 discloses a technique of ultrasonically welding both welded members by inserting an intermediate layer between the welded members, fixing the intermediate layer to an ultrasonic resonator horn and vibrating the intermediate layer. Has been done.
  • the strength of the welded part is expressed by the entanglement and crystallization of molecules due to molecular diffusion at the bonding interface.
  • ultrasonic welding and the like described in Patent Documents 1 to 3 have a problem that entanglement and crystallization of molecules due to molecular diffusion are insufficient, and sufficient bonding strength cannot be obtained.
  • the present invention has been made in view of such technical background, and is to firmly join materials such as metal, glass, ceramics, fiber reinforced plastics, resins, and rubbers to improve durability over a long period of time. It is an object of the present invention to provide a material with a primer capable of producing a material and related technology thereof.
  • the related technology means a method for producing a material with a primer, a conjugate using the material with a primer and a method for producing the same, and an in-situ polymerization type composition used for a primer layer of the material with a primer.
  • joining means connecting objects to each other, and adhesion and welding are subordinate concepts thereof.
  • Adhesion means that two adherends (those to be bonded) are put into a bonded state via an organic material (thermosetting resin, thermoplastic resin, etc.) such as tape or adhesive.
  • welding means that a thermoplastic resin or the like is melted by heat and entangled and crystallized by molecular diffusion by contact pressurization and cooling to form a bonded state.
  • a material with a primer which is a field-polymerized composition layer composed of a polymer of a field-polymerized composition containing at least one kind of resin.
  • a primer layer of the material with a primer according to any one of [1] to [4] is added to a material which is at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber.
  • the material layer comprises at least one selected from the group consisting of metal, glass, ceramic, fiber-reinforced plastic, resin and rubber, with the primer according to [6] or [7]. Method of manufacturing the material.
  • the primer layer of the material with a primer according to any one of [1] to [4] is added to a material which is at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber.
  • a method for manufacturing a bonded body to be welded [10] The method for producing a bonded body according to [9], wherein the welding is high frequency welding.
  • (1) Combination of bifunctional isocyanate compound and compound having bifunctional hydroxyl group (2) Combination of bifunctional isocyanate compound and compound having bifunctional amino group (3) Bifunctional epoxy compound and bifunctional hydroxyl group Combination with compound (4) Combination with bifunctional epoxy compound and bifunctional carboxy compound (5) Combination with two kinds of compounds selected from the group consisting of bifunctional epoxy compound and bifunctional thiol compound (6) Monofunctional Radical polymerizable monomer
  • a material with a primer capable of firmly joining materials such as metal, glass, ceramic, fiber reinforced plastic, resin, and rubber to improve durability over a long period of time, and related technology thereof. be able to.
  • the primer-attached material of the embodiment of the present invention (hereinafter, may be referred to as “the present embodiment”) and related techniques thereof will be described in detail.
  • (meth) acrylic means acrylic and / or methacrylic
  • (meth) acrylate means acrylate and / or methacrylate.
  • the material with a primer of the present embodiment has a material layer and one or a plurality of primer layers laminated on the material layer, and at least one layer of the primer layer is a vinyl chloride resin, a phenol resin, and a polyamide. It is a field-polymerized composition layer composed of a polymer of a field-polymerized composition containing at least one resin selected from the group consisting of.
  • the material 1 with a primer in one embodiment is a laminate having a material layer 2 and a single layer or a plurality of layers of the primer layers 3 laminated on the material layer 2.
  • at least one layer of the primer layer 3 is a field-polymerized composition comprising a polymer of a field-polymerized composition containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide.
  • the material layer 31 is a field-polymerized composition comprising a polymer of a field-polymerized composition containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide.
  • the field-polymerized composition is a radical addition reaction of a combination of reactive bifunctional compounds on the field, that is, on various materials, or a radical of a specific monofunctional monomer. It means a composition that forms a thermoplastic structure, that is, a linear polymer structure by a polymerization reaction. Unlike the thermosetting resin that forms a three-dimensional network with a crosslinked structure, the in-situ polymerization type composition does not form a three-dimensional network with a crosslinked structure and has thermoplasticity.
  • the primer layer is joined and integrated with a material (bonding target) such as metal, glass, ceramic, fiber reinforced plastic, resin, and rubber, for example, as in the case of a bonded body described later.
  • a material such as metal, glass, ceramic, fiber reinforced plastic, resin, and rubber, for example, as in the case of a bonded body described later.
  • bonding target such as metal, glass, ceramic, fiber reinforced plastic, resin, and rubber, for example, as in the case of a bonded body described later.
  • the field-polymerized composition layer 31 is preferably a layer formed of a composition containing a field-polymerized phenoxy resin.
  • the field-polymerized phenoxy resin is a resin also called a thermoplastic epoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and a bifunctional epoxy resin and a bifunctional phenol compound undergo a double addition reaction in the presence of a catalyst.
  • a thermoplastic structure that is, a linear polymer structure is formed.
  • the form of the material layer 2 is not particularly limited, and may be in the form of a lump or a film.
  • the material constituting the material layer 2 is not particularly limited, but is preferably at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic (FRP), resin and rubber.
  • Examples of the metal include aluminum, iron, copper, magnesium, steel and the like. Of these, aluminum is preferable from the viewpoint of weight reduction.
  • Examples of the glass include soda-lime glass, lead glass, borosilicate glass, quartz glass, and the like.
  • Examples of the ceramic include oxide-based ceramics such as alumina, zirconia and barium titanate, hydroxide-based ceramics such as hydroxyapatite, carbide-based ceramics such as silicon carbide, and nitride-based ceramics such as silicon nitride.
  • FRP fiber reinforced plastics
  • GFRP glass fiber reinforced plastics
  • CFRP carbon fiber reinforced plastics
  • BFRP boron fiber reinforced plastics
  • AFRP aramid fiber reinforced plastics
  • the resin examples include polypropylene (PP), polyamide 6 (PA6), polyamide 66 (PA66), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherimide (PEI), and polycarbonate (PC). , Polybutylene terephthalate (PBT), (meth) acrylic resin and other thermoplastic resins.
  • Examples of the rubber include natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylenepropylene diene rubber, butadiene acrylonitrile copolymer rubber, chloroprene rubber, silicon rubber, and fluororubber.
  • the material layer 2 is a metal
  • its thickness is preferably 1.5 ⁇ m or more, more preferably 1.6 ⁇ m or more, from the viewpoint of strength.
  • the upper limit of the thickness of the metal is not particularly limited, but is preferably 5 mm or less, more preferably 3 mm or less.
  • the material layer 2 is glass
  • its thickness is preferably 0.3 mm or more, more preferably 0.5 mm or more, from the viewpoint of strength.
  • the upper limit of the thickness of the glass is not particularly limited, but is preferably 30 mm or less, more preferably 10 mm or less, and further preferably 2 mm or less.
  • the thickness thereof is preferably 0.3 mm or more, more preferably 0.5 mm or more, respectively, from the viewpoint of strength.
  • the upper limit of the thickness of the FRP and the ceramic is not particularly limited, but is preferably 20 mm or less, more preferably 10 mm or less, still more preferably 2 mm or less.
  • the thickness thereof is preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, respectively, from the viewpoint of strength.
  • the upper limit of the thickness of the resin and rubber is not particularly limited, but is preferably 30 mm or less, more preferably 10 mm or less.
  • the material layer 2 may be surface-treated for the purpose of removing contaminants on the surface and / or an anchor effect.
  • the material layer 2 is a metal, glass, ceramic, or fiber reinforced plastic (FRP), it is preferable to perform a surface treatment before laminating the primer layer 3.
  • FRP fiber reinforced plastic
  • the surface treatment can form fine irregularities 21 on the surface of the material layer 2 to roughen the surface.
  • the adhesiveness between the surface of the material layer 2 and the primer layer 3 can be improved.
  • the surface treatment can also contribute to the improvement of the bondability with the bonding target.
  • the surface properties of the material layer 2 surface-treated by the above method may be different from those immediately after the surface treatment due to the formation of the primer layer 3 and the like on the surface-treated surface. be. Therefore, it is considered impossible or impractical to specify and express the surface properties of the surface-treated material layer. Therefore, in the present embodiment, the surface of the surface-treated material layer is specified by the surface-treating method.
  • Examples of the surface treatment include degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment, corona discharge treatment, laser treatment, etching treatment, frame treatment, chemical conversion treatment and the like.
  • a surface treatment for cleaning the surface of the material layer 2 or a surface treatment for making the surface uneven is preferable, and specifically, a degreasing treatment, a UV ozone treatment, a blast treatment, a polishing treatment, a plasma treatment, and a corona discharge treatment. And at least one selected from the group consisting of chemical conversion treatment is preferable. Only one type of surface treatment may be applied, or two or more types may be applied. As a specific method of these surface treatments, known methods can be used.
  • the degreasing treatment is a method of removing stains such as oils and fats on the surface of the material layer by dissolving them with an organic solvent such as acetone or toluene.
  • the UV and ozone treatment with a force of ozone (O 3) generated energy and thereby having a short wavelength ultraviolet ray emitted from a low-pressure mercury lamp, a process for modifying or cleaning the surface.
  • O 3 ozone
  • a cleaning surface modifier using a low-pressure mercury lamp is called a "UV ozone cleaner", a “UV cleaning apparatus”, an “ultraviolet surface modifier” or the like.
  • blasting treatment examples include wet blasting treatment, shot blasting treatment, sandblasting treatment, and the like. Above all, the wet blast treatment is preferable because a finer surface can be obtained as compared with the drive last treatment.
  • polishing treatment examples include buffing using a polishing cloth, roll polishing using polishing paper (sandpaper), electrolytic polishing, and the like.
  • the plasma treatment is to create a plasma beam with a high-voltage power supply and a rod and hit it against the surface of the material to excite molecules to make them in a functional state. Be done.
  • the corona discharge treatment includes a method applied to surface modification of a polymer film, and starts from a radical generated by cutting a polymer main chain or a side chain of a polymer surface layer by electrons emitted from an electrode. This is a method of generating a hydroxyl group or a polar group on the surface.
  • the laser treatment is a technique for improving surface characteristics by rapidly heating and cooling only the surface layer by laser irradiation, and is an effective method for roughening the surface.
  • Known laser processing techniques can be used.
  • the etching treatment includes, for example, a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method.
  • a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method
  • an electrochemical etching treatment such as an electrolytic etching method.
  • the frame treatment is a method of converting oxygen in the air into plasma by burning a mixed gas of combustion gas and air, and applying oxygen plasma to the object to be treated to make the surface hydrophilic.
  • a known frame processing technique can be used.
  • the chemical conversion treatment mainly forms a chemical conversion film on the surface of the material layer 2.
  • the chemical conversion treatment when the material layer is a metal include boehmite treatment and zirconium treatment.
  • a boehmite film is formed on the surface of the material layer 2 by treating the material layer 2 with hot water.
  • Ammonia, triethanolamine, or the like may be added to water as a reaction accelerator.
  • a film of a zirconium compound is formed on the surface of the material layer 2 by immersing the material layer 2 in a zirconium salt-containing liquid such as zirconium phosphate.
  • a zirconium salt-containing liquid such as zirconium phosphate.
  • the material layer 2 is immersed in a chemical agent for zirconium treatment (for example, "Palcoat 3762" manufactured by Nihon Parkerizing Co., Ltd., "Palcoat 3796", etc.) at 45 to 70 ° C. for 0.5 to 3 minutes. It is preferable to do this.
  • the zirconium treatment is preferably performed after the etching treatment by the caustic soda method.
  • the material layer 2 is subjected to a functional group addition treatment following the surface treatment before laminating the primer layer 3.
  • the functional group-imparting treatment contains a single layer or a plurality of layers laminated between the material layer 2 and the primer layer 3 in contact with the material layer 2 and the primer layer 3.
  • Layer 4 can be formed.
  • the functional groups of the functional group-containing layer 4 are the hydroxyl groups on the surface of the material layer 2 and the functional groups of the resin constituting the primer layer, respectively.
  • the chemical bond formed by the reaction has the effect of improving the adhesiveness between the material layer 2 and the primer layer 3.
  • the effect of improving the bondability with the bonding target can also be obtained. Therefore, the functional group in the functional group-containing layer 4 is preferably a functional group having reactivity with the hydroxyl group or the functional group of the resin constituting the primer layer.
  • Examples of the functional group include an epoxy group, an amino group, a mercapto group, an isocyanato group, a carboxy group, a hydroxyl group, a vinyl group, a (meth) acryloyloxy group, and the like.
  • the functional group-containing layer 4 is preferably a layer having a functional group introduced from at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound.
  • the functional group-containing layer 4 has at least one selected from the group consisting of a silane coupling agent, an isocyanate compound, and a thiol compound on the surface of the material layer 2 or the surface treated with the above surface before forming the primer layer 3. It can be formed by treating with seeds.
  • the method for forming the functional group-containing layer 4 with the silane coupling agent, the isocyanate compound, or the thiol compound is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • the material layer is immersed in a solution of a silane coupling agent having a concentration of 5 to 50% by mass at room temperature to 100 ° C. for 1 minute to 5 days, and then dried at room temperature to 100 ° C. for 1 minute to 5 hours. It can be done by a method such as making it.
  • the normal temperature refers to 5 to 35 ° C, preferably 15 to 25 ° C.
  • silane coupling agent for example, known ones used for surface treatment of glass fibers and the like can be used.
  • the silanol group generated by hydrolyzing a silane coupling agent or the silanol group obtained by oligomerizing the silanol group reacts with a hydroxyl group existing on the surface of the material layer 2 to bond with the primer layer 3, so that the silanol group can be chemically bonded to the primer layer 3.
  • a functional group based on the structure of the silane coupling agent can be imparted (introduced) to the material layer.
  • the silane coupling agent is not particularly limited, but a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having a (meth) acryloyl group, and the like. Can be used.
  • the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Examples thereof include 3-glycidoxypropyltriethoxysilane.
  • silane coupling agent having an amino group examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltri. Examples thereof include methoxysilane and 3-aminopropyltriethoxysilane. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and dithioltriazinepurpiltriethoxysilane.
  • silane coupling agent having a (meth) acryloyl group examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-Acryloxypropyltrimethoxysilane and the like.
  • silane coupling agents having a vinyl group such as 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane, 3-tri.
  • the isocyanate compound is a functional group based on the structure of the isocyanate compound which can be chemically bonded to the primer layer 3 by reacting and bonding the isocyanato group in the isocyanate compound with the hydroxyl group existing on the surface of the material layer 2. , Can be imparted (introduced) to the material layer.
  • the isocyanate compound is not particularly limited, but for example, other polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI). , 2-Isocyanate ethyl methacrylate (for example, “Karens MOI (registered trademark)” manufactured by Showa Denko Co., Ltd.), 2-isocyanate ethyl acrylate (for example, "Karens AOI” manufactured by Showa Denko Co., Ltd.), which is an isocyanate compound having a radically reactive group.
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • IPDI isophorone diisocyanate
  • the thiol compound is a functional group based on the structure of the thiol compound, which can be chemically bonded to the primer layer by reacting and bonding the mercapto group in the thiol compound with the hydroxyl group existing on the surface of the material layer 2. It can be applied (introduced) to the material layer.
  • the thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40” manufactured by Mitsubishi Chemical Corporation and “QE-340M” manufactured by Toray Fine Chemicals Co., Ltd.
  • Ether-based first-class thiols for example,“ Cup Cure 3-800 ”manufactured by Cognis
  • 1,4-bis (3-mercaptobutyryloxy) butane for example,“ Karenz MT ”manufactured by Showa Denko KK) (Registered trademark) BD1 ”)
  • Pentaerythritol tetrakis (3-mercaptobutylate) for example,“ Karenz MT (registered trademark) PE1 ”manufactured by Showa Denko KK
  • 1,3,5-Tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion for example, "Karensu MT (registered trademark) NR1" manufactured by Showa Denko KK) and the like can be mentioned.
  • Primer layer 3 is laminated on the material layer 2 directly or via the functional group-containing layer 4.
  • At least one layer of the primer layer is the field-polymerized composition layer 31 made of a polymer of the field-polymerized composition.
  • the field-polymerized composition layer 31 is formed by applying the field-polymerized composition dissolved in a solvent onto the material layer 2 or the functional group-containing layer 4, volatilizing the solvent, and then volatilizing the field-polymerized composition. Can be obtained by polymerizing. If the in-situ polymerization type composition is liquid, it is not necessary to use a solvent.
  • the solvent examples include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, toluene, xylene, tetrahydrofuran, water and the like.
  • the field-polymerized composition contains at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide, and preferably contains at least one resin selected from the group consisting of vinyl chloride resin and phenol resin.
  • the in-situ polymerization type composition can control elastic modulus, polarity, hydrogen bonding force and the like, and can control metal, glass and the like.
  • Ceramic, fiber reinforced plastic, resin, rubber and other materials can be firmly joined.
  • the vinyl chloride resin referred to here may be a polymer of a vinyl chloride monomer, but is generally called a hard vinyl chloride product or a soft vinyl chloride product to which a plasticizer and a stabilizer are added. It may be a thing.
  • the phenol resin referred to here is a resin synthesized from phenol and formaldehyde, and there are novolak type and resol type, and any type can be used.
  • polyamide as used herein means "n-nylon” synthesized by a polycondensation reaction of ⁇ amino acids and "n, m-nylon” synthesized by a ring-opening polymerization reaction of diamine and dicarboxylic acid.
  • nylon 6 synthesized by the ring-opening polymerization reaction of ⁇ -caprolactam is more preferable.
  • the polyamide a fine powder is preferable because it is easy to use.
  • the in-situ polymerization type composition preferably contains at least one of the following (1) to (6), more preferably contains the following (3), and the bifunctional epoxy resin and the bifunctional phenol compound. It is more preferred to contain a combination.
  • (1) Combination of bifunctional isocyanate compound and compound having bifunctional hydroxyl group (2) Combination of bifunctional isocyanate compound and compound having bifunctional amino group (3) Bifunctional epoxy compound and bifunctional hydroxyl group Combination with compound (4) Combination of bifunctional epoxy compound and bifunctional carboxy compound (5) Combination with two types of compounds selected from the group consisting of bifunctional epoxy compound and bifunctional thiol compound (6) Monofunctional Radical polymerizable monomer
  • the compounding amount ratio of the bifunctional isocyanate compound and the compound having a bifunctional hydroxyl group in (1) is preferably set so that the molar equivalent ratio of the isocyanate group to the hydroxyl group is 0.7 to 1.5. , More preferably 0.8 to 1.4, still more preferably 0.9 to 1.3.
  • the compounding amount ratio of the bifunctional isocyanate compound and the compound having a bifunctional amino group in (2) is set so that the molar equivalent ratio of the isocyanate group to the amino group is 0.7 to 1.5. Is preferable, more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.3.
  • the compounding amount ratio of the bifunctional epoxy compound and the compound having a bifunctional hydroxyl group in (3) is preferably set so that the molar equivalent ratio of the epoxy group to the hydroxyl group is 0.7 to 1.5. , More preferably 0.8 to 1.4, still more preferably 0.9 to 1.3.
  • the compounding amount ratio of the bifunctional epoxy compound and the bifunctional carboxy compound in (4) is preferably set so that the molar equivalent ratio of the epoxy group to the carboxy group is 0.7 to 1.5. It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
  • the compounding amount ratio of the bifunctional epoxy compound and the bifunctional thiol compound in (5) is preferably set so that the molar equivalent ratio of the epoxy group to the mercapto group is 0.7 to 1.5. It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
  • the bonding target can be firmly welded on the material layer 2.
  • the primer layer 3 may be composed of a plurality of layers including the in-situ polymerization type composition layer 31.
  • the primer layer 3 is composed of a plurality of layers, it is preferable that the essential in-situ polymerization type composition layer 31 is laminated so as to be the outermost surface on the opposite side of the material layer 2.
  • the field-polymerized composition layer 31 is made of a polymer of the field-polymerized composition.
  • the in-situ polymerization type composition layer 31 is a mixture of a composition containing at least one resin selected from the group consisting of the vinyl chloride resin, the phenol resin and the polyamide, and at least one of the above (1) to (5). However, it can be obtained by subjecting it to a polyaddition reaction in the presence of a catalyst.
  • a catalyst for the polyaddition reaction for example, tertiary amines such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; phosphorus compounds such as triphenylphosphine are preferably used.
  • the heavy addition reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 120 minutes, although it depends on the composition of the composition.
  • the in-situ polymerization type composition layer 31 contains at least one resin selected from the group consisting of the vinyl chloride resin, the phenol resin and the polyamide, and at least one of the above (1) to (5).
  • the composition to be coated is dissolved in a solvent and applied to the material layer 2, then the solvent is appropriately volatilized, and then the composition is heated to carry out a polyaddition reaction to obtain a more strongly bonded in-situ polymerization type composition layer 31. Can be formed.
  • the material layer 2 also includes those subjected to the surface treatment and / or the functional group imparting treatment.
  • the in-situ polymerization type composition layer 31 is a radical polymerization of a composition containing at least one resin selected from the group consisting of the vinyl chloride resin, the phenol resin and the polyamide and the monofunctional radically polymerizable monomer (6). It can also be obtained by reaction.
  • the radical polymerization reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 90 minutes, although it depends on the composition of the composition. In the case of photocuring, it is preferable to irradiate ultraviolet rays or visible light to carry out the polymerization reaction.
  • the in-situ polymerization type composition layer 31 contains at least one resin selected from the group consisting of the vinyl chloride resin, the phenol resin and the polyamide, and the monofunctional radically polymerizable monomer (6).
  • the composition is dissolved in a solvent and applied onto the material layer 2, and then heated or irradiated with light to carry out a radical polymerization reaction to form a more strongly bonded in-situ polymerization type composition layer 31. Can be done.
  • the material layer 2 also includes those subjected to the surface treatment and / or the functional group imparting treatment.
  • the proportion of the polymer of the field-polymerized composition contained in the field-polymerized composition layer 31 is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the method of the heavy addition reaction differs in the conditions under which the heavy addition reaction proceeds, the molecular weight distribution, etc. depending on the functional groups to be combined, and it is not possible to comprehensively express a specific mode based on the combination. Therefore, it can be said that it is impossible or impractical to directly specify the in-situ polymerization type composition layer formed by the polyaddition reaction by the structure or characteristics.
  • the bifunctional isocyanate compound is a compound having two isocyanato groups, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, dimerate diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) or a mixture thereof.
  • examples thereof include diisocyanate compounds such as p-phenylenediocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate (MDI).
  • TDI, MDI and the like are preferable from the viewpoint of the strength of the primer.
  • the compound having a bifunctional hydroxyl group is a compound having two hydroxy groups, and examples thereof include aliphatic glycols and bifunctional phenols.
  • examples of the aliphatic glycol include ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol and the like.
  • examples of the bifunctional phenol include bisphenols such as bisphenol A, bisphenol F, and bisphenol S. From the viewpoint of primer toughness, propylene glycol, diethylene glycol and the like are preferable.
  • bifunctional phenol is preferable, and the bisphenols are particularly preferable.
  • the compound having a bifunctional amino group is a compound having two amino groups, and examples thereof include a bifunctional aliphatic diamine and an aromatic diamine.
  • examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, and the like.
  • aromatic diamines examples include 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, and N-aminoethylpiperazine.
  • examples thereof include diaminodiphenylmethane and diaminodiphenylpropane.
  • 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine and the like are preferable from the viewpoint of primer toughness.
  • the bifunctional epoxy compound is a compound having two epoxy groups in one molecule.
  • aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, naphthalene type bifunctional epoxy resin, and aliphatic such as 1,6-hexanediol diglycidyl ether.
  • Epoxy compounds can be mentioned. Of these, one type may be used alone, or two or more types may be used in combination. Specifically, “jER (registered trademark) 828", “jER (registered trademark) 834", "jER (registered trademark) 1001", “jER (registered trademark) 1004", and the same, manufactured by Mitsubishi Chemical Corporation. Examples thereof include “jER (registered trademark) YX-4000".
  • Other bifunctional epoxy compounds with a special structure can also be used. Of these, one type may be used alone, or two or more types may be used in combination.
  • the bifunctional carboxy compound may be a compound having two carboxy groups, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, and terephthalic acid. Can be mentioned. Of these, isophthalic acid, terephthalic acid, adipic acid and the like are preferable from the viewpoint of primer strength and toughness.
  • the bifunctional thiol compound is a compound having two mercapto groups in the molecule.
  • the bifunctional secondary thiol compound 1,4-bis (3-mercaptobutyryloxy) butane (for example, Showa Denko KK) "Karens MT (registered trademark) BD1") manufactured by.
  • the monofunctional radically polymerizable monomer is a monomer having one ethylenically unsaturated bond.
  • styrene monomers styrene-based monomers such as ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, chlorostyrene, vinyltoluene, divinylbenzene, etc.
  • styrene ethyl (meth) acrylate, Methyl (meth) acrylate, -n-propyl (meth) acrylate, -i-propyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and phenoxyethyl (meth) Examples thereof include (meth) acrylic acid esters such as meta) acrylate and glycidyl (meth) acrylate.
  • One of the above compounds may be used, or two or more of the compounds may be used. Among them, from the viewpoint of primer strength and toughness, one or a combination of styrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate is preferable. ..
  • a solvent and, if necessary, an additive such as a colorant may be contained.
  • the monofunctional radically polymerizable monomer is the main component among the components of the radically polymerizable composition other than the solvent.
  • the main component means that the content of the monofunctional radically polymerizable monomer is 50 to 100% by mass.
  • the content is preferably 60% by mass or more, more preferably 80% by mass or more.
  • the polymerization initiator for the radical polymerization reaction for example, known organic peroxides, photoinitiators and the like are preferably used.
  • a room temperature radical polymerization initiator in which a cobalt metal salt or amines are combined with an organic peroxide may be used.
  • organic peroxides include those classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
  • the photoinitiator it is desirable to use an initiator capable of initiating polymerization with visible rays from ultraviolet rays.
  • the radical polymerization reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 90 minutes, although it depends on the type of the reaction compound and the like.
  • the polymerization reaction is carried out by irradiating with ultraviolet rays or visible light.
  • thermosetting resin layer 32 When the primer layer 3 is composed of a plurality of layers including the in-situ polymerization type composition layer 31, as shown in FIG. 3, the composition containing the thermosetting resin is cured below the in-situ polymerization type composition layer 31. It can also include a thermosetting resin layer 32 formed of an object. In addition, in the composition containing the thermosetting resin, in order to sufficiently proceed the curing reaction of the thermosetting resin and form a desired primer layer, a solvent and, if necessary, an additive such as a colorant are added. It may be included. In this case, it is preferable that the thermosetting resin is the main component among the components other than the solvent of the composition. The main component means that the content of the thermosetting resin is 40% by mass or more. The content is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
  • thermosetting resin examples include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.
  • the thermosetting resin layer 32 may be formed by one of these resins alone, or may be formed by mixing two or more of these resins.
  • the thermosetting resin layer 32 may be composed of a plurality of layers, and each layer may be formed of a composition containing a different type of thermosetting resin.
  • the coating method for forming the thermosetting resin layer 32 with the composition containing the monomer of the thermosetting resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • the thermosetting resin referred to in this embodiment broadly means a resin that is crosslink-cured, and includes not only a heat-curable type but also a room temperature-curable type and a photocurable type.
  • the photocurable type can be cured in a short time by irradiating with visible light or ultraviolet rays.
  • the photo-curing type may be used in combination with a heat-curing type and / or a room temperature curing type.
  • Examples of the photocurable type include vinyl ester resins such as "Lipoxy (registered trademark) LC-760" and "Lipoxy (registered trademark) LC-720" manufactured by Showa Denko KK.
  • the urethane resin is usually a resin obtained by reacting an isocyanato group of an isocyanate compound with a hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a coating material containing a polyisocyanate having a vehicle non-volatile component of 10 wt% or more".
  • the urethane resin corresponding to is preferable.
  • the urethane resin may be a one-component type or a two-component type.
  • the one-component urethane resin examples include an oil-modified type (which cures by oxidative polymerization of unsaturated fatty acid groups), a moisture-curing type (which cures by the reaction of isocyanato groups with water in the air), and a block type (which cures by the reaction of isocyanato groups with water in the air).
  • examples thereof include a lacquer type (a type in which a blocking agent is dissociated by heating and regenerated by reacting with an isocyanato group and a hydroxyl group to be cured), and a lacquer type (a type in which a solvent is volatilized and cured by drying).
  • a moisture-curable one-component urethane resin is preferably used from the viewpoint of ease of handling and the like. Specific examples thereof include "UM-50P" manufactured by Showa Denko KK.
  • Examples of the two-component urethane resin include a catalyst-curable type (a catalyst-curable type in which an isocyanato group reacts with water in the air to cure in the presence of a catalyst) and a polyol-curable type (a reaction between an isocyanato group and a hydroxyl group of a polyol compound). (Those that are cured by) and the like.
  • polyol compound in the polyol curing type examples include polyester polyols, polyether polyols, phenol resins and the like.
  • isocyanate compound having an isocyanato group in the polyol-curable type examples include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimerate diisocyanate; 2,4- or 2,6-tolylene diisocyanate.
  • TDI p-phenylenediisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and aromatic isocyanates such as polypeptide MDI which is a polynuclear mixture thereof; alicyclic isocyanates such as isophorone diisocyanate (IPDI) and the like.
  • the compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in the molar equivalent ratio of the hydroxyl group / isocyanato group.
  • urethanization catalyst used in the two-component urethane resin examples include triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyl etheramine, N, N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol-triethylamine and other amine-based catalysts; dibutyltindi Examples thereof include organic tin-based catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimalate. In the polyol curing type, it is generally preferable that 0.01 to 10 parts by mass of the urethanization catalyst is blended with respect to 100 parts by mass of the polyol compound.
  • the epoxy resin is a resin having at least two epoxy groups in one molecule.
  • the prepolymer before curing of the epoxy resin include ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, and cyclic aliphatic epoxy resin. , Ether-ester type epoxy resin and the like, and among these, bisphenol A type epoxy resin is preferably used. Of these, one type may be used alone, or two or more types may be used in combination.
  • Specific examples of the bisphenol A type epoxy resin include "jER (registered trademark) 828" and "jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
  • Specific examples of the novolak type epoxy resin include "DEN (registered trademark) 438 (registered trademark)” manufactured by The Dow Chemical Company.
  • Examples of the curing agent used for the epoxy resin include known curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts.
  • the curing agent is used in combination with a long-chain aliphatic amine and / or a thiol, the effect of having a large elongation rate and excellent impact resistance can be obtained.
  • Specific examples of the thiols include the same compounds as those exemplified as thiol compounds for forming a functional group-containing layer.
  • pentaerythritol tetrakis (3-mercaptobutyrate) for example, "Karenzu MT (registered trademark) PE1" manufactured by Showa Denko KK
  • Karenzu MT registered trademark
  • PE1 registered trademark
  • the vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (for example, styrene). Although it is also called an epoxy (meth) acrylate resin, the vinyl ester resin also includes a urethane (meth) acrylate resin.
  • a polymerizable monomer for example, styrene
  • the vinyl ester resin also includes a urethane (meth) acrylate resin.
  • the vinyl ester resin for example, those described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary” (Japan Society of Color Material, published in 1993), etc. shall also be used.
  • Lipoxy (registered trademark) R-802 "Lipoxy (registered trademark) R-804", “Lipoxy (registered trademark) R-806", etc. manufactured by Showa Denko KK, etc. Can be mentioned.
  • the urethane (meth) acrylate resin is obtained by, for example, reacting an isocyanate compound with a polyol compound and then reacting with a hydroxyl group-containing (meth) acrylic monomer (and, if necessary, a hydroxyl group-containing allyl ether monomer).
  • a hydroxyl group-containing (meth) acrylic monomer and, if necessary, a hydroxyl group-containing allyl ether monomer.
  • examples thereof include radically polymerizable unsaturated group-containing oligomers. Specific examples thereof include "Lipoxy (registered trademark) R-6545" manufactured by Showa Denko KK.
  • the vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
  • a catalyst such as an organic peroxide.
  • the organic peroxide is not particularly limited, but for example, ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxides. Oxide carbonates and the like can be mentioned. By combining these with a cobalt metal salt or the like, curing at room temperature is also possible.
  • the cobalt metal salt is not particularly limited, and examples thereof include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Of these, cobalt naphthenate and / and cobalt octylate are preferred.
  • the unsaturated polyester resin is a monomer (for example, styrene) in which a condensation product (unsaturated polyester) obtained by an esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is formed into a polymerizable monomer (for example, styrene). ) Is dissolved.
  • a condensation product unsaturated polyester obtained by an esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is formed into a polymerizable monomer (for example, styrene).
  • the unsaturated polyester resin those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary” (Japan Society of Color Material, published in 1993), etc. can also be used. Yes, and more specifically, "Rigolac (registered
  • the unsaturated polyester resin can be cured by radical polymerization by heating in the presence of a catalyst similar to that of the vinyl ester resin.
  • the primer layer 3 has excellent adhesiveness to the material layer 2.
  • the primer layer 3 imparts excellent bondability to another material (bonding material) to be bonded. Its zygosity is valid for a long period of several months or more.
  • the surface of the material layer 2 is protected by the primer layer 3, and deterioration such as dirt adhesion and oxidation can be suppressed.
  • the bonded body 5 in one embodiment is bonded to a material (bonding material) 6 which is at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber.
  • the primer layer 3 of the material 1 with a primer which is a material, is welded.
  • High-frequency welding refers to a method of melting and welding a material from the inside by dielectric heating with high frequency.
  • the device used for high-frequency welding include a high-frequency heating device having a power supply unit and a heating coil unit (high-frequency bar) for generating a strong high-frequency electric field.
  • Specific examples include a high-frequency welder manufactured by Yamamoto Vinita Co., Ltd.
  • a coil is arranged inside the heating coil portion of the high-frequency heating device, and a strong high-frequency electric field can be generated by passing an electric current through the coil.
  • the high frequency condition in the high frequency welding include a low RF frequency of an output of 3 to 100 kW and a generation frequency of 13.56 to 40.46 MHz.
  • the bonding material 6 has one or a plurality of primer layers on one surface of a material layer made of at least one material selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber.
  • In-situ polymerization type in which at least one layer of the primer layer comprises a polymer of a field-polymerization type composition containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide. It may be a composition layer.
  • the bonded body 5 in another embodiment has one or a plurality of primer layers 9 in which the bonding material 6 is laminated on the material layer 8, and at least one layer of the primer layer 9 is provided.
  • a primer-attached material 7 which is a field-polymerized composition layer composed of a polymer of a field-polymerized composition
  • a primer layer 9 of the primer-attached material 7 which is the bonding material and a primer-attached material which is a bonding material. It is formed by welding the primer layer 3 of 1.
  • a functional group-containing layer 10 can be formed between the material layer 8 and the primer layer 9 in the same manner as in the primer-attached material 1.
  • the thickness of the primer layer depends on the material of the bonding target and the contact area of the bonding portion, but from the viewpoint of obtaining excellent bonding strength with the bonding target and the coefficient of thermal expansion between dissimilar materials. From the viewpoint of suppressing thermal deformation of the bonded body due to the difference between the two, it is preferably 1 ⁇ m to 10 mm. It is more preferably 10 ⁇ m to 8 mm, and even more preferably 50 ⁇ m to 5 mm.
  • the thickness of the primer layer is the total thickness of each layer.
  • a method for producing the bonded body 5 at least one selected from the group consisting of high-frequency welding, ultrasonic welding, vibration welding, heat welding, hot air welding, induction welding, and injection welding of the primer layer 3 of the material 1 with a primer. Then, a method of welding to another bonding material 6 can be mentioned.
  • the field-polymerized composition of the present embodiment contains at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide, and at least one of the above (1) to (6), and is thermoplastic. It is used for the primer layer of the resin structure.
  • the total content of the vinyl chloride resin, the phenol resin and the polyamide contained in the total amount of the in-situ polymerization type composition is preferably 0.5 to 50% by mass, more preferably 1 to 1 to 50% by mass from the viewpoint of ease of welding of the primer. It is 30% by mass, more preferably 2 to 15% by mass.
  • the total content of the above is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the normal temperature in the examples is 23 ° C.
  • ⁇ Surface treatment_chemical conversion treatment> The aluminum (A6063) shown in Table 1 was immersed in a sodium hydroxide aqueous solution having a concentration of 5% by mass for 1.5 minutes and then neutralized with a nitric acid aqueous solution having a concentration of 5% by mass.
  • ⁇ Functional group addition treatment_silane coupling agent treatment> The chemical-treated aluminum and the sanding-treated CFRP, the sanding-treated copper, the sanding-treated ceramic, the glass in Table 1, the copper foil in Table 1, and the sanding treatment.
  • Each material of the GFRP was put into a silane coupling agent-containing solution at 70 ° C. in which 2 g of 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) was dissolved in 1000 g of industrial ethanol. Soaked for 20 minutes. Each of the materials was taken out and dried to form a functional group (amino group) layer.
  • test pieces thermoplastic resin
  • SE100V manufactured by Sumitomo Heavy Industries, Ltd.
  • test pieces for tensile test PA6 resin, PPS resin, PEI resin, PC resin, PBT resin (25 mm x 100 mm x) 1 mm) was obtained.
  • Bifunctional epoxy resin (“jER® 1007” manufactured by Mitsubishi Chemical Co., Ltd.) 100 g, bisphenol S 3.1 g, novolac type phenol resin (“Shonol BRG-556” manufactured by Aika Kogyo Co., Ltd.) 2.6 g and birds 0.4 g of phenylphosphine was dissolved in 197 g of methyl ethyl ketone to prepare a field-polymerized composition-1 (a phenol-resin-containing field-polymerized thermoplastic epoxy resin composition).
  • a primer layer-1 made of a cured product was formed.
  • silane coupling agent treated aluminum-1 Aluminum in Table 1 (hereinafter referred to as untreated aluminum), said silane coupling agent treated aluminum-1, CFRP after said silane coupling agent treated (hereinafter referred to as silane coupling agent treated CFRP-1), said silane coupling.
  • Agent-treated copper, glass after the silane coupling agent treatment hereinafter referred to as silane coupling agent-treated glass
  • ceramic after the silane coupling agent treatment hereinafter referred to as silane coupling agent-treated ceramic
  • silane coupling agent-treated ceramic On the surface of each one side of the GFRP treated with the agent (hereinafter referred to as GFRP treated with a silane coupling agent), the in-situ polymerization type composition-2 was applied by a spray method so that the thickness after drying was 20 ⁇ m.
  • a primer layer-2 made of a substance was formed.
  • the in-situ polymerization type composition-1 was applied by a spray method so that the thickness after drying was 20 ⁇ m. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 120 ° C. for 10 minutes to carry out a heavy addition reaction, and then allowed to cool to room temperature to allow the in-situ polymerization type composition-1. A primer layer-1 made of a cured product was formed.
  • the in-situ polymerization type composition-2 was applied by a spray method so that the thickness after drying was 20 ⁇ m. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 120 ° C. for 10 minutes to carry out a heavy addition reaction, and then allowed to cool to room temperature to allow the in-situ polymerization type composition-2. A primer layer-2 made of a cured product was formed.
  • the surface of each one side of the treated ultra-thin glass) and the silane coupling agent-treated acrylic resin film (hereinafter referred to as silane coupling agent-treated acrylic resin film) has a thickness of 2 ⁇ m after drying.
  • the field-polymerized composition-3 was applied by a spray method. After the solvent was volatilized by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 100 ° C. for 20 minutes to carry out a heavy addition reaction, and then allowed to cool to room temperature to allow the in-situ polymerization type composition-3.
  • a primer layer-3 made of a cured product was formed.
  • the surface on which the primer layer is formed is called the primer surface, and the surface on which the primer layer is not formed is called the primer-free surface. Further, in Tables 4 and 5 below, a surface having a primer layer is referred to as (with), and a surface without a primer layer is referred to as (absent).
  • Example 1 (High frequency welding) A high-frequency welder manufactured by Yamamoto Vinita Co., Ltd .: PLASEST-8 x XD with the primer layer-1 surface of sanding steel and the primer layer-1 surface of sanding steel overlapped so that the joint portion is 18 mm x 10 mm.
  • High-frequency welding was performed under the conditions of a high-frequency output of 8 kW, an oscillation frequency of 40.46 MHz, and a welding time of 1.5 seconds to obtain a test piece 1 (steel-steel joint).
  • the joint portion means a portion where the test piece materials are overlapped.
  • Examples 2 to 13 In the same manner as in Example 1, a tensile shear test piece was prepared with the combination of the object to be joined and the object to be joined shown in Table 4, and the tensile shear test was performed. The results are shown in Table 4.
  • the comparative in-situ polymerization type composition-1 was applied to the surface of one side of the sanding steel by a spray method so that the thickness after drying was 20 ⁇ m.
  • the solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -1.
  • Comparative test piece 1 (High frequency welding) Comparative test piece 1 (Similar to Example 1) except that the primer layer ratio-1 surface of the sanding steel and the primer layer ratio-1 surface of the sanding steel were overlapped so that the joint portion was 18 mm ⁇ 10 mm. Steel-steel joint) was obtained.
  • the comparative in-situ polymerization type composition-2 was sprayed onto the surfaces of each of the silane coupling agent-treated copper and the silane coupling agent-treated aluminum-1 so that the thickness after drying was 20 ⁇ m. ..
  • the solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -2.
  • Example 1 (High frequency welding) Example 1 except that the primer layer ratio-2 planes of the silane coupling agent-treated copper and the primer layer ratio-2 planes of the silane coupling agent-treated aluminum-1 were overlapped so that the joint portion was 18 mm ⁇ 10 mm.
  • a comparative test piece 2 (copper-aluminum joint) was obtained in the same manner as above.
  • the comparative in-situ polymerization type composition-3 was applied by a spray method to the surface of each one side of the silane coupling agent-treated ceramic and the silane coupling agent-treated GFRP so that the thickness after drying was 20 ⁇ m.
  • the solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -3.
  • Example 2 High frequency welding Same as in Example 1 except that the primer layer ratio-3 surfaces of the silane coupling agent-treated ceramic and the primer layer ratio-3 surfaces of the silane coupling agent-treated GFRP were overlapped so that the joint portion was 18 mm ⁇ 10 mm.
  • a comparative test piece 3 (ceramic-GFRP conjugate) was obtained.
  • Example 2 High frequency welding The same as in Example 1 except that the polymerized primer layer surface of the silane coupling agent-treated aluminum-1 and the polymerized primer layer surface of the silane coupling agent-treated copper were overlapped so that the joint portion was 18 mm ⁇ 10 mm.
  • a comparative test piece 4 (aluminum-copper joint) was obtained.
  • the comparative in-situ polymerization type composition-4 was applied to the surface of one side of the sanding steel by a spray method so that the thickness after drying was 20 ⁇ m.
  • the solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -4.
  • the comparative in-situ polymerization type composition-5 was applied by a spray method to the surfaces of each one side of the untreated aluminum and the PC in Table 2 so that the thickness after drying was 20 ⁇ m.
  • the solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of ⁇ 5.
  • Example 14 High frequency welding
  • Example 1 except that the primer layer-3 surface of the silane coupling agent treated aluminum-1 and the primer layer-3 surface of the silane coupling agent treated copper foil were overlapped so that the joint portion was 10 mm ⁇ 40 mm.
  • a test piece 14 of Example 14 (aluminum with a copper foil, which is an aluminum-copper foil joint) was obtained.
  • Example 15 High frequency welding Examples except that the primer layer-3 surfaces of the silane coupling agent-treated ultrathin glass and the primer layer-3 surfaces of the silane coupling agent-treated acrylic resin film were overlapped so that the joint portion was 10 mm ⁇ 40 mm.
  • a test piece 15 (ultra-thin glass-acrylic resin film joint) of Example 15 was obtained in the same manner as in 1.
  • Comparative Example 7 (Formation of primer layer) Comparative on-site polymerization type composition-3 prepared in Comparative Example 3 so that the thickness after drying was 2 ⁇ m on the surface of each one side of the silane coupling agent-treated aluminum-1 and the silane coupling agent-treated copper foil.
  • the solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -3.
  • a comparative test piece 7 (aluminum with a copper foil, which is an aluminum-copper foil joint) was obtained in the same manner as in 1.
  • ⁇ Surface treatment_boehmite treatment> The aluminum was immersed in a sodium hydroxide aqueous solution having a concentration of 5% by mass for 1.5 minutes, neutralized with a nitric acid aqueous solution having a concentration of 5% by mass, washed with water, and dried to perform an etching treatment. Next, the aluminum after the etching treatment was boiled in pure water for 10 minutes and then baked at 250 ° C. for 10 minutes to perform boehmite treatment.
  • silane coupling agent treated aluminum-2 One side of each of the aluminum after the silane coupling agent treatment (hereinafter referred to as silane coupling agent treated aluminum-2) and the CFRP after the silane coupling agent treatment (hereinafter referred to as silane coupling agent treated CFRP-2).
  • the in-situ polymerization type composition-1 was applied to the surface of the above by a spray method so that the thickness after drying was 2 mm. After the solvent was volatilized by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 150 ° C. for 30 minutes for a heavy addition reaction, allowed to cool to room temperature, and then allowed to cool to room temperature.
  • a primer layer made of a cured product was formed.
  • the surface on which the primer layer is formed is referred to as a primer surface, and the surface on which the primer layer is not formed is referred to as a primer-free surface.
  • Example 17 (High frequency welding) A silane coupling agent-treated aluminum-1 having a primer layer-3 formed on one side and a silane coupling agent-treated copper foil having a primer layer-3 formed on one side are placed in a high-temperature and high-humidity tank having a temperature of 85 ° C and a humidity of 85%. Was left for 1000 hours. After that, except that the primer layer-3 surfaces of the silane coupling agent-treated aluminum-1 and the primer layer-3 surfaces of the silane coupling agent-treated copper foil were superposed so that the joint portion was 10 mm ⁇ 40 mm, the examples were carried out. A test piece 17 (aluminum with a copper foil, which is an aluminum-copper foil joint) of Example 17 was obtained in the same manner as in 1.
  • Example 18 (High frequency welding) A silane coupling agent-treated ultra-thin glass having a primer layer-3 formed on one side and a silane coupling agent-treated acrylic resin film having a primer layer-3 formed on one side at a high temperature and high humidity of 85 ° C. and 85% humidity. It was left in the tank for 1000 hours. After that, except that the primer layer-3 surface of the silane coupling agent treated ultrathin glass and the primer layer-3 surface of the silane coupling agent treated acrylic resin film were overlapped so that the joint portion was 10 mm ⁇ 40 mm. A test piece 18 (ultra-thin glass-acrylic resin film joint) of Example 18 was obtained in the same manner as in Example 1.
  • the primer-equipped material according to the present invention is joined and integrated with other materials, for example, a door side panel, a bonnet, a roof, a tailgate, a steering hanger, an A pillar, a B pillar, a C pillar, a D pillar, a crash box, and the like.
  • Power control unit (PCU) housing electric compressor member (inner wall part, suction port part, exhaust control valve (ECV) insertion part, mount boss part, etc.), lithium ion battery (LIB) spacer, battery case, LED head lamp, etc.
  • bonded bodies according to the present invention those in which CFRP and metal are bonded are suitable for applications of multi-material materials such as automobiles, and those in which copper foil is bonded and bonded to ceramic, aluminum, FRP, etc. are electronic. Suitable for material substrate applications.

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  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

Ce matériau équipé d'une couche d'apprêt comprend une ou plusieurs couches d'apprêt qui sont disposées en couches sur une couche de matériau. Au moins l'une des couches d'apprêt est une couche de composition de type polymérisation in situ comprenant un polymère d'une composition de type polymérisation in situ contenant au moins un type de résine choisi dans le groupe constitué par une résine de chlorure de vinyle, une résine phénolique et un polyimide.
PCT/JP2021/015900 2020-04-21 2021-04-19 Matériau équipé d'une couche d'apprêt et corps assemblé WO2021215404A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002205335A (ja) * 1996-10-08 2002-07-23 Toyota Motor Corp 基体に硬質の樹脂製品を溶着する方法、ウインドガラスの製造方法及びウインドガラス
JP2013107814A (ja) * 2011-10-26 2013-06-06 Cemedine Co Ltd 合わせガラス及びこの合わせガラスを用いたディスプレイ装置
JP2014240283A (ja) * 2013-06-11 2014-12-25 レンゴー株式会社 板紙と熱可塑性樹脂製フィルムとの接合方法、及びその方法を用いた物品の固定・包装方法。
WO2019116879A1 (fr) * 2017-12-13 2019-06-20 昭和電工株式会社 Stratifié composite et son procédé de production, et produit lié résine-métal et son procédé de production

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005314445A (ja) * 2004-04-27 2005-11-10 Sanyo Chem Ind Ltd 反応性ホットメルト接着剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002205335A (ja) * 1996-10-08 2002-07-23 Toyota Motor Corp 基体に硬質の樹脂製品を溶着する方法、ウインドガラスの製造方法及びウインドガラス
JP2013107814A (ja) * 2011-10-26 2013-06-06 Cemedine Co Ltd 合わせガラス及びこの合わせガラスを用いたディスプレイ装置
JP2014240283A (ja) * 2013-06-11 2014-12-25 レンゴー株式会社 板紙と熱可塑性樹脂製フィルムとの接合方法、及びその方法を用いた物品の固定・包装方法。
WO2019116879A1 (fr) * 2017-12-13 2019-06-20 昭和電工株式会社 Stratifié composite et son procédé de production, et produit lié résine-métal et son procédé de production

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