JP6923707B1 - Primer material and conjugate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 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. SOLUTION: The primer layer 3 is one layer or a plurality of layers laminated on a material layer, and at least one layer of the primer layer is at least one selected from the group consisting of vinyl chloride resin, phenol resin and polyamide. A material with a primer, which is a field-polymerized composition layer composed of a polymer of a field-polymerized composition containing a resin. [Selection diagram] Fig. 1

Description

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.

Mechanical joining, adhesive joining, and welding are used in the assembly process of plastic products such as automobile parts, medical equipment, and home appliances. Welding is a highly reliable and productive joining method. Specifically, ultrasonic welding, vibration welding, heat welding, hot air welding, induction welding and the like are used. Welding is generally used for joining the same type of thermoplastic resin material, but it can also be used for joining different types of thermoplastic resin materials having similar solubility parameters (SP values). For example, 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.

JP-A-2017-202667 JP-A-2017-206014 Japanese Unexamined Patent Publication No. 2008-284862

The strength of the welded portion is expressed by the entanglement and crystallization of molecules due to molecular diffusion at the bonding interface. However, 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 the material with a primer, a bonded body using the material with a primer, and a method for producing the same.

The present invention provides the following means for achieving the above object.
In the present specification, 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. However, 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.

[1] It 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 selected from the group consisting of vinyl chloride resin, phenol resin and polyamide. 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.
[2] The material with a primer according to [1], wherein the in-situ polymerization type composition contains at least one of the following (1) to (6).
(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 types of compounds selected from the group consisting of bifunctional epoxy compound and bifunctional thiol compound (6) Monofunctional Radical polymerizable monomer [3] The material with a primer according to [1] or [2], wherein the material layer comprises at least one selected from the group consisting of metal, glass, ceramic, fiber-reinforced plastic, resin and rubber. ..
[4] The primer according to any one of [1] to [3], wherein the total content of the vinyl chloride resin, the phenol resin and the polyamide is 0.5 to 50% by mass in the total amount of the in-situ polymerization type composition. Attached material.

[5] 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 bonded body made by welding.

[6] The method according to any one of [1] to [4], wherein a field-polymerized composition containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide is polymerized on a material layer. Method of manufacturing material with primer.
[7] The method for producing a material with a primer according to [6], wherein the in-situ polymerization type composition contains at least one of the following (1) to (6).
(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 [8] 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.

[9] 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.

[11] An in-situ polymerization type composition for a primer layer containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide, and at least one of the following (1) to (6).
(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 [12] The site for a primer layer according to [11], wherein the total content of the vinyl chloride resin, the phenol resin and the polyamide is 0.5 to 50% by mass based on the total amount of the field-polymerized composition. Polymerized composition.

INDUSTRIAL APPLICABILITY According to the present invention, 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 are provided. be able to.

It is explanatory drawing which shows the structure of the material with a primer in one Embodiment of this invention. It is explanatory drawing which shows the structure of the material with a primer in another embodiment of this invention. It is explanatory drawing which shows the structure of the material with a primer in another embodiment of this invention. It is explanatory drawing which shows the structure of the bonded body in one Embodiment of this invention. It is explanatory drawing which shows the structure of the junction in another embodiment of this invention.

Hereinafter, 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.
In addition, in this specification, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means acrylate and / or methacrylate.

[Material with primer]
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 of the primer layers 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.

As shown in FIG. 1, 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. In the present embodiment, 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.

In the present embodiment, 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.

In the present embodiment, 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. At that time, it means a layer that is interposed between the material layer and the bonding target to improve the bonding strength of the material layer with respect to the bonding target.
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. By doing so, a thermoplastic structure, that is, a linear polymer structure is formed.

<Material layer 2>
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.

Examples of the fiber reinforced plastic (FRP) include glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), and aramid fiber reinforced plastic (AFRP). Molds made from glass fiber or carbon fiber SMC (sheet molding compound) can also be mentioned.

Examples of the resin 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 rubber include natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, ethylene propylene diene rubber, butadiene acrylonitrile copolymer rubber, chloroprene rubber, silicon rubber, and fluorine rubber. And so on.

When the material layer 2 is a metal, its thickness is preferably 1.5 μm or more, more preferably 1.6 μm 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.
When 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.
When the material layer 2 is FRP and ceramic, 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.
When the material layer 2 is resin and rubber, the thickness thereof is preferably 10 μm or more, more preferably 30 μm 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.

〔surface treatment〕
The material layer 2 may be surface-treated for the purpose of removing contaminants on the surface and / or an anchor effect.
When 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.

As shown in FIG. 1, the surface treatment can form fine irregularities 21 on the surface of the material layer 2 to roughen the surface. As a result, the adhesiveness between the surface of the material layer 2 and the primer layer 3 can be improved. In addition, 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.
As the surface treatment, 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. In the case of glass, it is one of the surface cleaning methods for removing organic impurities on the surface. Generally, 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.

Examples of the blasting treatment 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.

Examples of the polishing treatment include buffing polishing 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 it in a functional state. Be done.

The corona discharge treatment includes a method applied to surface modification of a polymer film, in which electrons emitted from an electrode cut a polymer main chain or side chain of a polymer surface layer and generate radicals as a starting point. 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. Can be mentioned.

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. Known frame processing techniques can be used.

When the material layer is a metal, the chemical conversion treatment mainly forms a chemical conversion film on the surface of the material layer 2.
Examples of the chemical conversion treatment when the material layer is a metal include boehmite treatment and zirconium treatment.
In the boehmite 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. For example, it is preferable to immerse the material layer 2 in hot water at 90 to 100 ° C. containing triethanolamine at a concentration of 0.1 to 5.0% by mass for 3 seconds to 5 minutes.
In the zirconium treatment, 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. For example, 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.

[Functional group addition treatment]
It is also possible to perform a functional group imparting treatment for imparting a functional group to the surface of the material layer 2.

It is preferable that the material layer 2 is subjected to a functional group addition treatment following the surface treatment before laminating the primer layer 3.

As shown in FIG. 2, 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.

When the functional group-containing layer 4 is formed by the functional group-imparting treatment, 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. In addition, 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. Specifically, 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.

〔Silane coupling agent〕
As the 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. Examples of 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-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be mentioned. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and dithioltriazinepurpiltriethoxysilane. Examples of the silane coupling agent having a (meth) acryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-Acryloxypropyltrimethoxysilane and the like. In addition, as other effective silane coupling agents, silane coupling agents having a vinyl group such as 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane, 3-tri. Ethethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris-( Trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, and the like. These may be used alone or in combination of two or more.

[Isocyanate compound]
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. (Registered trademark) ”,“ AOI-VM (registered trademark) ”), 1,1- (bisacryloyloxyethyl) ethyl isocyanate (for example,“ Karens BEI (registered trademark) ”manufactured by Showa Denko Co., Ltd.), etc. Be done.

[Thiol compound]
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-mercaptobutylyloxy) butane (for example,“ Karenz MT ”manufactured by Showa Denko KK) (Registered trademark) BD1 "), Pentaerythritol tetrakis (3-mercaptobutyrate) (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>
The primer layer 3 is laminated on the material layer 2 directly or via the functional group-containing layer 4.

[Field-polymerized composition layer 31]
As described above, 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.
Examples of the solvent 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. include. By including at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide, 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 bonded.
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.
The term "polyamide" as used herein means "n-nylon" synthesized by a polycondensation reaction of ω amino acids and "n, m-nylon" synthesized by a ring-opening polymerization reaction of diamine and dicarboxylic acid. However, "n-nylon" synthesized by the polycondensation reaction of ω amino acid is preferable, and among them, nylon 6 synthesized by the ring-opening polymerization reaction of ε-caprolactam is more preferable. Further, as 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.

By laminating the in-situ polymerization type composition layer 31 as the primer layer 3 on the material layer 2, 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. When 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. As the catalyst for the polyaddition reaction, for example, a phosphorus compound such as tertiary amine-triphenylphosphine such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol is 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.
Specifically, for example, 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, and then the solvent is appropriately volatilized, and then 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.
Specifically, for example, 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.

It should be noted that the method of the heavy addition reaction differs in the conditions under which the heavy addition reaction proceeds, the molecular weight distribution, and the like 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.

(Bifunctional isocyanate compound)
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). Among them, TDI, MDI and the like are preferable from the viewpoint of the strength of the primer.

(Compound having a bifunctional hydroxyl group)
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.
In the above (3), as the compound having a bifunctional hydroxyl group to be combined with the bifunctional epoxy compound, bifunctional phenol is preferable, and the bisphenols are particularly preferable.

(Compound having a bifunctional amino group)
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. Examples of aromatic diamines include 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, and N-aminoethylpiperazine. Examples thereof include diaminodiphenylmethane and diaminodiphenylpropane. Of these, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine and the like are preferable from the viewpoint of primer toughness.

(Bifunctional epoxy compound)
The bifunctional epoxy compound is a compound having two epoxy groups in one molecule. For example, 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.

(Bifunctional carboxy compound)
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.

(Bifunctional thiol compound)
The bifunctional thiol compound is a compound having two mercapto groups in the molecule. For example, the bifunctional secondary thiol compound 1,4-bis (3-mercaptobutyryloxy) butane (for example, Showa Denko KK) "Karens MT (registered trademark) BD1") manufactured by.

(Monofunctional radically polymerizable monomer)
The monofunctional radically polymerizable monomer is a monomer having one ethylenically unsaturated bond. For example, styrene monomers, styrene-based monomers such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, chlorostyrene, vinyltoluene, divinylbenzene, etc.; 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. ..
In order to allow the radical polymerization reaction to proceed sufficiently and form a desired primer layer, a solvent and, if necessary, an additive such as a colorant may be contained. In this case, it is preferable that 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.
As 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. Examples of organic peroxides include those classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. As 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. In the case of photocuring, 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.

Examples of the thermosetting resin 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. Alternatively, 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 the present embodiment broadly means a resin that is cross-linked and cured, and is not limited to the heat-curing type, but also includes a room temperature curing type and a photocuring 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.

(Urethane resin)
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.

Examples of the one-component urethane resin 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 (which cures when the solvent volatilizes and dries), a lacquer type (which cures when the isocyanato group which is dissociated by heating and regenerated and the hydroxyl group reacts with each other and cures). Among these, 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.

Examples of the polyol compound in the polyol curing type include polyester polyols, polyether polyols, phenol resins and the like.
Further, examples of the isocyanate compound having an isocyanato group in the polyol curable type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and diimmerate diisocyanate; 2,4- or 2,6-tolylene diisocyanate. (TDI) or a mixture thereof, 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. Be done.
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.

Examples of the urethanization catalyst used in the two-component urethane resin include triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol-triethylamine and other amine-based catalysts; dibutyltindi Examples thereof include organotin catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate and dibutyltin dimalate.
In the polyol curing type, it is generally preferable to add 0.01 to 10 parts by mass of the urethanization catalyst to 100 parts by mass of the polyol compound.

(Epoxy resin)
The epoxy resin is a resin having at least two epoxy groups in one molecule.
Examples of 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. When 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 described later. Among these, pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "Karenzu MT (registered trademark) PE1" manufactured by Showa Denko KK) is preferable from the viewpoint of elongation and impact resistance.

(Vinyl ester resin)
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.
As 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. In addition, specifically, "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). 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.
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.

(Unsaturated polyester resin)
The unsaturated polyester resin is a monomer (eg, styrene, etc.) 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 polymerized. ) Is dissolved.
As 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 trademark)" manufactured by Showa Denko KK can be mentioned.

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.

[Action of primer layer 3]
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.

[Joint 5]
As shown in FIG. 4, the joining body 5 in one embodiment is joined 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.
There are various methods for welding depending on the method of heating the primer layer 3, and specific examples thereof include high frequency welding, ultrasonic welding, vibration welding, heat welding, hot air welding, induction welding, and injection welding. Of these, high frequency welding is preferable.

High-frequency welding refers to a method of melting and welding a material from the inside by dielectric heating with high frequency. Examples of 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.
Examples of 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.
As shown in FIG. 5, 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. Is composed of a primer-attached material 7 which is a field-polymerized composition layer composed of a polymer of a field-polymerized composition, and 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. Similar to the primer-attached material 1, the primer-attached material 7 can form a functional group-containing layer 10 between the material layer 8 and the primer layer 9.

The thickness of the primer layer (thickness after drying) 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 μm to 10 mm. It is more preferably 10 μm to 8 mm, and even more preferably 50 μm to 5 mm. When the primer layer is a plurality of layers, the thickness of the primer layer (thickness after drying) is the total thickness of each layer.

As 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.

[In-situ polymerization type composition]
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.

As the compounds shown in (1) to (6), those described in the section [Material with Primer] can be used.

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 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.

Further, the sum of at least one resin selected from the group consisting of the vinyl chloride resin, the phenol resin and the polyamide contained in the total amount of the in-situ polymerization type composition and at least one of the above (1) to (6). The content is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.

Next, specific examples of the present invention will be described, but the present invention is not particularly limited to those of these examples.

[Materials for test pieces (inorganic materials and FRP)]
As the material for the test piece, each material (18 mm × 45 mm) in Table 1 was prepared.

<Surface treatment_Sanding treatment>
The surfaces of the steel, CFRP, copper, ceramic, and GFRP materials shown in Table 1 were polished with # 1000 sandpaper, washed with acetone, and degreased.

<Surface treatment_chemical conversion treatment>
The aluminum (A6063) shown in Table 1 was immersed in an aqueous solution of sodium hydroxide having a concentration of 5% by mass for 1.5 minutes and then neutralized with an aqueous solution of nitric acid having a concentration of 5% by mass.

<Functional group addition treatment_silane coupling agent treatment>
The chemical conversion-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.

[Material for test pieces (thermoplastic resin)]
Tensile test test piece: PA6 resin, PPS resin, PEI resin, PC resin, PBT resin (25 mm x 100 mm x) using an injection molding machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions shown in Table 2. 1 mm) was obtained.

[Materials for test pieces (film and thin glass)]
The films and thin glass shown in Table 3 were prepared.

<Surface treatment_Corona discharge treatment>
The acrylic resin film shown in Table 3 was prepared by corona discharge treatment.

<Functional group addition treatment_silane coupling agent treatment>
The ultra-thin glass in Table 3 and the corona discharge-treated acrylic resin film were prepared by dissolving 2 g of 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone Co., Ltd .; a silane coupling agent) in 1000 g of industrial ethanol at 70 ° C. Was immersed in the silane coupling agent-containing solution of the above for 20 minutes. Each of the materials was taken out and dried to form a functional group (amino group) layer.

<Preparation of in-situ polymerization type composition-1 for forming a primer layer>
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).

<Preparation of in-situ polymerization type composition-2 for forming a primer layer>
Diphenylmethane Diisocyanate 100 g, diaminodiphenylmethane 158 g and vinyl chloride resin (manufactured by Shin-Daiichi PVC Co., Ltd., “ZEST 700L”) 40 g were dissolved in acetone 480 g to form an in-situ polymerization type composition-2 (site containing vinyl chloride resin). Polymerized polyurea resin composition) was prepared.

<Preparation of in-situ polymerization type composition-3 for forming a primer layer>
100 g of diphenylmethane diisocyanate, 60.8 g of propylene glycol and 20 g of polyamide (manufactured by Toray Co., Ltd., fine particle nylon 6: "Amylan TR-1, average particle size: 13 μm") are dissolved in 480 g of acetone to form a field-polymerized composition. -3 (Polyamide-containing field-polymerized polyurethane resin composition) was prepared.

<Formation of primer layer>
Steel in Table 1 (hereinafter referred to as untreated steel), steel after the sanding treatment (hereinafter referred to as sanding steel), aluminum after the silane coupling agent treatment (hereinafter referred to as silane coupling agent treated aluminum-1), One side of each of the CFRP in Table 1 (hereinafter referred to as untreated CFRP), the copper in Table 1 (hereinafter referred to as untreated copper), and the copper after the silane coupling agent treatment (hereinafter referred to as silane coupling agent treated copper). The in-situ polymerization type composition-1 was applied to the surface of the steel by a spray method so that the thickness after drying was 20 μm. After volatilizing the solvent 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-1 made of a cured product was formed.

Aluminum in Table 1 (hereinafter referred to as untreated aluminum), the silane coupling agent-treated aluminum-1, CFRP after the silane coupling agent treatment (hereinafter referred to as silane coupling agent-treated CFRP-1), and the 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), and the silane coupling agent. The in-situ polymerization type composition-2 was applied to the surface of each one side of the treated GFRP (hereinafter referred to as silane coupling agent treated GFRP) by a spray method so that the thickness after drying was 20 μm. 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 for a heavy addition reaction, and then allowed to cool to room temperature to cure the in-situ polymerization type composition-2. A primer layer-2 made of a substance was formed.

For PEI and PBT (GF30% by mass) in Table 2, the in-situ polymerization type composition-1 was applied by a spray method so that the thickness after drying was 20 μm. 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 for a heavy addition reaction, allowed to cool to room temperature, and then allowed to cool to room temperature. A primer layer-1 made of a cured product was formed.

For PC, PA6 (GF30% by mass), and PPS in Table 2, the in-situ polymerization type composition-2 was applied by a spray method so that the thickness after drying was 20 μm. After the solvent was volatilized by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 120 ° C. for 10 minutes for a heavy addition reaction, allowed to cool to room temperature, and then the in-situ polymerization type composition-2. A primer layer-2 made of a cured product was formed.

Silane coupling agent treated aluminum-1, copper foil after silane coupling agent treatment (hereinafter referred to as silane coupling agent treated copper foil), ultrathin glass after silane coupling agent treatment (hereinafter referred to as silane coupling agent). The surface of each one side of the treated ultra-thin glass) and the acrylic resin film after the silane coupling agent treatment (hereinafter referred to as the silane coupling agent-treated acrylic resin film) has a thickness of 2 μm after drying. The in-situ polymerization type composition-3 was applied by a spray method. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 100 ° C. for 20 minutes for a heavy addition reaction, allowed to cool to room temperature, and then allowed to cool to room temperature. A primer layer-3 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. 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). Here, the joint portion means a portion where the test piece materials are overlapped.

(Tensile shear strength)
After leaving the test piece 1 at room temperature (23 ° C.) for 1 day, a tensile tester (universal tester Autograph "AG-IS" manufactured by Shimadzu Corporation); load cell 10 kN, based on JIS K 6850: 1999. , Tensile speed 5 mm / min, temperature 23 ° C., 50% RH), a tensile shear strength test was performed, and the joint strength was measured. The measurement results are shown in Table 4 below.

[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.

[Comparative Example 1]
(Preparation of in-situ polymerization type composition-1 for comparison)
Bifunctional epoxy resin ("jER (registered trademark) 828" manufactured by Mitsubishi Chemical Co., Ltd.) 100 g, 1,4-bis (3-mercaptobutyryloxy) butane ("Carens MT (registered trademark) BD1" manufactured by Showa Denko KK" ) 80.9 g and 7.2 g of 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were subjected to a heavy addition reaction at room temperature (25 ° C.) for 24 hours to obtain the polymerization. The product was dissolved in 197 g of methyl ethyl ketone to prepare a comparative in-situ polymerization type composition-1.

(Formation of primer layer)
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 μm. The solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -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.

(Tensile shear strength)
The comparative test piece 1 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 5 below.

[Comparative Example 2]
(Preparation of in-situ polymerization type composition-2 for comparison)
100 g of diphenylmethane diisocyanate, 60.8 g of propylene glycol and 0.16 g of 2,4,6-tris (dimethylaminomethyl) phenol were subjected to a double addition reaction at room temperature (25 ° C.) for 24 hours, and the obtained polymer was added in 299 g of acetone. To prepare a comparative in-situ polymerization type composition-2.

(Formation of primer layer)
A 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 μm. .. The solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of 2.

(High frequency welding)
Example 1 except that the primer layer ratio-2 surfaces of the silane coupling agent-treated copper and the primer layer ratio-2 surfaces 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 conjugate) was obtained in the same manner as above.

(Tensile shear strength)
The comparative test piece 2 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 5 below.

[Comparative Example 3]
(Preparation of in-situ polymerization type composition-3 for comparison)
100 g of diphenylmethane diisocyanate and 60.8 g of propylene glycol were subjected to a double addition reaction at room temperature (25 ° C.) for 24 hours, and the obtained polymer was dissolved in 480 g of acetone to prepare a comparative in-situ polymerization type composition-3. ..

(Formation of primer layer)
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 μm. The solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -3.

(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.

(Tensile shear strength)
The comparative test piece 3 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 5 below.

[Comparative Example 4]
(Formation of primer layer)
The in-situ polymerization type composition-1 is volatilized in a flask and then held at 150 ° C. for 30 minutes to obtain a thermoplastic epoxy resin (hereinafter, polymerized thermoplastic epoxy resin), and after cooling, acetone becomes 65% by mass. A polymerized thermoplastic epoxy resin solution was obtained by completely dissolving the mixture.
The polymerized thermoplastic epoxy resin solution was applied by a spray method to the surfaces of one side of each of the silane coupling agent-treated aluminum-1 and the silane coupling agent-treated copper so that the thickness after drying was 20 μm. .. It was dried at 50 ° C. for 5 hours to form a polymerized primer layer.

(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.

(Tensile shear strength)
The comparative test piece 4 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 5 below.

[Comparative Example 5]
(Preparation of in-situ polymerization type composition-4 for comparison)
100 g of a bifunctional epoxy resin (“jER® 1007” manufactured by Mitsubishi Chemical Corporation), 3.1 g of bisphenol S, and 0.4 g of triphenylphosphine were dissolved in 197 g of methyl ethyl ketone to form a comparative in-situ polymerization type composition. Object-4 was prepared.

(High frequency welding)
Comparative test piece 5 in the same manner as in Example 1 except that the primer layer ratio of sanding steel-4 surfaces and the primer layer ratio of sanding steel-4 surfaces were overlapped so that the joint portion was 18 mm × 10 mm. (Steel-Steel Primer) was obtained.

(Tensile shear strength)
The comparative test piece 5 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 5 below.

[Comparative Example 6]
(Preparation of in-situ polymerization type composition-5 for comparison)
100 g of diphenylmethane diisocyanate and 158 g of diaminodiphenylmethane were dissolved in 480 g of acetone to prepare a comparative in-situ polymerization type composition-5.

(High frequency welding)
Comparative test piece 6 in the same manner as in Example 1 except that the primer layer ratio -5 surfaces of untreated aluminum and the primer layer ratio -5 surfaces of PC were overlapped so that the joint portion was 18 mm × 10 mm. (Aluminum-PC conjugate) was obtained.

(Tensile shear strength)
The comparative test piece 6 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 5 below.

[Example 14]
(High frequency welding)
Example 1 and Example 1 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 overlapped so that the joint portion was 10 mm × 40 mm. Similarly, the test piece 14 of Example 14 (aluminum with copper foil, which is an aluminum-copper foil joint) was obtained.

(Peel test)
For the test piece 14, according to JIS C 6681: 1996, the end of the copper foil having a width of 18 mm was grasped, the pulling speed was 50 mm / min in the 90 ° direction, the peeling length was 40 mm, and the peel strength was measured. The measurement results are shown in Table 6 below.

[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.

(Peel test)
A peel test was performed on the test piece 15 by the same method as in Example 14. The measurement results are shown in Table 6 below.

[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 μm on the surface of each one side of the silane coupling agent-treated aluminum-1 and the silane coupling agent-treated copper foil. Was applied by the spray method. The solvent was volatilized by leaving it in the air at room temperature for 30 minutes to form a primer layer ratio of -3.

(High frequency welding)
Examples except that the primer layer ratio-3 surfaces of the silane coupling agent-treated aluminum-1 and the primer layer ratio-3 surfaces of the silane coupling agent-treated copper foil were overlapped so that the joint portion was 10 mm × 40 mm. 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.

(Peel test)
A peel test was conducted on the comparative test piece 7 by the same method as in Example 14. The measurement results are shown in Table 6 below.

[Material for test pieces]
Among the materials shown in Table 1, CFRP and aluminum (3 cm × 50 cm) were prepared as test piece materials.

<Surface treatment_Sanding treatment>
The sanding treatment was performed on the CFRP.

<Surface treatment_boehmite treatment>
The aluminum was immersed in an aqueous solution of sodium hydroxide having a concentration of 5% by mass for 1.5 minutes, neutralized with an aqueous solution of nitric acid 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.

<Functional group addition treatment_silane coupling agent treatment>
The boehmite-treated aluminum and the sanding-treated CFRP materials were mixed with 2 g of 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) and 1000 g of industrial ethanol. It was immersed in a solution containing a silane coupling agent at 70 ° C. dissolved in the solution for 20 minutes. Each of the materials was taken out and dried to form a functional group (amino group) layer.

<Formation of primer layer>
One-sided surfaces of the aluminum after the silane coupling agent treatment (hereinafter, silane coupling agent-treated aluminum-2) and the CFRP after the silane coupling agent treatment (hereinafter, silane coupling agent-treated CFRP-2). The in-situ polymerization type composition-1 was applied by a spray method so that the thickness after drying was 2 mm. After volatilizing the solvent 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 16]
(Heat welding)
The primer surface of the silane coupling agent-treated aluminum-2 and the primer surface of the silane coupling agent-treated CFRP-2 were combined and heat-welded by pressing at 150 ° C. for 5 minutes.

(evaluation)
The welded joint body was returned to room temperature and left in a room temperature environment, and it was observed whether or not the joint body was warped and the joint surface was peeled off.
No warpage or peeling was observed.

[Comparative Example 8]
(Heat welding)
An acrylic plate was sandwiched between the primer-free surface of the silane coupling agent-treated aluminum-2 and the primer-free surface of the silane coupling agent-treated CFRP-2, and press heat welding was performed at 180 ° C. for 5 minutes.

(evaluation)
The welded joint body was returned to room temperature and left in a room temperature environment, and it was observed whether or not the joint body was warped and the joint surface was peeled off.
In the process of returning to room temperature, the joint surface peeled off.

[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 overlapped 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.

(Peel test)
A peel test was performed on the test piece 17 by the same method as in Example 14. The measurement results are shown in Table 7 below.

[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 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 18 (ultra-thin glass-acrylic resin film joint) of Example 18 was obtained in the same manner as in Example 1.

(Peel test)
A peel test was performed on the test piece 18 by the same method as in Example 14. The measurement results are shown in Table 7 below.

[Comparative Example 9]
(High frequency welding)
A silane coupling agent-treated aluminum-1 having a primer layer ratio -3 formed on one side and a silane coupling agent-treated copper foil having a primer layer ratio -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, it was carried out except that the primer layer ratio-3 surfaces of the silane coupling agent-treated aluminum-1 and the primer layer ratio-3 surfaces of the silane coupling agent-treated copper foil were overlapped so that the joint portion was 10 mm × 40 mm. A comparative test piece 9 (aluminum with copper foil, which is an aluminum-copper foil joint) was obtained in the same manner as in Example 1.

(Peel test)
A peel test was performed on the comparative test piece 9 by the same method as in Example 14. The measurement results are shown in Table 7 below.

The material with primer according to the present invention is joined and integrated with other materials, for example, door side panel, bonnet roof, tailgate, steering hanger, A pillar, B pillar, C pillar, D pillar, crash box, power. Automobiles such as control unit (PCU) housing, electric compressor members (inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) spacer, battery case, LED headlamp, etc. It is used as a component for parts, a smartphone, a laptop computer, a tablet computer, a smart watch, a large LCD TV (LCD-TV), a structure for outdoor LED lighting, and the like, but is not particularly limited to these exemplified applications.
Among the 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.

1 Material with primer 2 Material layer 21 Fine unevenness 3 Primer layer 31 In-situ polymerization type composition layer 32 Thermosetting resin layer 4 Functional group-containing layer 5 Bonded body 6 Bonding material 7 Primered material 8 Material layer 9 Primer layer 10 Functional Group-containing layer

Claims (10)

It 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 at least one selected from the group consisting of vinyl chloride resin, phenol resin and polyamide. and the resin, Ri thermoplastic situ polymerizable composition layer der consisting polymer of thermoplastic situ polymerizable composition containing at least one of the following (1) to (6),
The thermoplastic in-situ polymerization type composition layer is a material with a primer, which is laminated on the outermost surface opposite to the material layer of the primer layer.
(1) Combination of bifunctional isocyanate compound and compound having bifunctional hydroxyl group
(2) Combination of bifunctional isocyanate compound and compound having a bifunctional amino group
(3) Combination of bifunctional epoxy compound and compound having bifunctional hydroxyl group
(4) Combination of bifunctional epoxy compound and bifunctional carboxy compound
(5) Combination of two kinds of compounds selected from the group consisting of a bifunctional epoxy compound and a bifunctional thiol compound.
(6) Monofunctional radically polymerizable monomer The primer-attached material according to claim 1 , wherein the material layer comprises at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber. The primer-attached material according to claim 1 or 2 , wherein the total content of the vinyl chloride resin, the phenol resin and the polyamide is 0.5 to 50% by mass in the total amount of the thermoplastic in-situ polymerization type composition. The primer layer of the material with a primer according to any one of claims 1 to 3 is welded to a material which is at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber. Becomes a primer. A thermoplastic in-situ polymerization type composition containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide and at least one of the following (1) to (6) is provided on the material layer. The method for producing a material with a primer according to any one of claims 1 to 3, which is to be polymerized.
(1) Combination of bifunctional isocyanate compound and compound having bifunctional hydroxyl group
(2) Combination of bifunctional isocyanate compound and compound having a bifunctional amino group
(3) Combination of bifunctional epoxy compound and compound having bifunctional hydroxyl group
(4) Combination of bifunctional epoxy compound and bifunctional carboxy compound
(5) Combination of two kinds of compounds selected from the group consisting of a bifunctional epoxy compound and a bifunctional thiol compound.
(6) Monofunctional radically polymerizable monomer The method for producing a material with a primer according to claim 5 , wherein the material layer comprises at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber. The primer layer of the material with a primer according to any one of claims 1 to 3 is welded to a material which is at least one selected from the group consisting of metal, glass, ceramic, fiber reinforced plastic, resin and rubber. Method of manufacturing a joint. The method for producing a bonded body according to claim 7 , wherein the welding is high frequency welding. A thermoplastic in- situ polymerization type composition for a primer layer containing at least one resin selected from the group consisting of vinyl chloride resin, phenol resin and polyamide, and at least one of the following (1) to (6).
(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 The thermoplastic field-polymerized composition for a primer layer according to claim 9 , wherein the total content of the vinyl chloride resin, the phenol resin and the polyamide is 0.5 to 50% by mass based on the total amount of the thermoplastic field-polymerized composition. thing.

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