TW202128423A - Joined body and primer-equipped material - Google Patents

Abstract

A joined body according to the present invention is obtained by joining: a to-be-joined member that includes a material layer A comprising at least one type of material selected from the group consisting of fiber-reinforced plastic (FRP), metal, glass, and ceramic; and a joining member that includes a material layer B comprising at least one type of material selected from the group consisting of fiber-reinforced plastic (FRP), metal, glass, and ceramic. The to-be-joined member includes one or a plurality of primer layers laminated onto the material layer A, and at least one of the primer layers is an in-situ-polymerization-type resin composition layer A comprising a polymerized product of an in-situ-polymerization-type resin composition. The joined body comprises a primer-equipped material A and is obtained by welding the primer layer, of the to-be-joined-member, to the joining member.

Description

Joint body and material with primer

The present invention relates to a joined body formed by joining any materials selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramics, and a method of manufacturing the same. The present invention relates to a material with a primer suitable for joining with any material selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics to form a joined body, and a manufacturing method thereof.

The weight reduction of conveying equipment represented by automobiles _{has become an important issue in order to reduce CO 2} emissions or to save energy. In recent years, "multi-materialization" has been actively progressed in the development of technologies related to this subject. The so-called multi-materialization is achieved through the combined use of high-tensile steel (high-tensile steel (highten)), aluminum (Al), carbon fiber reinforced plastic (CFRP) and other materials with different functions and/or materials (hereinafter referred to as dissimilar materials) Lightweight or high-strength materials. In the realization of multi-materialization, the technology of directly joining dissimilar materials to each other is indispensable.

In the past, as a means of directly joining dissimilar materials to each other, the method of using rivets or the method of using an adhesive was mainly used. The joining system using rivets is a point joining (point joining), which has the disadvantage of inferior fatigue characteristics compared with the surface joining using an adhesive (surface joining). Therefore, the joint body joined by rivets is not good for automobile components requiring handling safety, and has the problem of limited use. And as a means of joining CFRP and other materials, when rivets are used, it has also been pointed out that there is a problem of cutting carbon fiber. On the other hand, since the bonding by the adhesive is a surface bonding, it has the advantage of exhibiting excellent fatigue characteristics even when thin-filmed materials are bonded to each other, or it has the advantage of not requiring fastening parts such as rivets, which can achieve weight reduction. It has the advantages, but it has the disadvantage that it takes time to harden the adhesive.

As a means for joining dissimilar materials, a joint of dissimilar materials using welding is also disclosed (Patent Document 1). Patent Document 1 discloses a dissimilar material joint body in which a first member made of metal and a second member made of fiber-reinforced thermoplastic resin are welded via an insulating layer made of thermoplastic resin. The joining by welding can completely avoid the above-mentioned shortcomings or problems associated with joining by rivets or adhesives. [Prior Technical Literature] [Patent Literature]

Patent Document 1: JP 2016-36955 A

[The problem to be solved by the invention]

Welding is generally known as a joining method for joining the same kind of thermoplastic resin material. When welding is used in the joining of dissimilar materials, as in Patent Document 1, one of the objects to be joined or joined is made of a thermoplastic resin, and a thermoplastic resin layer is arranged on the joining surface of the other, or the joined object and A thermoplastic resin layer is arranged on the joining surfaces of the two joining objects, respectively, and is welded. Therefore, in the past, when welding was used for joining of dissimilar materials, there was a problem that the design freedom of the joined body was limited, or the operation of separately arranging a thermoplastic resin layer on the joining surfaces of the two was a problem that it took a lot of procedures. In addition, in the past, a joint body in which dissimilar materials are joined by welding has a problem that the adhesion between the thermoplastic resin disposed on the joint surface and the joint surface is weak, and sufficient joint strength cannot be obtained between dissimilar materials.

The present invention was completed in view of this technical background, and the subject is to provide a material to be joined that includes a material layer composed of at least one selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics, and A bonded body made of a bonding material composed of at least one material layer selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics, and no thermoplastic resin layer is arranged on the bonding surfaces of the two, and It is a joint body that can be welded firmly. And the subject of the present invention is to provide a primer with a bonding material that can be strongly fused with a bonding material comprising at least one material layer consisting of at least one material selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics的材料。 The material. [Means to solve the problem]

In order to achieve the above-mentioned object, the present invention provides the following means. In addition, in this specification, the term “joining” refers to the connection of objects and objects, and then refers to the subordinate concept, which means that two materials to be bonded ( The person to be succeeded) becomes an engaged state.

(Joint body) [1] A joined body formed by joining a material to be joined including a material layer A and a joining material including a material layer B, wherein the material layer A is selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, The material layer B is composed of at least one of the group consisting of ceramics, the material layer B is composed of at least one selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics, and the material to be joined is composed of a primer The aforementioned material A with primer has one or more primer layers laminated on the aforementioned material layer A, and at least one of the aforementioned primer layers is composed of an in-situ polymerized resin composition The in-situ polymerizable resin composition layer A composed of the polymer of, and the bonding system is formed by welding the primer layer of the bonded material to the bonding material. [2] The bonded body of [1], wherein the bonding material is composed of material B with a primer, and the material B with primer has one or more layers of primers laminated on the material layer B Layer, and at least one of the aforementioned primer layers is an in-situ polymerizable resin composition layer B composed of polymers of an in-situ polymerizable resin composition, and the bonding system is made by making the primer layer of the bonding material It is formed by welding with the primer layer of the material to be joined. [3] The junction body according to [1] or [2], wherein the in-situ polymerizable resin composition layer A is formed by polymerizing the in-situ polymerizable resin composition on the material layer A. [4] The junction body according to [2] or [3], wherein the in-situ polymerizable resin composition layer B is formed by polymerizing the in-situ polymerizable resin composition on the material layer B. [5] The bonded body according to any one of [1] to [4], wherein the in-situ polymerizable resin composition layer A is in direct contact with the material layer A. [6] The joined body according to any one of [2] to [5], wherein the in-situ polymerizable resin composition layer B is in direct contact with the material layer B. [7] The junction body according to any one of [1] to [6], wherein the in-situ polymerizable resin composition contains at least one of the following (1) to (7); (1) Combination of 2-functional isocyanate compound and diol, (2) The combination of a 2-functional isocyanate compound and a 2-functional amine compound, (3) Combination of 2-functional isocyanate compound and 2-functional thiol compound, (4) Combination of 2-functional epoxy compound and diol, (5) Combination of 2-functional epoxy compound and 2-functional carboxyl compound, (6) Combination of 2-functional epoxy compound and 2-functional thiol compound, (7) Monofunctional radical polymerizable monomer. [8] The junction body according to [7], wherein the in-situ polymerizable resin composition contains a combination of the (4) bifunctional epoxy compound and a diol, and the diol is a bifunctional phenol. [9] The joined body according to any one of [1] to [8], wherein at least one layer of the primer layer is formed of a resin composition containing a thermosetting resin. [10] The junction body according to [9], wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin . [11] The junction body according to any one of [1] to [10], wherein the material A with primer has a layer containing a functional group, and the layer containing the functional group is laminated on the material layer A and Between the aforementioned primer layers and in contact with the aforementioned material layer A and the aforementioned primer layer, The aforementioned functional group-containing layer includes at least one functional group selected from the group consisting of the following (A) to (G); (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound. [12] The junction body according to any one of [2] to [11], wherein the material B with primer has a layer containing a functional group, and the layer containing the functional group is laminated on the material layer B and Between the aforementioned primer layers and in contact with the aforementioned material layer B and the aforementioned primer layer, The aforementioned functional group-containing layer includes at least one functional group selected from the group consisting of the following (A) to (G); (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound. [13] The joined body according to any one of [1] to [12], wherein the total thickness of the primer layer of one or more layers is 1 μm to 10 mm. (Method of manufacturing joint body) [14] A method for manufacturing a joint body, which is the method for manufacturing a joint body as described in any one of [1] to [13], which is selected from ultrasonic welding method, vibration welding method, electromagnetic induction method, and high frequency method At least one method from the group consisting of a laser method and a hot pressing method to weld the primer layer of the material to be joined to the joining material. [15] The method for manufacturing a junction body as in [14], wherein the in-situ polymerizable resin composition that has been dissolved in the solvent is applied to the surface of the material layer A, and the aforementioned in-situ polymerizable resin composition is placed on the surface of the material layer A. The surface is polymerized to form the in-situ polymerizable resin composition layer A, and the material layer A is composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. [16] A method for manufacturing a bonded body, which is the method for manufacturing a bonded body as described in any one of [2] to [13], in which an in-situ polymerizable resin composition that has been dissolved in a solvent is applied to the material layer B, and polymerize the in-situ polymerizable resin composition on the surface to form the in-situ polymerizable resin composition layer B. The material layer B is selected from fiber reinforced plastic (FRP), metal, glass, It is composed of at least one of the group of ceramics.

(Material with primer) [17] A material with a primer, having one or more primer layers laminated on the material layer C, and at least one of the aforementioned primer layers is made of a polymer of an in-situ polymerizable resin composition The in-situ polymerized resin composition layer C is formed, and the material layer C is composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic. [18] The material with a primer according to [17], wherein the in-situ polymerizable resin composition layer C is formed by polymerizing the in-situ polymerizable resin composition on the material layer C. [19] The primer-attached material of [17] or [18], wherein the in-situ polymerizable resin composition layer C is directly in contact with the material layer C. [20] The material with primer according to any one of [17] to [19], wherein the aforementioned in-situ polymerizable resin composition contains at least one of the following (1) to (7); (1) Combination of 2-functional isocyanate compound and diol, (2) The combination of a 2-functional isocyanate compound and a 2-functional amine compound, (3) Combination of 2-functional isocyanate compound and 2-functional thiol compound, (4) Combination of 2-functional epoxy compound and diol, (5) Combination of 2-functional epoxy compound and 2-functional carboxyl compound, (6) Combination of 2-functional epoxy compound and 2-functional thiol compound, (7) Monofunctional radical polymerizable monomer. [21] The material with a primer according to [20], wherein the in-situ polymerizable resin composition contains a combination of the (4) bifunctional epoxy compound and a diol, and the diol is a bifunctional phenol. [22] The material with a primer according to any one of [17] to [21], wherein at least one of the primer layers is formed of a cured product of a resin composition containing a thermosetting resin . [23] The material with primer as in [22], wherein the thermosetting resin is selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin At least one. [24] The material with a primer according to any one of [17] to [23], wherein the material with the primer has a layer containing a functional group, and the layer containing the functional group is laminated on the material layer Between C and the aforementioned primer layer, and in contact with the aforementioned material layer C and the aforementioned primer layer, The aforementioned functional group-containing layer includes at least one functional group selected from the group consisting of the following (A) to (G); (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound. [25] The material with primer as described in any one of [17] to [24], wherein the total thickness of the aforementioned one or more primer layers is 1 μm to 10 mm. (Method of manufacturing material with primer) [26] A method for manufacturing a primer-attached material, which is the method of manufacturing a primer-attached material as in any one of [17] to [25], which involves in-situ polymerized resin that has been dissolved in a solvent The composition is coated on the surface of the material, and the in-situ polymerizable resin composition is polymerized on the surface to form the in-situ polymerized resin composition layer C. The material is selected from fiber reinforced plastics (FRP) and glass. , At least one of the group consisting of ceramics. [Effects of the invention]

According to the present invention of the joined body (hereinafter also referred to as the first invention), it is possible to provide a joined material layer comprising at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic The joint body is joined with a joint material containing at least one material layer selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics, and no thermoplastic is placed on the joint surfaces of the two. The resin layer is a joint body that can be welded firmly. According to the present invention of the material with primer (hereinafter also referred to as the second invention), it is possible to provide materials that can be composed of at least one selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics The bonding material of the layer is a material with primer for the bonded material to be bonded.

"First Invention_Joint Body"

Hereinafter, the joined body of the present invention will be described in detail.

The joined body of the present invention will include a material layer A consisting of at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramics, and a material to be joined including a material selected from fiber reinforced plastic (FRP) The bonding material of the material layer B consisting of at least one of the group consisting of metal, glass, and ceramic is formed by welding. In the present invention, "the material to be joined including the material layer A" also includes "the material to be joined consisting only of the material layer A", and the "joining material including the material layer B" also includes "the material to be joined consisting only of the material layer B" material". In the bonding system of the present invention, the material to be bonded is composed of material A with a primer, and the material A with primer has one or more primer layers laminated on the material layer A, and the primer layer At least one layer is an in-situ polymerizable resin composition layer A composed of a polymer of an in-situ polymerizable resin composition, and the bonding system uses the primer layer of the bonded material to be welded to the bonding material Become. The bonding system of one embodiment of the present invention is composed of a material B with a primer, and the material B with a primer has one or more primer layers laminated on the material layer B, and At least one layer of the primer layer is an in-situ polymerizable resin composition layer B composed of a polymer of an in-situ polymerizable resin composition, and the bonding system is made of the aforementioned bonding material with primer B The primer layer is welded to the primer layer of material A with primer of the material to be joined.

[Material A with primer and material B with primer] In the material A with primer of the bonding material and the material B with primer of the bonding material, the material layer A and material layer B of the constituent elements may be a combination of material layers made of the same material, or may be composed of A combination of material layers made of different materials. The same applies to the in-situ polymerizable resin composition and thermosetting resin. Therefore, in the following description, materials A and B with primer are only described as "materials with primer". For the material layers A and B, the descriptions of A and B are also omitted. As shown in FIG. 1, the material with primer 1 of one embodiment has a material layer 2 laminated on at least one selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics. A laminate of one or more primer layers 3 on top. In the present invention, at least one layer of the aforementioned primer layer 3 is an in-situ polymerizable resin composition layer 31 composed of a polymer of an in-situ polymerizable resin composition.

In the present invention, the so-called in-situ polymerizable resin composition means that a combination of reactive bifunctional compounds undergoes polyaddition reaction on various materials in situ, or by radical polymerization of specific monofunctional monomers. It reacts to form a resin composition with a thermoplastic structure, that is, a linear polymer structure. Here, the term “linear polymer structure” means a one-dimensional linear polymer structure without a cross-linked structure in the polymer molecule. The in-situ polymerized resin composition is different from the thermosetting resin that constitutes the three-dimensional network formed by the cross-linking structure, and does not constitute the three-dimensional network formed by the cross-linking structure, but has thermoplasticity. The aforementioned in-situ polymerizable resin composition layer 31 is preferably a layer formed of a resin composition containing an in-situ polymerizable phenoxy resin. In-situ polymerization type phenoxy resin is also known as thermoplastic epoxy resin, in-situ hardening phenoxy resin, in-situ hardening epoxy resin and other resins, so that bifunctional epoxy resin and bifunctional phenol compound exist in the catalyst Under the polyaddition reaction, a thermoplastic structure is formed, that is, a linear polymer structure.

In the present invention, the aforementioned primer layer means a bonding material including a material layer composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, as described later, and When the material to be joined including a material layer composed of at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramics is joined and integrated to obtain a joined body, it is separated between the joining material and A layer that improves the bonding strength between the materials to be joined.

＜Material layer 2＞ The material layer 2 is composed of at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. The shape of the material layer 2 is not particularly limited, and may be a block shape or a film shape. The fiber reinforced plastic (FRP), metal, glass, and ceramic constituting the material layer 2 are not particularly limited. Examples of fiber reinforced plastics (FRP) include glass fiber reinforced plastics (GFRP), carbon fiber reinforced plastics (CFRP), boron fiber reinforced plastics (BFRP), aramid fiber reinforced plastics (AFRP), and the like. Examples are also formed bodies from glass fiber or carbon fiber SMC (sheet molding compound). Examples of metals include aluminum, iron, copper, manganese, steel, and the like. Among them, aluminum is preferred from the viewpoint of weight reduction.

[Surface treatment] The material layer 2 can also be subjected to surface treatment for the purpose of removing surface contaminants and/or anchoring effect. The material layer 2 is selected from at least one of the group consisting of fiber reinforced plastic (FRP), metal, and ceramic, and the surface treatment is preferably performed before the primer layer 3 is laminated.

By surface treatment, as shown in FIG. 1, fine concavities and convexities 21 can be formed on the surface of the material layer 2 to roughen it.

By surface treatment, the adhesion between the material layer 2 and the primer layer 3 can be improved. Surface treatment can also help improve the bondability with the bonding object.

As the surface treatment, for example, washing with a solvent or the like, degreasing treatment, sandblasting treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, chemical treatment, etc. are exemplified. Among them, a surface treatment capable of generating hydroxyl groups on the surface of the material layer 2 is preferred, and specifically, sandblasting treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, chemical treatment, etc. are preferred. Only 1 type may be used for these surface treatments, and 2 or more types may be used together. As a specific method of these surface treatments, conventional methods can be used.

Examples of the aforementioned washing with a solvent or the like and/or the aforementioned degreasing treatment are treatments such as degreasing the surface of the material layer 2 using organic solvents such as acetone and toluene. The aforementioned washing with a solvent or the like and/or the aforementioned degreasing treatment are preferably performed before other surface treatments.

As the aforementioned sand blasting treatment, for example, jet blasting treatment, sand blasting treatment, etc. are exemplified.

As the aforementioned polishing treatment, for example, polishing polishing using a polishing cloth, roll polishing using sandpaper, electrolytic polishing, and the like are exemplified.

The so-called plasma treatment is the use of plasma treatment high-voltage power supply, so that the plasma beam released from the rod called the electrode and collide with the surface of the material, first wash the foreign matter and oil stains on the surface, and then put in the corresponding material. A method of exciting surface molecules by gas energy, and an atmospheric pressure slurry treatment method that can impart hydroxyl groups or polar groups to the surface.

The so-called laser treatment is a method to effectively roughen the surface by rapidly heating and cooling only the surface layer by laser irradiation to improve the surface characteristics. The conventional laser processing technology can be used.

As the aforementioned etching treatment, for example, chemical etching treatment such as alkali method, phosphoric acid-sulfuric acid method, fluoride method, chromic acid-sulfuric acid method, ferric chloride method, etc., and electrochemical etching treatment such as electrolytic etching method, etc. are exemplified. The etching treatment when the material layer 2 is made of aluminum is preferably an alkaline method using an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and particularly preferably a caustic soda method using an aqueous sodium hydroxide solution. The aforementioned alkaline method can be performed, for example, by immersing the material layer 2 in a sodium hydroxide or potassium hydroxide aqueous solution with a concentration of 3 to 20% by mass at 20 to 70°C for 1 to 15 minutes. Chelating agents, oxidizing agents, phosphates, etc. can also be added as additives. After the aforementioned immersion, it is preferably neutralized (descaled) with a 5-20% by mass nitric acid aqueous solution or the like, washed with water, and dried.

The aforementioned so-called chemical treatment is mainly used to form a chemical film on the surface of the material layer 2.

Examples of chemical treatments include gibbsite treatment and zirconium treatment. The gibbsite treatment system forms a gibbsite film on the surface of the material layer 2 by treating the material layer 2 with hot water, for example. Ammonia or triethanolamine can also be added to the water as a reaction accelerator. It can also be performed, for example, by immersing the material layer 2 in hot water containing triethanolamine at a concentration of 0.1 to 5.0% by mass at 90 to 100° C. for 3 seconds to 5 minutes. The zirconium treatment system forms a zirconium compound film on the surface of the material layer 2 by, for example, immersing the material layer 2 in a zirconium-containing salt solution such as zirconium phosphate. For example, it can also be performed by immersing the material layer 2 in a chemical agent for zirconium treatment (for example, "PALCOAT3762" manufactured by Nippon Parkerizing Co., Ltd., the same as "PALCOAT3796"), etc., in a liquid at 45 to 70°C for 0.5 to 3 minutes . The aforementioned zirconium treatment is preferably performed after the etching treatment by the aforementioned caustic soda method.

The material layer 2 is made of aluminum, and particularly preferably includes at least one surface treatment selected from etching treatment and gibbsite treatment.

[Functional group imparting treatment] The functional group imparting treatment of imparting functional groups to the surface of the material layer 2 may also be implemented.

When the material layer 2 is composed of at least one selected from the group consisting of aluminum, CFRP, copper, and ceramics, before laminating the primer layer 3, it is preferable to continue the aforementioned surface treatment and perform a functional group imparting treatment.

Through the functional group imparting treatment, as shown in FIG. 2, one layer or multiple layers can be laminated in contact with the material layer 2 and the primer layer 3 between the material layer 2 and the primer layer 3. Functional group layer 4.

When the functional group-containing layer 4 is formed by the functional group imparting treatment, the functional group of the functional group-containing layer 4 and the hydroxyl groups on the surface of the material layer 2 react with the functional groups of the resin constituting the primer layer respectively , Through the formed chemical bond, the effect of improving the adhesion between the material layer 2 and the primer layer 3 is obtained. And also obtain the effect of improving the bondability with the bonding object. Therefore, the functional group in the functional group-containing layer 4 is preferably a functional group reactive with the aforementioned hydroxyl group or the functional group of the resin constituting the aforementioned primer layer. Examples of the functional group include an epoxy group, an amino group, a mercapto group, an isocyanate group, a carboxyl group, a hydroxyl group, a vinyl group, and a (meth)acryloxy group.

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 aforementioned functional group-containing layer 4 preferably contains at least one functional group selected from the group consisting of the following (A) to (G). (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound.

The functional group-containing layer 4 can be prepared by treating the surface of the material layer 2 with at least one selected from the group consisting of a silane coupling agent, an isocyanate compound, and a thiol compound before the primer layer 3 is formed, or by performing the aforementioned surface treatment Face to form. Specifically, it can be formed by coating the surface of the material layer 2 or the surface subjected to the aforementioned surface treatment with a solution containing at least any one selected from the group consisting of the following (a) to (g). (a) Silane coupling agent having at least one functional group selected from the group consisting of epoxy group, amino group, (meth)acryloyl group and mercapto group (b) A silane coupling agent having an amine group and at least one compound selected from the group consisting of epoxy compounds and thiol compounds, (c) Silane coupling agent with mercapto group, and selected from epoxy compound, amino compound, isocyanate compound, compound having (meth)acrylic acid group and epoxy group, and having (meth)acrylic acid group and amino group At least one compound in the group of the compound (d) Silane coupling agent and mercaptan compound with (meth)acryloyl group (e) Silane coupling agent with epoxy group and at least one compound selected from the group consisting of amine-based compounds, thiol compounds, and compounds having amine groups and (meth)acrylic groups (f) Isocyanate compound (g) Thiol compound. The aforementioned compounds of (a) to (g) correspond to the aforementioned functional groups of (A) to (G), respectively, and these functional groups are generated. That is, the functional group-containing layer 4 containing the functional group of the aforementioned (A) can be formed by using the functional group imparting treatment of the solution containing the aforementioned (a). The same applies to the aforementioned (b) to (g). For example, when the amine group is reacted with the dithiol compound by the treatment of (b), the mercapto group of the functional group possessed by the dithiol compound is introduced into the terminal. Similarly, when the mercapto group is reacted with the polyfunctional isocyanate compound by the treatment of (c), the isocyanate group of the functional group possessed by the polyfunctional isocyanate compound is introduced into the terminal.

The method of forming the functional group-containing layer 4 by the silane coupling agent, the isocyanate compound, or the thiol compound is not particularly limited, but can be exemplified by a spray coating method, a dipping method, and the like. Specifically, the metal substrate can be immersed in a solution of a silane coupling agent with a concentration of 5-50% 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. And so on.

[Silane Coupling Agent] As the aforementioned silane coupling agent, for example, those conventionally used in the surface treatment of glass fibers can be used. By reacting the silanol groups generated by the hydrolysis of the silane coupling agent or the oligomerized silanol groups with the hydroxyl groups present on the surface-treated surface of the metal substrate 2, the metal substrate 2 can be given ( Introduce) a functional group based on the structure of the silane coupling agent that can chemically bond with the primer layer 3 or the bonding object.

The aforementioned silane coupling agent is not particularly limited, but as the silane coupling agent having an epoxy group, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxy Propyl methyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl tri Ethoxysilane, etc. As the silane coupling agent having an amino group, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amine Propylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane and so on. As the silane coupling agent having a mercapto group, 3-mercaptopropylmethyldimethoxysilane, dithiol triazinepropyltriethoxysilane, and the like are exemplified. As the silane coupling agent having a (meth)acryloyl group, exemplified are 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. In addition, examples of other effective silane coupling agents include 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, etc. Silane coupling agent with vinyl group, 3-triethoxysilyl-N-(1,3-dimethylbutylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminopropyl trimethoxysilane hydrochloride, tris(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxy Silane and so on. These may be used individually by 1 type, and may use 2 or more types together.

[Isocyanate compound] The aforementioned isocyanate compound can be imparted (introduced) to the metal substrate 2 by reacting the isocyanate group in the isocyanate compound with the hydroxyl group existing on the surface-treated surface of the metal substrate 2 and can be combined with the primer layer 3 Or the functional group of the structure of the isocyanate compound chemically bonded to the bonding object.

The isocyanate compound is not particularly limited, but for example, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate ( IPDI), etc., and exemplified by 2-isocyanatoethyl methacrylate (such as "CURRANTS MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.), an isocyanate compound having a radical reactive group, and acrylic 2-isocyanate Ethyl cyanate (e.g. "CURRANTS AOI (registered trademark)" manufactured by Showa Denko Co., Ltd., the same as "AOI-VM (registered trademark)"), 1,1-(bisacryloxyethyl) isocyanate Ethyl ester (for example, "CURRANTS BEI (registered trademark)" manufactured by Showa Denko Co., Ltd.), etc.

[Thiol compound] The aforementioned thiol compound reacts with the sulfhydryl group (thiol group) in the thiol compound and the hydroxyl group existing on the surface-treated surface of the metal substrate 2 to be imparted (introduced) to the metal substrate 2 based on The functional group of the structure of the thiol compound chemically bonded to the primer layer 3 or the bonding object.

The thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Co., Ltd., "QE-340M" manufactured by Toray Fine Chemical Co., Ltd.) , Ether-based first-class mercaptans (e.g. "CUPCURE 3-800" manufactured by Cognis), 1,4-bis(3-mercaptobutoxy)butane (e.g. "CURRANTS MT (registered trademark) manufactured by Showa Denko Co., Ltd.) BD1''), pentaerythritol tetrakis (3-mercaptobutyrate) (e.g. "CURRANTS MT (registered trademark) PE1" made by Showa Denko Co., Ltd.), 1,3,5-tris(3-mercaptobutyloxyethyl) )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (for example, "CURRANTS MT (registered trademark) NR1" manufactured by Showa Denko Co., Ltd.), etc.

＜Primer layer 3＞ The primer layer 3 is laminated on the material layer 2 directly or via the layer 4 containing functional groups.

[In-situ polymerization type resin composition layer 31] As mentioned above, at least one layer of the primer layer is the in-situ polymerized resin composition layer 31 composed of the polymer of the in-situ polymerized resin composition. The in-situ polymerizable resin composition layer 31 can be made by coating the in-situ polymerizable resin composition dissolved in a solvent on the material layer 2 or the layer 4 containing functional groups, and after the solvent is volatilized, the aforesaid It is obtained by polymerization of an in-situ polymerization type resin composition. The in-situ polymerizable resin composition layer 31 can also be made by coating the in-situ polymerizable resin composition dissolved in a solvent on the material layer 2 or the functional group-containing layer 4 to make the in-situ The polymerized resin composition is formed by polymerization.

The aforementioned in-situ polymerizable resin composition preferably contains at least one of the following (1) to (7), more preferably contains the following (4), and most preferably contains a combination of a bifunctional epoxy resin and a bifunctional phenol compound. (1) Combination of 2-functional isocyanate compound and diol, (2) The combination of a 2-functional isocyanate compound and a 2-functional amine compound, (3) Combination of 2-functional isocyanate compound and 2-functional thiol compound, (4) Combination of 2-functional epoxy compound and diol, (5) Combination of 2-functional epoxy compound and 2-functional carboxyl compound, (6) Combination of 2-functional epoxy compound and 2-functional thiol compound, (7) Monofunctional radical polymerizable monomer.

(1) The blending amount of the bifunctional isocyanate compound and the diol is preferably set to the molar equivalent ratio of the isocyanate group to the hydroxyl group of 0.7 to 1.5, more preferably 0.8 to 1.4, and still more preferably 0.9 to 1.3 . (2) It is better to set the molar equivalent ratio of the isocyanate group to the amine group of 0.7 to 1.5, more preferably 0.8 to 1.4, and even more preferably the blending amount of the bifunctional isocyanate compound and the bifunctional amino compound in (2) It is 0.9 to 1.3. (3) It is better to set the mixing amount of the bifunctional isocyanate compound and the bifunctional thiol compound so that the molar equivalent ratio of the isocyanate group to the thiol group is 0.7 to 1.5, more preferably 0.8 to 1.4, and more Preferably, it is 0.9 to 1.3. (4) The mixing amount of the bifunctional epoxy compound and the diol is preferably set as 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, and still more preferably 0.9 to 1.3 . (5) It is better to set the compounding amount of the bifunctional epoxy compound and the bifunctional carboxyl compound as the molar equivalent ratio of the epoxy group to the carboxyl group of 0.7 to 1.5, more preferably 0.8 to 1.4, and still more preferably 0.9 ~1.3. (6) The mixing amount of the bifunctional epoxy compound and the bifunctional thiol compound is better to set the molar equivalent ratio of the epoxy group to the thiol group to be 0.7 to 1.5, more preferably 0.8 to 1.4, and more Preferably, it is 0.9 to 1.3.

As the aforementioned in-situ polymerizable resin composition, a resin composition containing at least one of the aforementioned (1) to (7) can be exemplified.

By laminating the in-situ polymerizable resin composition layer 31 as the primer layer 3 on the material layer 2, the bonding object can be strongly bonded to the material layer 2.

The primer layer 3 may include the in-situ polymerizable resin composition layer 31 and be composed of multiple layers. When the primer layer 3 is composed of a plurality of layers, the necessary in-situ polymerizable resin composition layer 31 is preferably laminated so as to be the outermost surface on the side opposite to the material layer 2.

The in-situ polymerization type resin composition layer 31 is composed of the polymer of the aforementioned in-situ polymerization type resin composition. The in-situ polymerizable resin composition layer 31 can be obtained by polyaddition reaction of a resin composition containing at least one of the aforementioned (1) to (6) in the presence of a catalyst. As a catalyst for the polyaddition reaction, for example, tertiary amines such as triethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and phosphorus-based compounds such as triphenylphosphine can be suitably used. . Although the aforementioned polyaddition reaction depends on the composition of the resin composition, it is preferably carried out by heating at room temperature to 200°C for 5 to 120 minutes. Specifically, the in-situ polymerizable resin composition layer 31 can be formed by coating the material layer 2 with a polymer containing at least one resin composition of (1) to (6). In addition, the in-situ polymerizable resin composition layer 31 can also be prepared by dissolving a resin composition containing at least one of the aforementioned (1) to (6) in a solvent, and coating it on the aforementioned material layer 2, and then appropriately volatilizing the solvent. , Followed by heating for polyaddition reaction to form. The aforementioned material layer 2 also includes those subjected to the aforementioned surface treatment and/or the aforementioned functional group imparting treatment. The in-situ polymerizable resin composition layer can also be obtained by radical polymerization reaction of the resin composition containing the monofunctional radical polymerizable monomer of (7). The aforementioned radical polymerization reaction also depends on the composition of the resin composition, but it is preferably carried out by heating at room temperature to 200°C for 5 to 90 minutes. In the case of photocuring, it is preferable to irradiate ultraviolet rays or visible light for polymerization reaction. Specifically, for example, the in-situ polymerizable resin composition layer may also be formed by coating the material layer 2 with a polymer of the resin composition containing the monofunctional radical polymerizable monomer of (7). Moreover, the in-situ polymerizable resin composition layer can also be heated by dissolving the resin composition containing the functional radical polymerizable monomer of the aforementioned (7) in a solvent, coating it on the aforementioned material layer 2 The radical polymerization reaction can form a stronger bonding in-situ polymerized resin composition layer. The aforementioned material layer 2 also includes those subjected to the aforementioned surface treatment and/or the aforementioned functional group imparting treatment.

(2-functional isocyanate compound) The aforementioned bifunctional isocyanate compound is a compound having two isocyanate groups, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate, 2,4- or 2,6-toluene diisocyanate Diisocyanate compounds such as isocyanate (TDI) or mixtures thereof, p-phenylene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate (MDI). Among them, from the viewpoint of primer strength, TDI or MDI is preferred.

(Diol) The aforementioned diol is a compound having two hydroxyl groups, and examples thereof include aliphatic diols and bifunctional phenols. Examples of aliphatic diols include ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, and the like. Examples of bifunctional phenols include bisphenols such as bisphenol A, bisphenol F, and bisphenol S. From the viewpoint of the toughness of the primer, propylene glycol, diethylene glycol, etc. are preferred. In the aforementioned (4), the diol to be combined with the bifunctional epoxy compound is preferably a bifunctional phenol, and particularly preferably the aforementioned bisphenols.

(2-functional amino compound) The aforementioned bifunctional amine-based compound is a compound having two amine groups, and examples thereof include bifunctional aliphatic diamines and aromatic diamines. Examples of aliphatic diamines are ethylene diamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2, 5-Dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl) ) Methane, 1,3-diaminocyclohexane, N-aminoethylpiperazine, and the like. Examples of aromatic diamines include diaminodiphenylmethane, diaminodiphenylpropane, and the like. Among them, from the viewpoint of the toughness of the primer, 1,3-propanediamine, 1,4-diaminobutane, and 1,6-hexamethylenediamine are preferred.

(2-functional thiol compound) The aforementioned bifunctional thiol compound is a compound having two mercapto groups in the molecule, for example, 1,4-bis(3-mercaptobutanoyloxy)butane, which is a bifunctional secondary thiol compound (e.g. Showa Denko Co., Ltd. "CURRANTS MT (registered trademark) BD1").

(2-functional epoxy compound) The aforementioned bifunctional epoxy compound is a compound having two epoxy groups in one molecule. Examples are aromatic ester resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type bifunctional epoxy resin, etc., or 1, Aliphatic epoxy compounds such as 6-hexanediol diglycidyl ether. Among these, one type may be used alone, or two or more types may be used in combination. Specific examples are "jER (registered trademark) 828" manufactured by Mitsubishi Chemical Corporation, the same as "jER (registered trademark) 834", the same as "jER (registered trademark) 1001", the same as "jER (registered trademark) 1004", and the same "JER (registered trademark) YX4000" and so on. If it is bifunctional, epoxy compound with special structure can also be used. Among these, one type may be used alone, or two or more types may be used in combination.

(2-functional carboxyl compound) As the aforementioned bifunctional carboxyl compound, any compound having two carboxyl groups is sufficient, and examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, Terephthalic acid and so on. Among these, from the viewpoint of the strength or toughness of the primer, isophthalic acid, terephthalic acid, adipic acid, etc. are preferred.

(Monofunctional radical polymerizable monomer) The aforementioned monofunctional radically polymerizable monomer system has one ethylenically unsaturated group. Examples are styrene monomer, α-, o-, m-, p-alkyl, nitro, cyano, amido, ester derivatives, chlorostyrene, vinyl toluene, divinyl Styrenic monomers such as benzene; ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, hexyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ( (Meth) tetrahydrofuranyl acrylate, (meth) acetyl acetoxy ethyl acrylate, (meth) acrylate dicyclopentenyl oxy ethyl and (meth) phenoxy ethyl acrylate, ( (Meth)acrylates such as glycidyl meth)acrylate. Among the aforementioned compounds, one type may be used, or two or more types may be used. Among them, based on the strength or toughness of the primer, it is preferably one of styrene, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate. One type, or a combination of two or more types. In order to fully carry out the radical polymerization reaction and form the desired primer layer, it may also contain additives such as a solvent or a coloring agent as needed. In this case, among the components other than the solvent of the radical polymerizable composition, the monofunctional radical polymerizable monomer is preferably a main component. The aforementioned main component means that the content of the aforementioned monofunctional radical polymerizable monomer is 50 to 100% by mass. The aforementioned content is preferably 60% by mass or more, more preferably 80% by mass or more. As the polymerization initiator used for the radical polymerization reaction, for example, conventional organic peroxides or photoinitiators can be suitably used. Organic peroxides can also be used in combination with a cobalt metal salt or an amine at room temperature free radical polymerization initiator. Examples of organic peroxides include, for example, ketone peroxides, peroxy acetals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxy esters, and peroxy dicarbonates. By. As the photoinitiator, it is desirable to use one that can start polymerization by ultraviolet to visible light. The radical polymerization reaction also depends on the kind of reaction compound, etc., but it is preferably carried out by heating at room temperature to 200°C for 5 to 90 minutes. And the case of light hardening is to irradiate ultraviolet or visible light to carry out the polymerization reaction. Specifically, after the resin composition is applied, the radical polymerization reaction is performed by heating, whereby the in-situ polymerizable resin composition layer 31 made of the radical polymerizable compound can be formed.

[Thermosetting resin layer 32] The primer layer 3 includes the aforementioned in-situ polymerizable resin composition layer 31 composed of multiple layers. As shown in FIG. 3, the primer layer 3 may also include a cured product of a resin composition containing a thermosetting resin. Into the thermosetting resin layer 32. In addition, the aforementioned thermosetting resin-containing resin composition may contain additives such as a solvent or a coloring agent if necessary in order to fully advance the curing reaction of the aforementioned thermosetting resin to form a desired primer layer. In this case, among the components other than the solvent of the resin composition, the thermosetting resin is preferably used as the main component. The aforementioned main component means that the content of the thermosetting resin is 40% by mass or more. The aforementioned content is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more.

Examples of the aforementioned thermosetting resin include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin. The thermosetting resin layer 32 may be formed by one kind of these resins alone, or may be formed by mixing two or more kinds. Alternatively, the thermosetting resin layer 32 may be composed of a plurality of layers, and each layer is formed of a resin composition containing different types of thermosetting resins.

The coating method for forming the thermosetting resin layer 32 by the composition containing the monomer of the thermosetting resin is not particularly limited, but examples thereof include a spray coating method, a dipping method, and the like.

In addition, the thermosetting resin referred to in this embodiment broadly refers to a cross-linked and hardened resin, and is not limited to a heat-curing type, but also includes a room-temperature-curing type or a light-curing type. The aforementioned photo-curing type can be cured in a short time by irradiating visible light or ultraviolet light. The aforementioned light-curing type can also be used in combination with the heat-curing type and/or the room-temperature curing type. As the aforementioned photocurable type, for example, a vinyl ester resin such as "RIPOXY (registered trademark) LC-760" manufactured by Showa Denko Co., Ltd. and the same "RIPOXY (registered trademark) LC-720".

(Urethane resin) The aforementioned urethane resin is usually a resin obtained by the reaction between the isocyanate group of the isocyanate compound and the hydroxyl group of the polyol compound. The above-mentioned polyisocyanate paint" is a urethane resin. The aforementioned urethane resin may be a one-component type or a two-component type.

As one-liquid type urethane resins, for example, oil modified (hardened by oxidative polymerization of unsaturated fatty acid groups), moisture hardening type (resisted by the reaction of isocyanate groups with water in the air) Hardening), blocked type (the isocyanate group that is dissociated and regenerated by heating and hardens by the reaction of the isocyanate group and the hydroxyl group of the blocking agent), lacquer type (hardened by the volatilization and drying of the solvent), etc. Among these, from the viewpoint of ease of handling, a moisture-curable one-liquid urethane resin is suitably used. Specifically, for example, "UM-50P" manufactured by Showa Denko Co., Ltd., etc.

Examples of two-component urethane resins include, for example, a catalyst-curing type (which is cured by the reaction of isocyanate groups with water in the air equal to the presence of the catalyst), and a polyol-curing type (by isocyanate Hardened by the reaction of the acid group and the hydroxyl group of the polyol compound), etc.

As the polyol compound of the polyol curing type, for example, polyester polyols, polyether polyols, phenol resins, and the like are exemplified. In addition, as the aforementioned polyol-curable isocyanate compound having an isocyanate group, for example, aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimer acid diisocyanate; 2 ,4- or 2,6-toluene diisocyanate (TDI) or its mixture, p-phenylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate (MDI) or polymerizable MDI of its polynuclear mixture, etc. The aromatic isocyanate; isophorone diisocyanate (IPDI) and other alicyclic isocyanates. The compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably set such that the molar equivalent ratio of the hydroxyl group/isocyanate group is in the range of 0.7 to 1.5.

As the urethane catalyst used in the aforementioned two-component urethane resin, for example, triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethyl Hexane-1,6-diamine, dimethyl ether amine, N,N,N',N”,N”-pentamethyldipropylene triamine, N-methylmorpholine, bis(2 -Dimethylaminoethyl) ether, dimethylaminoethoxyethanol-triethylamine and other amine catalysts; dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, Organotin catalysts such as dibutyltin dimaleate. In the polyol curing type, it is generally preferable to mix 0.01 to 10 parts by mass of the urethane catalyst with respect to 100 parts by mass of the polyol compound.

(Epoxy resin) The aforementioned epoxy resin is a resin having at least two epoxy groups in one molecule. Examples of the prepolymer before curing of the aforementioned epoxy resin are, for example, ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic epoxy resin, and ester-based aromatics. Epoxy resins, cycloaliphatic epoxy resins, ether/ester type epoxy resins, etc., among which bisphenol A type epoxy resins are suitably used. These may be used individually by 1 type, and may use 2 or more types together. Examples of the bisphenol A epoxy resin include "jER (registered trademark) 828" manufactured by Mitsubishi Chemical Corporation, the same "jER (registered trademark) 1001", and the like. Examples of novolak-type epoxy resins include "D.E.N. (registered trademark) 438 (registered trademark)" manufactured by The Dow Chemical Company.

Examples of the hardener used in the aforementioned epoxy resin include conventional hardeners such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, mercaptans, imidazoles, cationic catalysts, and the like. The aforementioned curing agent is used in combination with long-chain aliphatic amines and/or mercaptans to obtain the effects of high elongation and excellent impact resistance. As specific examples of the aforementioned thiols, the same compounds as those exemplified for the thiol compound used for the formation of the functional group-containing layer described later are exemplified. Among these, from the viewpoint of elongation and impact resistance, for example, pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "CURRANTS MT (registered trademark) PE1" manufactured by Showa Denko Co., Ltd.) is preferred.

(Vinyl ester resin) As the aforementioned vinyl ester resin, a vinyl ester compound is dissolved in a polymerizable monomer (for example, styrene). Although it is also called an epoxy (meth)acrylate resin, the aforementioned vinyl ester resin also includes a urethane (meth)acrylate resin. As the aforementioned vinyl ester resin, for example, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Dictionary of Paint Terms" (Color Material Association, published in 1993), etc., and specific examples "RIPOXY (registered trademark) R-802" manufactured by Showa Denko Co., Ltd., same as "RIPOXY (registered trademark) R-804", and "RIPOXY (registered trademark) R-806", etc.

As the aforementioned urethane (meth)acrylate resin, for example, after reacting an isocyanate compound with a polyol compound, it is reacted with a hydroxyl-containing (meth)acrylic monomer (and if necessary, further with a hydroxyl-containing alkene (Propyl ether monomer) reaction to obtain an oligomer containing radically polymerizable unsaturated groups. A specific example is "RIPOXY (registered trademark) R-6545" manufactured by Showa Denko Corporation.

The aforementioned 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 examples include ketone peroxides, peroxy acetals, hydroperoxides, diallyl peroxides, and diacyl peroxides. , Peroxyesters, Peroxydicarbonate, etc. These may also be hardened at room temperature by combining with cobalt metal salts and the like. The cobalt metal salt is not particularly limited, but examples thereof include cobalt naphthenate, cobalt octoate, and cobalt hydroxide. Among these, cobalt naphthenate or/and cobalt octoate are preferred.

(Unsaturated polyester resin) The aforementioned unsaturated polyester resin is a condensation product (unsaturated polyester) obtained by the esterification reaction of a polyol compound and an unsaturated polybasic acid (and optionally a saturated polybasic acid) dissolved in a polymerizable monomer (e.g. Styrene, etc.). As the aforementioned unsaturated polyester resin, it is also possible to use those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Dictionary of Paint Terms" (Color Material Association, published in 1993), etc., and specific examples For example, "RIGOLAC (registered trademark)" manufactured by Showa Denko Corporation.

The aforementioned unsaturated polyester resin can be hardened by radical polymerization by heating in the presence of the same catalyst as in the aforementioned vinyl ester resin.

[The role of primer layer 3] The adhesion between the primer layer 3 and the material layer 2 is excellent. The primer layer 3 imparts excellent bonding properties to other bonding materials 6 to be bonded. The joint can be maintained for a long period of several months. The primer layer 3 can protect the surface of the material layer 2 and can inhibit the deterioration of dirt adhesion or oxidation.

[Joint body 5] As shown in FIG. 4, the bonded body 5 of one embodiment is formed by welding the primer layer 3 of the material 1 with primer of the material to be bonded and the bonding material 6 of the bonding target. The bonding material 6 includes a material layer composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. There are various methods of welding using a method of heating the resin member. Specifically, there are ultrasonic welding, vibration welding, thermal welding, hot air welding, induction welding, injection welding, and the like. As shown in FIG. 5, the bonding body 5 of other embodiments is composed of a material 7 with a primer, and the material 7 with a primer has one or more primer layers laminated on the material layer 8. 9. At least one layer of the aforementioned primer layer is an in-situ polymerizable resin composition layer made of polymers of an in-situ polymerizable resin composition, and the primer layer of the aforementioned bonding material with primer 7 is the primer layer It is formed by welding the primer layer of material 1 with primer of the material to be joined. The material 7 with a primer is the same as the material 1 with a primer, and a layer 10 containing a functional group can be formed between the material layer 8 and the primer layer 9.

The thickness of the primer layer (thickness after drying) is also determined according to the material of the bonding object or the contact area of the bonding part. From the viewpoint of thermal deformation of the joined body, it is preferably 1 μm to 10 mm. It is more preferably 10 μm to 8 mm, and still more preferably 50 μm to 5 mm. In addition, when the aforementioned 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 of manufacturing the bonded body 5, for example, at least one method selected from the group consisting of ultrasonic welding method, vibration welding method, electromagnetic induction method, high frequency method, laser method, and hot pressing method, The method in which the primer layer 3 of the material with primer 1 of the material to be joined is welded to the joining material 6 of the joining object, or the metal powder of the metal powder of the joining material 6 of the joining object is formed on the joined material by injection molding The method on the primer layer 3 of the material 1 with primer.

"Second Invention_Materials with Primer" The primer-coated material C of the present invention has one or more primer layers laminated on a material layer C composed of at least one selected from the group consisting of fiber reinforced plastics (FRP), glass, and ceramics. At least one layer of the aforementioned primer layer is an in-situ polymerized resin composition layer C made of a polymer of an in-situ polymerized resin composition.

The primer-coated material C of the present invention is used as the material to be joined, thereby obtaining a material layer containing at least one composition selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramics. Bonded body made of bonding materials. The description of the configuration common to the first invention is omitted below.

[Material C with primer] As shown in FIG. 6, the primer-attached material C1' of an embodiment has at least one material layer C2' selected from the group consisting of fiber reinforced plastics (FRP), glass, and ceramics and laminated on the aforementioned materials 1 layer or multiple layers of primer layer 3'laminated body. In the present invention, at least one layer of the aforementioned primer layer 3'is an in-situ polymerizable resin composition layer C31' made of a polymer of an in-situ polymerizable resin composition.

The aforementioned primer layer 3'means the bonding material between the primer-coated material C1' and the material layer comprising at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic When joining and integrating to obtain a joined body, the layer is interposed between the aforementioned material layer C2' and the joining material to increase the joining strength.

＜Choose at least one material layer C2’ from the group consisting of fiber reinforced plastics (FRP), glass, and ceramics＞ The shape of the material layer C2' is not particularly limited, and may be a block shape or a film shape. The fiber reinforced plastic (FRP), glass, and ceramic constituting the material layer C2' are not particularly limited.

[Surface treatment] The material layer C2' may also be subjected to surface treatment for the purpose of removing contaminants on the surface and/or anchoring effect. When the material layer C2' is fiber reinforced plastic (FRP) or ceramic, it is preferable to perform surface treatment before laminating the primer layer 3'.

By the surface treatment, as shown in FIG. 7, fine concavities and convexities 21' can be formed on the surface of the material layer C2' to roughen the surface.

The surface treatment can improve the adhesion between the material layer C2' and the primer layer 3'. The surface treatment also helps to improve the bondability with the bonding object.

[Functional group imparting treatment] It is also possible to perform a functional group imparting treatment for imparting a functional group to the surface of the material layer C2'.

When the material layer C2' is CFRP or ceramic, it is preferable to continue the aforementioned surface treatment and perform a functional group imparting treatment before laminating the primer layer 3'.

Through the functional group imparting treatment, as shown in FIG. 7, a layer that is in contact with the material layer C2' and the primer layer 3'can be formed between the material layer C2' and the primer layer 3'to be laminated Or a plurality of layers 4'containing functional groups. The functional group-containing layer 4'is composed of the same structure as the functional group-containing layer 4 of the first invention.

＜Primer layer 3’＞ The primer layer 3'is laminated on the material layer C2' directly or via the functional group-containing layer 4'. The primer layer 3'is composed of the same composition as the primer layer 3 of the first invention.

[Joint body 5'] As shown in Fig. 8, the primer layer 3'of the primer-coated material C1' of the present invention and the bonding material 6'to be bonded are welded to obtain a bonded body 5'. The bonding material 6'includes a material layer composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic.

As the aforementioned bonding material 6', similar to the aforementioned material 1 with primer, it is preferable to use a primer layer with a primer layer including an in-situ polymerized resin composition layer made of a polymer of an in-situ polymerized resin composition. The material of the primer makes the primer layers weld together. [Example]

Next, specific embodiments of the present invention will be described, but the present invention is not particularly limited by these embodiments.

[Materials for Test Pieces] As the material for the test piece, each material (25 mm×100 mm) in Table 1 was prepared.

＜Surface treatment_frosted treatment＞ Prepare to grind the surface of the steel, CFRP, copper, ceramic, and GFRP materials in Table 1 with #1000 sandpaper, then wash and degrease with acetone.

＜Surface treatment_Alliance treatment＞ Prepare the following: After immersing the aluminum (A6063) of Table 1 in an aqueous sodium hydroxide solution with a concentration of 5 mass% for 1.5 minutes, it is neutralized with an aqueous nitric acid solution with a concentration of 5 mass%, washed with water, and dried for etching. Secondly, the aluminum plate after the etching treatment is boiled in pure water for 10 minutes, and then baked at 250° C. for 10 minutes to perform the gibbsite treatment.

<Functional group imparting treatment_Silane coupling agent treatment> Prepare the following: Put the aforementioned aluminum hydrated aluminum, and the aforementioned frosted CFRP, copper, ceramics, and glass of Table 1 into 2g of 3-aminopropyltrimethoxysilane (Shin-Etsu KBM-903 manufactured by Silicon Oxide Co., Ltd.: Silane coupling agent) was dissolved in 1000 g of industrial ethanol and immersed in a solution containing a silane coupling agent at 70°C for 20 minutes. The materials were taken out and dried to form a layer with functional groups (amine groups).

Table 1 Material detail steel Steel plate JIS G3131 (SPHC) thickness: 1.6mm aluminum A6063, thickness: 2.0mm CFRP Showa Denko CF-SMC RIGOLAC RCS-1000BK (CF50wt%) 1500kN press, 140℃ for 5 minutes press molding product, thickness: 3.0mm copper H3100 C1100P thickness: 2.6mm grass Plate glass thickness: 2.0mm Copper foil Electrolytic copper foil 3EC-III (global standard foil) for printed wiring boards manufactured by Mitsui Mining, Inc. Thickness: 18μm ceramics Kyocera's thick film substrate (alumina) thickness: 1.0mm GFRP Lichang Industrial Glass Cloth Epoxy Laminate (EL-GEM/G-10) ES-3230J thickness 3.0mm

[Production of test piece: Example 1-9, Comparative Example 1-4] <Preparation of in-situ polymerized resin composition-1 for primer layer formation> 100g of bifunctional epoxy resin ("jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Co., Ltd.), 6.2g of bisphenol S and 0.4g of triethylamine were dissolved in 197g of acetone to prepare an in-situ polymerizable resin composition -1 (in-situ polymerization type thermoplastic epoxy resin composition).

＜Formation of primer layer＞ The steel in Table 1 (hereinafter referred to as untreated steel), the aforementioned frosted steel (hereinafter referred to as frosted steel), the aluminum in Table 1 (hereinafter referred to as untreated aluminum), the aforementioned aluminum treated with silane coupling agent (hereinafter referred to as Silane coupling agent-treated aluminum-1), CFRP in Table 1 (hereinafter referred to as untreated CFRP), CFRP after the aforementioned silane coupling agent treatment (hereinafter referred to as silane coupling agent-treated CFRP-1), and copper in Table 1 (hereinafter referred to as CFRP-1) (Referred to as untreated copper), copper treated with silane coupling agent (hereinafter referred to as copper treated with silane coupling agent), and glass treated with silane coupling agent (hereinafter referred to as glass treated with silane coupling agent) on each one-sided surface, The in-situ polymerizable resin composition-1 was applied by a spray method so that the thickness after drying became 80 μm. Place it in the air at room temperature for 30 minutes to volatilize the solvent, then place it in an oven at 150°C for 30 minutes to proceed with the polyaddition reaction. Let it cool to room temperature to form a primer layer made of thermoplastic epoxy resin. The surface on which the primer layer is formed is called a primer surface, and the surface on which the primer layer is not formed is called a primerless surface. In addition, in the following Tables 2 and 3, the surface with the primer layer is expressed as (Yes), and the surface without the primer layer is expressed as (None).

[Example 1] (Fusion) The primer surface of the frosted steel and the primer surface of the frosted steel were overlapped so that the joints became 25mm×13mm, fixed with paper clips, and held at 150°C for 5 minutes for thermal welding to obtain test piece 1 (steel- Steel joint). Here, the junction part means the part where the material for the test piece is overlapped.

(Tensile shear strength) Regarding test piece 1, after leaving it at room temperature for 1 day, use a tensile testing machine (manufactured by Shimadzu Corporation, universal testing machine AUTOGRAPH "AG-IS"; load element 10kN, tensile speed 5mm) in accordance with JIS K 6850: 1999 /min, temperature 23°C, 50%RH), conduct a tensile shear strength test, and measure the bonding strength. The measurement results are shown in Table 2 below.

[Example 2] (Fusion) The primer surface of the untreated steel and the primer surface of the untreated steel were overlapped so that the joint part became 25mm×13mm, fixed with a paper clip, and held at 150°C for 5 minutes for thermal welding to obtain a test piece 2 ( Steel-steel joint).

(Tensile shear strength) With respect to the test piece 2, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Example 3] (Fusion) The primer surface of aluminum-1 treated with silane coupling agent and the primer surface of untreated steel overlapped so that the joints became 25mm×13mm, fixed with paper clips, and held at 150°C for 5 minutes for thermal welding. A test piece 3 (aluminum-steel joined body) was obtained.

(Tensile shear strength) With respect to the test piece 3, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Example 4] (Fusion) The primer surface of untreated aluminum and the primer surface of copper treated with silane coupling agent are overlapped so that the joint becomes 25mm×13mm, fixed with paper clips, and held at 150°C for 5 minutes for thermal welding to obtain the test Sheet 4 (aluminum-copper joint).

(Tensile shear strength) With respect to the test piece 4, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Example 5] (Fusion) The primer surface of untreated CFRP and the primer surface of frosted steel were overlapped so that the joints became 25mm×13mm, fixed with paper clips, and held at 150°C for 5 minutes for thermal welding to obtain test piece 5 (CFRP) -Steel joint).

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

[Example 6] (Fusion) The primer surface of CFRP-1 treated with silane coupling agent and the primer surface of aluminum-1 treated with silane coupling agent are overlapped so that the joint becomes 25mm×13mm, fixed with a paper clip, and kept at 150°C for 5 The heat fusion was performed in minutes to obtain a test piece 6 (CFRP-aluminum joined body).

(Tensile shear strength) With respect to the test piece 6, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Example 7] (Fusion) The primer surface of untreated copper and the primer surface of frosted steel were overlapped so that the joints became 25mm×13mm, fixed with paper clips, and held at 150°C for 5 minutes for thermal welding to obtain test piece 7 (copper -Steel joint).

(Tensile shear strength) With respect to the test piece 7, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Example 8] (Fusion) The primer surface of copper treated with silane coupling agent and the primer surface of aluminum-1 treated with silane coupling agent are overlapped so that the joint becomes 25mm×13mm. Fix it with a paper clip and keep it at 150°C for 5 minutes. Heat-welded to obtain test piece 8 (copper-aluminum joined body).

(Tensile shear strength) With respect to the test piece 8, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Example 9] (Fusion) The primer surface of the glass treated with the silane coupling agent and the primer surface of the glass treated with the silane coupling agent are overlapped so that the joint becomes 25mm×13mm, fixed with a paper clip, and held at 150°C for 5 minutes for heat welding. , A test piece 9 (glass-glass joined body) was obtained.

(Tensile shear strength) With respect to the test piece 9, the tensile shear strength test was performed in the same method as in Example 1. The measurement results are shown in Table 2 below.

[Comparative Example 1] The primer-free surface of aluminum-1 treated with silane coupling agent and the non-primed surface of copper treated with silane coupling agent are overlapped so that the joint becomes 25mm×13mm, fixed with a paper clip, and kept at 150°C for 5 The heat welding was performed within minutes, but it was not joined, and a test piece could not be obtained.

[Comparative Example 2] The unprimed surface of CFRP-1 treated with silane coupling agent and the unprimed surface of CFRP-1 treated with silane coupling agent are overlapped so that the joint becomes 25mm×13mm, fixed with paper clips, at 150℃ The heat fusion was performed by keeping it for 5 minutes, but it was not joined and a test piece could not be obtained.

[Example 10] (Fusion) The untreated copper primer surface and the untreated aluminum unprimed surface overlapped so that the joints became 25mm×13mm, fixed with paper clips, and held at 150°C for 5 minutes for thermal welding to obtain test piece 10 (Copper-aluminum junction).

(Tensile shear strength) With respect to the test piece 10, the tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Production of test piece: Comparative Example 3] ＜Formation of primer layer＞ The in-situ polymerized composition-1 is vaporized in a flask and kept at 150°C for 30 minutes to obtain a thermoplastic epoxy resin (hereinafter referred to as polymerized thermoplastic epoxy resin). After cooling, add acetone to 65% by mass to completely dissolve it. Polymerized thermoplastic epoxy resin solution. On each single-sided surface of untreated aluminum and copper treated with silane coupling agent, spray the aforementioned polymerized thermoplastic epoxy resin solution so that the thickness after drying becomes 80 μm. Dry at 50°C for 5 hours to form a primer layer.

(Fusion) The untreated aluminum primer surface and the copper primer surface treated with silane coupling agent are overlapped so that the joint becomes 25mm×13mm, fixed with a paper clip, and heat-welded by holding it at 150°C for 5 minutes. Test piece 11 (aluminum-copper joint).

(Tensile shear strength) With respect to the test piece 11, a tensile shear strength test was performed in the same manner as in Example 1. The measurement results are shown in Table 2 below.

[Test piece: Examples 11-13, Comparative Example 4] <Preparation of in-situ polymerized resin composition-2 for primer layer formation> Dissolve 100g of diphenylmethane diisocyanate ("MILLIONATE MT" manufactured by TOSOH Co., Ltd.), 54.7g of propylene glycol and 15.8g of 4,4'-diaminodiphenylmethane in 287g of acetone to prepare in-situ polymerization Type resin composition-2 (in-situ polymerization type urethane resin composition).

＜Formation of primer layer＞ Single-sided surfaces of aluminum-1 treated with the aforementioned silane coupling agent, ceramics treated with the aforementioned silane coupling agent (hereinafter referred to as ceramics treated with silane coupling agent), and GFRP after the aforementioned frosting treatment (hereinafter referred to as frosted GFRP) Above, the in-situ polymerizable resin composition-2 was spray-coated so that the thickness after drying became 80 μm. Place it in the air at room temperature for 30 minutes to volatilize the solvent, then place it in an oven at 150°C for 30 minutes to proceed with the polyaddition reaction. Let it cool to room temperature to form a primer layer made of urethane resin. The surface on which the primer layer is formed is called a primer surface, and the surface on which the primer layer is not formed is called a primerless surface. In addition, in the following Table 4, the surface with the primer layer is expressed as (present), and the surface without the primer layer is expressed as (none).

[Example 11] (Fusion) Place the copper foil of Table 1 on the primer surface of aluminum-1 treated with silane coupling agent and press at 150°C for 3 minutes to obtain test piece 12 (aluminum-copper foil assembly, aluminum with copper foil).

(Peel test) For the test piece 12, the measurement of the peeling strength of the copper foil according to JIS C 5012:1993 was performed. The measurement results are shown in Table 3 below.

[Example 12] (Fusion) Place the copper foil of Table 1 on the primer surface of the ceramic treated with silane coupling agent and press at 150°C for 3 minutes to obtain test piece 13 (ceramic-copper foil assembly, ceramic with copper foil).

(Peel test) With respect to the test piece 13, the copper foil peeling strength of JIS C 5012:1993 was measured. The measurement results are shown in Table 3 below.

[Example 13] (Fusion) Place the copper foil of Table 1 on the frosted GFRP primer surface and press at 150°C for 3 minutes to obtain test piece 14 (GFRP-copper foil assembly, GFRP with copper foil).

(Peel test) For the test piece 14, the measurement of the peeling strength of the copper foil according to JIS C 5012:1993 was performed. The measurement results are shown in Table 3 below.

[Comparative Example 4] The copper foil of Table 1 was placed on the non-primed surface of the ceramic treated with the silane coupling agent, and pressure was applied at 150°C for 3 minutes, but no test piece was obtained.

[Materials for Test Pieces] As the test piece materials, CFRP and aluminum (3cm×50cm) in the materials listed in Table 1 were prepared.

＜Surface treatment＞ The aforementioned CFRP is subjected to the aforementioned frosting treatment, and the aforementioned aluminum is subjected to the aforementioned gibbsite treatment.

<Functional group imparting treatment_Silane coupling agent treatment> Prepare the following: The aluminum that has been subjected to gibbsite treatment and the CFRP that has been subjected to frosting treatment are combined with 2g of 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone Co., Ltd.) : Silane coupling agent) Dissolved in 1000 g of industrial ethanol and immersed in a solution containing silane coupling agent at 70°C for 20 minutes. The respective materials were taken out and dried to give functional groups (amine groups).

＜Formation of primer layer＞ On each single-sided surface of the aluminum treated with the silane coupling agent (hereinafter referred to as the aluminum-2 treated with the silane coupling agent) and the CFRP treated with the silane coupling agent (hereinafter referred to as the CFRP-2 treated with the silane coupling agent), The in-situ polymerizable resin composition-1 was applied by a spray method so that the thickness after drying became 2 mm. Place it in the air at room temperature for 30 minutes to volatilize the solvent, then place it in an oven at 150°C for 30 minutes to proceed with the polyaddition reaction. Let it cool to room temperature to form a primer layer made of thermoplastic epoxy resin. The surface on which the primer layer is formed is called a primer surface, and the surface on which the primer layer is not formed is called a primerless surface.

[Example 14] (Fusion) Connect the primer surface of aluminum-2 treated with silane coupling agent and the primer surface of CFRP-2 treated with silane coupling agent, and heat-weld under pressure at 150°C for 5 minutes.

(Evaluation) The welded joint is returned to normal temperature and placed in a normal temperature environment to observe whether the joint is warped and the joint surface is peeled off. No warpage or peeling was observed.

[Comparative Example 5] (Fusion) The non-primed surface of aluminum-2 treated with silane coupling agent and the non-primed surface of CFRP-2 treated with silane coupling agent were welded together with an acrylic plate at 180°C for 5 minutes.

(Evaluation) The welded joint is returned to normal temperature and placed in a normal temperature environment to observe whether the joint is warped and the joint surface is peeled off. During the process of returning to normal temperature, peeling of the joint surface occurs.

As shown in Examples 1-14, according to the first invention of the present invention, it is possible to provide a bonded 2A consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramics. Material, a joint body that is joined to a joint material comprising a material layer B consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramics, and is not arranged on the joint surfaces of the two Thermoplastic resin layer, which can be welded firmly. As shown in Example 13, according to the second invention of the present invention, it is possible to provide a bonding material that can be combined with a material layer composed of at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. It is a material with primer for the material to be joined for strong fusion. [Industrial availability]

The joint body of the present invention can be used as, for example, door side panels, engine hoods, roofs, tailgates, steering wheel covers, A-pillars, B-pillars, C-pillars, D-pillars, crash boxes, power control unit (PCU) covers, electric compression mechanisms Parts (internal wall, suction pump part, exhaust control valve (ECV) insertion part, mounting lug part, etc.), lithium ion battery (LIB) spacers, battery boxes, LED headlights and other automotive parts, or smart Mobile phones, notebook computers, tablet computers, smart watches, large liquid crystal televisions (LCD-TV), outdoor LED lighting structures, etc. are not particularly limited to the illustrated uses. In the bonded body of the present invention, CFRP and metal bonded can be used for multi-material applications such as automobiles, and ceramics, aluminum, FRP, and other bonded copper foils and bonded are suitable for electronic material substrates.

1,1’: Material with primer 2,2’: Material layer 21,21’: Fine bumps 3,3’: Primer layer 31, 31’: In-situ polymerized resin composition layer 32: Thermosetting resin layer 4,4’: layer containing functional groups 5,5’: Conjugation 6,6’: Joining material 7: Material with primer 8: Material layer 9: Primer layer 10: Layer containing functional groups

[Fig. 1] is an explanatory diagram showing the composition of a primer-attached material used for manufacturing a joined body according to an embodiment of the first invention. [Fig. 2] is an explanatory diagram showing the composition of a primer-attached material used for manufacturing a joined body according to another embodiment of the first invention. Fig. 3 is an explanatory diagram showing the composition of a primer-attached material used for manufacturing a joined body according to another embodiment of the first invention. Fig. 4 is an explanatory diagram showing the structure of the joined body in one embodiment of the first invention. [Fig. 5] An explanatory diagram showing the structure of a joined body according to another embodiment of the first invention. [Fig. 6] is an explanatory diagram showing the composition of the primer-attached material in one embodiment of the second invention. [Fig. 7] is an explanatory diagram showing the structure of a primer-attached material in another embodiment of the second invention. [Fig. 8] is an explanatory diagram showing the structure of a bonded body manufactured using the material with primer according to an embodiment of the second invention.

1: Material with primer

2: Material layer

3: Primer layer

21: Micro bumps

31: In-situ polymerized resin composition layer

Claims (26)

A joined body formed by joining a material to be joined including a material layer A and a joining material including a material layer B, wherein the material layer A is selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic The aforementioned material layer B is composed of at least one selected from the group consisting of fiber reinforced plastics (FRP), metal, glass, and ceramics, The material to be joined is composed of material A with a primer, and the material A with primer has one or more primer layers laminated on the material layer A, and at least one of the primer layers is In-situ polymerized resin composition layer A composed of polymers of in-situ polymerized resin composition, And this joining system is formed by welding the said primer layer of the said to-be-joined material to the said joining material. The bonded body of claim 1, wherein the bonding material is composed of a material B with a primer, and the material B with a primer has one or more primer layers laminated on the material layer B, and At least one layer of the aforementioned primer layer is an in-situ polymerizable resin composition layer B composed of a polymer of an in-situ polymerizable resin composition, And the bonding system is formed by welding the primer layer of the bonding material and the primer layer of the bonding material. The junction body of claim 1 or 2, wherein the in-situ polymerizable resin composition layer A is formed by polymerizing the in-situ polymerizable resin composition on the material layer A. The junction body of claim 2 or 3, wherein the in-situ polymerizable resin composition layer B is formed by polymerizing the in-situ polymerizable resin composition on the material layer B. The joined body according to any one of claims 1 to 4, wherein the in-situ polymerizable resin composition layer A is directly in contact with the layer of the material layer A. The bonded body according to any one of claims 2 to 5, wherein the in-situ polymerizable resin composition layer B is in direct contact with the layer of the material layer B. The joint body according to any one of claims 1 to 6, wherein the aforementioned in-situ polymerizable resin composition contains at least one of the following (1) to (7); (1) Combination of 2-functional isocyanate compound and diol, (2) The combination of a 2-functional isocyanate compound and a 2-functional amine compound, (3) Combination of 2-functional isocyanate compound and 2-functional thiol compound, (4) Combination of 2-functional epoxy compound and diol, (5) Combination of 2-functional epoxy compound and 2-functional carboxyl compound, (6) Combination of 2-functional epoxy compound and 2-functional thiol compound, (7) Monofunctional radical polymerizable monomer. The conjugate according to claim 7, wherein the in-situ polymerizable resin composition contains a combination of the (4) bifunctional epoxy compound and a diol, and the diol is a bifunctional phenol. The joined body according to any one of claims 1 to 8, wherein at least one layer of the primer layer is formed of a resin composition containing a thermosetting resin. The joined body according to claim 9, wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin. The junction body according to any one of claims 1 to 10, wherein the material A with primer has a layer containing a functional group, and the layer containing the functional group is laminated on the material layer A and the primer layer Between, and in contact with the aforementioned material layer A and the aforementioned primer layer, The aforementioned functional group-containing layer includes at least one functional group selected from the group consisting of the following (A) to (G); (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound. The junction body according to any one of claims 2 to 11, wherein the material B with primer has a layer containing a functional group, and the layer containing the functional group is laminated on the material layer B and the primer layer Between, and in contact with the aforementioned material layer B and the aforementioned primer layer, The aforementioned functional group-containing layer includes at least one functional group selected from the group consisting of the following (A) to (G); (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound. The joined body according to any one of claims 1 to 12, wherein the total thickness of the primer layer of one or more layers is 1 μm to 10 mm. A method of manufacturing a joined body, which is the method of manufacturing a joined body according to any one of claims 1-13, Use at least one method selected from the group consisting of ultrasonic welding method, vibration welding method, electromagnetic induction method, high frequency method, laser method, and hot pressing method to weld the primer layer of the bonded material To the aforementioned bonding material. The method for manufacturing a joined body of claim 14, wherein the in-situ polymerizable resin composition that has been dissolved in the solvent is applied to the surface of the material layer A, and the in-situ polymerizable resin composition is applied to the surface The in-situ polymerized resin composition layer A is formed by polymerization, and the material layer A is composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. A method for manufacturing a joined body, which is the method for manufacturing a joined body according to any one of claims 2-13, The in-situ polymerizable resin composition that has been dissolved in the solvent is applied to the surface of the material layer B, and the in-situ polymerizable resin composition is polymerized on the surface to form the in-situ polymerizable resin composition layer B , The aforementioned material layer B is composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. A material with a primer, which has one or more primer layers laminated on the material layer C, and at least one of the primer layers is an original polymer composed of an in-situ polymerizable resin composition The polymerized resin composition layer C, and the material layer C is composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramics. The material with a primer according to claim 17, wherein the in-situ polymerizable resin composition layer C is formed by polymerizing the in-situ polymerizable resin composition on the material layer C. The material with primer according to claim 17 or 18, wherein the in-situ polymerizable resin composition layer C is directly in contact with the layer of the material layer C. The material with primer according to any one of claims 17 to 19, wherein the aforementioned in-situ polymerizable resin composition contains at least one of the following (1) to (7); (1) Combination of 2-functional isocyanate compound and diol, (2) The combination of a 2-functional isocyanate compound and a 2-functional amine compound, (3) Combination of 2-functional isocyanate compound and 2-functional thiol compound, (4) Combination of 2-functional epoxy compound and diol, (5) Combination of 2-functional epoxy compound and 2-functional carboxyl compound, (6) Combination of 2-functional epoxy compound and 2-functional thiol compound, (7) Monofunctional radical polymerizable monomer. The material with a primer according to claim 20, wherein the in-situ polymerizable resin composition contains the combination of (4) a bifunctional epoxy compound and a diol, and the diol is a bifunctional phenol. The material with a primer according to any one of claims 17 to 21, wherein at least one layer of the primer layer is formed of a cured product of a resin composition containing a thermosetting resin. The material with primer of claim 22, wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin . The material with a primer according to any one of claims 17 to 23, wherein the material with the primer has a layer containing a functional group, and the layer with the functional group is laminated on the material layer C and the primer Between the layers and in contact with the aforementioned material layer C and the aforementioned primer layer, The aforementioned functional group-containing layer includes at least one functional group selected from the group consisting of the following (A) to (G); (A) The functional group derived from the silane coupling agent is at least one functional group selected from the group consisting of epoxy group, amine group, (meth)acrylic group and thiol group, (B) A functional group formed by reacting at least one selected from epoxy compounds and thiol compounds with an amine group derived from a silane coupling agent, (C) selected from the group consisting of epoxy compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and amino groups At least one functional group that reacts with the thiol group derived from the silane coupling agent, (D) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent, (E) At least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and an epoxy group derived from a silane coupling agent Functional group, (F) Isocyanate groups derived from isocyanate compounds; (G) A thiol group derived from a thiol compound. The material with primer according to any one of claims 17 to 24, wherein the total thickness of the aforementioned one or more primer layers is 1 μm to 10 mm. A method of manufacturing primer-attached materials, which is the method of manufacturing primer-attached materials as in any one of Claims 17-25, The in-situ polymerizable resin composition dissolved in the solvent is applied to the surface of the material layer C, and the in-situ polymerizable resin composition is polymerized on the surface to form the in-situ polymerizable resin composition layer C , The aforementioned material layer C is at least one selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic.

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