WO2021065390A1

WO2021065390A1 - Joined body and primer-equipped material

Info

Publication number: WO2021065390A1
Application number: PCT/JP2020/034060
Authority: WO
Inventors: 大谷　和男; 臣二沼尾; 高橋　信行; 良太新林
Original assignee: 昭和電工株式会社
Priority date: 2019-09-30
Filing date: 2020-09-09
Publication date: 2021-04-08
Also published as: TW202128423A; JP6967676B2; JPWO2021065390A1

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

Bonds and materials with primers

The present invention relates to a bonded body formed by joining arbitrary materials selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and a method for producing the same.
The present invention relates to a material with a primer suitable for use in forming a bonded body by joining with an arbitrary material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and a method for producing the same.

Weight reduction of transportation equipment such as automobiles has become an important issue for reducing _{CO 2 emissions and realizing energy saving.} In recent years, "multi-materialization" has been actively promoted in the technological development related to this problem.
Multi-materialization is a combination of materials with different functions and / or materials (hereinafter referred to as dissimilar materials) such as high tensile strength steel plate (HITEN), aluminum (Al), and carbon fiber reinforced plastic (CFRP). This is a method for reducing weight and increasing strength.
In order to realize multi-materials, technology for directly joining dissimilar materials is indispensable.

Conventionally, as a means for directly joining dissimilar materials to each other, a method using rivets and a method using an adhesive have been mainly adopted.
Joining with rivets is a point-like joint (point joint), and has a drawback that it is inferior in fatigue characteristics to a planar joint (surface joint) using an adhesive. For this reason, the rivet-joined joint has a problem that its use is limited, for example, it is not preferable for an automobile member that requires steering stability. It has also been pointed out that when rivets are used as a means for joining CFRP and other materials, carbon fibers are cut.
On the other hand, bonding with an adhesive has the advantage of exhibiting excellent fatigue characteristics even when thin-film materials are joined because it is a surface joint, and the advantage of being able to reduce weight without the need for fastening parts such as rivets. However, there is a drawback that it takes time to cure the adhesive.

A dissimilar material joint using welding as a means for bonding dissimilar materials is also disclosed (Patent Document 1). Patent Document 1 discloses a dissimilar material joint 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.
In the welding by welding, any of the drawbacks and problems associated with the above-mentioned joining by rivets or adhesives can be avoided.

Japanese Unexamined Patent Publication No. 2016-36955

Welding is generally known as a joining method used for joining the same type of thermoplastic resin material. When welding is used for joining dissimilar materials, as in Patent Document 1, one of the objects to be bonded or the object to be bonded is made of a thermoplastic resin, and a thermoplastic resin layer is arranged on the other bonding surface, or Welding is performed by arranging thermoplastic resin layers on the bonding surfaces of both the object to be bonded and the object to be bonded. Therefore, conventionally, when welding is used for joining dissimilar materials, there is a problem that the degree of freedom in designing the joined body is limited, and there is a problem that it takes time and effort to arrange a thermoplastic resin layer on both joint surfaces. there were.
In addition, conventionally, in a bonded body in which dissimilar materials are joined by welding, the adhesive force between the thermoplastic resin arranged on the joint surface and the joint surface is weak, and there is also a problem that sufficient bonding strength cannot be obtained between the dissimilar materials. there were.

The present invention has been made in view of such technical background, and includes a material to be joined including a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. A bonded body made by joining a bonding material containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic is arranged on both bonding surfaces with a thermoplastic resin layer. It is an object of the present invention to provide a bonded body which is firmly welded without doing so.
The present invention also provides a primer-attached material which is a material to be welded firmly to a bonding material containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. The task is to do.

The present invention provides the following means for achieving the above object.
In this specification, bonding means connecting objects to each other, and adhesion is a subordinate concept thereof, and organic materials such as tapes and adhesives (thermosetting resins, thermoplastic resins, etc.) are used. ) Means that the two adherends (those to be bonded) are put into a bonded state.

(Joint body)
[1] A material to be joined containing a material layer A composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass and ceramic, and fiber reinforced plastic (FRP), metal, glass and ceramic. A bonded body formed by bonding a bonding material containing a material layer B composed of at least one selected from the group, wherein the bonded material is a single layer or a plurality of primer layers laminated on the material layer A. It is made of a material A with a primer, wherein at least one layer of the primer layer is a field-polymerized resin composition layer A made of a polymer of the field-polymerized resin composition. A bonded body formed by welding the primer layer.
[2] The bonding material has one or a plurality of primer layers laminated on the material layer B, and at least one of the primer layers is a field-polymerized type in which a polymer of a field-polymerized resin composition is formed. The bonded body of [1], which is made of a material B with a primer, which is a resin composition layer B, and is formed by welding the primer layer of the bonding material and the primer layer of the material to be bonded.
[3] The conjugate of [1] or [2], wherein the field-polymerized resin composition layer A polymerizes the field-polymerized resin composition on the material layer A.
[4] The conjugate of [2] or [3], wherein the field-polymerized resin composition layer B polymerizes the field-polymerized resin composition on the material layer B.
[5] The bonded body according to any one of [1] to [4], wherein the in-situ polymerization type resin composition layer A is a layer that is in direct contact with the material layer A.
[6] The bonded body according to any one of [2] to [5], wherein the in-situ polymerization type resin composition layer B is a layer that is in direct contact with the material layer B.
[7] The conjugate according to any one of [1] to [6], wherein the in-situ polymerization type resin composition contains at least one of the following (1) to (7).
(1) Combination of bifunctional isocyanate compound and diol (2) Combination of bifunctional isocyanate compound and bifunctional amino compound (3) Combination of bifunctional isocyanate compound and bifunctional thiol compound (4) Combination of bifunctional epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radical polymerizable monomer [8] The field-polymerized resin composition is the above-mentioned. (4) The conjugate of [7], which contains a combination of a bifunctional epoxy compound and a diol, and the diol is a bifunctional phenol.
[9] The conjugate 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 bonded body of [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 material A with a primer has a functional group-containing layer laminated between the material layer A and the primer layer in contact with the material layer A and the primer layer.
The conjugate according to any one of [1] to [10], wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. Functional group (C) obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group. ) From the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound in an epoxy group derived from a functional group (E) silane coupling agent obtained by reacting an acryloyl group with a thiol compound. A functional group obtained by reacting at least one selected type (F) an isocyanato group derived from an isocyanate compound (G) a thiol group derived from a thiol compound [12] The material with a primer B is the material layer B and the primer layer. A functional group-containing layer laminated in contact with the material layer B and the primer layer is provided between the material layer B and the functional group-containing layer.
The conjugate according to any one of [2] to [11], wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from (C) A thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group (meth). ) A functional group obtained by reacting an acryloyl group with a thiol compound (E) From a group consisting of a compound having an amino group and a (meth) acryloyl group in an epoxy group derived from a silane coupling agent, an amino compound, and a thiol compound. A functional group obtained by reacting at least one selected kind (F) An isocyanato group derived from an isocyanate compound (G) A thiol group derived from a thiol compound [13] The total thickness of the primer layer of the one layer or the plurality of layers is The joined body according to any one of [1] to [12], which is 1 μm to 10 mm.
(Manufacturing method of joint)
[14] A method for producing a bonded body according to any one of [1] to [13], which is selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a heat pressing method. A method for producing a bonded body, wherein the bonding material is welded to the primer layer of the material to be bonded by at least one method.
[15] An in-situ polymerization type resin composition dissolved in a solvent is applied to the surface of a material layer A composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and on the surface. The method for producing a bonded body according to [14], wherein the field-polymerized resin composition is polymerized to form the field-polymerized resin composition layer A.
[16] A group consisting of a fiber reinforced plastic (FRP), a metal, a glass, and a ceramic in which a field-polymerized resin composition dissolved in a solvent is produced by the method for producing a bonded body according to any one of [2] to [13]. A method for producing a bonded body, which is applied to the surface of a material layer B composed of at least one selected from the above, and the in-situ polymerization type resin composition is polymerized on the surface to form the in-situ polymerization type resin composition layer B. ..

(Material with primer)
[17] It has one or a plurality of primer layers laminated on a material layer C composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic, and at least one layer of the primer layer. Is a material with a primer, which is a field-polymerized resin composition layer C composed of a polymer of the field-polymerized resin composition.
[18] The primer-attached material according to [17], wherein the field-polymerized resin composition layer C polymerizes the field-polymerized resin composition on the material layer C.
[19] The primer-attached material according to [17] or [18], wherein the in-situ polymerization type resin composition layer C is a layer that is in direct contact with the material layer C.
[20] The primer-attached material according to any one of [17] to [19], wherein the in-situ polymerization type resin composition contains at least one of the following (1) to (7).
(1) Combination of bifunctional isocyanate compound and diol (2) Combination of bifunctional isocyanate compound and bifunctional amino compound (3) Combination of bifunctional isocyanate compound and bifunctional thiol compound (4) Combination of bifunctional epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radical polymerizable monomer [21] The field-polymerized resin composition is the above-mentioned. (4) The primer-attached material according to [20], which contains a combination of a 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 layer of the primer layer is formed from a cured product of a resin composition containing a thermosetting resin.
[23] The primer-attached material according to [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.
[24] The material with a primer has a functional group-containing layer laminated between the material layer C and the primer layer in contact with the material layer C and the primer layer.
The material with a primer according to any one of [17] to [23], wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from (C) A thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group (meth). ) A functional group obtained by reacting an acryloyl group with a thiol compound (E) From a group consisting of a compound having an amino group and a (meth) acryloyl group in an epoxy group derived from a silane coupling agent, an amino compound, and a thiol compound. A functional group obtained by reacting at least one selected kind (F) An isocyanato group derived from an isocyanate compound (G) A thiol group derived from a thiol compound [25] The total thickness of the primer layer of the one layer or the plurality of layers is A material with a primer according to any one of [17] to [24], which is 1 μm to 10 mm.
(Manufacturing method of material with primer)
[26] The method for producing a material with a primer according to any one of [17] to [25], wherein the in-situ polymerization type resin composition dissolved in a solvent is composed of a group consisting of fiber reinforced plastic (FRP), glass, and ceramic. A method for producing a material with a primer, which is applied to the surface of at least one selected material and polymerized on the surface to form the field-polymerized resin composition layer C.

According to the present invention (hereinafter, also referred to as the first invention) relating to a bonded body, a material to be bonded containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. , A bonded body made by joining a bonding material containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and a thermoplastic resin layer on both bonding surfaces. It is possible to provide a bonded body that is firmly welded without being arranged.
According to the present invention (hereinafter, also referred to as the second invention) relating to a material with a primer, a bonding material containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. It is possible to provide a material with a primer, which is a material to be welded firmly.

It is explanatory drawing which shows the structure of the material with a primer used for manufacturing of the bonded body in one Embodiment of 1st invention. It is explanatory drawing which shows the structure of the material with a primer used for manufacturing the conjugate in another embodiment of 1st invention. It is explanatory drawing which shows the structure of the material with a primer used for manufacturing the conjugate in another embodiment of 1st invention. It is explanatory drawing which shows the structure of the bonded body in one Embodiment of 1st invention. It is explanatory drawing which shows the structure of the bonded body in another embodiment of 1st invention. It is explanatory drawing which shows the structure of the material with a primer in one Embodiment of 2nd invention. It is explanatory drawing which shows the structure of the material with a primer in another embodiment of the 2nd invention. It is explanatory drawing which shows the structure of the bonded body produced by using the material with a primer in one Embodiment of 2nd invention.

<< First invention_joint >>
The joined body of the present invention will be described in detail.

The bonded body of the present invention includes a material to be bonded containing a material layer A composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and fiber reinforced plastic (FRP), metal, and glass. , A bonding material containing a material layer B composed of at least one selected from the group consisting of ceramics is bonded by welding. In the present invention, the "bonded material containing the material layer A" also includes the "bonded material consisting of only the material layer A", and the "bonding material containing only the material layer B" includes the "coated material consisting of only the material layer B". Also includes "bonding material".
In the bonded body of the present invention, the material to be welded has one or a plurality of primer layers laminated on the material layer A, and at least one of the primer layers is a polymer of a field-polymerized resin composition. It is made of a material A with a primer, which is an in-situ polymerization type resin composition layer A composed of the above, and is formed by welding the primer layer of the material to be bonded to the bonding material.
The bonded body according to the embodiment of the present invention has one or a plurality of primer layers in which the bonding material is laminated on the material layer B, and at least one of the primer layers is a field-polymerized resin composition. The primer layer of the primer-attached material B, which is the bonding material, and the primer layer of the primer-attached material A, which is the bonding material, are composed of the primer-attached material B, which is the in-situ polymerization type resin composition layer B composed of the polymer of the above. And are welded together.

[Material A with primer and material B with primer]
In the primer-attached material A which is the material to be bonded and the primer-attached material B which is the bonding material, the material layer A and the material layer B, which are the constituent elements thereof, are made of different materials even if the material layers are made of the same material. It may be a combination of layers. The same applies to the in-situ polymerization type resin composition and the thermosetting resin. Therefore, in the following description, the materials A and B with a primer are simply referred to as "materials with a primer". Similarly, the notation of A and B is omitted for the material layers A and B.
As shown in FIG. 1, the material 1 with a primer in one embodiment is one layer laminated on a material layer 2 composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. It is a laminated body having a plurality of layers of primer layers 3. In the present invention, at least one layer of the primer layer 3 is a field-polymerized resin composition layer 31 made of a polymer of the field-polymerized resin composition.

In the present invention, the field-polymerized resin composition is a radical addition reaction of a combination of reactive bifunctional compounds on the field, that is, on various materials, or a radical of a specific monofunctional monomer. It means a resin composition that forms a thermoplastic structure, that is, a linear polymer structure by a polymerization reaction. Here, the linear polymer structure means a polymer structure that does not contain a crosslinked structure in the polymer molecule and is one-dimensional linear. Unlike the thermosetting resin that forms a three-dimensional network with a crosslinked structure, the in-situ polymerization type resin composition does not form a three-dimensional network with a crosslinked structure and has thermoplasticity.
The field-polymerized resin composition layer 31 is preferably a layer formed of a resin composition containing a field-polymerized phenoxy resin. The field-polymerized phenoxy resin is a resin also called a thermoplastic epoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and a bifunctional epoxy resin and a bifunctional phenol compound undergo a double addition reaction in the presence of a catalyst. By doing so, a thermoplastic structure, that is, a linear polymer structure is formed.

In the present invention, the primer layer is a bonding material containing at least one material layer selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and fiber reinforced plastic (FRP), as described later. When a material to be joined containing a material layer consisting of at least one selected from the group consisting of FRP), metal, glass, and ceramic is joined and integrated to obtain a bonded body, it is interposed between the bonded material and the material to be bonded. , It shall mean a layer that improves the bonding strength.

<Material layer 2>
The material layer 2 is made of at least one material selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic.
The form of the material layer 2 is not particularly limited, and may be in the form of a lump or a film.
The fiber reinforced plastic (FRP), metal, glass, and ceramic constituting the material layer 2 are not particularly limited.
Examples of the fiber reinforced plastic (FRP) include glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), and aramid fiber reinforced plastic (AFRP). Molds made from glass fiber or carbon fiber SMC (sheet molding compound) can also be mentioned.
Examples of the metal include aluminum, iron, copper, magnesium, steel and the like.
Of these, aluminum is preferable from the viewpoint of weight reduction.

〔surface treatment〕
The material layer 2 can also be subjected to surface treatment for the purpose of removing contaminants on the surface and / or an anchor effect.
When the material layer 2 is at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, and ceramic, it is preferable to perform surface treatment before laminating the primer layer 3.

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

By the surface treatment, the adhesiveness between the material layer 2 and the primer layer 3 can be improved.
The surface treatment can also contribute to the improvement of the bondability with the bonding target.

Examples of the surface treatment include cleaning with a solvent, degreasing treatment, blasting treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, chemical conversion treatment, and the like. Of these, surface treatment that generates hydroxyl groups on the surface of the material layer 2 is preferable, and specifically, blast treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, chemical conversion treatment, and the like are preferable. These surface treatments may be performed by only one type or by two or more types. As a specific method of these surface treatments, known methods can be used.

Examples of the cleaning and / or degreasing treatment with the solvent or the like include treatments such as degreasing the surface of the material layer 2 with an organic solvent such as acetone or toluene. It is preferable that the cleaning and / or the degreasing treatment with the solvent or the like is performed before the other surface treatment.

Examples of the blasting process include shot blasting and sandblasting.

Examples of the polishing treatment include buffing using a polishing cloth, roll polishing using polishing paper (sandpaper), electrolytic polishing, and the like.

Plasma treatment uses a high-pressure power supply for plasma treatment, hits the surface of the material with a plasma beam emitted from a rod called an electrode, first cleans the foreign matter oil film existing on the surface, and then inputs gas energy according to the material to the surface. It is a method of exciting a molecule, and examples thereof include an atmospheric pressure plasma treatment method capable of imparting a hydroxyl group or a polar group to the surface.

Laser treatment is a technology that rapidly heats and cools only the surface layer by laser irradiation to improve the surface characteristics, and is an effective method for roughening the surface. Known laser processing techniques can be used.

The etching treatment includes, for example, a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromium acid-sulfuric acid method, and an iron chloride method, and an electrochemical etching treatment such as an electrolytic etching method. Can be mentioned.
When the material layer 2 is made of aluminum, an alkaline method using an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable, and a caustic soda method using an aqueous solution of sodium hydroxide is particularly preferable. The alkaline method can be carried out, for example, by immersing the material layer 2 in an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 20% by mass at 20 to 70 ° C. for 1 to 15 minutes. As the additive, a chelating agent, an oxidizing agent, a phosphate or the like may be added. After the immersion, it is preferable to neutralize (de-smut) with a 5 to 20% by mass aqueous nitric acid solution, wash with water, and dry.

The chemical conversion treatment mainly forms a chemical conversion film on the surface of the material layer 2.

Examples of the chemical conversion treatment include boehmite treatment and zirconium treatment.
In the boehmite treatment, a boehmite film is formed on the surface of the material layer 2 by treating the material layer 2 with hot water. Ammonia, triethanolamine, or the like may be added to water as a reaction accelerator. For example, it is preferable to immerse the material layer 2 in hot water at 90 to 100 ° C. containing triethanolamine at a concentration of 0.1 to 5.0% by mass for 3 seconds to 5 minutes.
In the zirconium treatment, a film of a zirconium compound is formed on the surface of the material layer 2 by immersing the material layer 2 in a zirconium salt-containing liquid such as zirconium phosphate. For example, the material layer 2 is immersed in a chemical agent for zirconium treatment (for example, "Palcoat 3762" manufactured by Nihon Parkerizing Co., Ltd., "Palcoat 3796", etc.) at 45 to 70 ° C. for 0.5 to 3 minutes. It is preferable to do this. The zirconium treatment is preferably performed after the etching treatment by the caustic soda method.

When the material layer 2 is made of aluminum, it is particularly preferable to include at least one surface treatment selected from an etching treatment and a boehmite treatment.

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

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

As shown in FIG. 2, the functional group-imparting treatment contains a single layer or a plurality of layers laminated between the material layer 2 and the primer layer 3 in contact with the material layer 2 and the primer layer 3. Layer 4 can be formed.

When the functional group-containing layer 4 is formed by the functional group-imparting treatment, the functional groups of the functional group-containing layer 4 are the hydroxyl groups on the surface of the material layer 2 and the functional groups of the resin constituting the primer layer, respectively. The chemical bond formed by the reaction has the effect of improving the adhesiveness between the material layer 2 and the primer layer 3. In addition, the effect of improving the bondability with the bonding target can also be obtained.
Therefore, the functional group in the functional group-containing layer 4 is preferably a functional group having reactivity with the hydroxyl group or the functional group of the resin constituting the primer layer. Examples of the functional group include an epoxy group, an amino group, a mercapto group, an isocyanato group, a carboxy group, a hydroxyl group, a vinyl group, a (meth) acryloyloxy group, and the like.

The functional group-containing layer 4 is preferably a layer having a functional group introduced from at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound.
The functional group-containing layer 4 preferably contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from (C) A thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group (meth). ) A functional group obtained by reacting an acryloyl group with a thiol compound (E) From a group consisting of a compound having an amino group and a (meth) acryloyl group in an epoxy group derived from a silane coupling agent, an amino compound, and a thiol compound. A functional group obtained by reacting at least one selected type (F) A thiol group derived from an isocyanato group (G) thiol compound derived from an isocyanate compound.

The functional group-containing layer 4 has at least one selected from the group consisting of a silane coupling agent, an isocyanate compound, and a thiol compound on the surface of the material layer 2 or the surface treated with the above surface before forming the primer layer 3. It can be formed by treating with seeds. Specifically, it can be formed by applying a solution containing at least one selected from the group consisting of the following (a) to (g) to the surface of the material layer 2 or the surface treated as described above. ..
(A) Silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a mercapto group (b) A silane coupling agent having an amino group and an epoxy compound. And at least one compound selected from the group consisting of thiol compounds, (c) a silane coupling agent having a mercapto group, an epoxy compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and an epoxy group, and At least one compound selected from the group consisting of compounds having a (meth) acryloyl group and an amino group (d) A silane coupling agent having a (meth) acryloyl group and a silane coupling agent having a thiol compound (e) epoxy group. At least one compound selected from the group consisting of an agent, an amino compound, a thiol compound, and a compound having an amino group and a (meth) acryloyl group (f) isocyanate compound (g) thiol compound. ) Corresponds to the functional groups (A) to (G), respectively, and produces these functional groups. That is, the functional group-containing layer 4 containing the functional group of (A) can be formed by the functional group-imparting treatment using the solution containing (a). The same applies to the above (b) to (g).
For example, when a dithiol compound is reacted with an amino group in the treatment according to (b), a mercapto group, which is a functional group of the dithiol compound, is introduced at the terminal. Similarly, when a polyfunctional isocyanate compound is reacted with a mercapto group in the treatment according to (c), an isocyanato group, which is a functional group of the polyfunctional isocyanate compound, is introduced at the terminal.

The method for forming the functional group-containing layer 4 with the silane coupling agent, the isocyanate compound, or the thiol compound is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, the metal substrate is immersed in a solution of a silane coupling agent having a concentration of 5 to 50% by mass at room temperature to 100 ° C. for 1 minute to 5 days, and then immersed at room temperature to 100 ° C. for 1 minute to 5 hours. It can be carried out by a method such as drying.

〔Silane coupling agent〕
As the silane coupling agent, for example, known ones used for surface treatment of glass fibers and the like can be used. The silanol group generated by hydrolyzing the silane coupling agent or the silanol group obtained by oligomerizing the silanol group reacts with the hydroxyl group existing on the surface-treated surface of the metal substrate 2 to bond with the primer layer 3 and the primer layer 3. A functional group based on the structure of the silane coupling agent that can be chemically bonded to the object to be bonded can be imparted (introduced) to the metal substrate 2.

The silane coupling agent is not particularly limited, but examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxy. Examples thereof include propylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2-(. Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be mentioned. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and dithioltriazinepurpiltriethoxysilane. Examples of the silane coupling agent having a (meth) acryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-Acryloxypropyltrimethoxysilane and the like. In addition, as other effective silane coupling agents, silane coupling agents having a vinyl group such as 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane, 3-tri. Alkoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris-( Trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, and the like. These may be used alone or in combination of two or more.

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

The isocyanate compound is not particularly limited, but for example, other polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI). , 2-Isocyanate ethyl methacrylate (for example, "Karens MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.), 2-isocyanate ethyl acrylate (for example, "Karens AOI" manufactured by Showa Denko Co., Ltd.), which is an isocyanate compound having a radically reactive group. (Registered trademark) ”,“ AOI-VM (registered trademark) ”), 1,1- (bisacryloyloxyethyl) ethyl isocyanate (for example,“ Karens BEI (registered trademark) ”manufactured by Showa Denko Co., Ltd.), etc. Be done.

[Thiol compound]
The thiol compound is chemically bonded to the primer layer 3 and the object to be bonded by the mercapto group (thiol group) in the thiol compound reacting with the hydroxyl group existing on the surface-treated surface of the metal substrate 2 and binding to the thiol compound. A possible functional group based on the structure of the thiol compound can be imparted (introduced) to the metal substrate 2.

The thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Corporation and "QE-340M" manufactured by Toray Fine Chemicals Co., Ltd. ”), Ether-based first-class thiols (for example,“ Cup Cure 3-800 ”manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example,“ Karenz MT ”manufactured by Showa Denko KK) (Registered trademark) BD1 ”), Pentaerythritol tetrakis (3-mercaptobutylate) (for example,“ Karenz MT (registered trademark) PE1 ”manufactured by Showa Denko KK), 1,3,5-Tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Karensu MT (registered trademark) NR1" manufactured by Showa Denko KK) and the like can be mentioned.

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

[Field-polymerized resin composition layer 31]
As described above, at least one layer of the primer layer is the field-polymerized resin composition layer 31 made of a polymer of the field-polymerized resin composition.
In the field-polymerized resin composition layer 31, the field-polymerized resin composition dissolved in a solvent is applied onto the material layer 2 or the functional group-containing layer 4, the solvent is volatilized, and then the field-polymerized resin composition is formed. It can be obtained by polymerizing the resin composition.
In the field-polymerized resin composition layer 31, the field-polymerized resin composition dissolved in a solvent is applied to the surface of the material layer 2 or the functional group-containing layer 4, and the field-polymerized resin composition is polymerized on the surface. It can also be formed by letting it form.

The field-polymerized resin composition preferably contains at least one of the following (1) to (7), more preferably contains the following (4), and is a combination of a bifunctional epoxy resin and a bifunctional phenol compound. Is most preferable to contain.
(1) Combination of bifunctional isocyanate compound and diol (2) Combination of bifunctional isocyanate compound and bifunctional amino compound (3) Combination of bifunctional isocyanate compound and bifunctional thiol compound (4) Combination of bifunctional epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radical polymerizable monomer

The compounding amount ratio of the bifunctional isocyanate compound and the diol in (1) is preferably set so that the molar equivalent ratio of the isocyanate group to the hydroxyl group is 0.7 to 1.5, and more preferably 0. It is 8 to 1.4, more preferably 0.9 to 1.3.
The compounding amount ratio of the bifunctional isocyanate compound and the bifunctional amino compound in (2) is preferably set so that the molar equivalent ratio of the isocyanate group to the amino group is 0.7 to 1.5. It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
The compounding amount ratio of the bifunctional isocyanate compound and the bifunctional thiol compound in (3) is preferably set so that the molar equivalent ratio of the isocyanate group to the thiol group is 0.7 to 1.5. It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
The compounding amount ratio of the bifunctional epoxy compound and the diol in (4) is preferably set so that the molar equivalent ratio of the epoxy group to the hydroxyl group is 0.7 to 1.5, and more preferably 0. It is 8 to 1.4, more preferably 0.9 to 1.3.
The compounding amount ratio of the bifunctional epoxy compound and the bifunctional carboxy compound in (5) is preferably set so that the molar equivalent ratio of the epoxy group to the carboxy group is 0.7 to 1.5. It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
The compounding amount ratio of the bifunctional epoxy compound and the bifunctional thiol compound in (6) is preferably set so that the molar equivalent ratio of the epoxy group to the thiol group is 0.7 to 1.5. It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.

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

By laminating the in-situ polymerization type resin composition layer 31 as the primer layer 3 on the material layer 2, the bonding target can be firmly welded on the material layer 2.

The primer layer 3 may be composed of a plurality of layers including the in-situ polymerization type resin composition layer 31. When the primer layer 3 is composed of a plurality of layers, it is preferable that the essential in-situ polymerization type resin composition layer 31 is laminated so as to be the outermost surface on the opposite side of the material layer 2.

The field-polymerized resin composition layer 31 is made of a polymer of the field-polymerized resin composition.
The in-situ polymerization type resin composition layer 31 can be obtained by subjecting a resin composition containing at least one of the above (1) to (6) to a double addition reaction in the presence of a catalyst. As the catalyst for the polyaddition reaction, for example, a phosphorus compound such as tertiary amine-triphenylphosphine such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol is preferably used. The heavy addition reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 120 minutes, although it depends on the composition of the resin composition.
Specifically, for example, the in-situ polymerization type resin composition layer 31 can be formed by applying a polymer of a resin composition containing at least one of the above (1) to (6) to the material layer 2. Further, in the field polymerization type resin composition layer 31, the resin composition containing at least one of the above (1) to (6) is dissolved in a solvent and applied to the material layer 2, and then the solvent is appropriately volatilized. After that, it can be formed by heating and carrying out a polyaddition reaction. The material layer 2 also includes those subjected to the surface treatment and / or the functional group imparting treatment.
The in-situ polymerization type resin composition layer can also be obtained by a radical polymerization reaction of the resin composition containing the monofunctional radically polymerizable monomer (7). The radical polymerization reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 90 minutes, although it depends on the composition of the resin composition. In the case of photocuring, it is preferable to irradiate ultraviolet rays or visible light to carry out the polymerization reaction.
Specifically, for example, the in-situ polymerization type resin composition layer can be formed by applying a polymer of the resin composition containing the monofunctional radically polymerizable monomer (7) on the material layer 2. .. Further, in the in-situ polymerization type resin composition layer, the resin composition containing the monofunctional radically polymerizable monomer (7) is dissolved in a solvent, coated on the material layer 2, and then heated for a radical polymerization reaction. By performing the above, a more firmly bonded in-situ polymerization type resin composition layer can be formed. The material layer 2 also includes those subjected to the surface treatment and / or the functional group imparting treatment.

(Bifunctional isocyanate compound)
The bifunctional isocyanate compound is a compound having two isocyanato groups, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, dimerate diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) or a mixture thereof. Examples thereof include diisocyanate compounds such as p-phenylenediocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate (MDI). Among them, TDI, MDI and the like are preferable from the viewpoint of the strength of the primer.

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

(Bifunctional amino compound)
The bifunctional amino compound is a compound having two amino groups, and examples thereof include bifunctional aliphatic diamines and aromatic diamines. Examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, and the like. Examples of aromatic diamines include 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, and N-aminoethylpiperazine. Examples thereof include diaminodiphenylmethane and diaminodiphenylpropane. Of these, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine and the like are preferable from the viewpoint of primer toughness.

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

(Bifunctional epoxy compound)
The bifunctional epoxy compound is a compound having two epoxy groups in one molecule. For example, aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, naphthalene type bifunctional epoxy resin, and aliphatic such as 1,6-hexanediol diglycidyl ether. Epoxy compounds can be mentioned.
Of these, one type may be used alone, or two or more types may be used in combination.
Specifically, "jER (registered trademark) 828", "jER (registered trademark) 834", "jER (registered trademark) 1001", "jER (registered trademark) 1004", and the same, manufactured by Mitsubishi Chemical Corporation. Examples thereof include "jER (registered trademark) YX-4000". Other bifunctional epoxy compounds with a special structure can also be used. Of these, one type may be used alone, or two or more types may be used in combination.

(Bifunctional carboxy compound)
The bifunctional carboxy compound may be a compound having two carboxy groups, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, and terephthalic acid. Can be mentioned. Of these, isophthalic acid, terephthalic acid, adipic acid and the like are preferable from the viewpoint of primer strength and toughness.

(Monofunctional radically polymerizable monomer)
The monofunctional radically polymerizable monomer is a monomer having one ethylenically unsaturated bond. For example, styrene monomers, styrene-based monomers such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, chlorostyrene, vinyltoluene, divinylbenzene, etc.; ethyl (meth) acrylate, Methyl (meth) acrylate, -n-propyl (meth) acrylate, -i-propyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and phenoxyethyl (meth) Examples thereof include (meth) acrylic acid esters such as meta) acrylate and glycidyl (meth) acrylate. Of the above compounds, one type may be used, or two or more types may be used. Among them, from the viewpoint of primer strength and toughness, one of styrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate, or a combination of two or more thereof is preferable.
In order to allow the radical polymerization reaction to proceed sufficiently and form a desired primer layer, a solvent and, if necessary, an additive such as a colorant may be contained. In this case, it is preferable that the monofunctional radically polymerizable monomer is the main component among the components of the radically polymerizable composition other than the solvent. The main component means that the content of the monofunctional radically polymerizable monomer is 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.
As the polymerization initiator for the radical polymerization reaction, for example, known organic peroxides, photoinitiators and the like are preferably used. A room temperature radical polymerization initiator in which an organic peroxide is combined with a cobalt metal salt or amines may be used. Examples of organic peroxides include those classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. As the photoinitiator, it is desirable to use an initiator capable of initiating polymerization with visible rays from ultraviolet rays.
The radical polymerization reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 90 minutes, although it depends on the type of the reaction compound and the like. In the case of photocuring, the polymerization reaction is carried out by irradiating with ultraviolet rays or visible light. Specifically, the in-situ polymerization type resin composition layer 31 made of the radically polymerizable compound can be formed by applying the resin composition and then heating it to carry out a radical polymerization reaction.

[Thermosetting resin layer 32]
When the primer layer 3 is composed of a plurality of layers including the field-polymerized resin composition layer 31, as shown in FIG. 3, the primer layer 3 is formed of a cured product of a resin composition containing a thermosetting resin. The thermosetting resin layer 32 may also be included.
In addition, in the resin composition containing the thermosetting resin, in order to sufficiently proceed the curing reaction of the thermosetting resin and form a desired primer layer, a solvent and, if necessary, an additive such as a colorant are added. It may be included. In this case, it is preferable that the thermosetting resin is the main component among the components other than the solvent of the resin composition. The main component means that the content of the thermosetting resin is 40% by mass or more. The content is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more.

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

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

The thermosetting resin referred to in the present embodiment broadly means a resin that is crosslink-cured, and includes not only a heat-curable type but also a room temperature-curable type and a photocurable type. The photo-curing type can be cured in a short time by irradiating with visible light or ultraviolet rays. The photo-curing type may be used in combination with a heat-curing type and / or a room temperature curing type. Examples of the photocurable type include vinyl ester resins such as "Lipoxy (registered trademark) LC-760" and "Lipoxy (registered trademark) LC-720" manufactured by Showa Denko KK.

(Urethane resin)
The urethane resin is usually a resin obtained by reacting an isocyanato group of an isocyanate compound with a hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a coating material containing a polyisocyanate having a vehicle non-volatile component of 10 wt% or more". The urethane resin corresponding to is preferable. The urethane resin may be a one-component type or a two-component type.

Examples of the one-component urethane resin include an oil-modified type (which cures by oxidative polymerization of unsaturated fatty acid groups), a moisture-curing type (which cures by the reaction of isocyanato groups with water in the air), and a block type (which cures by the reaction of isocyanato groups with water in the air). Examples thereof include a lacquer type (which cures when the solvent volatilizes and dries), a lacquer type (which cures when the isocyanato group which is dissociated by heating and regenerated and the hydroxyl group reacts with each other and cures). Among these, a moisture-curable one-component urethane resin is preferably used from the viewpoint of ease of handling and the like. Specific examples thereof include "UM-50P" manufactured by Showa Denko KK.

Examples of the two-component urethane resin include a catalyst-curable type (a catalyst-curable type in which an isocyanato group reacts with water in the air to cure in the presence of a catalyst) and a polyol-curable type (a reaction between an isocyanato group and a hydroxyl group of a polyol compound). (Those that are cured by) and the like.

Examples of the polyol compound in the polyol curing type include polyester polyols, polyether polyols, phenol resins and the like.
Further, examples of the isocyanate compound having an isocyanato group in the polyol-curable type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and diimalate diisocyanate; 2,4- or 2,6-tolylene diisocyanate. (TDI) or a mixture thereof, p-phenylenediocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and aromatic isocyanates such as polypeptide MDI which is a polynuclear mixture thereof; alicyclic isocyanates such as isophorone diisocyanate (IPDI) and the like. Be done.
The compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in molar equivalent ratio of hydroxyl group / isocyanato group.

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

(Epoxy resin)
The epoxy resin is a resin having at least two epoxy groups in one molecule.
Examples of the prepolymer before curing of the epoxy resin include ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, and cyclic aliphatic epoxy resin. , Ether-ester type epoxy resin and the like, and among these, bisphenol A type epoxy resin is preferably used. Of these, one type may be used alone, or two or more types may be used in combination.
Specific examples of the bisphenol A type epoxy resin include "jER (registered trademark) 828" and "jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
Specific examples of the novolak type epoxy resin include "DEN (registered trademark) 438 (registered trademark)" manufactured by The Dow Chemical Company.

Examples of the curing agent used for the epoxy resin include known curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts. When the curing agent is used in combination with a long-chain aliphatic amine and / or a thiol, the effect of having a large elongation rate and excellent impact resistance can be obtained.
Specific examples of the thiols include the same compounds as those exemplified as thiol compounds for forming a functional group-containing layer described later. Among these, pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "Carens MT (registered trademark) PE1" manufactured by Showa Denko KK) is preferable from the viewpoint of elongation and impact resistance.

(Vinyl ester resin)
The vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (for example, styrene). Although it is also called an epoxy (meth) acrylate resin, the vinyl ester resin also includes a urethane (meth) acrylate resin.
As the vinyl ester resin, for example, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary" (Japan Society of Color Material, published in 1993), etc. shall also be used. In addition, specifically, "Lipoxy (registered trademark) R-802", "Lipoxy (registered trademark) R-804", "Lipoxy (registered trademark) R-806", etc. manufactured by Showa Denko KK, etc. Can be mentioned.

The urethane (meth) acrylate resin is obtained by, for example, reacting an isocyanate compound with a polyol compound and then reacting with a hydroxyl group-containing (meth) acrylic monomer (and, if necessary, a hydroxyl group-containing allyl ether monomer). Examples thereof include radically polymerizable unsaturated group-containing oligomers. Specific examples thereof include "Lipoxy (registered trademark) R-6545" manufactured by Showa Denko KK.

The vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
The organic peroxide is not particularly limited, but for example, ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxides. Oxide carbonates and the like can be mentioned. By combining these with a cobalt metal salt or the like, curing at room temperature is also possible.
The cobalt metal salt is not particularly limited, and examples thereof include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Of these, cobalt naphthenate and / and cobalt octylate are preferred.

(Unsaturated polyester resin)
The unsaturated polyester resin is a monomer (eg, styrene, etc.) in which a condensation product (unsaturated polyester) obtained by an esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is polymerized. ) Is dissolved.
As the unsaturated polyester resin, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary" (Japan Society of Color Material, published in 1993), etc. can also be used. Yes, and more specifically, "Rigolac (registered trademark)" manufactured by Showa Denko KK can be mentioned.

The unsaturated polyester resin can be cured by radical polymerization by heating in the presence of a catalyst similar to that of the vinyl ester resin.

[Action of primer layer 3]
The primer layer 3 has excellent adhesiveness to the material layer 2.
The primer layer 3 imparts excellent bondability to another bonding material 6 to be bonded. Its zygosity is maintained over a long period of several months.
The surface of the material layer 2 is protected by the primer layer 3, and deterioration such as adhesion of dirt and oxidation can be suppressed.

[Joint 5]
As shown in FIG. 4, the bonded body 5 in one embodiment is formed by welding the primer layer 3 of the primer-attached material 1 to be bonded and the bonding material 6 to be bonded.
The bonding material 6 includes a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic.
There are various methods for welding depending on the method of heating the resin member, and specifically, there are ultrasonic welding, vibration welding, hot welding, hot air welding, induction welding, injection welding and the like.
As shown in FIG. 5, the bonded body 5 in another embodiment has one or a plurality of primer layers 9 in which the bonding material 6 is laminated on the material layer 8, and at least one layer of the primer layer is formed. It is composed of a primer-attached material 7 which is a field-polymerized resin composition layer composed of a polymer of a field-polymerized resin composition, and a primer layer of a primer-attached material 7 which is a welding material and a primer-attached material which is a material to be welded. It is formed by welding the primer layer of 1. Similar to the primer-attached material 1, the primer-attached material 7 can form a functional group-containing layer 10 between the material layer 8 and the primer layer 9.

The thickness of the primer layer (thickness after drying) depends on the material of the bonding target and the contact area of the bonding portion, but from the viewpoint of obtaining excellent bonding strength with the bonding target and the coefficient of thermal expansion between dissimilar materials. From the viewpoint of suppressing thermal deformation of the bonded body due to the difference between the two, it is preferably 1 μm to 10 mm. It is more preferably 10 μm to 8 mm, and even more preferably 50 μm to 5 mm. When the primer layer is a plurality of layers, the thickness of the primer layer (thickness after drying) is the total thickness of each layer.

As a method for producing the bonded body 5, at least one method selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a heat pressing method is used for bonding to be bonded. A method of welding the primer layer 3 of the primer-attached material 1 which is the material to be bonded to the material 6, or the bonding material 6 to be bonded on the primer layer 3 of the primer-attached material 1 which is the material to be bonded. Examples thereof include a method of molding by metal powder injection molding using a metal metal powder.

<< Second Invention_Material with Primer >>
The primer-attached 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 plastic (FRP), glass, and ceramic. At least one layer of the primer layer is a field-polymerized resin composition layer C made of a polymer of the field-polymerized resin composition.

By using the primer-attached material C of the present invention as a material to be welded, a bonding material containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic is firmly welded. It is possible to obtain a composite body.
Hereinafter, the description of the configuration common to that of the first invention will be omitted.

[Material C with primer]
As shown in FIG. 6, the primer-attached material C1'in one embodiment is laminated on the material with at least one material layer C2' selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic. It is a laminated body having one layer or a plurality of layers of primer layers 3'. In the present invention, at least one layer of the primer layer 3'is a field-polymerized resin composition layer C31' composed of a polymer of the field-polymerized resin composition.

The primer layer 3'is a bonding material containing a material C1'with a primer and a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. When obtaining a body, it is meant to mean a layer that is interposed between the material layer C2'and the bonding material to improve the bonding strength.

<At least one material layer C2'selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic>
The form of the material layer C2'is not particularly limited, and may be in the form of a lump or a film.
The fiber reinforced plastic (FRP), glass, and ceramic constituting the material layer C2'are not particularly limited.

〔surface treatment〕
The material layer C2'can also be subjected to surface treatment for the purpose of removing contaminants on the surface and / or an anchor effect.
When the material layer C2'is a fiber reinforced plastic (FRP) or ceramic, it is preferable to perform a surface treatment before laminating the primer layer 3'.

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

By the surface treatment, the adhesiveness between the material layer C2'and the primer layer 3'can be improved.
The surface treatment can also contribute to the improvement of the bondability with the bonding target.

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

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

As shown in FIG. 7, a single layer or a plurality of layers laminated in contact with the material layer C2'and the primer layer 3'between the material layer C2'and the primer layer 3'by the functional group imparting treatment. The functional group-containing layer 4'of the above can be formed. The functional group-containing layer 4'has the same structure as the functional group-containing layer 4 of the first invention.

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

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

As the bonding material 6', a primer-attached material having a primer layer including a field-polymerized resin composition layer composed of a polymer of the field-polymerized resin composition is used as in the primer-attached material 1, and each primer layer is used. Is preferably welded.

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

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

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

<Surface treatment_boehmite treatment>
The aluminum (A6063) in Table 1 is immersed in a 5% by mass aqueous solution of sodium hydroxide for 1.5 minutes, neutralized with an aqueous nitric acid solution having a concentration of 5% by mass, washed with water, and dried for etching. Was done. Next, the etched aluminum plate was boiled in pure water for 10 minutes and then baked at 250 ° C. for 10 minutes to prepare a boehmite-treated aluminum plate.

<Functional group addition treatment_silane coupling agent treatment>
The boehmite-treated aluminum and the sanding-treated CFRP, copper, ceramic, and glass materials shown in Table 1 are mixed with 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone Co., Ltd .; silane cup). 2 g of the ring agent) was immersed in a silane coupling agent-containing solution at 70 ° C. dissolved in 1000 g of industrial ethanol for 20 minutes. Each of the materials was taken out and dried to form a functional group (amino group) layer.

[Preparation of test pieces: Example 1-9, Comparative Example 1-4]
<Preparation of field-polymerized resin composition-1 for forming a primer layer>
100 g of a bifunctional epoxy resin (“jER® 1001” manufactured by Mitsubishi Chemical Corporation), 6.2 g of bisphenol S, and 0.4 g of triethylamine were dissolved in 197 g of toluene to form a field-polymerized resin composition-1 ( In-situ polymerization type thermoplastic epoxy resin composition) was prepared.

<Formation of primer layer>
Steel in Table 1 (hereinafter referred to as untreated steel), steel after the sanding treatment (hereinafter referred to as sanding steel), aluminum in Table 1 (hereinafter referred to as untreated aluminum), aluminum after the silane coupling agent treatment (hereinafter referred to as untreated aluminum). Hereinafter, silane coupling agent-treated aluminum-1), CFRP in Table 1 (hereinafter referred to as untreated CFRP), CFRP after the silane coupling agent treatment (hereinafter referred to as silane coupling agent-treated CFRP-1), and Table. Copper 1 (hereinafter referred to as untreated copper), copper after the silane coupling agent treatment (hereinafter referred to as silane coupling agent treated copper), glass after the silane coupling agent treatment (hereinafter referred to as silane coupling agent treatment). A field-polymerized resin composition-1 was applied to the surface of each one side of glass) by a spray method so that the thickness after drying was 80 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes for a heavy addition reaction, allowed to cool to room temperature, and a primer layer made of a thermoplastic epoxy resin. Was formed.
The surface on which the primer layer is formed is referred to as a primer surface, and the surface on which the primer layer is not formed is referred to as a primer-free surface. Further, in Tables 2 and 3 below, a surface having a primer layer is referred to as (with), and a surface without a primer layer is referred to as (absent).

[Example 1]
(Welding)
In a state where the primer surface of the sanding steel and the primer surface of the sanding steel are overlapped so that the joint portion is 25 mm × 13 mm, they are clipped and held at 150 ° C. for 5 minutes for heat welding, and the test piece 1 (steel) -Steel joint) was obtained. Here, the joint portion means a portion where the test piece materials are overlapped.

(Tensile shear strength)
After leaving the test piece 1 at room temperature for 1 day, a tensile tester (universal tester Autograph "AG-IS" manufactured by Shimadzu Corporation; load cell 10 kN, tensile speed 5 mm) conforms to JIS K 6850: 1999. A tensile shear strength test was performed at / min, a temperature of 23 ° C., and 50% RH), and the joint strength was measured. The measurement results are shown in Table 2 below.

[Example 2]
(Welding)
The primer surface of the untreated steel and the primer-free surface of the untreated steel are overlapped so that the joint portion is 25 mm × 13 mm, clipped and held at 150 ° C. for 5 minutes for heat welding, and the test piece. 2 (steel-steel joint) was obtained.

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

[Example 3]
(Welding)
The primer surface of the silane coupling agent-treated aluminum-1 and the primer surface of the untreated steel are overlapped so that the joint portion is 25 mm × 13 mm, clipped and held at 150 ° C. for 5 minutes for heat welding. Then, a test piece 3 (aluminum-steel joint) was obtained.

(Tensile shear strength)
The test piece 3 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 2 below.

[Example 4]
(Welding)
The primer surface of untreated aluminum and the primer surface of silane coupling agent-treated copper were overlapped so that the joint portion was 25 mm × 13 mm, clipped and held at 150 ° C. for 5 minutes for heat welding. Test piece 4 (aluminum-copper joint) was obtained.

(Tensile shear strength)
The test piece 4 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 2 below.

[Example 5]
(Welding)
In a state where the primer surface of untreated CFRP and the primer surface of sanding steel are overlapped so that the joint portion is 25 mm × 13 mm, they are clipped and held at 150 ° C. for 5 minutes for heat welding, and the test piece 5 (test piece 5 ( CFRP-steel welder) was obtained.

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

[Example 6]
(Welding)
The primer surface of the silane coupling agent-treated CFRP-1 and the primer surface of the silane coupling agent-treated aluminum-1 are overlapped so that the joint portion is 25 mm × 13 mm, and then clipped and fastened at 150 ° C. for 5 minutes. It was held and heat-welded to obtain a test piece 6 (CFRP-aluminum conjugate).

(Tensile shear strength)
The test piece 6 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 2 below.

[Example 7]
(Welding)
In a state where the primer surface of untreated copper and the primer surface of sanding steel are overlapped so that the joint portion is 25 mm × 13 mm, they are clipped and held at 150 ° C. for 5 minutes for heat welding. Copper-steel joint) was obtained.

(Tensile shear strength)
The test piece 7 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 2 below.

[Example 8]
(Welding)
The primer surface of the silane coupling agent-treated copper and the primer surface of the silane coupling agent-treated aluminum-1 are overlapped so that the joint portion is 25 mm × 13 mm, and then clipped and held at 150 ° C. for 5 minutes. Test piece 8 (copper-aluminum joint) was obtained by heat welding.

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

[Example 9]
(Welding)
The primer surface of the silane coupling agent-treated glass and the primer surface of the silane coupling agent-treated glass are overlapped so that the joint portion is 25 mm × 13 mm, and then clipped and held at 150 ° C. for 5 minutes to heat. Welding was performed to obtain a test piece 9 (glass-glass joint).

(Tensile shear strength)
The test piece 9 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 2 below.

[Comparative Example 1]
The primer-free surface of the silane coupling agent-treated aluminum-1 and the primer-free surface of the silane coupling agent-treated copper are overlapped so that the joint portion is 25 mm × 13 mm, and then clipped and fastened at 150 ° C. for 5 minutes. It was held and heat welded, but it did not join, and no test piece was obtained.

[Comparative Example 2]
The primer-free surface of the silane coupling agent-treated CFRP-1 and the primer-free surface of the silane coupling agent-treated CFRP-1 are overlapped so that the joint portion is 25 mm × 13 mm, and clipped at 150 ° C. It was held for 5 minutes and heat-welded, but no bonding was performed, and no test piece was obtained.

[Example 10]
(Welding)
The primer surface of untreated copper and the primer-free surface of untreated aluminum were overlapped so that the joint portion was 25 mm × 13 mm, clipped and held at 150 ° C. for 5 minutes for heat welding, and the test piece was welded. 10 (copper-aluminum joint) was obtained.

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

[Preparation of test piece: Comparative Example 3]
<Formation of primer layer>
The in-situ polymerized resin composition-1 is held in a flask at 150 ° C. for 30 minutes after volatilizing the solvent to obtain a thermoplastic epoxy resin (hereinafter referred to as polymerized thermoplastic epoxy resin), and after cooling, the amount of acetone is 65% by mass. Was completely dissolved to obtain a polymerized thermoplastic epoxy resin solution.
The polymerized plastic epoxy resin solution was applied by a spray method to the surfaces of one side of each of the untreated aluminum and the silane coupling agent-treated copper so that the thickness after drying was 80 μm. It was dried at 50 ° C. for 5 hours to form a primer layer.

(Welding)
In a state where the primer surface of the untreated aluminum and the primer surface of the silane coupling agent-treated copper are overlapped so that the joint portion is 25 mm × 13 mm, they are clipped and held at 150 ° C. for 5 minutes for heat welding. , Test piece 11 (aluminum-copper joint) was obtained.

(Tensile shear strength)
The test piece 11 was subjected to a tensile shear strength test by the same method as in Example 1. The measurement results are shown in Table 2 below.

[Test piece: Example 11-13, Comparative Example 4]
<Preparation of field-polymerized resin composition-2 for forming primer layer>
100 g of diphenylmethane diisocyanate (“Millionate MT” manufactured by Tosoh Corporation), 54.7 g of propylene glycol, and 15.8 g of 4,4′-diaminodiphenylmethane were dissolved in 287 g of acetone to form a field-polymerized resin composition-2 ("Millionate MT"). In-situ polymerization type urethane resin composition) was prepared.

<Formation of primer layer>
One side of each of the silane coupling agent-treated aluminum-1, the ceramic after the silane coupling agent treatment (hereinafter referred to as silane coupling agent-treated ceramic), and the GFRP after the sanding treatment (hereinafter referred to as sanding-treated GFRP). The in-situ polymerized resin composition-2 was applied to the surface by a spray method so that the thickness after drying was 80 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes for a heavy addition reaction, and then allowed to cool to room temperature to form a primer layer made of urethane resin. did.
The surface on which the primer layer is formed is referred to as a primer surface, and the surface on which the primer layer is not formed is referred to as a primer-free surface. Further, in Table 4 below, a surface having a primer layer is referred to as (with), and a surface without a primer layer is referred to as (absent).

[Example 11]
(Welding)
The copper foil of Table 1 was placed on the primer surface of aluminum-1 treated with a silane coupling agent and pressed at 150 ° C. for 3 minutes to obtain a test piece 12 (aluminum-copper foil joint, aluminum with copper foil). ..

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

[Example 12]
(Welding)
The copper foil of Table 1 was placed on the primer surface of the silane coupling agent-treated ceramic and pressed at 150 ° C. for 3 minutes to obtain a test piece 13 (ceramic-copper foil joint, ceramic with copper foil).

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

[Example 13]
(Welding)
The copper foil of Table 1 was placed on the primer surface of the sanding-treated GFRP and pressed at 150 ° C. for 3 minutes to obtain a test piece 14 (GFRP-copper foil-bonded GFRP with copper foil).

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

[Comparative Example 4]
The copper foil shown in Table 1 was placed on the primer-free surface of the silane coupling agent-treated ceramic and pressed at 150 ° C. for 3 minutes, but no bonding was performed, and no test piece was obtained.

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

<Surface treatment>
The CFRP was subjected to the sanding treatment, and the aluminum was subjected to the boehmite treatment.

<Functional group addition treatment_silane coupling agent treatment>
The boehmite-treated aluminum and the sanding-treated CFRP materials were mixed with 2 g of 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) and 1000 g of industrial ethanol. It was immersed in a solution containing a silane coupling agent at 70 ° C. dissolved in 1 for 20 minutes. Each of the materials was taken out and dried to prepare a material to which a functional group (amino group) was added.

<Formation of primer layer>
One-sided surfaces of the aluminum after the silane coupling agent treatment (hereinafter, silane coupling agent-treated aluminum-2) and the CFRP after the silane coupling agent treatment (hereinafter, silane coupling agent-treated CFRP-2). The in-situ polymerization type resin composition-1 was applied by a spray method so that the thickness after drying was 2 mm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes for a heavy addition reaction, allowed to cool to room temperature, and a primer layer made of a thermoplastic epoxy resin. Was formed.
The surface on which the primer layer is formed is referred to as a primer surface, and the surface on which the primer layer is not formed is referred to as a primer-free surface.

[Example 14]
(Welding)
The primer surface of the silane coupling agent-treated aluminum-2 and the primer surface of the silane coupling agent-treated CFRP-2 were combined and heat-welded by pressing at 150 ° C. for 5 minutes.

(Evaluation)
The welded joint was returned to room temperature and left in a normal temperature environment, and it was observed whether or not the joint was warped and the joint surface was peeled off.
Neither warpage nor peeling was observed.

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

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

As shown in Examples 1 to 14, according to the first invention of the present invention, a material to be joined containing 2A consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. , Fiber reinforced plastic (FRP), metallic, glass, ceramic, a bonding material containing at least one material layer B selected from the group is bonded to each other, and a thermoplastic resin layer is provided on both bonding surfaces. It is possible to provide a bonded body that is firmly welded without arranging.
As shown in Example 13, according to the second invention of the present invention, it is firmly formed with a bonding material containing a material layer consisting of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass and ceramic. A material with a primer, which is a material to be welded, can be provided.

The joint according to the present invention includes, for example, a door side panel, a bonnet roof, a tailgate, a steering hanger, an A pillar, a B pillar, a C pillar, a D pillar, a crash box, a power control unit (PCU) housing, and an electric compressor member ( Inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) spacer, battery case, LED headlamps and other automobile parts, smartphones, laptops, tablet computers , A smart watch, a large liquid crystal television (LCD-TV), a structure for outdoor LED lighting, and the like, but the application is not particularly limited to these examples.
Among the bonded bodies according to the present invention, those in which CFRP and metal are bonded are suitable for applications of multi-material materials such as automobiles, and those in which copper foil is bonded and bonded to ceramic, aluminum, FRP, etc. are electronic. Suitable for material substrate applications.

1, 1'Material with primer 2, 2'Material layer 21, 21' Fine unevenness 3, 3'Primer layer 31, 31'Field polymerization type resin composition layer 32 Thermosetting resin layer 4, 4'Contains functional groups Layers 5, 5'joints 6, 6'joints 7 Primer-equipped materials 8 Material layers 9 Primer layers 10 Functional group-containing layers

Claims

Selected from the group consisting of fiber reinforced plastic (FRP), metallic, glass, and ceramic. The material to be bonded containing at least one material layer A selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic. It is a bonded body formed by bonding a bonding material containing a material layer B composed of at least one of the above.
A field-polymerized resin composition in which the material to be bonded has one or a plurality of primer layers laminated on the material layer A, and at least one of the primer layers is a polymer of a field-polymerized resin composition. It consists of a material A with a primer, which is a material layer A.
A bonded body formed by welding the primer layer of the material to be bonded to the bonding material.
A field-polymerized resin composition in which the bonding material has one or a plurality of primer layers laminated on the material layer B, and at least one of the primer layers is a polymer of the field-polymerized resin composition. It is composed of a material B with a primer, which is a layer B.
The bonded body according to claim 1, wherein the primer layer of the bonding material and the primer layer of the material to be bonded are welded together.
The bonded body according to claim 1 or 2, wherein the field-polymerized resin composition layer A polymerizes the field-polymerized resin composition on the material layer A.
The bonded body according to claim 2 or 3, wherein the field-polymerized resin composition layer B polymerizes the field-polymerized resin composition on the material layer B.
The bonded body according to any one of claims 1 to 4, wherein the in-situ polymerization type resin composition layer A is a layer that is in direct contact with the material layer A.
The bonded body according to any one of claims 2 to 5, wherein the in-situ polymerization type resin composition layer B is a layer that is in direct contact with the material layer B.
The bonded body according to any one of claims 1 to 6, wherein the field-polymerized resin composition contains at least one of the following (1) to (7).
(1) Combination of bifunctional isocyanate compound and diol (2) Combination of bifunctional isocyanate compound and bifunctional amino compound (3) Combination of bifunctional isocyanate compound and bifunctional thiol compound (4) Combination of bifunctional epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radical polymerizable monomer
The conjugate according to claim 7, wherein the in-situ polymerization type resin composition contains the combination of the bifunctional epoxy compound and the diol (4), and the diol is a bifunctional phenol.
The bonded 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 bonded 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 material A with a primer has a functional group-containing layer laminated between the material layer A and the primer layer in contact with the material layer A and the primer layer.
The conjugate according to any one of claims 1 to 10, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from (C) A thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group (meth). ) A functional group obtained by reacting an acryloyl group with a thiol compound (E) From a group consisting of a compound having an amino group and a (meth) acryloyl group in an epoxy group derived from a silane coupling agent, an amino compound, and a thiol compound. A functional group obtained by reacting at least one selected type (F) A thiol group derived from an isocyanato group (G) thiol compound derived from an isocyanate compound.
The material with a primer B has a functional group-containing layer laminated between the material layer B and the primer layer in contact with the material layer B and the primer layer.
The conjugate according to any one of claims 2 to 11, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from (C) A thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group (meth). ) A functional group obtained by reacting an acryloyl group with a thiol compound (E) From a group consisting of a compound having an amino group and a (meth) acryloyl group in an epoxy group derived from a silane coupling agent, an amino compound, and a thiol compound. A functional group obtained by reacting at least one selected type (F) A thiol group derived from an isocyanato group (G) thiol compound derived from an isocyanate compound.
The bonded body according to any one of claims 1 to 12, wherein the total thickness of the one-layer or a plurality of primer layers is 1 μm to 10 mm.
The method for producing a bonded body according to any one of claims 1 to 13.
The primer layer of the material to be welded is welded to the material to be welded by at least one method selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a hot pressing method. A method for manufacturing a welded body.
An in-situ polymerization type resin composition dissolved in a solvent is applied to the surface of a material layer A composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and the in-situ polymerization on the surface is applied. The method for producing a bonded body according to claim 14, wherein the mold resin composition is polymerized to form the in-situ polymerization type resin composition layer A.
The method for producing a bonded body according to any one of claims 2 to 13.
An in-situ polymerization type resin composition dissolved in a solvent is applied to the surface of a material layer B composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), metal, glass, and ceramic, and the in-situ polymerization on the surface is applied. A method for producing a bonded body, wherein the mold resin composition is polymerized to form the in-situ polymerization type resin composition layer B.
It 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 plastic (FRP), glass, and ceramic, and at least one layer of the primer layer is a field. A material with a primer, which is a field-polymerized resin composition layer C composed of a polymer of the polymerizable resin composition.
The primer-attached material according to claim 17, wherein the field-polymerized resin composition layer C polymerizes the field-polymerized resin composition on the material layer C.
The primer-attached material according to claim 17 or 18, wherein the in-situ polymerization type resin composition layer C is a layer that is in direct contact with the material layer C.
The primer-attached material according to any one of claims 17 to 19, wherein the field-polymerized resin composition contains at least one of the following (1) to (7).
(1) Combination of bifunctional isocyanate compound and diol (2) Combination of bifunctional isocyanate compound and bifunctional amino compound (3) Combination of bifunctional isocyanate compound and bifunctional thiol compound (4) Combination of bifunctional epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radical polymerizable monomer
The primer-attached material according to claim 20, wherein the in-situ polymerization type resin composition contains the combination of the bifunctional epoxy compound and the diol (4), and the diol is a bifunctional phenol.
The primer-attached material according to any one of claims 17 to 21, wherein at least one layer of the primer layer is formed from a cured product of a resin composition containing a thermosetting resin.
The primer-attached material according to 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 has a functional group-containing layer laminated between the material layer C and the primer layer in contact with the material layer C and the primer layer.
The primer-attached material according to any one of claims 17 to 23, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (A) to (G).
(A) A functional group derived from a silane coupling agent, at least one functional group (B) silane coupling agent selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a thiol group. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound with an amino group derived from (C) A thiol group derived from a silane coupling agent, an epoxy compound, an amino compound, an isocyanate compound, (meth ) Derived from a functional group (D) silane coupling agent obtained by reacting at least one selected from the group consisting of a compound having an acryloyl group and an epoxy group and a compound having a (meth) acryloyl group and an amino group (meth). ) A functional group obtained by reacting an acryloyl group with a thiol compound (E) From a group consisting of a compound having an amino group and a (meth) acryloyl group in an epoxy group derived from a silane coupling agent, an amino compound, and a thiol compound. A functional group obtained by reacting at least one selected type (F) A thiol group derived from an isocyanato group (G) thiol compound derived from an isocyanate compound.
The primer-attached material according to any one of claims 17 to 24, wherein the total thickness of the one-layer or a plurality of primer layers is 1 μm to 10 mm.
The method for producing a material with a primer according to any one of claims 17 to 25.
A field-polymerized resin composition dissolved in a solvent is applied to the surface of at least one material layer C selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic, and the field-polymerized resin composition is coated on the surface. A method for producing a material with a primer, which comprises polymerizing a material to form the in-situ polymerization type resin composition layer C.