JPWO2021100339A1 - Composite laminates and joints - Google Patents

Abstract

A composite laminate having a material layer consisting of at least one selected from the group consisting of fiber-reinforced plastics, glass, and ceramics, and one or a plurality of resin coating layers laminated on the material layer, wherein the resin is used. At least one of the coating layers is a modified polyolefin layer formed of a resin composition containing a modified polyolefin, and the modified polyolefin layer is a reaction between a maleic anhydride-modified polyolefin, a bifunctional epoxy resin and a bifunctional phenol compound. A composite laminate that is at least one selected from a layer containing a substance 1, a layer containing a reaction product 2 of a maleic anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin. body.

Description

The present invention comprises a composite laminate capable of bonding at least one material selected from the group consisting of fiber reinforced plastics, glass and ceramics to polyolefins with high strength, a method for producing the same, and joining the materials and polyolefins. The present invention relates to a bonded body and a method for producing the same.

In the electronic device industry and the automobile industry, technological evolution is further progressing, and the needs for materials are diversifying and becoming more sophisticated. In order to maximize the performance of products and realize multiple functions at the same time, it is indispensable to have a multi-material structure in which different materials (hereinafter referred to as different materials) are arranged in the right place. The multi-material structure is formed by joining dissimilar materials, and various joining techniques such as melt welding and bonding are being studied as the joining means.
Regarding the multi-material structure, for example, in smartphones, the entire surface is vitrified, and there is a demand for a technique for joining glass and a highly transparent resin such as polycarbonate by insert molding or the like.

As a method for joining glass and resin, a pellet-shaped engineering plastic is provided with an adhesive strength improving agent to the glass, and then the engineering plastic is melt-bonded to the glass by heating and melting the engineering plastic in contact with the glass. (Patent Document 1) is disclosed. In automobiles, there are scenes where FRP (fiber reinforced plastic) and resin are joined, and there is a demand for technology for firmly joining FRP and resin. Insulators such as insulating containers molded with resin using ceramic as an insert material are often used in power equipment, and there is a demand for a technique for firmly joining ceramic and resin.

Conventionally, when dissimilar materials are directly bonded to each other, there is a problem that stress is concentrated on the interface due to the difference in heat shrinkage between the materials, which causes cracks and peeling.
In relation to this problem, in the resin mold structure of the insulating container, a technique for preventing the occurrence of cracks at the internal interface of the resin mold structure by applying a silane coupling agent between the ceramic and the resin to perform interfacial treatment is available. It is disclosed (Non-Patent Document 1).

Ceramics used for the insulating container, in order to prevent contamination, it is often used in glazed vitreous _{(SiO 2 -10% Al 2 O} 3) on the surface thereof. Therefore, in the resin mold structure, the interface between the glaze on the ceramic surface and the resin is slippery.
In Non-Patent Document 1, paying attention to the above points, the adhesive strength of the internal interface of the resin mold structure is improved by the interface treatment with a silane coupling agent.

Japanese Unexamined Patent Publication No. 2006-297662

Proceedings of the Japan Society of Mechanical Engineers (Vol. A) Vol. 77, No. 774 (2011-2)

However, in the prior art, there is a problem that sufficient bonding strength cannot be realized between glass and resin in applications such as automobile parts and OA equipment.
Further, in the technique of Patent Document 1, it is necessary to reduce the upper limit of the injection pressure to about 60 MPa at the maximum as a measure against glass breakage during insert molding, and the problem that the injection pressure cannot be sufficiently increased and the demand for improvement of durability are met. There is a problem that it is difficult to respond. Further, the technique of Non-Patent Document 1 cannot solve the problem that stress is concentrated on the resin end of the interface due to the difference in heat shrinkage between the materials, and it is difficult to further improve the joint strength and durability.

The present invention has been made in view of such technical background, and is a composite suitable for applications in which at least one material selected from the group consisting of fiber reinforced plastics, glass and ceramics and polyolefins are firmly bonded to each other. An object of the present invention is to provide a laminate and its related technology. The related technology means a method for producing the composite laminate, a bonded body obtained by bonding the material and a polyolefin, and a method for producing the same.

The present invention provides the following means for achieving the above object.
In the present specification, joining means connecting objects to each other, and adhesion and welding are subordinate concepts thereof. Adhesion means that two adherends (those to be bonded) are put into a bonded state via an organic material (thermosetting resin, thermoplastic resin, etc.) such as tape or adhesive. However, welding means that the surface of a thermoplastic resin or the like, which is an adherend, is melted by heat, and entangled by molecular diffusion and crystallized by contact pressurization and cooling to form a bonded state.

[1] A composite laminate having a material layer made of at least one selected from the group consisting of fiber-reinforced plastics, glass and ceramics, and one or a plurality of resin coating layers laminated on the material layer. At least one layer of the resin coating layer is a modified polyolefin layer formed of a resin composition containing a modified polyolefin, and the modified polyolefin layer is a maleic anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenol compound. It is at least one selected from a layer containing the reaction product 1 of the above, a layer containing the reaction product 2 of the maleic anhydride-modified polyolefin and the thermoplastic epoxy resin, and a layer containing a mixture of the polyolefin and the thermoplastic epoxy resin. Composite laminate.
[2] The composite laminate according to [1], wherein the reaction product 1 is obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in a solution containing a maleic anhydride-modified polyolefin.
[3] The composite according to [1], wherein the reaction product 2 is formed by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. Laminated body.
[4] The composite laminate according to [1], wherein the mixture is a mixture of polypropylene and a thermoplastic epoxy resin.
[5] A resin composition in which the resin coating layer is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and at least one layer other than the modified polyolefin layer contains a thermoplastic epoxy resin. Any one of [1] to [4], which is at least one selected from a thermoplastic epoxy resin layer formed of a thermoplastic epoxy resin layer and a thermoplastic resin layer formed of a resin composition containing a thermosetting resin. The composite laminate described.
[6] The composite laminate according to [5], 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.
[7] A functional group-containing layer laminated in contact with the material layer and the resin coating layer is provided between the material layer and the resin coating layer.
The composite laminate according to any one of [1] to [6], wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3) A mercapto group derived from a silane coupling agent has an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group. A functional group obtained by reacting at least one selected from the group consisting of a compound and a compound having a (meth) acryloyl group and an amino group. (4) A thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent. (5) An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound
[8] The surface of the material layer is subjected to at least one pretreatment selected from the group consisting of degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and corona discharge treatment. [1] ] To the composite laminate according to any one of [7].

[9] The method for producing a composite laminate according to any one of [1] to [8], wherein the composite laminate has the material layer and the resin coating layer between the material layer and the resin coating layer. It has a functional group-containing layer laminated in contact with a resin coating layer, and the functional group-containing layer is at least one selected from the group consisting of the following (1') to (7') on the surface of the material layer. A method for producing a composite laminate, which is prepared by using.
(1') 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 (2') At least one selected from an epoxy compound and a thiol compound. And a combination of a silane coupling agent having an amino group (3') from an epoxy compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and an epoxy group, and a compound having a (meth) acryloyl group and an amino group. Combination of at least one selected from the group and a silane coupling agent having a mercapto group (4') Combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') Amino group and (meth) ) A combination of at least one selected from the group consisting of a compound having an acryloyl group, an amino compound, and a thiol compound and a silane coupling agent having an epoxy group (6') isocyanate compound (7') thiol compound.
[10] The method for producing a composite laminate according to [9], wherein the treatment is at least one selected from the following (2 ″) to (5 ″).
(2'') Treatment to add at least one selected from an epoxy compound and a thiol compound after treatment with a silane coupling agent having an amino group (3'') After treatment with 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 a treatment for adding at least one selected from the group consisting of a compound having a (meth) acryloyl group and an amino group (4'). ') Treatment to add a thiol compound after treatment with a silane coupling agent having a (meth) acryloyl group (5'') After treatment with a silane coupling agent having an epoxy group, amino groups and (meth) acryloyl groups Treatment to add at least one selected from the group consisting of a compound having, an amino compound, and a thiol compound.
[11] When the functional group-containing layer is formed before the resin coating layer is formed, the material layer is subjected to degreasing treatment, UV ozone treatment, blasting treatment, polishing treatment, etc. before forming the functional group-containing layer. The method for producing a composite laminate according to [9] or [10], wherein at least one pretreatment selected from the group consisting of plasma treatment and corona discharge treatment is performed.

[12] A bonded body in which the surface of the composite laminate according to any one of [1] to [8] on the resin coating layer side and the polyolefin are bonded and integrated.
[13] The method for producing a bonded body according to [12], at least one 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 producing a bonded body, wherein the polyolefin is welded to the surface of the composite laminate on the resin coating layer side.
[14] The method for producing a bonded body according to [12], wherein the polyolefin is welded to the surface of the composite laminate on the resin coating layer side by an injection molding method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composite laminate suitable for use in firmly bonding a polyolefin and at least one material selected from the group consisting of fiber reinforced plastics, glass and ceramics, and related techniques thereof. ..

It is explanatory drawing which shows the structure of the composite laminated body in one Embodiment of this invention. It is explanatory drawing which shows the structure of the composite laminated body in other embodiment of this invention. It is explanatory drawing which shows the structure of the bonded body in one Embodiment of this invention.

The composite laminate of the embodiment of the present invention and related techniques thereof will be described in detail.
In addition, in this specification, the term "(meth) acryloyl group" means an acryloyl group and / or a methacryloyl group. Similarly, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means acrylate and / or methacrylate.

[Composite laminate]
As shown in FIG. 1, the composite laminate 1 of the present embodiment is laminated on the material layer 2 composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), glass and ceramic. It is a composite laminate having one layer or a plurality of layers of a resin coating layer 3. At least one layer of the resin coating layer 3 is a modified polyolefin layer 31 formed of a resin composition containing a modified polyolefin.

<Material layer 2>
The form of the material layer 2 is not particularly limited, and may be in the form of a lump or a film.
The fiber reinforced plastic (FRP), glass, and ceramic constituting the material layer 2 are not particularly limited.
As fiber reinforced plastic (FRP), glass fiber reinforced plastic with improved strength by combining various fibers with thermosetting resin such as urethane resin, epoxy resin, vinyl ester resin, unsaturated polyester, polyamide resin, and phenol resin. (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), aramid fiber reinforced plastic (AFRP), and the like. Molds from glass fiber and carbon fiber SMC (sheet molding compound) can also be mentioned.
Examples of the glass include soda-lime glass, lead glass, borosilicate glass, quartz glass and the like.
Examples of the ceramic include oxide-based ceramics such as alumina, zirconia and barium titanate, hydroxide-based ceramics such as hydroxyapatite, carbide-based ceramics such as silicon carbide, and nitride-based ceramics such as silicon nitride.

In the material layer 2, the thickness of the glass is preferably 0.3 mm or more, more preferably 0.5 mm or more, from the viewpoint of strength. The upper limit of the thickness of the glass is not particularly limited, but is preferably 30 mm or less, more preferably 10 mm or less.
Further, in the material layer 2, the thickness of the FRP and the ceramic is preferably 1.0 mm or more, more preferably 2.0 mm or more, respectively, from the viewpoint of strength. The upper limit of the thickness of the FRP and the ceramic is not particularly limited, but is preferably 20 mm or less, more preferably 15 mm or less.

Before laminating the resin coating layer 3 on the material layer 2, it is preferable to pretreat the surface of the material layer 2 for the purpose of removing contaminants on the surface and / or an anchor effect. By the pretreatment, as shown in FIG. 1, fine irregularities 21 can be formed on the surface of the material layer 2 to roughen the surface. This makes it possible to improve the adhesiveness between the surface of the material layer 2 and the resin coating layer 3.

Examples of the pretreatment include degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment, corona discharge treatment, laser treatment, etching treatment, frame treatment and the like.
As the pretreatment, a pretreatment for cleaning the surface of the material layer 2 or a pretreatment for making the surface uneven is preferable, and specifically, a degreasing treatment, a UV ozone treatment, a blast treatment, a polishing treatment, a plasma treatment and a corona discharge treatment are preferable. At least one selected from the group consisting of is preferable.
The pretreatment may be performed with only one type or two or more types. As a specific method of these pretreatments, a known method can be used.
Normally, hydroxyl groups derived from resin or reinforcing material are present on the surface of FRP, and it is considered that hydroxyl groups are originally present on the surface of glass or ceramic. However, new hydroxyl groups are generated by the above pretreatment, and the material layer 2 The number of hydroxyl groups on the surface can be increased.

The degreasing treatment is a method of removing stains such as oils and fats on the surface of the material layer by dissolving them with an organic solvent such as acetone and toluene.

The UV and ozone treatment, with a force of ozone (O ₃₎ generated energy and thereby having a short wavelength ultraviolet ray emitted from a low-pressure mercury lamp, a process for modifying or cleaning the surface. In the case of glass, it is one of the surface cleaning methods for removing organic impurities on the surface. Generally, a cleaning surface reforming device using a low-pressure mercury lamp is called a "UV ozone cleaner", a "UV cleaning device", an "ultraviolet surface modifying device" or the like.

Examples of the blasting treatment include wet blasting treatment, shot blasting treatment, sandblasting treatment and the like. Above all, the wet blast treatment is preferable because a finer surface can be obtained as compared with the drive last treatment.

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

The plasma treatment is to create a plasma beam with a high-voltage power supply and a rod and hit it against the surface of the material to excite molecules to create a functional state. Be done.

The corona discharge treatment includes a method applied to surface modification of a polymer film, and a radical generated by cleaving a polymer main chain or a side chain of a polymer surface layer by electrons emitted from an electrode is used as a starting point. This is a method of generating a hydroxyl group or a polar group on the surface.

The laser treatment is a technique for rapidly heating and cooling 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 chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method. Can be mentioned.

The frame treatment is a method of converting oxygen in the air into plasma by burning a mixed gas of combustion gas and air, and applying oxygen plasma to the object to be treated to make the surface hydrophilic. Known frame processing techniques can be used.

<Resin coating layer 3>
[Modified polyolefin layer 31]
At least one layer of the resin coating layer is a modified polyolefin layer 31 formed of a resin composition containing a modified polyolefin.

By laminating such a predetermined resin coating layer on the material layer, the composite laminate of the present embodiment can exhibit excellent adhesiveness to polyolefin.

The resin coating layer is composed of a plurality of layers including the modified polyolefin layer 31 and a layer other than the modified polyolefin layer, and the layer other than the modified polyolefin layer is formed from a resin composition containing a thermoplastic epoxy resin. It may be at least one selected from the thermosetting resin layer 33 formed from the resin composition containing the plastic epoxy resin layer 32 and the thermosetting resin.

When the resin coating layer is composed of a plurality of layers, it is preferable that the essential modified polyolefin layer 31 is laminated so as to be the outermost surface on the opposite side to the material layer.

The modified polyolefin layer 31 is obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a maleic anhydride-modified polyolefin and at the same time reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton. A reaction product obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a layer containing the reaction product 1 and maleic anhydride in a maleic anhydride-modified polyolefin skeleton. It is preferably at least one selected from the group consisting of a layer containing 2 and a layer containing a mixture of a thermoplastic epoxy resin and a polyolefin.

(Reactant 1)
The reaction product 1 can be obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a catalyst in a solution of maleic anhydride-modified polyolefin. At this time, the maleic anhydride-modified polyolefin also reacts with the bifunctional epoxy resin, the bifunctional phenol compound, and the thermoplastic epoxy resin produced from the bifunctional epoxy resin and the bifunctional phenol compound described later in the section of the reactant 2. Conceivable.

(Maleic anhydride-modified polyolefin)
Examples of the maleic anhydride-modified polyolefin include maleic anhydride-modified polyolefin obtained by grafting maleic anhydride on the polyolefin, maleic anhydride-modified polyethylene, and maleic anhydride-modified polypropylene. Kayaku Akzo Corporation's Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW, Mitsubishi Chemical Corporation's Modic series and the like.
Further, SCONA TPPP2112GA, TPPP8112GA, and TPPP9212GA manufactured by BYK may be used in combination as a polypropylene additive functionalized with maleic anhydride.

(Bifunctional epoxy resin)
Examples of the bifunctional epoxy resin include bisphenol type epoxy resin and biphenyl type epoxy resin. 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) 1007" and "jER (registered trademark) YX-4000".

(Bifunctional phenol compound)
Examples of the bifunctional phenol compound include bisphenol and biphenol. Of these, one type may be used alone, or two or more types may be used in combination.
Examples of these combinations include bisphenol A type epoxy resin and bisphenol A, bisphenol A type epoxy resin and bisphenol F, biphenyl type epoxy resin and 4,4'-biphenol and the like. Further, for example, a combination of "WPE190" and "EX-991L" manufactured by Nagase ChemteX Corporation can be mentioned.

As the catalyst for the double addition reaction of the thermoplastic epoxy resin, for example, tertiary amines such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; phosphorus compounds such as triphenylphosphine are preferably used. Used.

(Reactant 2)
The reaction product 2 can be obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. As the maleic anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenol compound used in this reaction, the same compounds as those used for producing the reactant 1 can be used.

(Thermoplastic epoxy resin)
The thermoplastic epoxy resin used for producing the reaction product 2 is a resin also called a field-polymerized phenoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and includes a bifunctional epoxy resin and a bifunctional phenol compound. By the double addition reaction in the presence of a catalyst, a thermoplastic structure, that is, a linear polymer structure is formed. The thermoplastic epoxy resin has thermoplasticity unlike the thermosetting resin that constitutes a three-dimensional network with a crosslinked structure.

The total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in producing the reaction product 1 and the reaction product 2 shall be 5 to 100 parts by mass when the maleic anhydride-modified polyolefin is 100 parts by mass. Is more preferable, 5 to 60 parts by mass is more preferable, and 10 to 30 parts by mass is further preferable.

The reaction that occurs when the reaction product 1 and the reaction product 2 are obtained is a reaction between a maleic anhydride-modified polyolefin and a bifunctional epoxy resin, a reaction between a maleic anhydride-modified polyolefin and a bifunctional phenol compound, and maleic anhydride. A wide variety of reactions such as the reaction of epoxy connecting acids, the reaction of the epoxy group at the end of the thermoplastic epoxy resin with maleic anhydride, and the reaction of the secondary hydroxyl group in the frame of the thermoplastic epoxy resin with maleic anhydride. It is also not possible to comprehensively express the specific aspect based on this. Therefore, it can be said that it is impossible or impractical to directly specify the modified polyolefin obtained as the reactant 1 and the reactant 2 by the structure or property.

The mixture of the thermoplastic epoxy resin and the polyolefin can be obtained by mixing the same thermoplastic epoxy resin as that used in the production of the above-mentioned reaction product 2 with the polyolefin by a conventional method.

(Polyolefin)
As the polyolefin used for forming the mixture, the polyolefin used as the object to be bonded can be used as it is. The polyolefin is not particularly limited, and may be a general synthetic resin. For example, polyethylene, polypropylene and the like.

The resin coating layer is laminated on the surface of the material layer. As described above, the resin coating layer may be laminated on the surface of the material layer that has not been pretreated, or may be laminated on the surface of the material layer that has been pretreated. Alternatively, it may be laminated on the surface of the functional group-containing layer described later.

[Thermoplastic epoxy resin layer 32]
The resin coating layer 3 is composed of a plurality of layers of the modified polyolefin layer and other layers, and at least one layer other than the modified polyolefin layer is formed of a resin composition containing a thermoplastic epoxy resin. It can be composed of the thermoplastic epoxy resin layer 32.
The resin composition containing the thermoplastic epoxy resin preferably contains 40% by mass or more of the thermoplastic epoxy resin, and more preferably 70% by mass or more.

(Thermoplastic epoxy resin)
Similar to the thermoplastic epoxy resin used for producing the reactant 2, the thermoplastic epoxy resin has a thermoplastic structure by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to undergo a crosslink reaction in the presence of a catalyst. That is, it is a resin that forms a linear polymer structure, and has thermoplasticity unlike a thermosetting resin that constitutes a three-dimensional network with a crosslinked structure.
Since the thermoplastic epoxy resin has such characteristics, the thermoplastic epoxy resin layer 32 has excellent adhesion to the material layer and excellent adhesion to the modified polyolefin layer 31 by in-situ polymerization. Can be formed.

Therefore, when producing a composite laminate, it is preferable to form the thermoplastic epoxy resin layer 32 by subjecting a composition containing a monomer of the thermoplastic epoxy resin to a double addition reaction on the surface of the lower layer.
It is preferable that the heavy addition reaction of the composition containing the monomer of the thermoplastic epoxy resin is carried out as a lower layer on the surface of the functional group-containing layer described later. The resin coating layer 3 including the thermoplastic epoxy resin layer formed in such an embodiment is excellent in adhesiveness to the material layer and also excellent in adhesiveness to the object to be bonded, which will be described later.

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

In the composition containing the monomer of the thermoplastic epoxy resin, a solvent and, if necessary, a colorant and the like are added in order to sufficiently proceed the double addition reaction of the thermoplastic epoxy resin and form a desired resin coating layer. It may contain an agent. In this case, it is preferable that the monomer of the thermoplastic epoxy resin is the main component among the components other than the solvent of the composition. The main component means that the content of the thermoplastic epoxy resin is 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.

The monomer for obtaining the thermoplastic epoxy resin is preferably a combination of a bifunctional epoxy resin and a bifunctional phenolic compound.

The heavy addition reaction is preferably carried out by heating at 120 to 200 ° C. for 5 to 90 minutes, although it depends on the type of the reaction compound and the like. Specifically, the thermoplastic epoxy resin layer can be formed by coating the resin composition, volatilizing a solvent as appropriate, and then heating to carry out a double addition reaction.

[Thermosetting resin layer 33]
The resin coating layer 3 is composed of a plurality of layers including the modified polyolefin layer, and a layer other than the modified polyolefin layer is composed of a thermosetting resin layer 33 formed of a resin composition containing a thermosetting resin. You can also do it.

In the resin composition containing the thermosetting resin, a solvent and, if necessary, a coloring agent and the like are added in order to sufficiently proceed the curing reaction of the thermosetting resin and form a desired resin coating layer. It may contain an agent. 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 to 100% by mass. The content is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.

Examples of the thermosetting resin include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.

The thermosetting resin layer 33 may be formed by one of these resins alone, or may be formed by mixing two or more of them. Alternatively, the thermosetting resin layer 33 may be composed of a plurality of layers, and each layer may be formed of a resin composition containing different types of thermosetting resins.

The coating method for forming the thermosetting resin layer 33 with the composition containing the monomer of the thermosetting resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.

The thermosetting resin referred to in this embodiment broadly means a resin that is cross-linked and cured, and is not limited to the heat-curing type, but also includes a room temperature curing type and a photocuring type. Here, in the present specification, the normal temperature refers to 5 to 35 ° C, preferably 15 to 25 ° C.
The photo-curing type can be cured in a short time by irradiation 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 10 wt% or more of a vehicle non-volatile component polyisocyanate". The urethane resin corresponding to the above is preferable. The urethane resin may be a one-component type or a two-component type.

Examples of the one-component urethane resin include oil-modified type (cured by oxidative polymerization of unsaturated fatty acid group), moisture-curable type (cured by reaction between isocyanato group and water in air), and block type (cured by reaction between isocyanato group and water in air). Examples thereof include a lacquer type (a type in which a solvent is volatilized and cured by drying), a lacquer type (a type in which a blocking agent is dissociated by heating and regenerated, and a hydroxyl group reacts with each other to be cured). 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 group 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.
Examples of the isocyanate compound having an isocyanato group in the polyol-cured type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimerate diisocyanate; 2,4- or 2,6-tolylene diisocyanate. (TDI) or a mixture thereof, p-phenylenediisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and aromatic isocyanates such as polypeptide MDI which is a polynuclear mixture thereof; alicyclic isocyanates such as isophorone diisocyanate (IPDI) and the like. Will be.
The compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in the molar equivalent ratio of the hydroxyl group / isocyanato group.

Examples of the urethanization catalyst used in the two-component urethane resin include triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and other amine-based catalysts; dibutyltindi Examples thereof include organic tin-based catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimalate.
In the polyol curing type, it is generally preferable 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, novolak-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, "Karensu MT (registered trademark) PE1" manufactured by Showa Denko KK) is preferable from the viewpoint of elongation rate 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 be used. In addition, specifically, "Lipoxy (registered trademark) R-802", "Lipoxy (registered trademark) R-804", "Lipoxy (registered trademark) R-806" 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 "Ripoxy (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, pers. Examples thereof include oxygen peroxides. 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 between a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is used. ) 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. Also, 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.

The resin coating layer is formed on the surface of the material layer with excellent adhesiveness, and exhibits excellent adhesiveness with polyolefin. Further, the surface of the material layer is protected, and the adhesion of dirt on the surface of the material layer can be suppressed.

Therefore, the resin coating layer can impart excellent bondability between the material layer and the polyolefin to be bonded. Further, it is possible to obtain a composite laminate capable of maintaining a state in which excellent adhesiveness can be obtained for a long period of several months while the surface of the material layer is protected as described above.

As described above, the resin coating layer has an effect of imparting excellent bondability to the polyolefin to be bonded to the material layer. It can be said that the resin coating layer is a primer layer of the composite laminate.
The primer layer referred to here is a material that is interposed between the material layer and the bonding target when the material layer is bonded and integrated with a bonding target such as a resin material, for example, as in the case of a bonded body described later. It shall mean a layer that improves the adhesiveness of the layer to the object to be joined.

<Functional group-containing layer 4>
As shown in FIG. 2, between the material layer 2 and the resin coating layer 3, a one-layer or a plurality of functional group-containing layers 4 laminated in contact with the material layer 2 and the resin coating layer 3 are provided. You can also do it.
When the functional group-containing layer is provided, the functional group formed by the functional group reacting with the hydroxyl group on the surface of the material layer and the functional group of the resin constituting the resin coating layer, respectively, forms a chemical bond. It is possible to obtain the effect of improving the adhesiveness between the surface of the material layer and the resin coating layer, and also to contribute to the improvement of the bondability with the bonding target.

"process"
The functional group-containing layer 4 is preferably formed by treating the surface of the material layer 2 with at least one selected from the group consisting of the following (1') to (7'). Is more preferably at least one selected from the following (2 ″) to (5 ″).
(1') Silane coupling agent containing at least one functional group selected from the group consisting of an epoxy group, an amino group, a (meth) aquiloyl group and a mercapto group (2') At least one selected from an epoxy compound and a thiol compound. Combination of seed and silane coupling agent with amino group (3') Epoxy compound, amino compound, isocyanate compound, compound with (meth) acryloyl group and epoxy group, and compound with (meth) acryloyl group and amino group. Combination of at least one selected from the group consisting of a silane coupling agent having a mercapto group (4') and a combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') Amino group and ( Meta) A combination of at least one selected from the group consisting of a compound having an acryloyl group, an amino compound and a thiol compound and a silane coupling agent having an epoxy group (6') isocyanate compound (7') thiol compound.

(2'') Treatment to add at least one selected from an epoxy compound and a thiol compound after treatment with a silane coupling agent having an amino group (3'') After treatment with 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 a treatment for adding at least one selected from the group consisting of a compound having a (meth) acryloyl group and an amino group (4'). ') Treatment to add a thiol compound after treatment with a silane coupling agent having a (meth) acryloyl group (5'') After treatment with a silane coupling agent having an epoxy group, amino groups and (meth) acryloyl groups Treatment to add at least one selected from the group consisting of a compound having, an amino compound, and a thiol compound.

《Functional group》
The functional group-containing layer 4 preferably contains the functional group introduced by the above treatment, and specifically, preferably contains at least one functional group selected from the group consisting of the following (1) to (7). ..
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3) A mercapto group derived from a silane coupling agent has an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group. A functional group obtained by reacting at least one selected from the group consisting of a compound and a compound having a (meth) acryloyl group and an amino group. (4) A thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent. (5) An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound

Before forming the functional group-containing layer 4 in the material layer, the surface of the material layer can be pretreated. As the pretreatment, at least one selected from the group consisting of degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and corona discharge treatment is preferable.
By applying the pretreatment, the anchor effect due to the fine unevenness and the functional groups of the functional group-containing layer are the hydroxyl groups on the surface of the material layer and the functional groups of the resin constituting the resin coating layer 3. By the synergistic effect with the chemical bond formed by the reaction, the adhesiveness between the surface of the material layer and the resin coating layer and the bondability with the bonding target can be improved.

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

〔Silane coupling agent〕
As the silane coupling agent, for example, a known one used for surface treatment of glass fiber or the like can be used. A silanol group generated by hydrolyzing a silane coupling agent or a silanol group obtained by oligomerizing the silanol group reacts with a hydroxyl group existing on the surface of the material layer 2 and bonds to the resin coating layer 3 to be chemically bonded. A functional group based on the structure of the silane coupling agent can be imparted (introduced) to the material layer.

The silane coupling agent is not particularly limited, but is a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having a (meth) acryloyl group, and the like. Can be used. Examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Examples thereof include 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be mentioned. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and dithioltriazinepropyltriethoxysilane. 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. Further, as other effective silane coupling agents, silane coupling agents having a vinyl group such as 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane, 3-. Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, Tris- (Trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, and the like. These may be used alone or in combination of two or more.

[Isocyanate compound]
The isocyanate compound is a functional group based on the structure of the isocyanate compound which can be chemically bonded to the resin coating layer 3 by reacting and bonding the isocyanato group in the isocyanate compound with the hydroxyl group existing on the surface of the material layer 2. Can be imparted (introduced) to the material layer.

The isocyanate compound is not particularly limited, and is, for example, other than polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI). , 2-Isocyanate ethyl methacrylate (for example, "Karensu MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.), 2-isocyanate ethyl acrylate (for example, "Karenzu 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. Will be.

[Thiol compound]
The thiol compound is based on the structure of the thiol compound which can be chemically bonded to a resin coating layer or a bonding target by reacting and bonding a mercapto group in the thiol compound with a hydroxyl group existing on the surface of the material layer 2. Functional groups can be imparted (introduced) to the material layer.

The thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Corporation and "QE-340M" manufactured by Toray Fine Chemicals Co., Ltd. ”), Ether-based first-class thiols (for example,“ Cup Cure 3-800 ”manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example,“ Karenz MT ”manufactured by Showa Denko KK). (Registered trademark) BD1 ”), Pentaerythritol tetrakis (3-mercaptobutylate) (for example,“ Karens 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.

[Joint 5]
As shown in FIG. 3, in the bonded body 5 of the present embodiment, as described above, the resin coating layer 3 of the composite laminate 1 has the surface on the primer layer side and the polyolefin 6 bonded and integrated as a primer layer. It is a plasticized one.

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 when the bonding target is not a film, a viewpoint of obtaining excellent bonding strength with the bonding target. From the viewpoint of suppressing the concentration of stress on the resin end of the interface due to the difference in heat shrinkage between the materials, the thickness is preferably 1 μm to 10 mm. It is more preferably 20 μm to 3 mm, and even more preferably 40 μm to 1 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.
When the object to be bonded is a film, the thickness of the primer layer (thickness after drying) is preferably 0.1 μm to 1 mm, more preferably 0.1 μm to 100 μm.

The polyolefin in the bonded body is not particularly limited, and may be a general synthetic resin. For example, polyethylene, polypropylene and the like.
Polypropylene is generally a highly rigid homopolymer obtained by polymerizing only propylene, a highly transparent and flexible random polymer copolymerized with a small amount of ethylene, and a resistance to which the rubber component (EPR) is uniformly and finely dispersed in the homo-random polymer. It is classified as a block copolymer having high impact resistance, but any of them may be used. Further, a type containing talc, glass fiber and carbon fiber may be used to increase the strength. The product containing talc is manufactured by Sun Aromar, trade name TRC104N, the product containing glass fiber is manufactured by Daicel Polymer Co., Ltd., and the product name is PP-GF40-01 F02. -CF40-11 F008 and the like.

As a method for producing the bonded body, a composite laminate and a molded body of the resin material separately produced can be bonded and integrated.
Further, the resin material can be molded by injection molding, press molding, transfer molding or the like, and at the same time, the surface of the composite laminate on the primer layer side and the resin material can be joined and integrated. Specifically, 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 on the surface of the composite laminate on the primer layer side. Then, a method of welding the polyolefin and a method of injection welding the polyolefin to the surface of the composite laminate on the primer layer side can be mentioned.

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

<Manufacturing example 1>
Maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g and xylene: 95 g were placed in a flask and dissolved by raising the temperature to 125 ° C. with stirring. Next, a bifunctional epoxy resin (jER® 1001: bisphenol A and epichlorohydrin polycondensate manufactured by Mitsubishi Chemical Co., Ltd.): 1.01 g, bisphenol A: 0.24 g, 2,4,6- Tris (dimethylaminomethyl) phenol: 0.006 g was put into a flask, stirred at 125 ° C. for 30 minutes, and modified with a thermoplastic epoxy resin, a bifunctional epoxy resin, and a bifunctional phenol compound. Maleic anhydride-modified polypropylene: modified. Obtained PP-1.

<Manufacturing example 2>
Maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g and xylene: 95 g were placed in a flask and dissolved by raising the temperature to 125 ° C. with stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1004 manufactured by Mitsubishi Chemical Co., Ltd.): 0.49 g, bisphenol A: 0.06 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.003 g. It was put into a flask and stirred at 125 ° C. for 30 minutes to obtain a maleic anhydride-modified polypropylene modified with a thermoplastic epoxy resin, a bifunctional epoxy resin, and a bifunctional phenol compound: modified PP-2.

<Manufacturing example 3>
Talc-containing polypropylene (TRC104N manufactured by SunAllomer Ltd.): 5 g and xylene: 95 g were placed in a flask and dissolved by raising the temperature to 125 ° C. with stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Co., Ltd.): 1.01 g, bisphenol A: 0.24 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.006 g. It was put into a flask and stirred at 125 ° C. for 30 minutes to obtain a mixture of thermoplastic epoxy resin (20% by mass) and polypropylene: modified PP-3.

<Manufacturing example 4>
Fill the flask with xylene: 95 g, bifunctional epoxy resin (jER1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.20 g, bisphenol A: 0.066 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.003 g. The mixture was stirred at 125 ° C. for 30 minutes and reacted to obtain a thermoplastic epoxy resin solution. Next, 5 g of maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g was put into a flask and dissolved, and the maleic anhydride-modified polypropylene modified with a thermoplastic epoxy resin (20% by mass): Modified PP-4 was obtained.

<Example 1-1>
(Pretreatment process)
The surface of a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm × 45 mm and a thickness of 1.2 mm was degreased with acetone.

(Functional group-containing layer forming step)
Next, the glass substrate after the acetone degreasing treatment was prepared by dissolving 2 g of 3-aminopropyltrimethoxysilane (“KBM-903” manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) in 1000 g of industrial ethanol at 70 ° C. After immersing in the silane coupling agent-containing solution of silane for 20 minutes, the glass substrate was taken out and dried to form a functional group-containing layer on the surface of the glass substrate.

(Resin coating layer forming process)
Next, the modified PP-1 obtained in Production Example 1 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to thicken the surface of the functional group-containing layer. A composite laminate having a resin-coated layer of modified PP-1 having a thickness of 30 μm was produced.

<Example 1-2>
Polypropylene resin (PP resin) containing talc (TRC104N manufactured by Sun Aroma Co., Ltd.) (bonding target) was applied to the surface of the composite laminate produced in Example 1-1 on the resin coating layer side, and an injection molding machine (Sumitomo Heavy Industries, Ltd.) SE100V manufactured by the company; Cylinder temperature 200 ° C, tool temperature 30 ° C, injection speed 50 mm / sec, peak / holding pressure 60/55 [MPa / MPa]), by injection molding, a test piece for tensile test compliant with ISO19095. (PP resin, 10 mm × 45 mm × 3 mm, overlapping length of joint portion 5 mm, width 10 mm) (glass-polyolefin junction) was produced.

[Adhesion evaluation]
The test piece (glass-polyolefin conjugate) produced in Example 1-2 was left at room temperature (23 ° C.) for 1 day, and then subjected to a tensile tester (universal test manufactured by Shimadzu Corporation) in accordance with ISO19095 1-4. Machine autograph "AG-IS"; load cell 10 kN, tensile speed 10 mm / min, temperature 23 ° C., 50% RH) was used to perform a tensile shear joint strength test, and the joint strength was measured. The measurement results are shown in Table 1 below.

<Example 2-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate after the acetone degreasing treatment.

(Resin coating layer forming process: 1st layer)
A bifunctional epoxy resin (jER® 1001 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 24 g, and triethylamine: 0.4 g are dissolved in 250 g of acetone on the surface of the functional group-containing layer. The thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature (23 ° C) for 30 minutes, leave it in a furnace at 150 ° C for 30 minutes for a heavy addition reaction, and allow it to cool to room temperature (23 ° C). The first resin coating layer (thermoplastic epoxy resin layer 32) was formed.

(Resin coating layer forming process: second layer)
Next, the modified PP-2 obtained in Production Example 2 was applied to the surface of the thermoplastic epoxy resin layer to volatilize xylene and held at 150 ° C. for 30 minutes to apply the modified PP-2 to the surface of the thermoplastic epoxy resin layer. A composite laminate having a resin-coated layer (modified poreolefin layer 31) of modified PP-2 having a thickness of 30 μm was produced.

<Example 2-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 2-1 on the resin coating layer side of the second layer.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 3-1>
(Pretreatment process)
A glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm × 45 mm and a thickness of 1.2 mm was subjected to UV ozone treatment.

(Functional group-containing layer forming step)
Next, 0.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) was dissolved in 100 g of industrial ethanol in the UV ozone-treated glass substrate 70. After immersing in a silane coupling agent solution at ° C. for 5 minutes, the glass substrate was taken out and dried, and a functional group derived from the silane coupling agent was introduced on the surface of the glass substrate.
Further, a bifunctional thiol compound 1,4 bis (3-mercaptobutyryloxy) butane (Carens MT BD1 manufactured by Showa Denko KK): 0.6 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-) 30): After immersing 0.05 g in a solution of 0.05 g in 150 g of toluene at 70 ° C. for 10 minutes, the mixture was lifted and dried. In this way, two functional group-containing layers were formed.

(Resin coating layer forming process)
Next, the modified PP-3 obtained in Production Example 3 was applied to the surface of the functional group-containing layer of the glass substrate to volatilize xylene and held at 150 ° C. for 30 minutes to apply the modified PP-3 to the surface of the functional group-containing layer. A composite laminate having a resin-coated layer of modified PP-3 having a thickness of 30 μm was produced.

<Example 3-2>
The same operation as in Example 1-2 was carried out on the surface of the composite laminate prepared in Example 3-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 4-1>
(Pretreatment process)
A glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm × 45 mm and a thickness of 1.2 mm was subjected to wet blast treatment to form fine irregularities on the surface of the glass substrate.

(Resin coating layer forming process: 1st layer)
The same operation as in Example 2-1 was performed on the surface of the uneven surface to form the first resin coating layer (thermoplastic epoxy resin layer).

(Resin coating layer forming process: second layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 4-2>
The same operation as in Example 1-2 was carried out on the surface of the composite laminate prepared in Example 4-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Comparative Example 1-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

<Comparative Example 1-2>
The same injection molding operation as in Example 1-2 was performed without providing the functional group-containing layer and the resin coating layer on the surface of the glass substrate after the acetone degreasing treatment produced in Comparative Example 1-1, but the PP was described above. The resin did not adhere to the surface of the glass substrate, and a glass-polyolefin bonded body could not be produced.

<Comparative Example 2-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate after the acetone degreasing treatment.

(Resin coating layer forming process)
Next, a solution prepared by dissolving 5 g of maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation) in 95 g of xylene was applied to the surface of the functional group-containing layer to volatilize xylene, and 150 It was held at ° C. for 30 minutes to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 2-2>
The same operation as in Example 1-2 was carried out on the surface of the composite laminate prepared in Comparative Example 2-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 5-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, 2 g of 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) was dissolved in 1000 g of industrial ethanol in the glass substrate after the acetone degreasing treatment. After immersing in a silane coupling agent-containing solution at 70 ° C. for 20 minutes, the glass substrate was taken out and dried to form a functional group-containing layer on the surface of the glass substrate.

(Resin coating layer forming process)
Next, the modified PP-4 obtained in Production Example 4 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to thicken the surface of the functional group-containing layer. A composite laminate having a resin-coated layer of modified PP-4 having a thickness of 30 μm was produced.

<Example 5-2>
A polypropylene resin (PP resin) containing glass fibers (pp-GF40-01 F02 manufactured by Daicel Polymer Co., Ltd.) (to be bonded) was applied to the surface of the composite laminate produced in Example 5-1 on the resin coating layer side. A test piece for a tensile test was prepared by injection molding under the same conditions as in 1-2.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 6-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 5-1 was carried out to form a functional group-containing layer on the surface of the glass substrate after the acetone degreasing treatment.

(Resin coating layer forming process: 1st layer)
The same operation as in Example 2-1 was performed except that the epoxy resin was changed to jER® 1004 manufactured by Mitsubishi Chemical Co., Ltd. on the surface of the functional group-containing layer, and the first resin coating layer (thermoplastic) was performed. Epoxy resin layer) was formed.

(Resin coating layer forming process: second layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 30 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 6-2>
The same operation as in Example 5-2 was performed on the surface of the composite laminate prepared in Example 6-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 7-1>
(Pretreatment process)
Wet blasting was performed on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm × 45 mm and a thickness of 1.2 mm in the same manner as in Example 4-1. The unevenness was formed.

(Functional group-containing layer forming step)
Next, the same operation as in Example 3-1 was carried out on the glass substrate to form a functional group-containing layer.

(Resin coating layer forming process)
Next, the same operation as in Example 1-1 was carried out to prepare a composite laminate in which a resin-coated layer of modified PP-1 having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 7-2>
The same operation as in Example 5-2 was carried out on the surface of the composite laminate prepared in Example 7-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 8-1>
(Pretreatment process)
Wet blasting was performed on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm × 45 mm and a thickness of 1.2 mm in the same manner as in Example 4-1. The unevenness was formed.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate.

(Resin coating layer forming process: 1st layer)
The same operation as in Example 6-1 was performed to form the first resin coating layer (thermoplastic epoxy resin layer).

(Resin coating layer forming process: second layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 8-2>
The same operation as in Example 5-2 was carried out on the surface of the composite laminate prepared in Example 8-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Comparative Example 3-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

<Comparative Example 3-2>
The same injection molding operation as in Example 5-2 was performed without providing the functional group-containing layer and the resin coating layer on the surface of the glass substrate after the acetone degreasing treatment prepared in Comparative Example 3-1. The resin did not adhere to the surface of the glass substrate, and a glass-polyolefin bonded body could not be produced.

<Comparative Example 4-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate after the acetone degreasing treatment.

(Resin coating layer forming process)
Next, the same operation as in Comparative Example 2-1 was carried out to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 4-2>
The same operation as in Example 5-2 was carried out on the surface of the composite laminate prepared in Comparative Example 4-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 9-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate after the acetone degreasing treatment.

(Resin coating layer forming process)
Next, the same operation as in Example 5-1 was carried out to prepare a composite laminate in which a resin-coated layer of modified PP-4 having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 9-2>
A polypropylene resin (PP resin) containing carbon fibers (pp-GF40-01 F008 manufactured by Daicel Polymer Co., Ltd.) (to be bonded) was applied to the surface of the composite laminate produced in Example 9-1 on the resin coating layer side. A test piece for a tensile test was prepared by injection molding under the same conditions as in 1-2.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 10-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate after the acetone degreasing treatment.

(Resin coating layer forming process: 1st layer)
The same operation as in Example 2-1 was performed except that the epoxy resin was changed to jER® 1007 manufactured by Mitsubishi Chemical Co., Ltd. on the surface of the functional group-containing layer, and the first resin coating layer (thermoplastic) was performed. Epoxy resin layer) was formed.

(Resin coating layer forming process: second layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 30 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 10-2>
The same operation as in Example 9-2 was performed on the surface of the composite laminate prepared in Example 10-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 11-1>
(Pretreatment process)
The same operation as in Example 1-1 was carried out, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to introduce a functional group derived from a silane coupling agent onto the surface of the glass substrate after the acetone degreasing treatment.
Further, 2-isocyanate ethyl methacrylate (Showa Denko Corporation, Karens MOI (registered trademark)): 1.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g, and toluene 150 g. After immersing in the solution dissolved in the solution at 70 ° C. for 5 minutes, it was withdrawn and dried. In this way, a functional group-containing layer in which chemically bondable functional groups were extended in the three-dimensional direction was formed.

(Resin coating layer forming process)
Next, the same operation as in Example 1-1 was carried out to prepare a composite laminate in which a resin-coated layer of modified PP-1 having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 11-2>
The same operation as in Example 9-2 was performed on the surface of the composite laminate prepared in Example 11-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 12-1>
(Pretreatment process)
Wet blasting was performed on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm × 45 mm and a thickness of 1.2 mm in the same manner as in Example 4-1. The unevenness was formed.

(Functional group-containing layer forming step)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the glass substrate.

(Resin coating layer forming process: 1st layer)
Epoxy resin (jER® 1007 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 5.6 g, and triethylamine: 0.4 g are dissolved in 196 g of acetone on the surface of the functional group-containing layer. The thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature (23 ° C) for 30 minutes, leave it in a furnace at 150 ° C for 30 minutes for a heavy addition reaction, and allow it to cool to room temperature (23 ° C). The first resin coating layer (thermoplastic epoxy resin layer) was formed.

(Resin coating layer forming process: second layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 12-2>
The same operation as in Example 9-2 was performed on the surface of the composite laminate prepared in Example 12-1 on the resin coating layer side to prepare a test piece for a tensile test.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

[Material for test pieces]
The following materials were prepared as materials for test pieces.
(1) CFRP: CF-SMC Rigolac RCS-1000BK (CF: 50% by mass) manufactured by Showa Denko Corporation, pressure-molded at 140 ° C. for 5 minutes using a 1500 kN press. Dimensions: 18 mm x 45 mm x 1.5 mm.
(2) Ceramic: Kyocera Corporation thick film substrate (alumina). Dimensions: 18 mm x 45 mm x 1.5 mm.
(3) Polypropylene plate (PP plate): A PP plate of 10 mm × 45 mm × 3 mm for producing a test piece for a tensile test conforming to ISO19095 was molded by the molding method of Example 1-2.

<Example 13-1>
(Pretreatment process Wet blast treatment)
A CFRP having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the CFRP surface.

(Functional group-containing layer silane coupling agent treatment)
A silane coupling at 70 ° C. in which 2 g of 3-aminopropyltrimethoxysilane (“KBM-903” manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) was dissolved in 1000 g of industrial ethanol in the CFRP subjected to the wet blast treatment. After immersing in the agent-containing solution for 20 minutes, the CFRP was taken out and dried to form a functional group (amino group) -containing layer on the surface of the CFRP.

(Resin coating layer forming process)
Next, the modified PP-1 obtained in Production Example 1 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to have a thickness on the surface of the functional group-containing layer. A composite laminate on which a resin coating layer of modified PP-1 having a thickness of 30 μm was formed was prepared.

<Example 13-2: CFRP-polyolefin conjugate>
Next, with the CFRP resin coating layer surface and the PP plate overlapped so that the joints overlap and have a length of 5 mm and a width of 10 mm, the ultrasonic welder SONOPET-JII430T-M manufactured by Seidensha Electronics Co., Ltd. ( Specimen for tensile test according to ISO19095 of the same size as Example 1 by ultrasonic welding using 28.5 KHz): CFRP-PP junction (CFRP: 18 mm × 45 mm × 1.5 mm, PP: 10 mm × 45 mm × 3 mm, overlapping length of the joint portion: 5 mm, width 10 mm) was obtained.

[Tensile shear strength]
The prepared test piece (CFRP-polyolefin conjugate) was left at room temperature (23 ° C.) for 1 day, and then subjected to a tensile tester (Shimadzu Seisakusho Co., Ltd. universal tester Autograph "AG-" in accordance with ISO19095 1-4. IS ”; a tensile shear joint strength test was performed at a load cell of 10 kN, a tensile speed of 10 mm / min, a temperature of 23 ° C., and 50% RH), and the joint strength was measured. The measurement results are shown in Table 4 below.

<Example 14-1>
(Pretreatment process Wet blast treatment)
A CFRP having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the CFRP surface.

(Functional group-containing layer silane coupling agent treatment)
Next, the same operation as in Example 13-1 was carried out to form a functional group (amino group) -containing layer on the CFRP surface after the wet blast treatment.

(Resin coating layer forming process)
Next, the modified PP-2 obtained in Production Example 2 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to have a thickness on the surface of the functional group-containing layer. A composite laminate on which a resin coating layer of modified PP-2 having a thickness of 30 μm was formed was prepared.

<Example 14-2: CFRP-polyolefin conjugate>
Next, the same operation as in Example 13-2 was carried out, and the surface of the composite laminate prepared in Example 14-1 on the resin coating layer side and the PP plate were ultrasonically welded to prepare a test piece. The joint strength of the test piece was measured by the same method as in Example 13-2. The measurement results are shown in Table 4 below.

<Example 15-1>
(Pretreatment process Wet blast treatment)
Wet blasting was performed on a ceramic having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm in the same manner as in Example 4-1 to form fine irregularities on the surface of the ceramic.

(Functional group-containing layer silane coupling agent treatment)
Next, the same operation as in Example 13-1 was carried out to form a functional group (amino group) -containing layer on the ceramic surface after the wet blast treatment.

(Resin coating layer forming process)
Next, the modified PP-3 obtained in Production Example 3 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to have a thickness on the surface of the functional group-containing layer. A composite laminate on which a resin coating layer of modified PP-3 having a thickness of 30 μm was formed was prepared.

<Example 15-2: Ceramic-polyolefin conjugate>
Next, with the ceramic resin coating layer surface and the PP plate overlapped so that the joints overlap and have a length of 5 mm and a width of 10 mm, the ultrasonic welder SONOPET-JII430T-M manufactured by Seidensha Electronics Co., Ltd. ( Specimen for tensile test compliant with ISO1909 by ultrasonic welding using 28.5 KHz): Ceramic-PP junction (ceramic: 18 mm × 45 mm × 1.5 mm, PP: 10 mm × 45 mm × 3 mm, overlapping length of the joint portion: 5 mm, width 10 mm) was obtained. The joint strength of the test piece was measured by the same method as in Example 13-2. The measurement results are shown in Table 4 below.

<Example 16-1>
(Pretreatment process Wet blast treatment)
Wet blasting was performed on a ceramic having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm in the same manner as in Example 4-1 to form fine irregularities on the surface of the ceramic.

(Functional group-containing layer silane coupling agent treatment)
Next, the same operation as in Example 13-1 was carried out to form a functional group (amino group) -containing layer on the ceramic surface after the wet blast treatment.

(Resin coating layer forming process)
Next, the modified PP-4 obtained in Production Example 4 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to have a thickness on the surface of the functional group-containing layer. A composite laminate on which a resin coating layer of modified PP-4 having a thickness of 30 μm was formed was prepared.

<Example 16-2: Ceramic-polyolefin conjugate>
Next, the same operation as in Example 13-2 was carried out, and the surface of the composite laminate prepared in Example 16-1 on the resin coating layer side and the PP plate were ultrasonically welded to prepare a test piece. The joint strength of the test piece was measured by the same method as in Example 13-2. The measurement results are shown in Table 4 below.

<Comparative Example 5-1>
(Pretreatment process Wet blast treatment)
A CFRP having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the CFRP surface.

(Functional group-containing layer silane coupling agent treatment)
Next, the same operation as in Example 13-1 was carried out to form a functional group (amino group) -containing layer on the CFRP surface after the wet blast treatment.

(Resin coating layer forming process)
Next, the same operation as in Comparative Example 2-1 was carried out to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 5-2>
The same operation as in Example 13-2 was carried out, and the surface of the composite laminate prepared in Comparative Example 5-1 on the resin coating layer side and the PP plate were ultrasonically welded to prepare a test piece. The joint strength of the test piece was measured by the same method as in Example 13-2. The measurement results are shown in Table 4 below.

<Comparative Example 6-1>
(Pretreatment process Wet blast treatment)
A wet blast treatment was performed on a ceramic having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm in the same manner as in Example 4-1 to form fine irregularities on the surface of the ceramic.

(Functional group-containing layer silane coupling agent treatment)
Next, the same operation as in Example 13-1 was carried out to form a functional group (amino group) -containing layer on the ceramic surface after the wet blast treatment.

(Resin coating layer forming process)
Next, the same operation as in Comparative Example 2-1 was carried out to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 6-2>
The same operation as in Example 13-2 was carried out, and the surface of the composite laminate prepared in Comparative Example 6-1 on the resin coating layer side and the PP plate were ultrasonically welded to prepare a test piece. The joint strength of the test piece was measured by the same method as in Example 13-2. The measurement results are shown in Table 4 below.

The composite laminate according to the present invention is bonded and integrated with a polyolefin, 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, and a power control unit. (PCU) Automotive parts such as housings, electric compressor members (inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) spacers, battery cases, LED headlamps, etc. , A smartphone, a laptop computer, a tablet computer, 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.

1 Composite laminate 2 Material layer 21 Fine unevenness 3 Resin coating layer (primer layer)
31 Modified polyolefin layer 32 Thermoplastic epoxy resin layer 33 Thermosetting resin layer 4 Functional group-containing layer 5 Bonded body 6 Polyolefin

Claims (14)

A composite laminate having a material layer made of at least one selected from the group consisting of fiber reinforced plastics, glass and ceramics, and one or a plurality of resin coating layers laminated on the material layer.
At least one layer of the resin coating layer is a modified polyolefin layer formed of a resin composition containing a modified polyolefin.
The modified polyolefin layer includes a layer containing a reaction product 1 of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin and a bifunctional phenol compound, a layer containing a reaction product 2 of a maleic anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer containing the reaction product 2. A composite laminate, which is at least one selected from a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin. The composite laminate according to claim 1, wherein the reaction product 1 is formed by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in a solution containing maleic anhydride-modified polyolefin. The composite laminate according to claim 1, wherein the reaction product 2 is formed by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. The composite laminate according to claim 1, wherein the mixture is a mixture of polypropylene and a thermoplastic epoxy resin. The resin coating layer is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer.
At least one layer other than the modified polyolefin layer is a thermoplastic epoxy resin layer formed of a resin composition containing a thermoplastic epoxy resin and a thermosetting resin composed of a resin composition containing a thermosetting resin. The composite laminate according to any one of claims 1 to 4, which is at least one selected from the resin layer. The composite laminate according to claim 5, 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. A functional group-containing layer laminated in contact with the material layer and the resin coating layer is provided between the material layer and the resin coating layer.
The composite laminate according to any one of claims 1 to 6, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3) A mercapto group derived from a silane coupling agent has an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group. A functional group obtained by reacting at least one selected from the group consisting of a compound and a compound having a (meth) acryloyl group and an amino group. (4) A thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent. (5) An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound The surface of the material layer is subjected to at least one pretreatment selected from the group consisting of degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and corona discharge treatment, according to claims 1 to 7. The composite laminate according to any one of the above items. The method for producing a composite laminate according to any one of claims 1 to 8.
The composite laminate has a functional group-containing layer laminated between the material layer and the resin coating layer in contact with the material layer and the resin coating layer.
A method for producing a composite laminate, wherein the functional group-containing layer treats the surface of the material layer with at least one selected from the group consisting of the following (1') to (7').
(1') 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 (2') At least one selected from an epoxy compound and a thiol compound. And a combination of a silane coupling agent having an amino group (3') from an epoxy compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and an epoxy group, and a compound having a (meth) acryloyl group and an amino group. Combination of at least one selected from the group and a silane coupling agent having a mercapto group (4') Combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') Amino group and (meth) ) A combination of at least one selected from the group consisting of a compound having an acryloyl group, an amino compound, and a thiol compound and a silane coupling agent having an epoxy group (6') isocyanate compound (7') thiol compound. The method for producing a composite laminate according to claim 9, wherein the treatment is at least one selected from the following (2 ″) to (5 ″).
(2'') Treatment to add at least one selected from an epoxy compound and a thiol compound after treatment with a silane coupling agent having an amino group (3'') After treatment with 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 a treatment for adding at least one selected from the group consisting of a compound having a (meth) acryloyl group and an amino group (4'). ') Treatment to add a thiol compound after treatment with a silane coupling agent having a (meth) acryloyl group (5'') After treatment with a silane coupling agent having an epoxy group, amino groups and (meth) acryloyl groups Treatment to add at least one selected from the group consisting of a compound having, an amino compound, and a thiol compound. When the functional group-containing layer is formed before the resin coating layer is formed, the material layer is subjected to degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and plasma treatment before the functional group-containing layer is formed. The method for producing a composite laminate according to claim 9 or 10, wherein at least one pretreatment selected from the group consisting of corona discharge treatment is performed. A bonded body in which the surface of the composite laminate according to any one of claims 1 to 8 on the resin coating layer side and the polyolefin are bonded and integrated. The method for manufacturing a bonded body according to claim 12.
The polyolefin is applied to the surface of the composite laminate on the resin coating layer side 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 bonded body to be welded. The method for manufacturing a bonded body according to claim 12.
A method for producing a bonded body, in which the polyolefin is welded to the surface of the composite laminate on the resin coating layer side by an injection molding method.

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