JP6967953B2 - Etching agent for roughening the surface of a base material whose surface is at least all or part of aluminum or an aluminum alloy, a method for producing a roughened base material, a roughened base material, a base material-a cured resin product. Manufacturing method of the bonded body and the bonded body of the base material-resin cured product - Google Patents

Description

The present invention is an etching agent for roughening the surface of a base material (hereinafter, also referred to as "aluminum-containing base material") in which at least all or part of the surface is made of aluminum or an aluminum alloy. The present invention relates to a method for producing a base material, a roughened base material, a method for producing a base material-cured resin product joint, and a base material-cured resin product joint.

Injection molding joining, adhesive joining, etc. are being studied for joining technology between metal and resin.

For example, in Patent Document 1, an aluminum component is used with an alkaline etching agent containing an amphoteric metal ion, an oxidizing agent, and an alkaline source, or at least one of ferrous and ferric copper ions, and an acid etching agent containing an acid. A method for producing an aluminum-resin composite, which comprises a step of roughening the surface of the above, is disclosed.

Further, Patent Document 2 includes an aluminum / resin injection integral molding including a step of etching an aluminum shaped body made of an aluminum alloy with an etching solution consisting of an aqueous hydrochloric acid solution or an aqueous solution of phosphoric acid containing a halogen ion concentration in a specific range. The manufacturing method of the product is disclosed.

Japanese Unexamined Patent Publication No. 2013-52671 Japanese Unexamined Patent Publication No. 2013-177004

In the base material-resin cured product bonded body described in Patent Documents 1 and 2, the bonding strength between the base material and the resin may be insufficient. Therefore, there is a demand for a base material-resin cured product bonded body in which the base material and the resin are firmly bonded. Therefore, an object of the present invention is to provide an etching agent or the like capable of forming a rough surface having excellent bonding strength with a resin on an aluminum-containing base material.

As a result of diligent studies to solve the above problems, the present inventors have brought the aluminum-containing substrate into contact with an etching agent containing peroxodisulfate ion and chloride ion, whereby the crude material has excellent bonding strength with the resin. We have found that a surface can be formed, and have completed the present invention.

That is, the present invention
(1) An etching agent for roughening the surface of a base material whose surface is at least wholly or partially made of aluminum or an aluminum alloy, and which contains at least peroxodisulfate ion and chloride ion.
(2) A method for producing a roughened base material, which comprises an etching step of bringing the etching agent according to (1) into contact with the surface or surface of a base material having at least all or part of the surface made of aluminum or an aluminum alloy. ..
(3) The method for producing a roughened substrate according to (2), which comprises a zincate step of forming a zincate film on the surface of the substrate before the etching step.
(4) The roughened base material obtained by the method for producing a roughened base material according to (2) or (3).
(5) An etching step in which the etching agent according to (1) is brought into contact with the surface or surface of a base material whose surface is at least all or partly made of aluminum or an aluminum alloy, and the etching agent is brought into contact with the base. A method for producing a substrate-resin cured product bonded body, which comprises a step of putting a resin composition into a recess formed by roughening the material.
(6) The method for producing a substrate-resin cured product bonded body according to (5), which comprises a gincate step of forming a gincate film on the surface of the substrate before the etching step.
(7) A base material-resin cured product bonded body obtained by the production method according to (5) or (6). Consists of.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an etching agent or the like capable of forming a rough surface having excellent bonding strength with a resin on an aluminum-containing base material.

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

≪Etching agent≫
The etching agent according to the embodiment of the present invention is an aqueous solution containing at least peroxodisulfate ion and chloride ion. The surface of the base material can be roughened by bringing the etching agent into contact with the surface or the surface of the aluminum-containing base material. The etching agent is prepared by dissolving a peroxodisulfate compound and a chlorine compound in water. Elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the substrate may be present in the etching agent. Further, an element such as zinc may be mixed by dissolving the film formed in the zincating step described later.

Etching agent in accordance with an embodiment of the present invention comprises a peroxodisulfate ion (S 2 O 8 2-). As the peroxodisulfate ion source, for example, one or more suitable peroxodisulfate compounds can be selected from peroxodisulfate compounds such as sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate, but the present invention is limited thereto. It is not something that will be done. The etching agent according to the embodiment of the present invention preferably contains peroxodisulfate ion of 0.02 mol / L or more and 0.90 mol / L or less, more preferably 0.10 mol / L or more and 0.50 mol / L or less, and further preferably. Includes 0.15 mol / L or more and 0.40 mol / L or less.

The etching agent according to the embodiment of the present invention ^{contains chloride ion (Cl −} ). As the chloride ion source, for example, one or more suitable chloride compounds can be selected from chlorine compounds such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, and ammonium chloride, but the chloride ion source is limited to these. It's not a thing. However, it is preferable not to use chlorides of transition metals such as iron chloride. Further, it is preferable not to use hydrochloric acid because it may generate mist, which may damage the health of workers and corrode surrounding metallic parts and devices. The etching agent according to the embodiment of the present invention preferably contains chloride ions of 0.40 mol / L or more and 2.50 mol / L or less, more preferably 0.80 mol / L or more and 2.00 mol / L or less, and further preferably 1. Includes .20 mol / L or more and 1.70 mol / L or less.
The etching agent according to the embodiment of the present invention may be substantially free of phosphoric acid. Substantially not included means that it is below the detection limit.
The pH of the etching agent according to the embodiment of the present invention is preferably in the range of 6.0 or less, and more preferably in the range of 2.0 to 4.0.
The pH of the etching agent is not limited to commercially available pH measuring instruments and electrodes, and can be measured using these. Also, use a pH measuring device and a device whose electrodes have a temperature compensation function.
If the internal solution of the pH electrode and the commercially available pH standard solution are adjusted to the same temperature as the etching agent and the pH measuring device is calibrated, the pH at the temperature at which the etching agent or the like is used can be measured. can.

<< Manufacturing method of roughened base material and base material-Manufacturing method of bonded resin cured product >>
The method for producing a roughened base material according to an embodiment of the present invention includes an etching step of contacting the surface or surface of the base material with an etching agent containing at least peroxodisulfate ion and chloride ion. Further, in the method for producing a substrate-resin cured product bonded body according to an embodiment of the present invention, the etching step and the dent formed by contacting the etching agent to roughen the substrate are formed. Includes a step of adding the resin composition. It was formed by roughening the surface or surface of the roughened base material obtained by the method for producing a roughened base material according to the embodiment of the present invention, such as injection molding bonding or adhesive bonding. By performing the step of putting the resin composition in the dent (also referred to simply as the step of putting the resin composition in the dent), the base material and the resin composition can be firmly bonded. Further, in both the method for producing a roughened substrate and the method for producing a substrate-resin cured product bonded body according to the embodiment of the present invention, a zincate film is formed on the surface of the substrate before the etching step is performed. It is preferable to carry out a zincating step to form the above. In addition, in the method for producing a roughened base material and the method for producing a substrate-resin cured product bonded body according to the embodiment of the present invention, other steps may be present. Examples of the other steps include a surface cleaning step of cleaning the surface of the base material before each step. Further, after performing the etching step, and before performing the step of putting the resin composition into the recess, a post-treatment step of forming a film may be performed. Each step may be repeated if necessary.

The method for producing a roughened base material according to an embodiment of the present invention may include an etching step and other optional steps described later as exemplified below. Step of degreasing the base material (arbitrary) → step of alkaline washing the base material (arbitrary) → step of pickling the base material (arbitrary) → ginkating step (arbitrary) → etching process. The order of the steps of alkaline washing the base material and pickling the base material may be reversed, and may contain only one of them, or may not contain either of them.
The method for producing a substrate-resin cured product bonded body according to an embodiment of the present invention includes an etching step, a step of inserting the resin composition into a recess, and any other steps described below as exemplified below. But it may be. Step of degreasing the base material (arbitrary) → Step of alkaline washing treatment of the base material (arbitrary) → Step of pickling the base material (arbitrary) → Ginkating process (arbitrary) → Etching process → Post-treatment process (arbitrary) → The process of putting the resin composition into the dent. The order of the steps of alkaline washing the base material and pickling the base material may be reversed, and may contain only one of them, or may not contain either of them.
Hereinafter, the base material and each process will be described in detail.

<Base material>
The base material applied to the embodiment of the present invention is not particularly limited as long as the base material has at least all or part of the surface made of aluminum or an aluminum alloy. The base material contains a casting material and a die casting material, and may be heat-treated. Further, the base material may be subjected to other processing and / or other processing, and may be subjected to processing such as cutting, grinding, blasting, polishing (wrapping), and drilling. Further, in addition to the plate material, the shape of the base material such as rods, bands, pipes, wires, foils, cast and forged products, bearings, etc. is not particularly limited. The base material may be a molded product or a material before molding. Further, the entire or part of the surface of the base material may be a film of aluminum or an aluminum alloy, and the method for forming the film includes, for example, a plating method, a thermal spraying method, and the like, but is not limited thereto. If all or part of the surface of the base material is aluminum or an aluminum alloy, the portion other than the surface of the base material may be a material other than aluminum or an aluminum alloy, for example, a metal other than aluminum or an aluminum alloy. Examples thereof include, but are not limited to, resins, rubbers, woods, ceramics, and composite materials. Examples of alloy components other than aluminum in the aluminum alloy include magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc.

<Ginkating process>
As a pretreatment for the etching step, a zincate step of forming a zincate film on the surface of the base material may be performed. As the zincating step, a known step can be used as long as it is a zincating step for aluminum. In the zincating step, for example, a sodium hydroxide aqueous solution in which zinc oxide is dissolved is used, the bath temperature is maintained at 40.0 ° C. or lower, and the substrate is immersed for about 1.0 second to 5.0 minutes for natural oxidation. A zinc oxide film can be formed at the same time as the film is removed. Further, the operation of dissolving the formed film with the etching agent or nitric acid and forming the film again may be performed once or more. In addition to the essential components, the treatment liquid used in these zincating steps may contain metals such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper and zinc derived from the substrate. ..
The pH of the treatment liquid used in the zincating step is not limited as long as it is within a known range. For example, in the case of a treatment liquid showing a pH on the alkaline side, it may be 10.0 or more, and may be 13.0 or more. May be good. It is preferably in the range of 11.0 to 13.0. To adjust the pH of the zincate solution, sodium hydroxide or potassium hydroxide can be used to raise the pH.

<Etching process>
In the method for producing a roughened base material and the method for producing a substrate-resin cured product bonded body according to an embodiment of the present invention, an etching step of bringing the etching agent into contact with the surface or the surface of the base material is indispensable. be. The etching agent preferably has a liquid temperature of 10.0 to 70.0 ° C. The base material is brought into contact with this etching agent, for example, by immersing it. When the method for producing a roughened substrate and the method for producing a substrate-resin cured product bonded body according to an embodiment of the present invention include a zincating step, the etching agent is brought into contact with the substrate after the zincating step. The contact time varies depending on the liquid temperature and pH, but is, for example, in the range of 1.0 second to 3600.0 seconds. The temperature of the etching step is preferably 5.0 to 70.0 ° C, more preferably 20.0 to 40.0 ° C.

<Other processes>
(Surface cleaning process)
The production method according to the embodiment of the present invention may include a surface cleaning step of cleaning the surface of the base material in advance before performing all the steps. For example, as an example of the surface cleaning step, a step of degreasing the surface of the base material can be mentioned. The method of degreasing treatment is not particularly limited, and examples thereof include a method using a solvent-based, water-based or emulsion-based degreasing agent. Here, the degreasing agent may contain an alkaline salt, a surfactant and the like. The time of the degreasing treatment step is preferably 0.5 to 30.0 minutes. The temperature of the step of degreasing treatment is preferably 30.0 to 70.0 ° C. Further, as an example of the surface cleaning step, a step of alkaline washing the surface of the base material can be mentioned. Known chemicals can be applied as the chemicals used in the alkaline washing treatment. After the degreasing treatment step, an alkaline washing treatment step may be performed.
The time of the alkaline washing process is preferably 0.5 to 30.0 minutes. The temperature of the alkaline washing process is preferably 30.0 to 70.0 ° C. Further, as an example of the surface cleaning step, a step of pickling the surface of the base material can be mentioned. As the chemical used in the pickling treatment, known agents can be applied. After the degreasing treatment step, a pickling treatment step may be performed. The time of the pickling treatment step is preferably 0.5 to 30.0 minutes. The temperature of the pickling step is preferably 30.0 to 70.0 ° C.

(Post-treatment process)
After the etching step by the manufacturing method according to the embodiment of the present invention, a film may be formed on the surface of the base material. The method of forming the film may be a coating type or a reaction type, and examples of the film to be formed include an alumite film, a chemical conversion film (phosphate film, chromate film, silicate film, lithium chemical conversion film, and calcium chemical formation). (Film, zirconium oxide film, etc.), silane coupling agent cured film, plating film, etc., but are not limited thereto.

(Other processing processes)
In addition to the above-mentioned steps, other steps may be appropriately performed as needed. For example, the water washing step may be performed after all the steps {all steps such as various treatments (for example, surface cleaning step and zincating step), etching step, post-treatment step, etc. performed before the etching step}. Further, a drying step may be appropriately performed after each step.

<Step of putting the resin composition into the dent formed by roughening the base material>
A resin composition is formed in the dents of the roughened base material formed by roughening the surface of the base material after obtaining the roughened base material through an etching step of bringing the etching agent into contact with the surface or the surface of the base material. It is a process to put in. Examples of the resin composition include thermoplastic resins and adhesives described later. As an example of the step of putting the resin composition into the recess of the roughened base material, injection molding or adhesive bonding can be mentioned.
Examples of injection molding include insert molding and outsert molding. When performing insert molding, it is preferable to prepare a mold, insert the aluminum alloy into the injection molding mold, inject the resin composition, and when the mold is released as it is, it is already joined and integrated. By putting the resin composition into the recess formed by roughening the base material by injection molding, the base material and the resin can be firmly bonded to each other. Hereinafter, this method may be referred to as injection molding joining. In addition, there may be a film formed in the zincate step or a film formed in the post-treatment step on the surface or the surface of the rough surface. The resin constituting the resin composition mainly used for injection molding may be a thermoplastic resin or a thermosetting resin, for example, polyvinyl resin, polyalkylene resin, polystyrene resin, acrylonitrile, butadiene, and styrene. Polymerized resin, acrylonitrile / styrene copolymer resin, polyacrylic resin, polyalkylene terephthalate resin, polyalkylene naphthalate resin, polyoxyalkylene resin, polyamide resin, polyimide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyphenylene One or two suitable ones or two from sulfide resin, polyarylate resin, liquid crystal polymer, syndiotactic polystyrene resin, phenol resin, epoxy resin, urea resin, melamine resin, alkyd resin, polyurethane resin, silicon resin, fluororesin, etc. The above can be selected, but the present invention is not limited to these. Further, the resin may contain a filler, and is suitable from, for example, glass fiber, carbon fiber, metal fiber, ceramic fiber, glass bead, carbon powder, metal powder, ceramic powder, aluminum oxide powder, pigment and the like. One type or two or more types can be selected, but the present invention is not limited thereto.

As a method of joining the adhesive, for example, an adhesive as a resin composition is applied to the rough surface, the adhesive is put into the dent of the roughened base material, and then the mating material is bonded to apply the adhesive. Examples thereof include a mode in which the bonding is performed by curing. At this time, by putting the adhesive in the recess formed by roughening the base material, it is possible to firmly bond the base material and the adhesive. The mating material may be any material including not only resin materials but also metals, rubbers, woods, ceramics and composite materials. Further, the shape of the mating material is not particularly limited, and may be a plate, a rod, a band, a tube, a wire, a film or the like. The adhesives include, for example, vinyl chloride resin adhesives, vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyacrylic adhesives, polyamide adhesives, cellulose adhesives, α-olefin adhesives, and water-based adhesives. Polymer-isocyanate adhesive, cyanoacrylate adhesive, urea resin adhesive, melamine resin adhesive, phenol resin adhesive, resorcinol resin adhesive, epoxy resin adhesive, silicon resin adhesive, Polyester adhesives, polyurethane adhesives, polyaromatic adhesives, chloroprene rubber adhesives, nitrile rubber adhesives, styrene / butadiene rubber adhesives, polysulfide adhesives, butyl rubber adhesives, silicon rubber adhesives One or two or more suitable adhesives can be selected from adhesives, acrylic rubber adhesives, urethane rubber adhesives, etc., but the present invention is not limited thereto.

The substrate-resin cured product bonded body according to the embodiment of the present invention may be composed of only the roughened base material and the cured product of the resin composition, or the roughened group. In addition to the cured product of the material and the resin composition, it may contain a mating material that comes into contact with the cured product. After the step of putting the resin composition into the recess of the roughened base material formed by roughening the resin composition, if the resin composition is a thermoplastic resin composition, it is cooled by cooling. If the resin composition is an adhesive, it can be cured by being left or heated to form a substrate-resin cured product bond.

<< Use of roughened base material and base material-bonded body of cured resin according to the embodiment of the present invention >>
A laminating process for forming one layer or two or more laminated layers may be performed on the surface or the surface of the roughened base material obtained by the method for producing a roughened base material according to the embodiment of the present invention. The roughened base material is useful as a material for heat dissipation members and sliding members. The base material-resin cured product bonded body obtained by the method for producing a base material-resin cured product bonded body according to an embodiment of the present invention is a member for an automobile, a member for an aircraft, a member for an electronic device, or a member for a mobile device. It is useful as a member for OA equipment, a member for home electric appliances, and a member for medical equipment. The bonded body of the roughened base material and the base material-cured resin product obtained by the production method of the embodiment of the present invention is not limited to the above applications.

Hereinafter, the present invention and its effects will be specifically described with reference to Examples with Comparative Examples. The base material used in the examples and the chemicals used for all the treatments are arbitrarily selected from commercially available materials and reagents, and do not limit the actual use of the present invention.

≪Manufacturing of bonded body of base material-cured resin product≫
<Base material>
There is no particular notice in the production of the base material-resin cured product bonded body by injection molding bonding and the base material-resin cured product bonded body by adhesive bonding according to Examples 1 to 13 and Comparative Examples 1 to 12. As long as the base material was 20 mm × 45 mm × t1.5 mm, an aluminum material or an aluminum alloy material was used.

<Manufacturing method of base material-residue cured product>
Unless otherwise specified, the substrate-resin cured product bonded bodies according to Examples 1 to 13 and Comparative Examples 1 to 4 are [surface cleaning step → gincate step → etching step → injection molding joining step and adhesive joining step. It was manufactured through the processing step of [one of the steps].
The substrate-resin cured product conjugate according to Comparative Examples 5 to 12 was produced through the same treatment steps as described above except that the zincating step was not included.
Hereinafter, each process of the process will be described.

(Surface cleaning process)
In the surface cleaning step, after alkaline degreasing {Fine Cleaner 315E Nippon Parkering Co., Ltd., 30 g / L (solid content concentration), 70 ° C., immersion time 1 minute}, alkaline washing (sodium hydroxide 100 g / L, 50 ° C., Soaking time 1 minute) was carried out, and washing with water was carried out after each step. In Examples 11, 12, and 13, after alkaline washing (sodium hydroxide 2.5 mol / L, 50 ° C., immersion time 1 minute), further pickling (55% by weight hydrofluoric acid: 60% by weight). Nitric acid = 1: 9 (mass ratio), 25 ° C., immersion time 30 seconds) was carried out.

(Ginkating process)
In the zinge step, the base material was immersed in the zinge liquid.

(Etching process)
In the etching step, the substrate was immersed in the etching agent. Regarding the pH adjustment of the etching agent, the pH was lowered by using an aqueous hydrochloric acid solution and the pH was raised by using an aqueous sodium hydroxide solution.

(Injection molding joining process)
In the injection molding joining step, polyphenylene sulfide (PPS resin) containing 30% of glass fiber as a resin composition was injection molded and bonded to the base material that had undergone the steps up to the etching step. An electric servo injection molding machine (Si-50III) manufactured by Toyo Machinery Metals Co., Ltd. was used for injection molding. The injection molding conditions were preheat 125 ° C., molding temperature 320 ° C., mold temperature 135 ° C., injection speed 30 mm / sec, injection pressure 1000 kgf, holding pressure 1200 kgf, and cooling time 15 seconds. The molded substrate-resin cured product has a size of 10 mm × 45 mm × t3 mm. The bonding area with the base material is 10 mm × 5 mm.

(Adhesive joining process)
In the adhesive bonding step, the epoxy adhesive AR-S30 manufactured by Nichiban Co., Ltd., which contains 10% of glass beads BZ-02 manufactured by AS ONE Co., Ltd., is applied to the two base materials that have undergone the steps up to the etching step. , Joined. The bonding area of the two substrates is 10 mm × 20 mm.

Hereinafter, based on the above-mentioned base material and process, a base material-resin cured product bonded body according to Examples 1 to 13 and Comparative Examples 1 to 12 was produced. The procedures and the like in Examples and Comparative Examples will be described below.

[Example 1]
(Examples and Comparative Examples Using a Base Material Made of A5052)
As the base material, A5052 specified by JIS H4000 was used. No zincating process was performed. As the etching step, the substrate was immersed for 480 seconds using the following etching agent (1). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 1] were obtained.
Etching agent (1)
<Ingredients>
・ Water ・ Sodium peroxodisulfate: 0.35 mol / L
-Sodium chloride: 1.70 mol / L
<pH>
3.0

[Example 2]
A substrate-resin cured product bonded body was produced in the same manner as in [Example 1] except that the zinge step was carried out. Specifically, as the ginking step, the substrate was immersed for 30 seconds using the following ginking solution. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 2] were obtained. The pH of the zincate solution was adjusted to 12.5 by using an aqueous hydrochloric acid solution.
Zincate liquid <ingredients>
-Water / zinc oxide: 0.25 mol / L
-Sodium hydroxide: 3.80 mol / L
-Tartaric acid: 0.07 mol / L
<pH>
12.5
<Temperature of ginkgo process>
40.0 ℃

[Example 3]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 480 seconds using the following etching agent (2). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 3] were obtained.
Etching agent (2)
<Ingredients>
・ Water ・ Potassium persulfate: 0.30 mol / L
-Potassium chloride: 1.40 mol / L
<pH>
3.0

[Example 4]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 480 seconds using the following etching agent (3). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 4] were obtained.
Etching agent (3)
<Ingredients>
・ Water ・ Ammonium peroxodisulfate: 0.36 mol / L
-Sodium chloride: 1.70 mol / L
<pH>
3.0

[Example 5]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 480 seconds using the etching agent (4) in Table 1. In this way, the base material-resin cured product bonded body by injection molding bonding and the base material-base material bonded body by adhesive bonding according to [Example 5] were obtained.
Etching agent (4)
<Ingredients>
・ Water ・ Sodium peroxodisulfate: 0.35 mol / L
-Calcium chloride: 0.90 mol / L
<pH>
3.0

[Comparative Example 1]
A substrate-resin cured product bonded body was obtained in the same manner as in [Example 2] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 480 seconds using the following etching agent (5). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 1] were obtained.
Etching agent (5)
<Ingredients>
・ Water ・ Sodium peroxodisulfate: 0.35 mol / L
<pH>
3.0

[Comparative Example 2]
A substrate-resin cured product bonded body was obtained in the same manner as in [Example 2] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 480 seconds using the following etching agent (6). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 2] were obtained.
Etching agent (6)
<Ingredients>
・ Water ・ Sodium chloride: 1.70 mol / L
<pH>
3.0

[Comparative Example 3]
A substrate-resin cured product bonded body was obtained in the same manner as in [Example 1] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 300 seconds using the following etching agent (7). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 3] were obtained.
Etching agent (7)
<Ingredients>
-Water / phosphoric acid: 5.10 mol / L
-Sodium chloride: 0.85 mol / L
<pH>
1.0

[Comparative Example 4]
A substrate-resin cured product bonded body was obtained in the same manner as in [Example 1] except that the etching process was changed. Specifically, as an etching step, the substrate was immersed for 300 seconds using the following etching agent (8). In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 4] were obtained.
Etching agent (8)
<Ingredients>
・ Water / sulfuric acid: 0.50 mol / L
-Sodium chloride: 1.70 mol / L
<pH>
1.0

[Tension shear test]
The tensile shear strength of the joints of the base material-cured resin product obtained by injection molding bonding and the base material-cured resin product formed by adhesive bonding in Examples 1 to 5 and Comparative Examples 1 to 4 was measured. The tensile shear test was performed using an autograph precision universal testing machine (AG-100kNX) manufactured by Shimadzu Corporation. The tensile speed was 10 mm / min, and the tensile shear strength (MPa) was calculated as the ^{fracture load (N) / joint area (50 mm 2).} The results are shown in Table 1.

(Examples and Comparative Examples Using Other Base Materials Made of Aluminum or Aluminum Alloy) [Example 6]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, A1050 standardized by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 6] were obtained.

[Example 7]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, A2017 specified by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 7] were obtained.

[Example 8]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, A3003 standardized by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 8] were obtained.

[Example 9]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, A4032 specified by JIS H4140 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 9] were obtained.

[Example 10]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, A6063 specified by JIS H4040 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 10] were obtained.

[Example 11]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, A7075 specified by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 11] were obtained.

[Example 12]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, AC8A specified by JIS H5202 was used as the base material. In this way, [Example 12]
A bonded body of a base material-cured resin product by injection molding bonding and a bonded body of a base material-cured resin product by adhesive bonding were obtained.

[Example 13]
A base material-resin cured product bonded body was produced in the same manner as in [Example 2] except that the base material was changed. Specifically, ADC12 standardized by JIS H5302 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Example 13] were obtained.

[Comparative Example 5]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, A1050 standardized by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 5] were obtained.

[Comparative Example 6]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, A2017 specified by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 6] were obtained.

[Comparative Example 7]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, A3003 standardized by JIS H4000 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 7] were obtained.

[Comparative Example 8]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, A4032 specified by JIS H4140 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 8] were obtained.

[Comparative Example 9]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, A6063 specified by JIS H4040 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 9] were obtained.

[Comparative Example 10]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, A7075 specified by JIS H4000 was used as the base material. In this way, the bonded body of the base material-cured resin product by injection molding bonding and the bonded body of the base material-cured resin product by adhesive bonding according to [Comparative Example 10] were obtained.

[Comparative Example 11]
A base material-resin cured product bonded body was produced in the same manner as in [Comparative Example 4] except that the base material was changed. Specifically, AC8A specified by JIS H5202 was used as the base material. In this way, a substrate-resin cured product bonded body by injection molding bonding and a base material-resin cured product bonded body by adhesive bonding according to [Comparative Example 11] were obtained.

[Comparative Example 12]
A bonded body of the base material-cured resin product of [Comparative Example 12] was produced by the same method as in [Comparative Example 4] except that the base material was changed. Specifically, ADC12 was used as a base material. In this way, a base material-cured resin product bonded body and a base material-base material bonded body according to [Comparative Example 12] were obtained.

The tensile shear strength was measured for the base material-resin cured product bonded body by injection molding bonding and the base material-resin cured product bonded body by adhesive bonding in Examples 6 to 13 and Comparative Examples 5 to 12. The results are shown in Table 3.

Claims (7)

An etching agent for roughening the surface of a base material whose surface is at least all or partly made of aluminum or an aluminum alloy.
Etching agents containing at least peroxodisulfate ions and chloride ions (excluding etching agents containing iron chloride and etching agents containing hydrochloric acid) . A method for producing a roughened base material, which comprises an etching step of bringing the etching agent according to claim 1 into contact with the surface or surface of a base material having at least all or part of the surface made of aluminum or an aluminum alloy. The method for producing a roughened base material according to claim 2, further comprising a ginkate step of forming a gincate film on the surface of the base material before the etching step. A roughened base material obtained by the method for producing a roughened base material according to claim 2 or 3. On the surface or surface of a substrate of which at least all or part of the surface is made of aluminum or an aluminum alloy.
The etching step of contacting the etching agent according to claim 1 and
A step of putting the resin composition into the recess formed by bringing the etching agent into contact and roughening the base material, and
A method for producing a substrate-resin cured product bonded body, which comprises. The method for producing a substrate-resin cured product bonded body according to claim 5, further comprising a zincating step of forming a zincate film on the surface of the substrate before the etching step. A substrate-resin cured product bonded body obtained by the production method according to claim 5 or 6.