JP2019099864A - Etching agent for roughening surface of base material, at least all or part of the surface composed of aluminum or aluminum alloy, method for producing roughened base material, roughened base material, method for producing joint of base material-resin cured product, and joint of base material-resin cured product - Google Patents

Abstract

To provide an etching agent that allows a rough surface having excellent joint strength with a resin to be formed on an aluminum-containing base material.SOLUTION: The present invention provides an etching agent for roughening a surface of a base material, at least all or part of the surface composed of aluminum or aluminum alloy, comprising at least peroxodisulfate ions and chloride ions.SELECTED DRAWING: None

Description

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

  Injection molding bonding, adhesive bonding, and the like have been studied as a bonding technology between metal and resin.

  For example, in Patent Document 1, the aluminum component is made of an alkaline etching agent containing an amphoteric metal ion, an oxidizing agent, and an alkali source, or an acid etching agent containing at least one of a ferric ion and a cupric ion, and an acid. A process for producing an aluminum-resin composite is disclosed which comprises the step of roughening the surface of

  Moreover, in patent document 2, aluminum / resin injection integral molding including the process of performing an etching process with the etching solution which consists of hydrochloric acid aqueous solution or phosphoric acid aqueous solution containing halogen ion concentration in a specific range with respect to the aluminum shaped object made of aluminum alloy A method of manufacturing an article is disclosed.

JP, 2013-52671, A JP, 2013-177004, A

  There are cases where the bonding strength between the base and the resin of the base-resin cured product described in Patent Documents 1 and 2 is insufficient. Therefore, there is a demand for a base-resin cured product in which the base and the resin are strongly bonded. Then, an object of this invention is to provide the etching agent etc. which can form the rough surface excellent in the joint strength with resin with respect to the aluminum containing base material.

  As a result of intensive studies to solve the above problems, the present inventors roughly contact the aluminum-containing substrate with an etching agent containing a peroxodisulfate ion and a chloride ion to obtain a rough bonding strength with the resin. It has been found that a surface can be formed, and the present invention has been completed.

That is, the present invention
(1) An etching agent for roughening the surface of a substrate at least the whole surface of which is partially or entirely made of aluminum or an aluminum alloy, the etching agent containing at least peroxodisulfate ion and chloride ion.
(2) A method for producing a roughened substrate, comprising an etching step in which the etching agent according to (1) is brought into contact with the surface or the surface of a substrate at least the whole surface of which is partially or partially aluminum or aluminum alloy. .
(3) The method for producing a roughened substrate according to (2), including a zincate step of forming a zincate film on the surface of the substrate before the etching step.
(4) A roughened substrate obtained by the method for producing a roughened substrate 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 the surface of a substrate at least the whole surface of which is partially or entirely made of aluminum or an aluminum alloy; And D. placing the resin composition in the depression formed by roughening the material.
(6) The manufacturing method of the conjugate | zygote of the base-resin cured | curing material as described in (5) including the zincate process which forms a zincate film | membrane in the surface of the said base material before the said etching process.
(7) A bonded substrate-resin cured product obtained by the method according to (5) or (6). It consists of

  ADVANTAGE OF THE INVENTION By this invention, the etching agent etc. which can form the rough surface which is excellent in the joint strength with resin with respect to an aluminum containing base material can be provided.

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

«Etchant»
The etching agent according to the embodiment of the present invention is an aqueous solution containing at least peroxodisulfate ion and chloride ion. The substrate can be roughened by bringing the etching agent into contact with the surface or surface of the aluminum-containing substrate. The etchant is prepared by dissolving a peroxodisulfuric acid compound and a chlorine compound in water. In the etching agent, an element such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, zinc or the like derived from the base material may be present. Moreover, elements, such as zinc, may be mixed by melt | dissolving the film | membrane formed at the zincate process mentioned later.

An etchant according to an embodiment of the present invention comprises peroxodisulfate ion (S ₂ O ₈ ²⁻ ). As a source of peroxodisulfate ion, for example, one or more suitable ones can be selected from peroxodisulfate compounds such as sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, etc. It is not something to be done. The etching agent according to the embodiment of the present invention is preferably 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, more preferably peroxodisulfate ion. Including 0.15 mol / L or more and 0.40 mol / L or less.

An etchant according to an embodiment of the present invention comprises chloride ion (Cl ⁻ ). As a chloride ion source, for example, one or more suitable ones can be selected from chlorine compounds such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, ammonium chloride and the like, but are limited thereto It is not a thing. However, it is preferable not to use a chloride of a transition metal such as iron chloride. In addition, it is preferable not to use hydrochloric acid because it may generate mist, which may cause health damage to workers and may corrode surrounding metal parts and devices. The etching agent according to the embodiment of the present invention preferably has a chloride ion 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, still more preferably 1 20 mol / L or more and 1.70 mol / L or less are included.
The etching agent according to the embodiment of the present invention may be substantially free of phosphoric acid. Substantially not included means 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, 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 devices and electrodes, and can be measured using these. In addition, pH measuring equipment and equipment using temperature compensating function,
If the pH measuring equipment is calibrated by adjusting the internal solution of the pH electrode and the commercially available pH standard solution to the same temperature as the etching agent etc., the pH at the temperature used for the etching agent etc. can also be measured. it can.

<< Method of Producing Roughened Substrate and Method of Producing Bond of Base Material-Resin Cured Product >>
The method for producing a roughened substrate according to an embodiment of the present invention includes an etching step of contacting the surface or surface of the substrate with an etchant containing at least peroxodisulfate ion and chloride ion. Further, in the method of manufacturing a bonded base material-cured resin product according to an embodiment of the present invention, the etching step and the recess formed by bringing the etching agent into contact to roughen the base material are used. And D. placing the resin composition. The surface or surface of the roughened substrate obtained by the method for producing a roughened substrate according to an embodiment of the present invention is formed by roughening such as injection molding bonding and adhesive bonding. By performing the step of placing the resin composition in the recess (also referred to as simply the step of placing the resin composition in the recess), the base material and the resin composition can be firmly bonded. Further, in any of the method for producing a roughened substrate and the method for producing a bonded base-resin cured product according to an embodiment of the present invention, a zincate film is provided on the surface of the substrate before the etching step is performed. Preferably, a zincate step is carried out to form In addition, another process may exist in the manufacturing method of the roughening base material which concerns on embodiment of this invention, and the manufacturing method of the conjugate | zygote of a base material-resin cured material. As an example of the said other process, the surface cleaning process of which the surface of the said base material is cleaned before performing each process can be mentioned. Moreover, after performing an etching process, before performing the process of putting a resin composition into a dent, you may perform the post-processing process which forms a film. Each step may be repeated if necessary.

The method for producing a roughened substrate according to the embodiment of the present invention may include the etching step and other optional steps described below as exemplified below. Step of degreasing the substrate (optional) → step of alkaline cleaning the substrate (optional) → step of pickling the substrate (optional) → zincate step (optional) → etching step In addition, the order of the process of carrying out the alkali washing process of a base material, and the process of carrying out an acid washing process of a base material may be reverse, may contain only any one, and does not need to contain both.
The method for producing a bonded base material-cured resin product according to an embodiment of the present invention includes an etching step and a step of putting a resin composition in a recess, and other optional steps described below as exemplified below. May be. Step of degreasing the substrate (optional) → step of alkaline cleaning the substrate (optional) → step of pickling the substrate (optional) → zincate step (optional) → etching step → post treatment step (optional) → A step of putting the resin composition into a recess. In addition, the order of the process of carrying out the alkali washing process of a base material, and the process of carrying out an acid washing process of a base material may be reverse, may contain only any one, and does not need to contain both.
Hereinafter, a base material and each process are explained in full detail.

<Base material>
The base material applied to the embodiment of the present invention is not particularly limited as long as at least all or part of the surface is a base material composed of aluminum or an aluminum alloy. The base material may include a cast material and a die cast material, and may be heat-treated. In addition, the base material may be subjected to other processing and / or other processing, for example, processing such as cutting, grinding, blasting, polishing (lapping), and the like may be performed. Moreover, the shape of the said base materials, such as a rod, a band, a pipe | tube, a wire, a foil, a cast forging, a bearing other than a board | plate material, is not specifically limited. The base material may be a molded product or a material before molding. Furthermore, all or part of the surface of the substrate may be a film of aluminum or an aluminum alloy, and the method of forming the film may be, for example, a plating method or a thermal spraying method, but is not limited thereto. If all or part of the surface of the substrate is aluminum or an aluminum alloy, parts other than the surface of the substrate may be materials other than aluminum or aluminum alloy, for example, metals other than aluminum or aluminum alloy, Examples include, but are not limited to, resins, rubbers, woods, ceramics, and composite materials. In addition, as alloy components other than aluminum in aluminum alloy, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, zinc can be mentioned, for example.

<Zincate process>
A zincate step may be performed to form a zincate film on the surface of the substrate as a pretreatment of the etching step. As the zincate process, any known process can be used as long as it is a zincate process for aluminum. In the zincate step, for example, using a sodium hydroxide aqueous solution in which zinc oxide is dissolved, the bath temperature is maintained at 40.0 ° C. or less, and the substrate is immersed for about 1.0 seconds to 5.0 minutes to allow natural oxidation. The zincate film can be formed at the same time as removing the film. In addition, the formed film may be dissolved with the etching agent or nitric acid, and the operation of forming the film again may be performed once or more. In the processing solution used in these zincate steps, metals such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, zinc and the like derived from the base may be present in addition to the essential components. .
The pH of the treatment liquid used in the zincate step is not limited as long as it is within a known range, and may be, for example, 10.0 or more and 13.0 or more in the case of a treatment liquid exhibiting a pH on the alkaline side. It is also good. Preferably, it is in the range of 11.0 to 13.0. Sodium hydroxide or potassium hydroxide can be used to raise the pH to adjust the pH of the zincate solution.

<Etching process>
In the method for producing a roughened substrate and the method for producing a bonded base-resin cured product according to an embodiment of the present invention, it is essential to use an etching step to bring the etching agent into contact with the surface or the surface of the substrate. is there. The etchant preferably has a solution temperature of 10.0 to 70.0 ° C. The substrate is brought into contact with the etchant, for example, by immersion. When the method for producing a roughened substrate and the method for producing a bonded base-resin cured product according to an embodiment of the present invention include a zincate step, the etching agent is brought into contact with the substrate after the zincate 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., and more preferably 20.0 to 40.0 ° C.

<Other process>
(Surface cleaning process)
The manufacturing method according to the embodiment of the present invention may include a surface cleaning step of cleaning the surface of the substrate in advance before performing all the steps. For example, the process of degreasing the surface of the said base material can be mentioned as an example of a surface cleaning process. The method of the 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 alkali salt, a surfactant and the like. The time of the above-mentioned degreasing process is preferably 0.5 to 30.0 minutes. The temperature of the degreasing step is preferably 30.0 to 70.0 ° C. Moreover, the process of carrying out the alkali cleaning process of the surface of the said base material can be mentioned as an example of a surface cleaning process. A publicly known thing can be applied as an agent used by alkaline washing treatment. After the degreasing step, an alkaline washing step may be performed.
It is preferable that the time of the process of the said alkali cleaning treatment is 0.5 to 30.0 minutes. It is preferable that the temperature of the said process of carrying out the said alkali cleaning is 30.0 to 70.0 degreeC. Moreover, the process of pickling the surface of the said base material can be mentioned as an example of a surface cleaning process. A publicly known thing can be applied as a medicine used by acid wash processing. A step of pickling may be performed after the step of degreasing. It is preferable that the time of the process of the said acid wash process is 0.5 to 30.0 minutes. It is preferable that the temperature of the process of the said acid wash process is 30.0 to 70.0 degreeC.

(Post-processing process)
After the etching process by the manufacturing method according to the embodiment of the present invention, a film may be formed on the surface of the substrate. The film may be formed by a coating method or a reaction method. Examples of the film to be formed include an alumite film, a chemical conversion film (phosphate film, chromate film, silicate film, lithium conversion film, calcium conversion Although a film, a zirconium oxide film, etc., a silane coupling agent hardened film, a plating film, etc. are mentioned, it is not limited to these.

(Other processing steps)
Other than the above-described steps, other steps may be performed as appropriate. For example, the water washing step may be performed after all steps {all kinds of processing (for example, surface cleaning step and zincate step) performed before etching step, etching step, post treatment step, etc.}. Moreover, you may perform a drying process suitably after each process.

<Step of placing the resin composition in the recess formed by roughening the substrate>
A resin composition is provided in the depression of the roughened substrate formed by roughening after obtaining the roughened substrate through an etching step of bringing the etching agent into contact with the surface or the surface of the substrate. Is the process of putting As said resin composition, the thermoplastic resin and adhesive agent which are mentioned later can be mentioned. Injection molding or adhesive bonding can be mentioned as an example of the process of putting the said resin composition in the dent of the said roughening base material.
Injection molding may include insert molding and outsert molding. In the case of insert molding, it is preferable to prepare a mold, insert an aluminum alloy into an injection mold, inject a resin composition, and once bonded and integrated as it is after mold release. It is possible to firmly bond the base and the resin by placing the resin composition by injection molding in a recess formed by roughening the base. Hereinafter, this method may be referred to as injection molding bonding. In addition, the film | membrane formed at the zincate process and the film | membrane formed at the post-process process may exist on the surface or surface of a 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 / styrene copolymer Polymer resin, acrylonitrile / styrene copolymer resin, polyacrylic resin, polyalkylene terephthalate resin, polyalkylene naphthalate resin, polyoxyalkylene resin, polyamide resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyphenylene Sulfide resin, polyarylate resin, liquid crystal polymer, syndiotactic polystyrene resin, phenol resin, epoxy resin, urea resin, melamine resin, alkyd resin, polyurethane resin, Recon resins, those suitable of fluororesin or the like can be selected one or more, but is not limited thereto. Further, the resin may contain a filler, for example, suitable from glass fiber, carbon fiber, metal fiber, ceramic fiber, glass bead, carbon powder, metal powder, ceramic powder, aluminum oxide powder, pigment and the like. Although 1 type, or 2 or more types of things can be selected, it is not limited to these.

As a method for bonding the adhesive, for example, an adhesive as a resin composition is applied to the rough surface, an adhesive is put in a recess of the roughened substrate, and then a mating material is pasted, and the adhesive is The aspect which hardens | cures and joins can be mentioned. At this time, it is possible to firmly bond the adhesive to the base by putting the adhesive in the recess formed by roughening the base. The mating material may be any material including metal, rubber, wood, ceramic and composite material as well as resin material. Further, the shape of the mating material is not particularly limited, and may be a plate, a bar, a band, a tube, a line, a film, or the like. The adhesive includes, for example, vinyl chloride resin adhesive, vinyl acetate resin adhesive, polyvinyl alcohol adhesive, polyacrylic adhesive, polyamide adhesive, cellulose adhesive, α-olefin adhesive, aqueous Polymer-isocyanate adhesive, cyanoacrylate adhesive, urea resin adhesive, melamine resin adhesive, phenol resin adhesive, resorcinol resin adhesive, epoxy resin adhesive, silicone resin adhesive, Polyester adhesive, polyurethane adhesive, polyaromatic adhesive, chloroprene rubber adhesive, nitrile rubber adhesive, styrene butadiene rubber adhesive, polysulfide adhesive, butyl rubber adhesive, silicone rubber Suitable from adhesives, acrylic rubber adhesives, urethane rubber adhesives, etc. It can be selected one or more, but is not limited thereto.

  The bonded base-resin cured product according to the embodiment of the present invention may be composed only of the roughened base 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 include a counterpart material in contact with the cured product. The resin composition is cooled by cooling if the resin composition is a thermoplastic resin composition after the step of placing the resin composition in the depression of the roughened base material formed by roughening. When the resin composition is an adhesive, it is cured by being left or heated to form a bonded substrate-resin cured product.

<< Application of Roughened Substrate and Substrate-Resin Cured Product Bonding Body According to Embodiment of the Present Invention >>
The surface or surface of the roughened substrate obtained by the method for producing a roughened substrate according to the embodiment of the present invention may be subjected to lamination to form one or more laminate layers. The roughened substrate is useful as a material for a heat dissipating member and a sliding member. The bonded base-resin cured product obtained by the method for producing a bonded base-resin cured product according to the embodiment of the present invention is a member for automobiles, a member for aircraft, a member for electronic devices, a member for mobile devices It is useful as a member for office automation equipment, a member for home appliances, and a member for medical equipment. In addition, the conjugate | zygote of the said roughened base material and the said base-resin cured material obtained by the manufacturing method of embodiment of this invention is not limited to said use.

  Hereinafter, the present invention and its effects will be specifically described by citing examples together with comparative examples. In addition, the base material used in the Example and the chemical | medical agent used for all the processes are arbitrarily selected from commercially available materials and reagents, and do not limit the actual use of this invention.

«Production of bonded base-resin cured product»
<Base material>
In the production of a bonded base material-cured resin product by injection molding bonding and a bonded base material-cured resin product by adhesive bonding according to Examples 1 to 13 and Comparative Examples 1 to 12, no particular mention is made. As long as a 20 mm x 45 mm x t1.5 mm aluminum material or aluminum alloy material was used as a base material.

<Manufacturing method of base material-bonded resin cured product>
The bonded base material-cured resin product according to Examples 1 to 13 and Comparative Examples 1 to 4 is [surface cleaning step → zincate step → etching step → injection molding bonding step and adhesive bonding step, unless otherwise specified. It manufactured through the process process of any process of].
The joined product of the base material-cured resin according to Comparative Examples 5 to 12 was manufactured through the same treatment process as described above except that it did not include the zincate process.
Hereinafter, each process of the said process process is demonstrated.

(Surface cleaning process)
In the surface cleaning step, after alkaline degreasing {Fine Cleaner 315E (manufactured by Nippon Parkerizing Co., Ltd., 30 g / L (solid content concentration), 70 ° C., immersion time 1 min), alkaline cleaning (sodium hydroxide 100 g / L, 50 ° C., An immersion time of 1 minute was carried out, and water washing 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 wt% hydrofluoric acid: 60 wt%) Nitric acid = 1: 9 (mass ratio), 25 ° C., immersion time 30 seconds) was carried out.

(Zincate process)
In the zincate step, the substrate was dipped in zincate solution.

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

(Injection molding joining process)
In the injection molding and bonding step, polyphenylene sulfide (PPS resin) containing 30% of glass fibers as a resin composition was injection molded and bonded to the base material having undergone the steps up to the etching step. For injection molding, an electric servo injection molding machine (Si-50III) manufactured by Toyo Machine Metals Co., Ltd. was used. 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 bonded base material-cured resin product is 10 mm × 45 mm × t3 mm. Moreover, the bonding area with a base material is 10 mm x 5 mm.

(Adhesive bonding process)
In the adhesive bonding step, an epoxy-based adhesive AR-S30 manufactured by Nichiban Co., Ltd. containing 10% of glass beads BZ-02 manufactured by As One Co., Ltd. is applied to two substrates obtained through the steps up to the etching step. , Joined. The bonding area of the two base materials is 10 mm × 20 mm.

  Hereinafter, based on the base material and process which were mentioned above, the conjugate | zygote of the base material-resin cured material which concerns on Example 1 to 13 and Comparative Example 1 to 12 was manufactured. Below, the procedure in an Example and a comparative example, etc. are described.

Example 1
(Examples and Comparative Examples Using a Substrate Consisting of A5052)
As said base material, A5052 standardized by JIS H4000 was used. The zincate step was not performed. As the etching step, the substrate was immersed for 480 seconds using the following etchant (1). In this manner, a bonded base-resin cured product by injection molding bonding according to [Example 1] and a bonded base-resin cured product by adhesive bonding were obtained.
Etchant (1)
<Component>
-Water-Sodium peroxodisulfate: 0.35 mol / L
Sodium chloride: 1.70 mol / L
<PH>
3.0

Example 2
A bonded substrate-resin cured product was produced in the same manner as in [Example 1] except that the zincate step was performed. Specifically, the substrate was immersed for 30 seconds using the following zincate solution as the zincate step. In this manner, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to Example 2 were obtained. The pH of the zincate solution was adjusted to 12.5 using a hydrochloric acid aqueous solution.
Zincate liquid <component>
・ Water ・ Zinc oxide: 0.25 mol / L
Sodium hydroxide: 3.80 mol / L
-Tartaric acid: 0.07 mol / L
<PH>
12.5
<Temperature of zincate process>
40.0 ° C

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

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

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

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

Comparative Example 2
A bonded substrate-resin cured product was obtained by the same method as in [Example 2] except that the etching step was changed. Specifically, as the etching step, the substrate was immersed for 480 seconds using the following etchant (6). Thus, a bonded body of the base material-cured resin by injection molding bonding and a bonded body of the cured base material-resin by adhesive bonding according to [Comparative Example 2] were obtained.
Etchant (6)
<Component>
-Water-Sodium chloride: 1.70 mol / L
<PH>
3.0

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

Comparative Example 4
A bonded substrate-resin cured product was obtained by the same method as in [Example 1] except that the etching step was changed. Specifically, as the etching step, the substrate was immersed for 300 seconds using the following etchant (8). Thus, a bonded body of the base material-cured resin by injection molding bonding and a bonded body of the cured base material-resin by adhesive bonding according to [Comparative Example 4] were obtained.
Etchant (8)
<Component>
Water and sulfuric acid: 0.50 mol / L
-Sodium chloride: 1.70 mol / L
<PH>
1.0

[Tensile shear test]
The tensile shear strength was measured for each of the bonded base material-cured resin products by injection molding bonding and the bonded base material-cured resin product by adhesive bonding in Examples 1 to 5 and Comparative Examples 1 to 4. The tensile shear test was performed using an automatic graph precision universal tester (AG-100 kNX) manufactured by Shimadzu Corporation. The tensile speed was 10 mm / min, and the tensile shear strength (MPa) was calculated as the breaking load (N) / the area of the joint (50 mm ² ). The results are shown in Table 1.

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

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

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

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

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

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

[Example 12]
A base-resin cured product was produced by the same method as in [Example 2] except that the base was changed. Specifically, AC 8A standardized by JIS H5202 was used as a substrate. Thus, [Example 12]
According to the present invention, there is obtained 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.

[Example 13]
A base-resin cured product was produced by the same method as in [Example 2] except that the base was changed. Specifically, ADC 12 standardized by JIS H5302 was used as a substrate. In this manner, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to [Example 13] were obtained.

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

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

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

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

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

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

Comparative Example 11
A bonded substrate-resin cured product was produced in the same manner as in [Comparative Example 4] except that the substrate was changed. Specifically, AC 8A standardized by JIS H5202 was used as a substrate. In this manner, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to [Comparative Example 11] were obtained.

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

  The tensile shear strength was measured for each of the bonded base material-cured resin products by injection molding bonding and the bonded base material-cured resin product 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 substrate at least the whole of which surface or part is made of aluminum or aluminum alloy,
An etchant comprising at least peroxodisulfate ion and chloride ion.   A method for producing a roughened substrate, comprising an etching step of bringing the etching agent according to claim 1 into contact on the surface or the surface of a substrate at least the whole surface of which or part of the surface is made of aluminum or aluminum alloy.   The method for producing a roughened substrate according to claim 2, further comprising a zincate step of forming a zincate film on the surface of the substrate before the etching step.   The roughened base material obtained by the manufacturing method of the roughened base material of Claim 2 or 3. On the surface or the surface of a substrate at least all or part of the surface of which is made of aluminum or an aluminum alloy
An etching step of contacting the etching agent according to claim 1;
Placing the resin composition in the depression formed by contacting the etching agent and roughening the substrate;
The manufacturing method of the conjugate | zygote of a base material-resin cured material containing C.   The manufacturing method of the conjugate | zygote of the base-resin hardened | cured material of Claim 5 including the zincate process which forms a zincate film | membrane in the surface of the said base material before the said etching process.   A bonded substrate-resin cured product obtained by the manufacturing method according to claim 5.