KR102330886B1 - Resin-metal bonded body and its manufacturing method - Google Patents

Abstract

[Project] To provide a bonded body of resin and stainless steel.
[Solutions] The present invention is a resin-metal bonded body formed by bonding stainless steel and a thermoplastic resin member,
The stainless steel and the thermoplastic resin member are joined by an anodized film having a thickness of 20 to 2000 nm.
The present invention also provides a resin metal bonded body and a method for manufacturing the same, wherein a degreasing step of washing stainless steel with an alkali solution, an acid treatment step of washing stainless steel with an acidic solution after the degreasing step, an acid treatment step of washing the stainless steel with an acid solution, and the stainless steel after the acid treatment step An activation treatment process for activating steel with an acidic solution or an alkaline solution, using the stainless steel as an anode, and applying a current density of 0.1 A/dm2 or more and less than 1.5 A/dm2 in an aqueous solution at 20 to 90° C., the stainless steel A step of forming an anodized film having a film thickness of 20 to 2000 nm thereon, a water washing step of washing the stainless steel with the anodized film formed thereon with water at a temperature of 5°C or higher and less than 60°C, and the anodized film after washing with water It is characterized in that the stainless steel and the thermoplastic resin are joined by a step of insert molding a thermoplastic resin into the formed stainless steel.

Description

Resin-metal bonded body and its manufacturing method

The present invention relates to a resin-metal bonded body formed by bonding stainless steel and a thermoplastic resin member, and a method for manufacturing the same, and more particularly, to a resin-metal bonded body for bonding stainless steel and a thermoplastic resin member by using an anodized film as a bonding film, and It relates to a manufacturing method thereof.

In recent years, in various fields such as home appliances and automobile parts, weight reduction has been demanded, and a replacement of a metal member with a resin member is also made.

However, it is difficult to replace a metal member with a resin member in a field requiring high rigidity, strength, conductivity, or thermal conductivity characteristic of a metal, and in this field, a joint between a metal and a resin is being studied.

As a method for manufacturing a bonded body between a metal member and a resin member, a method using an adhesive or chemical etching to form micron-sized fine irregularities on the metal surface, resin enters into the irregularities and hardens, thereby realizing a strong bonding according to the anchor effect. Amalpha treatment technology, a method of forming a film of triazinethiol on the surface of a metal member by electrodeposition, and a method through laser processing. However, the method using an adhesive is inferior in terms of bonding strength, and the method through Amalpha processing technology and laser processing has a problem in terms of cost. In addition, the method of utilizing the coating of triazinethiol has many achievements in aluminum and copper, but there is no performance in stainless steel.

In recent years, among metals, the demand for combining the excellent characteristics of stainless steel and the light weight of resin is increasing, and the request|requirement with respect to the joined body of resin and stainless steel is growing.

[Patent Document 1] Japanese Patent Laid-Open No. 2012-193448

An object of the present invention is to provide a bonded body of a resin and stainless steel.

The present invention is a resin-metal bonded body formed by bonding stainless steel and a thermoplastic resin member, wherein the stainless steel and the thermoplastic resin member are joined by an anodized film having a thickness of 20 to 2000 nm.

In addition, the present invention is a resin-metal bonded body formed by bonding stainless steel and a thermoplastic resin member, the stainless steel, the thermoplastic resin member, and an anodized film in which triazinethiol having a film thickness of 20 to 2000 nm is present inside and on the top. It is a resin stainless steel joined body characterized in that it is joined.

The anodized film is characterized in that it has a composition of 3% or less of Si, 30% of Cr 1 or less, 1% of Mn or less, 10% or less of Ni, and the balance is 80% of Fe 30 by weight%.

Further, the present invention is a manufacturing method for manufacturing a resin stainless steel joined body, wherein the resin processing is performed by washing the stainless steel with an alkali solution;

After the resin process, an acid treatment process of washing stainless steel with an acidic solution;

After the acid treatment step, an activation treatment step of activating the stainless steel with an acidic solution or an alkaline solution;

Using the stainless steel as an anode, a current density of 0.1 A/dm2 or more and less than 1.5 A/dm2 is applied in an aqueous solution at 20 to 90° C. to form an anodized film having a film thickness of 20 to 2000 nm on the stainless steel. process to do,

a water washing step of washing the stainless steel with the anodized film in water at a temperature of 5°C or higher and lower than 60°C;

a step of insert molding a thermoplastic resin into the stainless steel having the anodized film formed thereon after washing with water;

It is characterized in that the stainless steel and the thermoplastic resin are joined by the

In addition, the present invention is a manufacturing method for manufacturing a resin stainless steel joined body,

A degreasing process for cleaning stainless steel with an alkali solution,

After the degreasing process, an acid treatment process of washing stainless steel with an acidic solution;

After the acid treatment step, an activation treatment step of activating the stainless steel with an acidic solution or an alkaline solution;

Using the stainless steel as an anode, in an aqueous solution containing a triazinethiol derivative at 20 to 90° C., a current density of 0.1 A/dm2 or more and less than 1.5 A/dm2 is applied, and a film thickness of 20 The process of forming an anodization film of ~2000 nm,

A water washing step of washing the stainless steel with an anodized film in which the triazinethiol is present with water at a temperature of 5°C or more and less than 60°C;

a step of insert molding a thermoplastic resin into the stainless steel having an anodized film in which the triazinethiol is present after washing with water;

It is characterized in that the stainless steel and the thermoplastic resin are joined by the

ADVANTAGE OF THE INVENTION According to this invention, the joined body of resin and stainless steel whose joint strength is 30-40 MPa and airtightness of 10-9 Pam 3/s or less of helium leak can be obtained.

Fig. 1 is a flowchart showing the manufacturing process of the present invention.
[Fig. 2] It is a cross-sectional view of the anodized film in which triazinethiol of the present invention is present.
3 is a graph showing the tensile test results of the joined body of the present invention.
4 is a graph showing the tensile test results of the joined body of the present invention.
[Fig. 5] A diagram of a sample used in an embodiment of the present invention.
[Fig. 6] It is a photograph of the sample used in the Example of the present invention.
[Fig. 7] Fig. 7 is a view showing the surface of SUS 304 after TRI treatment according to an embodiment of the present invention.
[Fig. 8] A view showing the surface of SUS 316L material after TRI treatment in an embodiment of the present invention.
[Fig. 9] It is a photograph of the jig holding the sample used in the Example of the present invention.
[Fig. 10] It is a photograph of the sample after insert molding used in the Example of the present invention.
[Fig. 11] Fig. 11 is a cross-sectional photograph of the SUS 304 material and the resin side of the cross-sectional view after the qualification test in the embodiment of the present invention.
[Fig. 12] A photograph of a sample for a helium leak test in an embodiment of the present invention.
[Fig. 13] It is a diagram showing the experimental situation of the present invention.

The resin-stainless steel joined body of the present invention is a resin-metal joined body in which stainless steel and a thermoplastic resin member are joined, and the stainless steel and the thermoplastic resin member are anodized in an anodized film in which triazinethiol having a film thickness of 20 to 2000 nm is present inside and on the top. The anodized film in which the triazine thiol is present has a composition of Si 3% or less, Cr 1 30%, Mn 1% or less, Ni 10% or less, and the balance is Fe.

The stainless steels applicable to the resin stainless steel joined body are SUS 304 and SUS 316L shown in the table below.

JIS C Si Mn P S Ni Cr Mo SUS304 ≤0.08 ≤1.0 ≤2.0 ≤0.045 ≤0.030 8.0-10.5 18.00~20.00 SUS316L ≤0.08 ≤1.0 ≤2.0 ≤0.045 ≤0.030 10.0 to 14.0 16.00~18.00 2.00~3.00

The thermoplastic resin that can be used in the resin-metal bonded body of the present invention is polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, unsaturated polyester, polyester, polyamide, and polyether. , polyurethane elastomer, polystyrene, polysulfone, polyethersulfone, polyarylate, polyacetal, polyethylene terephthalate, polycarbonate, polyphenylene ether, polyphenylene oxide, polyphenylene sulfide, polybutadiene, polybutylene tere Phthalate, polymethylpentene, polymethylpentene, and liquid crystal polymers.

Triazinethiol (sulfur compound) is known to be a multifunctional and stable substance that reacts well with metals. Therefore, the present technology is to vacuum-deposit triazinethiol on the mold surface to make a film that is difficult to peel, and to utilize its water repellency for release property. The film thickness is 0.05

Since it can be set to about 0.1 u, it becomes possible to mold a mold with a single order of magnitude higher than that of a conventional mold release agent.

When the material is immersed in a triazinethiol solution, dithiol triazinyl groups are bonded to the surface, which acts as an adhesive.

After sufficiently cleaning the surface of the adherend, oxidation treatment is performed using corona discharge or Fenton's solution. This is to generate an OH group having excellent reactivity with the dithiol triazinyl group on the surface of the adherend.

Hereinafter, the manufacturing method of the resin stainless steel joined body of this invention is demonstrated.

BRIEF DESCRIPTION OF THE DRAWINGS It is a flowchart which shows the manufacturing process of the resin stainless steel joined body of this invention.

The basic process of anodizing treatment is as follows.

Pretreatment → pretreatment → anodization treatment → post treatment

1. Preliminary processing

It is a process performed outside the production line of a resin-stainless steel bonded body, and it is a process that affects the film finish, such as buffing, hairline, eggplant, and patterning.

2. Pretreatment

In the process of cleaning and dissolving the surface of a base material, such as resin and etching, when this process is bad, a stain etc. will generate|occur|produce. The pretreatment of the manufacturing method according to the present invention is

A degreasing process consisting of 1 to 10 minutes immersion in NAOH, KOH, or NA2CO3 + cationic activator at 50 ° C. at room temperature;

Acid treatment process by immersing in 5 to 50% hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid bath for 1 to 10 minutes at 50 °C at room temperature,

It consists of an activation treatment process by immersing the anode or cathode of a 5 to 50% hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid bath at a constant voltage of 0.2 to 5 V at room temperature at 50° C. for 1 to 10 minutes.

3. Anodizing

In the step of forming an anodized film, in order to satisfy the required film quality, it is necessary to select optimal conditions such as an electrolytic bath, a power supply waveform, a bath temperature, agitation, and an electrolysis time.

The anodizing treatment of the manufacturing method according to the present invention uses stainless steel as an anode, and sulfuric acid, phosphoric acid, hydrochloric acid each 10 to 30% acidic agent, or NAOH, KOH 5 to 50% + sodium phosphate 1 to 5% + carbonate In an acidic solution at 80° C. at room temperature containing a triazinethiol derivative in an alkaline agent of 1 to 5% sodium, a current density of 0.1A/dm2 or more and less than 1.5A/dm2 is applied, immersed for 1 to 40 minutes, and the stainless steel On the steel, an anodized film with a film thickness of 70 to 1500 nm and a triazinethiol derivative present therein and thereon is formed.

4. Post-processing

In the present invention, as a post-treatment reel of the manufacturing method, a water washing step of washing stainless steel with an anodized film in which triazinethiol is present with water at a temperature of 5°C or higher and less than 60°C is performed, and after washing with water, the anode in which triazinethiol is present The process of insert-molding a thermoplastic resin is followed by the stainless steel in which the oxide film was formed.

It can be seen that the resin-metal bonded body obtained by the above production method of the present invention has a bonding strength of 40 MPa or more, as shown in Figs.

The left column of FIG. 4 shows the values at room temperature, the middle column shows the values after thermal shock application of reciprocating between -40°C and 80°C for 30 minutes and 150 cycles, and the right column is in an environment with a temperature of 80°C and a humidity of 95%. As a result of the high-temperature, high-humidity test after leaving it to stand for 200 hours, as shown in FIGS. 3 and 4, the bonding strength at room temperature, the addition of thermal shock, and the high-temperature, high-humidity state has an average value of 45 MPa or more.

Hereinafter, an embodiment of the present invention will be described.

As shown in Fig. 5, the SUS 304 and SUS 316L plates used were 3 mm in thickness x 12 mm in width x 40 mm in length.

7 and 8 show that the SUS304 and SUS316L plates are TRI-treated, and it can be seen that clear irregularities are formed on the surface of the sample.

Fig. 10 is a photograph of a sample subjected to insert molding, and Fig. 11 is a photograph of a cross-sectional view of SUS 304 and a resin portion of the fracture surface of the joint when the sample is subjected to an accreditation test.

12 is a photograph of a sample for a helium leak test.

In the TRI system sealing (airtightness) test, argon gas is widely used as a pressurized gas, but the test temperature at that time is 25° C., the pressurization pressure is 7 kgf/cm 2 , and the pressurization test time is 5 minutes.

In the Example by helium of this invention, the joint strength was 30-40 MPa, and airtightness was 10-9 Pam 3/s or less of a helium leak.

9 is a photograph of a jig for sample processing, and FIG. 13 is a diagram illustrating a test situation in a laboratory.

Claims (5)

It is a resin-metal joined body formed by joining stainless steel and a thermoplastic resin member by an anodizing film,
The anodized film has a film thickness of 20 to 2000 nm, and triazinethiol is present inside and on the top,
The stainless steel is SUS304 or SUS316L.
It is a manufacturing method for manufacturing the resin-metal bonded body of claim 1,
A pretreatment process of treating the stainless steel surface before anodizing;
Using the stainless steel as an anode, in an aqueous solution containing a triazinethiol derivative at 20 to 90° C., ^{a current density of 0.1 A/dm 2} or more and less than 1.5 A/dm ² is applied, and a film thickness is applied on the stainless steel. forming an anodized film of 20 to 2000 nm;
a step of washing the stainless steel with an anodized film in which the triazinethiol derivative is present with water at a temperature of 5°C or more and less than 60°C;
a step of inserting a thermoplastic resin into the stainless steel having an anodized film in which the triazinethiol is present after the step of washing with water;
The pretreatment process includes a step of immersing in an aqueous solution containing a kind of alkali and a cation activator selected from NaOH, KOH, and Na ₂ CO ₃ , a step of immersing in a kind of acid bath selected from hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid, hydrochloric acid , sulfuric acid, phosphoric acid, and acetic acid, a method of producing a resin-metal bonded body characterized in that it consists of a step of immersing the anode or cathode in a state in which a constant voltage of 0.2 to 5 V is applied in an acid bath. delete delete delete

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