JP6546313B1 - Resin carbon steel joined body and method for producing the same - Google Patents

Abstract

A resin carbon steel joined body having joining strength and a method for producing the joined body are provided. A method for producing a resin-carbon steel joined body according to the present invention includes a degreasing step of cleaning a carbon steel member with an alkaline solution, an acid treatment step of cleaning the carbon steel member with an acidic solution, and a carbon steel member. An activation treatment step in which a constant voltage or constant current is applied to the electrode by immersion in an alkaline solution, and a carbon steel member is used as an anode, and a predetermined current density is applied in an alkaline solution containing a triazine thiol derivative, and carbon A step of forming an anodized film having a thickness of 30 to 2000 nm on a steel member, a washing step of washing the carbon steel member having the anodized film formed with water, and a carbon steel member having the anodized film formed thereon; And insert-molding a thermoplastic or thermosetting resin. [Selected figure] Figure 1

Description

  The present invention relates to a resin-carbon-steel joined body and a method for producing the same, and more particularly to a resin-carbon-steel joined body capable of strongly joining a resin member and a carbon steel member and a method for producing the same.

  Weight reduction of parts can be performed by using a metal member as a joined body of a metal member and a resin member as an example. Patent Document 1 discloses, as a technique for bonding a resin member and a metal member, an electro-chemical surface treatment method of forming a film containing triazine thiol (sulfur organic compound) on the surface of the metal member. Examples of metals include copper, nickel, aluminum, iron, cobalt, tin and stainless steel. By forming the coating on the metal surface, the bonding strength with the resin member can be improved.

  However, specifically, a coating of triazinethiol is formed on the surface of a SM45C, SS400, or HT590 carbon steel member, and a resin member is bonded to form a resin-metal joint to obtain sufficient bonding strength. There is no disclosure.

Tokuhei 5-51671

  An object of the present invention is to provide a resin-carbon-steel joined body capable of improving the bonding strength between a resin member and a carbon steel member, and to provide a method for producing a resin-carbon-steel joined body having good joint strength.

  The resin carbon steel joined body according to the present invention is a resin carbon steel joined body formed by joining a carbon steel member and a thermoplastic or thermosetting resin member, wherein the carbon steel member and the resin member are It is characterized in that it is joined by an anodized film having a thickness of 30 to 2,000 nm.

  Another resin carbon steel bonded body according to the present invention is a resin carbon steel bonded body formed by bonding a carbon steel member and a thermoplastic or thermosetting resin member, and the carbon steel member and the resin member It is characterized in that it is joined by an anodic oxide film in which a triazine thiol derivative having a film thickness of 30 to 2000 nm is present inside and outside.

  The anodic oxide film is, by weight, 1 to 60% of oxygen (O), 30 to 90% of iron (Fe), 5% or less of silicon (Si), 1% or less of aluminum (Al), phosphorus ( P) 3% or less, zinc (Zn) 3% or less, manganese (Mn) 3% or less, nickel (Ni) 3% or less, sulfur (S) 3% or less, carbon (C) 10% It is characterized by having the following component composition.

  The method for producing a resin-carbon-steel alloy joined body according to the present invention is a method for producing a resin-carbon-steel joined body, comprising: a degreasing step of washing a carbon steel member with an alkaline solution; and a carbon steel member after the degreasing step. Acid treatment step of washing with an acidic solution, an activation treatment step of immersing the carbon steel member in an alkaline solution to apply a constant voltage or constant current to the electrode after the acid treatment step, and the carbon steel member Anodized film with a thickness of 30 to 2000 nm on the carbon steel member by applying an electric current density of 1 A / dm 2 or more and less than 20 A / dm 2 for 1 to 40 minutes in an alkaline solution at 20 to 80 ° C. as an anode. A step of forming a carbon steel member on which the anodized film is formed, and a step of washing the carbon steel member on which the anodized film is formed with water, and a carbon steel member on which the anodic oxide film is formed after the water washing step. Resin for Comprising a step of shot molding, a said carbon steel member, and a resin member molded by the resin, characterized in that it is joined by the anodic oxide coating.

  Another method for producing a resin-carbon-steel joined body according to the present invention is a method for producing a resin-carbon-steel joined body, comprising: a degreasing step of washing a carbon steel member with an alkaline solution; An acid treatment step of washing the member with an acidic solution, an activation treatment step of immersing the carbon steel member in an alkaline solution after the acid treatment step and applying a constant voltage or constant current to an electrode, the carbon steel member A current density of 1 A / dm 2 or more and 20 A / dm 2 or less is applied for 1 to 40 minutes in an alkaline solution containing a triazine thiol derivative at 20 to 80 ° C. as an anode, and the film thickness is 30 to 30 nm on the carbon steel member. A process of forming an anodic oxide film of 2000 nm, a water washing process of washing the carbon steel member having the anodic oxide film formed thereon with water, and a thermal treatment of the carbon steel member having the anodic oxide film formed after the water washing process; Plasticity or Comprising a step of insert molding a thermosetting resin, and a the carbon steel member, and a resin member molded by the resin, characterized in that it is joined by the anodic oxide coating.

In the resin-carbon steel joined body according to the present invention, an anodic oxide film having a thickness of 30 to 2000 nm is formed in advance on the surface of the carbon steel member, so that the resin member and the carbon steel member can be joined well. Can be Further, the airtightness between the resin member and the carbon steel member can be reduced to a helium leak amount of 10 ⁻⁹ Pa · m ³ / s or less in a leak test using helium. In addition, waterproofness can be secured.

Another resin carbon steel joined body according to the present invention has anodized film in which a triazinethiol derivative having a film thickness of 30 to 2000 nm is present inside and outside on the surface of a carbon steel member in advance. Steel members can be joined well. The bonding strength can be 30 MPa or more. Further, the airtightness between the resin member and the carbon steel member can be reduced to a helium leak amount of 10 ⁻⁹ Pa · m ³ / s or less in a leak test using helium.

  Since the anodized film is a porous film, the resin member and the carbon steel member can be joined well.

According to the method for producing a resin-carbon-steel joined body according to the present invention, (a) immersion, degreasing step for removing fats on the surface of carbon steel member, (b) acid treatment step, and (c) immersion in alkaline solution (D) forming an anodized film in an alkaline solution using (d) a carbon steel member as an anode, and (e) forming an anodized film. After that, a carbon steel member was washed with water, and (f) an insert step of insert molding a thermoplastic or thermosetting resin and joining it to the carbon steel member was performed, so molding by insert molding The resin member and the carbon steel member can be joined well, the joint strength can be 30 MPa or more, and the airtightness can make the helium leak amount be 10 ⁻⁹ Pam ³ / s or less in the leak test using helium.

According to another method of producing a resin-carbon steel joined body according to the present invention, (a) a degreasing step for removing fats from the surface of a carbon steel member by immersion, (b) an acid treatment step, and (c) an alkaline solution (D) carbon steel member as an anode and forming an anodic oxide film in an alkaline solution containing a triazine thiol derivative (TRI) And (e) water-washing the carbon steel member with water after forming the anodized film, and (f) insert molding the thermoplastic or thermosetting resin and joining it to the carbon steel member The joint strength of the resin member and the carbon steel member formed by insert molding can be made to be 30 MPa or more, and the airtightness is 10 ^-9 Pam ³ of helium leak amount in the leak test using helium. / S It can be done below.

It is a flowchart which shows the manufacturing method of the resin carbon steel joined body by this invention. It is a figure which shows the shape of a carbon steel member. (A) is a front view, (B) is a right side view, and (C) is a perspective view. It is a component table of a typical carbon steel member. It is a photograph of the hanging jig of a carbon steel member. It is a photograph of a degreasing tank. It is a photograph of an acid treatment tank and an activation tank. It is a photograph of a TRI electrolytic processing tank. It is a photograph which shows the cross section of an anodic oxidation film. It is a photograph of the carbon steel member and the test body for a tension test. It is a table showing the tensile strength of a resin carbon steel joined object. It is a table showing the tensile strength after a thermal shock test. It is a table showing tensile strength after a high temperature and high humidity test. It is a photograph of the test body for the airtight test. It is a table | surface which shows the result of an airtight test. It is a surface microscope picture of a carbon steel member. It is a surface microscope picture after an acid treatment process. It is the surface photograph after TRI electrolytic processing. It is a component analysis table of the surface oxide film after TRI electrolytic processing. It is a table | surface which shows the joint strength of the resin carbon steel joined body in the case where triazine thiol derivative is added, and the case where it is not added.

  Hereinafter, a resin-carbon-steel joined body according to the present invention and a method for producing the same will be described in detail with reference to the drawings.

FIG. 1 is a flow chart showing a method of producing a resin-carbon steel joint according to the present invention. A resin carbon steel joined body joins a carbon steel member and a resin member, and is shape | molded integrally. The formation of the resin-carbon-steel joint is performed in the following six steps s1 to s6. In the degreasing step (s1), a cationic surfactant is added to an aqueous solution of alkaline series of NAOH, KOH, or NA ₂ CO ₃ , and the carbon steel member 1 is immersed for 1 to 10 minutes. The temperature of the aqueous solution is in the range of normal temperature to 70 ° C. Thereby, the oil on the surface of the carbon steel member 1 can be removed. The carbon steel member 1 is a plate-like member.

  Next, in the acid treatment step (s2), the carbon steel member 1 in an aqueous solution of 5 to 50% hydrochloric acid, 1 to 5% sulfuric acid or 1 to 2% sulfuric acid or 1 to 5% oxalic acid, 1 to 5% fluoride by weight% Soak for 1 to 10 minutes. The temperature of the aqueous solution is in the range of normal temperature to 50 ° C. Thus, the surface of the carbon steel member 1 is cleaned to remove the oxide film and the like.

  In the activation step (s3), a small amount of cationic surfactant is added to an aqueous solution of caustic soda or potassium hydroxide 1 to 30, and sodium hydroxide 1 to 20% by weight, and carbon steel member 1 is added to the solution. Soak for 10 minutes and apply a constant voltage of 0.2-5 V to the anode or cathode. The temperature of the aqueous solution is normal temperature to 50 ° C. Pulsed or DC voltage is applied to the electrodes. Sonicate also for 100 to 2000 watts at 50 Hz for 1 to 10 minutes simultaneously.

The oxide film forming step (s4) is referred to as a TRI electrolytic step. Carbon steel member 1 is connected as an anode. Triazine thiol in an aqueous solution of 3-20% caustic soda or 3-20% potassium hydroxide, 1-5% sodium triphosphate or ammonium phosphate, 1-3% sodium carbonate, 1-3% sodium citrate in weight percent A small amount of derivative is added, the carbon steel member 1 is immersed in the aqueous solution, and a current density of 1 to 20 A / dm ² is applied between the anode and the cathode. The temperature of the solution is normal temperature to 80 ° C. A voltage of 5 to 40 V is applied between the anode and the cathode. The anodic oxidation film 4 containing a triazine thiol derivative with a film thickness of 30 to 2000 nm is formed on the surface of the carbon steel member by electrolysis for 1 to 40 minutes. A porous film can be formed. In addition, an oxide film formation process (s4) can also be performed with the aqueous solution which does not add a triazine thiol derivative.

  The anodic oxide film 4 is 1% to 60% of oxygen (O), 30 to 90% of iron (Fe), 5% or less of silicon (Si), 1% or less of aluminum (Al), phosphorus by weight% P) 3% or less, zinc (Zn) 3% or less, manganese (Mn) 3% or less, nickel (Ni) 3% or less, sulfur (S) 3% or less, carbon (C) 10% It has the following component composition.

  The water washing step (s5) is a step of washing the carbon steel member 1 having the anodized film formed on the surface with water. In addition, let it dry after washing with water.

  In the insert molding step (s6), the carbon steel member 1 on which the anodized film is formed is loaded into a mold, and a thermoplastic or thermosetting resin to be the resin member 2 is injected, and the resin member 2 and the carbon steel member 1 is joined to form a resin-carbon-steel joined body 3.

  FIG. 2 is a view showing the shape of the carbon steel member 1. (A) is a front view, (B) is a right side view, and (C) is a perspective view. a is a hole for a tensile test having a diameter of 4 mm. f is 3 mm in thickness. Longitudinal (e) × lateral (b) is a plate of 40 mm × 12 mm, e is 40 mm, b is 12 mm, c is 6 mm, and d is 5 mm.

  FIG. 3 is a table showing types and components of carbon steel. The carbon steels of this embodiment are SM45C, SS400 and HT590. SM45C is called carbon steel for machine structural use, and contains 0.42 to 0.48% of carbon (C) as shown in the table. The number 45 of SM45C indicates that the median value of carbon (C) content is 0.45%. SS400 is a steel material which is called a general structural rolled steel and has a large amount of circulation. The numeral 400 of SS 400 indicates that the lower limit of the tensile strength is 400 MPa. The components are more loose than other steels, and only phosphorus (P) and sulfur (S) are specified. The carbon (C) of SS400 is generally 0.25% or less. HT 590 is called high-tensile steel and is stronger than general structural rolled steel and has a tensile strength of about 490 MPa.

FIG. 4 is a photograph of the hanging jig 7 of the carbon steel member 1. The hanging jig 7 has a plurality of hooks, and ten carbon steel members 1 can be attached. FIG. 5 is a photograph of the degreasing tank. The degreasing tank is filled with an aqueous solution of NAOH, KOH, or NA ₂ CO ₃ plus a cationic surfactant. FIG. 6 is a photograph of an acid treatment tank and an activation tank. FIG. 7 is a photograph of a TRI electrolytic treatment tank. Several electrodes are prepared in a tank.

  FIG. 8 is a photograph showing a cross section of the anodized film. In (A), the anodized film 4 having a thickness of 84.88 to 165.2 nm is formed. In (B), the anodic oxide film 4 with a thickness of 483.7 to 177.6 nm is formed. In (C), the anodic oxide film 4 with a thickness of 73.73 to 112 nm is formed.

FIG. 9 shows a photograph of the carbon steel member 1 and a photograph of a test body for a tensile test. Test body 3 (3a) is manufactured by the manufacturing method shown in FIG. 1 and used for a tensile test. As shown in FIG. 9, the end face of 12 mm × 3 mm (= 36 mm ² ) of the carbon steel member 1 and the resin member 2 are joined. The test body 3 (3a) is obtained by integrally molding the resin member 2 on the carbon steel member 1 by insert molding. In the insert molding, the carbon steel member 1 is loaded in a mold (not shown), and a thermoplastic or thermosetting resin is pressed into, thereby integrally molding the carbon steel member 1 and the resin member 2. As the thermoplastic resin, polybutylene terephthalate (PBT) or polyphenylene sulfide (PPS) can be used. A urethane resin or an epoxy resin can be used as the thermosetting resin.

FIG. 10 is a table showing the tensile strength of the resin-carbon-steel joined body 3 (3a). In the present embodiment, four are PPS and four are PBT. The tensile strengths of the eight test bodies are as shown in the table, and are the values when the bonding area is 36 mm ² (= 12 mm × 3 mm). According to this, a tensile strength of approximately 30 MPa can be secured with a bonding area of 36 mm ² .

  FIG. 11 is a table showing tensile strengths after a thermal shock test. In the resin member 2 of the resin-carbon-steel joined body 3 (3a), four are PPS and four are PBT. The thermal shock test is repeated for 150 cycles, with the temperature varied between -40C and 80C every 30 minutes. The tensile strength was measured before and after the test. According to the table of FIG. 11, it can be seen that the tensile strength is lower than the average of 37 MP before the thermal shock test, because the average after the thermal shock test is 30.38 MPa.

  FIG. 12 is a table showing the tensile strength after the high temperature and high humidity test. In the resin member 2 of the resin-carbon-steel joined body 3 (3a), four are PPS and four are PBT. The high temperature and high humidity test was performed after the test at a temperature of 80 ° C., a humidity of 95%, and a time of 200 hours. The left side of the table is the tensile strength of the resin carbon steel joined body 3 (3a) before the high temperature high humidity test, and the right side is the tensile strength of the resin carbon steel joined body 3 (3a) after the high temperature high humidity test. According to FIG. 12, it can be seen that the tensile strength is an average of 31.63 MPa after the high temperature and high humidity test and lower than the average of 40.88 MP before the high temperature and high humidity test.

  FIG. 13 is a photograph of a test body for an airtightness test. In the test body 3 (3b) for the airtightness test, the carbon steel member 1 penetrates the disc-shaped resin member 2 and is integrally joined. A test vessel 3 (3b) for air tightness test is loaded in a cylindrical container, helium gas is blown to one side from which the carbon steel member 1 protrudes, and the other side from which the carbon steel member 1 protrudes is evacuated, helium Inspect for leaks.

FIG. 14 is a table showing the results of the airtightness test. If the amount of vacuum evacuation is increased or decreased, the amount of leaked helium (He) is also increased or decreased, but under this condition, the amount of leakage can be made 1 × 10 ⁻⁹ Pam ³ / s or less in both of the samples 1 and 2.

  FIG. 15 is a surface micrograph of a carbon steel member.

  FIG. 16 is a surface micrograph after the acid treatment step.

  FIG. 17 is a surface photograph after TRI electrolytic treatment.

  FIG. 18 is a component analysis table of the surface oxide film after TRI electrolytic treatment. Taking the sample 1 as an example, the components of the anodized film are, by weight, 4.7% of carbon (C), 6.46% of oxygen (O), and 88.84% of iron (Fe). .

  FIG. 19 is a table showing the bonding strength of the resin-carbon-steel joined body with and without the triazine thiol derivative. In step s4 of FIG. 1, an anodic oxide film was formed without adding the triazine thiol derivative to the aqueous solution, and a resin-carbon-steel joined body 3 (3a) was manufactured. On the other hand, at step s4 in FIG. 1, a triazine thiol derivative was added to the aqueous solution to form an anodic oxide film, and a resin-carbon-steel joined body 3 (3a) was manufactured. The bonding strengths of five resin-carbon steel joints were compared. The numerical values are slightly better when the triazine thiol derivative is added. However, even without the addition of the triazine thiol derivative, it sufficiently withstands use.

  The resin-carbon-steel joined body and the method for producing the same according to the present invention integrally join a carbon steel member and a resin member, and are suitable for weight reduction of parts.

DESCRIPTION OF SYMBOLS 1 Carbon steel member 2 Resin member 3 Resin carbon steel joined body 3a Test body for tension test 3b Test body for airtightness test 4 Anodized film 7 Suspension jig s1 to s6 Each process of manufacturing method

Claims (2)

A resin-carbon-steel joined body formed by joining a carbon steel member and a thermoplastic or thermosetting resin member,
The carbon steel member and the resin member are joined by an anodic oxide film having a thickness of 30 to 2000 nm ,
The anodized film comprises a triazine thiol derivative,
The said carbon steel member is SM45C, The resin carbon steel joined body characterized by the above-mentioned . It is a manufacturing method which manufactures the resin carbon steel joined object according to claim 1 ,
A degreasing step of cleaning the carbon steel member with an alkaline solution;
An acid treatment step of washing the carbon steel member with an acidic solution after the degreasing step;
After the acid treatment step, the carbon steel member is immersed in an alkaline solution to apply a constant voltage or a constant current to the electrode;
The carbon steel member is used as an anode by applying a current density of 1 A / dm ² or more and 20 A / dm ^{2 or} less for 1 to 40 minutes in an alkaline solution containing triazine thiol derivative at 20 to 80 ° C. Forming an anodic oxide film having a thickness of 30 to 2000 nm on the film;
Rinsing the carbon steel member having the anodized film formed thereon with water;
Insert molding a thermoplastic or thermosetting resin on the carbon steel member on which the anodized film has been formed after the water-washing step;
A method of manufacturing a resin-carbon-steel alloy joined body, wherein the carbon steel member and a resin member formed of the resin are joined by the anodized film.

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