JP2013022761A - Method of manufacturing copper-resin complex - Google Patents

Abstract

Provided is a method for producing a copper-resin composite that can improve the adhesion between copper and a resin composition without using an adhesive and has a favorable working environment.
A method for producing a copper-resin composite according to the present invention includes a roughening step of roughening a surface of a copper part with an etching agent, and an attaching step of attaching a resin composition to the roughened surface. Wherein the etching agent is an aqueous solution containing sulfuric acid, hydrogen peroxide, phenyltetrazole, nitrobenzotriazole, benzenesulfonic acid and chloride ion. And
[Selection] Figure 4

Description

  The present invention relates to a method for producing a copper-resin composite in which a resin composition is adhered to the surface of a copper part.

  Technology that integrates copper and resin has been developed in a wide range of industrial fields, mainly in the electric and automobile fields. Conventionally, an adhesive is generally used for joining copper and resin, and many adhesives have been developed for this purpose. However, the use of the adhesive complicates the production process and increases the cost of the product. In addition, when an adhesive is used, the bonding strength at high temperatures decreases, making it difficult to apply to applications that require heat resistance such as automobiles.

  Therefore, in recent years, techniques for integrating copper and resin without using an adhesive have been studied. For example, in Patent Document 1 below, a polyphenylene sulfide resin or a polybutylene terephthalate resin is formed on a treated surface in which a nano-size irregularity is formed on the surface of a copper alloy and then a thin layer of copper oxide is formed by an oxidizing agent under strong basicity. A technique for obtaining a copper-resin composite by injection-molding a thermoplastic resin composition containing a resin has been proposed.

  According to the method described in Patent Document 1, since the anchor effect is obtained when the thermoplastic resin composition penetrates into the extremely fine irregularities formed on the copper surface, the copper and resin composition can be used without using an adhesive. Can be integrated.

International Publication WO2008 / 047811 Pamphlet

  However, the method described in Patent Document 1 has a problem that the working environment is deteriorated because it is necessary to carry out the treatment at a high temperature under a strongly basic oxidizing agent.

  The present invention has been made in view of the above-described problems of the prior art, and can improve the adhesiveness between copper and the resin composition without using an adhesive, and has a good working environment. A method for producing a composite is provided.

  The method for producing a copper-resin composite according to the present invention is a copper which performs a roughening step of roughening a surface of a copper part with an etching agent and an adhesion step of attaching a resin composition to the roughened surface. -A method for producing a resin composite, wherein the etching agent is an aqueous solution containing sulfuric acid, hydrogen peroxide, phenyltetrazoles, nitrobenzotriazoles, benzenesulfonic acids and chloride ions.

In the present invention, an aqueous solution containing sulfuric acid, hydrogen peroxide, phenyltetrazoles, nitrobenzotriazoles, benzenesulfonic acids, and chloride ions is used as an etching agent for roughening the parts. Since the etching agent has good handleability and does not require treatment at high temperature, the working environment can be maintained well.
Moreover, in this invention, since the etching agent containing phenyltetrazole and nitrobenzotriazole is used, a component surface can be uniformly roughened. Thereby, the unevenness | corrugation suitable for the adhesive improvement between copper-resin compositions is formed, and the adhesiveness between copper-resin compositions improves by the anchor effect.

  The “copper” in the present invention may be made of copper or a copper alloy. Further, in this specification, “copper” refers to copper or a copper alloy.

  Further, the “roughening treatment” in the present invention refers to a treatment in which the surface roughness (Ra) of the surface of the copper part is made larger than that before the treatment by bringing an etching agent into contact with the copper part. .

  According to the present invention, since the surface of the copper part is roughened with a specific etching agent, the adhesion between copper and the resin composition can be improved without using an adhesive, and the working environment is good. A method for producing a resin composite can be provided.

The perspective view which shows the copper-resin composite for a test used in the present Example. (A) is a top view showing a test copper-resin composite used in this example, (b) is a side view of (a), and (c) is a cross-sectional view taken along line AA of (a). Sectional drawing of the testing apparatus used for the airtightness test and watertightness test of a present Example. The scanning electron micrograph of the surface of the copper component of one Example (photographing angle 45 degree magnification 3000 times). The scanning electron micrograph of the surface of the copper component of one Example (photographing angle right above, magnification 1000 times). The scanning electron micrograph of the surface of the copper component of one Example (photographing angle right above, magnification 5000 times). The scanning electron microscope photograph (1000-times multiplication factor) of the cross section of the copper components of one Example. The scanning electron micrograph of the cross section of the copper component of one Example (magnification 5000 times).

  Below, the manufacturing method of the copper-resin composite concerning this invention is demonstrated.

  The manufacturing method of the copper-resin composite of this embodiment implements the roughening process which roughens the surface of copper components with an etching agent, and the adhesion process which adheres a resin composition to the said roughened surface. A method for producing a copper-resin composite, wherein the etching agent is an aqueous solution containing sulfuric acid, hydrogen peroxide, phenyltetrazole, nitrobenzotriazole, benzenesulfonic acid and chloride ion.

[Copper parts]
A copper part (hereinafter also referred to as “part”) that can be used in the present embodiment has a shape that allows a resin composition to adhere to form a copper-resin composite (hereinafter also referred to as “composite”). As long as it is not particularly limited. For example, from copper lump, plate material, bar material, etc. to plastic processing, sawing, milling, electrical discharge machining, drilling, pressing, grinding, polishing, etc. alone or in combination with these processes into the desired shape Machined ones can be used.

  It is desirable that the copper part does not have a thick film made of an oxide film or hydroxide on the surface to which the resin composition is attached. In order to remove such a thick film, the surface layer may be polished by mechanical polishing such as sand blasting, shot blasting, grinding, barrel processing, or chemical polishing before the treatment with the etching agent.

[Etching agent]
In this embodiment, an aqueous solution containing sulfuric acid, hydrogen peroxide, phenyltetrazoles, nitrobenzotriazoles, benzenesulfonic acids, and chloride ions is used as an etching agent for roughening the parts. Since the etching agent has good handleability and does not require treatment at high temperature, the working environment can be maintained well.

Since the etching agent contains phenyltetrazole and nitrobenzotriazole, the surface of the component can be uniformly roughened. Thereby, the unevenness | corrugation suitable for the adhesive improvement between copper-resin compositions is formed, and it is thought that the adhesiveness between copper-resin compositions improves by the anchor effect. The etching agent has a function of improving the adhesion by a chemical action in addition to a function of improving the adhesion between copper and the resin composition by an anchor effect by roughening the surface of the component. Conceivable.
With regard to this chemical action, for example, phenyltetrazole and nitrobenzotriazole adhere to the surface of the component, so that these components and copper ions form a film, and this film adheres to the resin composition. It can be considered that the adhesion improves.

Furthermore, the treatment with the etching agent can prevent moisture and moisture from entering from the interface between copper and the resin composition. That is, by performing the treatment with the etching agent, the air tightness and water tightness at the adhesion interface of the composite can be improved.
Therefore, the manufacturing method of this embodiment is suitable for manufacturing various electrode terminal parts, various sensor parts, various switch parts and the like that require high airtightness and watertightness.

  Hereinafter, each component of the etching agent that can be used in the present embodiment will be described.

(Sulfuric acid)
The sulfuric acid concentration in the etching agent is adjusted according to the etching rate and the copper dissolution tolerance of the etching agent, but is preferably 60 to 220 g / L, more preferably 90 to 150 g / L. In the case of 60 g / L or more, since the etching rate is increased, the surface of the component can be rapidly roughened. On the other hand, in the case of 220 g / L or less, it can prevent that the melt | dissolved copper precipitates as copper sulfate.

(hydrogen peroxide)
The concentration of hydrogen peroxide in the etching agent is adjusted according to the etching rate and surface roughening ability, but is preferably 5 to 70 g / L, more preferably 7 to 56 g / L, and more preferably 10 to 30 g / L. Further preferred. In the case of 5 g / L or more, since the etching rate is increased, the part surface can be rapidly roughened. On the other hand, in the case of 70 g / L or less, the part surface can be more uniformly roughened.

(Phenyltetrazole)
Examples of the phenyltetrazole in the etching agent include 1-phenyltetrazole and derivatives thereof, 5-phenyltetrazole and derivatives thereof, and the like.
Especially, in order to improve the adhesiveness of copper and a resin composition by the synergistic effect with nitrobenzotriazoles, it is especially preferable that the said phenyltetrazole is 5-phenyltetrazole. Examples of the derivative include a compound into which a —SH group is introduced, such as 1-phenyl-5-mercapto-1H tetrazole, a compound into which a —NH ₂ group is introduced, such as 5 (3-aminophenyl) 1H tetrazole, and the like. Can be illustrated.
In addition, a metal salt of 1-phenyltetrazole or a metal salt of 5-phenyltetrazole may be used. Counter ions of these metal salts include calcium ions, cuprous ions, cupric ions, lithium ions, Examples thereof include magnesium ions and sodium ions.

  The concentration of phenyltetrazole in the etching agent is adjusted according to the roughened shape and the copper dissolution tolerance of the etching agent, but is preferably 0.01 to 0.7 g / L, preferably 0.03 to 0.6 g. / L is more preferable, and 0.05 to 0.4 g / L is more preferable. In the case of 0.01 g / L or more, since the etching rate is increased, the surface of the component can be rapidly roughened. On the other hand, in the case of 0.7 g / L or less, phenyltetrazole can be prevented from being precipitated in the etching agent.

(Nitrobenzotriazoles)
Examples of the nitrobenzotriazoles in the etching agent include 4-nitrobenzotriazole and derivatives thereof, 5-nitrobenzotriazole and derivatives thereof, and the like. Among these, in order to enhance the adhesion between copper and the resin composition by synergistic effect with phenyltetrazole, the nitrobenzotriazole is 4-nitrobenzotriazole, 5-nitrobenzotriazole, or 4-nitrobenzotriazole. And a mixture of 5-nitrobenzotriazole. In particular, when 4-nitrobenzotriazole is used, it is preferable because precipitates hardly occur in the etching agent.

  The concentration of nitrobenzotriazoles in the etching agent is adjusted according to the roughened shape and the copper dissolution tolerance of the etching agent, but is preferably 0.01 to 1.5 g / L, preferably 0.1 to 1. 0 g / L is more preferable, and 0.2 to 0.8 g / L is more preferable. In the case of 0.01 g / L or more, the part surface can be roughened more uniformly. On the other hand, in the case of 1.5 g / L or less, precipitation of nitrobenzotriazoles in the etching agent can be prevented.

  In order to further improve the adhesion between copper and the resin composition and to further improve the airtightness and watertightness at the adhesion interface of the composite, the concentration of the phenyltetrazole is Ag / L, and the nitrobenzotriazoles When the concentration of is Bg / L, B / A is preferably 1.0 to 3.0, more preferably 1.5 to 3.0.

(Benzenesulfonic acids)
In order to suppress the decomposition of hydrogen peroxide when a large amount of copper is treated continuously by using the etching agent, benzenesulfonic acids are blended. It is known that the benzenesulfonic acids are oxidized by hydrogen peroxide in a conventional etching agent to generate a brown or black precipitate (see JP-A-11-140669).
In the present embodiment, by using benzenesulfonic acids in combination with phenyltetrazoles and nitrobenzotriazoles, an action of inhibiting the decomposition of hydrogen peroxide is exhibited without producing brown precipitates.

  Examples of the benzenesulfonic acids in the etching agent include benzenesulfonic acid, toluenesulfonic acid, m-xylenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, sulfosalicylic acid, m-nitrobenzenesulfonic acid, p-aminobenzenesulfonic acid, and the like. Can be mentioned.

  The concentration of benzenesulfonic acids in the etching agent is preferably 2 to 10 g / L, more preferably 2 to 4 g / L, from the viewpoint of hydrogen peroxide stability.

(Chloride ion)
The etching agent contains chloride ions in order to deepen the dent on the surface of the component after the roughening treatment. Chloride ions can be included in the etchant by blending a chloride ion source. Examples of the chloride ion source include sodium chloride, potassium chloride, ammonium chloride, hydrochloric acid and the like. Although the density | concentration of a chloride ion is adjusted according to a roughening shape and an etching rate, 1-60 ppm is preferable and 2-30 ppm is more preferable. Within this range, the part surface can be sufficiently roughened. In order to obtain a stable etching rate, a copper compound such as copper sulfate, copper chloride, or copper acetate may be dissolved. The concentration of these copper compounds is usually about 5 to 60 g / L as the copper concentration.

<Other ingredients>
In the etching agent that can be used in this embodiment, a surfactant may be added to prevent unevenness due to surface contaminants such as fingerprints on the surface of the copper part, and other antifoaming agents may be added as necessary. Additives may be added. When these other components are added, the content is preferably about 0.001 to 0.1 g / L.

  The etching agent of this embodiment can be easily prepared by dissolving the above-described components in ion-exchanged water or the like.

[Roughening process]
Next, the roughening process which roughens the surface of components using the etching agent mentioned above is demonstrated.

  In the case where there is significant contamination such as machine oil on the surface of the part to be processed, after the degreasing, the roughening treatment with the etching agent may be performed. Examples of the roughening treatment method include treatment methods such as immersion and spraying. The treatment temperature is preferably 20 to 40 ° C., and the treatment time is preferably about 10 to 300 seconds. After the treatment, washing and drying are usually performed.

The surface of the component is roughened into a concavo-convex shape by the roughening treatment using the etching agent. The etching amount (dissolution amount) in the depth direction during the roughening treatment is preferably 0.1 to 20 μm, preferably 1.5 to 20 μm, when calculated from the weight, specific gravity and surface area of the dissolved copper. It is more preferable that the thickness is 1.5 to 10 μm. If the etching amount is 0.1 μm or more, the surface of the component can be uniformly roughened.
Moreover, if the etching amount is 20 μm or less, excessive etching of the formed protrusions can be prevented. Therefore, if the etching amount is within the above range, a good roughened shape suitable for improving the adhesion between the copper-resin composition can be obtained. The etching amount can be adjusted by the processing temperature, processing time, and the like.

In this embodiment, when roughening the part using the etching agent, the entire surface of the part may be roughened, and only the surface to which the resin composition is adhered is partially roughened. May be.
Further, the azole-containing film formed on the surface of the part after the roughening treatment may be removed with an aqueous sodium hydroxide solution or the like. In this case, after removing the film, it is preferable to neutralize with sulfuric acid or the like, and further apply a rust prevention treatment.

In the present embodiment, the roughening process may be performed in combination with wet etching using other etching agents or various dry etchings in the roughening step within a range not impairing the effects of the present invention.
Further, after the roughening treatment, the treatment surface may be further subjected to chemical conversion treatment such as various plating treatments and chromate treatment. Examples of the type of plating include nickel plating, tin plating, and zinc plating. By applying plating, weather resistance and long-term reliability can be improved.

[Adhesion process of resin composition]
Next, the adhesion process of the resin composition which makes a resin composition adhere on the surface of the said copper parts roughened by the said roughening process process is implemented.
A copper-resin composite is obtained by attaching the resin composition on the roughened surface of the roughened copper part.
In this embodiment, since the unevenness | corrugation suitable for the adhesive improvement between copper-resin compositions is formed by processing with the said specific etching agent, between copper-resin compositions without using an adhesive agent. Adhesion can be ensured.
The method for adhering the resin composition onto the roughened part surface is not particularly limited, and is injection molding, extrusion molding, heat press molding, compression molding, transfer molding, casting molding, laser welding molding, reaction. Resin molding methods such as injection molding (RIM molding) and rim molding (LIM molding) can be employed.
Moreover, when manufacturing the composite body which consists of a copper-resin composition film | membrane which coated the resin composition film | membrane on the copper surface, the coating method which dissolves or disperse | distributes a resin composition to a solvent, and other various coating methods Can be adopted. Examples of other coating methods include baking coating, electrodeposition coating, electrostatic coating, powder coating, and ultraviolet curable coating. Among these, injection molding is preferable from the viewpoint of the degree of freedom of the shape of the resin composition part and productivity. As the molding conditions of the above-described molding methods, known conditions can be adopted depending on the resin composition.

[Resin composition]
The resin composition that can be used in the present embodiment is not particularly limited as long as the resin composition can be attached to the surface of the component by the above-described molding method, and can be used from among thermoplastic resin compositions and thermosetting resin compositions. Can be selected accordingly.

(Thermoplastic resin composition)
When the thermoplastic resin composition is used, the main thermoplastic resin is polyamide resin such as polyamide 6 or polyamide 66, polyethylene resin, polypropylene resin, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene / styrene copolymer. Resin, polyvinyl chloride resin, polycarbonate resin, polyacetal resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyphenylene sulfide resin, liquid crystalline polyester resin, polyimide resin, syndiotactic polystyrene resin, polycyclohexanedimethylene terephthalate Resin, fluororesin, polyvinyl acetate resin, modified polyphenylene ether resin, polyether sulfone resin, amorphous polyarylate tree , And the like can be exemplified a combination aromatic polyether ketone resin, ethylene-vinyl acetate copolymer resin, an ethylene-acrylic acid copolymer resin, etc., ethylene-methacrylic acid copolymer resin, a two or more thereof.
Among these, polyamide resins, polybutylene terephthalate resins, and polyphenylene sulfide resins that can be easily molded are preferable, and polyamide resins and polyphenylene sulfide resins are more preferable from the viewpoint of improving the adhesion between the copper-resin composition.
Moreover, a polyamide resin is more preferable from the viewpoint of improving airtightness and watertightness at the adhesion interface of the composite, and polyamide 6 is more preferable.

  As the thermoplastic resin composition that can be used in the present embodiment, it may be a composition comprising the above-mentioned thermoplastic resins, and to the extent that the effects of the present invention are not impaired, Various conventionally known inorganic and organic fillers, flame retardants, flame retardant aids, UV absorbers, heat stabilizers, light stabilizers, colorants, carbon black, processing aids, nucleating agents, mold release agents, plasticizers, etc. The composition which added these additives may be sufficient. Among these, in order to prevent interfacial peeling between the copper-resin composition caused by the difference in linear expansion coefficient between copper and the resin composition, the inorganic filler is added in an amount of 10 to 200 with respect to 100 parts by weight of the above-mentioned thermoplastic resin. It is preferable to add parts by weight.

(Thermosetting resin composition)
When the thermosetting resin composition is used as the resin composition, the thermosetting resin as the main component includes phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyimide resin, diallyl phthalate resin, Examples include alkyd resins, polyurethane resins, cyanate resins, silicone resins, and combinations of these two or more.
Among them, phenol resin, epoxy resin, and unsaturated polyester resin that are easy to mold are preferable, and the viewpoint of improving the adhesion between the copper-resin composition and the air tightness and water tightness at the adhesion interface of the composite are improved. From this viewpoint, a phenol resin is more preferable.

  The thermosetting resin composition that can be used in the present embodiment may be a composition composed of the above-mentioned thermosetting resins, and the above-mentioned thermosetting resins are used to the extent that the effects of the present invention are not impaired. On the other hand, various conventionally known inorganic and organic fillers, flame retardants, flame retardant aids, ultraviolet absorbers, heat stabilizers, light stabilizers, colorants, carbon black, processing aids, nucleating agents, mold release agents, It may be a composition to which an additive such as a plasticizer is added. Among these, in order to prevent interfacial delamination between the copper-resin composition caused by the difference in coefficient of linear expansion between copper and the resin composition, the inorganic filler is added to 10 parts by weight with respect to 100 parts by weight of the above-mentioned thermosetting resin. It is preferable to add 200 parts by weight.

(Other resin composition)
As the resin composition that can be used in this embodiment, in addition to the above-described resin compositions, a photocurable resin composition containing an acrylic resin, a styrene resin, etc., or a reactive curable resin composition containing a rubber, an elastomer, and the like. And various resin compositions.

The manufacturing method of the composite of the present invention exemplified in this embodiment is used for manufacturing various machine parts such as parts for electronic equipment, parts for household electrical appliances, parts for transport machinery, and the like. It is suitable for manufacturing various electronic device parts, home appliance parts, medical equipment parts, vehicle structural parts, vehicle mounting parts, other electrical parts, heat dissipation parts, etc.
When applied to the manufacture of heat dissipation components, the surface area of the copper component is increased by roughening the surface of the copper component, so that the contact area between the copper-resin composition increases and the thermal resistance of the contact interface can be reduced. . Therefore, when the method of the present invention is applied to the manufacture of a heat dissipation component, the effect of improving heat dissipation can be obtained in addition to the effect of improving adhesion, airtightness and watertightness.

  Next, examples of the present invention will be described together with comparative examples. In addition, this invention is limited to a following example and is not interpreted.

[Tensile shear test]
(Examples 1 to 3 and Comparative Example 1)
A plate material of tough pitch copper (C1100) having a thickness of 2 mm was cut into a length of 110 mm and a width of 25 mm.
This copper part was dipped in an etching agent (30 ° C.) having the composition shown in Table 1 and swung to etch only the etching amount shown in Table 2, then washed with water and dried.
Using the copper parts after treatment and the resin composition shown in Table 2, injection molding was performed under the molding conditions shown in Table 3 (device used: model TH60-9VSE (single acting), manufactured by Nissei Plastic Industry Co., Ltd.). 1, a composite in which the copper part 1 and the resin composition 2 were vertically overlapped at one end side was obtained.
Note that the length of the overlapping portion a is 12.5 mm. The resin composition 2 has a length of 110 mm, a width of 25 mm, and a thickness of 2 mm.
With respect to the obtained composite, the tensile tester (universal tester manufactured by Instron Co., Ltd., model: 1175) was pulled in the direction X shown in FIG. It was.
The etching amount is an etching amount calculated from the weight difference between the copper parts before and after the etching process, the specific gravity of copper, and the surface area of the copper parts, and was adjusted by the etching time. The same applies to the “etching amount” shown below.
As Comparative Example 1, a composite was molded under the same conditions except that the roughening treatment was not performed in Example 3, and the tensile shear strength was measured in the same manner as in Example 3.
The results are shown in Table 2.

From the results shown in Table 2, the composites of Examples 1 to 3 were all good in tensile shear strength.
The composite of Comparative Example 1 could not be measured because a part of the resin composition was peeled off from the copper part after injection molding.

[Vertical indentation test]
(Examples 4 to 6 and Comparative Examples 2 and 3)
Next, the vertical indentation test will be described.
A plate material of tough pitch copper (C1100) having a thickness of 2 mm was cut into a size of 80 mm × 80 mm, and a hole of 20 mmφ was made in the center to obtain a copper part for testing.
This copper part was dipped in an etching agent (30 ° C.) having the composition shown in Table 1 and swung to etch the etching amount shown in Table 4, then washed with water and dried. Using the copper parts after the treatment and the resin compositions shown in Table 4, transfer molding was performed by a transfer molding machine (apparatus model: TA-37, manufactured by Shindo Metal Industry Co., Ltd.). A composite 3 for test in which the copper part 10 having the shape shown in (c) and the resin composition 20 were laminated was obtained (Examples 4 and 5).
The molding conditions were set to a mold temperature of 155 ° C. and an injection pressure of 17.7 MPa.
Moreover, about Example 6, after performing even the roughening process similar to the said Example 5, using the resin composition shown in Table 4, on the molding conditions similar to the said Example 1, FIG. ) To (c) to obtain the test composite 3 in which the copper part 10 and the resin composition 20 having the shape shown in FIG. 1 were laminated. The molded composite was tested with a testing machine (Instron Universal Testing Machine, model: 1175), the strength (MPa) when the resin was peeled from the copper part by pushing in the direction Y shown in FIG. 2 (b) at a pushing speed of 1 mm / min was defined as the vertical pushing strength.
As Comparative Example 2, a composite was molded under the same conditions except that the roughening treatment was not performed in Example 4, and the vertical indentation strength was measured in the same manner as described above.
Further, as Comparative Example 3, a composite was molded under the same conditions except that the roughening treatment was not performed in Example 6, and the vertical indentation strength was measured in the same manner as described above.
In addition, about evaluation of Example 4, 5 and the comparative example 2, after obtaining a composite_body | complex, what was aged by leaving to stand at 25-30 degreeC atmospheric temperature for 1 week was used.
The results are shown in Table 4.

  As shown in Table 4, in each example, the vertical indentation strength is a predetermined strength or more, but the composite of each comparative example is measured by peeling off a part of the resin composition from the copper part after injection molding. I couldn't.

[Airtightness test and watertightness test]
(Examples 7 to 9 and Comparative Examples 4 and 5)
Composites were molded in the same procedure as in Examples 4 to 6 to obtain composites for evaluation in Examples 7 to 9, respectively.
Further, composites were molded in the same procedure as in Comparative Examples 2 and 3, and composites for evaluation in Comparative Examples 4 and 5 were obtained.
About each obtained composite_body | complex, the airtightness test and the watertightness test were done by the method shown below.
In addition, about evaluation of Example 7, 8 and the comparative example 4, after obtaining a composite_body | complex, what was aged by leaving to stand at 25-30 degreeC atmospheric temperature for 1 week was used.

<Airtight / watertight test method>
Evaluation was performed using the test apparatus shown in FIG. First, the composite 3 was set in the metal container 11 of the pressure-tight airtight container via the rubber O-ring 12 and fixed so as to sandwich the composite with the metal upper lid 11a.
As an airtight test method, a pressure-tight airtight container in which the composite 3 is set is put into a water tank, an air valve (not shown) is gradually opened to increase the pressure in the pressure-tight airtight container, and the composite adheres. The presence or absence of air leakage from the interface was confirmed. At this time, if there was no air leakage in a stationary state for 3 minutes with a predetermined pressure applied, it was judged that the airtightness under the pressure was good.
The test started from a pressure of 0.1 MPa. If there was no air leak, the test was sequentially increased by 0.1 MPa, and the test was performed up to a maximum of 0.4 MPa. And, when there is an air leak at 0.1 MPa, ×, when there is no air leak at 0.2 to 0.3 MPa, and when there is an air leak at 0.4 MPa, Δ, no air leak at 0.4 MPa The airtightness was evaluated with ○ as the case.
As the watertight test method, the same method was used except that the pressure tight airtight container was not put into the water tank and water was injected instead of air and the presence or absence of water leakage was evaluated. X when there is water leakage at 1 MPa, Δ when there is no water leakage between 0.2 and 0.3 MPa, and when there is water leakage at 0.4 MPa, and when there is no water leakage at 0.4 MPa. ○ was evaluated for water tightness.
The results are shown in Table 5.

  As shown in Table 5, in each example, both airtightness and watertightness were good, but in each comparative example, air leakage and water leakage occurred at 0.1 MPa.

<Surface observation, cross-sectional observation>
The surface and cross section of the copper part treated under the same conditions as in the roughening step of Example 1 were observed with a scanning electron microscope (SEM) (model JSM-7000F, manufactured by JEOL Ltd.). SEM photographs at that time are shown in FIGS.

1, 10: Copper parts
2, 20: resin composition,
3: Complex,
11: Metal container part,
11a: Metal upper lid,
12: O-ring.

Claims (5)

A method for producing a copper-resin composite, comprising: a roughening step of roughening a surface of a copper part with an etching agent; and an adhesion step of attaching a resin composition to the roughened surface,
The method for producing a copper-resin composite, wherein the etching agent is an aqueous solution containing sulfuric acid, hydrogen peroxide, phenyltetrazoles, nitrobenzotriazoles, benzenesulfonic acids, and chloride ions.   The etching agent is sulfuric acid 60-220 g / L, hydrogen peroxide 5-70 g / L, phenyltetrazole 0.01-0.7 g / L, nitrobenzotriazole 0.01-1.5 g / L, benzenesulfone The method for producing a copper-resin composite according to claim 1, which is an aqueous solution containing acids 2 to 10 g / L and chloride ions 1 to 60 ppm.   The method for producing a copper-resin composite according to claim 1 or 2, wherein when the surface of the copper part is roughened, a processing temperature of the etching agent is 20 to 40C.   The method for producing a copper-resin composite according to any one of claims 1 to 3, wherein the attaching step is performed by injection molding.   The method for producing a copper-resin composite according to any one of claims 1 to 4, wherein the resin composition contains one or more selected from a polyamide resin, a polyphenylene sulfide resin, and a phenol resin.