Surface treatment agent for copper material

Abstract

To provide: a surface treatment agent capable of forming a film which has excellent insulation properties after heat exposure at high temperatures and which enhances adhesion between a resin material and the surface of a copper material; a surface treatment method for using the surface treatment agent to form the film, which includes a copper oxide on the surface of a copper material; and a copper material having the film.SOLUTION: An embodiment of the present invention is a surface treatment agent for a copper material, the surface treatment agent for a copper material including water, copper (II) ions, sulfate ions, and an organic acid, where the concentration of the sulfate ions is 1.0-55.0 g / L.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a surface treatment agent for copper materials.

Background Art

[0002] There is a need for a method of surface-treating copper materials to improve adhesion to resins. For example, Patent Document 1 discloses a technique for roughening the surface of a wiring including a copper layer with a micro-etching agent for copper composed of an aqueous solution containing cupric ions, an organic acid, halide ions, an amino group-containing compound having a molecular weight of 17 to 400, and a polymer, thereby improving adhesion to a solder resist or the like.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, in order to improve the performance of electronic components containing copper materials, insulation in a high-temperature environment has been required. That is, there is a need for a technique capable of improving the adhesion of a resin film to a copper material in a high-temperature environment.

[0005] Therefore, an object of the present invention is to provide a surface treatment agent applicable to electronic components containing copper materials. More specifically, an object of the present invention is to provide a surface treatment agent capable of enhancing the adhesion between the surface of a copper material and a resin material and forming a film excellent in insulation after high-temperature heat exposure, and a copper material having a film containing copper oxide obtained by using the surface treatment agent.

Means for Solving the Problems

[0006] The present invention for achieving the above object may include the following.

[0007] One aspect of the present invention is a surface treatment agent for copper materials. The surface treatment agent for copper materials contains water, copper (II) ions, sulfate ions, and an organic acid, and the concentration of the sulfate ions is preferably 1.0 g / L or more and 55.0 g / L or less.

[0008] The organic acid preferably includes an organic acid having one or two carboxyl groups and being soluble in water. The organic acid preferably includes an organic acid having one carboxyl group and one hydroxyl group and being soluble in water. The concentration of the copper (II) ions is preferably 0.05 g / L or more and 40.0 g / L or less. When the molar concentrations of the copper (II) ions and the sulfate ions are A and B, respectively, it is preferable that 1.0 < B / A ≤ 10. The pH of the surface treatment agent for copper materials is preferably 2.0 or more and 6.0 or less. The organic acid preferably includes at least one selected from glycolic acid, lactic acid, and malonic acid. The surface treatment agent for copper materials preferably contains a water-soluble polymer having an amino group.

[0009] Another aspect of the present invention is a method for surface-treating a copper material or a method for manufacturing a copper material with a copper oxide-containing film, which includes a step of bringing the surface treatment agent for copper materials into contact with the surface of the copper material to form a copper oxide-containing film.

[0010] Another aspect of the present invention is a method for manufacturing a copper material with a coating film, which includes a step of forming a coating film on the surface of the copper oxide-containing film.

[0011] Another aspect of the present invention is a copper material with a copper oxide-containing film obtained by the method for surface-treating a copper material or the method for manufacturing a copper material with a copper oxide-containing film, or a copper material with a coating film obtained by the method for manufacturing a copper material with a coating film.

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a surface treatment agent capable of enhancing the adhesion between the surface of a copper material and a resin material and forming a film excellent in insulation after high-temperature heat exposure, and a copper material having a film containing copper oxide obtained by using the surface treatment agent.

Mode for Carrying Out the Invention

[0013] In this specification, when an upper limit value and a lower limit value are separately described, a numerical range obtained by combining any upper limit value and any lower limit value is regarded as being substantially disclosed.

[0014] In this specification, when a certain compound is described, its isomers are also regarded as being described simultaneously.

[0015] In this specification, unless otherwise specified, various measurements are carried out with the environmental temperature being room temperature (25°C).

[0016] Hereinafter, specific embodiments will be shown and the present invention will be described in detail, but the present invention is not limited thereto.

[0017] <Surface Treatment Agent for Copper Material> The surface treatment agent for copper material in this embodiment (hereinafter, may be simply referred to as a surface treatment agent) contains copper (II) ions, sulfate ions, and an organic acid.

[0018] <Copper (II) Ions> The surface treatment agent in this embodiment contains copper (II) ions. The concentration of copper (II) ions in the surface treatment agent is not particularly limited, but is preferably 0.05 g / L or more and 25.0 g / L or less, more preferably 0.1 g / L or more and 20.0 g / L or less, and still more preferably 1.0 g / L or more and 15.0 g / L or less. A surface treatment agent having the concentration within this range can form a film excellent in adhesion between the copper material and the resin material. The concentration of copper (II) ions contained in the surface treatment agent can be measured by redox titration [the method specified in JIS K 8983:2016 (iodine titration)].

[0019] The compound serving as the copper(II) ion source is not particularly limited. As the compound serving as the copper(II) ion source, a compound that is soluble in water as the solvent and does not inhibit film formation is preferable. Examples of the compound serving as the copper(II) ion source include inorganic copper salts or organic copper salts such as copper(II) sulfate, copper(II) nitrate, copper(II) formate, copper(II) acetate, copper(II) propionate, copper(II) butyrate, copper(II) lactate, copper(II) malonate, copper(II) glutarate, etc., or hydrates thereof. In this embodiment, two or more selected from these may be used in combination. Among them, copper(II) sulfate is preferable, and copper(II) sulfate pentahydrate is more preferable. Copper(II) sulfate can also serve as the sulfate ion source described later.

[0020] <Sulfate ion> The compound serving as the sulfate ion source is not particularly limited. As the compound serving as the sulfate ion source, a compound that is soluble in water as the solvent and does not inhibit film formation is preferable. Examples of the compound serving as the sulfate ion source include sulfates such as copper sulfate (preferably copper(II) sulfate), sodium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, iron sulfate, nickel sulfate, ammonium sulfate, etc. In this embodiment, two or more selected from these may be used in combination. Using copper(II) sulfate as the compound serving as the sulfate ion source is preferable because it can also serve as the copper(II) ion source and it is possible to increase the proportion of the active ingredient in the solid content in the surface treatment liquid according to this embodiment. Here, when using copper(II) sulfate as the sulfate ion source, further, by blending a copper(II) ion source or a sulfate ion source different from copper(II) sulfate, the concentration of sulfate ions and the concentration of copper(II) ions in the treatment liquid may be adjusted individually. Specifically, when using copper(II) sulfate as the compound serving as the sulfate ion source and it is desired to increase the sulfate ion concentration in the treatment liquid, it is preferable to further use sodium sulfate as the compound serving as the sulfate ion source.

[0021] The sulfate ion concentration contained in the surface treatment agent of the present embodiment is not particularly limited, but it is preferably 1.0 g / L or more, 2.0 g / L or more, 3.0 g / L or more, 5.0 g / L or more, 8.0 g / L, or 10.0 g / L or more, and it is preferably 55.0 g / L or less, 45.0 g / L or less, 35.0 g / L or less, or 25.0 g / L or less. More specifically, the sulfate ion concentration is preferably 1.0 g / L or more and 55.0 g / L or less, and particularly preferably 3.0 g / L or more and 25.0 g / L or less. By setting the sulfate ion concentration within such a range, it is easy to form a film that has excellent insulation properties after high-temperature heat exposure while enhancing the initial insulation properties (insulation properties before high-temperature heat exposure).

[0022] When the molar concentrations of copper (II) ions and sulfate ions contained in the surface treatment agent are A and B, respectively, it is preferably 1.0 < B / A < 20, and more preferably 1.0 < B / A ≤ 10. In other words, B / A is preferably 1.1 or more, 1.2 or more, or 1.4 or more, and preferably less than 20, 15 or less, or 10 or less. By setting B / A within such a range, the actions of copper (II) ions and sulfate ions are balanced, and it is easy to form a film that has excellent insulation properties after high-temperature heat exposure while enhancing the initial insulation properties (insulation properties before high-temperature heat exposure).

[0023] <Organic acid> The organic acid preferably has one or two carboxyl groups. The organic acid may be either one having a hydroxyl group or one not having a hydroxyl group.

[0024] An organic acid that is soluble in water can be used. In the present embodiment, "soluble in water" or "water-soluble" means dissolving 1 g or more in 1 L of water at 25°C.

[0025] More specifically, examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, glycolic acid, lactic acid, hydroxybutyric acid, malonic acid, succinic acid, glutaric acid, and adipic acid. In this embodiment, two or more selected from these may be used in combination. It is more preferable that the organic acid is at least one selected from glycolic acid, lactic acid, and malonic acid.

[0026] In addition, the organic acid in this embodiment may be in the form of an organic acid salt. Further, in this embodiment, when the surface treatment agent contains an organic acid, it is intended to include a form in which the surface treatment agent contains an organic acid salt, an organic acid ion derived from an organic acid or an organic acid salt, etc. In this case, it is preferable that the organic acid salt is one or more selected from the alkali metal salts of the aforementioned organic acids (for example, lithium salt, sodium salt, potassium salt, etc.). Further, the organic acid salt of copper (II) (for example, copper (II) malonate, etc.) is treated as an organic acid and also serves as a copper (II) ion source.

[0027] When the molar concentrations of copper (II) ions and the organic acid contained in the surface treatment agent are A and C, respectively, it is preferable that 1.0 ≦ C / A ≦ 10, and more preferably 1.5 ≦ C / A ≦ 4.0. By setting C / A within such a range, the stability of the treatment liquid can be enhanced (precipitation can be suppressed), and since the etching action by the organic acid can be made appropriate, it is easy to stably form a film. The concentration or molar concentration of the organic acid in the surface treatment agent refers to the concentration or molar concentration in terms of the total organic acid of the organic acid, organic acid salt, and organic acid ion in the surface treatment agent.

[0028] The concentration of the organic acid contained in the surface treatment agent is not particularly limited, but is preferably 0.5 to 20.0 g / L, more preferably 1.0 to 10.0 g / L, and even more preferably 3.0 to 7.5 g / L.

[0029] <Polymer> The polymer is not particularly limited, but is preferably a water-soluble polymer, and more preferably a water-soluble polymer having an amino group. Examples of the water-soluble polymer having an amino group include water-soluble polymers having a heterocyclic amine structure, and more specifically, water-soluble polymers having a structural unit represented by the following formula (i).

[0030]

Chemical formula

[0031] Examples of the polymer having a structural unit represented by the above formula (i) include diallylamine homopolymers; salts of diallylamine homopolymers such as diallylamine methyl sulfate homopolymer, diallylamine sulfate homopolymer, and diallylamine acetate homopolymer; copolymers having a structural unit represented by the above formula (i) or salts thereof; and the like. Examples of the copolymer or salt having a structural unit represented by the above formula (i) include those containing a structural unit represented by the above formula (i) and a structural unit such as acrylamide, acrylic acid, maleic acid, sulfur dioxide, and allylamine. More specifically, diallylamine sulfate acrylamide copolymer, diallylamine sulfate maleic acid copolymer, diallylamine sulfate sulfur dioxide copolymer, diallylamine acetate sulfur dioxide copolymer, allylamine sulfate diallylamine sulfate copolymer, allylamine acetate diallylamine acetate copolymer, and the like can be mentioned.

[0032] The degree of polymerization of the water-soluble polymer is not particularly limited, but the weight average molecular weight is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 150,000, and even more preferably in the range of 5,000 to 100,000. The weight average molecular weight is measured by GPC (gel permeation column chromatography) and is a value converted with polystyrene.

[0033] The content of the polymer (preferably a water-soluble polymer) relative to the total amount of the surface treatment agent is not particularly limited, but is preferably in the range of 1 to 1000 mg / L as a solid content mass concentration, more preferably in the range of 3 to 500 mg / L, and even more preferably in the range of 5 to 200 mg / L. A surface treatment agent having a polymer content within the above range can form a film with excellent adhesion between the copper material and the resin material.

[0034] The water-soluble polymer may be a commercially available product. Examples of commercially available water-soluble polymers include Uniseance KCA103LU (diallylamine / acrylamide sulfate copolymer manufactured by Senka Corporation: active ingredient 40%), PAA-D19A (allylamine acetate / diallylamine acetate copolymer manufactured by Nitto Boehringer Medical Co., Ltd.: active ingredient 20%), PAA-03 (allylamine polymer manufactured by Nitto Boehringer Medical Co., Ltd.: active ingredient 20%), and the like.

[0035] <Other components> The surface treatment agent for copper material of the present embodiment may or may not contain substances other than the above substances (other components) as long as the characteristics of the surface treatment agent are not inhibited. Examples of other components include halides and compounds containing transition metals other than copper(II). In addition, examples of other components include pH adjusters described later.

[0036] <pH of the surface treatment agent> The pH of the surface treatment agent of the present embodiment is preferably 2.0 or more and 6.0 or less, and more preferably 4.5 or more and 5.5 or less. A surface treatment agent having a pH within this range can form a film with excellent adhesion between the copper material and the resin material. The pH of the surface treatment agent is measured with a pH meter at 25°C.

[0037] The pH of the surface treatment agent can be adjusted using a pH adjuster such as an acid component such as nitric acid, or an alkali component such as ammonia, lithium hydroxide, or potassium hydroxide. The pH adjuster is not limited to these components. Note that one or more pH adjusters may be used.

[0038] <Method for Manufacturing Surface Treatment Agent> Copper Material The surface treatment agent for copper material in this embodiment is mixed by a known mixing method and mixing apparatus. The order of mixing the substances contained in the surface treatment agent for copper material in this embodiment is not particularly limited. Further, the above substances may be mixed at once or divided and mixed.

[0039] <Surface Treatment Method> The surface treatment method in this embodiment is a method including a step of bringing the above surface treatment agent into contact with a copper material.

[0040] <Copper Material> The object of the surface treatment with the surface treatment agent in this embodiment is a copper material. The copper material is not particularly limited as long as it is a material containing copper, and examples thereof include pure copper and copper alloys. Examples of pure copper include oxygen-free copper, tough pitch copper, and phosphor deoxidized copper. Examples of alloy components other than copper in copper alloys include zinc, phosphorus, aluminum, iron, and nickel. Specific examples of copper alloys include those containing 50% by mass or more of copper (for example, brass containing 30 to 40% by mass of zinc and the balance being copper). The shape, structure, etc. of the copper material are not particularly limited. Examples of the shape of the copper material include plate-like, foil-like, rod-like, etc.

[0041] <Surface Treatment Method> The surface treatment method using the copper material in this embodiment (a method of forming a film by bringing the surface treatment agent in this embodiment into contact with the surface of the copper material) is not particularly limited. Examples thereof include dipping treatment, spraying treatment, and pouring treatment. Further, two or more of these methods can be used in combination. Also, the presence or absence of stirring of the treatment agent in dipping, the spray pressure in spraying treatment, and the type of spray nozzle are not particularly limited.

[0042] The temperature at the time of bringing the copper material into contact with the above surface treatment agent is not particularly limited, but is preferably 20°C or higher and 60°C or lower, more preferably 35°C or higher and 45°C or lower.

[0043] When contacting the copper material with the above surface treatment agent, the time is not particularly limited and can be set as appropriate. For example, it can be treated for 1 second to 15 minutes.

[0044] After the copper material is contacted with the surface treatment agent, it is preferable to perform water washing. The water used can be tap water, industrial water, well water, etc., but deionized water is optimal. Also, the temperature of the washing water is not particularly limited and may be heated to speed up drying.

[0045] In the surface treatment method of this embodiment, before contacting the copper material with the above surface treatment agent, it is preferable to perform one or both of the pretreatment steps of degreasing treatment and pickling treatment. The degreasing solution and pickling solution are not particularly limited. After the above pretreatment, it may or may not be washed with water and then dried.

[0046] In the surface treatment method of this embodiment, after contacting the copper material with the above surface treatment agent, it may be further post-treated with a rust inhibitor, post-treatment agent, pH adjuster, coupling agent, etc. After the above post-treatment, it may or may not be washed with water and then dried.

[0047] <Film> A film containing copper(I) oxide and / or copper(II) oxide (referred to as a copper oxide film or a copper oxide-containing film) is formed by the surface treatment method of this embodiment. In other words, a copper material with a copper oxide film (a copper material with a copper oxide-containing film) is obtained by the surface treatment method of this embodiment. The ratio of copper(I) oxide to copper(II) oxide in the copper oxide film is not particularly limited. Also, when the surface treatment liquid contains a polymer (particularly, a water-soluble polymer, a water-soluble polymer having an amino group, or a water-soluble polymer having a structural unit represented by the above formula (i)), a film containing the polymer (resin film) is also formed simultaneously with this copper oxide film. Here, the film formed by the surface treatment method of this embodiment may sometimes be referred to as a surface treatment film. The surface treatment film may be either a film containing a copper oxide film and not containing a resin film, or a film containing a copper oxide film and a resin film.

[0048] The thickness of the copper oxide film formed by the surface treatment agent for the copper material of the present embodiment is 1 nm or more and 100 nm or less, preferably 3 nm or more and 70 nm or less, and more preferably 5 nm or more and 50 nm or less. The copper material with the thickness of the formed copper oxide film within this range can exhibit excellent adhesion to the resin material. Note that the thickness of the copper oxide film is converted from the mass of copper oxide calculated by the electrochemical reduction method to the thickness.

[0049] The mass of the resin film (for example, a film formed of a water-soluble polymer having a structural unit represented by the above formula (i)) formed by the surface treatment agent for the copper material of the present embodiment is 0.5 mg / m 2 or more and 20 mg / m 2 or less, preferably 1 mg / m 2 or more and 15 mg / m 2 or less, and more preferably 2 mg / m 2 or more and 10 mg / m 2 or less. The copper material with the formed resin film within this range can exhibit excellent adhesion to the resin material. Note that the mass of the resin film in the surface treatment film is measured by measuring the C deposition amount using a fluorescent X-ray analyzer and regarding it as the mass of the resin film.

[0050] <Adhesive> By joining the copper material and the resin material through the surface treatment film formed by surface-treating the copper material by the above-described surface treatment method for the copper material, an adhesive showing high adhesion can be obtained. The resin material is not particularly limited and may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include AS resin, ABS resin, fluororesin, polyamide, polyethylene, polyethylene terephthalate, polyvinylidene chloride, polycarbonate, polystyrene, polysulfone, polypropylene, liquid crystal polymer, and the like. Examples of the thermosetting resin include epoxy, phenol, polyimide, polyurethane, bismaleimide-triazine, modified polyphenyl ether, cyanate ester, and the like. These resin materials may be modified by functional groups.

[0051] The method of joining a copper material and a resin material through a surface treatment film is not particularly limited, and known methods can be adopted. For example, a resin material is applied to a part or the whole of the copper material with a surface treatment film formed by bringing the surface of the copper material into contact with the surface treatment agent of the present embodiment, and then pressure-bonded; or a method of bonding the copper material with the surface treatment film and the resin material using an adhesive or an adhesive sheet; a method of applying a joining material by electrodeposition coating, powder coating, solvent coating, etc.; or a method combining these can be mentioned.

Example

[0052] The present invention will be described in detail by the following examples. However, these inventions are not limited to these examples.

[0053] <Fabrication of test plates> Test plates were fabricated as follows.

[0054] First, a copper material (150 mm (length) × 70 mm (width) × 0.8 mm (thickness)) was degreased (Fine Cleaner E6400, manufactured by Nippon Parkerizing Co., Ltd., trade name, 60 °C × 5 minutes dip treatment), and then washed with water to make it clean.

[0055] Next, a surface treatment agent in which the components described in each example and comparative example in Table 1 were dissolved in water to the corresponding concentrations was prepared, and the cleaned copper material was immersed in the surface treatment agent to perform surface treatment. In Table 1, "-" indicates that the corresponding component is not contained. In addition, the pH of each surface treatment agent is shown in Table 1. The pH of the surface treatment agent was adjusted with an aqueous sodium hydroxide solution and sulfuric acid. The immersion time of the copper material in the surface treatment agent was uniformly 2 minutes in any example, and the temperature was 40 °C.

[0056] Next, using the coating methods shown in Table 1, the surface-treated copper material was coated so that the dry film thickness became 20 μm to obtain test plates for each example and comparative example.

[0057] The specific conditions for each painting method (electrocoating, powder coating, solvent coating) shown in Table 1 are as follows.

[0058] <Electrocoating> The test panels were immersed in Electron KG400 (manufactured by Kansai Paint Co., Ltd.), and the voltage was increased to reach 200 V in 30 seconds. After reaching 200 V, it was applied to hold for 150 seconds to deposit an uncured electrocoating film on the test panels. Subsequently, these test panels were heated at 180 °C for 26 minutes to form an electrocoating film.

[0059] <Powder coating> Using Innobax P series (manufactured by Shin-Toyo Paint Co., Ltd.), coating was performed using an electrostatic powder coating apparatus manufactured by Parker Engineering Co., Ltd. to apply an uncured powder coating film on the test panels. Subsequently, these test panels were heated at 180 °C for 20 minutes to form a powder coating film.

[0060] <Solvent coating> Highmerit Primer No300 (manufactured by Natco Co., Ltd.) was used. The above paint and thinner M No15 were mixed at a ratio of 100:30 to dilute the paint. An air spray was performed on the test panels to apply a solvent coating film. Subsequently, these test panels were heated at 140 °C for 20 minutes to form a solvent coating film.

[0061] <Evaluation> Regarding the test panels (surface-treated copper materials with coating films) obtained by the above method, various evaluations were performed as follows. The results are shown in Table 1.

[0062] <Coating adhesion after high-temperature exposure> Each test panel was left standing in an oven set at 220 °C for 625 hours. After 625 hours, the adhesion (cross-cut adhesion) of the coating film defined in JIS K 5600 was evaluated. Using a cutter knife or the like, 100 cuts penetrating to the substrate were made in a grid pattern, and cellophane tape was attached to those locations. It was judged by the presence or absence of coating film peeling caused by peeling off the cellophane tape, and those without coating film peeling were regarded as qualified.

[0063] <Measurement of Dielectric Breakdown Voltage> The dielectric breakdown voltage (dielectric breakdown voltage per unit film thickness) of each test board was measured using a withstand voltage tester (TOS9201, manufactured by Kikusui Electronics Industry Co., Ltd.). The measurement was carried out under the conditions of an initial voltage of 0 V, a voltage increase rate of 50 V / second, and a cut-off current of 1.0 mA.

[0064] <Insulation Property after High-Temperature Exposure> Each test board was left standing in an oven set at 220°C for 625 hours. The dielectric breakdown voltage per unit film thickness of the test board before (initial) and 625 hours after being left standing in the oven was measured, the ratio of the value after the passage of the standing time to the initial value of each test board was calculated, and this was defined as the dielectric breakdown voltage retention rate, and each was compared. A dielectric breakdown voltage retention rate of 85% or more was considered to be qualified.

[0065]

Table 1

Industrial Applicability

[0066] Since the surface treatment agent of the present invention can enhance the adhesion between the surface of the copper material and the resin material and form a film excellent in insulation property after high-temperature heat exposure, it can be applied to the surface treatment of the copper material when manufacturing a bonding material for an electronic component in which the copper material and the resin material are bonded.

Claims

1. A surface treatment agent for copper materials, comprising water, copper (II) ions, sulfate ions, and an organic acid, wherein the concentration of the sulfate ions is 1.0 g / L or more and 55.0 g / L or less.

2. The surface treatment agent for copper materials according to Claim 1, wherein the organic acid includes an organic acid having one or two carboxyl groups and being soluble in water.

3. The surface treatment agent for copper materials according to Claim 1, wherein the concentration of the copper (II) ions is 0.05 g / L or more and 40.0 g / L or less.

4. The surface treatment agent for copper materials according to Claim 1, wherein when the molar concentrations of the copper (II) ions and the sulfate ions are A and B, respectively, 1.0 < B / A ≤ 10.

5. The surface treatment agent for copper materials according to Claim 1, wherein the pH is 2.0 or more and 6.0 or less.

6. The surface treatment agent for copper materials according to Claim 1, wherein the organic acid includes at least one selected from glycolic acid, lactic acid, and malonic acid.

7. The surface treatment agent for copper materials according to Claim 1, comprising a water-soluble polymer having an amino group.

8. A method for manufacturing a copper material with a copper oxide-containing film, comprising a step of bringing the surface treatment agent for copper materials according to any one of Claims 1 to 7 into contact with the surface of a copper material to form a copper oxide-containing film.

9. A method for manufacturing a copper material with a coating film, comprising a step of forming a coating film on the surface of the copper oxide-containing film according to Claim 8.

10. A copper material with a copper oxide-containing film obtained by the method according to Claim 8.

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