Basic copper carbonate, copper oxide, method for producing basic copper carbonate, and method for producing copper oxide

Abstract

Provided is a copper oxide, for which the specific surface area measured by a nitrogen adsorption method is 2.9 m2 / g or more, and the tap density measured in accordance with JIS Z 2512: 2012 is less than 1.1 g / cm3.

Description

Basic copper carbonate, copper oxide, method for producing basic copper carbonate, and method for producing copper oxide

[0001] This invention relates to basic copper carbonate, copper oxide, a method for producing basic copper carbonate, and a method for producing copper oxide.

[0002] Copper plating technology is used in the manufacture of many electronic materials, including printed circuit board wiring, printing rolls, electrolytic foils, and wires. Consequently, there is a demand for technologies related to copper oxide used in copper plating, and basic copper carbonate, which is used as a raw material for copper oxide.

[0003] Patent Document 1 discloses a method for producing copper oxide, which includes the steps of: preparing a copper ammonia solution with a copper content of 90 to 140 g / L by placing solid copper in a dissolution tank and carrying out an initial reaction in an environment containing 100 to 150 g / L of aqueous ammonia, 60 to 110 g / L of carbon dioxide, pure water, and air; refluxing the unreacted gas from the initial reaction process back to the dissolution tank via a reflux unit and circulation means, both connected to the dissolution tank, and repeating the initial reaction; preparing basic copper carbonate and a mixed gas by carrying out an ammonia distillation reaction with the copper ammonia solution using steam at 125 to 143°C; recovering the mixed gas back to the dissolution tank via the circulation device and repeating the initial reaction; separating the basic copper carbonate by solid-liquid separation; and calcining the separated basic copper carbonate at a temperature of 250 to 600°C for 1 to 4 hours to form copper oxide. Patent Document 1 states that the invention of Patent Document 1 aims to provide a method for producing copper oxide and equipment for producing copper oxide, which allows raw materials to be repeatedly circulated in the manufacturing process by providing a reflux unit and a circulation device to reduce the amount of raw materials used, and also allows the concentration of the copper ammonia solution to be effectively increased to increase the amount of copper oxide produced.

[0004] Japanese Patent Publication No. 2015-157741

[0005] One aspect of the present invention provides basic copper carbonate that can be used as a raw material for copper oxide and that can improve the dissolution rate of copper oxide in an aqueous copper sulfate solution. Another aspect of the present invention provides copper oxide that can improve the dissolution rate of copper oxide in an aqueous copper sulfate solution.

[0006] The present invention is as follows: [1] Specific surface area of ​​2.9 m² obtained by nitrogen adsorption method ２ [1] Basic copper carbonate having a concentration of 1 / g or more. [2] The basic copper carbonate according to [1], wherein the Na content in the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours is 100 ppm or less. [3] The basic copper carbonate according to [1] or [2], wherein the Ca content in the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours is 100 ppm or less. [4] Volume-based median diameter D of the basic copper carbonate by laser diffraction scattering method. ５０ Basic copper carbonate according to any one of [1] to [3], wherein the particle size is 10 μm or more and 60 μm or less. [5] The particle size D in the volume frequency particle size distribution of the basic copper carbonate by laser diffraction scattering method, where the cumulative value is 10% １０ and particle size D where the cumulative value is 90% ９０ D calculated from ９０ / D １０ Basic copper carbonate as described in any of [1] to [4], wherein the tap density of the basic copper carbonate, as measured in accordance with JIS Z2512:2012, is 1.4 g / cm³. ３The basic copper carbonate described in any of [1] to [5] below. [7] The basic copper carbonate described in any of [1] to [6], wherein the angle of repose of the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours is 30 degrees or more and 60 degrees or less, as measured in accordance with JIS R9301-2-2:1999. [8] The basic copper carbonate described in any of [1] to [7], wherein the dissolution time of the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours, as measured by [Method 1] below, is 120 sec or less. [Method 1] An aqueous copper sulfate solution (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of copper(II) sulfate pentahydrate with a purity of 98.5% or higher, 89.3 g of 98% concentrated sulfuric acid, and 438.3 g of water is stirred at 300 rpm and kept at 25°C, and 5.0 g of the copper oxide is added thereto, and the time required until the dissolution of the copper oxide can be visually confirmed is defined as the dissolution time. [9] The basic copper carbonate according to any one of [1] to [8], wherein the basic copper carbonate can be used in the production of copper oxide.

[10] The basic copper carbonate according to [9], wherein the copper oxide can be used as a copper source for plating.

[11] A method for producing basic copper carbonate according to any one of [1] to

[10] , comprising the step of dissolving metallic copper in a solution containing ammonium ions.

[12] The method for producing basic copper carbonate according to

[11] , comprising the step of vacuum distillation of the solution in which metallic copper has been dissolved in a solution containing ammonium ions.

[13] Tap density measured in accordance with JIS Z2512:2012 is 1.1 g / cm³ ３Copper oxide having a content of less than

[14] . The copper oxide according to

[13] , wherein the content of Na in the copper oxide is 100 ppm or less.

[15] The copper oxide according to

[13] or

[14] , wherein the content of Ca in the copper oxide is 100 ppm or less.

[16] The copper oxide according to any one of

[13] to

[15] , wherein the angle of repose measured in accordance with JIS R9301-2-2:1999 of the copper oxide is 30 degrees or more and 60 degrees or less.

[17] The copper oxide according to any one of

[13] to

[16] , wherein the dissolution time of the copper oxide measured by the following [Method 2] is 120 sec or less. [Method 2] A copper sulfate aqueous solution (copper concentration: 3.2 mass%, pH: -0.3) containing 76.1 g of copper (II) sulfate pentahydrate with a purity of 98.5%, 89.3 g of 98% concentrated sulfuric acid, and 438.3 g of water is maintained at 25 °C while stirring at 300 rpm, and 5.0 g of the copper oxide is added thereto. The time required until it can be visually confirmed that the copper oxide has dissolved is defined as the dissolution time.

[18] The copper oxide according to any one of

[13] to

[17] , which can be used as a copper source for plating.

[19] A production method for producing the copper oxide according to any one of

[13] to

[18] , which includes a step of calcining basic copper carbonate.

[20] A production method for producing copper oxide, which includes a step of calcining the basic copper carbonate according to any one of [1] to

[10] .

[21] A production method for producing copper oxide, which includes a step of calcining the basic copper carbonate obtained by the production method of the basic copper carbonate according to

[11] .

[0007] According to one aspect of the present invention, it is possible to provide basic copper carbonate that can be used as a raw material for copper oxide and can improve the dissolution rate of copper oxide in an aqueous copper sulfate solution. According to one aspect of the present invention, it is possible to provide copper oxide that can improve the dissolution rate in an aqueous copper sulfate solution.

[0008] Hereinafter, an explanation will be given based on each embodiment of the present invention.

[0009] <First Embodiment> 1. Basic Copper Carbonate Hereinafter, the basic copper carbonate of the first embodiment will be described.

[0010] The basic copper carbonate of the first embodiment has a specific surface area by the nitrogen adsorption method of 2.9 m ２From the viewpoint of further improving the dissolution rate of copper oxide, which is derived from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the amount is preferably 2.9 m / g or more. ２ / g or more 5.0m ２ / g or less, more preferably 3.0m ２ / g or more 5.0m ２ / g or less, more preferably 3.1m ２ / g or more 4.8m ２ / g or less, more preferably 3.2m ２ / g or more 4.5m ２ / g or less, more preferably 3.3m ２ / g or more 4.3m ２ / g or less, more preferably 3.4m ２ / g or more 4.1m ２ / g or less, more preferably 3.5m ２ / g or more 4.0m ２ / g or less, more preferably 3.6m ２ / g or more 3.9m ２ / g or less, more preferably 3.7m ２ / g or more 3.9m ２ It is less than or equal to / g. The specific surface area of ​​basic copper carbonate by nitrogen adsorption in the first embodiment can be adjusted, for example, by adjusting the production conditions of basic copper carbonate, the composition of the copper ammonia solution during basic copper carbonate production, and the conditions during vacuum distillation. In particular, the copper content in the copper ammonia solution during basic copper carbonate production, the temperature, time, and rotation speed during vacuum distillation are important.

[0011] The Na content in the copper oxide obtained by calcining the basic copper carbonate of the first embodiment at 290°C for 4 hours may be, for example, 0.001 ppm or more, 0.01 ppm or more, or 0.1 ppm or more. From the viewpoint of further improving the dissolution rate of copper oxide using the basic copper carbonate of the first embodiment as a raw material in an aqueous copper sulfate solution, it is preferably 100 ppm or less, more preferably 85 ppm or less, even more preferably 70 ppm or less, even more preferably 55 ppm or less, even more preferably 40 ppm or less, even more preferably 30 ppm or less. More preferably, the Na content is 25 ppm or less, and from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate of the first embodiment as a raw material in an aqueous copper sulfate solution, it is preferably 0.001 ppm to 100 ppm, more preferably 0.001 ppm to 85 ppm, even more preferably 0.01 ppm to 70 ppm, even more preferably 0.1 ppm to 55 ppm, even more preferably 0.1 ppm to 40 ppm, even more preferably 0.1 ppm to 30 ppm, and even more preferably 0.1 ppm to 25 ppm. The Na content in copper oxide obtained by calcining basic copper carbonate of the first embodiment at 290°C for 4 hours can be measured, for example, by atomic absorption spectrophotometry.

[0012] The Ca content in the copper oxide obtained by calcining the basic copper carbonate of the first embodiment at 290°C for 4 hours may be, for example, 0.001 ppm or more, 0.01 ppm or more, or 0.1 ppm or more, and from the viewpoint of further improving the dissolution rate of copper oxide using the basic copper carbonate of the first embodiment as a raw material in an aqueous copper sulfate solution, it is preferably 100 ppm or less, more preferably 85 ppm or less, even more preferably 70 ppm or less, even more preferably 55 ppm or less, and even more preferably 40 ppm. The following is more preferably 30 ppm or less, and from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate of the first embodiment as a raw material in an aqueous copper sulfate solution, it is preferably 0.001 ppm to 100 ppm, more preferably 0.001 ppm to 85 ppm, even more preferably 0.01 ppm to 70 ppm, even more preferably 0.1 ppm to 55 ppm, even more preferably 0.1 ppm to 40 ppm, and even more preferably 0.1 ppm to 30 ppm. The Ca content in copper oxide obtained by calcining basic copper carbonate of the first embodiment at 290°C for 4 hours can be measured, for example, by atomic absorption spectrophotometry.

[0013] Volume-based D of basic copper carbonate by laser diffraction scattering method in the first embodiment １０ From the viewpoint of further improving the dissolution rate of copper oxide, which is produced from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the particle size is preferably 1 μm to 50 μm, more preferably 3 μm to 50 μm, even more preferably 4 μm to 45 μm, even more preferably 10 μm to 40 μm, even more preferably 20 μm to 35 μm, even more preferably 21 μm to 32 μm, and even more preferably 23 μm to 30 μm.

[0014] Volume-based median diameter D of basic copper carbonate by laser diffraction scattering method in the first embodiment ５０From the viewpoint of further improving the dissolution rate of copper oxide, which is produced from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the particle size is preferably 10 μm to 60 μm, more preferably 20 μm to 55 μm, even more preferably 25 μm to 50 μm, even more preferably 30 μm to 45 μm, and even more preferably 33 μm to 40 μm.

[0015] Volume-based D of basic copper carbonate by laser diffraction scattering method in the first embodiment ９０ From the viewpoint of further improving the dissolution rate of copper oxide, which is produced from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the particle size is preferably 20 μm to 80 μm, more preferably 30 μm to 70 μm, even more preferably 35 μm to 60 μm, even more preferably 40 μm to 55 μm, and even more preferably 46 μm to 50 μm.

[0016] In the volume frequency particle size distribution of basic copper carbonate by laser diffraction scattering method of the first embodiment, the particle size D at which the cumulative value reaches 10% １０ and particle size D where the cumulative value is 90% ９０ D calculated from ９０ / D １０ From the viewpoint of further improving the dissolution rate of copper oxide, which is derived from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the value is preferably 1.5 to 20.0, more preferably 1.5 to 15.0, even more preferably 1.5 to 10.0, even more preferably 1.5 to 5.0, even more preferably 1.6 to 2.5, and even more preferably 1.7 to 1.9.

[0017] The tap density of the basic copper carbonate of the first embodiment, measured in accordance with JIS Z2512:2012, is preferably 0.9 g / cm³, from the viewpoint of further improving the dissolution rate of copper oxide, using the basic copper carbonate of the first embodiment as a raw material, in an aqueous copper sulfate solution. ３ 1.4g / cm or more ３ More preferably, 1.0 g / cm³ ３ 1.4g / cm or more ３ More preferably, 1.1 g / cm³ ３ 1.4g / cm or more ３More preferably, 1.2 g / cm³ ３ 1.4g / cm or more ３ More preferably, 1.3 g / cm³ ３ 1.4g / cm or more ３ The following applies:

[0018] The specific surface area of ​​copper oxide obtained by nitrogen adsorption by calcining basic copper carbonate of the first embodiment at 290°C for 4 hours is, for example, 30.0 m². ２ It may be 32.0 m or more. ２ It may be 34.0 m or more, and may be 34.0 m ２ It may be 36.0 m or more, and may be 36.0 m ２ It may be 36.5 m or more per g. ２ It may be 36.7 m or more per g. ２ It may be 37.0 m or more per g. ２ It may be 1 / g or more, and for example, 60.0 m ２ It may be less than or equal to 55.0 m ２ It may be less than or equal to 50.0 m ２ It may be less than or equal to 45.0 m ２ It may be less than or equal to 40.0 m ２ It may be less than or equal to / g, and 39.0m ２ It may be less than or equal to / g, and 38.5m ２ It may be less than or equal to / g, and for example, 30.0m ２ / g or more 60.0m ２ It may be less than or equal to / g, and 32.0m ２ / g or more 60.0m ２ It may be less than or equal to / g, and 34.0m ２ / g or more 55.0m ２ It may be less than or equal to / g, and 36.0m ２ / g or more 50.0m ２ It may be less than or equal to / g, and 36.5m ２ / g or more 45.0m ２ It may be less than or equal to / g, and 36.7m ２ / g or more 40.0m ２ It may be less than or equal to / g, and 37.0m ２ / g or more 39.0m ２ It may be less than or equal to / g, and 37.0m ２ / g or more 38.5m２ It may be less than or equal to / g.

[0019] The angle of repose of copper oxide obtained by calcining basic copper carbonate of the first embodiment at 290°C for 4 hours, as measured in accordance with JIS R9301-2-2:1999, is preferably 30°C to 60°C, more preferably 32°C to 50°C, even more preferably 34°C to 47°C, even more preferably 36°C to 45°C, even more preferably 39°C to 43°C, and even more preferably 40°C to 42°C, from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate of the first embodiment as a raw material in an aqueous copper sulfate solution.

[0020] The dissolution time of copper oxide obtained by calcining the basic copper carbonate of the first embodiment at 290°C for 4 hours, as measured by [Method 1] below, is preferably 1 sec to 120 sec, more preferably 5 sec to 80 sec, even more preferably 8 sec to 60 sec, even more preferably 10 sec to 52 sec, even more preferably 20 sec to 51 sec, and even more preferably 30 sec to 45 sec. [Method 1] An aqueous solution of copper sulfate (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of 98.5% pure copper(II) sulfate pentahydrate (for example, industrial-grade copper(II) sulfate pentahydrate manufactured by Onahama Smelting Co., Ltd.), 89.3 g of 98% concentrated sulfuric acid (for example, manufactured by Furukawa Chemicals Co., Ltd.), and 438.3 g of water is kept at 25°C while being stirred at 300 rpm. 5.0 g of copper oxide from the first embodiment is added thereto, and the time required until the dissolution of copper oxide from the first embodiment can be visually confirmed is defined as the dissolution time.

[0021] The uses of the basic copper carbonate of the first embodiment are not particularly limited, but for example, it can be used as a raw material for copper oxide. Furthermore, the basic copper carbonate according to the first embodiment may be used as a raw material for paints, ceramic materials, pesticides, and plating.

[0022] The basic copper carbonate of the first embodiment provides a basic copper carbonate that can improve the dissolution rate of copper oxide, which is made from the basic copper carbonate of the first embodiment, into an aqueous copper sulfate solution. Therefore, preferably, the basic copper carbonate of the first embodiment can be used in the production of copper oxide, and more preferably, the copper oxide of the first embodiment can be used as a copper source for plating.

[0023] 2. Method for Producing Basic Copper Carbonate The method for producing basic copper carbonate according to the first embodiment will be described below.

[0024] The method for producing basic copper carbonate according to the first embodiment includes a step of dissolving metallic copper in a solution containing ammonium ions. According to the step of dissolving metallic copper in a solution containing ammonium ions according to the first embodiment, a solution in which metallic copper is dissolved in a solution containing ammonium ions can be obtained.

[0025] The method for producing basic copper carbonate according to the first embodiment preferably includes a step of vacuum distillation (hereinafter sometimes referred to as a vacuum distillation step) of a solution obtained by dissolving metallic copper in a solution containing ammonium ions (hereinafter sometimes referred to as a copper ammonia solution) from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate according to the first embodiment as a raw material in an aqueous copper sulfate solution.

[0026] The method for vacuum distillation of the copper ammonia solution of the first embodiment is not particularly limited, but for example, vacuum distillation can be performed by placing the reaction solution in a reaction vessel, placing it under a reduced pressure environment, and heating and stirring it.

[0027] In the vacuum distillation process of the first embodiment, the Cu content in the copper ammonia solution of the first embodiment is preferably 6.0% by mass or more and 15.0% by mass or less, more preferably 7.0% by mass or more and 13.0% by mass or less, even more preferably 8.0% by mass or more and 12.0% by mass or less, even more preferably 9.0% by mass or more and 11.0% by mass or less, and even more preferably 9.0% by mass or more and 10.0% by mass or less, from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate as a raw material in the first embodiment.

[0028] CO in the copper ammonia solution of the first embodiment in the vacuum distillation process of the first embodiment２ From the viewpoint of further improving the dissolution rate of copper oxide, which is derived from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the content is preferably 1.0% by mass or more and 15.0% by mass or less, more preferably 2.0% by mass or more and 12.0% by mass or less, even more preferably 3.0% by mass or more and 10.0% by mass or less, even more preferably 3.5% by mass or more and 8.0% by mass or less, even more preferably 4.0% by mass or more and 7.6% by mass or less, even more preferably 4.5% by mass or more and 7.0% by mass or less, and even more preferably 5.0% by mass or more and 6.5% by mass or less.

[0029] NH in the copper ammonia solution of the first embodiment in the vacuum distillation process of the first embodiment ３ From the viewpoint of further improving the dissolution rate of copper oxide, which is produced from basic copper carbonate in the first embodiment, into an aqueous solution of copper sulfate, the content is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably 2.0% by mass or more and 20.0% by mass or less, even more preferably 2.5% by mass or more and 15.0% by mass or less, even more preferably 3.0% by mass or more and 11.0% by mass or less, even more preferably 3.5% by mass or more and 10.0% by mass or less, even more preferably 4.0% by mass or more and 9.0% by mass or less, even more preferably 4.5% by mass or more and 8.0% by mass or less, and even more preferably 5.0% by mass or more and 7.0% by mass or less.

[0030] From the viewpoint of further improving the dissolution rate of copper oxide, which is produced using basic copper carbonate as a raw material in the first embodiment, the temperature inside the reaction vessel in the vacuum distillation process is preferably 65°C to 150°C, more preferably 70°C to 120°C, even more preferably 75°C to 100°C, and even more preferably 80°C to 90°C.

[0031] In the vacuum distillation process of the first embodiment, the degree of vacuum relative to atmospheric pressure is preferably -0.101 MPa or more and -0.01 MPa or less, more preferably -0.100 MPa or more and -0.03 MPa or less, and even more preferably -0.095 MPa or more and -0.05 MPa or less, from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate as a raw material in the first embodiment in the aqueous copper sulfate solution.

[0032] From the viewpoint of further improving the rate of dissolution of copper oxide, using basic copper carbonate as a raw material in the first embodiment, into an aqueous copper sulfate solution, the rotation speed of the stirring is preferably 50 rpm to 800 rpm, more preferably 100 rpm to 600 rpm, even more preferably 150 rpm to 550 rpm, even more preferably 180 rpm to 500 rpm, even more preferably 210 rpm to 450 rpm, and even more preferably 250 rpm to 400 rpm.

[0033] From the viewpoint of further improving the dissolution rate of copper oxide, using basic copper carbonate as a raw material in the first embodiment, in aqueous copper sulfate solution, the reaction time of the vacuum distillation step is preferably 1 hour to 48 hours, more preferably 5 hours to 48 hours, even more preferably 7 hours to 30 hours, even more preferably 8 hours to 24 hours, and even more preferably 12 hours to 20 hours.

[0034] The method for producing basic copper carbonate according to the first embodiment may include steps other than the vacuum distillation step, for example, a step of washing the obtained basic copper carbonate (hereinafter sometimes referred to as the washing step) and a step of drying the obtained basic copper carbonate (hereinafter sometimes referred to as the drying step).

[0035] In the cleaning process of the first embodiment, for example, cleaning can be performed with deionized water.

[0036] The completion of the cleaning step in the first embodiment can be determined, for example, by the conductivity of basic copper carbonate. Specifically, cleaning is performed until the conductivity of basic copper carbonate is preferably 1 mS / cm or less, more preferably 0.5 mS / cm or less, and even more preferably 0.3 mS / cm or less.

[0037] The drying method in the drying step of the first embodiment is not particularly limited, but for example, drying can be performed by reduced-pressure drying.

[0038] 3. Method for producing copper oxide The method for producing copper oxide according to the first embodiment will be described below.

[0039] The method for producing copper oxide according to the first embodiment includes the step of calcining the basic copper carbonate according to the first embodiment.

[0040] The method for producing copper oxide according to the first embodiment preferably includes a step of calcining the basic copper carbonate obtained by the method for producing basic copper carbonate according to the first embodiment (hereinafter sometimes referred to as the calcination step), from the viewpoint of further improving the dissolution rate of copper oxide using basic copper carbonate as a raw material in an aqueous copper sulfate solution according to the first embodiment.

[0041] The calcination method in the calcination process of the first embodiment is not particularly limited, but for example, calcination can be performed by placing the basic copper carbonate of the first embodiment into a reaction furnace and heating it.

[0042] The temperature of the reaction furnace in the calcination process of the first embodiment may be, for example, 150°C or higher, 200°C or higher, and for example, 600°C or lower, 500°C or lower, 350°C or lower, or 300°C or lower.

[0043] The duration of the baking process in the first embodiment may be, for example, one hour or more, four hours or more, and for example, 24 hours or less, or 12 hours or less.

[0044] The completion of the calcination process in the first embodiment can be determined, for example, by the copper oxide content. Specifically, calcination is carried out until the copper oxide content is preferably 90% by mass or more, more preferably 93% by mass or more, and even more preferably 95% by mass or more.

[0045] The present invention is not limited to the first embodiment described above, and any modifications or improvements that can achieve the objectives of the present invention are included in the present invention.

[0046] <Second Embodiment> 1. Copper Oxide The copper oxide of the second embodiment will be described below.

[0047] The tap density of copper oxide in the second embodiment, measured in accordance with JIS Z2512:2012, is, for example, 0.7 g / cm³. ３ It may be greater than or equal to 0.8 g / cm³. ３ It may be greater than or equal to 0.85 g / cm³. ３It may be as described above, and 1.1 g / cm ３ is less than this, and from the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution, it is preferably 1.05 g / cm ３ or less, more preferably 1.0 g / cm ３ or less, still more preferably 0.9 g / cm ３ or less, and from the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution, it is preferably 0.7 g / cm ３ or more and less than 1.1 g / cm ３ more preferably 0.8 g / cm ３ or more and 1.05 g / cm ３ or less, still more preferably 0.85 g / cm ３ or more and 1.0 g / cm ３ or less, still more preferably 0.85 g / cm ３ or more and 0.9 g / cm ３ or less. The tapped density of the copper oxide of the second embodiment can be adjusted, for example, by adjusting the production conditions of basic copper carbonate which is the raw material of copper oxide, the composition of the copper ammonia solution during the production of basic copper carbonate, the calcination conditions of basic copper carbonate, etc. In particular, the copper content in the copper ammonia solution during the production of basic copper carbonate, the temperature during vacuum distillation, the temperature and time when calcining basic copper carbonate, etc. are important.

[0048] The Na content in the copper oxide of the second embodiment may be, for example, 0.001 ppm or more, 0.01 ppm or more, 0.1 ppm or more, and from the viewpoint of further improving the dissolution rate of the copper oxide of the second embodiment in the aqueous copper sulfate solution, it is preferably 100 ppm or less, more preferably 80 ppm or less, even more preferably 60 ppm or less, even more preferably 40 ppm or less, even more preferably 30 ppm or less, even more preferably 25 ppm or less, and even more preferably 20 ppm. The Na content in the copper oxide of the second embodiment can be measured, for example, by atomic absorption spectrophotometry.

[0049] The Ca content in the copper oxide of the second embodiment may be, for example, 0.001 ppm or more, 0.01 ppm or more, or 0.1 ppm or more, and from the viewpoint of further improving the dissolution rate of the copper oxide of the second embodiment in an aqueous copper sulfate solution, it is preferably 100 ppm or less, more preferably 70 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, even more preferably 20 ppm or less, and even more preferably 15 ppm or less, and from the viewpoint of further improving the dissolution rate of the copper oxide of the second embodiment in an aqueous copper sulfate solution, it is preferably 0.001 ppm or more and 100 ppm or less, more preferably 0.001 ppm or more and 70 ppm or less, even more preferably 0.01 ppm or more and 50 ppm or less, even more preferably 0.1 ppm or more and 30 ppm or less, even more preferably 0.1 ppm or more and 20 ppm or less, and even more preferably 0.1 ppm or more and 15 ppm or less. The Ca content in the copper oxide of the second embodiment can be measured, for example, by atomic absorption spectrophotometry.

[0050] The specific surface area of the copper oxide according to the nitrogen adsorption method in the second embodiment is preferably 10.0 m ２ / g or more and 60.0 m ２ / g or less, more preferably 15.0 m ２ / g or more and 55.0 m ２ / g or less, still more preferably 20.0 m ２ / g or more and 50.0 m ２ / g or less, still more preferably 25.0 m ２ / g or more and 45.0 m ２ / g or less from the viewpoint of further improving the dissolution rate in the aqueous copper sulfate solution.

[0051] The angle of repose of the copper oxide in the second embodiment measured in accordance with JIS R9301-2-2:1999 is preferably 30 degrees or more and 60 degrees or less, more preferably 33 degrees or more and 55 degrees or less, still more preferably 36 degrees or more and 50 degrees or less, still more preferably 37 degrees or more and 45 degrees or less from the viewpoint of further improving the dissolution rate in the aqueous copper sulfate solution.

[0052] The volume-based median diameter D ５０ of the copper oxide in the second embodiment by the laser diffraction scattering method is preferably 10 μm or more and 60 μm or less, more preferably 15 μm or more and 55 μm or less, still more preferably 20 μm or more and 50 μm or less, still more preferably 25 μm or more and 45 μm or less, still more preferably 25 μm or more and 40 μm or less from the viewpoint of further improving the dissolution rate in the aqueous copper sulfate solution.

[0053] The dissolution time of the copper oxide of the second embodiment, as measured by [Method 2] below, is preferably 120 sec or less, more preferably 1 sec to 120 sec, even more preferably 5 sec to 100 sec, even more preferably 8 sec to 80 sec, even more preferably 10 sec to 75 sec, even more preferably 15 sec to 70 sec, even more preferably 20 sec to 65 sec, and even more preferably 25 sec to 60 sec. [Method 2] An aqueous solution of copper sulfate (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of 98.5% pure copper(II) sulfate pentahydrate (for example, industrial-grade copper(II) sulfate pentahydrate manufactured by Onahama Smelting Co., Ltd.), 89.3 g of 98% concentrated sulfuric acid (for example, manufactured by Furukawa Chemicals Co., Ltd.), and 438.3 g of water is kept at 25°C while being stirred at 300 rpm. 5.0 g of copper oxide from the second embodiment is added thereto, and the time required until the dissolution of copper oxide from the second embodiment can be visually confirmed is defined as the dissolution time.

[0054] The copper oxide of the second embodiment may contain impurities other than copper oxide. If the copper oxide of the second embodiment contains impurities, the copper oxide content in the copper oxide of the second embodiment may be, for example, 95.0% by mass or more, 97.0% by mass or more, or 97.5% by mass or more. The copper oxide content in the copper oxide of the second embodiment can be measured, for example, by a chemical analysis method.

[0055] The uses of copper oxide in the second embodiment are not particularly limited, but for example, it can be used as a raw material for pesticides and plating.

[0056] The copper oxide of the second embodiment can improve the dissolution rate in an aqueous copper sulfate solution. Therefore, the copper oxide of the second embodiment can be suitably used as a copper source for plating.

[0057] 2. Method for producing copper oxide The method for producing copper oxide according to the second embodiment will be described below.

[0058] The method for producing copper oxide according to the second embodiment is a method for producing copper oxide according to the second embodiment, and includes a step of calcining basic copper carbonate (hereinafter sometimes referred to as the calcination step).

[0059] The calcination method in the calcination process of the second embodiment is not particularly limited, but for example, calcination can be performed by placing the basic copper carbonate of the second embodiment into a reaction furnace and heating it.

[0060] In the second embodiment, the temperature of the reaction furnace in the calcination process is preferably 240°C to 320°C, more preferably 250°C to 300°C, and even more preferably 260°C to 295°C, from the viewpoint of further improving the dissolution rate into the copper sulfate aqueous solution.

[0061] In the second embodiment, the calcination process time is preferably 1 hour to 12 hours, more preferably 2 hours to 10 hours, even more preferably 3 hours to 8 hours, and even more preferably 3.5 hours to 7.5 hours, from the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution.

[0062] The completion of the calcination process in the second embodiment can be determined, for example, by the copper oxide content. Specifically, calcination is carried out until the copper oxide content is preferably 90% by mass or more, more preferably 93% by mass or more, and even more preferably 95% by mass or more.

[0063] The method for producing basic copper carbonate used as a raw material in the copper oxide production method of the second embodiment preferably includes a step of vacuum distillation (hereinafter sometimes referred to as a vacuum distillation step) of a solution obtained by dissolving metallic copper in a solution containing ammonium ions (hereinafter sometimes referred to as a copper ammonia solution) from the viewpoint of further improving the dissolution rate in an aqueous copper sulfate solution.

[0064] The method for vacuum distillation of the copper ammonia solution in the second embodiment is not particularly limited, but for example, vacuum distillation can be performed by placing the reaction solution in a reaction vessel, placing it under a reduced pressure environment, and heating and stirring it.

[0065] In the vacuum distillation process of the second embodiment, the Cu content in the copper ammonia solution of the second embodiment is preferably 7.0% by mass or more and 15.0% by mass or less, more preferably 8.0% by mass or more and 14.0% by mass or less, and even more preferably 8.5% by mass or more and 12.0% by mass or less, from the viewpoint of further improving the dissolution rate into the copper sulfate aqueous solution.

[0066] CO in the copper ammonia solution of the second embodiment in the vacuum distillation process of the second embodiment ２ From the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution, the content is preferably 4.0% by mass or more and 10.0% by mass or less, more preferably 4.5% by mass or more and 9.5% by mass or less, and even more preferably 5.0% by mass or more and 9.0% by mass or less.

[0067] NH in the copper ammonia solution of the second embodiment in the vacuum distillation process of the second embodiment ３ From the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution, the content is preferably 5.0% by mass or more and 20.0% by mass or less, more preferably 5.5% by mass or more and 18.5% by mass or less, even more preferably 6.0% by mass or more and 17.0% by mass or less, and even more preferably 6.5% by mass or more and 16.5% by mass or less.

[0068] In the second embodiment, the temperature inside the reaction vessel during the vacuum distillation process is preferably 65°C to 100°C, more preferably 70°C to 95°C, and even more preferably 75°C to 90°C, from the viewpoint of further improving the dissolution rate into the copper sulfate aqueous solution.

[0069] In the vacuum distillation process of the second embodiment, the degree of vacuum relative to atmospheric pressure is preferably -0.101 MPa or more and -0.06 MPa or less, more preferably -0.100 MPa or more and -0.07 MPa or less, and even more preferably -0.09 MPa or more and -0.08 MPa or less, from the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution.

[0070] In the second embodiment, the rotational speed of stirring in the vacuum distillation process is preferably 150 rpm to 500 rpm, more preferably 180 rpm to 400 rpm, and even more preferably 200 rpm to 350 rpm, from the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution.

[0071] In the second embodiment, the reaction time for the vacuum distillation step is preferably 10 hours or more and 30 hours or less, more preferably 12 hours or more and 20 hours or less, and even more preferably 13 hours or more and 18 hours or less, from the viewpoint of further improving the dissolution rate in the copper sulfate aqueous solution.

[0072] The method for producing basic copper carbonate according to the second embodiment may include steps other than the vacuum distillation step, for example, a step of washing the obtained basic copper carbonate (hereinafter sometimes referred to as the washing step) and a step of drying the obtained basic copper carbonate (hereinafter sometimes referred to as the drying step).

[0073] In the cleaning process of the second embodiment, for example, cleaning can be performed with deionized water.

[0074] The completion of the cleaning step in the second embodiment can be determined, for example, by the conductivity of basic copper carbonate. Specifically, the cleaning is performed until the conductivity of basic copper carbonate is preferably 1 mS / cm or less, more preferably 0.5 mS / cm or less, and even more preferably 0.3 mS / cm or less.

[0075] The drying method in the drying step of the second embodiment is not particularly limited, but for example, drying can be performed by reduced-pressure drying.

[0076] The present invention is not limited to the second embodiment described above, and any modifications or improvements that can achieve the objectives of the present invention are included in the present invention.

[0077] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope of achieving the objectives of the present invention are included.

[0078] The first embodiment of the present invention will be described in more detail below with reference to examples, but the first embodiment of the present invention is not limited to these examples.

[0079] <<Examples 1A to 3A and Comparative Examples 1A to 2A>> The first embodiment of the present invention will be described in detail below with reference to Examples 1A to 3A and Comparative Examples 1A to 2A. However, the first embodiment is not limited in any way to the description in these examples.

[0080] Example 1A: First, prepare 5,500 g of copper ammonia solution (Cu(NH) ３ ) ４ CO ３The mixture was placed in a 5 L separable round-bottom flask and heated with a mantle heater set to 80°C. Vacuum distillation was performed for 16 hours under conditions of a relative pressure of -0.09 MPa with stirring at 300 rpm to obtain basic copper carbonate. Next, the obtained basic copper carbonate was washed with deionized water until the conductivity of the basic copper carbonate was 0.3 mS / cm or less. Then, the washed basic copper carbonate was recovered by filtration and dried under reduced pressure to obtain basic copper carbonate. Next, the obtained basic copper carbonate was placed in a reaction furnace and calcined at 290°C for 4 hours to obtain copper oxide. Note that the copper ammonia solution contained Cu, CO ２ and NH ３ The content of each is shown in Table 1A.

[0081] Examples 2A to 3A and Comparative Examples 1A to 2A: Basic copper carbonate and copper oxide were obtained under the same conditions as in Example 1A, except that the vacuum distillation conditions during the production of basic copper carbonate were as shown in Table 1A.

[0082] Using a specific surface area measuring device (Shimadzu Corporation, model name: FlowSorb III), the specific surface areas of basic copper carbonate and copper oxide obtained by the BET method using low-temperature, low-humidity physical adsorption of an inert gas, specifically the nitrogen adsorption method using nitrogen gas, were measured. The results are shown in Table 1A.

[0083] Using a laser diffraction scattering particle size distribution analyzer (Microtrac-Bell, model: MT3300EX II), the volume-based D of the obtained basic copper carbonate was measured by laser diffraction scattering. １０ , D ５０ and D ９０ The following measurements were taken. The results are shown in Table 1A. Here, 1 g of basic copper carbonate was suspended in 100 mL of dispersion medium (water), and the measurement was taken after irradiating it with ultrasound at an output of 40 W for 3 minutes.

[0084] In accordance with the metal powder-tap density measurement method specified in JIS Z2512:2012, the tap density of the obtained basic copper carbonate was measured using a sample amount of 100 g and tapping conditions of 3000 cycles. The results are shown in Table 1A.

[0085] Using an atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science Corporation, the Na content in the obtained copper oxide was measured by atomic absorption spectrophotometry with a sample amount of 0.5 g, irradiation conditions of lamp current value of 10 mA, wavelength of 589.0 nm, and fuel gas flow rate of 2.0 L / min. Furthermore, using an atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science Corporation, the Ca content in the obtained copper oxide was measured by atomic absorption spectrophotometry with a sample amount of 0.5 g, irradiation conditions of lamp current value of 7.5 mA, wavelength of 422.7 nm, and fuel gas flow rate of 2.2 L / min. The results are shown in Table 1A.

[0086] In accordance with JIS R9301-2-2:1999, the angle of repose of the obtained copper oxide was measured using an angle of repose measuring instrument (KRS-605, manufactured by Kuramochi Scientific Instruments Co., Ltd.) under conditions of 23°C and 50-65% RH. The results are shown in Table 1A.

[0087] The dissolution time of copper oxide obtained by the following [Method 1] in an aqueous copper sulfate solution was measured. The results are shown in Table 1A. [Method 1] An aqueous copper sulfate solution (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of 98.5% pure copper(II) sulfate pentahydrate (industrial-grade copper(II) sulfate pentahydrate manufactured by Onahama Smelting Co., Ltd.), 89.3 g of 98% concentrated sulfuric acid (manufactured by Furukawa Chemicals Co., Ltd.), and 438.3 g of water was kept at 25°C while being stirred at 300 rpm. 5.0 g of copper oxide from the first embodiment was added thereto, and the time it took until the dissolution of copper oxide could be visually confirmed was defined as the dissolution time.

[0088]

[0089] As shown in Table 1A, the copper oxide derived from basic copper carbonate in Examples 1A to 3A showed improved dissolution rates in aqueous copper sulfate solutions. This indicates that the copper oxide derived from basic copper carbonate in the first embodiment can improve dissolution rates in aqueous copper sulfate solutions.

[0090] The second embodiment of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0091] <<Examples 1B-4B and Comparative Examples 1B-3B>> The second embodiment of the present invention will be described in detail below with reference to Examples 1B-4B and Comparative Examples 1B-3B. However, the second embodiment is not limited in any way to the description in these examples.

[0092] Example 1B: First, prepare 5,500 g of copper ammonia solution (Cu(NH) ３ ) ４ CO ３ The mixture was placed in a 5 L separable round-bottom flask and heated with a mantle heater set to 80°C. Vacuum distillation was performed for 14 hours under conditions where the relative pressure reduction to atmospheric pressure was -0.08 MPa while stirring at 300 rpm to obtain basic copper carbonate. The amounts of each component in the copper ammonia solution were Cu: 9.2% by mass, CO ２ :5.5% by mass, NH ３ The concentration was 8.4% by mass. Next, the obtained basic copper carbonate was washed with deionized water until the conductivity of the basic copper carbonate was 0.3 mS / cm or less. Then, the washed basic copper carbonate was filtered and recovered, and dried under reduced pressure to obtain basic copper carbonate. Next, the obtained basic copper carbonate was placed in a reaction furnace and calcined under the calcination conditions described in Table 1B to obtain copper oxide.

[0093] Examples 2B to 4B and Comparative Examples 1B to 3B: Copper oxide was obtained under the same conditions as in Example 1B, except that the vacuum distillation conditions and calcination conditions for basic copper carbonate were as shown in Table 1B.

[0094] In accordance with the metal powder tap density measurement method specified in JIS Z2512:2012, the tap density of the obtained copper oxide was measured using a sample amount of 100 g and tapping conditions of 3000 cycles. The results are shown in Table 1B.

[0095] Using a laser diffraction scattering particle size distribution analyzer (Microtrac-Bell, model: MT3300EX II), the volume-based D of copper oxide obtained by laser diffraction scattering was measured. ５０ The following measurements were taken. The results are shown in Table 1B. Here, 1 g of copper oxide was suspended in 100 mL of dispersion medium (water), and after irradiation with ultrasound at an output of 40 W for 3 minutes, the measurements were taken. The results are shown in Table 1B.

[0096] The copper oxide content in the obtained copper oxide was measured by chemical analysis. Specifically, 0.2 g of copper oxide was dissolved in an acidic solution, and the copper oxide content of the resulting solution was measured by iodine titration. The results are shown in Table 1B.

[0097] Using an atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science Corporation, the Na content in the obtained copper oxide was measured by atomic absorption spectrophotometry with a sample amount of 0.5 g, irradiation conditions of lamp current value of 10 mA, wavelength of 589.0 nm, and fuel gas flow rate of 2.0 L / min. Furthermore, using an atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science Corporation, the Ca content in the obtained copper oxide was measured by atomic absorption spectrophotometry with a sample amount of 0.5 g, irradiation conditions of lamp current value of 7.5 mA, wavelength of 422.7 nm, and fuel gas flow rate of 2.2 L / min. The results are shown in Table 1B.

[0098] The specific surface area of ​​copper oxide was measured using a specific surface area measuring device (Shimadzu Corporation, model name: FlowSorb III) by the BET method, specifically the nitrogen adsorption method using nitrogen gas, which involves low-temperature, low-humidity physical adsorption of an inert gas. The results are shown in Table 1B.

[0099] In accordance with JIS R9301-2-2:1999, the angle of repose of the obtained copper oxide was measured using an angle of repose measuring instrument (KRS-605, manufactured by Kuramochi Scientific Instruments Co., Ltd.) under conditions of 23°C and 50-65% RH. The results are shown in Table 1B.

[0100] The dissolution time of copper oxide obtained by the following [Method 2] in an aqueous copper sulfate solution was measured. The results are shown in Table 1B. [Method 2] An aqueous copper sulfate solution (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of 98.5% pure copper(II) sulfate pentahydrate (industrial-grade copper(II) sulfate pentahydrate manufactured by Onahama Smelting Co., Ltd.), 89.3 g of 98% concentrated sulfuric acid (manufactured by Furukawa Chemicals Co., Ltd.), and 438.3 g of water was kept at 25°C while being stirred at 300 rpm. 5.0 g of copper oxide from the second embodiment was added thereto, and the time it took until the dissolution of the copper oxide could be visually confirmed was defined as the dissolution time.

[0101]

[0102] As shown in Table 1B, the copper oxide of Examples 1B to 4B improved the dissolution rate in the copper sulfate aqueous solution. From this, it can be seen that the copper oxide of the second embodiment can also improve the dissolution rate in the copper sulfate aqueous solution.

[0103] This application claims priority based on Japanese Patent Application No. 2024-163650 and Japanese Patent Application No. 2024-163651, filed on 20 September 2024, and incorporates all of their disclosures herein.

Claims

1. Specific surface area of ​​2.9 m² obtained by nitrogen adsorption method. ２ Basic copper carbonate with a concentration of 1 / g or more.

2. The basic copper carbonate according to claim 1, wherein the Na content in the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours is 100 ppm or less.

3. The basic copper carbonate according to claim 1 or 2, wherein the Ca content in the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours is 100 ppm or less.

4. Volume-based median diameter D of the basic copper carbonate as determined by laser diffraction scattering. ５０ The basic copper carbonate according to any one of claims 1 to 3, wherein the particle size is 10 μm or more and 60 μm or less.

5. The particle size D at which the cumulative value in the volume frequency particle size distribution of the basic copper carbonate obtained by laser diffraction scattering is 10%. １０ and particle size D where the cumulative value is 90% ９０ D calculated from ９０ / D １０ Basic copper carbonate according to any one of claims 1 to 4, wherein the ratio is 1.5 or more and 20.0 or less.

6. The tap density of the basic copper carbonate, as measured in accordance with JIS Z2512:2012, is 1.4 g / cm³. ３ The basic copper carbonate according to any one of claims 1 to 5, which is as follows:

7. The basic copper carbonate according to any one of claims 1 to 6, wherein the angle of repose of the copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours is 30 degrees or more and 60 degrees or less, as measured in accordance with JIS R9301-2-2:1999.

8. The basic copper carbonate according to any one of claims 1 to 7, wherein the dissolution time of copper oxide obtained by calcining the basic copper carbonate at 290°C for 4 hours, as measured by [Method 1] below, is 120 sec or less. [Method 1] An aqueous solution of copper sulfate (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of copper(II) sulfate pentahydrate with a purity of 98.5% or more, 89.3 g of 98% concentrated sulfuric acid, and 438.3 g of water is kept at 25°C while being stirred at 300 rpm, and 5.0 g of the copper oxide is added thereto, and the time required until the dissolution of the copper oxide can be visually confirmed is defined as the dissolution time.

9. The basic copper carbonate according to any one of claims 1 to 8, wherein the basic copper carbonate can be used in the production of copper oxide.

10. The basic copper carbonate according to claim 9, wherein the copper oxide can be used as a copper source for plating.

11. A method for producing basic copper carbonate according to any one of claims 1 to 10, comprising the step of dissolving metallic copper in a solution containing ammonium ions.

12. A method for producing basic copper carbonate according to claim 11, comprising the step of vacuum distillation of a solution obtained by dissolving metallic copper in a solution containing ammonium ions.

13. Tap density measured in accordance with JIS Z2512:2012 is 1.1 g / cm³. ３ Less than copper oxide.

14. The copper oxide according to claim 13, wherein the Na content in the copper oxide is 100 ppm or less.

15. The copper oxide according to claim 13 or 14, wherein the Ca content in the copper oxide is 100 ppm or less.

16. The copper oxide according to any one of claims 13 to 15, wherein the angle of repose of the copper oxide, as measured in accordance with JIS R9301-2-2:1999, is 30 degrees or more and 60 degrees or less.

17. The copper oxide according to any one of claims 13 to 16, wherein the dissolution time of the copper oxide measured by the following [Method 2] is 120 sec or less. [Method 2] An aqueous solution of copper sulfate (copper concentration: 3.2% by mass, pH: -0.3) containing 76.1 g of 98.5% pure copper(II) sulfate pentahydrate, 89.3 g of 98% concentrated sulfuric acid, and 438.3 g of water is kept at 25°C while being stirred at 300 rpm, and 5.0 g of the copper oxide is added thereto, and the time required until the dissolution of the copper oxide can be visually confirmed is defined as the dissolution time.

18. Copper oxide according to any one of claims 13 to 17, which can be used as a copper source for plating.

19. A method for producing copper oxide according to any one of claims 13 to 18, comprising the step of calcining basic copper carbonate.

20. A method for producing copper oxide, comprising the step of calcining basic copper carbonate according to any one of claims 1 to 10.

21. A method for producing copper oxide, comprising the step of calcining the basic copper carbonate obtained by the method for producing basic copper carbonate according to claim 11.

Images