TW201422535A - Copper (ii) oxide fine powder and method for producing same - Google Patents

Copper (ii) oxide fine powder and method for producing same Download PDF

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TW201422535A
TW201422535A TW102137471A TW102137471A TW201422535A TW 201422535 A TW201422535 A TW 201422535A TW 102137471 A TW102137471 A TW 102137471A TW 102137471 A TW102137471 A TW 102137471A TW 201422535 A TW201422535 A TW 201422535A
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copper
powder
oxide
fine powder
electrolytic copper
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TWI580643B (en
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Hiroshi Okada
Yu Yamashita
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Sumitomo Metal Mining Co
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Powder Metallurgy (AREA)

Abstract

Provided is a copper (II) oxide fine powder having both excellent purity and excellent solubility in a plating solution. A production method according to the present invention involves: a dry-mode pulverization step (S1) of pulverizing an electrolytic copper powder having an oxide coating film formed on the surface of particles thereof in a dry mode; and an oxidization step (S2) of oxidizing the electrolytic copper fine powder produced in the dry-mode pulverization step. It is preferred that the oxide coating film is formed by washing an electrolytic copper powder, which is produced by the electrolysis of a solution containing copper ions, with water and then drying the washed electrolytic copper powder at a temperature of 70 to 150 not C in an oxygen-containing atmosphere. It is also preferred that the dry-mode pulverization step (S1) is carried out in an oxygen-containing atmosphere and the oxidization step (S2) is carried out by heating the electrolytic copper fine powder at 300 to 700 not C.

Description

氧化銅(II)微粉末及其製造方法 Copper (II) oxide powder and preparation method thereof

本發明係關於一種氧化銅(II)微粉末及其製造方法。 The present invention relates to a copper (II) oxide fine powder and a method of producing the same.

氧化銅(II)微粉末係用於顏料、塗料、觸媒、陶瓷器之著色劑或鍍銅液之補給用銅源等，其製造方法大致分為濕式法與乾式法。 The copper (II) oxide powder is used as a coloring agent for pigments, paints, catalysts, ceramics, or a copper source for copper plating, and the manufacturing method thereof is roughly classified into a wet method and a dry method.

作為濕式法之一例，可列舉於氯化銅或硫酸銅之水溶液中添加氫氧化鈉而生成氫氧化銅後，對該氫氧化銅進行加熱(參照專利文獻1)。更詳細而言，可列舉利用苛性鹼(NaOH)中和含有氯化銅之印刷基板的蝕刻廢液，將該經中和之銅溶液與苛性鹼水溶液同時滴加於保持在溫度40~50℃之水溶液中並進行混合，一面將該混合之水溶液之pH值維持在弱酸性至弱鹼性之範圍，一面生成銅之水合物。繼而，將pH值調整為12~13，並保持於70~80℃之溫度30分鐘後，進行水洗、固液分離而製造氧化銅(II)。 As an example of the wet method, sodium hydroxide is added to an aqueous solution of copper chloride or copper sulfate to form copper hydroxide, and then the copper hydroxide is heated (see Patent Document 1). More specifically, an etching waste liquid in which a printed circuit board containing copper chloride is neutralized by caustic alkali (NaOH) may be mentioned, and the neutralized copper solution and the aqueous caustic solution are simultaneously added dropwise at a temperature of 40 to 50 ° C. The aqueous solution is mixed and the pH of the mixed aqueous solution is maintained in a range of weakly acidic to weakly alkaline to form a copper hydrate. Then, the pH was adjusted to 12 to 13, and the temperature was maintained at 70 to 80 ° C for 30 minutes, and then washed with water and solid-liquid separated to produce copper (II) oxide.

作為濕式法之另一例，可列舉使硫酸銅水溶液與氫氧化鈉水溶液於30℃以下之溫度下反應而生成氫氧化銅(II)，將該氫氧化銅(II)加熱至60~80℃之溫度並熟化而形成氧化銅(II)(參照專利文獻2)。通常，利用濕式法製造之氧化銅(II)粉末具有對鍍銅液之溶解性較快之優點。 As another example of the wet method, copper sulfate aqueous solution and sodium hydroxide aqueous solution are reacted at a temperature of 30 ° C or lower to form copper (II) hydroxide, and the copper (II) hydroxide is heated to 60 to 80 ° C. The temperature is ripened to form copper (II) oxide (see Patent Document 2). Generally, the copper (II) oxide powder produced by the wet method has the advantage of being more soluble in the copper plating solution.

然而，若利用濕式法製造氧化銅(II)粉末，則具有除Na 以外，源自硫酸根離子之S等之殘留濃度容易變得相對較高的課題。若將含有較多雜質之氧化銅(II)粉末添加至鍍液中，則可能因雜質而引起鍍敷不良。例如，於專利文獻1所記載之方法中，於所使用之蝕刻廢液中除包含對印刷基板進行蝕刻時溶解之銅以外之雜質外，亦於中和時副生成作為雜質之氯化鈉(NaCl)等，因此為了去除雜質，需有水洗步驟。進而，亦存在即便進行水洗亦難以完全去除之課題，利用引用文獻1所記載之方法製造之氧化銅因為會將雜質添加至鍍液中，故存在隨著添加，鍍敷皮膜特性劣化，而必需更換鍍液的課題。 However, if the copper (II) oxide powder is produced by the wet method, it has Na in addition to Na. In addition, the residual concentration of S or the like derived from sulfate ions tends to be relatively high. If a copper (II) oxide powder containing a large amount of impurities is added to the plating solution, plating may be poor due to impurities. For example, in the method described in Patent Document 1, in addition to the impurities other than copper dissolved when the printed substrate is etched, the etching waste liquid used also generates sodium chloride as an impurity during neutralization ( NaCl), etc., therefore, in order to remove impurities, a water washing step is required. Further, there is a problem that it is difficult to completely remove it even if it is washed with water. The copper oxide produced by the method described in the above-mentioned document 1 has impurities added to the plating solution, so that it is necessary to deteriorate the plating film characteristics with the addition. The problem of replacing the plating solution.

又，作為對漿料狀之氧化銅(II)微粉末進行乾燥之方法，已知有：藉由加熱容器使溶劑氣化而進行乾燥之方法；一面於容器內進行攪拌一面加熱而乾燥之方法；或於藉由熱風而流動之氧化鋁等介質中投入漿料，於介質表面乾燥之粉剝落並隨熱風一起被排出，利用旋風器、過濾袋等以乾燥粉體進行回收的介質流動式乾燥方法等。該等方法係作為乾燥方法而於工業上確立之效率良好之方法。然而，存在難以將乾燥之氧化銅(II)微粉末之2次粒子控制為凝集形狀，難以將溶解性或操作性控制為固定的課題。 Moreover, as a method of drying the slurry-formed copper (II) oxide fine powder, a method of drying a solvent by heating a container is known, and a method of heating and drying while stirring in a container is known. Or the slurry is poured into a medium such as alumina flowing by hot air, and the powder dried on the surface of the medium is peeled off and discharged together with the hot air, and the medium which is recovered by the dry powder by a cyclone, a filter bag or the like is flow-dried. Method, etc. These methods are industrially established methods that are effective as a drying method. However, it is difficult to control the secondary particles of the dried copper (II) fine powder to agglomerated shape, and it is difficult to control the solubility or workability to be fixed.

另一方面，作為乾式法之一例，可列舉於空氣中將硝酸銅、硫酸銅、碳酸銅、氫氧化銅等加熱至600℃左右之溫度而熱分解的方法(非參照專利文獻1)。通常，乾式法與濕式法相比，獲得之氧化銅(II)之純度較高，且對鍍液之溶解性優異。 On the other hand, as an example of the dry method, a method of thermally decomposing copper nitrate, copper sulfate, copper carbonate, copper hydroxide or the like to a temperature of about 600 ° C in air is used (see Non-Patent Document 1). In general, the dry method has higher purity of copper (II) oxide than that of the wet method, and is excellent in solubility in the plating solution.

然而，於乾式法中可能有氧化銅(II)粉末彼此容易燒結，氧化銅(II)粉末粗大化而對鍍液之溶解速度變得極慢的情況。為了提高溶 解性，要求獲得之氧化銅粉為微細之粉末狀態，但利用乾式法獲得之氧化銅(II)粉由於燒結而粒子增大，因此必需粉碎增大之氧化銅(II)粉。特別是於將金屬銅用於原料之情形時，若於熱處理前進行粉碎，則因金屬銅柔軟且具有延展性，故難以微細地粉碎。因此，為了進行熱處理至完全成為氧化銅，必需加熱至更高溫度，但由於會因高溫下之熱處理而再次產生銅粒子之燒結，因此就產生熱處理後再次進行粉碎之必要等方面而言，乾式法不可謂為高效之方法。 However, in the dry method, there may be cases where the copper (II) oxide powder is easily sintered to each other, and the copper (II) oxide powder is coarsened and the dissolution rate of the plating solution becomes extremely slow. In order to improve dissolution For the solvability, the copper oxide powder to be obtained is in a fine powder state, but the copper (II) oxide powder obtained by the dry method has an increased particle size due to sintering, and therefore it is necessary to pulverize the enlarged copper (II) oxide powder. In particular, when metal copper is used as a raw material, if it is pulverized before heat treatment, since metallic copper is soft and ductile, it is difficult to finely pulverize. Therefore, in order to perform the heat treatment until it is completely copper oxide, it is necessary to heat it to a higher temperature. However, since the sintering of the copper particles occurs again due to the heat treatment at a high temperature, it is necessary to perform the pulverization again after the heat treatment, and the like. Law can not be described as an efficient method.

為了提高乾式法之效率，提出利用噴射磨機粉碎法粉碎硫酸銅溶液中製作之電解銅粉(參照專利文獻3~5)。根據專利文獻3~5，為了將電解銅粉微細地粉碎，成為粉碎原料之電解銅粉之粒徑可謂為重要之要素。例如於專利文獻3中揭示有為了獲得10μm以下之銅粉，作為原料之電解銅粉之大小以比表面積計必需為2000cm2/g以上之大小。又，於專利文獻5中，即便將利用噴射磨機之粉碎法自使粒子相互碰撞之方式變更為碰撞至碰撞板之碰撞板方式的噴射磨機，作為粉碎原料之電解銅粉之平均粒徑亦設為20~35μm。 In order to improve the efficiency of the dry method, electrolytic copper powder produced by pulverizing a copper sulfate solution by a jet mill pulverization method has been proposed (see Patent Documents 3 to 5). According to Patent Documents 3 to 5, in order to finely pulverize the electrolytic copper powder, the particle size of the electrolytic copper powder which is a pulverized raw material is an important factor. For example, in Patent Document 3, in order to obtain copper powder of 10 μm or less, the size of the electrolytic copper powder as a raw material must be 2,000 cm 2 /g or more in terms of specific surface area. Further, in Patent Document 5, even if the particles are collided with each other by the pulverization method of the jet mill, the average particle diameter of the electrolytic copper powder as the pulverized raw material is changed to the collision mill of the collision plate type which collides with the collision plate. Also set to 20~35μm.

電解銅粉之形成形態係成長為樹枝狀之結構，因此於使粒子碰撞而進行粉碎之情形時，藉由自樹枝狀之枝之部分折斷而微細地進行粉碎，故而為了使粉碎後之粒子變微細，必需使作為粉碎原料之電解銅粉之形狀變微細。為了進行較樹枝狀之枝更微細之粉碎，噴射磨機方式存在極限。然而，若利用作為其他粉碎機之破碎機、球磨機、振磨機進行粉碎，則由於金屬銅之延展性等特性，粉碎後之電解銅粉成為凝集者或平板狀者，因此依然難以使電解銅粉微細化。 Since the form of the electrolytic copper powder grows into a dendritic structure, when the particles are collided and pulverized, the pulverized particles are finely pulverized by being partially broken from the dendritic branches. Finely, it is necessary to make the shape of the electrolytic copper powder as a pulverized raw material fine. In order to perform finer pulverization than the dendritic branches, there is a limit to the jet mill method. However, when the pulverization is carried out by a crusher, a ball mill, or a vibrating mill as another pulverizer, the electrolytic copper powder after pulverization becomes agglomerator or a flat plate due to characteristics such as ductility of metallic copper, and thus it is still difficult to make electrolytic copper. The powder is fine.

[專利文獻1]日本特開平5-319825號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 5-319825

[專利文獻2]日本特開平3-80116號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 3-80116

[專利文獻3]日本特開昭62-199705號公報 [Patent Document 3] Japanese Patent Laid-Open No. 62-199705

[專利文獻4]日本特開平2-182809號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2-182809

[專利文獻5]日本特開2000-80408號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-80408

[非專利文獻1]第4版 實驗化學講座 無機化合物，日本化學會編，丸善股份有限公司，1993年12月 [Non-Patent Document 1] 4th Edition Experimental Chemistry Lecture Inorganic Compound, edited by the Chemical Society of Japan, Maruzen Co., Ltd., December 1993

因此，本發明係著眼於使電解銅粉微細化，提高對鍍液之溶解性而完成者，其課題在於延續先前乾式法之優點即高純度，並且提高對鍍液之溶解性。 Therefore, the present invention has been made in order to refine the electrolytic copper powder and improve the solubility in the plating solution, and the object thereof is to continue the high purity of the prior dry method and to improve the solubility in the plating solution.

本發明人等為解決上述課題反覆進行潛心研究，結果發現，藉由以乾式粉碎表面具有氧化皮膜之電解銅粉，並使利用該粉碎獲得之電解銅微粉末氧化，可達成上述目的，從而完成本發明。 The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that the above object can be attained by dry-pulverizing electrolytic copper powder having an oxide film on the surface and oxidizing the electrolytic copper fine powder obtained by the pulverization. this invention.

具體而言，於本發明中提供如下述者。 Specifically, the following are provided in the present invention.

(1)本發明係一種氧化銅(II)微粉末之製造方法，其包含如下步驟：乾式粉碎步驟，以乾式粉碎表面具有氧化皮膜之電解銅粉；氧化步驟，其氧化藉由該乾式粉碎步驟獲得之電解銅微粉末。 (1) The present invention is a method for producing a copper (II) oxide powder, comprising the steps of: a dry pulverization step of dry-pulverizing electrolytic copper powder having an oxide film on a surface; and an oxidation step of oxidizing by the dry pulverization step The obtained electrolytic copper fine powder.

(2)又，本發明係如(1)記載之氧化銅(II)微粉末之製 造方法，其中，上述氧化皮膜係藉由對利用含銅離子溶液之電解獲得之電解銅粉進行水洗後，於含氧環境中以70℃~150℃之溫度乾燥而形成。 (2) Further, the present invention is produced by the copper (II) oxide powder described in (1). In the method, the oxide film is formed by washing an electrolytic copper powder obtained by electrolysis using a copper ion-containing solution, and then drying it in an oxygen-containing atmosphere at a temperature of 70 ° C to 150 ° C.

(3)又，本發明係如(1)或(2)記載之氧化銅(II)微粉末之製造方法，其中，上述乾式粉碎步驟係於含氧環境中進行。 (3) The method of producing a copper (II) oxide powder according to (1) or (2), wherein the dry pulverization step is carried out in an oxygen-containing atmosphere.

(4)又，本發明係如(1)至(3)中任一項記載之氧化銅(II)微粉末之製造方法，其中，上述氧化步驟係藉由將上述電解銅微粉末以300℃~700℃加熱來進行。 (4) The method for producing a copper (II) oxide powder according to any one of (1) to (3), wherein the oxidizing step is performed by using the electrolytic copper fine powder at 300 ° C Heated at ~700 °C.

(5)又，本發明係一種鍍銅方法，將藉由(1)至(4)中任一項記載之製造方法而獲得之氧化銅(II)微粉末溶解而得的硫酸銅水溶液用作電鍍銅裝置之電解液。 (5) Further, the present invention is a copper plating method in which a copper sulfate aqueous solution obtained by dissolving a copper (II) oxide fine powder obtained by the production method according to any one of (1) to (4) is used as Electrolyte for electroplating copper devices.

(6)又，本發明係一種氧化銅(II)微粉末，其平均粒徑為5μm以下，最大粒徑為15μm以下，於將10g之氧化銅(II)微粉末浸漬於25℃之含硫酸溶液1L中而進行之溶解試驗中，溶解時間為1分鐘以下，其中，該含硫酸溶液含有228g/L之CuSO4‧5H2O、68g/L之游離H2SO4、及60mg/L之氯化物離子。 (6) Further, the present invention is a copper (II) oxide fine powder having an average particle diameter of 5 μm or less and a maximum particle diameter of 15 μm or less, and immersing 10 g of the copper (II) oxide fine powder in a sulfuric acid at 25 ° C In the dissolution test performed in 1 L of the solution, the dissolution time was 1 minute or less, wherein the sulfuric acid-containing solution contained 228 g/L of CuSO 4 ‧5H 2 O, 68 g/L of free H 2 SO 4 , and 60 mg/L. Chloride ion.

根據本發明，可提供一種氧化銅之純度高，且對鍍液之溶解性高之氧化銅(II)微粉末。該氧化銅(II)微粉末可較佳地用作工業上所使用之鍍銅液之補給用銅源。 According to the present invention, it is possible to provide a copper (II) oxide fine powder having high purity of copper oxide and high solubility in a plating solution. The copper (II) oxide fine powder can be preferably used as a copper source for replenishing a copper plating liquid used in the industry.

圖1係用以說明本發明之製造方法之圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view for explaining the manufacturing method of the present invention.

圖2係表示於表面具有氧化皮膜的氧化銅粉之掃描電子顯微鏡圖像(SEM圖像)。 Fig. 2 is a scanning electron microscope image (SEM image) showing copper oxide powder having an oxide film on its surface.

圖3係表示實施例1之電解銅微粉末之SEM圖像。 Fig. 3 is a SEM image showing the electrolytic copper fine powder of Example 1.

圖4係表示比較例1之電解銅微粉末之SEM圖像。 Fig. 4 is a SEM image showing the electrolytic copper fine powder of Comparative Example 1.

圖5係表示比較例2之電解銅微粉末之SEM圖像。 Fig. 5 is a SEM image showing the electrolytic copper fine powder of Comparative Example 2.

圖6係表示實施例1之氧化銅(II)微粉末之X射線繞射圖案。 Fig. 6 is a view showing an X-ray diffraction pattern of the copper (II) oxide fine powder of Example 1.

以下，對本發明之具體之實施形態詳細地進行說明，但本發明並不受以下實施形態任何限定，可於本發明之目的之範圍內適當加以變更而實施。 In the following, the specific embodiments of the present invention are described in detail, but the present invention is not limited to the following embodiments, and can be appropriately modified and implemented within the scope of the object of the present invention.

<氧化銅(II)微粉末之製造方法> <Method for Producing Copper (II) Oxide Powder>

本發明之製造方法包含以乾式粉碎表面具有氧化皮膜之電解銅粉之乾式粉碎步驟S1，及氧化藉由該乾式粉碎步驟S1獲得之電解銅微粉末之氧化步驟S2。再者，於本說明書中，為了明確地區分電解銅或氧化銅之狀態，將乾式粉碎前之電解銅稱為「電解銅粉」，將乾式粉碎後但氧化前之電解銅稱為「電解銅微粉末」，將氧化後之氧化銅稱為「氧化銅(II)微粉末」。 The production method of the present invention comprises a dry pulverization step S1 of dry-pulverizing electrolytic copper powder having an oxide film on the surface, and an oxidation step S2 of oxidizing the electrolytic copper fine powder obtained by the dry pulverization step S1. In addition, in the present specification, in order to clearly distinguish the state of electrolytic copper or copper oxide, the electrolytic copper before dry pulverization is referred to as "electrolytic copper powder", and the electrolytic copper after dry pulverization but before oxidation is referred to as "electrolytic copper. "Micropowder", the oxidized copper oxide is referred to as "copper (II) oxide powder."

[氧化皮膜形成步驟S0] [Oxide film forming step S0]

於本發明中，只要乾式粉碎步驟S1中使用之電解銅粉為表面具有氧化皮膜者，則氧化皮膜之形成方法可為任意方法，作為一例，可列舉藉由於硫酸銅溶液中進行銅之電解而使電解銅粉於電極表面析出並進行回收後，經由於該電解銅粉之表面形成氧化皮膜之氧化皮膜形成步驟S0而成者。 In the present invention, as long as the electrolytic copper powder used in the dry pulverization step S1 has an oxide film on its surface, the method for forming the oxide film may be any method, and as an example, copper electrolysis may be used in the copper sulfate solution. After the electrolytic copper powder is deposited on the surface of the electrode and recovered, the oxide film forming step S0 of the oxide film is formed on the surface of the electrolytic copper powder.

電解銅粉例如可藉由以CuSO4‧5H2O：5~50g/L、游離H2SO4：50~250g/L之浴組成，於電流密度5~30A/dm2、浴溫20~60℃之條件下進行電解，電沈積於陰極上而製造。 The electrolytic copper powder can be composed, for example, by a bath of CuSO 4 ‧5H 2 O: 5 to 50 g/L, free H 2 SO 4 : 50 to 250 g/L, at a current density of 5 to 30 A/dm 2 , and a bath temperature of 20~ Electrolysis was carried out at 60 ° C and electrodeposition was carried out on a cathode.

獲得之電解銅粉於藉由水洗而洗淨後，為了去除水分，較佳為於含氧環境中以70~150℃之溫度乾燥。 The obtained electrolytic copper powder is washed by washing with water, and is preferably dried at 70 to 150 ° C in an oxygen-containing atmosphere in order to remove moisture.

所謂含氧環境係指至少以大氣程度含有氧氣之狀態，可為空氣環境，亦可為人工供給氧氣之狀態下，但若考慮量產成本，則較佳為空氣環境。 The oxygen-containing environment refers to a state in which oxygen is contained at least in an atmosphere, and may be in an air environment or in a state in which oxygen is manually supplied. However, in consideration of mass production costs, an air environment is preferred.

藉由進行上述乾燥，而使電解銅粉與氣體中之氧反應，於電解銅粉之表面形成氧化皮膜。無需特別控制氧化皮膜之形成程度，於大氣中在通常之乾燥器中使水洗後之電解銅粉乾燥即足夠，但較佳為進行相對於電解銅粉全部皆完全地氧化為氧化銅(II)之情形的理論重量之20%以上之氧化，更佳為進行30%以上，進而較佳為進行40%以上。 By performing the above drying, the electrolytic copper powder reacts with oxygen in the gas to form an oxide film on the surface of the electrolytic copper powder. It is not necessary to particularly control the degree of formation of the oxide film, and it is sufficient to dry the electrolytic copper powder after washing in a normal drier in the atmosphere, but it is preferred to completely oxidize all of the electrolytic copper powder to copper (II) oxide. In the case of the oxidation of 20% or more of the theoretical weight, it is more preferably 30% or more, and still more preferably 40% or more.

[乾式粉碎步驟S1] [Dry pulverization step S1]

本發明包含以乾式粉碎表面具有氧化皮膜之電解銅粉而獲得電解銅微粉末之乾式粉碎步驟S1。 The present invention comprises a dry pulverization step S1 of obtaining electrolytic copper fine powder by dry-pulverizing electrolytic copper powder having an oxide film on its surface.

電解銅粉柔軟且具有延展性，故而難以微細地粉碎。因此，電解銅粉之粉碎較佳為於含氧環境中進行。藉由於含氧環境中進行粉碎，可使藉由粉碎而露出之金屬表面氧化，故而結果形成新的氧化皮膜。因此，可抑制電解銅粉之延展性，可效率良好地使電解銅粉微細化。 Electrolytic copper powder is soft and malleable, so it is difficult to finely pulverize. Therefore, the pulverization of the electrolytic copper powder is preferably carried out in an oxygen-containing atmosphere. By pulverizing in an oxygen-containing atmosphere, the surface of the metal exposed by pulverization can be oxidized, so that a new oxide film is formed. Therefore, the ductility of the electrolytic copper powder can be suppressed, and the electrolytic copper powder can be efficiently refined.

粉碎方法並無特別限定，若考慮製造成本或效率，則較佳為於流體中使電解銅粉彼此碰撞、或使電解銅粉與碰撞板碰撞而進行粉碎之 方式，具體而言，可列舉以噴射磨機、旋風磨機等名稱市售之裝置。 The pulverization method is not particularly limited, and in consideration of the production cost or efficiency, it is preferred that the electrolytic copper powder collides with each other in the fluid or that the electrolytic copper powder collides with the collision plate to be pulverized. Specifically, a device commercially available under the names of a jet mill or a cyclone mill can be cited.

又，藉由組合粉碎裝置與分級裝置，可更高效地獲得電解銅微粉末。 Further, by combining the pulverizing device and the classifying device, the electrolytic copper fine powder can be obtained more efficiently.

電解銅微粉末之粒徑並無特別限定，但為了可高效地進行繼而說明之氧化步驟S2，平均粒徑較佳為5μm以下，更佳為4μm以下，進而較佳為3μm以下。又，最大粒徑較佳為15μm以下，更佳為10μm以下。再者，於本說明書中，只要未特別說明，則將粒徑設為使用雷射粒度分佈測定器Microtrac(日機裝公司製造)進行測定時之由近似於體積球之直徑所得者。 The particle size of the electrolytic copper fine powder is not particularly limited. However, in order to efficiently perform the oxidation step S2 described above, the average particle diameter is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less. Further, the maximum particle diameter is preferably 15 μm or less, and more preferably 10 μm or less. In addition, in the present specification, the particle size is obtained by a diameter similar to that of a volumetric ball when measured by a laser particle size distribution measuring instrument Microtrac (manufactured by Nikkiso Co., Ltd.) unless otherwise specified.

[氧化步驟S2] [Oxidation step S2]

本發明包含氧化藉由乾式粉碎步驟S1獲得之電解銅微粉末之氧化步驟S2。 The present invention comprises an oxidation step S2 of oxidizing the electrolytic copper fine powder obtained by the dry pulverization step S1.

氧化步驟S2較佳為藉由將電解銅微粉末以300℃~700℃加熱而進行。只要為該溫度範圍，則熱處理之溫度並無特別限定，但較佳為根據電解銅微粉末之粒徑進行設定。例如電解銅微粉末之平均粒徑為5μm以下之情形時，可利用相對低溫下之熱處理而將電解銅微粉末製成氧化銅(II)微粉末。另一方面，於電解銅微粉末之平均粒徑超過5μm之情形時，需要可使氧化電解銅微粉末之表面及中心皆氧化之相對高溫下之熱處理。 The oxidation step S2 is preferably carried out by heating the electrolytic copper fine powder at 300 ° C to 700 ° C. The temperature of the heat treatment is not particularly limited as long as it is in this temperature range, but it is preferably set according to the particle diameter of the electrolytic copper fine powder. For example, when the average particle diameter of the electrolytic copper fine powder is 5 μm or less, the electrolytic copper fine powder can be made into a copper (II) oxide fine powder by heat treatment at a relatively low temperature. On the other hand, in the case where the average particle diameter of the electrolytic copper fine powder exceeds 5 μm, heat treatment at a relatively high temperature at which both the surface and the center of the oxidized electrolytic copper fine powder are oxidized is required.

然而，若於高溫下進行熱處理，則雖然刻意將電解銅粉粉碎而獲得電解銅微粉末，但電解銅微粉末彼此燒結而增大粒徑。若如此，則電解氧化銅(II)微粉末對鍍液之溶解特性變低。 However, if the heat treatment is performed at a high temperature, although the electrolytic copper powder is intentionally pulverized to obtain electrolytic copper fine powder, the electrolytic copper fine powder is sintered to each other to increase the particle diameter. If so, the electrolytic properties of the electrolytic copper (II) fine powder on the plating solution become low.

為了避免電解氧化銅(II)微粉末對鍍液之溶解特性變低， 即便於電解銅微粉末彼此燒結之情形時，亦只要再次粉碎燒結之氧化銅(II)粉而製成電解氧化銅(II)微粉末即可，但再次粉碎會導致製造成本之上漲，因此粉碎之次數較佳為限於1次。就該觀點而言，電解銅微粉末之平均粒徑較佳為10μm以下，最大粒徑較佳為15μm以下。 In order to avoid the electrolytic copper oxide (II) fine powder, the solubility characteristics of the plating solution are low, That is, in the case where the electrolytic copper fine powder is sintered to each other, the sintered copper (II) powder may be pulverized again to form an electrolytic copper (II) fine powder, but the pulverization may cause an increase in the production cost, so that the pulverization is performed. The number of times is preferably limited to one. From this point of view, the average particle diameter of the electrolytic copper fine powder is preferably 10 μm or less, and the maximum particle diameter is preferably 15 μm or less.

又，熱處理之時間取決於熱處理溫度，於熱處理溫度為300℃~500℃之情形時，較佳為將熱處理時間設為5小時以下，於熱處理溫度為500℃~700℃之情形時，較佳為將熱處理時間設為3小時以下。 Further, the heat treatment time depends on the heat treatment temperature. When the heat treatment temperature is 300 ° C to 500 ° C, the heat treatment time is preferably 5 hours or less, and when the heat treatment temperature is 500 ° C to 700 ° C, preferably. In order to set the heat treatment time to 3 hours or less.

由於電解銅微粉末彼此之燒結，而使電解氧化銅(II)微粉末之粒徑變得大於電解銅微粉末之粒徑，為了提高對硫酸銅鍍液之溶解性，較佳為儘量抑制該燒結。因此，電解氧化銅(II)微粉末之粒徑較佳為與電解銅微粉末之粒徑相同之程度，具體而言，平均粒徑較佳為5μm以下，更佳為4μm以下，進而較佳為設為3μm以下。又，最大粒徑較佳為15μm以下，更佳為10μm以下。 Since the electrolytic copper fine powder is sintered to each other, the particle diameter of the electrolytic copper (II) fine powder becomes larger than the particle diameter of the electrolytic copper fine powder, and in order to improve the solubility to the copper sulfate plating solution, it is preferable to suppress the powder as much as possible. sintering. Therefore, the particle diameter of the electrolytic copper (II) fine powder is preferably the same as the particle diameter of the electrolytic copper fine powder, and specifically, the average particle diameter is preferably 5 μm or less, more preferably 4 μm or less, and further preferably It is set to 3 μm or less. Further, the maximum particle diameter is preferably 15 μm or less, and more preferably 10 μm or less.

因此，藉由上述製造方法獲得之氧化銅(II)微粉末可較佳地用作電解鍍銅裝置之電解液之原料。投入至鍍液中之氧化銅(II)微粉末不可為產生溶解殘渣者。特別是氧化亞銅不溶解於鍍液中而成為殘渣，因此必需避免生成氧化亞銅微粉末。因此，氧化銅(II)微粉末中之氧化銅(II)微粉末之純度較佳為較高，較佳為99%以上，更佳為99.5%以上。藉由本發明之製造方法獲得之氧化銅(II)微粉末係藉由熱處理使粉碎之電解銅微粉末氧化而成者，因此可使電解銅完全地氧化為氧化銅(II)。其結果，可抑制產生氧化亞銅。 Therefore, the copper (II) oxide fine powder obtained by the above production method can be preferably used as a raw material of an electrolytic solution of an electrolytic copper plating apparatus. The copper (II) oxide powder which is put into the plating solution is not required to be dissolved. In particular, cuprous oxide does not dissolve in the plating solution and becomes a residue. Therefore, it is necessary to avoid the formation of fine cuprous oxide powder. Therefore, the purity of the copper (II) oxide fine powder in the copper (II) oxide fine powder is preferably high, preferably 99% or more, more preferably 99.5% or more. The copper (II) oxide powder obtained by the production method of the present invention is obtained by oxidizing the pulverized electrolytic copper fine powder by heat treatment, so that the electrolytic copper can be completely oxidized to copper (II) oxide. As a result, the production of cuprous oxide can be suppressed.

又，銅源對鍍液之供給必需於每當鍍液所含有之銅源減少時 迅速地進行。因此，氧化銅(II)微粉末對鍍液之溶解度較佳為較高。若將藉由上述製造方法獲得之氧化銅(II)微粉末10g浸漬於25℃之含硫酸溶液1L中，則於1分鐘以內溶解，其中，該含硫酸溶液含有228g/L之CuSO4‧5H2O、68g/L之游離H2SO4、及60mg/L之氯化物離子。就該方面而言，藉由上述製造方法獲得之氧化銅(II)微粉末可較佳地用作電鍍銅裝置之電解液原料。 Further, the supply of the copper source to the plating solution must be rapidly performed every time the copper source contained in the plating solution is reduced. Therefore, the solubility of the copper (II) oxide powder to the plating solution is preferably high. When 10 g of the copper (II) oxide fine powder obtained by the above production method is immersed in 1 L of a sulfuric acid solution at 25 ° C, it is dissolved in 1 minute, wherein the sulfuric acid-containing solution contains 228 g/L of CuSO 4 ‧5H 2 O, 68 g/L of free H 2 SO 4 , and 60 mg/L of chloride ion. In this respect, the copper (II) oxide fine powder obtained by the above production method can be preferably used as an electrolyte raw material for a copper plating apparatus.

<使用氧化銅(II)微粉末之鍍銅方法> <Copper plating method using copper (II) oxide powder>

藉由上述製造方法獲得之氧化銅(II)微粉末可較佳地用作電鍍銅裝置之電解液原料。 The copper (II) oxide fine powder obtained by the above production method can be preferably used as an electrolyte raw material for a copper plating apparatus.

對銅進行電鍍時所使用之鍍銅液(硫酸銅水溶液)多數情況下使用含有硫酸銅、硫酸及氯化物離子，且pH值低於1者。並且，於該鍍銅液中添加有用以提高鍍銅品質之公知之添加劑。 The copper plating solution (copper sulfate aqueous solution) used for electroplating copper is often used in the case of containing copper sulfate, sulfuric acid, and chloride ions, and having a pH lower than one. Further, a known additive for improving the quality of copper plating is added to the copper plating solution.

另一方面，若進行銅之電鍍，則鍍液中之銅析出，鍍液之銅濃度下降。因此，為了防止鍍液之銅濃度下降，已知有於陽極使用銅，一面使陽極溶解一面進行電解鍍銅之方法；於陽極使用由利用導電性氧化物陶瓷等覆蓋之鈦等所構成之不溶性陽極，並且具備對鍍液供給銅之機構之方法。 On the other hand, when copper plating is performed, copper in the plating solution is precipitated, and the copper concentration of the plating solution is lowered. Therefore, in order to prevent a decrease in the copper concentration of the plating solution, it is known that copper is electrolytically plated while the anode is dissolved in the anode, and insolubilization by titanium or the like covered with a conductive oxide ceramic or the like is used for the anode. An anode and a method of supplying a mechanism for supplying copper to a plating solution.

然而，於後者之方法之情形時，如何設置對鍍液供給銅之機構成為課題。於對鍍液供給銅時要求：(I)銅源(銅或含有銅之化合物)迅速地溶解於鍍液中；(II)未因銅源溶解而大幅改變鍍液中之硫酸根離子等之比率；(III)鍍液中所含有之添加劑不分解。 However, in the case of the latter method, how to provide a mechanism for supplying copper to the plating solution has become a problem. When supplying copper to the plating solution, it is required that: (I) the copper source (copper or a compound containing copper) is rapidly dissolved in the plating solution; (II) the sulfate ion in the plating solution is not largely changed by the dissolution of the copper source; Ratio; (III) The additive contained in the plating solution does not decompose.

藉由上述製造方法獲得之氧化銅(II)微粉末符合上述(I) ~(III)中之任一者。 The copper (II) oxide powder obtained by the above production method conforms to the above (I) Any of ~(III).

於使用電鍍裝置將氧化銅(II)微粉末供給於硫酸銅水溶液中時，只要另外設置與電鍍裝置之進行鍍敷之鍍敷槽不同的溶解氧化銅(II)微粉末之氧化銅(II)溶解槽，使水溶液(鍍液)於鍍敷槽與氧化銅(II)溶解槽之間循環即可。 When the copper (II) oxide fine powder is supplied to the copper sulfate aqueous solution using an electroplating apparatus, copper oxide (II) which dissolves the copper oxide (II) fine powder different from the plating bath which is plated by the plating apparatus is separately provided. Dissolving the tank, the aqueous solution (plating solution) may be circulated between the plating tank and the copper (II) oxide dissolution tank.

該氧化銅(II)溶解槽將下述水溶液送回至鍍敷槽，該水溶液係使氧化銅(II)微粉末溶解於鍍敷槽供給之水溶液中而形成者。於使用之氧化銅(II)溶解槽中，較佳為附帶螺旋漿等攪拌機構。又，亦可於鍍敷槽與氧化銅(II)溶解槽之間具備用以去除廢物或異物等之公知之各種過濾器。 The copper (II) oxide dissolution tank returns the following aqueous solution to a plating tank which is formed by dissolving the copper (II) oxide fine powder in an aqueous solution supplied from the plating tank. In the copper (II) copper oxide dissolution tank to be used, a stirring mechanism such as a propeller is preferably used. Further, various known filters for removing waste, foreign matter, and the like may be provided between the plating tank and the copper (II) oxide dissolution tank.

[實施例] [Examples]

以下，藉由實施例而進一步詳細地說明本發明，但本發明並不受該等記載任何限制。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited.

<實施例1> <Example 1>

首先，使用含有32g/L之CuSO4‧5H2O、及55g/L之游離H2SO4之硫酸銅水溶液，於通電電流密度10A/dm2、浴溫25℃之條件下製備電解銅粉。將該電解銅粉充分水洗後，使用乾燥器以105℃之溫度乾燥一晚。 First, an electrolytic copper powder was prepared under the conditions of an electric current density of 10 A/dm 2 and a bath temperature of 25 ° C using a copper sulfate aqueous solution containing 32 g/L of CuSO 4 ‧5H 2 O and 55 g/L of free H 2 SO 4 . . The electrolytic copper powder was sufficiently washed with water, and dried at 105 ° C for one night using a drier.

繼而，使用噴射磨機(裝置名：Nano Grinding Mill NJ-50，德壽工作所公司製造)將該氧化銅粉於空氣環境下進行乾式粉碎。乾式粉碎係於粉碎壓力：1MPa、供給速度：300g/h之條件下進行。 Then, the copper oxide powder was dry-pulverized in an air atmosphere using a jet mill (device name: Nano Grinding Mill NJ-50, manufactured by Deshou Laboratories Co., Ltd.). Dry pulverization was carried out under the conditions of a pulverization pressure of 1 MPa and a supply rate of 300 g/h.

繼而，將粉碎之電解銅微粉末於電爐內在空氣環境下以加熱溫度500℃保持3小時而氧化電解銅粉，獲得實施例1之氧化銅(II)微粉末。 Then, the pulverized electrolytic copper fine powder was oxidized in an electric furnace at a heating temperature of 500 ° C for 3 hours to oxidize the electrolytic copper powder, and the copper (II) oxide fine powder of Example 1 was obtained.

<實施例2> <Example 2>

將乾式粉碎時之供給速度設為500g/h，及將粉碎之電解銅微粉末於電爐內在空氣環境下以加熱溫度700℃保持2小時而氧化電解銅粉，除此以外，利用與實施例1所記載之方法相同之方法而獲得實施例2之氧化銅(II)微粉末。 The supply speed of the dry pulverization was set to 500 g/h, and the pulverized electrolytic copper fine powder was oxidized in an electric furnace at a heating temperature of 700 ° C for 2 hours to oxidize the electrolytic copper powder, and the same as in Example 1 The copper (II) oxide fine powder of Example 2 was obtained in the same manner as described.

<實施例3> <Example 3>

反覆進行乾式粉碎3次、及將粉碎之電解銅微粉末於電爐內在空氣環境下以加熱溫度300℃保持5小時而氧化電解銅粉，除此以外，利用與實施例1所記載之方法相同之方法而獲得實施例3之氧化銅(II)微粉末。 The dry pulverization was repeated three times, and the pulverized electrolytic copper fine powder was oxidized at a heating temperature of 300 ° C for 5 hours in an electric furnace to oxidize the electrolytic copper powder, and the same method as described in Example 1 was used. The copper (II) oxide fine powder of Example 3 was obtained by the method.

<比較例1> <Comparative Example 1>

使用市售之電解銅粉(商品名：MF-D2，三井金屬鑛業(股)公司製造)，及將粉碎之電解銅粉於電爐內在空氣環境下以加熱溫度700℃保持3小時而氧化電解銅粉，除此以外，利用與實施例1所記載之方法相同之方 法而獲得比較例1之氧化銅(II)微粉末。 Commercially available electrolytic copper powder (trade name: MF-D2, manufactured by Mitsui Mining & Mining Co., Ltd.), and oxidized electrolytic copper powder by holding the pulverized electrolytic copper powder in an electric furnace at a heating temperature of 700 ° C for 3 hours in an air atmosphere In addition to the powder, the same method as that described in the first embodiment is used. The copper (II) oxide fine powder of Comparative Example 1 was obtained by the method.

<比較例2> <Comparative Example 2>

於真空下進行電解銅粉之乾燥、及將粉碎之電解銅微粉末於電爐內在空氣環境下以加熱溫度700℃保持3小時而氧化電解銅粉，除此以外，利用與實施例1所記載之方法相同之方法而獲得比較例2之氧化銅(II)微粉末。 The electrolytic copper powder was dried under vacuum, and the pulverized electrolytic copper fine powder was oxidized in an electric furnace at a heating temperature of 700 ° C for 3 hours to oxidize the electrolytic copper powder, and the same as described in Example 1. The copper (II) oxide fine powder of Comparative Example 2 was obtained in the same manner as in the method.

<評價> <evaluation>

[關於電解銅粉] [About electrolytic copper powder]

[表面之色相] [the hue of the surface]

利用目視觀察乾燥電解銅粉後電解銅粉之表面之色相。將結果示於表2。實施例1~3中之電解銅粉之表面變色成褐色。其結果，利用目視確認於表面形成有氧化皮膜。另一方面，比較例1及2中之電解銅粉呈紅色。根據該情況，利用目視確認於表面基本上未形成氧化皮膜。 The hue of the surface of the electrolytic copper powder after drying the electrolytic copper powder was visually observed. The results are shown in Table 2. The surfaces of the electrolytic copper powders of Examples 1 to 3 were discolored to brown. As a result, it was confirmed by visual observation that an oxide film was formed on the surface. On the other hand, the electrolytic copper powders of Comparative Examples 1 and 2 were red. According to this case, it was confirmed by visual observation that the oxide film was not substantially formed on the surface.

[氧化之程度] [degree of oxidation]

針對乾燥後之電解銅粉，藉由將乾燥後之電解銅粉之重量與電解銅粉全部完全地氧化為氧化銅(II)之情形之理論重量進行對比而推定氧化之程度。將結果示於表2。實施例1~3中之電解銅粉進行了相對於理論重量為約40%之氧化。根據該情況，定量確認到實施例1~3中之電解銅粉於表面形成有氧化皮膜。另一方面，比較例1中之電解銅粉僅進行了相對於理論重量約0.4%之氧化，比較例2中之電解銅粉僅進行了相對於理論重量約0.5%之氧化。根據該情況，定量確認到比較例1及2中之電解銅粉於表面基本上未形成氧化皮膜。 With respect to the dried electrolytic copper powder, the degree of oxidation is estimated by comparing the weight of the dried electrolytic copper powder with the theoretical weight of the case where the electrolytic copper powder is completely oxidized to copper (II) oxide. The results are shown in Table 2. The electrolytic copper powders of Examples 1 to 3 were oxidized by about 40% with respect to the theoretical weight. Based on this, it was quantitatively confirmed that the electrolytic copper powders of Examples 1 to 3 were formed with an oxide film on the surface. On the other hand, the electrolytic copper powder of Comparative Example 1 was only oxidized by about 0.4% with respect to the theoretical weight, and the electrolytic copper powder of Comparative Example 2 was only oxidized by about 0.5% with respect to the theoretical weight. Based on this, it was quantitatively confirmed that the electrolytic copper powders of Comparative Examples 1 and 2 did not substantially form an oxide film on the surface.

[氧化銅粉之SEM圖像] [SEM image of copper oxide powder]

拍攝乾燥後之電解銅粉之掃描電子顯微鏡圖像(以下，亦稱為「SEM圖像」)。將結果之一例示於圖2。圖2係實施例1之乾燥後之電解銅粉之SEM圖像。 A scanning electron microscope image (hereinafter also referred to as "SEM image") of the dried electrolytic copper powder was taken. One of the results is illustrated in Fig. 2. 2 is an SEM image of the dried electrolytic copper powder of Example 1.

[平均粒徑] [The average particle size]

使用雷射粒度分佈測定器Microtrac(日機裝公司製造)測定乾燥後之電解銅粉之平均粒徑(近似體積球之直徑)。將結果示於表2。 The average particle diameter (approximate volume of the volumetric ball) of the dried electrolytic copper powder was measured using a laser particle size distribution analyzer Microtrac (manufactured by Nikkiso Co., Ltd.). The results are shown in Table 2.

[關於乾式粉碎後之電解銅微粉末] [About electrolytic copper powder after dry pulverization]

[形狀] [shape]

對乾式粉碎後之電解銅微粉末拍攝SEM圖像。然後，根據該SEM圖像觀察實施例及比較例中之電解銅微粉末之形狀。將SEM圖像之一例示於圖3~圖5。圖3係實施例1之電解銅微粉末之SEM圖像，圖4係比較例1之電解銅微粉末之SEM圖像，圖5係比較例2之電解銅微粉末之SEM圖像。又，將對形狀進行觀察之結果示於表2。實施例1~3中之電解銅微粉末以粒狀之狀態被粉碎。另一方面，比較例1及2中之電解銅微粉末不僅包含粒狀者，亦包含扁平狀之粒子。推測其原因在於：因表面不具有氧化皮膜，故金屬銅之延展性發揮作用而無法微細地粉碎電解銅粉。 An SEM image was taken of the electrolytically pulverized electrolytic copper fine powder after dry pulverization. Then, the shape of the electrolytic copper fine powder in the examples and the comparative examples was observed from the SEM image. One of the SEM images is illustrated in FIGS. 3 to 5. 3 is an SEM image of the electrolytic copper fine powder of Example 1, FIG. 4 is an SEM image of the electrolytic copper fine powder of Comparative Example 1, and FIG. 5 is an SEM image of the electrolytic copper fine powder of Comparative Example 2. Further, the results of observing the shape are shown in Table 2. The electrolytic copper fine powders of Examples 1 to 3 were pulverized in a granular state. On the other hand, the electrolytic copper fine powders of Comparative Examples 1 and 2 contain not only granular but also flat particles. It is presumed that the reason is that since the surface does not have an oxide film, the ductility of the metal copper acts and the electrolytic copper powder cannot be finely pulverized.

[平均粒徑及最大粒徑] [Average particle size and maximum particle size]

測定電解銅微粉末之平均粒徑及最大粒徑。該等粒徑係使用雷射粒度分佈測定器Microtrac(日機裝公司製造)進行測定，並取決於近似體積球之直徑。將結果示於表2。實施例1~3中之電解銅微粉末之平均粒徑為3.5μm以下，最大粒徑為10μm以下。根據該情況，可定量確認到實施例1~3中之電解銅微粉末以粒狀之狀態被粉碎。另一方面，比較例1及2中 之電解銅微粉末之平均粒徑為5.2μm以上，最大粒徑為20μm以上。根據該情況，可定量確認到比較例1及2中之電解銅微粉末係包含未被適當粉碎之粒子者。 The average particle diameter and the maximum particle diameter of the electrolytic copper fine powder were measured. These particle diameters were measured using a laser particle size distribution analyzer Microtrac (manufactured by Nikkiso Co., Ltd.), and depended on the diameter of the approximate volume sphere. The results are shown in Table 2. The electrolytic copper fine powders of Examples 1 to 3 had an average particle diameter of 3.5 μm or less and a maximum particle diameter of 10 μm or less. According to this, it was confirmed quantitatively that the electrolytic copper fine powders of Examples 1 to 3 were pulverized in a granular state. On the other hand, in Comparative Examples 1 and 2 The electrolytic copper fine powder has an average particle diameter of 5.2 μm or more and a maximum particle diameter of 20 μm or more. According to this case, it can be quantitatively confirmed that the electrolytic copper fine powders in Comparative Examples 1 and 2 contain particles which are not appropriately pulverized.

[關於氧化後之氧化銅(II)微粉末] [About oxidized copper (II) oxide powder]

[形狀] [shape]

對氧化後之氧化銅(II)微粉末拍攝SEM圖像進行確認，狀態未因氧化而變化，與圖3~圖5所示之氧化前之狀態相同。 The SEM image of the copper oxide (II) fine powder after oxidation was confirmed, and the state was not changed by oxidation, and it was the same as the state before oxidation shown in FIG. 3 to FIG.

[顏色] [colour]

利用目視觀察實施例及比較例之氧化銅(II)微粉末之顏色。將結果示於表3。試樣均呈黑色。 The color of the copper (II) oxide powder of the examples and the comparative examples was visually observed. The results are shown in Table 3. The samples were all black.

[相] [phase]

為了確認實施例及比較例之氧化銅(II)微粉末之相狀態，對氧化銅(II)微粉末進行X射線繞射。將結果之一例示於圖6及表3。圖6係實施例1之氧化銅(II)微粉末之XRD圖案。根據該XRD圖案，確認實施例1之氧化銅(II)微粉末為CuO單一相。再者，雖省略圖示，但其他實施例及比較例之氧化銅(II)微粉末亦顯示同樣之XRD圖案，而確認均為CuO單一相。 In order to confirm the phase state of the copper (II) oxide fine powder of the examples and the comparative examples, the copper (II) oxide fine powder was subjected to X-ray diffraction. One of the results is illustrated in Fig. 6 and Table 3. Figure 6 is an XRD pattern of the copper (II) oxide powder of Example 1. From the XRD pattern, it was confirmed that the copper (II) oxide fine powder of Example 1 was a CuO single phase. Further, although not shown in the drawings, the copper oxide (II) fine powders of the other examples and comparative examples also showed the same XRD pattern, and were confirmed to be all CuO single phases.

[純度] [purity]

對實施例及比較例之氧化銅(II)微粉末進行電解重量分析。將結果示於表3。確認任一氧化銅(II)微粉末之氧化銅(II)濃度均為99.6重量%。 Electrolytic gravimetric analysis was carried out on the copper (II) oxide powders of the examples and the comparative examples. The results are shown in Table 3. It was confirmed that the copper (II) oxide concentration of any of the copper (II) oxide powders was 99.6% by weight.

[平均粒徑及最大粒徑] [Average particle size and maximum particle size]

測定氧化銅(II)微粉末之平均粒徑及最大粒徑。粒徑之測定方法係與 電解銅微粉末中之測定方法相同。將結果示於表3。根據粒徑之測定結果，定量確認到實施例1~3中之氧化銅(II)微粉末為粒狀，及比較例1、2中之氧化銅(II)微粉末為包含粒狀以外之粒子者。 The average particle diameter and the maximum particle diameter of the copper (II) oxide powder were measured. The method of measuring the particle size is The measurement method in the electrolytic copper fine powder is the same. The results are shown in Table 3. According to the measurement results of the particle diameter, it was quantitatively confirmed that the fine powder of copper (II) oxide in Examples 1 to 3 was granular, and the fine powder of copper (II) oxide in Comparative Examples 1 and 2 was a particle containing particles other than particles. By.

[對鍍液之溶解性之評價] [Evaluation of Solubility of Plating Solution]

對鍍液之溶解性係藉由將實施例及比較例之氧化銅(II)微粉末10g於25℃下一面利用攪拌器進行攪拌一面添加至1L之鍍液中，測定自該添加起至上述氧化銅(II)微粉末完全溶解之時間而進行評價。鍍液係設為含有228g/L之CuSO4‧5H2O、68g/L之游離H2SO4、及60mg/L之氯化物離子之溶液。將結果示於表3。實施例之氧化銅(II)微粉末可於35秒以內溶解於鍍液中。根據該情況，確認即便為乾式法亦可提供具有對鍍液之較高溶解性之氧化銅(II)微粉末。另一方面，比較例之氧化銅(II)微粉末即便經過20分鐘亦無法完全地溶解於鍍液中。 The solubility in the plating solution was added to 1 L of the plating solution by stirring 10 g of the copper oxide (II) fine powder of the examples and the comparative examples while stirring at 25 ° C, and measured from the addition to the above. The copper (II) oxide powder was evaluated for the time of complete dissolution. The plating solution was a solution containing 228 g/L of CuSO 4 ‧5H 2 O, 68 g/L of free H 2 SO 4 , and 60 mg/L of chloride ions. The results are shown in Table 3. The copper (II) oxide fine powder of the examples can be dissolved in the plating solution within 35 seconds. Based on this, it was confirmed that a copper (II) oxide fine powder having a high solubility to a plating solution can be provided even in a dry method. On the other hand, the copper (II) oxide powder of the comparative example could not be completely dissolved in the plating solution even after 20 minutes.

如上所述，確認經由以乾式粉碎表面具有氧化皮膜之電解銅粉之乾式粉碎步驟與氧化藉由該乾式粉碎步驟獲得之電解銅微粉末之氧化步驟而製造的氧化銅(II)微粉末兼具先前之乾式法之優點即高純度、與先前之濕式法之優點即對鍍液之高溶解性兩者。其結果，確認本發明之氧化銅(II)微粉末可極佳地用作工業上所使用之鍍銅液之補給用銅源。 As described above, it was confirmed that the copper (II) oxide powder produced by the dry pulverization step of electrolytic copper powder having an oxide film on the surface of the dry pulverization and the oxidation step of oxidizing the electrolytic copper fine powder obtained by the dry pulverization step have both The advantages of the previous dry process are high purity, both of the advantages of the previous wet process, that is, the high solubility of the bath. As a result, it was confirmed that the copper (II) oxide fine powder of the present invention can be excellently used as a copper source for replenishing a copper plating liquid used in the industry.

另一方面，於未使用表面具有氧化皮膜之電解銅粉之情形時，即便經過20分鐘亦無法完全地溶解於鍍液中(比較例1、2)。就該方面而言，確認作為鍍銅液之補給用銅源可能會產生障礙。 On the other hand, in the case where the electrolytic copper powder having an oxide film on the surface was not used, it was not completely dissolved in the plating solution even after 20 minutes (Comparative Examples 1 and 2). In this respect, it has been confirmed that the copper source for replenishment as a copper plating solution may cause an obstacle.

Claims (7)

一種氧化銅(II)微粉末之製造方法，包含如下步驟：乾式粉碎步驟，以乾式粉碎表面具有氧化皮膜之電解銅粉；及氧化步驟，氧化藉由該乾式粉碎步驟獲得之電解銅微粉末。 A method for producing a copper (II) oxide powder, comprising the steps of: a dry pulverization step of dry-pulverizing an electrolytic copper powder having an oxide film on a surface thereof; and an oxidizing step of oxidizing the electrolytic copper fine powder obtained by the dry pulverization step. 如申請專利範圍第1項之氧化銅(II)微粉末之製造方法，其中，該氧化皮膜係藉由對利用含銅離子溶液之電解獲得之電解銅粉進行水洗後，於含氧環境中以70℃~150℃之溫度乾燥而形成。 The method for producing a copper (II) oxide powder according to the first aspect of the invention, wherein the oxide film is washed with water in an oxygen-containing environment by electrolytically washing the electrolytic copper powder obtained by electrolysis using a copper ion-containing solution. It is formed by drying at a temperature of 70 ° C to 150 ° C. 如申請專利範圍第1或2項之氧化銅(II)微粉末之製造方法，其中，該乾式粉碎步驟係於含氧環境中進行。 A method for producing a copper (II) oxide powder according to claim 1 or 2, wherein the dry pulverization step is carried out in an oxygen-containing atmosphere. 如申請專利範圍第1或2項之氧化銅(II)微粉末之製造方法，其中，該氧化步驟係藉由將該電解銅微粉末以300℃~700℃加熱來進行。 The method for producing a copper (II) oxide fine powder according to claim 1 or 2, wherein the oxidation step is carried out by heating the electrolytic copper fine powder at 300 ° C to 700 ° C. 如申請專利範圍第3項之氧化銅(II)微粉末之製造方法，其中，該氧化步驟係藉由將該電解銅微粉末以300℃~700℃加熱來進行。 A method for producing a copper (II) oxide powder according to the third aspect of the invention, wherein the oxidation step is carried out by heating the electrolytic copper fine powder at 300 ° C to 700 ° C. 一種鍍銅方法，將藉由申請專利範圍第1至5項中任一項之製造方法而獲得之氧化銅(II)微粉末溶解而得的硫酸銅水溶液用作電鍍銅裝置之電解液。 A copper plating method in which a copper sulfate aqueous solution obtained by dissolving a copper (II) oxide fine powder obtained by the production method of any one of claims 1 to 5 is used as an electrolytic solution of a copper plating apparatus. 一種氧化銅(II)微粉末，其平均粒徑為5μm以下，最大粒徑為15μm以下，於將10g之氧化銅(II)微粉末浸漬於25℃的含硫酸溶液1L中而進行之溶解試驗中，溶解時間為1分鐘以下，其中，該含硫酸溶液含有228g/L之CuSO4‧5H2O、68g/L之游離H2SO4、及60mg/L之氯化物離子。 A copper (II) oxide fine powder having an average particle diameter of 5 μm or less and a maximum particle diameter of 15 μm or less, which is subjected to a dissolution test by immersing 10 g of the copper (II) oxide fine powder in 1 L of a sulfuric acid-containing solution at 25 ° C. The dissolution time was 1 minute or less, wherein the sulfuric acid-containing solution contained 228 g/L of CuSO 4 ‧5H 2 O, 68 g/L of free H 2 SO 4 , and 60 mg/L of chloride ions.
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