JPH02294414A - Production of fine copper powder - Google Patents
Production of fine copper powderInfo
- Publication number
- JPH02294414A JPH02294414A JP11642689A JP11642689A JPH02294414A JP H02294414 A JPH02294414 A JP H02294414A JP 11642689 A JP11642689 A JP 11642689A JP 11642689 A JP11642689 A JP 11642689A JP H02294414 A JPH02294414 A JP H02294414A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper powder
- cuprous oxide
- soln
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 13
- 150000001413 amino acids Chemical class 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 5
- 239000008103 glucose Substances 0.000 abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 235000001014 amino acid Nutrition 0.000 description 8
- 229940024606 amino acid Drugs 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 5
- 239000001433 sodium tartrate Substances 0.000 description 5
- 229960002167 sodium tartrate Drugs 0.000 description 5
- 235000011004 sodium tartrates Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 3
- -1 hydrazine compound Chemical class 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 2
- 229930064664 L-arginine Natural products 0.000 description 2
- 235000014852 L-arginine Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycylglycine Chemical compound [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010008488 Glycylglycine Proteins 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940043257 glycylglycine Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、微粒子銅粉末の製造方法に関し、更に詳しく
は銅塩を水溶液中で還元して銅粉末を得る方法の改良に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing fine-particle copper powder, and more particularly to an improvement in a method for obtaining copper powder by reducing a copper salt in an aqueous solution.
［従来の技術］
微粒子銅粉末はこれを有機バインダーや溶媒によりペー
スト化し、厚膜ＩＣの電極や電子部品の電極として用い
られる。電極の細線化や焼付温度を低下させるために微
粒子の銅粉が要望されている。[Prior Art] Fine-particle copper powder is made into a paste using an organic binder or a solvent and used as electrodes for thick film ICs and electronic components. Fine particle copper powder is required to thin the electrodes and lower the baking temperature.
従来銅粉末の製法としては還元銅と電解銅の２種の方法
がある。前者は銅塩水溶液に中和剤として水酸化ナトリ
ウムを加え、水酸化銅を析出せしめ、更に還元糖である
グルコースなどを加え、亜酸化銅とし、これを更にヒド
ラジンで還元して銅粉末を得る方法であり、後者は銅塩
水溶液を電気分解し、陰極に銅を析出させ、これを粉砕
して銅粉末を得る方法であり、共に銅粉末の製法として
広く採用されている。しかし、これらの銅粉末は電解銅
粉末の場合は５ミクロン以上である。There are two conventional methods for producing copper powder: reduced copper and electrolytic copper. The former involves adding sodium hydroxide as a neutralizing agent to an aqueous copper salt solution to precipitate copper hydroxide, then adding reducing sugar such as glucose to form cuprous oxide, which is further reduced with hydrazine to obtain copper powder. The latter method involves electrolyzing an aqueous copper salt solution, depositing copper on the cathode, and pulverizing it to obtain copper powder. Both methods are widely adopted as methods for producing copper powder. However, these copper powders are 5 microns or more in the case of electrolytic copper powders.
前者の還元銅粉末を場合、この前段の還元糖による銅塩
の還元に際し、銅イオンを錯体化させるために従来酒石
酸ナトリウムが使用されていたが、酒石酸ナトリウムを
使用すると、得られる銅粉末は凝集し、分散性の悪い、
いわゆる「のび」の悪いものとなり、また粒径も０，７
〜３ミクロンと大きいものである。In the case of the former reduced copper powder, sodium tartrate was conventionally used to complex the copper ions during the reduction of the copper salt with the reducing sugar in the first step, but when sodium tartrate is used, the resulting copper powder will aggregate. and poor dispersion,
The so-called "spreadability" is poor, and the particle size is also 0.7.
It is large, ~3 microns.
特に厚膜ＩＣの導体として使用される銅ペーストにおい
ては、粒径が微粒子で凝集が少なく、分散性のよい、い
わゆる「のび」のよい銅微粒子が望まれている。Particularly in copper pastes used as conductors in thick-film ICs, fine copper particles with fine particle size, less agglomeration, and good dispersibility, so-called "spreadability", are desired.
［発明が解決しようとする課題］
本発明は、粒径のより小さい、かつ凝集が少なく、分散
性のよい、いわゆる「のび」のよい銅粉末を製造できる
方法を提供しようとするものである。[Problems to be Solved by the Invention] The present invention aims to provide a method for producing copper powder that has a smaller particle size, less agglomeration, and good dispersibility, so-called "spreadability".
［課題を解決するための手段］
本発明は、この課題を従来使用されていた酒石酸ナトリ
ウムに代えて、アミノ酸またはその塩、アンモニアまた
はアンモニア塩、有機アミノ類、もしくはジメチルグリ
オキシムを用いることにより解決した。[Means for Solving the Problem] The present invention solves this problem by using an amino acid or a salt thereof, ammonia or an ammonia salt, organic aminos, or dimethylglyoxime in place of the conventionally used sodium tartrate. did.
すなわち、本発明の方法ではこれらの添加物の少くとも
１種の存在下、銅塩水溶液に水酸化ナトリウム、水酸化
カリウムなどの水酸化アルカリを加え、更に還元糖を加
えて亜酸化銅を水溶液中に析出させ、更にヒドラジンを
加えて、亜酸化銅を還元して、粒径の小さい「のび」の
よい銅微粉末を得る。That is, in the method of the present invention, an alkali hydroxide such as sodium hydroxide or potassium hydroxide is added to an aqueous copper salt solution in the presence of at least one of these additives, and reducing sugar is further added to form a solution of cuprous oxide in an aqueous solution. Then, hydrazine is added to reduce the cuprous oxide to obtain fine copper powder with small particle size and good spreadability.
還元に供する銅塩としては、水溶性塩であればいずれも
使用でき、硫酸銅、塩化銅、硝酸銅などの銅無機塩、酢
酸銅などの銅有機塩が例示できる。As the copper salt to be subjected to reduction, any water-soluble salt can be used, and examples include copper inorganic salts such as copper sulfate, copper chloride, and copper nitrate, and copper organic salts such as copper acetate.
銅塩の亜酸化銅への還元にはグルコースなどの還元剤を
用い、さらに亜酸化銅の銅への還元には、抱水ヒドラジ
ン、無水ヒドラジンなどのヒドラジン化合物を用いて行
う。還元剤の使用量は従来の方法と同様である。A reducing agent such as glucose is used to reduce the copper salt to cuprous oxide, and a hydrazine compound such as hydrazine hydrate or anhydrous hydrazine is used to further reduce the cuprous oxide to copper. The amount of reducing agent used is the same as in the conventional method.
アミノ酸またはその塩は、既知のものの中から適宜選択
することができ、天然アミノ酸または合成アミノ酸のい
ずれでもよい。The amino acid or its salt can be appropriately selected from known amino acids, and may be either a natural amino acid or a synthetic amino acid.
例えば、グリシン、ヒスチジン、アラニン、パリン、ア
スパラギン、アスパラギン酸、グルタミン酸またはその
ナトリウム塩、アルギン、リジン、グリシルグリシン、
エチレンジアミン四酢酸などが好ましい。For example, glycine, histidine, alanine, parine, asparagine, aspartic acid, glutamic acid or its sodium salt, algine, lysine, glycylglycine,
Ethylenediaminetetraacetic acid and the like are preferred.
アンモニウムまたはアンモニウム塩としてアンモニウム
水、酢酸アンモニウム、塩化アンモニウムなどが好まし
く、また有機アミン類としてはエタノールアミン、エチ
レンアミンなどが例示できる。Ammonium or ammonium salts are preferably ammonium water, ammonium acetate, ammonium chloride, etc., and organic amines include ethanolamine, ethyleneamine, etc.
これらの添加物はいずれも従来法の酒石酸上り銅イオン
との錯体安定度定数が大きい。錯体安定化定数が大きい
ほど、微粒子で「のび」のよい銅微粉末が得られ、添加
物のｌ種または２種以上の混合物を適当に用いることに
より、得られる銅粉末「のび」および拉径を制御するこ
とができる。All of these additives have a large complex stability constant with the copper ion of tartrate in the conventional method. The larger the complex stabilization constant, the finer the particles and the better the "spreadability" of the fine copper powder. By appropriately using l type or a mixture of two or more types of additives, the "spreadability" and the diameter of the copper powder obtained can be improved. can be controlled.
アミノ酸をはじめとするこれらの添加物は、本発明の方
法では触媒的に反応に関与するので、それほど多量に使
用する必要はない。たとえば、銅塩１モルに対して添加
物ｏ．ｏｏｓ〜０．０２モルの量で十分である。水酸化
アルカリによる水酸化銅の析出反応、還元糖による還元
反応は、常温で行うこともできるが、反応を促進する為
に８０℃程度以下、好ましくは６０〜７０℃程度に加熱
するのがよい。反応圧力は常圧でよい。また、この還元
反応は、従来法と同じく水酸化アルカリによるアルカリ
側のｐＨで行うのが好ましい。また、亜酸化銅が析出し
たのちに該溶液にヒドラジンの化合物を加え、同様の温
度で還元を行うのがよい。Since these additives including amino acids participate in the reaction catalytically in the method of the present invention, they do not need to be used in large amounts. For example, additive o. Amounts from oos to 0.02 mol are sufficient. The precipitation reaction of copper hydroxide with alkali hydroxide and the reduction reaction with reducing sugar can be carried out at room temperature, but in order to accelerate the reaction, it is better to heat it to about 80°C or less, preferably about 60 to 70°C. . The reaction pressure may be normal pressure. Further, this reduction reaction is preferably carried out at an alkaline pH using an alkali hydroxide, as in the conventional method. Further, it is preferable to add a hydrazine compound to the solution after cuprous oxide has precipitated, and to perform reduction at the same temperature.
水溶液中に生成した銅粉末を濾過回収してもよいが、水
分散液のままペンゾトリアゾールなどにより防錆処理を
行なってもよい。The copper powder produced in the aqueous solution may be collected by filtration, but the aqueous dispersion may also be subjected to rust prevention treatment using penzotriazole or the like.
本発明の方法では、得られた銅粉末に、たとえアミノ酸
などの添加物が含まれていたとしても、加熱により分解
除去できる。In the method of the present invention, even if the obtained copper powder contains additives such as amino acids, they can be decomposed and removed by heating.
本発明の方法により製造される銅微粉末の平均粒径、タ
ップ密度および「のび」の特性は表−１の通りであり、
従来法に比べて微粒子で、タップ密度も高く、「のび」
もよい。The average particle size, tap density and "spread" characteristics of the fine copper powder produced by the method of the present invention are shown in Table 1.
Compared to the conventional method, the particles are finer, the tap density is higher, and it is "spreadable".
Good too.
本発明により製造される銅粉末は銅ペーストに好適な性
質を持っている。The copper powder produced according to the present invention has properties suitable for copper paste.
平均粒径はＢＥＴ法（窒素ガス吸着法、島津一マイクロ
メリテックス製２２００型）の比表面積より求めた粒径
であり、タップ密度は９〜１０ｇの銅粉末を内径１５＋
ｍφのガラスシリンダーに入れ、高さ２０ｃｍから５０
回タッピングした時の値である。「のび」特性は、試料
０．０ １ ５ｇをワープロ用紙（コクヨ社製）上にと
り、指先でおさえて、ほぼ指巾にひき伸ばした時の長さ
（ｃｍ）で示す。The average particle size is the particle size determined from the specific surface area of the BET method (nitrogen gas adsorption method, Shimadzu Micromeritex Model 2200), and the tap density is 9 to 10 g of copper powder with an inner diameter of 15+.
Place it in a mφ glass cylinder, and use it from a height of 20cm to 50mm.
This is the value when tapped twice. The "spreading" property is expressed as the length (cm) when 0.015 g of a sample is placed on word processing paper (manufactured by KOKUYO), held down with a fingertip, and stretched to approximately the width of a finger.
実施例
水３２０ｍｌにＣｕＳＯ− ・５ＨｔＯ結晶４０．０ｇ
（０．１６モル）とグリシン、アルギニンなどのアミノ
酸（０。００３５モル）のうちの１種類を溶かした水溶
液に、温度６０℃で、２規定−ＮａＯＨ水溶液を加え、
溶液のｐＨを１０．６〜１１．６とする。次にこの溶液
にブドウ糖１４．４ｇを加え、撹拌しながら３０分間保
持した。次に液温を２５℃に冷却したのち抱水ヒドラジ
ン（８０％）３５＋ｎｌを加え、７０℃まで約１℃／分
の平均昇温速度で加熱する。７０℃で２時間保持したの
ち濾過・水洗・エタノール洗浄を行う。得られた沈澱物
は９０℃、３時間真空乾燥を行った。この方法で合成さ
れた銅粉末はいずれも亜酸化銅を含まない純銅である。Example: 40.0 g of CuSO- 5HtO crystal in 320 ml of water.
(0.16 mol) and one type of amino acid (0.0035 mol) such as glycine or arginine are dissolved in an aqueous solution at a temperature of 60°C, and a 2N-NaOH aqueous solution is added.
The pH of the solution is set to 10.6-11.6. Next, 14.4 g of glucose was added to this solution and held for 30 minutes while stirring. Next, after cooling the liquid temperature to 25°C, 35+nl of hydrazine hydrate (80%) is added and heated to 70°C at an average heating rate of about 1°C/min. After holding at 70°C for 2 hours, filtration, washing with water, and washing with ethanol are performed. The obtained precipitate was vacuum dried at 90°C for 3 hours. All copper powders synthesized by this method are pure copper containing no cuprous oxide.
表−２に添加物の種類、溶液のｐＨ、合成銅粉のタップ
密度、のび特性、ＢＥＴ法による比表面積およびそれか
ら求めた粒径を示した。表−２の最初のものは比較のた
め従来法の酒石酸ソーダを添加した場合の結果である。Table 2 shows the types of additives, the pH of the solution, the tap density of the synthetic copper powder, the spreading properties, the specific surface area determined by the BET method, and the particle size determined therefrom. The first one in Table 2 shows the results when sodium tartrate was added in the conventional method for comparison.
表−２
酒石酸ソーダ １１．６
グリシン １１．６
ヒスチジン １１．６
Ｌ−アルギニン ｌ１．６
Ｌ−アルギニン １０．６
グルタミン酸 １１．６
１．８７ ８ １．０２２．６ｇ
３３ １．４３３．４４ ５９
１１２３．５６ ４３ １．８７２．
９４ １３０ ？．３９３．３２
３７ １．１００．７０
０．３５
０．０９
０．６０
アンモニア水 １１．６ ２．１０
アンモニア水 ＩＱ．６ ２．５５Table-2 Sodium tartrate 11.6 Glycine 11.6 Histidine 11.6 L-Arginine 11.6 L-Arginine 10.6 Glutamic acid 11.6 1.87 8 1.022.6g
33 1.433.44 59
1123.56 43 1.872.
94 130? ．． 393.32
37 1.100.70 0.35 0.09 0.60 Ammonia water 11.6 2.10 Ammonia water IQ. 6 2.55
Claims (1)
ウム塩、有機アミン類ならびにジメチルグリオキシムか
ら成る群から選択された少くとも１種の化合物の存在下
、銅塩水溶液に水酸化アルカリを加え、還元糖を加えて
亜酸化銅を水溶液中に析出させ、これにヒドラジンを加
えて亜酸化銅を還元して銅粉末を得ることを特徴とする
微粒子銅粉末の製造方法。1. In the presence of at least one compound selected from the group consisting of amino acids and their salts, ammonia and ammonium salts, organic amines, and dimethylglyoxime, add alkali hydroxide to an aqueous copper salt solution, and add reducing sugar. 1. A method for producing fine-particle copper powder, which comprises precipitating cuprous oxide in an aqueous solution, and adding hydrazine to the precipitate to reduce the cuprous oxide to obtain copper powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11642689A JP2728726B2 (en) | 1989-05-10 | 1989-05-10 | Method for producing fine copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11642689A JP2728726B2 (en) | 1989-05-10 | 1989-05-10 | Method for producing fine copper powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02294414A true JPH02294414A (en) | 1990-12-05 |
| JP2728726B2 JP2728726B2 (en) | 1998-03-18 |
Family
ID=14686800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11642689A Expired - Lifetime JP2728726B2 (en) | 1989-05-10 | 1989-05-10 | Method for producing fine copper powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2728726B2 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04116109A (en) * | 1990-09-06 | 1992-04-16 | Sumitomo Metal Ind Ltd | Production of fine copper powder |
| EP0887132A2 (en) * | 1997-06-04 | 1998-12-30 | Mitsui Mining & Smelting Co., Ltd. | Copper fine powder and method for preparing the same |
| JP2001220607A (en) * | 1999-12-01 | 2001-08-14 | Dowa Mining Co Ltd | Copper powder and method for producing copper powder |
| KR100405970B1 (en) * | 2001-09-18 | 2003-11-14 | 한국과학기술연구원 | Synthesis of Cu Fine Particles by Glycothermal Process |
| WO2006062160A1 (en) * | 2004-12-10 | 2006-06-15 | Mitsubishi Materials Corporation | Fine metal particle, process for producing the same, composition containing the same, and use thereof |
| CN1299865C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nuclear shell structured nano-gold copper powder |
| CN1299864C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nano-bronze powder |
| CN1305772C (en) * | 2005-04-26 | 2007-03-21 | 黄德欢 | Process for preparing nano cuprous oxide powder |
| JP2007254846A (en) * | 2006-03-24 | 2007-10-04 | Mitsui Mining & Smelting Co Ltd | Production method for copper powder and copper powder obtained by the production method |
| JP2008274408A (en) * | 2007-03-14 | 2008-11-13 | Phibro-Tech Inc | Method of producing fine-particle copper powders |
| JP2010150619A (en) * | 2008-12-26 | 2010-07-08 | Mitsui Mining & Smelting Co Ltd | Method for producing copper nanoparticle |
| CN104227012A (en) * | 2013-06-14 | 2014-12-24 | 中国振华集团云科电子有限公司 | Preparation method for ultra-fine copper powder |
| JP2016191095A (en) * | 2015-03-30 | 2016-11-10 | Ｄｏｗａエレクトロニクス株式会社 | Method for producing copper nanostructure |
| JP2016204733A (en) * | 2015-04-28 | 2016-12-08 | 日立化成株式会社 | Manufacturing method of copper particle, copper particle, copper paste and semiconductor device |
| JP2017115199A (en) * | 2015-12-24 | 2017-06-29 | 三井金属鉱業株式会社 | Manufacturing method of copper particles |
| JP2019002054A (en) * | 2017-06-16 | 2019-01-10 | 三井金属鉱業株式会社 | Copper particle |
| JP2020176334A (en) * | 2020-07-15 | 2020-10-29 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder and conductive paste |
| JP2021014633A (en) * | 2019-07-16 | 2021-02-12 | Ｊｘ金属株式会社 | Surface-treated copper powder |
-
1989
- 1989-05-10 JP JP11642689A patent/JP2728726B2/en not_active Expired - Lifetime
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04116109A (en) * | 1990-09-06 | 1992-04-16 | Sumitomo Metal Ind Ltd | Production of fine copper powder |
| EP0887132A2 (en) * | 1997-06-04 | 1998-12-30 | Mitsui Mining & Smelting Co., Ltd. | Copper fine powder and method for preparing the same |
| US6174344B1 (en) | 1997-06-04 | 2001-01-16 | Mitsui Mining And Smelting Co., Ltd. | Copper fine powder and method for preparing the same |
| EP0887132A3 (en) * | 1997-06-04 | 2001-11-14 | Mitsui Mining & Smelting Co., Ltd. | Copper fine powder and method for preparing the same |
| US6391087B1 (en) | 1997-06-04 | 2002-05-21 | Mitsui Mining And Smelting Co., Ltd. | Copper fine powder and method for preparing the same |
| JP4701426B2 (en) * | 1999-12-01 | 2011-06-15 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder and copper powder manufacturing method |
| JP2001220607A (en) * | 1999-12-01 | 2001-08-14 | Dowa Mining Co Ltd | Copper powder and method for producing copper powder |
| KR100405970B1 (en) * | 2001-09-18 | 2003-11-14 | 한국과학기술연구원 | Synthesis of Cu Fine Particles by Glycothermal Process |
| KR101346972B1 (en) * | 2004-12-10 | 2014-01-15 | 다이닛뽄도료가부시키가이샤 | Fine metal particle, process for producing the same, composition containing the same, and use thereof |
| JP2006169544A (en) * | 2004-12-10 | 2006-06-29 | Mitsubishi Materials Corp | Metal particulate, method for producing the same, composition containing the same and application thereof |
| WO2006062160A1 (en) * | 2004-12-10 | 2006-06-15 | Mitsubishi Materials Corporation | Fine metal particle, process for producing the same, composition containing the same, and use thereof |
| US7846976B2 (en) | 2004-12-10 | 2010-12-07 | Mitsubishi Materials Corporation | Metallic fine particles, process for producing the same, composition containing the same, and use thereof |
| JP4665499B2 (en) * | 2004-12-10 | 2011-04-06 | 三菱マテリアル株式会社 | Metal fine particles, production method thereof, composition containing the same, and use thereof |
| CN1299864C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nano-bronze powder |
| CN1305772C (en) * | 2005-04-26 | 2007-03-21 | 黄德欢 | Process for preparing nano cuprous oxide powder |
| CN1299865C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nuclear shell structured nano-gold copper powder |
| JP2007254846A (en) * | 2006-03-24 | 2007-10-04 | Mitsui Mining & Smelting Co Ltd | Production method for copper powder and copper powder obtained by the production method |
| JP2008274408A (en) * | 2007-03-14 | 2008-11-13 | Phibro-Tech Inc | Method of producing fine-particle copper powders |
| JP2010150619A (en) * | 2008-12-26 | 2010-07-08 | Mitsui Mining & Smelting Co Ltd | Method for producing copper nanoparticle |
| CN104227012A (en) * | 2013-06-14 | 2014-12-24 | 中国振华集团云科电子有限公司 | Preparation method for ultra-fine copper powder |
| JP2016191095A (en) * | 2015-03-30 | 2016-11-10 | Ｄｏｗａエレクトロニクス株式会社 | Method for producing copper nanostructure |
| JP2016204733A (en) * | 2015-04-28 | 2016-12-08 | 日立化成株式会社 | Manufacturing method of copper particle, copper particle, copper paste and semiconductor device |
| JP2017115199A (en) * | 2015-12-24 | 2017-06-29 | 三井金属鉱業株式会社 | Manufacturing method of copper particles |
| JP2019002054A (en) * | 2017-06-16 | 2019-01-10 | 三井金属鉱業株式会社 | Copper particle |
| JP2021014633A (en) * | 2019-07-16 | 2021-02-12 | Ｊｘ金属株式会社 | Surface-treated copper powder |
| JP2020176334A (en) * | 2020-07-15 | 2020-10-29 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder and conductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2728726B2 (en) | 1998-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH02294414A (en) | Production of fine copper powder | |
| JP2638271B2 (en) | Production method of copper fine powder | |
| JP2003503300A (en) | Method for producing cobalt hydroxide or cobalt mixed hydroxide of high density and large particle size and product produced by this method | |
| JPH02294415A (en) | Production of fine copper powder | |
| JP2900650B2 (en) | Method for producing nickel fine powder | |
| JP3921805B2 (en) | Method for producing nickel fine powder | |
| JP2020007633A (en) | Nickel coupling particle and manufacturing method therefor | |
| JPH0323220A (en) | Preparation of white electrically- conductive zinc oxide | |
| JPH09183620A (en) | Bismuth oxycarbonate powder and its production | |
| JP7342227B2 (en) | Tantalum acid dispersion and tantalate compound | |
| JPH07278619A (en) | Production of nickel powder | |
| JP5674083B2 (en) | Iron oxyhydroxide sol and method for producing the same | |
| JP4352121B2 (en) | Copper powder manufacturing method | |
| JPH03131533A (en) | Production of ruthenium nitrate solution | |
| JP3245965B2 (en) | Production method of copper powder | |
| JP2004211191A (en) | Chemical for producing nickel fine powder | |
| JP6491595B2 (en) | Method for producing platinum palladium rhodium alloy powder | |
| JPH03287707A (en) | Production of copper powder | |
| JP5416979B2 (en) | Copper powder and method for producing the same | |
| JP3577330B2 (en) | Method of coating red light-emitting phosphor particles with hematite, red light-emitting phosphor particles obtained by this method, and color picture tube using the particles | |
| JPH04321523A (en) | Production of tricobalt tetroxide | |
| JPH0211707A (en) | Production of silver fine particle | |
| US20210268583A1 (en) | Method of producing spherical silver powder | |
| JP2736693B2 (en) | Method for producing jarosite particle powder | |
| JPH07107172B2 (en) | Method for producing fine silver particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071212 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081212 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081212 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091212 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091212 Year of fee payment: 12 |