JP2022007624A - Production method for copper powder - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 238
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 76
- 239000010949 copper Substances 0.000 claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 claims abstract description 57
- 238000006722 reduction reaction Methods 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 30
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 58
- 239000011248 coating agent Substances 0.000 abstract description 44
- 238000000576 coating method Methods 0.000 abstract description 44
- 230000032798 delamination Effects 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 90
- 239000002245 particle Substances 0.000 description 79
- 230000000052 comparative effect Effects 0.000 description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 32
- 239000000460 chlorine Substances 0.000 description 32
- 229910052801 chlorine Inorganic materials 0.000 description 32
- 239000011362 coarse particle Substances 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000112 cooling gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 239000010453 quartz Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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Abstract
Description
本発明は、銅粉の製造方法に関する。 The present invention relates to a method for producing copper powder.
微細な金属粒子の集合体である金属粉や金属粉を含む導電性ペーストは、低温同時焼成セラミックス（ＬＴＣＣ）基板の配線や端子、積層セラミックコンデンサ（ＭＬＣＣ）の内部電極や外部電極など、各種電子部品を製造するための原材料として幅広く利用されている。特に、銅粉は、銅の高い導電性に起因し、ＭＬＣＣの内部電極の薄膜化や外部電極の小型が可能であること、周波数特性の大幅な改善が可能であることから、従来多用されてきたニッケル粉や銀粉に替わる材料として期待されている（特許文献１～特許文献５参照）。 Conductive paste containing metal powder or metal powder, which is an aggregate of fine metal particles, is used for various electrons such as wiring and terminals of low-temperature co-fired ceramics (LTCC) substrate, internal electrodes and external electrodes of laminated ceramic capacitors (MLCC). It is widely used as a raw material for manufacturing parts. In particular, copper powder has been widely used in the past because of the high conductivity of copper, which enables thinning of the internal electrode of MLCC, miniaturization of the external electrode, and significant improvement of frequency characteristics. It is expected as a material to replace nickel powder and silver powder (see Patent Documents 1 to 5).
しかしながら、銅の融点（約１０８３度）はニッケルの融点（約１４５５度）よりも低い。また、銅粉の微細化に伴って、銅粉の比表面積が増加するため、銅粉の融点（焼結開始温度）はさらに低下する。そのため、ＭＬＣＣの電極層として微細な銅粉を用いた場合、ニッケル粉よりも低温で溶融が開始されることになる。この場合、ＭＬＣＣの誘電層の焼結開始温度と電極層の焼結温度との温度差が大きくなり、降温時の電極層の収縮によって電極層にクラックが発生する問題や誘電層と電極層との剥離（デラミネーション）が発生する問題があった。したがって、銅粉をＭＬＣＣの電極層に用いるためには、電極層の焼結開始温度を誘電層の焼結開始温度に近づける、すなわち、焼結開始温度が高く、かつ、塗膜の平滑性に優れる銅粉が要求されていた。 However, the melting point of copper (about 1083 degrees) is lower than the melting point of nickel (about 1455 degrees). Further, as the copper powder becomes finer, the specific surface area of the copper powder increases, so that the melting point (sintering start temperature) of the copper powder further decreases. Therefore, when fine copper powder is used as the electrode layer of MLCC, melting is started at a lower temperature than nickel powder. In this case, the temperature difference between the sintering start temperature of the dielectric layer of the MLCC and the sintering temperature of the electrode layer becomes large, and the problem that cracks occur in the electrode layer due to the shrinkage of the electrode layer at the time of temperature decrease and the dielectric layer and the electrode layer There was a problem that peeling (delamination) occurred. Therefore, in order to use the copper powder for the electrode layer of MLCC, the sintering start temperature of the electrode layer is brought close to the sintering start temperature of the dielectric layer, that is, the sintering start temperature is high and the coating film is smooth. Excellent copper powder was required.
本発明は、上記問題に鑑み、高い焼結開始温度を有し、かつ、塗膜の平滑性に優れた銅粉の製造方法を提供することを課題の一つとする。 In view of the above problems, one of the problems of the present invention is to provide a method for producing a copper powder having a high sintering start temperature and excellent smoothness of a coating film.
本発明の一実施形態に係る銅粉の製造方法は、銅と塩素ガスとを反応させて塩化銅ガスを生成し、塩化銅ガスと還元性ガスとを反応させ、還元反応により銅粉を生成することを含み、還元反応における塩化銅ガスの分圧は、１０％以上４０％以下であり、生成された銅粉は、２０００℃／秒以上９０００℃／秒以下の冷却速度で冷却される。 In the method for producing copper powder according to an embodiment of the present invention, copper and chlorine gas are reacted to generate copper chloride gas, copper chloride gas and a reducing gas are reacted, and copper powder is produced by a reduction reaction. The partial pressure of the copper chloride gas in the reduction reaction is 10% or more and 40% or less, and the produced copper powder is cooled at a cooling rate of 2000 ° C./sec or more and 9000 ° C./sec or less.
塩化銅ガスの分圧が２０％以上３０％以下であってもよい。また、冷却速度が３０００℃／秒以上５０００℃／秒以下であってもよい。 The partial pressure of the copper chloride gas may be 20% or more and 30% or less. Further, the cooling rate may be 3000 ° C./sec or more and 5000 ° C./sec or less.
本発明の一実施形態に係る銅粉の製造方法によれば、高い焼結開始温度を有し、かつ、塗膜の平滑性に優れた銅粉を製造することができる。また、本発明に係る銅粉の製造方法によって製造された銅粉をＭＬＣＣの電極層に用いれば、電極層の焼結開始温度と誘電層の焼結開始温度との温度差が小さくなるため、電極層のクラックやデラミネーションを抑制することができる。 According to the method for producing copper powder according to an embodiment of the present invention, it is possible to produce copper powder having a high sintering start temperature and excellent smoothness of a coating film. Further, if the copper powder produced by the method for producing copper powder according to the present invention is used for the electrode layer of MLCC, the temperature difference between the sintering start temperature of the electrode layer and the sintering start temperature of the dielectric layer becomes small. It is possible to suppress cracks and delamination of the electrode layer.
以下、本発明の実施形態について詳細に説明する。但し、本発明は、その要旨を逸脱しない範囲において様々な態様で実施することができ、以下に例示する実施形態または実施例の記載内容に限定して解釈されるものではない。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention can be carried out in various embodiments without departing from the gist thereof, and is not construed as being limited to the contents of the embodiments or examples illustrated below.
また、以下の実施形態または実施例においては、銅粉の利用として、ＭＬＣＣの電極層への適用を例示するが、本発明の一実施形態に係る銅粉製造方法によって製造された銅粉は、これに限られず、その他の電子部品へ適用することも可能である。 Further, in the following embodiments or examples, the application of MLCC to the electrode layer is exemplified as the use of copper powder, but the copper powder produced by the copper powder production method according to the embodiment of the present invention is used. Not limited to this, it can also be applied to other electronic components.
［１．銅粉の製造方法］
図１を参照して、本発明の一実施形態に係る銅粉の製造方法の概要について説明する。図１は、本発明の一実施形態に係る銅粉の製造方法を示すフローチャートである。本実施形態に係る銅粉の製造方法は、塩素ガスの生成工程（Ｓ１００）、塩化銅の還元工程（Ｓ２００）、塩素成分の低減工程（Ｓ３００）、酸素成分の低減工程（Ｓ４００）、および表面処理工程（Ｓ５００）を含む。なお、各工程は、必ずしも明確に分離されていなくてもよく、例えば、塩素ガスの生成工程（Ｓ１００）と塩化銅の還元工程（Ｓ２００）とが同時に行われるような構成であってもよい。また、一部の工程を省略する構成であってもよい。
[1. Copper powder manufacturing method]
An outline of a method for producing copper powder according to an embodiment of the present invention will be described with reference to FIG. 1. FIG. 1 is a flowchart showing a method for producing copper powder according to an embodiment of the present invention. The method for producing copper powder according to the present embodiment includes a chlorine gas generation step (S100), a copper chloride reduction step (S200), a chlorine component reduction step (S300), an oxygen component reduction step (S400), and a surface. The processing step (S500) is included. It should be noted that each step does not necessarily have to be clearly separated, and may be configured such that, for example, the chlorine gas generation step (S100) and the copper chloride reduction step (S200) are performed at the same time. Further, the configuration may omit some steps.
以下、各工程について詳細に説明する。 Hereinafter, each step will be described in detail.
［１－１．塩化銅ガスの生成工程（Ｓ１００）］
本実施形態に係る銅粉の製造方法では、塩化銅ガスと還元性ガスとの還元反応を利用して銅粉を生成する。ここでは、還元反応で用いる塩化銅ガスの製造方法について説明する。
[1-1. Copper chloride gas generation step (S100)]
In the method for producing copper powder according to the present embodiment, copper powder is produced by utilizing a reduction reaction between copper chloride gas and a reducing gas. Here, a method for producing copper chloride gas used in the reduction reaction will be described.
塩化銅ガスは、金属銅を原料として、金属銅と塩素含有ガスとを反応させることにより生成する。具体的には、金属銅を加熱して塩素含有ガスと反応させることによって、塩化銅ガスを生成させることができる。生成された塩化銅ガスは、原料として塩化銅ではなく、塩化銅よりも安価な金属銅を用いているため、塩化銅ガスの製造コストを抑制することができる。また、金属銅を用いることで塩化銅ガスの生成量を制御することができるため、塩化銅ガスの供給量を安定化させることができる。 Copper chloride gas is produced by reacting metallic copper with a chlorine-containing gas using metallic copper as a raw material. Specifically, copper chloride gas can be generated by heating metallic copper and reacting it with a chlorine-containing gas. Since the produced copper chloride gas uses metallic copper, which is cheaper than copper chloride, instead of copper chloride as a raw material, the production cost of copper chloride gas can be suppressed. Further, since the amount of copper chloride gas produced can be controlled by using metallic copper, the amount of copper chloride gas supplied can be stabilized.
図２は、本発明の一実施形態に係る銅粉の製造方法に用いる金属塩化物生成装置１０の概略図である。金属塩化物生成装置１０は、塩化炉１００、投入口１１０、導入管１２０、回収管１３０、およびヒータ１４０を含む。投入口１１０、導入管１２０、および回収管１３０の各々は、塩化炉１００に連結されている。金属銅は投入口１１０から投入され、塩素含有ガスは導入管１２０から供給される。すなわち、投入された金属銅と供給された塩素含有ガスとが塩化炉１００内で反応し、その反応によって生成された塩化銅ガスが回収管１３０を通じて回収される。
FIG. 2 is a schematic view of a
塩化炉１００は、ヒータ１４０によって加熱することができる。塩化炉１００の加熱温度は、塩化炉１００内で金属銅が溶融しない温度、すなわち、銅の融点（約１０８３度）以下である。
The
ここで、塩化炉１００の加熱温度とは、加熱された塩化炉１００内の温度をいうが、塩化炉１００内の温度を直接測定することが困難である場合は、金属塩化物生成装置１０において設定した塩化炉１００の設定温度とすることもできる。
Here, the heating temperature of the
供給された塩素含有ガスは、塩化炉１００に充満し、自然流によって回収管１３０の方向に流れる。そのため、塩素含有ガスの流量を調整することにより、塩化炉１００内に滞留する塩素含有ガスの量を調整し、生成される塩化銅ガスの量を制御することができる。
The supplied chlorine-containing gas fills the
塩素含有ガスは、塩素ガスのみであってもよく、塩素ガスに希釈用の不活性ガスを含有した混合ガスであってもよい。不活性ガスとしては、窒素ガスまたはアルゴンガスなどを用いることができる。また、生成される塩化銅ガスの量は、不活性ガスの量を調整することにより、塩化炉１００内の塩素ガスの量を調整し、生成される塩化銅ガスの量を制御することができる。
The chlorine-containing gas may be only chlorine gas, or may be a mixed gas containing an inert gas for dilution in chlorine gas. As the inert gas, nitrogen gas, argon gas or the like can be used. Further, the amount of copper chloride gas produced can be adjusted by adjusting the amount of inert gas to adjust the amount of chlorine gas in the
塩素含有ガスは、加熱されて塩化炉１００に導入されてもよい。塩素含有ガスの加熱は、塩素含有ガスが導入管１２０に供給される前に行われてもよく、塩素含有ガスが導入管１２０に供給された後、導入管１２０を加熱することによって行われてもよい。また、塩素含有ガスが塩素ガスと不活性ガスとの混合ガスである場合、加熱した不活性ガスと塩素ガスとを混合してもよい。
The chlorine-containing gas may be heated and introduced into the
ここで、塩素含有ガスの加熱温度とは、加熱された塩素含有ガスの温度をいうが、塩素含有ガスの温度を直接測定することが困難である場合は、塩素含有ガスを加熱するヒータの設定温度とすることもできる。 Here, the heating temperature of the chlorine-containing gas means the temperature of the heated chlorine-containing gas, but if it is difficult to directly measure the temperature of the chlorine-containing gas, a heater for heating the chlorine-containing gas is set. It can also be the temperature.
以上、塩化銅ガスの生成工程（Ｓ１００）では、塩化炉１００の加熱温度、塩素含有ガスの流量、塩素含有ガスに占める不活性ガスの割合、または塩素含有ガスの加熱温度などの条件を調整することで、塩化銅ガスの生成量を精密に制御することが可能となる。
As described above, in the copper chloride gas generation step (S100), conditions such as the heating temperature of the
［１－２．塩化銅の還元工程（Ｓ２００）］
次に、生成された塩化銅ガスと還元性ガスとを反応させて塩化銅を還元し、銅粉を生成する。
[1-2. Copper chloride reduction step (S200)]
Next, the generated copper chloride gas is reacted with the reducing gas to reduce copper chloride to produce copper powder.
図３は、本発明の一実施形態に係る銅粉の製造方法に用いる還元装置２０の概略図である。還元装置２０は、還元炉２００、第１導入管２１０、第２導入管２２０、回収管２３０、およびヒータ２４０を含む。第１導入管２１０、第２導入管２２０、および回収管２３０の各々は、還元炉２００に連結されている。塩化銅ガスは第１導入管２１０から供給され、還元性ガスは第２導入管２２０から供給される。すなわち、供給された塩化銅ガスと還元性ガスとが還元炉２００内で反応し、その反応によって生成された銅粉が回収管２３０を通じて回収される。なお、金属塩化物生成装置１０の回収管１３０と還元装置２０の第１導入管２１０とが連結され、金属塩化物生成装置１０で生成された塩化銅ガスを還元装置２０に直接供給することもできる。
FIG. 3 is a schematic view of a reducing
還元炉２００は、ヒータ２４０によって加熱することができる。
The
ここで、還元炉２００の加熱温度とは、加熱された還元炉２００内の温度をいうが、還元炉２００内の温度を直接測定することが困難である場合は、還元装置２０において設定した還元炉２００の設定温度とすることもできる。
Here, the heating temperature of the
還元性ガスとしては、例えば、水素、ヒドラジン、アンモニア、またはメタンなどを用いることができる。 As the reducing gas, for example, hydrogen, hydrazine, ammonia, methane and the like can be used.
塩化銅ガスに対する還元性ガスの比率は、第１導入管２１０からの塩化銅ガスの流量と、第２導入管２２０からの還元性ガスの流量とを調整することにより可能である。
The ratio of the reducing gas to the copper chloride gas can be adjusted by adjusting the flow rate of the copper chloride gas from the
気相成長法の塩化銅ガスと還元性ガスとの還元反応において、塩化銅ガスの分圧とは、還元反応時に塩化炉から供給されるガス全体に対する塩化銅ガスの分圧のことをいう。例えば、反応系に存在するガスが塩化銅ガスおよび窒素ガスである場合における塩化銅ガスの分圧は、塩化銅ガスおよび窒素ガスの合計のモル数に対して占める塩化銅ガスのモル数の割合として得られる。 In the reduction reaction between the copper chloride gas and the reducing gas in the vapor phase growth method, the partial pressure of the copper chloride gas means the partial pressure of the copper chloride gas with respect to the entire gas supplied from the chloride furnace during the reduction reaction. For example, when the gas present in the reaction system is copper chloride gas and nitrogen gas, the partial pressure of copper chloride gas is the ratio of the number of moles of copper chloride gas to the total number of moles of copper chloride gas and nitrogen gas. Obtained as.
塩化銅ガスの分圧は、例えば、１０％以上４０％以下であり、好ましくは２０％以上３０％以下である。塩化銅ガスの分圧が４０％超である場合には、還元反応が十分に進行せず、未反応の粗粒が発生するため、後述する銅粉の個数５０％径（Ｄ５０ＳＥＭ）が大きくなり、塗膜の平滑性が悪くなるという問題が生じることがある。一方、塩化銅ガスの分圧が１０％未満である場合には、個数５０％径（Ｄ５０ＳＥＭ）が小さくなり、銅粉の焼結開始温度が低下するという問題が生じることがある。また、凝集性が強くなるため、塗膜の平滑性が悪くなるという問題が生じることがある。 The partial pressure of the copper chloride gas is, for example, 10% or more and 40% or less, preferably 20% or more and 30% or less. When the partial pressure of the copper chloride gas exceeds 40%, the reduction reaction does not proceed sufficiently and unreacted coarse particles are generated. Therefore, the number of copper powders described later, 50% diameter (D 50SEM ), is large. Therefore, there may be a problem that the smoothness of the coating film is deteriorated. On the other hand, when the partial pressure of the copper chloride gas is less than 10%, the number 50% diameter (D 50SEM ) becomes small, and there may be a problem that the sintering start temperature of the copper powder decreases. In addition, since the cohesiveness becomes strong, there may be a problem that the smoothness of the coating film deteriorates.
塩化銅ガスと還元性ガスとの還元反応によって生成された銅粉は回収管２３０を通じて回収されるが、冷却ガスを供給して銅粉を冷却してから回収してもよい。冷却ガスは、銅粉に対して不活性なガスであればよく、例えば、窒素ガス、ヘリウムガス、アルゴンガス、ネオンガス、または水素ガス、もしくはこれらの混合ガスである。冷却ガスの温度は、通常、０℃以上１００℃以下、好ましくは０℃以上５０℃以下、より好ましくは０℃以上３０℃以下である。
The copper powder produced by the reduction reaction between the copper chloride gas and the reducing gas is recovered through the
還元反応によって生成された銅粉の冷却速度は、銅粉の連結粒子や粗大粒子の形成に影響を及ぼすため、銅粉の冷却速度の調整は重要である。銅粉の冷却速度は、例えば、２０００℃／秒以上９０００℃／秒以下であり、好ましくは３０００℃／秒以上５０００℃／秒以下である。銅粉の冷却速度が９０００℃／秒超である場合には、結晶性が悪くなるため、銅粉の焼結開始温度が低下するという問題が生じることがある。一方、銅粉の冷却速度が２０００℃／秒未満である場合には、冷却が不十分であるため、連結粒子や粗大粒子が多く発生し、塗膜の平滑性が悪くなるという問題が生じることがある。 Since the cooling rate of the copper powder produced by the reduction reaction affects the formation of the connecting particles and coarse particles of the copper powder, it is important to adjust the cooling rate of the copper powder. The cooling rate of the copper powder is, for example, 2000 ° C./sec or more and 9000 ° C./sec or less, preferably 3000 ° C./sec or more and 5000 ° C./sec or less. When the cooling rate of the copper powder is more than 9000 ° C./sec, the crystallinity is deteriorated, which may cause a problem that the sintering start temperature of the copper powder is lowered. On the other hand, when the cooling rate of the copper powder is less than 2000 ° C./sec, the cooling is insufficient, so that many connecting particles and coarse particles are generated, which causes a problem that the smoothness of the coating film is deteriorated. There is.
ここで、銅粉の冷却速度とは、還元反応で生成された銅粉の温度と、冷却ガスに接触させて温度が低下した銅粉の温度との温度差を、当該温度差を得るのに要した時間で除した値をいう。 Here, the cooling rate of the copper powder is the temperature difference between the temperature of the copper powder produced by the reduction reaction and the temperature of the copper powder whose temperature has dropped due to contact with the cooling gas, in order to obtain the temperature difference. The value divided by the time required.
以上、塩化銅の還元工程（Ｓ２００）では、還元性ガスの種類、塩化銅ガスの分圧、冷却ガスの種類、または銅粉の冷却速度などの条件を調整することで、高い焼結開始温度を有する銅粉を製造することが可能となる。 As described above, in the copper chloride reduction step (S200), a high sintering start temperature is obtained by adjusting conditions such as the type of reducing gas, the partial pressure of copper chloride gas, the type of cooling gas, or the cooling rate of copper powder. It becomes possible to produce copper powder having.
［１－３．塩素成分の低減工程（Ｓ３００）］
塩化銅の還元工程（Ｓ２００）においては、銅粉とともに塩化水素が生成される。また、未反応の塩素が還元性ガスと反応することによっても塩化水素が生成される。これらの塩化水素は、塩化水素に由来する塩素が塩化銅として銅粉の中に残留することになり、銅粉の純度を低下させる。また、銅粉の中に残留した塩化銅は、ＭＬＣＣの電極層にも取り込まれ、ＭＬＣＣの電極層の劣化を加速させる要因となり得る。そこで、塩化銅の還元工程（Ｓ２００）によって得られた銅粉に対し、銅紛が含有する塩素成分を低減するための処理を行ってもよい。
[1-3. Chlorine component reduction step (S300)]
In the copper chloride reduction step (S200), hydrogen chloride is produced together with the copper powder. Hydrogen chloride is also produced by the reaction of unreacted chlorine with the reducing gas. In these hydrogen chlorides, chlorine derived from hydrogen chloride remains in the copper powder as copper chloride, which lowers the purity of the copper powder. Further, the copper chloride remaining in the copper powder is also taken into the electrode layer of the MLCC, which can be a factor of accelerating the deterioration of the electrode layer of the MLCC. Therefore, the copper powder obtained in the copper chloride reduction step (S200) may be subjected to a treatment for reducing the chlorine component contained in the copper powder.
具体的には、銅紛を塩基の水溶液あるいは懸濁液で処理することで、塩素成分の除去を行うことができる。塩基の水溶液としては、水酸化ナトリウムや水酸化カリウムなどのアルカリ金属の水酸化物が挙げられる。塩基濃度は、０．１モル／Ｌ以上、あるいは０．５モル／Ｌ以上でよく、１．５モル／Ｌ以下、あるいは１．２モル／Ｌ以下とすることができる。 Specifically, the chlorine component can be removed by treating the copper powder with an aqueous solution or suspension of a base. Examples of the aqueous solution of the base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. The base concentration may be 0.1 mol / L or more, 0.5 mol / L or more, and may be 1.5 mol / L or less, or 1.2 mol / L or less.
［１－４．酸素成分の低減工程（Ｓ４００）］
銅は比較的酸化されやすい金属であるため、銅粉の酸化は、銅粒子の表面だけでなく内部まで進行しやすい。酸化が進行すると銅粒子の表面に酸化銅の層が形成されるとともに、凹凸が発生する。このような酸化に起因する凹凸は、ＭＬＣＣの電極層の導電性を低下させ、または電極層の表面の平坦性を低下させる要因となり得る。すなわち、酸素成分の多い銅粉を用いた電極層は、電気抵抗の増大し、接触不良を誘発する。また、銅粒子の表面に凹凸があると、電極層の焼結時において収縮率が増大するため、デラミネーションが生じやすくなる。そこで、塩素成分の低減工程（Ｓ３００）によって得られた銅粉に対して、銅粉の酸素成分を低減するために、酸化銅を除去し、または酸素含有量を低減する処理を行ってもよい。
[1-4. Oxygen component reduction step (S400)]
Since copper is a metal that is relatively easily oxidized, the oxidation of copper powder tends to proceed not only to the surface of the copper particles but also to the inside. As the oxidation progresses, a layer of copper oxide is formed on the surface of the copper particles, and unevenness is generated. The unevenness caused by such oxidation can be a factor that lowers the conductivity of the electrode layer of MLCC or lowers the flatness of the surface of the electrode layer. That is, the electrode layer using the copper powder having a large oxygen component increases the electric resistance and induces poor contact. Further, if the surface of the copper particles is uneven, the shrinkage rate increases when the electrode layer is sintered, so that delamination is likely to occur. Therefore, in order to reduce the oxygen component of the copper powder, the copper powder obtained in the chlorine component reduction step (S300) may be subjected to a treatment of removing copper oxide or reducing the oxygen content. ..
具体的には、塩素成分の低減工程（Ｓ３００）によって得られた銅粉を、アスコルビン酸、ヒドラジン、またはクエン酸などを含む溶液、もしくは懸濁液を洗浄液として用いて処理する。その後、銅粉を水で洗浄し、ろ過し、乾燥する。 Specifically, the copper powder obtained in the chlorine component reduction step (S300) is treated with a solution or suspension containing ascorbic acid, hydrazine, citric acid or the like as a cleaning solution. The copper powder is then washed with water, filtered and dried.
［１－５．表面処理工程（Ｓ５００）］
上述したように、銅は比較的酸化されやすい金属である。そこで、銅粒子の表面の酸化を抑制するため、酸素成分の低減工程（Ｓ４００）によって得られた銅粉に対して、表面処理を行ってもよい。
[1-5. Surface treatment step (S500)]
As mentioned above, copper is a metal that is relatively easily oxidized. Therefore, in order to suppress the oxidation of the surface of the copper particles, the copper powder obtained in the oxygen component reduction step (S400) may be surface-treated.
具体的には、表面処理剤を含む溶液または懸濁液で銅紛を処理する。表面処理剤としては、ベンゾトリアゾールとその誘導体、トリアゾールとその誘導体、チアゾールとその誘導体、ベンゾチアゾールとその誘導体、イミダゾールとその誘導体、およびベンズイミダゾールとその誘導体などの含窒素ヘテロ芳香族化合物に例示される材料を使用することができる。 Specifically, the copper powder is treated with a solution or suspension containing a surface treatment agent. Examples of surface treatment agents include nitrogen-containing heteroaromatic compounds such as benzotriazole and its derivatives, triazole and its derivatives, thiazole and its derivatives, benzothiazole and its derivatives, imidazole and its derivatives, and benzimidazole and its derivatives. Materials can be used.
［１－６．その他の工程］
その他の任意の工程として、得られる銅粉を乾燥、分級、解砕、または篩別などの工程を行ってもよい。分級は乾式分級でも湿式分級でもよく、乾式分級では、気流分級、重力場分級、慣性力場分級、遠心力場分級など、任意の方式を採用できる。解砕は、例えば、ジェットミルを用いて行うことができる。篩別は、所望のメッシュサイズを有する篩を振動させ、これに銅粉を通過させることで行うことができる。分級、解砕、または篩別などの工程を行うことで、銅粉の粒子径分布をより小さくすることが可能である。
[1-6. Other processes]
As any other step, the obtained copper powder may be dried, classified, crushed, or sieved. The classification may be dry classification or wet classification, and in the dry classification, any method such as air flow classification, gravitational field classification, inertial force field classification, centrifugal force field classification, etc. can be adopted. Crushing can be performed using, for example, a jet mill. Sieve separation can be performed by vibrating a sieve having a desired mesh size and passing copper powder through the sieve. It is possible to make the particle size distribution of the copper powder smaller by performing steps such as classification, crushing, and sieving.
以上、本実施形態に係る銅粉の製造方法によれば、上述した各工程の条件を調整することにより、高い焼結開始温度を有し、かつ、塗膜の平滑性に優れた銅粉を製造することができる。また、本実施形態に係る銅粉の製造方法によって製造された銅粉をＭＬＣＣの電極層に用いれば、電極層の焼結開始温度と誘電層の焼結開始温度との温度差が小さくなるため、電極層のクラックやデラミネーションを抑制することができる。 As described above, according to the method for producing copper powder according to the present embodiment, by adjusting the conditions of each of the above-mentioned steps, a copper powder having a high sintering start temperature and excellent smoothness of a coating film can be obtained. Can be manufactured. Further, if the copper powder produced by the method for producing copper powder according to the present embodiment is used for the electrode layer of MLCC, the temperature difference between the sintering start temperature of the electrode layer and the sintering start temperature of the dielectric layer becomes small. , Cracks and delamination of the electrode layer can be suppressed.
［２．銅粉の評価］
本発明の一実施形態に係る銅粉の製造方法によって製造された銅粉の評価における定義と測定方法は、以下の通りである。
[2. Evaluation of copper powder]
The definition and measurement method in the evaluation of the copper powder produced by the method for producing copper powder according to the embodiment of the present invention are as follows.
［２－１．個数５０％径（Ｄ５０ＳＥＭ）］
銅粉の個数５０％径（Ｄ５０ＳＥＭ）とは、銅粉の粒子径ヒストグラムにおける累積頻度が５０％になるときの粒子径のことをいう。銅粉の個々の銅粒子の粒子径は、銅粉を電子顕微鏡で観察したときに得られる個々の銅粒子の像に内接する最小円の直径、あるいは最小長方形の長辺として得られる。銅粉の個数５０％径（Ｄ５０ＳＥＭ）は、１００個から１００００個、典型的には５００個の銅粒子を観測した結果の粒子径ヒストグラムにおける累積頻度が５０％になるときの粒子径として得られる。例えば、銅粉の個数５０％径（Ｄ５０ＳＥＭ）は、走査型電子顕微鏡（ＳＥＭ：株式会社日立ハイテクノロジーズ製、ＳＵ５０００）の倍率１５０００倍におけるＳＥＭ像の一つの視野中に存在する約５００個の銅粒子を、画像解析ソフト（株式会社マウンテック製Ｍａｃｖｉｅｗ４．０）を用いて解析することによって得ることができる。
[2-1. Number 50% diameter (D 50SEM )]
The number of copper powders 50% diameter (D 50SEM ) means the particle size when the cumulative frequency in the particle size histogram of the copper powder reaches 50%. The particle size of the individual copper particles of the copper powder is obtained as the diameter of the smallest circle inscribed in the image of the individual copper particles obtained when the copper powder is observed with an electron microscope, or as the long side of the smallest rectangle. The number of copper powders 50% diameter (D 50SEM ) is obtained as the particle diameter when the cumulative frequency in the particle size histogram as a result of observing 100 to 10,000, typically 500 copper particles is 50%. Be done. For example, the number of copper powders 50% diameter (D 50SEM ) is about 500 existing in one field of view of an SEM image at a magnification of 15,000 times of a scanning electron microscope (SEM: Hitachi High-Technologies Co., Ltd., SU5000). Copper particles can be obtained by analyzing with image analysis software (Macview 4.0 manufactured by Mountech Co., Ltd.).
本実施形態に係る銅粉の製造方法によって製造された銅粉の個数５０％径（Ｄ５０ＳＥＭ）は、例えば、１００ｎｍ以上４００ｎｍ以下であり、好ましくは２００ｎｍ以上３００ｎｍ以下である。また、個数５０％径（Ｄ５０ＳＥＭ）の下限は１００ｎｍ以上であることが必要である。個数５０％径（Ｄ５０ＳＥＭ）の下限が小さい銅粉は、製造することが困難であり、個数５０％径（Ｄ５０ＳＥＭ）が小さすぎると、銅粒子同士が凝集し易くなり、取り扱いが困難になる場合がある。個数５０％径（Ｄ５０ＳＥＭ）が１００ｎｍ以上４００ｎｍ以下の銅粉は、上述した本実施形態に係る銅粉の製造方法において、各工程の条件を適正に調整することで得られる。 The number 50% diameter (D 50SEM ) of the copper powder produced by the method for producing copper powder according to the present embodiment is, for example, 100 nm or more and 400 nm or less, preferably 200 nm or more and 300 nm or less. Further, the lower limit of the number 50% diameter (D 50SEM ) needs to be 100 nm or more. Copper powder having a small lower limit of 50% diameter (D 50SEM ) is difficult to manufacture, and if the 50% diameter (D 50SEM ) is too small, copper particles tend to aggregate with each other, making handling difficult. May be. The copper powder having a 50% diameter (D 50SEM ) of 100 nm or more and 400 nm or less can be obtained by appropriately adjusting the conditions of each step in the above-mentioned method for producing copper powder according to the present embodiment.
［２－２．平均結晶子径］
結晶子径とは、単結晶とみなせる領域の長さを表す指標である。個々の銅粒子は、単一または複数の結晶子を有している。平均結晶子径は、個々の銅粒子の結晶子の大きさの平均値である。平均結晶子径は、銅粉に対してＸ線回折の測定によって得られる各種のパラメータ（使用するＸ線の波長λ、回折Ｘ線の広がりの半値幅β、ブラッグ角θ）を、下記の（式１）に示すシェラーの式に代入して計算することで得られる値として定義される。ここで、Ｋはシェラー定数である。
[2-2. Average crystallite diameter]
The crystallite diameter is an index showing the length of a region that can be regarded as a single crystal. Each copper particle has a single crystallite or multiple crystallites. The average crystallite diameter is the average value of the crystallite size of each copper particle. The average crystallite diameter has various parameters (wavelength λ of X-rays used, half width β of spread of diffracted X-rays, Bragg angle θ) obtained by measuring X-ray diffraction with respect to copper powder. It is defined as a value obtained by substituting into the Scherrer's equation shown in equation 1) and calculating. Here, K is a Scheller constant.
平均結晶子径の具体的な測定条件としては、加速電圧４５ｋＶ、放電電流４０ｍＡの条件を用いることができ、例えば、Ｘ線回折装置（スペクトリス株式会社製、Ｘ’ＰｅｒｔＰｒｏ）を用いて、ＣｕＫα線で銅結晶の（１１１）面の回折ピークの半値幅を求め、上記（式１）のシェラーの式により平均結晶子径を算出することができる。なお、本明細書においては、平均結晶子径を、（式１）に示すようにＤとして記載する。 As specific measurement conditions for the average crystallite diameter, conditions of an acceleration voltage of 45 kV and a discharge current of 40 mA can be used. The half width of the diffraction peak of the (111) plane of the copper crystal can be obtained, and the average crystallite diameter can be calculated by the Scherrer equation of the above (Equation 1). In this specification, the average crystallite diameter is described as D as shown in (Equation 1).
本実施形態に係る銅紛の製造方法によって製造された銅粉の平均結晶子径Ｄは、個数５０％径（Ｄ５０ＳＥＭ）に対する平均結晶子径Ｄの比（Ｄ／Ｄ５０ＳＥＭ）で評価する。個数５０％径（Ｄ５０ＳＥＭ）が小さくなると平均結晶子径Ｄも小さくなるため、平均結晶子径Ｄは、個数５０％径（Ｄ５０ＳＥＭ）で規格化したＤ／Ｄ５０ＳＥＭで評価する。本実施形態に係る銅粉の製造方法によって製造された銅粉の個数５０％径（Ｄ５０ＳＥＭ）に対する平均結晶子径Ｄの比Ｄ／Ｄ５０ＳＥＭは、０．５０以上０．７５以下であることが好ましく、０．６０以上０．７０以下であることがさらに好ましい。Ｄ／Ｄ５０ＳＥＭが０．５０以上であると平均結晶子径Ｄが大きく、焼結開始温度が高くなる効果があるので好ましい。個数５０％径（Ｄ５０ＳＥＭ）に対する平均結晶子径Ｄの比Ｄ／Ｄ５０ＳＥＭが０．５０以上０．７５以下である銅粉は、上述した本実施形態に係る銅粉の製造方法において、各工程の条件を適正に調整することで得られる。また、気相成長法は、高温で成長させることができるため、銅粉の平均結晶子径Ｄが大きくなりやすい。 The average crystallite diameter D of the copper powder produced by the method for producing copper powder according to the present embodiment is evaluated by the ratio of the average crystallite diameter D to the number 50% diameter (D 50SEM ) (D / D 50SEM ). Since the average crystallite diameter D also decreases as the number 50% diameter (D 50SEM ) decreases, the average crystallite diameter D is evaluated by the D / D 50SEM standardized by the number 50% diameter (D 50SEM ). The ratio D / D 50SEM of the average crystallite diameter D to the number 50% diameter (D 50SEM ) of the number of copper powders produced by the method for producing copper powder according to the present embodiment shall be 0.50 or more and 0.75 or less. Is preferable, and more preferably 0.60 or more and 0.70 or less. When the D / D 50SEM is 0.50 or more, the average crystallite diameter D is large and the sintering start temperature is high, which is preferable. The copper powder having the ratio D / D 50SEM of the average crystallite diameter D to the number 50% diameter (D 50SEM ) of 0.50 or more and 0.75 or less is used in the above-described method for producing copper powder according to the present embodiment. It can be obtained by properly adjusting the conditions of the process. Further, in the vapor phase growth method, since the copper powder can be grown at a high temperature, the average crystallite diameter D of the copper powder tends to be large.
［２－３．連結粒子］
銅粉には、凝集のない独立した一次粒子に加え、一次粒子が凝集した二次粒子も含まれ得る。「連結粒子」とは、例えば、ジェットミル等の公知の解砕装置によって解砕してもなお、銅粉中に残留する二次粒子であり、典型的には、一次粒子同士が互いに融着してなる二次粒子のことを意味する。このような連結粒子のなかでも、球形度（真球度ともいう）が低い粒子、特に、複数の一次粒子が一列に連なった、特定の基準の長さを超える細長い形状の連結粒子の割合が、塗膜の平滑性に大きな影響を与えることが分かった。
[2-3. Linked particles]
The copper powder may include secondary particles in which the primary particles are aggregated, in addition to independent primary particles in which the primary particles are agglomerated. The "connected particles" are secondary particles that remain in the copper powder even after being crushed by a known crushing device such as a jet mill, and typically, the primary particles are fused to each other. It means a secondary particle made of copper. Among such connected particles, the proportion of particles having a low sphericity (also called sphericity), particularly elongated connected particles having a plurality of primary particles connected in a row and exceeding a specific reference length, is used. It was found that the smoothness of the coating film was greatly affected.
なお、本明細書中では、特に説明がない限り、便宜上、「連結粒子」とは、銅粉を走査電子顕微鏡により撮影したＳＥＭ像中の粒子のうち、当該ＳＥＭ像において「アスペクト比」が１．２以上であり、「円形度」が０．６７５以下であり、「長径」が銅粉の個数５０％径の３倍以上である二次粒子をいう。 In the present specification, unless otherwise specified, for convenience, the "connected particles" are particles in an SEM image obtained by photographing copper powder with a scanning electron microscope, and the "aspect ratio" is 1 in the SEM image. .2 or more, the "circularity" is 0.675 or less, and the "major axis" is 3 times or more the diameter of 50% of the number of copper powders.
ここで、「長径」とは、銅粒子の投影像に外接する最小面積の長方形の長辺の長さであり、「アスペクト比」とは、当該長方形における長辺の長さを短辺の長さで除した値である。 Here, the "major axis" is the length of the long side of the rectangle having the minimum area circumscribing the projected image of the copper particles, and the "aspect ratio" is the length of the long side in the rectangle as the length of the short side. It is the value divided by the value.
また、「円形度」は、下記の（式２）により求められる値である。円形度が１のとき、粒子の投影像は真円であり、当該粒子の立体形状は真球状に近いと予想できる。また、円形度が０に近づくにつれて、撮影された粒子の立体形状には、凹凸が多く存在し、複雑な形状であると予想できる。 Further, the "circularity" is a value obtained by the following (Equation 2). When the circularity is 1, the projected image of the particles is a perfect circle, and it can be expected that the three-dimensional shape of the particles is close to a true sphere. Further, as the circularity approaches 0, the three-dimensional shape of the photographed particles has many irregularities and can be expected to be a complicated shape.
銅粉中の連結粒子の割合（以下、「連結粒子率」と表記することもある）は、走査電子顕微鏡により銅粉のＳＥＭ像を撮影し、そのＳＥＭ像に撮影された約４０，０００個の銅粒子から、画像解析ソフトを使用して、アスペクト比が１．２以上であり、円形度が０．６７５以下であり、長径が金属粉末の個数５０％径の３倍以上である銅粒子の数を計測して得られる。すなわち、連結粒子の割合は、計測した全ての銅粒子の数に対する連結粒子の数の割合を意味する。なお、銅粉のＳＥＭ像を撮影するための試料を調製する条件等は、後述する実施例を参照することができる。 The ratio of the connected particles in the copper powder (hereinafter, also referred to as "connected particle ratio") is about 40,000 pieces taken by taking an SEM image of the copper powder with a scanning electron microscope and taking the SEM image. Copper particles with an aspect ratio of 1.2 or more, a circularity of 0.675 or less, and a major axis of 3 times or more the diameter of 50% of the number of metal powders, using image analysis software. It is obtained by measuring the number of particles. That is, the ratio of the connected particles means the ratio of the number of connected particles to the measured number of all copper particles. For the conditions for preparing a sample for photographing the SEM image of the copper powder, the examples described later can be referred to.
本実施形態において、銅粉に含まれる連結粒子の割合は、個数基準で５００ｐｐｍ以下であることが好ましい。連結粒子の割合がこの範囲であることにより、銅粉の電極ペースト中での分散性を改善し、電極中の銅粉の充填率を高くすることができるため、塗膜の平滑性が向上するという効果を得ることができる。銅粉の個数５０％径が４００ｎｍ以下の超微粉であっても、上記の効果が得られる。したがって、この銅粉を内部電極用導電ペーストのフィラーとして用いることにより、電極の欠陥によるコンデンサの容量の低下を防ぐことができる。 In the present embodiment, the ratio of the connecting particles contained in the copper powder is preferably 500 ppm or less on the basis of the number of particles. When the ratio of the connecting particles is in this range, the dispersibility of the copper powder in the electrode paste can be improved, and the filling rate of the copper powder in the electrode can be increased, so that the smoothness of the coating film is improved. You can get the effect. The above effect can be obtained even if the number of copper powders is 50% and the diameter is 400 nm or less. Therefore, by using this copper powder as a filler for the conductive paste for an internal electrode, it is possible to prevent a decrease in the capacity of the capacitor due to a defect in the electrode.
［２－４．粗大粒子］
銅粉には、連結粒子だけでなく、粗大粒子が含まれ得る。ここで、「粗大粒子」とは、アスペクト比が１．２未満、または円形度が０．６７５を超える球状または略球状粒子であって、長径が銅粉の個数５０％径の３倍以上である銅粒子をいう。つまり、粗大粒子とは、アスペクト比または円形度が連結粒子の要件を満たしていないが、連結粒子と同様に長径が大きく、球形状に近い一次粒子または二次粒子である。銅粉中に含まれる粗大粒子の割合は、個数基準で１５ｐｐｍ以下であることが好ましい。連結粒子率が５００ｐｐｍ以下である銅粉において、粗大粒子の割合がこの範囲であることにより、積層セラミックコンデンサの内部電極の導電ペーストフィラーとして用いるときに、電極層を平滑にすることができ、電極間のショート等の不良を防止することができる。
[2-4. Coarse particles]
The copper powder may contain coarse particles as well as connecting particles. Here, the "coarse particles" are spherical or substantially spherical particles having an aspect ratio of less than 1.2 or a circularity of more than 0.675, and have a major axis of 3 times or more the diameter of 50% of the number of copper powders. A certain copper particle. That is, the coarse particles are primary particles or secondary particles having a large major axis and a nearly spherical shape, similar to the connected particles, although the aspect ratio or the circularity does not satisfy the requirements for the connected particles. The ratio of coarse particles contained in the copper powder is preferably 15 ppm or less on a number basis. In copper powder having a linked particle ratio of 500 ppm or less, the ratio of coarse particles in this range makes it possible to smooth the electrode layer when used as a conductive paste filler for the internal electrode of a laminated ceramic capacitor, and the electrode. It is possible to prevent defects such as short circuits between them.
銅粉中の「粗大粒子」の割合（以下、「粗大粒子率」と表記することもある）は、走査電子顕微鏡により銅粉のＳＥＭ像を撮影し、そのＳＥＭ像に撮影された銅粒子約６０，０００個から、画像解析ソフトを使用して、アスペクト比が１．２未満、または円形度が０．６７５以上であり、長径が銅粉の個数５０％径の３倍以上である銅粒子の数を計測して得られる。すなわち、粗大粒子の割合は、計測した全ての銅粒子の数に対する粗大粒子の数の割合を意味する。 The ratio of "coarse particles" in the copper powder (hereinafter, also referred to as "coarse particle ratio") is about the copper particles photographed in the SEM image of the copper powder by taking an SEM image of the copper powder with a scanning electron microscope. From 60,000 copper particles, using image analysis software, the aspect ratio is less than 1.2, the circularity is 0.675 or more, and the major axis is 3 times or more the diameter of 50% of the number of copper powders. It is obtained by measuring the number of particles. That is, the ratio of coarse particles means the ratio of the number of coarse particles to the total number of measured copper particles.
［２－３．焼結開始温度］
銅粉の焼結開始温度とは、銅粉を加熱し、銅粉の溶融が開始される温度をいう。銅粉の焼結開始温度は、例えば、熱機械分析装置（株式会社 リガク製、商品名 ＴＭＡ８３１０）を用いて、１．５体積％水素－窒素の還元性ガス雰囲気下、大気圧、昇温速度５℃／分の条件で測定することができる。なお、銅粉の焼結開始温度は、銅粉の体積が５％収縮する温度としてもよい。
[2-3. Sintering start temperature]
The sintering start temperature of the copper powder is the temperature at which the copper powder is heated and the melting of the copper powder is started. The sintering start temperature of the copper powder is, for example, using a thermomechanical analyzer (manufactured by Rigaku Co., Ltd., trade name TMA8310) under a reducing gas atmosphere of 1.5% by volume hydrogen-nitrogen, atmospheric pressure, and heating rate. It can be measured under the condition of 5 ° C./min. The sintering start temperature of the copper powder may be a temperature at which the volume of the copper powder shrinks by 5%.
本実施形態に係る銅粉の製造方法によって製造された銅粉の焼結開始温度は、６８０℃以上であることが好ましい。銅の融点（約１０８３℃）はニッケルの融点（約１４５５℃）よりも低いことから、銅粉の焼結開始温度はニッケル粉の焼結開始温度より低くなる。そのため、可能な限りニッケル粉の焼結開始温度に近づけるため、銅粉の焼結開始温度は、好ましくは６８０℃以上であり、さらに好ましくは７２０℃以上である。焼結開始温度が６８０℃以上である銅粉は、上述した本実施形態に係る銅粉の製造方法において、各工程の条件を適正に調整することで得られる。 The sintering start temperature of the copper powder produced by the method for producing copper powder according to the present embodiment is preferably 680 ° C. or higher. Since the melting point of copper (about 1083 ° C.) is lower than the melting point of nickel (about 1455 ° C.), the sintering start temperature of copper powder is lower than the sintering start temperature of nickel powder. Therefore, in order to bring the nickel powder to the sintering start temperature as close as possible, the sintering start temperature of the copper powder is preferably 680 ° C. or higher, more preferably 720 ° C. or higher. The copper powder having a sintering start temperature of 680 ° C. or higher can be obtained by appropriately adjusting the conditions of each step in the copper powder production method according to the present embodiment described above.
本実施形態に係る銅粉の製造方法によって製造された銅粉は、焼結開始温度が高く、かつ、塗膜の平滑性に優れているため、デラミネーションが発生しにくい。焼結開始温度が高く、かつ、塗膜の平滑性に優れている銅粉は、上述した本実施形態に係る銅粉の製造方法において、各工程の条件を適正に調整することで得られる。 The copper powder produced by the method for producing copper powder according to the present embodiment has a high sintering start temperature and excellent smoothness of the coating film, so that delamination is unlikely to occur. The copper powder having a high sintering start temperature and excellent smoothness of the coating film can be obtained by appropriately adjusting the conditions of each step in the above-described method for producing copper powder according to the present embodiment.
以下に実施例をあげて、本発明を更に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
（実施例１）
塩化炉に、原料として平均直径１．５ｃｍの球状の金属銅を設置し、塩化炉の温度を９００℃に加熱した。塩化炉の上部の塩素導入管から導入された混合ガスの塩素ガスと窒素ガスの体積比は２９：６１であった。また、塩化炉の下部の塩素導入管から導入された混合ガスの塩素ガスと窒素ガスの体積比は２：９８であった。その結果、塩化炉の上部の塩素導入菅および下部の塩素導入管から導入された混合ガスの塩素ガスと窒素ガスの体積比は１：０．１７であった。このような条件の下で、金属銅と塩素ガスとを反応させて、塩化銅ガスを生成させた。また、塩化銅ガスの分圧は、１０％であった。
(Example 1)
Spherical copper with an average diameter of 1.5 cm was installed in the chloride furnace as a raw material, and the temperature of the chloride furnace was heated to 900 ° C. The volume ratio of chlorine gas and nitrogen gas of the mixed gas introduced from the chlorine introduction pipe at the top of the chlorination furnace was 29:61. The volume ratio of chlorine gas to nitrogen gas in the mixed gas introduced from the chlorine introduction pipe at the bottom of the chlorination furnace was 2:98. As a result, the volume ratio of the chlorine gas and the nitrogen gas of the mixed gas introduced from the chlorine introduction tube at the upper part and the chlorine introduction pipe at the lower part of the chloride furnace was 1: 0.17. Under such conditions, metallic copper and chlorine gas were reacted to generate copper chloride gas. The partial pressure of the copper chloride gas was 10%.
生成させた塩化銅ガスを１１５０℃に加熱した還元炉に導入した。また、塩化銅ガスに対して４６００モル％の水素ガス、および塩化銅ガスに対して２４６００モル％の窒素ガスを還元炉に導入した。塩化銅が還元され、銅を生成させた。生成させた銅を窒素ガスで冷却速度２０００℃／秒で冷却して個々の銅粒子とし、銅粒子の集合体として銅粉を得た。 The generated copper chloride gas was introduced into a reduction furnace heated to 1150 ° C. Further, 4600 mol% of hydrogen gas with respect to copper chloride gas and 24600 mol% of nitrogen gas with respect to copper chloride gas were introduced into the reduction furnace. Copper chloride was reduced to produce copper. The produced copper was cooled with nitrogen gas at a cooling rate of 2000 ° C./sec to form individual copper particles, and copper powder was obtained as an aggregate of the copper particles.
その後、表面安定化処理を行った。具体的には、アスコルビン酸水溶液で処理した銅紛に対し、室温で０．３３重量％のベンゾトリアゾールを表面処理剤として含む水溶液（約３００ｍＬ）を加え、得られた混合物を３０分間攪拌した。攪拌終了後、混合物を静置し、上澄みを除去し、乾燥することにより、実施例１の銅粉を得た。 Then, surface stabilization treatment was performed. Specifically, an aqueous solution (about 300 mL) containing 0.33 wt% benzotriazole as a surface treatment agent was added to the copper powder treated with the ascorbic acid aqueous solution, and the obtained mixture was stirred for 30 minutes. After the stirring was completed, the mixture was allowed to stand, the supernatant was removed, and the mixture was dried to obtain the copper powder of Example 1.
［個数５０％径（Ｄ５０ＳＥＭ）］
実施例１の銅粉を走査型電子顕微鏡（ＳＥＭ：株式会社 日立ハイテクノロジーズ製、商品名 ＳＵ５０００）を用いて、倍率１５０００倍におけるＳＥＭ像の一つの視野中に存在する５００個の銅粒子を画像解析ソフト（株式会社 マウンテック製、商品名 Ｍａｃｖｉｅｗ４．０）を用いて解析した結果、個数５０％径（Ｄ５０ＳＥＭ）は１００ｎｍであった。
[Number 50% diameter (D 50SEM )]
Using a scanning electron microscope (SEM: Hitachi High-Technologies Corporation, trade name SU5000), the copper powder of Example 1 is imaged with 500 copper particles existing in one field of view of an SEM image at a magnification of 15,000 times. As a result of analysis using analysis software (manufactured by Mountech Co., Ltd., trade name: Microscope 4.0), the number 50% diameter (D 50SEM ) was 100 nm.
［Ｄ／Ｄ５０ＳＥＭ］
実施例１の銅粉をＸ線回折装置（株式会社 スペクトリス製、商品名 Ｘ’ＰｅｒｔＰｒｏ）を用いて、加速電圧４５ｋＶ、放電電流４０ｍＡの条件で発生させたＣｕＫα線で得られた銅結晶の（１１１）面の回折ピークの半値幅とシェラーの式により平均結晶子径（Ｄ）を算出した結果、６５ｎｍであった。また、Ｄ／Ｄ５０ＳＥＭは０．６５であった。
[D / D 50SEM ]
The copper powder of Example 1 was generated from CuKα rays using an X-ray diffractometer (manufactured by Spectris Co., Ltd., trade name X'PertPro) under the conditions of an acceleration voltage of 45 kV and a discharge current of 40 mA. 111) As a result of calculating the average crystallite diameter (D) by the half width of the diffraction peak of the plane and Scherrer's equation, it was 65 nm. The D / D 50 SEM was 0.65.
［連結粒子率］
走査電子顕微鏡（株式会社 日本電子製、商品名 ＪＳＭ－７８００Ｆ）により銅粉のＳＥＭ像を撮影し、そのＳＥＭ像から画像解析ソフト（株式会社 マウンテック製、商品名 ＭａｃＶｉｅｗ４．０）を使用して、約４０，０００個の銅粒子のうち、アスペクト比が１．２以上かつ円形度が０．６７５以下の連結粒子であって、長径が個数５０％径の３倍以上である粒子の数を数えて算出した。その結果、連結粒子率は５００ｐｐｍであった。
[Connected particle ratio]
An SEM image of copper powder was taken with a scanning electron microscope (manufactured by JEOL Ltd., trade name JSM-7800F), and image analysis software (manufactured by Mountech Co., Ltd., trade name MacView 4.0) was used from the SEM image. Of the approximately 40,000 copper particles, the number of connected particles having an aspect ratio of 1.2 or more and a circularity of 0.675 or less and having a major axis of 3 times or more the number of 50% diameters is counted. Calculated. As a result, the linked particle ratio was 500 ppm.
［粗大粒子率］
走査電子顕微鏡（株式会社 日本電子製、商品名 ＪＳＭ－７８００Ｆ）により金属銅粉末の写真を撮影し、その写真から画像解析ソフト（株式会社 マウンテック製、商品名 ＭａｃＶｉｅｗ４．０）を使用して、粒子約６００，０００個のうち、アスペクト比が１．２未満、もしくは円形度が０．６７５を超える球状または略球状粒子で、個数５０％径の３倍以上の長径を持つ粒子の数を算出した。その結果、粗大粒子率は１４ｐｐｍであった。
[Coarse particle ratio]
Take a picture of the metallic copper powder with a scanning electron microscope (manufactured by JEOL Ltd., trade name JSM-7800F), and use image analysis software (manufactured by Mountech Co., Ltd., trade name MacView 4.0) to obtain particles from the picture. Of the approximately 600,000 particles, the number of spherical or substantially spherical particles having an aspect ratio of less than 1.2 or an circularity of more than 0.675 and having a major axis three times or more the diameter of 50% was calculated. .. As a result, the coarse particle ratio was 14 ppm.
［焼結開始温度］
実施例１の銅粉末１ｇ、樟脳３重量％、およびアセトン３重量％を混合し、この混合物を内径５ｍｍ、長さ１０ｍｍの円柱状金属容器に充填し、５００ＭＰａで圧縮して試験ペレットを作製した。この試験ペレットの熱収縮挙動を、熱機械分析装置（株式会社 リガク製、商品名 ＴＭＡ８３１０）を使用し、１．５体積％水素－窒素の還元性ガス雰囲気下、大気圧、昇温速度５℃／分の条件で測定した。試験ペレットの体積が５％収縮した温度、すなわち、焼結開始温度は６８０℃であった。
[Sintering start temperature]
1 g of copper powder of Example 1, 3% by weight of camphor, and 3% by weight of acetone were mixed, and this mixture was filled in a cylindrical metal container having an inner diameter of 5 mm and a length of 10 mm and compressed at 500 MPa to prepare test pellets. .. The heat shrinkage behavior of these test pellets was measured using a thermomechanical analyzer (manufactured by Rigaku Co., Ltd., trade name TMA8310) under a reducing gas atmosphere of 1.5% by volume hydrogen-nitrogen, atmospheric pressure, and heating rate of 5 ° C. It was measured under the condition of / minute. The temperature at which the volume of the test pellet shrank by 5%, that is, the sintering start temperature was 680 ° C.
［塗膜の平滑性の評価］
実施例１の銅粉末０．５ｇにポリカルボン酸系分散剤５重量％水溶液１００ｍｌを加え、超音波分散機（株式会社 ギンセン製、商品名 ＧＳＤ６００ＡＴ）を使用して出力６００Ｗ、振幅幅３０μｍで６０秒分散した。分散したスラリーを１０分間静置して沈降させた後、上澄みを捨て、沈降したスラリー約１００ｍｇを５μｍのアプリケータで石英板上に塗布した。石英板上の銅塗膜を電気炉（株式会社 モトヤマ製、商品名 ＳＬＴ－２０３５Ｄ）を使用して、１．５体積％水素－窒素の還元性ガス雰囲気下、大気圧、昇温速度５℃／分の条件で昇温し、１，０００℃で１時間焼成した。焼成した塗膜の表面粗さ（Ｓｚ：最大高さ；最高ピークと最深谷との間の高さ）をデジタルマイクロスコープ（株式会社 キーエンス製、商品名 ＶＨＸ－１０００）で測定し、塗膜の平滑性を（Ｓｚ値／銅粉の個数５０％径）の値で表１のように評価した。
[Evaluation of coating film smoothness]
To 0.5 g of the copper powder of Example 1, 100 ml of a 5 wt% aqueous solution of a polycarboxylic acid-based dispersant was added, and an ultrasonic disperser (manufactured by Ginsen Co., Ltd., trade name GSD600AT) was used to output 600 W and an amplitude width of 30 μm. Distributed for seconds. After allowing the dispersed slurry to stand for 10 minutes to settle, the supernatant was discarded, and about 100 mg of the settled slurry was applied onto a quartz plate with a 5 μm applicator. Using an electric furnace (manufactured by Motoyama Co., Ltd., trade name SLT-2035D), the copper coating on the quartz plate is subjected to a 1.5% by volume hydrogen-nitrogen reducing gas atmosphere, atmospheric pressure, and a heating rate of 5 ° C. The temperature was raised under the condition of / minute, and the mixture was fired at 1,000 ° C. for 1 hour. The surface roughness (Sz: maximum height; height between the highest peak and the deepest valley) of the fired coating film was measured with a digital microscope (manufactured by KEYENCE Co., Ltd., trade name VHX-1000), and the coating film was coated. The smoothness was evaluated as shown in Table 1 by the value of (Sz value / number of copper powders 50% diameter).
実施例１の銅粉の（Ｓｚ値／銅粉の個数５０％径）の値は１．０以上１．５未満であった。そのため、実施例１の銅粉の塗膜の平滑性は、〇（良）であった。 The value of the copper powder of Example 1 (Sz value / 50% diameter of the number of copper powders) was 1.0 or more and less than 1.5. Therefore, the smoothness of the coating film of the copper powder of Example 1 was 〇 (good).
（実施例２）
塩化銅の分圧を４０％とした以外は、実施例１と同様の条件で製造し、実施例２の銅粉を得た。実施例２の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４００ｎｍ、平均結晶子径（Ｄ）は２６０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は５００ｐｐｍ、粗大粒子率は１４ｐｐｍ、焼結開始温度は７００℃、塗膜の平滑性は、〇（良）であった。
(Example 2)
It was produced under the same conditions as in Example 1 except that the partial pressure of copper chloride was 40%, and the copper powder of Example 2 was obtained. When the copper powder of Example 2 was evaluated, the number 50% diameter (D 50SEM ) was 400 nm, the average crystallite diameter (D) was 260 nm, the D / D 50SEM was 0.65, the linked particle ratio was 500 ppm, and the coarse particle ratio. Was 14 ppm, the sintering start temperature was 700 ° C., and the smoothness of the coating film was 〇 (good).
（実施例３）
塩化銅の分圧を２０％、冷却速度を３０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例３の銅粉を得た。実施例３の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は２００ｎｍ、平均結晶子径（Ｄ）は１３０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は４００ｐｐｍ、粗大粒子率は１２ｐｐｍ、焼結開始温度は７２０℃、塗膜の平滑性は、◎（最良）であった。
(Example 3)
The copper powder of Example 3 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 20% and the cooling rate was 3000 ° C./sec. When the copper powder of Example 3 was evaluated, the number 50% diameter (D 50SEM ) was 200 nm, the average crystallite diameter (D) was 130 nm, the D / D 50SEM was 0.65, the linked particle ratio was 400 ppm, and the coarse particle ratio. Was 12 ppm, the sintering start temperature was 720 ° C, and the smoothness of the coating film was ⊚ (best).
（実施例４）
塩化銅の分圧を３０％、冷却速度を３０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例４の銅粉を得た。実施例４の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は３００ｎｍ、平均結晶子径（Ｄ）は１９５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は４００ｐｐｍ、粗大粒子率は１２ｐｐｍ、焼結開始温度は７５０℃、塗膜の平滑性は、◎（最良）であった。
(Example 4)
The copper powder of Example 4 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 30% and the cooling rate was 3000 ° C./sec. When the copper powder of Example 4 was evaluated, the number 50% diameter (D 50SEM ) was 300 nm, the average crystallite diameter (D) was 195 nm, the D / D 50SEM was 0.65, the linked particle ratio was 400 ppm, and the coarse particle ratio. Was 12 ppm, the sintering start temperature was 750 ° C., and the smoothness of the coating film was ⊚ (best).
（実施例５）
塩化銅の分圧を２０％、冷却速度を４０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例５の銅粉を得た。実施例５の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は２００ｎｍ、平均結晶子径（Ｄ）は１３０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は３００ｐｐｍ、粗大粒子率は１０ｐｐｍ未満、焼結開始温度は７２０℃、塗膜の平滑性は、◎（最良）であった。
(Example 5)
The copper powder of Example 5 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 20% and the cooling rate was 4000 ° C./sec. When the copper powder of Example 5 was evaluated, the number 50% diameter (D 50SEM ) was 200 nm, the average crystallite diameter (D) was 130 nm, the D / D 50SEM was 0.65, the linked particle ratio was 300 ppm, and the coarse particle ratio. Was less than 10 ppm, the sintering start temperature was 720 ° C., and the smoothness of the coating film was ⊚ (best).
（実施例６）
塩化銅の分圧を３０％、冷却速度を４０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例６の銅粉を得た。実施例６の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は３００ｎｍ、平均結晶子径（Ｄ）は１９５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は３００ｐｐｍ、粗大粒子率は１０ｐｐｍ、焼結開始温度は７５０℃、塗膜の平滑性は、◎（最良）であった。
(Example 6)
The copper powder of Example 6 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 30% and the cooling rate was 4000 ° C./sec. When the copper powder of Example 6 was evaluated, the number 50% diameter (D 50SEM ) was 300 nm, the average crystallite diameter (D) was 195 nm, the D / D 50SEM was 0.65, the linked particle ratio was 300 ppm, and the coarse particle ratio. Was 10 ppm, the sintering start temperature was 750 ° C., and the smoothness of the coating film was ⊚ (best).
（実施例７）
塩化銅の分圧を２０％、冷却速度を５０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例７の銅粉を得た。実施例７の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は２００ｎｍ、平均結晶子径（Ｄ）は１３０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は２００ｐｐｍ、粗大粒子率は８ｐｐｍ、焼結開始温度は７２０℃、塗膜の平滑性は、◎（最良）であった。
(Example 7)
The copper powder of Example 7 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 20% and the cooling rate was 5000 ° C./sec. When the copper powder of Example 7 was evaluated, the number 50% diameter (D 50SEM ) was 200 nm, the average crystallite diameter (D) was 130 nm, the D / D 50SEM was 0.65, the linked particle ratio was 200 ppm, and the coarse particle ratio. Was 8 ppm, the sintering start temperature was 720 ° C, and the smoothness of the coating film was ⊚ (best).
（実施例８）
塩化銅の分圧を３０％、冷却速度を５０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例８の銅粉を得た。実施例８の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は３００ｎｍ、平均結晶子径（Ｄ）は１９５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は２００ｐｐｍ、粗大粒子率は８ｐｐｍ、焼結開始温度は７５０℃、塗膜の平滑性は、◎（最良）であった。
(Example 8)
The copper powder of Example 8 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 30% and the cooling rate was 5000 ° C./sec. When the copper powder of Example 8 was evaluated, the number 50% diameter (D 50SEM ) was 300 nm, the average crystallite diameter (D) was 195 nm, the D / D 50SEM was 0.65, the linked particle ratio was 200 ppm, and the coarse particle ratio. Was 8 ppm, the sintering start temperature was 750 ° C., and the smoothness of the coating film was ⊚ (best).
（実施例９）
冷却速度を７０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例９の銅粉を得た。実施例９の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は１００ｎｍ、平均結晶子径（Ｄ）は６０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６０、連結粒子率は１５０ｐｐｍ、粗大粒子率は７ｐｐｍ、焼結開始温度は６８０℃、塗膜の平滑性は、◎（最良）であった。
(Example 9)
It was produced under the same conditions as in Example 1 except that the cooling rate was set to 7000 ° C./sec, and the copper powder of Example 9 was obtained. When the copper powder of Example 9 was evaluated, the number 50% diameter (D 50SEM ) was 100 nm, the average crystallite diameter (D) was 60 nm, the D / D 50SEM was 0.60, the linked particle ratio was 150 ppm, and the coarse particle ratio. Was 7 ppm, the sintering start temperature was 680 ° C, and the smoothness of the coating film was ⊚ (best).
（実施例１０）
塩化銅の分圧を４０％、冷却速度を７０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例１０の銅粉を得た。実施例１０の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４００ｎｍ、平均結晶子径（Ｄ）は２４０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６０、連結粒子率は１５０ｐｐｍ、粗大粒子率は７ｐｐｍ、焼結開始温度は６９０℃、塗膜の平滑性は、◎（最良）であった。
(Example 10)
The copper powder of Example 10 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 40% and the cooling rate was 7000 ° C./sec. When the copper powder of Example 10 was evaluated, the number 50% diameter (D 50SEM ) was 400 nm, the average crystallite diameter (D) was 240 nm, the D / D 50SEM was 0.60, the linked particle ratio was 150 ppm, and the coarse particle ratio. Was 7 ppm, the sintering start temperature was 690 ° C., and the smoothness of the coating film was ⊚ (best).
（実施例１１）
冷却速度を９０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例１１の銅粉を得た。実施例１１の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は１００ｎｍ、平均結晶子径（Ｄ）は６０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６０、連結粒子率は１００ｐｐｍ、粗大粒子率は６ｐｐｍ、焼結開始温度は６８５℃、塗膜の平滑性は、◎（最良）であった。
(Example 11)
It was produced under the same conditions as in Example 1 except that the cooling rate was set to 9000 ° C./sec, and the copper powder of Example 11 was obtained. When the copper powder of Example 11 was evaluated, the number 50% diameter (D 50SEM ) was 100 nm, the average crystallite diameter (D) was 60 nm, the D / D 50SEM was 0.60, the linked particle ratio was 100 ppm, and the coarse particle ratio. Was 6 ppm, the sintering start temperature was 685 ° C, and the smoothness of the coating film was ⊚ (best).
（実施例１２）
塩化銅の分圧を４０％、冷却速度を９０００℃／秒とした以外は、実施例１と同様の条件で製造し、実施例１２の銅粉を得た。実施例１２の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４００ｎｍ、平均結晶子径（Ｄ）は２４０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６０、連結粒子率は１００ｐｐｍ、粗大粒子率は６ｐｐｍ、焼結開始温度は６９０℃、塗膜の平滑性は、◎（最良）であった。
(Example 12)
The copper powder of Example 12 was obtained by manufacturing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 40% and the cooling rate was 9000 ° C./sec. When the copper powder of Example 12 was evaluated, the number 50% diameter (D 50SEM ) was 400 nm, the average crystallite diameter (D) was 240 nm, the D / D 50SEM was 0.60, the linked particle ratio was 100 ppm, and the coarse particle ratio. Was 6 ppm, the sintering start temperature was 690 ° C, and the smoothness of the coating film was ⊚ (best).
（比較例１）
冷却速度を１０００℃／秒とした以外は、実施例１と同様の条件で製造し、比較例１の銅粉を得た。比較例１の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は１００ｎｍ、平均結晶子径（Ｄ）は６５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は２０００ｐｐｍ、粗大粒子率は１００ｐｐｍ、焼結開始温度は６５０℃、塗膜の平滑性は、×（不良）であった。
(Comparative Example 1)
It was produced under the same conditions as in Example 1 except that the cooling rate was 1000 ° C./sec, and the copper powder of Comparative Example 1 was obtained. When the copper powder of Comparative Example 1 was evaluated, the number 50% diameter (D 50SEM ) was 100 nm, the average crystallite diameter (D) was 65 nm, the D / D 50SEM was 0.65, the linked particle ratio was 2000 ppm, and the coarse particle ratio. Was 100 ppm, the sintering start temperature was 650 ° C., and the smoothness of the coating film was × (defective).
（比較例２）
塩化銅の分圧を４０％、冷却速度を１０００℃／秒とした以外は、実施例１と同様の条件で製造し、比較例２の銅粉を得た。比較例２の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４００ｎｍ、平均結晶子径（Ｄ）は２６０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は２０００ｐｐｍ、粗大粒子率は１００ｐｐｍ、焼結開始温度は６５０℃、塗膜の平滑性は、×（不良）であった。
(Comparative Example 2)
The copper powder of Comparative Example 2 was obtained by producing under the same conditions as in Example 1 except that the partial pressure of copper chloride was 40% and the cooling rate was 1000 ° C./sec. When the copper powder of Comparative Example 2 was evaluated, the number 50% diameter (D 50SEM ) was 400 nm, the average crystallite diameter (D) was 260 nm, the D / D 50SEM was 0.65, the linked particle ratio was 2000 ppm, and the coarse particle ratio. Was 100 ppm, the sintering start temperature was 650 ° C., and the smoothness of the coating film was × (defective).
（比較例３）
冷却速度を１００００℃／秒とした以外は、実施例１と同様の条件で製造し、比較例３の銅粉を得た。比較例３の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は１００ｎｍ、平均結晶子径（Ｄ）は４５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．４５、連結粒子率は８０ｐｐｍ、粗大粒子率は５ｐｐｍ、焼結開始温度は４００℃、塗膜の平滑性は、◎（最良）であった。
(Comparative Example 3)
It was produced under the same conditions as in Example 1 except that the cooling rate was set to 10000 ° C./sec, and the copper powder of Comparative Example 3 was obtained. When the copper powder of Comparative Example 3 was evaluated, the number 50% diameter (D 50SEM ) was 100 nm, the average crystallite diameter (D) was 45 nm, the D / D 50SEM was 0.45, the linked particle ratio was 80 ppm, and the coarse particle ratio. Was 5 ppm, the sintering start temperature was 400 ° C., and the smoothness of the coating film was ⊚ (best).
（比較例４）
塩化銅の分圧を４０％、冷却速度を１００００℃／秒とした以外は、実施例１と同様の条件で製造し、比較例４の銅粉を得た。比較例４の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４００ｎｍ、平均結晶子径（Ｄ）は１８０ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．４５、連結粒子率は８０ｐｐｍ、粗大粒子率は５ｐｐｍ、焼結開始温度は４５０℃、塗膜の平滑性は、◎（最良）であった。
(Comparative Example 4)
It was produced under the same conditions as in Example 1 except that the partial pressure of copper chloride was 40% and the cooling rate was 10000 ° C./sec, to obtain the copper powder of Comparative Example 4. When the copper powder of Comparative Example 4 was evaluated, the number 50% diameter (D 50SEM ) was 400 nm, the average crystallite diameter (D) was 180 nm, the D / D 50SEM was 0.45, the linked particle ratio was 80 ppm, and the coarse particle ratio. Was 5 ppm, the sintering start temperature was 450 ° C., and the smoothness of the coating film was ⊚ (best).
（比較例５）
塩化銅の分圧を５％とした以外は、実施例１と同様の条件で製造し、比較例５の銅粉を得た。比較例５の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は５０ｎｍ、平均結晶子径（Ｄ）は３２．５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は１５００ｐｐｍ、粗大粒子率は６０ｐｐｍ、焼結開始温度は６００℃、塗膜の平滑性は、×（不良）であった。
(Comparative Example 5)
It was produced under the same conditions as in Example 1 except that the partial pressure of copper chloride was 5%, and the copper powder of Comparative Example 5 was obtained. When the copper powder of Comparative Example 5 was evaluated, the number 50% diameter (D 50SEM ) was 50 nm, the average crystallite diameter (D) was 32.5 nm, the D / D 50 SEM was 0.65, the linked particle ratio was 1500 ppm, and the coarse size. The particle ratio was 60 ppm, the sintering start temperature was 600 ° C., and the smoothness of the coating film was × (poor).
（比較例６）
塩化銅の分圧を４５％とした以外は、実施例１と同様の条件で製造し、比較例６の銅粉を得た。比較例６の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４５０ｎｍ、平均結晶子径（Ｄ）は２９２．５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．６５、連結粒子率は１５００ｐｐｍ、粗大粒子率は６０ｐｐｍ、焼結開始温度は６８０℃、塗膜の平滑性は、×（不良）であった。
(Comparative Example 6)
It was produced under the same conditions as in Example 1 except that the partial pressure of copper chloride was 45%, and the copper powder of Comparative Example 6 was obtained. When the copper powder of Comparative Example 6 was evaluated, the number 50% diameter (D 50SEM ) was 450 nm, the average crystallite diameter (D) was 292.5 nm, the D / D 50 SEM was 0.65, the linked particle ratio was 1500 ppm, and the coarse size. The particle ratio was 60 ppm, the sintering start temperature was 680 ° C, and the smoothness of the coating film was × (poor).
（比較例７）
塩化銅の分圧を５％、冷却速度を９０００℃／秒とした以外は、実施例１と同様の条件で製造し、比較例７の銅粉を得た。比較例７の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は５０ｎｍ、平均結晶子径（Ｄ）は２５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．５０、連結粒子率は３００ｐｐｍ、粗大粒子率は２４ｐｐｍ、焼結開始温度は４００℃、塗膜の平滑性は、×（不良）であった。
(Comparative Example 7)
It was produced under the same conditions as in Example 1 except that the partial pressure of copper chloride was 5% and the cooling rate was 9000 ° C./sec, to obtain the copper powder of Comparative Example 7. When the copper powder of Comparative Example 7 was evaluated, the number 50% diameter (D 50SEM ) was 50 nm, the average crystallite diameter (D) was 25 nm, the D / D 50SEM was 0.50, the linked particle ratio was 300 ppm, and the coarse particle ratio. Was 24 ppm, the sintering start temperature was 400 ° C., and the smoothness of the coating film was × (poor).
（比較例８）
塩化銅の分圧を４５％、冷却速度を９０００℃／秒とした以外は、実施例１と同様の条件で製造し、比較例８の銅粉を得た。比較例８の銅粉を評価したところ、個数５０％径（Ｄ５０ＳＥＭ）は４５０ｎｍ、平均結晶子径（Ｄ）は２２５ｎｍ、Ｄ／Ｄ５０ＳＥＭは０．５０、連結粒子率は３００ｐｐｍ、粗大粒子率は２４ｐｐｍ、焼結開始温度は４８０℃、塗膜の平滑性は、×（不良）であった。
(Comparative Example 8)
It was produced under the same conditions as in Example 1 except that the partial pressure of copper chloride was 45% and the cooling rate was 9000 ° C./sec, to obtain the copper powder of Comparative Example 8. When the copper powder of Comparative Example 8 was evaluated, the number 50% diameter (D 50SEM ) was 450 nm, the average crystallite diameter (D) was 225 nm, the D / D 50 SEM was 0.50, the linked particle ratio was 300 ppm, and the coarse particle ratio. Was 24 ppm, the sintering start temperature was 480 ° C., and the smoothness of the coating film was × (poor).
実施例１～実施例１２および比較例１～比較例８の評価結果を表２に示す。 Table 2 shows the evaluation results of Examples 1 to 12 and Comparative Examples 1 to 8.
表２からわかるように、実施例１～実施例１２においては、焼結開始温度が６８０℃以上と高く、かつ、塗膜の平滑性が優れていることが確認された。また、その中でも、実施例３～実施例８においては、焼結開始温度が７２０℃以上と非常に高く、かつ、塗膜の平滑性が非常に優れていることが確認された。 As can be seen from Table 2, in Examples 1 to 12, it was confirmed that the sintering start temperature was as high as 680 ° C. or higher and the smoothness of the coating film was excellent. In addition, it was confirmed that in Examples 3 to 8, the sintering start temperature was as high as 720 ° C. or higher, and the smoothness of the coating film was very excellent.
一方、比較例１および比較例２においては、焼結開始温度が６５０℃であり、かつ、塗膜の平滑性は不良であることが確認された。比較例３および比較例４においては、塗膜の平滑性は優れてはいるものの、焼結開始温度が４５０℃以下と低いことが確認された。比較例５は、塗膜の平滑性が不良であることが確認された。比較例６は、焼結開始温度が６８０℃と高いものの、塗膜の平滑性が不良であることが確認された。比較例７および比較例８においては、焼結開始温度が４８０℃以下と低く、かつ、塗膜の平滑性も不良であることが確認された。 On the other hand, in Comparative Example 1 and Comparative Example 2, it was confirmed that the sintering start temperature was 650 ° C. and the smoothness of the coating film was poor. In Comparative Example 3 and Comparative Example 4, it was confirmed that the sintering start temperature was as low as 450 ° C. or lower, although the smoothness of the coating film was excellent. In Comparative Example 5, it was confirmed that the smoothness of the coating film was poor. In Comparative Example 6, although the sintering start temperature was as high as 680 ° C., it was confirmed that the smoothness of the coating film was poor. In Comparative Example 7 and Comparative Example 8, it was confirmed that the sintering start temperature was as low as 480 ° C. or lower, and the smoothness of the coating film was also poor.
本発明の一実施形態は、相互に矛盾しない限りにおいて、適宜構成要素を組み合わせて実施することができる。また、本発明の一実施形態を基にして、当業者が適宜構成要素の追加、削除または設計変更を行ったもの、もしくは工程の追加、省略または条件変更を行ったものも、本発明の要旨を備えている限り、本発明の範囲に含まれる。 One embodiment of the present invention can be carried out by appropriately combining components as long as they do not contradict each other. Further, a gist of the present invention also includes a product to which a person skilled in the art appropriately adds, deletes, or changes a design based on an embodiment of the present invention, or a process to which a process is added, omitted, or a condition is changed. Is included in the scope of the present invention as long as it is provided.
また、本発明の一実施形態によりもたらされる作用効果とは異なる他の作用効果であっても、本明細書の記載から明らかなもの、または当業者において容易に予測し得るものについては、当然に本発明によりもたらされるものと解される。 In addition, even if the action and effect are different from the action and effect brought about by one embodiment of the present invention, those that are clear from the description of the present specification or those that can be easily predicted by those skilled in the art are of course. It is understood that it is brought about by the present invention.
本発明による銅粉は、焼結開始温度が高く、かつ、塗膜の平滑性に優れている特徴を有する。そのため、ＭＬＣＣの電極に利用すれば、降温時の電極層の収縮による誘電層と電極層との剥離（デラミネーション）を抑制することができる。 The copper powder according to the present invention has the characteristics that the sintering start temperature is high and the smoothness of the coating film is excellent. Therefore, if it is used for the electrode of MLCC, it is possible to suppress the separation (delamination) between the dielectric layer and the electrode layer due to the shrinkage of the electrode layer at the time of lowering the temperature.
Claims (3)
前記塩化銅ガスと還元性ガスとを反応させ、還元反応により銅粉を生成することを含み、
前記還元反応における前記塩化銅ガスの分圧は、１０％以上４０％以下であり、
生成された前記銅粉は、２０００℃／秒以上９０００℃／秒以下の冷却速度で冷却されることを特徴とする銅粉の製造方法。 Copper and chlorine gas are reacted to generate copper chloride gas,
It involves reacting the copper chloride gas with a reducing gas to produce copper powder by the reduction reaction.
The partial pressure of the copper chloride gas in the reduction reaction is 10% or more and 40% or less.
A method for producing copper powder, wherein the produced copper powder is cooled at a cooling rate of 2000 ° C./sec or more and 9000 ° C./sec or less.
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