JP2003166100A - Copper powder used for copper plating, and method for using copper powder - Google Patents
Copper powder used for copper plating, and method for using copper powderInfo
- Publication number
- JP2003166100A JP2003166100A JP2002262713A JP2002262713A JP2003166100A JP 2003166100 A JP2003166100 A JP 2003166100A JP 2002262713 A JP2002262713 A JP 2002262713A JP 2002262713 A JP2002262713 A JP 2002262713A JP 2003166100 A JP2003166100 A JP 2003166100A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper powder
- powder
- electrolytic
- mesh
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 318
- 239000010949 copper Substances 0.000 title claims abstract description 122
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 111
- 238000007747 plating Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims description 36
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 30
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 229940116318 copper carbonate Drugs 0.000 claims description 43
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 43
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 39
- 239000005751 Copper oxide Substances 0.000 claims description 37
- 229910000431 copper oxide Inorganic materials 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- -1 iron ions Chemical class 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 15
- 239000005749 Copper compound Substances 0.000 claims description 10
- 150000001880 copper compounds Chemical class 0.000 claims description 10
- 239000012756 surface treatment agent Substances 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910003202 NH4 Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 41
- 239000000463 material Substances 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract 2
- 229910001448 ferrous ion Inorganic materials 0.000 abstract 2
- 229910001447 ferric ion Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 229910001868 water Inorganic materials 0.000 description 22
- 230000008018 melting Effects 0.000 description 19
- 238000002844 melting Methods 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 6
- 239000011646 cupric carbonate Substances 0.000 description 6
- 235000019854 cupric carbonate Nutrition 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えば電解メッキ
処理に用いられる銅粉及び銅粉の使用方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper powder used for electrolytic plating and a method of using the copper powder.
【０００２】[0002]
【従来の技術】被メッキ体に銅メッキ処理を施す手法の
一つに、不溶解性陽極を用いる手法がある。この手法
は、陽極として例えばチタンの表面に触媒をコーティン
グしたものを用い、メッキ槽と、銅の溶解槽とを用意
し、溶解槽にて銅メッキ材料例えば酸化銅や炭酸銅、金
属銅等を溶解して、これをメッキ槽中の電解液に供給
し、不溶性陽極と陰極をなす被メッキ体との間で通電し
てメッキ処理を行うというものである。2. Description of the Related Art One of the methods for subjecting an object to be plated with copper is to use an insoluble anode. This method uses, for example, a titanium surface coated with a catalyst as an anode, a plating bath and a copper dissolution bath are prepared, and a copper plating material such as copper oxide, copper carbonate, or metallic copper is prepared in the dissolution bath. It is melted and supplied to an electrolytic solution in a plating tank, and a plating treatment is carried out by supplying electricity between an insoluble anode and an object to be plated forming a cathode.
【０００３】ところで不溶解性陽極を用いた場合、陽極
では銅の溶解反応が起こらないため水の分解反応が進行
して酸素が発生するが、この酸素の発生により次のよう
な問題が起こる。つまりメッキ液（電解液）中にはメッ
キ物の平滑性を保持する成分や光沢を出す有機物成分等
が添加剤として混合されているが、酸素が発生するとこ
の発生期の酸素によって添加剤が分解されてしまう。こ
れにより分解された添加剤を補充する必要があり、コス
トアップを招く上、添加剤の分解生成物が多量になる
と、メッキ表面に悪影響を及ぼす。By the way, when an insoluble anode is used, a dissolution reaction of copper does not occur at the anode and a decomposition reaction of water proceeds to generate oxygen, but the generation of this oxygen causes the following problems. In other words, the plating solution (electrolyte) contains a component that maintains the smoothness of the plated product and an organic component that produces gloss, but when oxygen is generated, the additive is decomposed by oxygen during this generation period. Will be done. As a result, it is necessary to supplement the decomposed additive, which leads to an increase in cost, and when the decomposition product of the additive becomes large, it adversely affects the plating surface.
【０００４】このため不溶解性陽極を用いた場合であっ
ても、陽極での酸素の発生を抑えるシステムが提案され
ている。このシステムは、電解メッキ処理を行うための
電解槽と、溶解槽とを備え、電解槽内の電解液が溶解槽
を介して電解槽へ循環されるようになっている。電解槽
には予め電解液として２価の鉄イオン（Ｆe2+イオン）
を含む溶液が供給されており、ここで陽極では酸素発生
に先行してＦe2+イオンが３価の鉄イオン（Ｆe3+イオ
ン）に酸化される反応が進行し、酸素発生反応が抑制さ
れる。一方溶解槽には、例えば無酸素銅ボールよりなる
銅源が供給されており、ここに電解槽のＦe3+イオンを
含む電解液を供給して、２Ｆe3+＋Ｃｕ→２Ｆe2+＋Ｃｕ
2+の反応を進行させ、こうして生成したＣｕ2+イオンは
電解槽に供給される（例えば、非特許文献１参照。）。
これにより電解槽内での酸素の発生を抑制するというも
のである。Therefore, a system has been proposed which suppresses the generation of oxygen at the anode even when an insoluble anode is used. This system is provided with an electrolytic bath for performing electrolytic plating treatment and a dissolving bath, and the electrolytic solution in the electrolytic bath is circulated to the electrolytic bath through the dissolving bath. Divalent iron ions (Fe2 + ions) were previously used as electrolytic solutions in the electrolytic cell.
Is supplied to the anode, where the reaction of oxidizing Fe2 + ions into trivalent iron ions (Fe3 + ions) proceeds prior to oxygen generation, and the oxygen generation reaction is suppressed. On the other hand, a copper source composed of, for example, oxygen-free copper balls is supplied to the melting tank, and an electrolytic solution containing Fe3 + ions in the electrolytic tank is supplied to the melting source, and 2Fe3 ++ Cu → 2Fe2 ++ Cu is supplied.
The 2+ reaction proceeds, and the Cu2 + ions thus generated are supplied to the electrolytic cell (see, for example, Non-Patent Document 1).
This suppresses the generation of oxygen in the electrolytic cell.
【０００５】[0005]
【非特許文献１】高橋正明著、「プリント配線基板用水
平連続めっき装置」、表面技術 Vol.51 No.9 2000、社
団法人表面技術協会、平成１２年９月発行、ｐ.３９−
４０[Non-patent Document 1] Masaaki Takahashi, "Horizontal Continuous Plating Equipment for Printed Wiring Boards", Surface Technology Vol.51 No.9 2000, Japan Surface Technology Association, published in September 2000, p.39-
40
【０００６】[0006]
【発明が解決しようとする課題】しかしながら上述のシ
ステムでは、従来より溶解槽に供給する銅源として例え
ばボール径が２７ｍｍφ〜５５ｍｍφ程度の大きさの無
酸素銅ボールを用いているが、この無酸素銅ボールは比
表面積が小さいため、電解液（メッキ液）への溶解速度
が小さく、電流密度を上げて陰極での銅の析出速度を大
きくしようとすると、電解槽への銅イオンの供給が間に
合わなくなってしまう。また陽極反応で生成するＦｅ3+
イオンは銅を溶解する性質があることからメッキ膜に対
しては悪影響を与える物質であり、直ちにＦｅ2+イオン
に還元することが要求され、溶液中のＦｅ3+イオンがほ
とんど存在しない濃度で管理したいという背景もある。
このため電解槽内のメッキ液中の銅濃度や鉄濃度を安定
に管理するためには、溶解槽側では多量の無酸素銅ボー
ルを準備して、銅の所定の溶解量を確保する必要があり
濃度管理も難しく、結果として装置が大型化し、コスト
アップを招くという問題がある。However, in the above-mentioned system, oxygen-free copper balls having a ball diameter of, for example, 27 mmφ to 55 mmφ have been conventionally used as a copper source to be supplied to the melting tank. Since the copper balls have a small specific surface area, their dissolution rate into the electrolytic solution (plating solution) is low, and when attempting to increase the current density and increase the copper deposition rate at the cathode, the supply of copper ions to the electrolytic cell will be delayed. It's gone. Fe3 + produced by anodic reaction
Ions have a property of dissolving copper, so they are substances that adversely affect the plating film. Immediate reduction to Fe2 + ions is required, and it is necessary to control the concentration of Fe3 + ions in the solution so that they do not exist. There is also.
Therefore, in order to stably control the copper concentration and iron concentration in the plating solution in the electrolytic bath, it is necessary to prepare a large amount of oxygen-free copper balls on the melting bath side to secure a predetermined amount of copper dissolved. However, there is a problem that concentration control is difficult, resulting in an increase in size of the apparatus and an increase in cost.
【０００７】一方、溶解槽に供給する銅源の溶解性をよ
くするために、超微粒子化された銅粉を銅源として用い
る手法が検討されているが、粒径を小さくしすぎると例
えば袋詰された銅源を作業員が溶解槽に供給する際に粉
塵となって雰囲気中に飛散してしまい、作業員の体に悪
影響を及ぼす懸念がある。また飛散した粉塵がメッキ浴
内に入ってしまうと、パーティクルとなってメッキ膜に
付着して膜の品質を低下させる場合があり、更には粉塵
を捕集するための空気清浄設備を設けたのでは設備コス
トが高くなるなどの問題がある。On the other hand, in order to improve the solubility of the copper source supplied to the melting tank, a method of using ultrafine-grained copper powder as a copper source has been studied, but if the particle size is made too small, for example, a bag When the worker supplies the clogged copper source to the melting tank, it becomes dust and scatters in the atmosphere, which may adversely affect the worker's body. In addition, if the scattered dust enters the plating bath, it may become particles and adhere to the plating film, degrading the quality of the film. Furthermore, an air cleaning facility was installed to collect the dust. However, there are problems such as high equipment costs.
【０００８】本発明はこのような背景の下になされたも
のであり、その目的は溶解槽で銅の溶解速度を大きくす
ることにより、銅メッキ材料として好適な銅粉に関する
技術を提供することにある。The present invention has been made under such a background, and an object thereof is to provide a technique relating to copper powder suitable as a copper plating material by increasing the rate of copper dissolution in a dissolution tank. is there.
【０００９】[0009]
【課題を解決するための手段】本発明の銅メッキ方法に
使用される銅粉は、不溶性陽極と陰極をなす被メッキ体
とが設けられ、２価の鉄イオンと銅イオンとを含む電解
液を用いて電気分解を行ない、陰極をなす被メッキ体に
銅を析出させ、２価の鉄イオンを３価の鉄イオンに酸化
する銅メッキ処理工程と、前記銅メッキ処理工程にて得
られた３価の鉄イオンを含む電解液に銅を溶解させて、
２価の鉄イオンと銅イオンとを含む電解液を生成する還
元工程と、前記還元工程にて得られた２価の鉄イオンと
銅イオンとを含む電解液を電解槽に供給させる工程と、
を備えた銅メッキ方法において、還元工程で電解液に溶
解される銅粉であって、この銅粉は、粒子径が５ｍｍ以
下の大きさの銅粉を主成分として含むことを特徴とす
る。The copper powder used in the copper plating method of the present invention is provided with an insoluble anode and an object to be plated forming a cathode, and an electrolytic solution containing divalent iron ions and copper ions. Was obtained by the copper plating treatment step in which copper is deposited on the object to be plated forming the cathode to oxidize divalent iron ions to trivalent iron ions, and the copper plating treatment step. Dissolve copper in an electrolytic solution containing trivalent iron ions,
A reducing step of generating an electrolytic solution containing divalent iron ions and copper ions, and a step of supplying the electrolytic solution containing the divalent iron ions and copper ions obtained in the reducing step to an electrolytic cell,
In the copper plating method, the copper powder is dissolved in the electrolytic solution in the reducing step, and the copper powder contains copper powder having a particle diameter of 5 mm or less as a main component.
【００１０】ここで銅粉としては、例えば粒度５０メッ
シュ以下の大きさの銅粉を主成分として含む銅粉であっ
てもよく、また粒度２５０メッシュより大きい銅粉を主
成分として含む銅粉であってもよい。更には、例えば電
解銅粉やアトマイズ銅粉、置換析出銅粉、銅化合物の還
元粉などよりなる銅粉を主成分として含む銅粉であって
もよく、例えば炭酸銅及び／又は酸化銅を１００℃〜４
００℃に加熱しながら還元して得た銅粉を含む銅粉、例
えば電気銅及び／又は銅線を粉砕処理して得られる銅粉
（粉砕物）を使用することもできる。また前記炭酸銅
は、塩化銅、硫酸銅または硝酸銅の水溶液とアルカリ金
属、アルカリ土類金属またはＮＨ4 の炭酸塩の水溶液と
を混合して加熱しながら反応させ、これにより析出した
反応生成物を濾過分離して得たものであることが好まし
く、炭酸銅を還元雰囲気とはならない雰囲気下で加熱し
て熱分解することにより生成されたものであることが好
ましい。更には銅粉は表面処理剤を含まないのが好まし
い。Here, the copper powder may be, for example, a copper powder having a particle size of 50 mesh or less as a main component, or a copper powder having a particle size of 250 mesh or more as a main component. It may be. Further, for example, it may be a copper powder containing, as a main component, an electrolytic copper powder, an atomized copper powder, a copper powder deposited by substitution, a reduced powder of a copper compound, or the like, and for example, copper carbonate and / or copper oxide may be 100 ℃ ~ 4
It is also possible to use copper powder containing copper powder obtained by reduction while heating to 00 ° C., for example, copper powder (crushed product) obtained by crushing electrolytic copper and / or copper wire. Further, the copper carbonate is prepared by mixing an aqueous solution of copper chloride, copper sulfate or copper nitrate with an aqueous solution of an alkali metal, alkaline earth metal or NH4 carbonate and heating them to react with each other. It is preferably obtained by filtration and separation, and is preferably produced by heating and thermally decomposing copper carbonate in an atmosphere that does not become a reducing atmosphere. Furthermore, it is preferable that the copper powder does not contain a surface treatment agent.
【００１１】本発明によれば、銅メッキ処理後の電解液
に対して、後段の還元工程にて銅源を溶解させている
が、この銅源として粒子径の小さい銅粉を用いることに
より、当該銅粉は電解液に素早く溶解する。このため電
解液に銅を素早く補給することができ、かつメッキ時に
生成した３価の鉄イオンが２価の鉄イオンに還元される
のでメッキ膜に悪影響を及ぼすのが抑えることができ
る。また銅を溶解させる際に粉塵となって飛散するのが
抑えられる。即ち、本発明に係る銅粉は、銅メッキ処理
を行うための銅メッキ材料（銅源）として好適な材料と
して用いることができる。According to the present invention, the copper source is dissolved in the electrolytic solution after the copper plating in the subsequent reduction step. By using copper powder having a small particle size as the copper source, The copper powder quickly dissolves in the electrolytic solution. Therefore, the electrolytic solution can be quickly replenished with copper, and the trivalent iron ions generated at the time of plating are reduced to divalent iron ions, so that adverse effects on the plated film can be suppressed. In addition, it is possible to prevent dust from scattering when melting copper. That is, the copper powder according to the present invention can be used as a material suitable as a copper plating material (copper source) for performing a copper plating treatment.
【００１２】[0012]
【発明の実施の形態】先ず本発明の銅粉が銅メッキ材料
の補給材として用いられる銅メッキ装置の一実施の形態
について図１により説明する。図中１は電解槽（メッキ
浴槽）であり、この中には電解液である例えば硫酸（Ｈ
2ＳＯ4）水溶液に銅（Ｃｕ）粉を溶解したメッキ液が満
たされている。図中１１は例えばチタン板に白金属の白
金、イリジウムを７：３の割合でコーディングしたもの
より構成された不溶性陽極、１２は被メッキ材例えば被
メッキ用金属板よりなる陰極であり、これら不溶性陽極
１１、陰極１２は、夫々図示しない直流電源の正極側、
負極側に接続され、前記メッキ液に浸漬されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an embodiment of a copper plating apparatus in which the copper powder of the present invention is used as a supplementary material for a copper plating material will be described with reference to FIG. In the figure, 1 is an electrolytic bath (plating bath), in which an electrolytic solution such as sulfuric acid (H
2SO4) solution is filled with a plating solution in which copper (Cu) powder is dissolved. In the figure, reference numeral 11 denotes an insoluble anode composed of a titanium plate coated with white metal platinum and iridium at a ratio of 7: 3, and 12 denotes a cathode made of a material to be plated, for example, a metal plate to be plated. The anode 11 and the cathode 12 are the positive electrode side of a DC power source (not shown),
It is connected to the negative electrode side and immersed in the plating solution.
【００１３】このような電解槽１にて、粒度が例えば５
０メッシュ以下、好ましくは２５０メッシュより大きく
５０メッシュ以下、より好ましくは２５０メッシュより
大きく１００メッシュ以下の大きさの銅粉を溶解させた
銅濃度が３〜６ｇ／リットルの硫酸銅水溶液のメッキ液
を用い、例えば直流電源から不溶性陽極１１と陰極１２
とに、電流密度２〜１０Ａ／ｄｍ2で電位差を与えて電
気分解を行うと、陰極１２の表面上に銅が析出し、こう
して皮膜が形成されて、銅メッキ処理が行われる。In such an electrolytic cell 1, the particle size is, for example, 5
0 mesh or less, preferably more than 250 mesh and 50 mesh or less, more preferably a plating solution of copper sulfate solution having a copper concentration of 3 to 6 g / liter in which copper powder having a size of more than 250 mesh and 100 mesh or less is dissolved. Used, for example, from a DC power source to insoluble anode 11 and cathode 12
Further, when a potential difference is applied at a current density of 2 to 10 A / dm2 and electrolysis is performed, copper is deposited on the surface of the cathode 12, thus forming a film and performing a copper plating treatment.
【００１４】図中２は撹拌手段２１を備えた溶解槽であ
り、ここには補給源であるホッパ２２から銅粉が所定量
補給されるように構成され、ここでは銅濃度が低下した
メッキ液に銅粉を添加し、溶液を撹拌することにより当
該溶液に銅粉を溶解させ、所定のメッキ液が調製される
ようになっている。前記電解槽１内からオーバーフロー
した使用済のメッキ液は供給ライン３１により溶解槽２
に供給され、溶解槽２内の新たに調製されたメッキ液は
供給ライン３２によりポンプＰ１を作動させて所定の流
量で電解槽１に供給されるようになっている。Ｆは、例
えば銅粉に含まれる不溶解性の不純物等を除去するため
のフィルタである。直流電源への電力の供給開始や停
止、ホッパ２２からの銅粉の供給開始や停止、撹拌手段
２１やポンプＰ１の作動のタイミング等は、図示しない
制御部により制御されるようになっている。In the figure, reference numeral 2 denotes a melting tank equipped with a stirring means 21, which is configured so that a predetermined amount of copper powder is replenished from a hopper 22 which is a replenishment source, and here, a plating solution having a reduced copper concentration. Copper powder is added to the solution and the solution is stirred to dissolve the copper powder in the solution to prepare a predetermined plating solution. The used plating liquid overflowing from the inside of the electrolytic bath 1 is dissolved by the supply line 31 into the dissolving bath 2
The newly prepared plating solution in the melting tank 2 is supplied to the electrolytic tank 1 at a predetermined flow rate by operating the pump P1 by the supply line 32. F is a filter for removing, for example, insoluble impurities contained in the copper powder. The control unit (not shown) controls the start and stop of power supply to the DC power supply, the start and stop of copper powder supply from the hopper 22, the timing of operation of the stirring means 21 and the pump P1, and the like.
【００１５】このようなメッキ装置では、例えば溶解槽
２から所定流量で調整されたメッキ液が電解槽１内に供
給され、これにより電解槽１からオーバーフローしたメ
ッキ液は供給ライン３１を介して溶解槽２に供給する。
そしてこの溶液にホッパ２２より不足分の銅を補うため
に所定量の銅粉を添加し、銅粉を当該溶液に溶解させて
硫酸銅水溶液（メッキ液）を再生する。In such a plating apparatus, for example, the plating solution adjusted at a predetermined flow rate is supplied from the melting tank 2 into the electrolytic tank 1, and the plating solution overflowing from the electrolytic tank 1 is dissolved through the supply line 31. Supply to tank 2.
Then, a predetermined amount of copper powder is added to the solution from the hopper 22 to make up for the shortage of copper, and the copper powder is dissolved in the solution to regenerate the copper sulfate aqueous solution (plating solution).
【００１６】以上のメッキ装置では、不溶解性陽極１１
を用いていても、陽極での酸素の発生を抑えることがで
きる。これは、次のような理由に因ると推察される。つ
まり電解槽１では、予めＦｅ2+イオンが存在するが、こ
のＦｅ2+は、酸化電位が０．５５Ｖ（ｖｓ Ａｇ／Ａｇ
Ｃｌ）であり、水の酸化による酸素発生電位１．０Ｖ
（ｖｓ Ａｇ／ＡｇＣｌ）よりも低い。このため陽極１
１では、次の（１）式の反応が優先し、これにより酸素
の発生を伴う陽極酸化反応が抑えられる。In the above plating apparatus, the insoluble anode 11
Even if is used, the generation of oxygen at the anode can be suppressed. This is presumed to be due to the following reasons. That is, in the electrolytic cell 1, Fe2 + ions already exist, but the oxidation potential of Fe2 + is 0.55 V (vs Ag / Ag).
Cl) and the oxygen generation potential of 1.0 V due to the oxidation of water
(Vs Ag / AgCl). Therefore, the anode 1
In No. 1, the reaction of the following formula (1) is prioritized, which suppresses the anodizing reaction accompanied by the generation of oxygen.
【００１７】
２Ｆｅ2+ → ２Ｆｅ3+ ＋ ２ｅ- （１）
一方溶解槽２では、銅濃度が低くなり、Ｆｅ3+イオン濃
度が高くなったメッキ液に銅粉を所定量添加することに
より、次の（２）式のＦｅ3+イオンの還元反応が行われ
る。つまりここではＦｅ3+イオンのＦｅ2+イオンへの還
元と、Ｃｕ2+イオンの補給とが同時に行われる。こうし
て還元反応により、銅濃度、Ｆｅ2+イオン濃度が高めら
れるので、新たなメッキ液が調製されることとなり、こ
こで得られたメッキ液は次のメッキ処理に用いられる。2Fe2 + → 2Fe3 + + 2e- (1) On the other hand, in the melting tank 2, a predetermined amount of copper powder is added to the plating solution in which the copper concentration is low and the Fe3 + ion concentration is high. Fe3 + ion reduction reaction is performed. That is, here, reduction of Fe3 + ions to Fe2 + ions and replenishment of Cu2 + ions are simultaneously performed. In this way, the copper concentration and the Fe2 + ion concentration are increased by the reduction reaction, so that a new plating solution is prepared, and the plating solution obtained here is used for the next plating treatment.
【００１８】
Ｃｕ ＋ ２Ｆｅ3+ → Ｃｕ2+ ＋ ２Ｆｅ2+ （２）
このシステムでは、陽極酸化反応を抑えるために、メッ
キ液としては酸素発生よりも低い電位で反応する物質で
あって、メッキへの悪影響が少ない物質を用いることが
望ましい。また陽極１１で酸化された物質が溶解槽２に
て補給される銅を溶解し、自らが還元される必要があ
る。このためにはメッキ液として硫酸鉄や塩化鉄等の鉄
イオン物質を用いることが望ましい。Cu + 2Fe3 + → Cu2 + + 2Fe2 + (2) In this system, in order to suppress the anodic oxidation reaction, the plating liquid is a substance that reacts at a potential lower than that of oxygen generation and has little adverse effect on plating. Is preferred. Further, it is necessary that the substance oxidized at the anode 11 dissolves the copper supplied in the melting tank 2 and is reduced by itself. For this purpose, it is desirable to use an iron ion substance such as iron sulfate or iron chloride as the plating solution.
【００１９】続いて上述のメッキ装置の溶解槽２にてメ
ッキ液に添加される銅粉について説明する。前記システ
ムに用いられる銅粉に要求される性質としては、鉄（II
I）イオンを含む水溶液への溶解性が良いこと、還元力
があること、不純物が少ないこと、流動性が良いこと、
表面処理剤を使わないことなどが挙げられ、本発明者が
種々検討した結果、鉄（III）イオンを含む水溶液への
溶解性を向上させるには、粒子が細かく、比表面積が大
きいことが求められ、これらの性質を満たす銅粉として
は、粒度５０メッシュ以下、好ましくは２５０メッシュ
より大きく５０メッシュ以下、より好ましくは２５０メ
ッシュより大きく１００メッシュ以下の大きさの電解銅
粉又はアトマイズ銅粉、置換析出銅粉、銅化合物の還元
銅粉であり、電解槽１であるメッキ浴槽中への有機系不
純物の混入を抑えるために例えばベンゾトリアゾールや
イミダゾール、ステアリン酸、および防錆剤などの表面
処理剤が含まれないことが望ましい。Next, the copper powder added to the plating solution in the melting tank 2 of the plating apparatus will be described. The properties required for the copper powder used in the system are iron (II
I) Good solubility in an aqueous solution containing ions, good reducing power, low impurities, good fluidity,
As a result of various investigations by the present inventors, such as not using a surface treatment agent, it is required that the particles are fine and have a large specific surface area in order to improve the solubility in an aqueous solution containing iron (III) ions. As the copper powder satisfying these properties, a particle size of 50 mesh or less, preferably more than 250 mesh and 50 mesh or less, more preferably electrolytic copper powder or atomized copper powder having a size of more than 250 mesh and 100 mesh or less, substitution A surface treatment agent such as benzotriazole, imidazole, stearic acid, and a rust preventive agent, which is a deposited copper powder, is a reduced copper powder of a copper compound, and is used to suppress the mixing of organic impurities in the plating bath which is the electrolytic bath 1. Should not be included.
【００２０】したがって上述のメッキ装置にてメッキ液
に添加される銅粉としては、粒度５０メッシュ以下、好
ましくは２５０メッシュより大きく５０メッシュ以下、
より好ましくは２５０メッシュより大きく１００メッシ
ュ以下の大きさの電解銅粉又はアトマイズ銅粉、置換析
出銅粉、銅化合物の還元粉を主成分として用いることが
望ましい。ここで主成分として上述の銅粉を用いると
は、例えば銅粉のうち粒度２５０メッシュより大きく１
００メッシュ以下の大きさの銅粉等の割合が約９０重量
％程度であるという意味であり、前記の電解銅粉やアト
マイズ銅粉、置換析出銅粉、銅化合物の還元粉を組み合
わせて用いるようにしても良い。Therefore, the copper powder added to the plating solution in the above plating apparatus has a grain size of 50 mesh or less, preferably more than 250 mesh and 50 mesh or less,
More preferably, electrolytic copper powder or atomized copper powder having a size of more than 250 mesh and 100 mesh or less, substitutionally deposited copper powder, and reduced powder of copper compound are preferably used as main components. Here, using the above-mentioned copper powder as the main component means, for example, that the particle size of the copper powder is larger than 250 mesh and 1
This means that the proportion of copper powder or the like having a size of 00 mesh or less is about 90% by weight, so that the electrolytic copper powder, atomized copper powder, substitution-precipitated copper powder, and reduced copper compound powder may be used in combination. You can
【００２１】以下にこれら銅粉について個別に説明す
る。The copper powders will be individually described below.
【００２２】（電解銅粉）先ず電解浴中にて電気銅を陽
極として電気分解を行い、陽極で溶け出した銅イオン
を、陰極側にて板状にならないような条件で析出させて
銅粉を得る。これにより得られた粉末を洗浄液例えば純
水中に投入して、洗浄液を撹拌することにより洗浄した
後、脱水し、乾燥させ、電解銅粉を得る。この後篩い機
にて所定の粒度に篩い分けし、粒度５０メッシュ以下、
好ましくは２５０メッシュより大きく５０メッシュ以
下、より好ましくは２５０メッシュより大きく１００メ
ッシュ以下の大きさの電解銅粉を得る。(Electrolytic copper powder) First, electrolytic copper is electrolyzed in an electrolytic bath by using electrolytic copper as an anode, and copper ions dissolved at the anode are deposited on the cathode side under conditions that do not form a plate-like copper powder. To get The powder thus obtained is put into a cleaning liquid, for example, pure water, and the cleaning liquid is washed by stirring and then dehydrated and dried to obtain electrolytic copper powder. After that, it is sieved to a predetermined particle size with a sieving machine, and the particle size is 50 mesh or less,
Preferably, electrolytic copper powder having a size of more than 250 mesh and 50 mesh or less, more preferably more than 250 mesh and 100 mesh or less is obtained.
【００２３】（アトマイズ銅粉）噴霧装置例えばサイク
ロンにガスタンクからコンプレッサーを介して高圧のガ
スを供給できるようにして、高圧ガスの吹き出し口に溶
けた銅を供給し、これにより銅を高圧のガスでサイクロ
ン内に噴霧する。この後篩い機にて所定の粒度に篩い分
けし、粒度が５０メッシュ以下、好ましくは２５０メッ
シュより大きく５０メッシュ以下、より好ましくは２５
０メッシュより大きく１００メッシュ以下の大きさの電
解銅粉を得る。ここでアトマイズ銅粉としては、高圧の
水で噴霧する方法により得られる水アトマイズ銅粉と、
高圧のガスで噴霧する方法により得られるガスアトマイ
ズ銅粉がある。(Atomized copper powder) spraying device For example, a high pressure gas can be supplied to a cyclone from a gas tank through a compressor, and molten copper is supplied to a high pressure gas outlet, whereby copper is converted into a high pressure gas. Spray into cyclone. After that, it is sieved to a predetermined particle size with a sieving machine, and the particle size is 50 mesh or less, preferably more than 250 mesh and 50 mesh or less, more preferably 25 mesh.
An electrolytic copper powder having a size of more than 0 mesh and 100 mesh or less is obtained. Here, as the atomized copper powder, water atomized copper powder obtained by a method of spraying with high-pressure water,
There is a gas atomized copper powder obtained by a method of spraying with a high-pressure gas.
【００２４】（置換析出銅粉）銅イオンを含む溶液に銅
よりも卑な電位を有する（イオン化傾向の大きい）金属
の粉末を加えることにより、銅イオンが還元されて銅粉
が析出する。加える金属としては鉄やアルミニウムなど
を用いることができる。銅イオンを含む溶液としては、
塩化鉄の銅エッチング廃液や塩化銅エッチング廃液、硫
酸銅溶液、シアン化銅溶液などがある。析出した銅粉は
純水などで洗浄後、脱水、乾燥して置換析出銅粉を得
る。(Substitution-precipitated copper powder) By adding a metal powder having a base potential (higher ionization tendency) than copper to a solution containing copper ions, the copper ions are reduced and copper powder is deposited. As the metal to be added, iron or aluminum can be used. As a solution containing copper ions,
There are copper chloride etching waste liquid, copper chloride etching waste liquid, copper sulfate solution, copper cyanide solution and the like. The deposited copper powder is washed with pure water or the like, then dehydrated and dried to obtain substitutionally deposited copper powder.
【００２５】（炭酸銅又は酸化銅を還元して得られた銅
粉（銅化合物の還元銅粉））ここでは銅化合物の還元銅
粉として、炭酸銅又は酸化銅を１００℃〜４００℃で還
元して得られた銅粉を例にして説明する。このほか亜酸
化銅、水酸化銅、シュウ酸銅、ピロリン酸銅等の銅化合
物の還元銅粉を用いるようにしてもよい。この手法は、
例えば図２に示すように、炭酸銅又は酸化銅を還元装置
にて還元して銅粉を得る手法である。前記還元装置とし
ては例えば図２に示すような水素還元炉４を用いること
ができ、この還元炉について簡単に説明すると、図２中
４１は石英管であり、この内部には例えば磁性ボート
（またはステンレス製ボート）４２が置かれるようにな
っている。石英管４１は外周囲に設けられた例えば抵抗
発熱体よりなるヒ−タ４３により加熱されるようになっ
ており、また石英管４１の内部には、水素ガスが通流さ
れるように構成されている。(Copper powder obtained by reducing copper carbonate or copper oxide (reduced copper powder of copper compound)) Here, as the reduced copper powder of the copper compound, copper carbonate or copper oxide is reduced at 100 ° C to 400 ° C. The copper powder thus obtained will be described as an example. In addition, reduced copper powder of a copper compound such as cuprous oxide, copper hydroxide, copper oxalate, and copper pyrophosphate may be used. This technique
For example, as shown in FIG. 2, it is a method of reducing copper carbonate or copper oxide by a reducing device to obtain copper powder. As the reducing device, for example, a hydrogen reducing furnace 4 as shown in FIG. 2 can be used. Briefly explaining the reducing furnace, reference numeral 41 in FIG. 2 is a quartz tube, and inside thereof is, for example, a magnetic boat (or A stainless steel boat) 42 is placed. The quartz tube 41 is adapted to be heated by a heater 43 which is provided on the outer periphery and is made of, for example, a resistance heating element, and hydrogen gas is allowed to flow inside the quartz tube 41. There is.
【００２６】このような水素還元炉４では、この磁性ボ
ート４２上に炭酸銅又は酸化銅を例えば１０ｍｍ程度の
厚さで堆積させ、例えば内径４０ｍｍ、長さ１ｍの大き
さの石英管４１内に水素ガスを例えば２リットル／分程
度の流量で通流させながら、ヒータ４３により石英管４
１の内部を例えば１００℃〜４００℃に加熱することに
より、炭酸銅又は酸化銅の還元処理を所定時間例えば
１．５時間程度を行う。これにより炭酸銅又は酸化銅は
次の（３）式及び（４）式の反応により銅に還元され
る。この銅粉を例えば２００メッシュの篩い機により篩
い分けし、粒度２００メッシュ以下の銅粉を得る。In the hydrogen reduction furnace 4 as described above, copper carbonate or copper oxide is deposited on the magnetic boat 42 to a thickness of, for example, about 10 mm, and the quartz tube 41 having an inner diameter of 40 mm and a length of 1 m is provided. While flowing hydrogen gas at a flow rate of, for example, about 2 l / min, the quartz tube 4 is heated by the heater 43.
By heating the inside of 1 to, for example, 100 ° C. to 400 ° C., reduction treatment of copper carbonate or copper oxide is performed for a predetermined time, for example, about 1.5 hours. As a result, copper carbonate or copper oxide is reduced to copper by the reactions of the following equations (3) and (4). This copper powder is sieved with, for example, a 200-mesh sieving machine to obtain copper powder having a particle size of 200 mesh or less.
【００２７】
ＣｕＣＯ3＋Ｈ2 → Ｃｕ＋Ｈ2Ｏ＋ＣＯ2 （３）
ＣｕＯ＋Ｈ2 → Ｃｕ＋Ｈ2Ｏ （４）
この炭酸銅又は酸化銅の還元は、後述の実験例により石
英管４１内を１００℃〜４００℃に加熱して行うことが
好ましい。炭酸銅又は酸化銅の底部まで水素と十分に反
応させるためには、水素ガスを拡散しやすくして、炭酸
銅又は酸化銅の底部まで水素ガスを浸透させる必要があ
り、このためには磁性ボート４２をメッシュ状に構成し
て、炭酸銅又は酸化銅の底部側へ水素ガスが通流できる
ようにしたり、流動炉を用いることが好ましい。CuCO3 + H2 → Cu + H2O + CO2 (3) CuO + H2 → Cu + H2O (4) This reduction of copper carbonate or copper oxide is preferably carried out by heating the inside of the quartz tube 41 to 100 ° C. to 400 ° C. according to an experimental example described later. In order to fully react with hydrogen to the bottom of copper carbonate or copper oxide, it is necessary to facilitate the diffusion of hydrogen gas and allow hydrogen gas to permeate to the bottom of copper carbonate or copper oxide. It is preferable to configure 42 in a mesh shape so that hydrogen gas can flow to the bottom side of copper carbonate or copper oxide, or to use a fluidized furnace.
【００２８】上述の手法にて、還元対象となる炭酸銅及
び酸化銅は市販品のものを購入してもよいが、次のよう
に製造されることが望ましい。図３はこの場合の製造フ
ロ−を示す説明図であり、例えば銅濃度が１０重量％で
ある例えばエッチング廃液よりなる塩化第二銅（ＣｕＣ
ｌ2 ）の水溶液とアルカリ金属の炭酸塩例えば炭酸濃度
が７重量％である炭酸ナトリウム（Ｎａ2 ＣＯ3 ）の水
溶液とを例えば混合液のｐＨが７〜９となるように反応
槽５内に投入し、混合液の温度が例えば７０℃となるよ
うに加熱しながら撹拌手段５１により例えば３０分間撹
拌して反応させる。混合液の加熱は例えば反応槽５１内
に図示しないが散気管などからなるバブリング手段を設
け、このバブリング手段から蒸気を混合液にバブリング
することにより行われる。[0028] Although the commercially available copper carbonate and copper oxide to be reduced may be purchased by the above-mentioned method, it is desirable that they are manufactured as follows. FIG. 3 is an explanatory view showing a manufacturing flow in this case, for example, cupric chloride (CuC) made of, for example, an etching waste liquid having a copper concentration of 10% by weight.
l2) and an alkali metal carbonate, for example, an aqueous solution of sodium carbonate (Na2 CO3) having a carbonic acid concentration of 7% by weight, are charged into the reaction vessel 5 so that the pH of the mixed solution is 7-9, While heating so that the temperature of the mixed solution becomes, for example, 70 ° C., the mixture is stirred by the stirring means 51 for, for example, 30 minutes to react. The mixed solution is heated, for example, by providing a bubbling means (not shown) such as an air diffuser in the reaction tank 51, and bubbling steam from the bubbling means into the mixed solution.
【００２９】上述の反応は次のように進行する。先ず
（５）式のように炭酸銅が生成され、
Ｎａ2 ＣＯ3 ＋ＣｕＣｌ2 →ＣｕＣＯ3 ＋２ＮａＣｌ （５）
続いて（６）式のように炭酸銅が水和して塩基性炭酸銅
の二水塩が生成され、
ＣｕＣＯ3 ＋３／２Ｈ2 Ｏ→１／２｛ＣｕＣＯ3 ・Ｃｕ（ＯＨ)2・２Ｈ
2 Ｏ｝＋１／２ＣＯ2 （６）
更に（７）式のように上記の二水塩から水が抜け、無水
の塩基性炭酸銅が生成される。
ＣｕＣＯ3 ・Ｃｕ（ＯＨ)2・２Ｈ2 Ｏ→ＣｕＣＯ3 ・Ｃｕ（ＯＨ)2＋２
Ｈ2 Ｏ （７）
こうして塩基性炭酸銅が析出生成されて粉体となって沈
殿する。そしてバルブ５２を開いて沈殿物であるスラリ
−を抜き出して遠心分離機５３に送り、ここで遠心分離
により固形分を母液から分離し、その固形分を乾燥機５
４に入れて乾燥し、塩基性炭酸銅の粉体を得る。The above reaction proceeds as follows. First, copper carbonate is formed as in formula (5), and Na2 CO3 + CuCl2 → CuCO3 + 2NaCl (5). Then, as shown in formula (6), copper carbonate is hydrated to form a dihydrate of basic copper carbonate. , CuCO3 + 3 / 2H2 O → 1/2 {CuCO3.Cu (OH) 2 · 2H2O} + 1 / 2CO2 (6) Further, as shown in formula (7), water is removed from the above dihydrate salt to give an anhydrous base. Copper carbonate is produced. CuCO3 · Cu (OH) 2 · 2H2O → CuCO3 · Cu (OH) 2 + 2H2O (7) In this way, basic copper carbonate is deposited and formed into a powder. Then, the valve 52 is opened and the slurry as the precipitate is extracted and sent to the centrifuge 53, where the solid content is separated from the mother liquor by centrifugation, and the solid content is dried by the dryer 5.
Put in 4 and dry to obtain a powder of basic copper carbonate.
【００３０】塩基性炭酸銅の原料である銅イオン源とし
ては塩化銅の他に例えば硫酸銅または硝酸銅などの銅塩
の水溶液を用いることができる。炭酸イオン源としては
炭酸ナトリウムの他に炭酸水素ナトリウム、炭酸カリウ
ムなどのアルカリ金属の炭酸塩、または炭酸カルシウ
ム、炭酸マグネシウム、炭酸バリウムなどのアルカリ土
類金属の炭酸塩あるいは炭酸アンモニウム（（ＮＨ4)2
ＣＯ3 ）などを用いることができる。As a copper ion source which is a raw material for basic copper carbonate, an aqueous solution of a copper salt such as copper sulfate or copper nitrate can be used in addition to copper chloride. As the carbonate ion source, in addition to sodium carbonate, alkali metal carbonates such as sodium hydrogen carbonate and potassium carbonate, or alkaline earth metal carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, or ammonium carbonate ((NH4) 2
CO3) or the like can be used.
【００３１】次に粉体である前記塩基性炭酸銅を加熱
炉、例えばロ−タリキルン６に供給し、ここで例えば２
５０℃以上で８００℃以下の温度に加熱して熱分解す
る。この例では加熱炉として、管軸を回転軸として回転
する例えばステンレス製の回転管６１を僅かに傾斜して
設け、この回転管６１の周囲をヒ−タ６２により囲み、
回転管６１を回転させることにより塩基性炭酸銅の粉体
を移送するロ−タリキルン６を用いている。このように
して塩基性炭酸銅を加熱すれば加熱雰囲気が還元雰囲気
にならない。塩基性炭酸銅を直接バ−ナで加熱しない理
由は、還元雰囲気にすると、炭酸銅そのものや炭酸銅が
酸化銅に分解された後、一部が還元されて亜酸化銅（Ｃ
ｕ2 Ｏ）や金属銅（Ｃｕ）を生成してしまうので、これ
を避けるためである。Next, the basic copper carbonate as a powder is fed to a heating furnace, for example, a rotary kiln 6, where, for example, 2
It is thermally decomposed by heating it at a temperature of 50 ° C or higher and 800 ° C or lower. In this example, as a heating furnace, a rotary tube 61 made of, for example, stainless steel, which rotates about a tube axis as a rotary axis, is provided with a slight inclination, and the rotary tube 61 is surrounded by a heater 62.
A rotary kiln 6 for transferring the powder of basic copper carbonate by rotating the rotary tube 61 is used. By heating the basic copper carbonate in this way, the heating atmosphere does not become a reducing atmosphere. The reason why basic copper carbonate is not directly heated by a burner is that when a reducing atmosphere is used, copper carbonate itself or copper carbonate is decomposed into copper oxide and then partially reduced to form cuprous oxide (C
This is to avoid this since it will generate u2 O) and metallic copper (Cu).
【００３２】また加熱温度については、２５０℃であれ
ば例えば２時間程度加熱することにより酸化銅が得られ
るが，２００℃では熱分解しない。２２０℃では示差熱
分析においても熱分解しきれていないことを把握してい
ることから、２５０℃以上で加熱することが必要である
が、熱分解の時間を短くして生産効率を高くするために
は３５０℃以上であることが好ましい。８００℃を越え
ると、得られる酸化銅の易溶解性が小さくなってしまう
ので８００℃以下であることが必要である。更により易
溶解性の大きな酸化銅を得ようとすると６００℃以下に
することが好ましい。Regarding the heating temperature, if the temperature is 250 ° C., copper oxide can be obtained by heating for about 2 hours, but at 200 ° C., it does not thermally decompose. It is necessary to heat at 250 ° C or higher because it is known that thermal decomposition has not been completed even in differential thermal analysis at 220 ° C, but in order to shorten the thermal decomposition time and increase production efficiency. It is preferably 350 ° C. or higher. If the temperature exceeds 800 ° C, the solubility of the obtained copper oxide will be reduced, so the temperature must be 800 ° C or lower. Further, in order to obtain copper oxide having higher solubility, the temperature is preferably 600 ° C. or lower.
【００３３】このようにして酸化銅を得た後、この酸化
銅を洗浄液である純水の入った洗浄槽６３内に投入し、
撹拌手段６３ａにより撹拌して水洗する。そしてバルブ
６４を開いて水と酸化銅との混合スラリ−を洗浄槽６３
から抜き出し、遠心分離機６５またはろ過機により水分
を飛ばしてから乾燥機６６で乾燥させ、粉体である酸化
銅を得る。洗浄液としては蒸留水やイオン交換水などの
純水を用いることができるが、その他それより不純分が
少ない水、例えば超純水などを用いることもできる。こ
うして得られた炭酸銅又は酸化銅を還元して得られた銅
粉は、粒度が２００メッシュ以下と細かく、多孔質であ
り、さらに丸い形状であることが認められている。After the copper oxide is obtained in this manner, the copper oxide is put into a cleaning tank 63 containing pure water as a cleaning liquid,
It is stirred by the stirring means 63a and washed with water. Then, the valve 64 is opened and the mixed slurry of water and copper oxide is washed in the washing tank 63.
The powder is extracted from the product, the water content is removed by the centrifuge 65 or the filter, and the product is dried by the dryer 66 to obtain copper oxide as powder. Pure water such as distilled water or ion-exchanged water can be used as the cleaning liquid, but water having less impurities than that, such as ultrapure water, can also be used. It is recognized that the copper powder obtained by reducing the thus obtained copper carbonate or copper oxide has a fine particle size of 200 mesh or less, is porous, and has a round shape.
【００３４】このように本発明では、後述の実験例より
明らかなように粒度５０メッシュ以下、好ましくは２５
０メッシュより大きく５０メッシュ以下、より好ましく
は２５０メッシュより大きく１００メッシュ以下の大き
さの表面処理剤を用いていない銅粉を銅メッキ材料とし
て用いており、これら銅粉は無酸素銅ボールに比べて比
表面積が非常に大きいので、鉄（III）イオンを含む水
溶液への溶解速度が大きい。このため溶解槽２にてメッ
キ液を調製する際、メッキ液へ溶解しやすいので、銅メ
ッキ材料として好適である。As described above, in the present invention, the particle size is 50 mesh or less, preferably 25, as is apparent from the experimental examples described later.
Copper powder with no surface treatment agent having a size of more than 0 mesh and less than 50 mesh, more preferably more than 250 mesh and less than 100 mesh is used as the copper plating material. And has a very large specific surface area, the dissolution rate in an aqueous solution containing iron (III) ions is high. Therefore, when the plating solution is prepared in the dissolution tank 2, it is easily dissolved in the plating solution, and thus it is suitable as a copper plating material.
【００３５】さらにメッキ液へ溶解しやすいことから、
大量の銅粉を添加しなくても銅の溶解量を確保すること
ができる。このように溶解槽２内への銅粉を添加量が無
酸素銅ボールを添加する場合に比べて少ないので、小型
の溶解槽２でも十分に銅の溶解量を確保することができ
る。このため装置全体の小型化が図れ、コストダウンに
繋がる。またこのような銅粉はメッキ液へ溶解しやすい
ことから調製時間が短縮できスループットの向上を図る
ことができる。Further, since it is easily dissolved in the plating solution,
The amount of copper dissolved can be secured without adding a large amount of copper powder. Since the amount of copper powder added to the melting tank 2 is smaller than that in the case where oxygen-free copper balls are added, a sufficient amount of copper can be secured even in a small melting tank 2. Therefore, the size of the entire device can be reduced, which leads to cost reduction. Further, since such copper powder is easily dissolved in the plating solution, the preparation time can be shortened and the throughput can be improved.
【００３６】さらに炭酸銅や酸化銅を還元して得られた
銅粉を用いた場合には、この銅粉は多孔質であることか
ら、よりメッキ液への溶解速度が大きく、Ｆｅ3+イオン
の還元力が大きいという利点がある。また純度の高い電
解銅粉やアトマイズ銅粉に比べて安価であり、コスト的
に有利である。When copper powder obtained by further reducing copper carbonate or copper oxide is used, since the copper powder is porous, the dissolution rate in the plating solution is higher and the Fe3 + ion is reduced. It has the advantage of great power. Moreover, it is cheaper than electrolytic copper powder or atomized copper powder having high purity, and is advantageous in cost.
【００３７】さらにまた塩化第二銅水溶液とアルカリ金
属の炭酸塩より得られた、炭酸銅又は酸化銅を還元して
得られた銅粉を用いた場合には、塩化第二銅エッチング
廃液の有効利用を図ることができる上、表面処理剤を使
用していないので、有機物系の不純物がほとんどないと
いう点で有効である。またこの手法により得られた銅粉
は丸い形状を有しているので、流動性がよく、例えば溶
解槽２にてホッパ２２から定量供給を行うことができ
て、管理が容易となる。Furthermore, when copper powder obtained by reducing copper carbonate or copper oxide obtained from an aqueous solution of cupric chloride and a carbonate of an alkali metal is used, the effectiveness of the cupric chloride etching waste liquid is improved. It is effective in that it can be used and that it contains almost no organic impurities because no surface treatment agent is used. Further, since the copper powder obtained by this method has a round shape, it has good fluidity, and for example, a fixed amount can be supplied from the hopper 22 in the melting tank 2 and management becomes easy.
【００３８】さらにまた本発明の銅粉は、メッキ液への
溶解力が大きく、表面処理剤などの有機系不純物が少な
いので、不溶解残渣となる成分の生成が抑えられ、フィ
ルタにほとんど負荷がかからないと共に、メッキ液の銅
イオン濃度の管理が容易となる。またこのように不純物
濃度が少ないことから、不純物濃度が管理上の上限に達
するまでの時間が長くなり、建浴に至るまでの時間が長
くなって、コストアップを抑えることができる。Furthermore, since the copper powder of the present invention has a large dissolving power in the plating solution and a small amount of organic impurities such as a surface treatment agent, the generation of components which become insoluble residues is suppressed, and the load on the filter is almost zero. Not only will this not occur, but the control of the copper ion concentration of the plating solution will be easier. Further, since the impurity concentration is low as described above, it takes a long time until the impurity concentration reaches the upper limit in terms of management, and it takes a long time to reach the building bath, so that the cost increase can be suppressed.
【００３９】また本発明においては、溶解槽に供給する
銅粉は、粒度５０メッシュ以下のものに限られず、粒子
径が５．０ｍｍ以下の銅粉であってもよい。この銅粉
は、上述の銅粉であってもよいが、例えばＪＩＳ規格
（ＪＩＳ Ｈ ２１２１）に準ずる電気銅及び／又は銅線
例えば１号銅線くずを粉砕処理して得られる銅粒子（１
号ナゲット銅）をなす粉砕物であってもよい。ここで前
記銅粒子（銅粉）は例えば９９．９％以上の銅純度を有
し、かつ上述の銅粉と同様に表面処理剤を含まないのが
望ましい。この場合、後述する実施例からも明らかなよ
うに、上述の銅粉（５０メッシュ以下の銅粉）と比べる
と比表面積が小さく溶解性は劣ることになるが、無酸素
銅ボールに比べると高い溶解性を示すので上述の場合と
同様の効果を得ることができる。更に例えばメッキ膜の
製造量を同じくして溶解槽１の小型化した場合、銅粉の
投入回数を増やすかあるいは１回の供給量を多くするこ
とが必要となり、そのため供給時に銅粉が粉塵となり易
くなるが、本発明の銅粉にあっては粒径をある程度大き
くとることで銅粉の比重が大きくなるため当該銅粉が粉
塵となることが少ない。なお、銅粉の粒子径を大きくと
りすぎるとその分溶解性が低くなり、またホッパ２２を
用いて銅粉を定量供給する際に、供給量がばらつかない
ように制御するのが難しくなるといった理由から粒子径
は５ｍｍ以下にすることが望ましい。Further, in the present invention, the copper powder supplied to the melting tank is not limited to the one having a particle size of 50 mesh or less, and may be a copper powder having a particle diameter of 5.0 mm or less. This copper powder may be the above-mentioned copper powder, but for example, copper particles obtained according to JIS standard (JIS H 2121) and / or copper wire, for example, copper particles obtained by pulverizing No. 1 copper wire scraps (1
No. Nugget copper) may be used. Here, it is desirable that the copper particles (copper powder) have a copper purity of, for example, 99.9% or more, and do not contain a surface treatment agent like the above-mentioned copper powder. In this case, as is clear from the examples described later, the specific surface area is small and the solubility is inferior as compared with the above-mentioned copper powder (copper powder of 50 mesh or less), but it is higher than the oxygen-free copper balls. Since it exhibits solubility, the same effect as in the above case can be obtained. Further, for example, when the melting tank 1 is miniaturized with the same production amount of the plating film, it is necessary to increase the number of times the copper powder is charged or to supply the copper powder once, so that the copper powder becomes dust during the supply. However, in the copper powder of the present invention, the specific gravity of the copper powder increases by increasing the particle size to some extent, so that the copper powder rarely becomes dust. It should be noted that if the particle size of the copper powder is too large, the solubility decreases accordingly, and it becomes difficult to control the supply amount when the copper powder is quantitatively supplied using the hopper 22. For the reason, it is desirable that the particle diameter be 5 mm or less.
【００４０】更に本発明においては、銅粉は前記した電
解銅粉又はアトマイズ銅粉、置換析出銅粉、銅化合物の
還元粉および電気銅及び／又は銅線の粉砕物のなかから
選択される混合物であってもよい。このような場合であ
っても上述と同様の効果を得ることができる。Further, in the present invention, the copper powder is a mixture selected from the above-mentioned electrolytic copper powder or atomized copper powder, substitutionally deposited copper powder, reduced powder of copper compound and pulverized product of electrolytic copper and / or copper wire. May be Even in such a case, the same effect as described above can be obtained.
【００４１】[0041]
【実施例】続いて本発明の効果を確認するために行った
実施例について説明する。
（実施例１）本例は、市販のアトマイズ銅粉および電解
銅粉に対して、溶解性、見掛密度、流動性、平均粒子径
の分析を以下のように行った実施例１である。サンプル
は、粒度３５０メッシュ以下、２５０メッシュ以下、１
００メッシュ以下、５０メッシュ以下、３０メッシュ以
下の大きさの水アトマイズ銅粉、粒度１００メッシュ以
下の大きさのガスアトマイズ銅粉、２５０メッシュ以下
の大きさの電解銅粉などを用いた。
溶解性試験：鉄濃度が５ｇ／リットルである硫酸第二鉄
水溶液２．５リットルに、銅粉サンプル５ｇを添加し、
液中の酸化還元電位の変化をエレクトロメータ（北斗電
工製：ＨＥ−１０４）で測定する。ここで酸化還元電位
の変化量が大きいほど溶解力が大きいことを示し、酸化
還元電位変化量が２００ｍＶになると、投入した銅粉の
約９０％が溶解することになる（実施例２、３について
も同様である）。
流動度試験：孔径φ２．６３ｍｍのオリフィスを用い
て、ＪＩＳ２５０２−１９７９の流動度の測定法に基づ
いて分析した。
平均粒子径の測定：回折式粒度分布測定装置（島津レー
ザー製：ＳＡＬＤ―１０００）を用いて各銅粉の平均サ
ンプル（抜き取りサンプル）の粒子径を測定した。EXAMPLES Next, examples carried out to confirm the effects of the present invention will be described. (Example 1) This example is Example 1 in which the solubility, apparent density, fluidity, and average particle size of commercially available atomized copper powder and electrolytic copper powder were analyzed as follows. Sample size is 350 mesh or less, 250 mesh or less, 1
Water atomized copper powder having a size of 00 mesh or less, 50 mesh or less, 30 mesh or less, gas atomized copper powder having a particle size of 100 mesh or less, electrolytic copper powder having a size of 250 mesh or less, and the like were used. Solubility test: 5 g of a copper powder sample was added to 2.5 liters of an aqueous ferric sulfate solution having an iron concentration of 5 g / liter,
The change in the redox potential in the liquid is measured with an electrometer (Hokuto Denko: HE-104). Here, it is shown that the larger the amount of change in the redox potential, the greater the dissolving power, and when the amount of change in the redox potential becomes 200 mV, about 90% of the charged copper powder is dissolved (for Examples 2 and 3). Is also the same). Flowability test: An orifice having a diameter of 2.63 mm was used for analysis based on the method of measuring flowability according to JIS2502-1979. Measurement of average particle diameter: The particle diameter of an average sample (sampled sample) of each copper powder was measured using a diffraction type particle size distribution measuring device (Shimadzu Laser: SALD-1000).
【００４２】（実施例２）本例は、図２、図３に記載の
手法で得た酸化銅還元銅粉に対して、溶解性、流動度、
平均粒子径を分析した実施例２である。分析の手法およ
び条件は実施例１と同じである。ここでサンプルとして
用いた酸化銅は、上述の還元装置にて既述の条件で、炉
内温度を３００℃に加熱して約９０分間還元処理を行
い、この処理により得られた銅粉を篩にかけて得られた
粒度が２００メッシュ以下の大きさの銅粉である。(Example 2) In this example, the solubility, fluidity, and flow rate of copper oxide reduced copper powder obtained by the method described in FIGS.
It is Example 2 which analyzed the average particle diameter. The analysis method and conditions are the same as in Example 1. The copper oxide used here as a sample was heated in the furnace to 300 ° C. under the conditions described above in the reducing apparatus for reduction treatment for about 90 minutes, and the copper powder obtained by this treatment was sieved. It is a copper powder having a particle size of 200 mesh or less obtained by subjecting to copper.
【００４３】なお、得られた銅粉の重量を測定して還元
減量を調べ還元されているかどうかを確認すると共に、
Ｘ線回折により還元状態を分析したところ、還元減量が
２０重量％程度であり、Ｃｕ／ＣｕＯに相当すること、
及びＸ線回折の結果から銅粉への還元が良好に行われ、
更には容易に篩機により篩い分けされて、２００メッシ
ュ以下の大きさの銅粉を容易に得ることができることを
確認している。In addition, the weight of the obtained copper powder is measured to examine the reduction weight loss to confirm whether or not it has been reduced.
When the reduction state was analyzed by X-ray diffraction, the reduction amount was about 20% by weight, which corresponds to Cu / CuO.
From the results of X-ray diffraction and reduction to copper powder were performed well,
Furthermore, it has been confirmed that copper powder having a size of 200 mesh or less can be easily obtained by sieving with a sieving machine.
【００４４】（実施例３）本例は、銅粒子（１号ナゲッ
ト銅）に対して、溶解性の分析した実施例３である。分
析の手法および条件は実施例１と同じである。ここで各
サンプルは、ＪＩＳ Ｈ ２１２１規格に準ずる市販品の
電気銅および１号銅線くずを粉砕処理した例えば粒子径
５ｍｍ以下の大きさの銅粒子を用いた。なおサンプルの
銅純度は９９．９％であり、表面処理剤は含まれていな
い。
（比較例１）本例は、無酸素銅ボールの溶解性を分析し
た比較例１である。サンプルとしてボール径がφ２７ｍ
ｍの市販の無酸素銅ボールを１個（約９０ｇ）用いたこ
とを除いて分析の手法および条件は実施例１と同じであ
る。(Example 3) This example is Example 3 in which the solubility of copper particles (No. 1 nugget copper) was analyzed. The analysis method and conditions are the same as in Example 1. Here, as each sample, commercially available electrolytic copper according to JIS H 2121 standard and No. 1 copper wire scraps were pulverized and used, for example, copper particles having a particle diameter of 5 mm or less were used. The copper purity of the sample was 99.9%, and no surface treatment agent was included. Comparative Example 1 This example is Comparative Example 1 in which the solubility of oxygen-free copper balls was analyzed. Ball diameter is φ27m as a sample
The analytical method and conditions are the same as in Example 1 except that one commercially available oxygen-free copper ball of m (about 90 g) was used.
【００４５】（実施例１、２、３および比較例１の溶解
性の分析結果と考察）実施例１、２、３および比較例１
の溶解性の結果を図４に示す。図４は、硫酸第二鉄水溶
液にサンプルを添加してからの硫酸第二鉄水溶液の酸化
還元電位の測定結果についてその変化量をプロットした
ものである。但し、３５０メッシュ以下の大きさの水ア
トマイズ銅粉は３００℃で加熱した酸化銅の還元銅粉と
ほぼ同じ溶解性を示したので、作図上の都合により酸化
銅の還元銅粉の図示を省略してある。(Solubility Analysis Results and Consideration of Examples 1, 2, 3 and Comparative Example 1) Examples 1, 2, 3 and Comparative Example 1
The results of the solubility of are shown in FIG. FIG. 4 is a plot of the amount of change in the measurement result of the redox potential of the aqueous ferric sulfate solution after the sample was added to the aqueous ferric sulfate solution. However, since the water atomized copper powder having a size of 350 mesh or less showed almost the same solubility as the reduced copper powder of copper oxide heated at 300 ° C., the reduced copper powder of copper oxide was not shown for convenience of drawing. I am doing it.
【００４６】図４に示す結果から明らかなように、各サ
ンプルとも添加してから急速に酸化還元電位が上昇し、
例えば９０秒後にあっては水アトマイズ銅粉（２５０メ
ッシュ以下）、電解銅粉（２５０メッシュ以下）、水ア
トマイズ銅粉（１００メッシュ以下）および酸化銅還元
銅粉（３００℃）は変化量２００ｍＶ（溶解率９０％）
を越えており、またガスアトマイズ銅粉（１００メッシ
ュ以下）および水アトマイズ銅粉（５０メッシュ以下）
は２００ｍＶ近くまで達している。そして、これらに続
いて水アトマイズ銅粉（３０メッシュ以下）は１２８ｍ
Ｖ、銅粒子（５ｍｍ以下）は９９ｍＶの変化量であり、
比較例１の無酸素銅ボールの変化量が最も小さい６７ｍ
Ｖであった。即ち、硫酸鉄（III）水溶液に対する溶解
性は、その銅粉の製造方法の種類に関わらず、粒径を小
さくして比表面積を大きくするほど溶解性が良くなるこ
とが確認された。更には、粒度が５０メッシュ以下、よ
り好ましくは１００メッシュ以下の大きさにすることに
より極めて高い溶解性を得られることが確認された。As is clear from the results shown in FIG. 4, the oxidation-reduction potential rapidly increased after addition in each sample,
For example, after 90 seconds, the water atomized copper powder (250 mesh or less), the electrolytic copper powder (250 mesh or less), the water atomized copper powder (100 mesh or less) and the copper oxide reduced copper powder (300 ° C) have a change amount of 200 mV ( 90% dissolution rate)
, And gas atomized copper powder (100 mesh or less) and water atomized copper powder (50 mesh or less)
Has reached nearly 200 mV. And, following these, water atomized copper powder (30 mesh or less) is 128m
V, copper particles (5 mm or less) is the change amount of 99 mV,
The oxygen-free copper ball of Comparative Example 1 has the smallest change amount of 67 m.
It was V. That is, it was confirmed that the solubility in the iron (III) sulfate aqueous solution was improved as the particle size was decreased and the specific surface area was increased, irrespective of the type of the manufacturing method of the copper powder. Further, it was confirmed that extremely high solubility can be obtained by setting the particle size to 50 mesh or less, more preferably 100 mesh or less.
【００４７】さらにこれら電解銅粉、アトマイズ銅粉、
炭酸銅及び／又は酸化銅を還元して得た銅粉、電気銅の
粉砕物および銅粒子（１号ナゲット銅）を、銅メッキ材
料として用いて、図１のシステムにて実際にメッキ処理
を行ったところ、陰極１２の表面（析出銅）は非常に平
坦で平滑であることが確認している。Further, these electrolytic copper powder, atomized copper powder,
A copper powder obtained by reducing copper carbonate and / or copper oxide, a pulverized product of electrolytic copper, and copper particles (No. 1 nugget copper) are used as a copper plating material to actually perform a plating treatment in the system of FIG. As a result, it was confirmed that the surface of the cathode 12 (precipitated copper) was very flat and smooth.
【００４８】（実施例１、２の流動度と平均密度の分析
結果と考察）実施例１、２の流動度の分析結果を図５に
示す。図５は各サンプルの流動度および平均粒子径の結
果を示している。ここで流動度とは、５０ｇの銅粉がオ
リフィスを通過するのに要した時間を示すものである。
また図中「ブリッジング」とは、粉がオリフィス部分で
橋かけ状に詰まって流れ落ちない状態（架橋現象）をい
い、２５０メッシュ以下ではこのブリッジングが発生す
ることが認められた。これにより銅粉の供給時の操作性
を考慮すると、２５０メッシュより大きいことが望まし
いことが理解される。(Analysis result and consideration of flowability and average density of Examples 1 and 2) The analysis result of flowability of Examples 1 and 2 is shown in FIG. FIG. 5 shows the results of the fluidity and average particle size of each sample. Here, the fluidity refers to the time required for 50 g of copper powder to pass through the orifice.
Further, "bridging" in the figure refers to a state in which powder is blocked in the orifice portion in a bridge shape and does not flow down (crosslinking phenomenon), and it was confirmed that this bridging occurs at 250 mesh or less. From this, it is understood that it is preferable that the size is larger than 250 mesh in consideration of the operability when supplying the copper powder.
【００４９】さらに酸化銅を還元して得た銅粉をＳＥＭ
（日本電子製ＪＳＭ−Ｔ２０）により観察したところ、
多孔質球状粉であることが認められた。これにより比表
面積が大きくなり、より硫酸鉄（III）水溶液に溶解し
やすいことが認められたさらにまた同様の分析を炭酸銅
より得られた銅粉についても行ったところ、ほぼ炭酸銅
を還元して得た銅粉と同様の結果が得られ、硫酸鉄（II
I）水溶液に対して溶解力が大きいことを確認してい
る。Further, the copper powder obtained by reducing the copper oxide was subjected to SEM.
When observed with (JSM-T20 manufactured by JEOL Ltd.),
It was confirmed to be a porous spherical powder. As a result, the specific surface area was increased, and it was confirmed that the specific surface area was more easily dissolved in the iron (III) sulfate aqueous solution. Furthermore, when the same analysis was performed on the copper powder obtained from copper carbonate, it was found that copper carbonate was almost reduced. The same result as the copper powder obtained by
I) It has been confirmed that it has a high dissolving power in aqueous solutions.
【００５０】[0050]
【発明の効果】以上のように本発明によれば、銅粉は比
表面積が大きく、二価の鉄イオンを含む電解液への溶解
力が大きいので、電解メッキにおける銅メッキ材料とし
て好適に用いることができる。そしてこの銅粉を銅メッ
キ材料として電解メッキを行うと、良好なメッキ処理を
行うことができる。As described above, according to the present invention, since the copper powder has a large specific surface area and a large dissolving power in the electrolytic solution containing divalent iron ions, it is preferably used as a copper plating material in electrolytic plating. be able to. When electrolytic plating is performed using this copper powder as a copper plating material, good plating processing can be performed.
【図１】本発明のメッキ方法に用いられるメッキ装置の
一例を示す構成図である。FIG. 1 is a configuration diagram showing an example of a plating apparatus used in a plating method of the present invention.
【図２】本発明のメッキ方法に用いられる炭酸銅又は酸
化銅の還元装置の一例を示す構成図である。FIG. 2 is a configuration diagram showing an example of a copper carbonate or copper oxide reducing apparatus used in the plating method of the present invention.
【図３】炭酸銅及び／又は酸化銅の製造方法を説明する
ための工程図である。FIG. 3 is a process drawing for explaining a method for producing copper carbonate and / or copper oxide.
【図４】本発明の銅粉の分析結果を示す特性図である。FIG. 4 is a characteristic diagram showing an analysis result of the copper powder of the present invention.
【図５】本発明の銅粉の分析結果を示す特性図である。FIG. 5 is a characteristic diagram showing an analysis result of the copper powder of the present invention.
１ 電解槽 １１ 不溶性陽極 １２ 陰極 ２ 溶解槽 ２２ ホッパ ３１，３２ 供給ライン ４ 水素還元炉 ４１ 石英管 ４２ 磁性ボート ４３ ヒータ ５ 反応槽 ６ ロータリキルン ６３ 洗浄槽 1 electrolysis tank 11 Insoluble anode 12 cathode 2 Melting tank 22 hoppers 31,32 supply line 4 Hydrogen reduction furnace 41 quartz tube 42 Magnetic Boat 43 heater 5 reaction tanks 6 rotary kiln 63 washing tank
Claims (18)
設けられ、２価の鉄イオンと銅イオンとを含む電解液を
用いて電気分解を行ない、陰極をなす被メッキ体に銅を
析出させ、２価の鉄イオンを３価の鉄イオンに酸化する
銅メッキ処理工程と、 前記銅メッキ処理工程にて得られた３価の鉄イオンを含
む電解液に銅を溶解させて、２価の鉄イオンと銅イオン
とを含む電解液を生成する還元工程と、 前記還元工程にて得られた２価の鉄イオンと銅イオンと
を含む電解液を電解槽に供給させる工程と、を備えた銅
メッキ方法において、還元工程で電解液に溶解される銅
粉であって、 この銅粉は、粒子径が５ｍｍ以下の大きさの銅粉を主成
分として含むことを特徴とする銅メッキ方法に使用され
る銅粉。1. An insoluble anode and an object to be plated forming a cathode are provided, electrolysis is performed using an electrolytic solution containing divalent iron ions and copper ions, and copper is deposited on the object to be plated forming the cathode. Then, the copper plating treatment step of oxidizing the divalent iron ions into the trivalent iron ions, and dissolving the copper in the electrolytic solution containing the trivalent iron ions obtained in the copper plating treatment step, and divalent And a step of supplying the electrolytic solution containing the divalent iron ion and the copper ion obtained in the reducing step to the electrolytic cell. In the copper plating method, the copper powder is dissolved in an electrolytic solution in a reducing step, and the copper powder contains copper powder having a particle size of 5 mm or less as a main component. Copper powder used for.
きさの銅粉を主成分として含むことを特徴とする請求項
１記載の銅メッキ方法に使用される銅粉。2. The copper powder used in the copper plating method according to claim 1, wherein the copper powder contains copper powder having a particle size of 50 mesh or less as a main component.
きい銅粉を主成分として含むことを特徴とする請求項１
又は２記載の銅メッキ方法に使用される銅粉。3. The copper powder contains copper powder having a particle size of 250 mesh or more as a main component.
Alternatively, a copper powder used in the copper plating method described in 2.
粉、置換析出銅粉、銅化合物の還元粉のいずれかを含む
ことを特徴とする請求項１ないし３のいずれかに記載の
銅メッキ方法に使用される銅粉。4. The copper according to claim 1, wherein the copper powder contains any one of electrolytic copper powder, atomized copper powder, substitution deposited copper powder, and copper compound reduced powder. Copper powder used for plating method.
砕処理して得られる銅粉であることを特徴とする請求項
１ないし３のいずれかに記載の銅メッキ方法に使用され
る銅粉。5. The copper plating method according to claim 1, wherein the copper powder is a copper powder obtained by pulverizing electrolytic copper and / or copper wire. Copper powder.
きさの銅粉の代わりに、炭酸銅及び／又は酸化銅を１０
０℃〜４００℃に加熱しながら還元して得た銅粉を含む
ことを特徴とする請求項２記載の銅メッキ方法に使用さ
れる銅粉。6. The copper powder contains copper carbonate and / or copper oxide in an amount of 10 in place of the copper powder having a particle size of 50 mesh or less.
The copper powder used in the copper plating method according to claim 2, comprising a copper powder obtained by reducing while heating to 0 ° C to 400 ° C.
たは硝酸銅の水溶液とアルカリ金属、アルカリ土類金属
またはＮＨ4 の炭酸塩の水溶液とを混合して加熱しなが
ら反応させ、これにより析出した反応生成物を分離して
得たものであることを特徴とする請求項６記載の銅メッ
キ方法に使用される銅粉。7. The copper carbonate according to claim 6, wherein an aqueous solution of copper chloride, copper sulfate or copper nitrate and an aqueous solution of an alkali metal, alkaline earth metal or NH4 carbonate are mixed and reacted with heating. 7. The copper powder used in the copper plating method according to claim 6, which is obtained by separating the reaction product deposited by.
気とはならない雰囲気下で加熱して熱分解することによ
り生成されたものであることを特徴とする請求項６又は
７記載の銅メッキ方法に使用される銅粉。8. The copper oxide according to claim 6 is produced by heating copper carbonate in an atmosphere that does not become a reducing atmosphere to thermally decompose the copper carbonate. Copper powder used for copper plating method.
徴とする請求項１ないし８のいずれかに記載の銅メッキ
方法に使用される銅粉。9. The copper powder used in the copper plating method according to claim 1, wherein the copper powder does not contain a surface treatment agent.
が設けられ、２価の鉄イオンと銅イオンとを含む電解液
を用いて電気分解を行ない、陰極をなす被メッキ体に銅
を析出させ、２価の鉄イオンを３価の鉄イオンに酸化す
る銅メッキ処理工程と、 前記銅メッキ処理工程にて得られた３価の鉄イオンを含
む電解液に銅を溶解させて、２価の鉄イオンと銅イオン
とを含む電解液を生成する還元工程と、 還元工程にて得られた２価の鉄イオンと銅イオンとを含
む電解液を電解槽に供給させる工程と、を備えた銅メッ
キ方法において、 粒子径５ｍｍ以下の大きさの銅粉を主成分として含む銅
粉を、前記還元工程で電解液に溶解される銅粉として使
用することを特徴とする銅粉の使用方法。10. An insoluble anode and an object to be plated forming a cathode are provided, electrolysis is performed using an electrolytic solution containing divalent iron ions and copper ions, and copper is deposited on the object to be plated forming the cathode. Then, the copper plating treatment step of oxidizing the divalent iron ions into the trivalent iron ions, and dissolving the copper in the electrolytic solution containing the trivalent iron ions obtained in the copper plating treatment step, and divalent And a step of supplying the electrolytic solution containing the divalent iron ion and the copper ion obtained in the reducing step to the electrolytic cell. In the copper plating method, a copper powder containing, as a main component, a copper powder having a particle diameter of 5 mm or less is used as the copper powder dissolved in the electrolytic solution in the reducing step.
を主成分として含む銅粉を、前記還元工程で電解液に溶
解される銅粉として使用することを特徴とする請求項１
０記載の銅粉の使用方法。11. The copper powder containing copper powder having a particle size of 50 mesh or less as a main component is used as the copper powder dissolved in the electrolytic solution in the reducing step.
The method of using the copper powder according to 0.
主成分として含む銅粉を、前記還元工程で電解液に溶解
される銅粉として使用することを特徴とする請求項１０
又は１１記載の銅粉の使用方法。12. The copper powder containing, as a main component, a copper powder having a particle size of more than 250 mesh is used as the copper powder dissolved in the electrolytic solution in the reducing step.
Or the method of using the copper powder according to item 11.
粉、置換析出銅粉、銅化合物の還元粉のいずれかを含む
ことを特徴とする請求項１０ないし１２のいずれかに記
載の銅粉の使用方法。13. The copper according to claim 10, wherein the copper powder contains any one of electrolytic copper powder, atomized copper powder, substitution deposited copper powder, and reduced powder of copper compound. How to use the powder.
粉砕処理して得られる銅粉であることを特徴とする請求
項１０ないし１３のいずれかに記載の銅メッキ方法に使
用される銅粉。14. The copper plating method according to claim 10, wherein the copper powder is a copper powder obtained by pulverizing electrolytic copper and / or copper wire. Copper powder.
の代わりに、炭酸銅及び／又は酸化銅を１００℃〜４０
０℃に加熱しながら還元して得た銅粉を還元工程にて電
解液に溶解させることを特徴とする請求項１１記載の銅
粉の使用方法。15. Instead of copper powder having a particle size of 50 mesh or less, copper carbonate and / or copper oxide is used at 100 ° C. to 40 ° C.
The method of using copper powder according to claim 11, wherein the copper powder obtained by reducing while heating to 0 ° C is dissolved in the electrolytic solution in the reducing step.
銅または硝酸銅の水溶液とアルカリ金属、アルカリ土類
金属またはＮＨ4 の炭酸塩の水溶液とを混合して加熱し
ながら反応させ、これにより析出した反応生成物を分離
して得たものであることを特徴とする請求項１５記載の
銅粉の使用方法。16. The copper carbonate according to claim 15, wherein an aqueous solution of copper chloride, copper sulfate or copper nitrate and an aqueous solution of alkali metal, alkaline earth metal or NH4 carbonate are mixed and reacted with heating, 16. The method for using copper powder according to claim 15, wherein the reaction product precipitated by the above is separated and obtained.
雰囲気とはならない雰囲気下で加熱して熱分解すること
により生成されたものであることを特徴とする請求項１
５又は１６記載の銅粉の使用方法。17. The copper oxide according to claim 15 is produced by heating copper carbonate in an atmosphere which does not become a reducing atmosphere and thermally decomposing it.
The method of using the copper powder according to 5 or 16.
特徴とする請求項１０ないし１７のいずれかに記載の銅
粉の使用方法。18. The method of using a copper powder according to claim 10, wherein the copper powder does not contain a surface treatment agent.
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| JP2002262713A JP2003166100A (en) | 2001-09-21 | 2002-09-09 | Copper powder used for copper plating, and method for using copper powder |
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|---|---|---|---|
| JP2001-288640 | 2001-09-21 | ||
| JP2001288640 | 2001-09-21 | ||
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