JPH0225431B2 - - Google Patents
Info
- Publication number
- JPH0225431B2 JPH0225431B2 JP58166674A JP16667483A JPH0225431B2 JP H0225431 B2 JPH0225431 B2 JP H0225431B2 JP 58166674 A JP58166674 A JP 58166674A JP 16667483 A JP16667483 A JP 16667483A JP H0225431 B2 JPH0225431 B2 JP H0225431B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- powder
- core material
- aqueous suspension
- electroless plating
- 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.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 63
- 239000011162 core material Substances 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 26
- 239000007900 aqueous suspension Substances 0.000 claims description 24
- 238000007772 electroless plating Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
Description
本発明は粉粒状芯材に無電解メツキすることに
関し、その目的とするところは、芯材表面に均一
で任意の厚さのメツキ皮膜を付与した物品を提供
することにある。
一般に、無電解メツキはその技術の進歩と用途
の開発によつて、今日では有機または無機の材質
を問わないことは勿論、その形状や大きさも関係
なく、適用されている。とは云え多くの場合、基
材は板状または成型体が多く、粉末または粒状の
芯材についてはその用途開発が新しいだけに最近
のことであつて、確立された製造方法はなく、僅
かに従来の一般的方法に従つて処理されているの
が現状である。
即ち、無電解メツキする場合通常、予め調製さ
れたメツキ液に被メツキ基材を浸漬して予め推測
により定められた時間反応させた後、反応を停止
させる方法がとられている。
被メツキ基材が粉末または粒状体についても、
上記と同様な方法が採られるがこの場合は速やか
にメツキ液に添加してメツキを施し、反応後はメ
ツキ液の過、急冷または希釈等の停止を行なわ
なければならない。
基材が粉粒体（粉末または粉状体）である場合
は他の基材に比して著しく比表面積が大きいため
メツキ反応速度が異常に速い。
従つてメツキ液のPHや各成分の変動も激しいの
でPHの調節や各成分の補給によりメツキ液を安全
に保持することは極めて困難であるのみならず、
その度にめつき速度も不定となる。
他方、粉粒体を一挙によくメツキ液に投入でき
れば問題はないが時間をかけて投入した場合始め
と終りとではメツキ皮膜の膜厚に差が生じ不均一
となる。
特に、粉粒体をメツキする場合に問題なのは凝
集した二次粒子にメツキ皮膜が施されるとその使
用に際して、二次粒子が壊われて未被覆面の露出
による被覆の欠陥が現われる。
従つて粉粒体をメツキする場合には可能な限
り、二次粒子の少ない状態によく分散したものに
メツキ皮膜を施すことが最も重要なことになる
が、従来の方法では全く期待できないものであつ
た。
このような粉粒体の微細粒子をメツキするに際
して上記の事実を鑑み、本発明者は、鋭意研究し
たところ、芯材を分散させた懸濁体にメツキ液を
添加することにより所望のメツキ皮膜が形成され
ることの知見に基づいて本発明を完成した。
すなわ本発明は、粉粒状芯材に無電解メツキを
するに当り粉粒状芯材を分散させた水性懸濁体に
無電解メツキ液を制抑して添加しながら、該芯材
を無電解メツキすることを特徴とする粉粒体メツ
キ品の製造法である。
本発明において、無電解メツキに供せられる基
材としての粉粒状芯材というのはその粒子径は特
に限定するものではなく、コロイド状微粒子から
数mm程度の粒子まで外観上粉末状態または粉粒体
のいずれでもよい。またその形状を顕微鏡的観察
によつて球状、板状、棒状、針状、中空状または
繊維状のいずれの形状であつてもよい。要するに
被メツキ基材が外観上粒状または粉状として扱れ
ているものを芯材として対象とするものである。
また芯材の材質は、有機質又は無機質を問わず無
電解メツキ可能な材質は全て包含する。尤も、芯
材は当然のことながら、実質的に水不溶性または
水難溶性でなければならない。また、芯材は化学
的に均一な組成であることを要しないのはもちろ
んであるが、それが結晶質または非晶質のいずれ
であつてもよい。重要なことは、芯の表面が化学
的にメツキ液と反応して皮膜の形成能であること
であり、外観上、粉状ないし粒状であるというこ
とである。
かかる芯材を例示的に列挙すれば、無機芯材と
しては、金属粉末、金属または非金属の酸化物
（含水物も含む）、アルミノ珪酸塩を含む金属珪酸
塩、金属炭化物、金属窒化物、金属炭酸塩、金属
硫酸塩、金属燐酸塩、金属硫化物、金属酸塩、金
属ハロゲン化物または炭素などであり、有機芯材
としては天然繊維、天然樹脂、ポリエチレン、ポ
リプロピレン、ポリ塩化ビニル、ポリスチレン、
ポリブテン、ポリアミド、ポリアクリル酸エステ
ル、ポリアクリルニトリル、ポリアセタアール、
アイオノマー、ポリエステルなどの熱可塑性樹
脂、アルキツド樹脂、フエノール樹脂、尿素樹
脂、メラミン樹脂、キシレン樹脂、シリコーン樹
脂またはジアリルフタレート樹脂の如き熱硬化性
樹脂などがあげられる。それらは、一種または二
種以上の混合物であつてもよい。この混合物とい
うのは化学的に組成が不均質のものから芯材とし
て混合物であるいずれの場合も含むものである。
かかる芯材表面上に無電解メツキするに当りま
ず、よく分散された水性懸濁体を調製する。ここ
に水性懸濁体というのは媒体が水は勿論であるが
実質的に、無電解メツキが生じない濃度の薄い無
電解メツキ液のいずれかが適当である。
水懸濁体の分散性は芯材の物性によつて異なる
ので、分散方法は、適宜所望の手段、例えば、通
常撹拌から高速撹拌、あるいはコロイドミルまた
はホモジナイザーの如きセン断分散装置を通過さ
せたセン断分散、その他超音波分散などを用い、
芯材のアグロメレートをできるだけ除去した一次
粒子に近い分散状態の水性懸濁体を調製すること
が望ましい。なお芯材を分散させるに際し例え
ば、苛性アルカリ、珪酸ソーダ等のアルカリ、ポ
リリン酸アルカリ、または界面活性剤などの分散
剤を必要に応じて用いることができる。水性懸濁
体の濃度は、特に限定する理由はないが、スラリ
ー濃度が低いとメツキ濃度が低下するので処理容
量が大となるから経済的でなく、また、逆にその
濃度が濃くなると芯材の分散性が悪くなるので芯
材の物性に応じ適宜所望のスラリー濃度に設定す
ればよいが、多くの場合50ｇ／〜700ｇ／好
ましくは100ｇ／〜500ｇ／の範囲にある。ま
たこの懸濁体中の芯材をメツキするに当り、メツ
キが効果的に実施されるべく懸濁体の温度をメツ
キ可能温度に予め調節しておくことが望ましい。
なお、これら芯材をメツキ処理するに当り、予
め洗浄、エツチング、増感および活性化処理など
芯材の物性に応じた前処理を施すことは云うまで
もない。この前処理も前記の如く水性懸濁体にし
て行うことが好ましいが、その他の方法で行つて
も差支えない。
例えば洗浄処理はアルカリ剤で行い増感処理は
可溶性第１錫塩水溶液にて行い、更に活性化処理
は可溶性パラジウム塩水溶液にて、それぞれ芯材
と接触処理することにより前処理すればよいが、
これらは既に公知のことであり、本発明において
格別の前処理を行う必要はない。
従つて水性懸濁体は、前処理操作の一部または
全部の操作の過程で調整する場合、予め何らかの
手段で前処理したものを水性懸濁体として調製す
るかまたは調製した水性懸濁体について前処理操
作を施し、次いでその懸濁体をメツキ処理に移行
させる場合など、前処理と懸濁体の調製との兼ね
合いで、幾つかの態様があげられるが、それは、
実際の操作と芯材との関係において適合した合理
的な態様を適宜選定して行えばよい。
かくして調製された水性懸濁体に無電解メツキ
液の制御しながら添加する。懸濁体には分散状態
が保たれるよう、必要に応じた、撹拌、超音波分
散処理などを与えておくことが望ましく、また温
度も制御できるように設定しておくことが望まし
い。無電解メツキ液は、水性懸濁体に添加してそ
の容量の大小に応じて稀釈されるために、通常の
メツキ液濃度の浴に被メツキ基材を浸漬処理して
メツキ操作を行うのと異なり、通常のメツキ液濃
度よりも濃い方がよい。
ここで無電解メツキ液を制御しながら添加する
というのは液濃度と共に添加速度がメツキ反応に
直接的に影響し、また、この要素は芯材の物性特
に表面特性にも著しく関係するのでこれらの要素
を十分に考慮した上で、メツキむらの生じないよ
う均一かつ強固なメツキ皮膜を形成させるために
メツキ液の添加速度を設定するということであり
多くの場合徐々に添加する方がよい。
また、このメツキ液の添加と共に多くの場合要
すれば、水性懸濁体のPH調整のため、アルカリ剤
を個別的かつ同時に添加することが望ましい。こ
の理由はメツキ液の添加によつてメツキ反応が進
行し、液中の次亜リン酸ソーダの如き還元剤が酸
化されるに従つて水素イオン濃度が増加し、次第
に水性懸濁体のPHが低下することによる。それ故
当初に設定したPHを一定に保持するためにメツキ
液とPH調整剤とを上記の如く併行して添加するの
がよい。添加方法はPH計をコントロールしなが
ら、添加する方法もよいが、還元剤の酸化還元反
応に見合つた量のアルカリ量を所定の濃度にして
添加することでもよい。
このようにして、無電解メツキを水性懸濁体に
制御して添加することにより懸濁体中で速やかな
メツキ反応が生じ分散した芯材表面に均一かつ強
固なメツキ皮膜が形成されてゆく。従つて、添加
量に応じてメツキ皮膜の膜厚を調節することがで
き、用途に応じて、添加量は設定すればよい。
本発明にかかる方法において適用されるメツキ
皮膜は特に限定なく、従来知られている無電解メ
ツキはすべて適用でき、例えば、代表的にはニツ
ケルメツキ、コバルトメツキ、銅メツキ、合金メ
ツキ、金メツキ、銀メツキなどがあげられる。
かくして、本発明にかかる方法によれば粉末ま
たは粒状の芯材について実質的に一次粒状に近い
状態で均一なメツキ皮膜を付与することができ、
またその膜厚は精度よく自由に設定することがで
きる。
他方、メツキ操作の面からみるとメツキ反応は
完全に停止するまで行われるのでメツキ薬剤を効
率よく使用できること、メツキ雰囲気が安定して
いるので各成分濃度の適節が不要であるのみなら
ずPHの変動も実質的に回避できその為の調整装置
も特に必要としないなど従来法に比べて数々の利
点があげられる。
本発明にかかるメツキ品は、例えば電導性顔料
として塗料分野、あるいは電磁遮蔽用樹脂に添加
する導電材、各種粉末冶金材料、その他複合材
料、触媒として有用である。
実施例 １
平均粒径5μのα−Al2O3粉末100ｇについてニ
ツケルメツキを次の方法で行つて、粉末メツキ品
を製造した。
前処理操作：塩化第１錫１ｇ／および塩酸１
ml／の水溶液１に試料粉末を添加し、常温で
５分間撹拌する。次いで過洗浄して増感処理し
た。次いで塩化パラジウム0.1ｇ／、塩酸0.1
ml／水溶液１に前記処理物を投入して常温で
５分間撹拌して芯材の活性化処理を行つた後過
洗浄して前処理を行つた。次いでこの前処理を行
つた試料を65℃に加温した脱塩水200mlに添加し
て充分にアグロメレートの分散が達成されるよう
に撹拌して水性懸濁体を調製した。次いで無電解
ニツケルメツキ液（硫酸ニツケル：180ｇ／、
次亜リン酸ソーダ：218ｇ／、エチレンジアミ
ン：20ｇ／、PH：7.0）１を50ml／分および
164ｇ／の苛性ソーダ水溶液500mlを25ml／分の
割合で撹拌下の上記水性懸濁体に個別かつ同時に
添加し、添加終了後は水素の発生が停止するまで
65℃に保持しながら撹拌を続けた。
かくして、メツキ反応により、α−Al2O3粒子
表面に均一かつ強固なニツケル皮膜のある粉末を
得た。
実施例 ２
平均粒径20μのフエノール系樹脂粉末（ベルパ
ール、鐘紡社製商標名）50ｇについて実施例１と
同じ条件で前処理を行つた後、実施例１で用いた
老化メツキ液（硫酸ニツケル：0.7ｇ／、次亜
リン酸ソーダ：０ｇ／、エチレンジアミン：16
ｇ／、亜リン酸ソーダ：210ｇ／、硫酸ソー
ダ：81ｇ／）200mlに分散させて70℃に加温し
十分撹拌分散させて水性懸濁体を調製した。次い
で、実施例１と同一組成の濃厚ニツケルメツキ液
１および苛性ソーダ500mlを上記懸濁体へ撹拌
下それぞれ50ml／分および25ml／分の割合で個別
が同時に添加してメツキ操作を行い添加終了後
は、水素の発生が停止したところで保温と撹拌を
終了させてメツキ反応終了させた。
かくして、粒子径の揃つた均一なニツケル皮膜
のあるフエノール系樹脂粉末を得た。
実施例 ３
平均粒径50μの中空ガラスビース30ｇを実施例
１と同一条件で前処理した後、85℃に加温した脱
塩水200mlに分散させて十分撹拌して水性懸濁体
を調製した。次いで、濃厚ニツケルメツキ液（硫
酸ニツケル：150ｇ／、次亜リン酸ソーダ：180
ｇ／、クエン酸ソーダ：25ｇ／、酢酸ソー
ダ：15ｇ／）１および実施例１と同じ苛性ソ
ーダ水溶液500mlを上記懸濁体の撹拌下にそれぞ
れ50ml／分および25ml／分の割合で個別かつ同時
に添加し、添加終了後は、水素の発生が終了した
ところでメツキ操作を終了させた。
かくして粒径の揃つた均質なニツケル皮膜を付
与したガラスビーズを得た。
実施例 ４〜８
被メツキ基材である各種の芯材を実施例１と全
く同じ条件で前処理したものについて、水性懸濁
体を調製してメツキ液とアルカリ剤を個別かつ同
時に添加してそれぞれメツキ処理したが、その条
件と結果は第１表および第２表の如くであつた。
The present invention relates to electroless plating of a powdery core material, and its purpose is to provide an article having a uniform plating film of any thickness on the surface of the core material. In general, due to the advancement of technology and the development of applications, electroless plating is now applied regardless of the material, organic or inorganic, and regardless of its shape or size. However, in many cases, the base material is plate-shaped or molded, and the use of powdered or granular core materials has only recently been developed, and there is no established manufacturing method. Currently, it is processed according to conventional general methods. That is, when performing electroless plating, a method is generally used in which the substrate to be plated is immersed in a plating solution prepared in advance, allowed to react for a predetermined time, and then the reaction is stopped. Even if the base material to be plated is powder or granular,
The same method as above is used, but in this case, it must be added to the plating solution immediately to perform plating, and after the reaction, the plating solution must be stopped by filtration, rapid cooling, dilution, etc. When the base material is a granular material (powder or granular material), the plating reaction rate is abnormally fast because the specific surface area is significantly larger than that of other base materials. Therefore, since the PH and each component of the plating solution fluctuate rapidly, it is not only extremely difficult to maintain the plating solution safely by adjusting the PH and replenishing each component.
Each time, the plating speed becomes unstable. On the other hand, if the powder and granules can be added to the plating solution all at once, there is no problem, but if the powder is added over time, there will be a difference in the thickness of the plating film between the beginning and the end, resulting in non-uniformity. Particularly, when plating powder or granules, a problem is that if a plating film is applied to aggregated secondary particles, the secondary particles will be broken during use and coating defects will appear due to exposure of the uncoated surface. Therefore, when plating powder or granular materials, it is most important to apply a plating film to a well-dispersed material with as few secondary particles as possible, but this cannot be expected at all with conventional methods. It was hot. In view of the above facts when plating such fine particles of powder or granular materials, the present inventor conducted extensive research and found that a desired plating film can be obtained by adding a plating liquid to a suspension in which a core material is dispersed. The present invention was completed based on the knowledge that . In other words, in the present invention, when performing electroless plating on a powdery core material, the core material is electrolessly plated while suppressing and adding an electroless plating liquid to an aqueous suspension in which the powdery core material is dispersed. This is a method for producing plated powder products characterized by plating. In the present invention, the particle size of the powder core material used as a base material to be subjected to electroless plating is not particularly limited, and may range from colloidal fine particles to particles of several millimeters in size, and may be powdery or powdery in appearance. Any part of the body is fine. Further, the shape may be determined by microscopic observation to be spherical, plate-like, rod-like, needle-like, hollow, or fibrous. In short, the core material is a base material to be plated that can be treated as granular or powdery in appearance.
Moreover, the material of the core material includes all materials that can be electrolessly plated, regardless of whether they are organic or inorganic. Of course, the core material must be substantially water-insoluble or sparingly water-soluble. Furthermore, it goes without saying that the core material does not need to have a chemically uniform composition, but it may be either crystalline or amorphous. What is important is that the surface of the core has the ability to chemically react with the plating solution to form a film, and that it has a powdery or granular appearance. Examples of such core materials include metal powders, metal or nonmetal oxides (including hydrated materials), metal silicates including aluminosilicates, metal carbides, and metal nitrides. , metal carbonate, metal sulfate, metal phosphate, metal sulfide, metal acid salt, metal halide, or carbon, and organic core materials include natural fiber, natural resin, polyethylene, polypropylene, polyvinyl chloride, polystyrene,
Polybutene, polyamide, polyacrylic ester, polyacrylonitrile, polyacetaal,
Examples include thermoplastic resins such as ionomers and polyesters, thermosetting resins such as alkyd resins, phenolic resins, urea resins, melamine resins, xylene resins, silicone resins, and diallyl phthalate resins. They may be one type or a mixture of two or more types. This mixture includes anything from chemically heterogeneous compositions to mixtures used as core materials. In performing electroless plating on the surface of such a core material, first a well-dispersed aqueous suspension is prepared. Here, the aqueous suspension is not limited to water as a medium, but it is suitable to use any electroless plating solution having a low concentration that does not substantially cause electroless plating. Since the dispersibility of the aqueous suspension differs depending on the physical properties of the core material, the dispersion method may be determined by any desired means, such as normal stirring, high-speed stirring, or passing through a shear dispersion device such as a colloid mill or homogenizer. Using shear dispersion, other ultrasonic dispersion, etc.
It is desirable to prepare an aqueous suspension in a state of dispersion close to that of primary particles, with the agglomerates of the core material removed as much as possible. In addition, when dispersing the core material, a dispersant such as a caustic alkali, an alkali such as sodium silicate, an alkali polyphosphate, or a surfactant may be used as necessary. There is no particular reason to limit the concentration of the aqueous suspension, but if the slurry concentration is low, the plating concentration will be low and the processing capacity will be large, making it uneconomical. Since the dispersibility of the slurry becomes poor, the slurry concentration may be appropriately set to a desired value depending on the physical properties of the core material, but in most cases it is in the range of 50 g/-700 g/preferably 100 g/-500 g/. Further, when plating the core material in this suspension, it is desirable to adjust the temperature of the suspension in advance to a temperature that allows plating so that plating can be carried out effectively. It goes without saying that before plating these core materials, pretreatments such as cleaning, etching, sensitization, and activation treatments are performed in accordance with the physical properties of the core materials. Although this pretreatment is preferably carried out in the form of an aqueous suspension as described above, other methods may also be used. For example, the cleaning treatment may be performed with an alkaline agent, the sensitization treatment may be performed with a soluble tin salt aqueous solution, and the activation treatment may be pretreated with a soluble palladium salt aqueous solution by contact treatment with the core material.
These are already known, and there is no need for special pretreatment in the present invention. Therefore, when an aqueous suspension is prepared in the course of some or all of the pretreatment operations, the aqueous suspension must be pretreated by some means beforehand and then prepared as an aqueous suspension, or the aqueous suspension prepared There are several ways to balance the pretreatment and preparation of the suspension, such as when a pretreatment operation is performed and then the suspension is transferred to plating treatment.
It is sufficient to appropriately select a rational mode that is suitable for the actual operation and the relationship with the core material. An electroless plating solution is added in a controlled manner to the aqueous suspension thus prepared. It is desirable that the suspension be subjected to stirring, ultrasonic dispersion treatment, etc., as necessary, in order to maintain its dispersed state, and it is also desirable that the temperature be set so as to be controllable. Since the electroless plating solution is added to an aqueous suspension and diluted according to its volume, it is different from plating by immersing the substrate to be plated in a bath with a normal plating solution concentration. Differently, it is better to have a higher concentration than normal plating solution. The reason why the electroless plating solution is added in a controlled manner is that the addition rate as well as the solution concentration directly affect the plating reaction, and these factors are also significantly related to the physical properties, especially the surface properties, of the core material. The rate of addition of the plating solution is set after fully considering the factors in order to form a uniform and strong plating film to prevent uneven plating, and in many cases it is better to add the plating solution gradually. In addition, in many cases, it is desirable to add an alkaline agent separately and simultaneously with the addition of the plating solution in order to adjust the pH of the aqueous suspension, if necessary. The reason for this is that the plating reaction progresses with the addition of the plating liquid, and as the reducing agent such as sodium hypophosphite in the liquid is oxidized, the hydrogen ion concentration increases, and the pH of the aqueous suspension gradually increases. By decreasing. Therefore, in order to maintain the initially set pH constant, it is preferable to add the plating solution and the pH adjuster simultaneously as described above. The addition method may be one in which the alkali is added while controlling the PH meter, but it is also possible to add the alkali in an amount commensurate with the redox reaction of the reducing agent at a predetermined concentration. In this way, by adding electroless plating to the aqueous suspension in a controlled manner, a rapid plating reaction occurs in the suspension, forming a uniform and strong plating film on the surface of the dispersed core material. Therefore, the thickness of the plating film can be adjusted depending on the amount added, and the amount added can be set depending on the application. The plating film applied in the method of the present invention is not particularly limited, and all conventionally known electroless platings can be applied. For example, typical examples include nickel plating, cobalt plating, copper plating, alloy plating, gold plating, and silver plating. Examples include Metsuki. Thus, according to the method of the present invention, a uniform plating film can be applied to a powder or granular core material in a state substantially close to the primary granular shape,
Further, the film thickness can be freely set with high precision. On the other hand, from the viewpoint of the plating operation, the plating reaction is carried out until it completely stops, so the plating chemical can be used efficiently, and since the plating atmosphere is stable, there is no need to adjust the concentration of each component, and the PH It has many advantages over conventional methods, such as substantially avoiding fluctuations in the amount of water and not requiring any special adjusting device for that purpose. The plated product according to the present invention is useful, for example, in the paint field as a conductive pigment, as a conductive material added to electromagnetic shielding resins, various powder metallurgical materials, other composite materials, and catalysts. Example 1 100 g of α-Al 2 O 3 powder with an average particle size of 5 μm was nickel-plated in the following manner to produce a powder-plated product. Pretreatment operation: 1 g of stannous chloride and 1 g of hydrochloric acid
Add the sample powder to 1/ml of the aqueous solution and stir for 5 minutes at room temperature. Then, it was overwashed and sensitized. Then palladium chloride 0.1g/, hydrochloric acid 0.1
The treated product was added to 1 ml/aqueous solution and stirred for 5 minutes at room temperature to activate the core material, followed by overwashing and pretreatment. Next, the pretreated sample was added to 200 ml of demineralized water heated to 65° C. and stirred to obtain sufficient agglomerate dispersion to prepare an aqueous suspension. Next, electroless nickel oxide liquid (nickel sulfate: 180g/,
Sodium hypophosphite: 218g/, ethylenediamine: 20g/, PH: 7.0) 1 at 50ml/min and
500 ml of 164 g/min of caustic soda aqueous solution were added separately and simultaneously to the above aqueous suspension under stirring at a rate of 25 ml/min until hydrogen evolution ceased after the addition was complete.
Stirring was continued while maintaining the temperature at 65°C. As a result of the plating reaction, a powder with a uniform and strong nickel film on the surface of the α-Al 2 O 3 particles was obtained. Example 2 50 g of phenolic resin powder (Bell Pearl, trade name manufactured by Kanebo Co., Ltd.) with an average particle size of 20 μm was pretreated under the same conditions as in Example 1, and then treated with the aged plating solution (nickel sulfate: 0.7g/, Sodium hypophosphite: 0g/, Ethylenediamine: 16
g/, sodium phosphite: 210 g/, sodium sulfate: 81 g/), heated to 70° C., and sufficiently stirred and dispersed to prepare an aqueous suspension. Next, a concentrated nickel plating solution 1 having the same composition as in Example 1 and 500 ml of caustic soda were individually added simultaneously to the above suspension at a rate of 50 ml/min and 25 ml/min, respectively, with stirring, and a plating operation was performed. After the addition was completed, When the generation of hydrogen ceased, the heating and stirring were terminated to complete the plating reaction. In this way, a phenolic resin powder having a uniform nickel film with a uniform particle size was obtained. Example 3 30 g of hollow glass beads with an average particle size of 50 μm were pretreated under the same conditions as in Example 1, and then dispersed in 200 ml of demineralized water heated to 85° C. and sufficiently stirred to prepare an aqueous suspension. Next, concentrated nickel liquid (nickel sulfate: 150 g/, sodium hypophosphite: 180
g/, sodium citrate: 25 g/, sodium acetate: 15 g/) 1 and 500 ml of the same caustic soda aqueous solution as in Example 1 were added separately and simultaneously to the above suspension at a rate of 50 ml/min and 25 ml/min, respectively, while stirring. However, after the addition was completed, the plating operation was terminated when hydrogen generation was completed. In this way, glass beads with uniform particle size and a homogeneous nickel film were obtained. Examples 4 to 8 Various core materials to be plated were pretreated under exactly the same conditions as in Example 1, an aqueous suspension was prepared, and a plating solution and an alkaline agent were added separately and simultaneously. Each was plated, and the conditions and results were as shown in Tables 1 and 2.
【表】【table】
【表】【table】
【表】
比較例
実施例１で用いたα−Al2O3粉末100ｇを実施
例１と同一の条件と方法で前処理した。
他方予め調製したニツケルメツキ浴（硫酸ニツ
ケル：25ｇ／、次亜リン酸ソーダ：30ｇ／、
エチレンジアミン16ｇ／：PH7.0）10を65℃
に加温し、撹拌状態にして、前記の粉末を一挙に
加えて10分間メツキ反応させた後速やかに過し
た。得られたメツキ粉末は明らかに凝集した二次
粒子にメツキされており、不揃の粒子のメツキ粉
末であつた。
なお、実施例及び比較例で得られたメツキ粉末
を試料ごとに10等分し、それぞれの粉末の金属分
を化学分析により定量したところ、下記の表の如
き結果が得られた。[Table] Comparative Example 100 g of α-Al 2 O 3 powder used in Example 1 was pretreated under the same conditions and method as in Example 1. On the other hand, pre-prepared nickel metal bath (nickel sulfate: 25g/, sodium hypophosphite: 30g/,
Ethylenediamine 16g/:PH7.0) 10 at 65℃
The powder was added all at once to the mixture, and the mixture was plated for 10 minutes, followed by rapid filtration. The resulting plating powder was clearly plated into agglomerated secondary particles, and was a plated powder with irregular particles. The plating powder obtained in Examples and Comparative Examples was divided into 10 equal parts for each sample, and the metal content of each powder was determined by chemical analysis, and the results shown in the table below were obtained.
Claims (1)
粒状芯材を分散させた水性懸濁体に無電解メツキ
液を制御して添加しながら、該芯材を無電解メツ
キすることを特徴とする粉粒体メツキ品の製造
法。 ２ 水性懸濁体は水または無電解メツキが実質的
に生じない濃度の無電解メツキ液を媒体とする懸
濁体である特許請求の範囲第１項記載の粉粒体メ
ツキ品の製造法。 ３ 水性懸濁体は無電解メツキの可能な温度に加
温されていることを特徴とする特許請求の範囲第
１項記載の粉粒体メツキ品の製造法。 ４ 無電解メツキがニツケルメツキであることを
特徴とする特許請求の範囲第１項記載の粉粒体メ
ツキ品の製造法。[Claims] 1. When performing electroless plating on a powdery core material, the core material is electrolessly plated while controlling and adding an electroless plating solution to an aqueous suspension in which the powdery core material is dispersed. A method for producing powder-plated products characterized by electrolytic plating. 2. The method for producing a powder plated product according to claim 1, wherein the aqueous suspension is a suspension using water or an electroless plating solution having a concentration that substantially does not cause electroless plating. 3. The method for producing a powder plated product according to claim 1, wherein the aqueous suspension is heated to a temperature that allows electroless plating. 4. The method for producing a powder plated product according to claim 1, wherein the electroless plating is nickel plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58166674A JPS6059070A (en) | 1983-09-12 | 1983-09-12 | Manufacture of plated fine grain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58166674A JPS6059070A (en) | 1983-09-12 | 1983-09-12 | Manufacture of plated fine grain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6059070A JPS6059070A (en) | 1985-04-05 |
| JPH0225431B2 true JPH0225431B2 (en) | 1990-06-04 |
Family
ID=15835617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58166674A Granted JPS6059070A (en) | 1983-09-12 | 1983-09-12 | Manufacture of plated fine grain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6059070A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61276979A (en) * | 1985-05-30 | 1986-12-06 | Nippon Chem Ind Co Ltd:The | Manufacture of nickel plated material |
| JPS62107073A (en) * | 1985-11-01 | 1987-05-18 | Nippon Chem Ind Co Ltd:The | Production of noble metal plated material |
| JPS6421082A (en) * | 1987-07-15 | 1989-01-24 | Nippon Chemical Ind | Production of powdery plated material |
| JPH01225776A (en) * | 1988-03-07 | 1989-09-08 | Mitsubishi Metal Corp | Silver-coated spherical phenolic resin powder |
| WO2009054387A1 (en) | 2007-10-22 | 2009-04-30 | Nippon Chemical Industrial Co., Ltd. | Coated conductive powder and conductive adhesive using the same |
| KR101505227B1 (en) | 2007-10-22 | 2015-03-23 | 니폰 가가쿠 고교 가부시키가이샤 | Coated conductive powder and conductive adhesive using the same |
| KR101586659B1 (en) | 2013-09-10 | 2016-01-20 | 한국기계연구원 | A Controlling Method of Oxidizing Film of High explosive characteristics |
| JP6863170B2 (en) * | 2016-12-21 | 2021-04-21 | 住友金属鉱山株式会社 | A method for measuring the plating treatment time of an electroless plating solution, a sample preparation method for preparing a sample for evaluating an electroless plating solution, and a method for evaluating an electroless plating solution. |
| KR102568485B1 (en) * | 2020-12-30 | 2023-08-21 | 한국수력원자력 주식회사 | Passive cooling device for cooling main control room of nuclear power plant |
-
1983
- 1983-09-12 JP JP58166674A patent/JPS6059070A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6059070A (en) | 1985-04-05 |
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