JP4802008B2 - Electroless plating solution and plating method - Google Patents
Electroless plating solution and plating method Download PDFInfo
- Publication number
- JP4802008B2 JP4802008B2 JP2006039552A JP2006039552A JP4802008B2 JP 4802008 B2 JP4802008 B2 JP 4802008B2 JP 2006039552 A JP2006039552 A JP 2006039552A JP 2006039552 A JP2006039552 A JP 2006039552A JP 4802008 B2 JP4802008 B2 JP 4802008B2
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- plating
- plating solution
- solution
- sulfoxide
- 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 - Fee Related
Links
- 238000007747 plating Methods 0.000 title claims description 94
- 238000007772 electroless plating Methods 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 19
- 239000002253 acid Substances 0.000 claims description 26
- 150000003462 sulfoxides Chemical class 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 8
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical class 0.000 claims description 5
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- 229910052759 nickel Inorganic materials 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 231100000481 chemical toxicant Toxicity 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012764 semi-quantitative analysis Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Description
本発明は、非水溶液を用いる置換型無電解メッキ法および無電解メッキ液に関する。 The present invention relates to a substitutional electroless plating method using a nonaqueous solution and an electroless plating solution.
電気材料、電子材料、および、それらの配線材料には、導電性の面から銅または銅合金が主として用いられている。通常、かかる材料では、銅または銅合金の表面酸化を防ぐために、バリヤーとして、その表面にニッケル下地メッキが施され、さらに、金メッキ処理または銀メッキ処理が施される。 From the viewpoint of conductivity, copper or copper alloys are mainly used for electric materials, electronic materials, and wiring materials thereof. Usually, in such a material, in order to prevent surface oxidation of copper or a copper alloy, a nickel base plating is applied to the surface as a barrier, and further, a gold plating process or a silver plating process is applied.
近年、電気部品や電子部品として使用される銅プリント配線基板では、配線ピッチが狭くなる傾向にある。従来の電解メッキでは、配線ピッチに限界があることから、必要な大きさの電極を、配線部に確保することが困難であることから、無電解メッキが多用されるようになっている。 In recent years, a copper printed wiring board used as an electrical component or an electronic component tends to have a narrow wiring pitch. In the conventional electrolytic plating, since there is a limit to the wiring pitch, it is difficult to secure an electrode having a required size in the wiring portion, and therefore, electroless plating is frequently used.
公知の無電解メッキ浴は、有毒なシアン化合物を用いるシアン系浴と、有毒なヒドラジンや次亜リン酸塩等の還元剤を必要とする還元型メッキである非シアン系浴とに区別される。また、無電解金メッキでは、添加剤としてタリウム化合物などの有毒な物質が使用される。 Known electroless plating baths are classified into cyan baths that use toxic cyan compounds and non-cyan baths that are reductive plating that requires reducing agents such as toxic hydrazine and hypophosphite. . In electroless gold plating, toxic substances such as thallium compounds are used as additives.
ニッケル下地メッキを施す方法としては、例えば、特開２００４−３５９９８６号公報に、次亜リン酸塩等を還元剤として使用する無電解メッキ法が記載されている。このような無電解メッキ法では、次亜リン酸塩由来のリンまたはホウ素等の不純物がニッケル下地メッキ層中に含有されてしまい、硬質クロムメッキ並みの高い硬度をニッケル下地メッキ層に付与することになる。従って、フレキシブルプリント配線板に適用した場合、ベース層の銅箔の硬度とニッケル下地メッキ層の硬度との違いが大きく、使用される際に折り曲げられて、ニッケル下地メッキ層にクラックが入ったり、剥離する等の不都合を生じる。 As a method for performing nickel base plating, for example, JP-A No. 2004-359986 describes an electroless plating method using hypophosphite or the like as a reducing agent. In such an electroless plating method, impurities such as phosphorus or boron derived from hypophosphite are contained in the nickel base plating layer, and the nickel base plating layer has a hardness as high as that of hard chrome plating. become. Therefore, when applied to a flexible printed wiring board, the difference between the hardness of the copper foil of the base layer and the hardness of the nickel base plating layer is large, it is bent when used, and the nickel base plating layer cracks, Inconvenience such as peeling occurs.
本発明は、かかる問題点に鑑みてなされたものであって、シアン化合物、タリウム化合物、ヒドラジンなどの有毒な化学物質を用いることなく、かつ、得られるメッキ層中に、リンまたはホウ素等の不純物を含有させることのない無電解メッキ液および無電解メッキ法を提供することを目的とする。 The present invention has been made in view of such problems, and does not use toxic chemicals such as cyanide, thallium, and hydrazine, and impurities such as phosphorus or boron in the obtained plating layer. An object of the present invention is to provide an electroless plating solution and an electroless plating method that do not contain selenium.
本発明に係る無電解メッキ液は、スルホキシドをメッキ液として用いる。 The electroless plating solution according to the present invention uses sulfoxide as a plating solution.
前記スルホキシドは、化学構造：Ｒ1−Ｓ（＝Ｏ）−Ｒ2（Ｒ1とＲ2はｎ＝１〜３のアルキル基である。Ｒ1とＲ2は同じアルキル基であっても、異なるアルキル基であってもよい。）を有するスルホキシド、または、テトラメチレンスルホキシド（Ｃ4Ｈ8ＳＯ）であり、特に、ジメチルスルホキシド（ＤＭＳＯ；（ＣＨ3）2ＳＯ）を用いることが好ましい。 The sulfoxide has a chemical structure: R 1 —S (═O) —R 2 (R 1 and R 2 are alkyl groups having n = 1 to 3; R 1 and R 2 may be the same alkyl group; A sulfoxide having a different alkyl group) or tetramethylene sulfoxide (C 4 H 8 SO), and particularly preferably dimethyl sulfoxide (DMSO; (CH 3 ) 2 SO).
メッキ金属のハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかが酸である場合には、これらの酸金属塩をスルホキシドからなるメッキ液に添加して、無電解メッキ液とする。その添加量は、無電解メッキ液の総量に対して、好ましくは、１ｇ／Ｌ〜１００ｇ／Ｌであり、より好ましくは、５ｇ／Ｌ〜８５ｇ／Ｌである。 When any of the plating metal halide, nitrate, acetate and citrate is an acid, these acid metal salts are added to a plating solution made of sulfoxide to form an electroless plating solution. The addition amount is preferably 1 g / L to 100 g / L, and more preferably 5 g / L to 85 g / L with respect to the total amount of the electroless plating solution.
一方、メッキ金属のハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかが酸ではない場合、これらの金属塩を、塩化アンモニウム（ＮＨ4Ｃｌ）、臭化アンモニウム（ＮＨ4Ｂｒ）、および、チオシアン酸アンモニウム（ＮＨ4ＳＣＮ）のいずれか１種とともに、スルホキシドからなるメッキ液に添加して、無電解メッキ液とする。その添加量は、金属塩および、塩化アンモニウム、臭化アンモニウム、および、チオシアン酸アンモニウムのいずれか１種のいずれについても、それぞれ、無電解メッキ液の総量に対して、好ましくは、１ｇ／Ｌ〜１００ｇ／Ｌであり、より好ましくは、５ｇ／Ｌ〜８５ｇ／Ｌである。 On the other hand, if any of the plating metal halides, nitrates, acetates and citrates is not an acid, these metal salts can be converted to ammonium chloride (NH 4 Cl), ammonium bromide (NH 4 Br), and Together with any one of ammonium thiocyanate (NH 4 SCN), it is added to a plating solution made of sulfoxide to form an electroless plating solution. The amount of the metal salt and any one of ammonium chloride, ammonium bromide, and ammonium thiocyanate is preferably 1 g / L to the total amount of the electroless plating solution, respectively. 100 g / L, more preferably 5 g / L to 85 g / L.
このように、スルホキシドをメッキ液とする無電解メッキ液を作製した後、該無電解メッキ液に被メッキ材料を浸漬すればよい。 Thus, after producing the electroless-plating liquid which uses sulfoxide as a plating solution, what is necessary is just to immerse a to-be-plated material in this electroless-plating liquid.
本発明の無電解メッキ法により得られるメッキ層は、メッキ金属のみからなり、不純物を含有するという従来のような不都合を生じない。また、従来の無電解メッキのように、有毒な化学物質を用いる必要がない。さらに、ヒドラジンまたは次亜リン酸塩などの還元剤を必要としない。 The plating layer obtained by the electroless plating method of the present invention is made only of a plating metal and does not cause the conventional disadvantage of containing impurities. Moreover, it is not necessary to use a toxic chemical substance unlike the conventional electroless plating. Furthermore, no reducing agent such as hydrazine or hypophosphite is required.
以上のように、本発明では、作業場および環境を汚染する可能性が低く、また、優れたメッキ特性を有する、高純度なメッキ層の形成が可能であり、工業的にきわめて有用である。 As described above, according to the present invention, there is a low possibility of contaminating the work place and the environment, and a high-purity plating layer having excellent plating characteristics can be formed, which is extremely useful industrially.
本発明者らは、上述の課題に対して、無電解メッキ法に用いることができるメッキ液の新たな材料を種々検討し、スルホキシドをメッキ液として用いることで、上記課題を解決できるとの知見を得た。 The present inventors have studied various new materials for plating solutions that can be used in the electroless plating method, and have found that the above problems can be solved by using sulfoxide as a plating solution. Got.
すなわち、本発明では、無電解メッキ法において、スルホキシドをメッキ液として用いることに特徴がある。 That is, the present invention is characterized in that sulfoxide is used as a plating solution in the electroless plating method.
スルホキシドは、一般式Ｒ2Ｓ＝Ｏ（Ｒはアルキル基またはアリール基）で表される化合物の総称である。本発明では、スルホキシドとして、化学構造：Ｒ1−Ｓ（＝Ｏ）−Ｒ2（Ｒ1とＲ2はｎ＝１〜３のアルキル基である。Ｒ1とＲ2は同じアルキル基であっても、異なるアルキル基であってもよい。）を有するスルホキシド、または、テトラメチレンスルホオキシド（Ｃ4Ｈ8ＳＯ）が用いられる。 Sulfoxide is a general term for compounds represented by the general formula R 2 S═O (R is an alkyl group or aryl group). In the present invention, as the sulfoxide, the chemical structure: R 1 —S (═O) —R 2 (R 1 and R 2 are alkyl groups having n = 1 to 3; R 1 and R 2 are the same alkyl group. Or a different alkyl group may be used) or tetramethylene sulfoxide (C 4 H 8 SO).
特に、合成繊維製造、医・農薬原料製造、食品添加物製造、染・顔料製造等に広く用いられ、ＬＳＩ、ＬＣＤ等を中心に、高純度および高品位が要求される電子部品関係の剥離液または洗浄液としても、大量に用いられているため、価格的に最も安価なジメチルスルホオキシド（ＤＭＳＯ；（ＣＨ3）2ＳＯ）を用いることが、工業的に好ましい。 In particular, it is widely used for synthetic fiber production, medical / agrochemical raw material production, food additive production, dyeing / pigment production, etc., and it is a stripping solution for electronic parts that require high purity and high quality, mainly LSI, LCD, etc. Alternatively, since the cleaning liquid is used in a large amount, it is industrially preferable to use dimethyl sulfoxide (DMSO; (CH 3 ) 2 SO), which is the cheapest in price.
本発明のメッキ原理は、メッキ材料と被メッキ材料との金属イオンの置換反応である。従って、均質で良好なメッキ層を得るには、被メッキ材料の金属がメッキ液中に溶解移行する速度と、メッキ液中からメッキ材料の金属イオンが被メッキ材料の表面に析出する速度とのバランスをとることが、重要な因子となる。 The plating principle of the present invention is a metal ion substitution reaction between a plating material and a material to be plated. Therefore, in order to obtain a uniform and good plating layer, the speed at which the metal of the plating material dissolves and moves into the plating liquid and the speed at which the metal ions of the plating material precipitate from the plating liquid on the surface of the plating material. Balancing is an important factor.
本発明では、メッキ材料であるハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかを、スルホキシドからなるメッキ液に添加することにより、無電解メッキ液を作製する。金属塩としては、工業的に最も入手が容易な塩化物を用いることが好ましい。 In the present invention, an electroless plating solution is prepared by adding any one of halide, nitrate, acetate, and citrate, which is a plating material, to a plating solution made of sulfoxide. As the metal salt, it is preferable to use a chloride which is most easily available industrially.
これらのハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかが酸である場合には、これらの酸金属塩を単独でスルホキシドからなるメッキ液に添加すれば、無電解メッキ液とすることができる。なお、ハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかの酸を単独で添加する場合には、添加後に１１０℃〜１２０℃の温度で加熱することが必要とされる。これは、メッキ反応を促進させるためである。 When any of these halides, nitrates, acetates, and citrates is an acid, an electroless plating solution can be obtained by adding these acid metal salts alone to a plating solution made of sulfoxide. it can. In addition, when adding any one acid of a halide, nitrate, acetate, and a citrate, it is required to heat at the temperature of 110 to 120 degreeC after addition. This is to promote the plating reaction.
一方、上述の溶解移行速度と表面析出速度とのバランスの観点から、これらの金属塩が酸でない場合には、これらに加えて、塩化アンモニウム（ＮＨ4Ｃｌ）、臭化アンモニウム（ＮＨ4Ｂｒ）、および、チオシアン酸アンモニウム（ＮＨ4ＳＣＮ）のいずれか１種を、スルホキシドからなるメッキ液に添加することで、無電解メッキ液が得られる。 On the other hand, from the viewpoint of the balance between the dissolution transfer rate and the surface deposition rate, when these metal salts are not acids, in addition to these, ammonium chloride (NH 4 Cl), ammonium bromide (NH 4 Br) In addition, an electroless plating solution can be obtained by adding any one of ammonium thiocyanate (NH 4 SCN) to a plating solution made of sulfoxide.
また、上述のバランスの観点より、酸であるハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかの添加量は、無電解メッキ液の総量に対して、１ｇ／Ｌ〜１００ｇ／Ｌとすることが好ましく、５ｇ／Ｌ〜８５ｇ／Ｌとすることがさらに好ましい。 In addition, from the viewpoint of the above balance, the addition amount of any of halides, nitrates, acetates, and citrates that are acids is 1 g / L to 100 g / L with respect to the total amount of the electroless plating solution. It is preferably 5 g / L to 85 g / L, and more preferably.
一方、ハロゲン化物、硝酸塩、酢酸塩およびクエン酸塩のいずれかと、塩化アンモニウム、臭化アンモニウム、および、チオシアン酸アンモニウムのいずれか１種とを添加する場合、これらの添加量は、無電解メッキ液の総量に対して、それぞれ、１ｇ／Ｌ〜１００ｇ／Ｌとすることが好ましく、５ｇ／Ｌ〜８５ｇ／Ｌとすることがさらに好ましい。 On the other hand, when any one of halide, nitrate, acetate, and citrate and any one of ammonium chloride, ammonium bromide, and ammonium thiocyanate are added, these addition amounts are determined by electroless plating solution. The total amount is preferably 1 g / L to 100 g / L, and more preferably 5 g / L to 85 g / L.
１ｇ／Ｌ未満では、反応速度が遅くなって好ましくなく、１００ｇ／Ｌを超えても効果が上がらないので好ましくない。また、実用上の観点から５ｇ／Ｌ〜８５ｇ／Ｌとすることが望ましい。 If it is less than 1 g / L, the reaction rate is undesirably slow, and if it exceeds 100 g / L, the effect does not increase. Moreover, it is desirable to set it as 5 g / L-85 g / L from a practical viewpoint.
メッキ層を合金層とするには、合金を構成する２種類以上の金属について、それぞれ、金属の塩化物を添加すればよい。メッキの最適条件はそれぞれのメッキ材料によって異なるが、被メッキ材料の表面にメッキ層を形成するためには、メッキ前処理が施された被メッキ材料を、５０〜１００℃の範囲に保たれた本発明に係る無電解メッキ液に２〜２０分間、浸漬すればよい。 In order to use the plating layer as an alloy layer, a metal chloride may be added to each of two or more kinds of metals constituting the alloy. The optimum plating conditions differ depending on the plating material, but in order to form a plating layer on the surface of the material to be plated, the material to be plated that has been pre-plated was kept in the range of 50 to 100 ° C. What is necessary is just to immerse in the electroless-plating liquid concerning this invention for 2 to 20 minutes.
（実施例１）
まず、厚さが１８μｍの電解銅箔に、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
Example 1
First, an electrolytic copper foil with a thickness of 18 μm was degreased and washed with an acidic degreasing solution, acid washed with a (1 + 1) aqueous hydrochloric acid solution, washed with water, then subjected to chemical polishing and washing, and then subjected to pretreatment for plating. .
次に、ジメチルスルホキシド（純度９９．９９％）に、塩化アンモニウムを２０ｇ／Ｌ、無水塩化ニッケルを６０ｇ／Ｌとなるように、それぞれ添加し、無電解メッキ液を作製した。 Next, dimethyl sulfoxide (purity 99.99%) was added with ammonium chloride at 20 g / L and anhydrous nickel chloride at 60 g / L to prepare an electroless plating solution.
該無電解メッキ液を８５℃〜９０℃に保ち、メッキ前処理を施した電解銅箔を該無電解メッキ液に、１０分間、浸漬し、表面にニッケルメッキ層を形成した。 The electroless plating solution was kept at 85 ° C. to 90 ° C., and the electrolytic copper foil subjected to the plating pretreatment was immersed in the electroless plating solution for 10 minutes to form a nickel plating layer on the surface.
得られたメッキ面を、ＥＰＭＡ−１６００（島津製作所製）を用いて、元素定性分析を行った。元素定性分析の結果を、図１に示す。 The obtained plated surface was subjected to element qualitative analysis using EPMA-1600 (manufactured by Shimadzu Corporation). The results of element qualitative analysis are shown in FIG.
また、該ＥＰＭＡを用いて、半定量分析を行った。測定結果は、検出される元素のＸ線強度から装置固有の相対感度曲線を用いて強度比を求めた後、合計が１００％となるように計算した（スタンダードレス法による）。計算結果を、図２に示す。 Moreover, semiquantitative analysis was performed using the EPMA. The measurement results were calculated so that the total would be 100% (by the standardless method) after obtaining the intensity ratio from the X-ray intensity of the detected element using a relative sensitivity curve unique to the apparatus. The calculation results are shown in FIG.
測定結果が示すように、リンまたはホウ素等の不純物は含有されておらず、純ニッケルからなるメッキ層が形成されていることが理解される。 As the measurement results show, it is understood that impurities such as phosphorus or boron are not contained, and a plating layer made of pure nickel is formed.
メッキ面のＳＥＭ写真を、Ｓ−８００（日立製作所製）を用いて撮影した。ＳＥＭ写真を、図３に示す。 An SEM photograph of the plated surface was taken using S-800 (manufactured by Hitachi, Ltd.). A SEM photograph is shown in FIG.
（実施例２）
まず、厚さが１ｍｍのニッケル板に、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
(Example 2)
First, a nickel plate having a thickness of 1 mm was degreased and washed with an acidic degreasing solution, acid washed with a (1 + 1) hydrochloric acid aqueous solution, washed with water, then subjected to chemical polishing and washing, thereby performing a plating pretreatment.
次に、ジメチルスルホキシド（純度９９．９９％）に、塩化金酸（ＨＡｕＣｌ4・４Ｈ2Ｏ）を１０ｇ／Ｌとなるように添加し、１１０℃〜１２０℃で３０分間の加熱処理を行い、無電解メッキ液を作製した。 Next, chloroauric acid (HAuCl 4 .4H 2 O) is added to dimethyl sulfoxide (purity 99.99%) so as to be 10 g / L, and heat treatment is performed at 110 ° C. to 120 ° C. for 30 minutes, An electroless plating solution was prepared.
該無電解メッキ液を６０℃に保ち、メッキ前処理を施したニッケル板を、該無電解メッキ液に、３分間、浸漬し、表面に金メッキ層を形成した。 The electroless plating solution was kept at 60 ° C., and the nickel plate subjected to the plating pretreatment was immersed in the electroless plating solution for 3 minutes to form a gold plating layer on the surface.
得られた金メッキ層の表面状態は良好で、メッキ厚みは、０．１μｍ〜０．１２μｍであった。 The surface condition of the obtained gold plating layer was good, and the plating thickness was 0.1 μm to 0.12 μm.
（実施例３）
まず、真鍮製の接点材料に、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
(Example 3)
First, a pre-plating treatment was performed on a brass contact material by degreasing and washing with an acidic degreasing solution, acid washing with a (1 + 1) aqueous hydrochloric acid solution, washing with water, chemical polishing and washing with water.
次に、ジメチルスルホキシド（純度９９．９９％）に、塩化アンモニウムを１５ｇ／Ｌ、塩化銀（ＡｇＣｌ）を１５ｇ／Ｌとなるように、それぞれ添加し、無電解メッキ液を作製した。 Next, dimethyl sulfoxide (purity 99.99%) was added with ammonium chloride at 15 g / L and silver chloride (AgCl) at 15 g / L to prepare an electroless plating solution.
該無電解メッキ液を７０℃に保ち、メッキ前処理を施した真鍮製の接点材料を該無電解メッキ液に、３分間、浸漬し、表面に銀メッキ層を形成した。 The electroless plating solution was kept at 70 ° C., and the contact material made of brass subjected to the plating pretreatment was immersed in the electroless plating solution for 3 minutes to form a silver plating layer on the surface.
得られた銀メッキ層の表面状態は良好で、粘着テープを用いて引き剥がし試験を３回、繰り返したが、銀メッキ層の剥離は見られなかった。銀メッキ層の厚みは、０．２μｍ〜０．２５μｍであった。 The surface condition of the obtained silver plating layer was good, and the peeling test was repeated three times using an adhesive tape, but no peeling of the silver plating layer was observed. The thickness of the silver plating layer was 0.2 μm to 0.25 μm.
メッキ面のＳＥＭ写真を、Ｓ−８００（日立製作所製）を用いて撮影した。ＳＥＭ写真を、図４に示す。 An SEM photograph of the plated surface was taken using S-800 (manufactured by Hitachi, Ltd.). A SEM photograph is shown in FIG.
（実施例４）
まず、厚さが１ｍｍのニッケル板に、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
Example 4
First, a nickel plate having a thickness of 1 mm was degreased and washed with an acidic degreasing solution, acid washed with a (1 + 1) hydrochloric acid aqueous solution, washed with water, then subjected to chemical polishing and washing, thereby performing a plating pretreatment.
次に、ジメチルスルホキシド（純度９９．９９％）に、塩化白金酸（Ｈ2ＰｔＣｌ6・６Ｈ2Ｏ）を白金量で１０ｇ／Ｌとなるように添加し、１００℃〜１２０℃で３０分間の加熱処理を行い、無電解メッキ液を作製した。 Next, chloroplatinic acid (H 2 PtCl 6 .6H 2 O) was added to dimethyl sulfoxide (purity 99.99%) so that the amount of platinum was 10 g / L, and the reaction was performed at 100 ° C. to 120 ° C. for 30 minutes. Heat treatment was performed to produce an electroless plating solution.
該無電解メッキ液を９０℃に保ち、メッキ前処理を施したニッケル板を該無電解メッキ液に、１分間、浸漬し、表面に白金メッキ層を形成した。 The electroless plating solution was kept at 90 ° C., and the nickel plate subjected to the plating pretreatment was immersed in the electroless plating solution for 1 minute to form a platinum plating layer on the surface.
得られた白金メッキ層の表面状態は良好で、メッキ厚みは０．０９μｍであった。また、粘着テープを用いて引き剥がし試験を３回、繰り返したが、白金メッキ層の剥離は見られなかった。 The surface condition of the obtained platinum plating layer was good, and the plating thickness was 0.09 μm. Further, the peeling test was repeated three times using an adhesive tape, but no peeling of the platinum plating layer was observed.
（実施例５）
まず、厚さが１ｍｍの銅板に、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
(Example 5)
First, a pre-plating treatment was performed on a copper plate having a thickness of 1 mm by degreasing and washing with an acid degreasing solution, (1 + 1) acid washing with an aqueous hydrochloric acid solution, washing with water, chemical polishing and washing with water.
次に、ジメチルスルホキシド（純度９９．９９％）に、臭化アンモニウムを１５ｇ／Ｌ、塩化銀（ＡｇＣｌ）を１５ｇ／Ｌとなるように、それぞれ添加し、無電解メッキ液を作製した。 Next, an electroless plating solution was prepared by adding ammonium bromide to 15 g / L and silver chloride (AgCl) to 15 g / L respectively to dimethyl sulfoxide (purity 99.99%).
該無電解メッキ液を７０℃に保ち、メッキ前処理を施した銅板を該無電解メッキ液に、５分間、浸漬し、表面に銀メッキ層を形成した。 The electroless plating solution was kept at 70 ° C., and the copper plate subjected to the plating pretreatment was immersed in the electroless plating solution for 5 minutes to form a silver plating layer on the surface.
得られた銀メッキ層の表面状態は良好で、メッキ厚みは０．５５μｍであった。 The surface condition of the obtained silver plating layer was good, and the plating thickness was 0.55 μm.
（実施例６）
まず、厚さが１ｍｍの銅板に、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
(Example 6)
First, a pre-plating treatment was performed on a copper plate having a thickness of 1 mm by degreasing and washing with an acid degreasing solution, (1 + 1) acid washing with an aqueous hydrochloric acid solution, washing with water, chemical polishing and washing with water.
次に、ジメチルスルホオキシド（純度９９．９９％）に、チオシアン酸アンモニウムを１５ｇ／Ｌ、塩化銀（ＡｇＣｌ）を１５ｇ／Ｌとなるように、それぞれ添加し、無電解メッキ液を作製した。 Next, an electroless plating solution was prepared by adding ammonium thiocyanate at 15 g / L and silver chloride (AgCl) at 15 g / L to dimethyl sulfoxide (purity 99.99%).
該無電解メッキ液を７０℃に保ち、メッキ前処理を施した銅板を該無電解メッキ液に、５分間、浸漬し、表面に銀メッキ層を形成した。 The electroless plating solution was kept at 70 ° C., and the copper plate subjected to the plating pretreatment was immersed in the electroless plating solution for 5 minutes to form a silver plating layer on the surface.
得られた銀メッキ層の表面状態は良好で、メッキ厚みは０．９μｍ〜１．０μｍであった。 The surface condition of the obtained silver plating layer was good, and the plating thickness was 0.9 μm to 1.0 μm.
（実施例７）
まず、厚さが０．２ｍｍで、呼び孔径５０μｍのニッケル製発泡金属シートに、酸性脱脂液で脱脂洗浄および水洗し、（１＋１）塩酸水溶液で酸洗浄して、水洗後、化学研磨および水洗することにより、メッキ前処理を施した。
(Example 7)
First, a nickel foam metal sheet having a thickness of 0.2 mm and a nominal pore diameter of 50 μm is degreased and washed with an acid degreasing solution, (1 + 1) acid washed with an aqueous hydrochloric acid solution, washed with water, then subjected to chemical polishing and washing. Thus, a pre-plating treatment was performed.
次に、ジメチルスルホキシド（純度９９．９９％）に、塩化白金酸（Ｈ2ＰｔＣｌ6・６Ｈ2Ｏ）を白金量で１０ｇ／Ｌとなるように添加し、１００℃〜１２０℃で３０分間の加熱処理を行い、無電解メッキ液を作製した。 該無電解メッキ液を９０℃に保ち、メッキ前処理を施したニッケル製発砲金属シートを該無電解メッキ液に、２分間、浸漬し、表面に白金メッキ層を形成した。 Next, chloroplatinic acid (H 2 PtCl 6 .6H 2 O) was added to dimethyl sulfoxide (purity 99.99%) so that the amount of platinum was 10 g / L, and the reaction was performed at 100 ° C. to 120 ° C. for 30 minutes. Heat treatment was performed to produce an electroless plating solution. The electroless plating solution was kept at 90 ° C., and a nickel-fired metal sheet subjected to pre-plating treatment was immersed in the electroless plating solution for 2 minutes to form a platinum plating layer on the surface.
白金の含有量を分析したところ、０．１４質量％であった。白金メッキが施されたニッケル製発砲金属シートは、白金担持触媒として用いることができる。 When the platinum content was analyzed, it was 0.14% by mass. The nickel-fired metal sheet with platinum plating can be used as a platinum-supported catalyst.
本発明は、具体的には、電気部品および電子部品の配線材料、金属装飾品などのメッキ、化学触媒および燃料電池などの白金担持触媒への適用が可能である。 Specifically, the present invention can be applied to wiring materials for electrical parts and electronic parts, plating for metal ornaments, etc., chemical catalysts, and platinum-supported catalysts such as fuel cells.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006039552A JP4802008B2 (en) | 2006-02-16 | 2006-02-16 | Electroless plating solution and plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006039552A JP4802008B2 (en) | 2006-02-16 | 2006-02-16 | Electroless plating solution and plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007217751A JP2007217751A (en) | 2007-08-30 |
| JP4802008B2 true JP4802008B2 (en) | 2011-10-26 |
Family
ID=38495350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006039552A Expired - Fee Related JP4802008B2 (en) | 2006-02-16 | 2006-02-16 | Electroless plating solution and plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4802008B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2382831C1 (en) * | 2008-07-22 | 2010-02-27 | Галина Кузьминична Струкова | Method of coating from gold and its alloys on metallic parts and compositions of ingredients for method implementation |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272787A (en) * | 1988-04-25 | 1989-10-31 | Ishihara Chem Co Ltd | Iron-dysprosium alloy plating solution |
| JPH01316487A (en) * | 1988-06-13 | 1989-12-21 | Katsuhisa Sugimoto | Iron-terbium alloy plating solution |
| JPH02232392A (en) * | 1989-03-06 | 1990-09-14 | Katsuhisa Sugimoto | Iron-terbium-cobalt ternary alloy plating solution |
| JPH03260084A (en) * | 1990-03-09 | 1991-11-20 | Katsuhisa Sugimoto | Cobalt-samarium binary alloy plating solution |
| JP3779791B2 (en) * | 1997-03-31 | 2006-05-31 | 株式会社日本アルミ | Electroless silver plating method |
| US7147767B2 (en) * | 2002-12-16 | 2006-12-12 | 3M Innovative Properties Company | Plating solutions for electrochemical or chemical deposition of copper interconnects and methods therefor |
-
2006
- 2006-02-16 JP JP2006039552A patent/JP4802008B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007217751A (en) | 2007-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0184889B1 (en) | Acid Palladium Strike Bath | |
| JP2004502871A (en) | Electroless silver plating | |
| EP0060294A1 (en) | PLATING OF ALLOYS WITHOUT ELECTRICAL CURRENT. | |
| Barker | Electroless deposition of metals | |
| JP5887381B2 (en) | Method for obtaining yellow gold alloy deposits by electroplating without using toxic or semi-metals | |
| US9650719B1 (en) | Method for electroless plating of palladium phosphorus directly on copper, and a plated component therefrom | |
| JP2004502872A (en) | Electroless self-catalytic platinum plating | |
| JP2018003108A (en) | Electroless platinum plating bath | |
| JP4802008B2 (en) | Electroless plating solution and plating method | |
| JPS647153B2 (en) | ||
| KR102137300B1 (en) | Iron boron alloy coatings and a process for their preparation | |
| KR20170018228A (en) | Electroless silver plating solution and it used silver plating method | |
| JP6544792B2 (en) | Method of selecting a stabilizer for electroless platinum plating solution and electroless platinum plating solution | |
| JP2004323963A (en) | Gold plating liquid | |
| JP2560842B2 (en) | Method for manufacturing corrosion resistant film | |
| Selvam | Electroless silver deposition on ABS plastic using Co (II) as reducing agent | |
| JP4740711B2 (en) | Pd / Sn colloidal catalyst adsorption promoter | |
| TW202208682A (en) | Electroless nickel plating bath | |
| JPH0631167A (en) | Oxidation catalyst and method for producing the same | |
| JP5517275B2 (en) | Post-treatment agent for etching treatment with chromic acid-sulfuric acid mixture | |
| JP2004332037A (en) | Electroless gold plating method | |
| TWI765877B (en) | Cyanide-free liquid composition for immersion gold plating | |
| JP5364880B2 (en) | Post-treatment agent for etching treatment with chromic acid-sulfuric acid mixture | |
| JP6842475B2 (en) | Cyan-free substituted gold plating solution composition | |
| JP2004332035A (en) | Electroless nickel-gold plating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090119 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090623 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110315 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110614 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110712 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110808 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140812 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |