JP2019052327A - Method of forming electroless nickel phosphorus plating coating on aluminum material - Google Patents
Method of forming electroless nickel phosphorus plating coating on aluminum material Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 34
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 title abstract description 35
- 239000011248 coating agent Substances 0.000 title abstract description 4
- 238000000576 coating method Methods 0.000 title abstract description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 52
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 39
- 238000005406 washing Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003750 conditioning effect Effects 0.000 description 10
- 238000005530 etching Methods 0.000 description 9
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000013527 degreasing agent Substances 0.000 description 4
- 238000005237 degreasing agent Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、アルミニウム系材料に無電解ニッケルリンめっき皮膜を形成する方法に関する。 The present invention relates to a method of forming an electroless nickel phosphorus plating film on an aluminum-based material.
無電解ニッケルめっき法は、複雑な形状のアルミニウム、マグネシウム、チタン等の部品に均一な厚みのめっきを施すことができるため、電子部品、精密機械部品等の分野で活用されている。 The electroless nickel plating method is used in the fields of electronic parts, precision machine parts, and the like because it can apply plating of uniform thickness to parts such as aluminum, magnesium, and titanium having complicated shapes.
アルミニウム部品に無電解ニッケルめっきする場合には、めっき皮膜とアルミニウム部品との密着性を確保するために、前処理として、アルミニウム部品を亜鉛置換処理（ジンケート処理）、特に、精密機械部品の場合には、亜鉛置換処理を２回繰り返して行うダブルジンケート処理が一般的に行われている。ダブルジンケート処理の後にｐＨ４〜５．５の無電解ニッケルリンめっき浴でめっきを行うことで、良好な密着強度を有する皮膜が得られるが、皮膜の硬度が低いという問題がある。一方、ダブルジンケート処理の後にｐＨ６以上の無電解ニッケルリンめっき浴でめっきを行うことで、高硬度の皮膜が得られるが、密着強度は低く、皮膜の剥離が起こる。 When electroless nickel plating is applied to aluminum parts, as a pretreatment to ensure the adhesion between the plating film and the aluminum parts, the aluminum parts are treated with zinc replacement (zincate treatment), especially for precision machine parts. In general, double zincate treatment in which zinc substitution treatment is repeated twice is generally performed. By performing plating with an electroless nickel phosphorus plating bath having a pH of 4 to 5.5 after the double zincate treatment, a film having good adhesion strength can be obtained, but there is a problem that the hardness of the film is low. On the other hand, by performing plating with an electroless nickel phosphorus plating bath having a pH of 6 or more after the double zincate treatment, a high hardness film can be obtained, but the adhesion strength is low and the film peels off.
特許文献１及び２、並びに非特許文献１には、ダブルジンケート処理後のアルミニウムに下地ニッケルめっきを施した後、機能ニッケルめっきを施す方法が記載されている。しかしながら、上記の方法は、めっきを２回行うため、２種類のめっき液を管理する必要があり、煩雑である。 Patent Documents 1 and 2 and Non-Patent Document 1 describe a method of performing functional nickel plating after applying base nickel plating to aluminum after double zincate treatment. However, since the above method performs plating twice, it is necessary to manage two types of plating solutions, which is complicated.
かかる状況において、本発明が解決しようとする課題は、アルミニウム系材料に対して、１回のめっき処理で、高硬度のニッケルリン皮膜を良好な密着強度で形成することができる方法を提供することである。 In such a situation, the problem to be solved by the present invention is to provide a method capable of forming a high-hardness nickel-phosphorus film with good adhesion strength in a single plating process on an aluminum-based material. It is.
本発明者らが、アルミニウム系材料に対して、１回のめっき処理で、高硬度のニッケルリン皮膜を良好な密着強度で形成することができる方法を開発すべく鋭意検討した結果、被めっき物であるアルミニウム系材料に対して、ジンケート処理を行った後に所定の表面調整処理を行い、その後、ｐＨ６以上で無電解ニッケルリンめっきを行うことにより、１回のめっき処理で、高硬度のニッケルリン皮膜を良好な密着強度で形成することができ、上記課題を解決できることを見出した。本発明は、このような知見に基づき完成されたものである。 As a result of intensive investigations by the present inventors to develop a method capable of forming a high-hardness nickel-phosphorus film with good adhesion strength in a single plating process on an aluminum-based material, The aluminum-based material is subjected to zincate treatment and then subjected to predetermined surface conditioning treatment, and then electroless nickel phosphorus plating at a pH of 6 or higher, so that high-hardness nickel phosphorus can be obtained by one plating treatment. It has been found that a film can be formed with good adhesion strength and the above problems can be solved. The present invention has been completed based on such findings.
本発明は、下記項１〜項４に示すアルミニウム系材料に無電解ニッケルリンめっき皮膜を形成する方法に係る。
項１． アルミニウム系材料に無電解ニッケルリンめっきを行う方法であって、ジンケート処理後のアルミニウム系材料の表面を、有機酸を含む表面調整剤で処理した後に、ｐＨ６以上で無電解ニッケルリンめっきを行う、方法。
項２． 前記有機酸が、クエン酸、リンゴ酸、乳酸、コハク酸、及び酢酸からなる群から選択される少なくとも１種である、上記項１に記載の方法。
項３． 前記表面調整剤で、前記ジンケート処理後のアルミニウム系材料表面に残存する亜鉛の量を０．４〜１．２ｍｇ／ｄｍ２に調整する、上記項１又は２に記載の方法。
項４． 前記ジンケート処理が、ダブルジンケート処理である、上記項１〜３のいずれか１項に記載の方法。
The present invention relates to a method for forming an electroless nickel phosphorus plating film on the aluminum-based material shown in the following items 1 to 4.
Item 1. A method of performing electroless nickel phosphorous plating on an aluminum material, wherein the surface of the aluminum material after zincate treatment is treated with a surface conditioner containing an organic acid, and then electroless nickel phosphorous plating is performed at a pH of 6 or more. Method.
Item 2. Item 2. The method according to Item 1, wherein the organic acid is at least one selected from the group consisting of citric acid, malic acid, lactic acid, succinic acid, and acetic acid.
Item 3. Item 3. The method according to Item 1 or 2, wherein the amount of zinc remaining on the surface of the aluminum-based material after the zincate treatment is adjusted to 0.4 to 1.2 mg / dm 2 with the surface conditioner.
Item 4. Item 4. The method according to any one of Items 1 to 3, wherein the zincate treatment is a double zincate treatment.
本発明の方法によれば、アルミニウム系材料に対して、１回のめっき処理で、硬度の高いニッケルリン皮膜を良好な密着強度で形成することができる。従来の下地めっきを行った後にｐＨ６以上で無電解ニッケルリンめっきを行う方法では、２種類のめっき液を管理する必要があるのに対して、本発明の方法では１種類のめっき液を管理すればよいため、めっき液の管理にかかる煩雑さを軽減することができる。 According to the method of the present invention, a nickel phosphorus film having high hardness can be formed with good adhesion strength by a single plating process on an aluminum-based material. In the conventional method of performing electroless nickel phosphorous plating at a pH of 6 or higher after performing base plating, it is necessary to manage two types of plating solutions, whereas in the method of the present invention, one type of plating solution must be managed. Therefore, the complexity of managing the plating solution can be reduced.
本発明の方法は、アルミニウム系材料に無電解ニッケルリンめっき皮膜を形成する方法である。 The method of the present invention is a method of forming an electroless nickel phosphorus plating film on an aluminum-based material.
本発明の処理対象（被処理物）であるアルミニウム系材料としては、被処理物の全てがアルミニウム又はアルミニウム合金で形成されているもの、及び、非アルミニウム材（例えば、シリコン、ＦＲＡ（プリント基板の基材）等）の表面又は一部をアルミニウム又はアルミニウム合金で被覆しているもののいずれであってもよい。前記アルミニウム又はアルミニウム合金の形態は特に限定されず、例えば、ブランク材、圧延材、鋳造材、皮膜等が挙げられる。なお、アルミニウム又はアルミニウム合金の皮膜を非アルミニウム材の表面に形成する場合、該皮膜の形成方法は特に限定されない。形成方法としては、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法等の気相めっき法が好ましい。該皮膜の厚みは、アルミニウム又はアルミニウム合金素地を確実に残存させる観点から、通常０．５μｍ以上、好ましくは１μｍ以上である。該厚みの上限は、特に限定されず、通常１００μｍ以下である。前記皮膜のアルミニウム以外の成分は、アルミニウム合金を形成するものであれば特に限定されない。アルミニウム合金として、例えば、Ａｌ−Ｓｉ（Ｓｉ含有率０．５〜１質量％）、Ａｌ−Ｃｕ（Ｃｕ含有率０．５〜１質量％）等が挙げられる。 The aluminum-based material that is the object to be treated (the object to be treated) of the present invention includes a material in which all the object to be treated is formed of aluminum or an aluminum alloy, and a non-aluminum material (for example, silicon, FRA (printed circuit board Any of those in which the surface or a part of the base material) is coated with aluminum or an aluminum alloy. The form of the aluminum or aluminum alloy is not particularly limited, and examples thereof include a blank material, a rolled material, a cast material, and a film. In the case where an aluminum or aluminum alloy film is formed on the surface of a non-aluminum material, the method for forming the film is not particularly limited. As the formation method, for example, a vapor phase plating method such as a vacuum evaporation method, a sputtering method, or an ion plating method is preferable. The thickness of the coating is usually 0.5 μm or more, preferably 1 μm or more, from the viewpoint of reliably leaving aluminum or an aluminum alloy substrate. The upper limit of the thickness is not particularly limited, and is usually 100 μm or less. Components other than aluminum in the coating are not particularly limited as long as they form an aluminum alloy. Examples of the aluminum alloy include Al—Si (Si content: 0.5 to 1% by mass), Al—Cu (Cu content: 0.5 to 1% by mass), and the like.
本発明の方法では、被処理物であるアルミニウム系材料に対して、ジンケート処理を行った後に表面調整処理を行い、その後、ｐＨ６以上で無電解ニッケルリンめっきを行うことが必要である。 In the method of the present invention, it is necessary to subject the aluminum-based material to be treated to a surface adjustment treatment after performing a zincate treatment, and then to electroless nickel phosphorus plating at pH 6 or higher.
本発明の方法では、被処理物に対してジンケート処理が行われていればよく、これ以外の前処理は特に制限されない。ジンケート処理が効果的に行われるために、アルミニウム系材料に対して一般的に行われる前処理が行われていることが好ましい。 In the method of the present invention, it is only necessary that a zincate process is performed on an object to be processed, and other pretreatments are not particularly limited. In order to effectively perform the zincate treatment, it is preferable that a pretreatment generally performed on an aluminum-based material is performed.
以下、本発明における処理工程の好ましい例について説明する。なお、各処理工程の間には、通常、水洗処理を行うが、その記載は省略する。 Hereinafter, preferable examples of the processing steps in the present invention will be described. In addition, although the water washing process is normally performed between each process process, the description is abbreviate | omitted.
アルミニウム系材料の表面には、指紋、油脂等の有機物；静電気作用による塵等の付着物等の汚れが存在するので、これらの汚れを除去するために、被処理物の表面を清浄化することが好ましい。処理液としては、公知の脱脂剤を用いられる。例えば、アルカリタイプの脱脂剤等を使用し、常法に従って脱脂処理を行うことができる。アルカリタイプの脱脂剤として、例えば、５０ｇ／Ｌ程度のリン酸塩及び３〜６ｇ／Ｌ程度の界面活性剤を含む脱脂剤を挙げることができる。 The surface of the aluminum-based material contains organic matter such as fingerprints, oils and fats; dirt such as dust and other deposits due to electrostatic action. The surface of the object to be treated must be cleaned to remove these stains. Is preferred. A known degreasing agent is used as the treatment liquid. For example, a degreasing treatment can be performed according to a conventional method using an alkaline type degreasing agent or the like. Examples of the alkaline type degreasing agent include a degreasing agent containing about 50 g / L phosphate and about 3 to 6 g / L surfactant.
次いで、必要に応じて、被処理物をエッチングする。エッチングにより、アルミニウム系材料表面の不均一な自然酸化膜を除去することができる。エッチングは、常法に従って行えばよく、例えば、水酸化ナトリウムをベースとした高アルカリ溶液を用い、適度に加温した溶液中に被処理物を浸漬することにより行うことができる。水酸化ナトリウムをベースとした高アルカリ溶液として、例えば、５０ｇ／Ｌ程度の水酸化ナトリウム及び３〜６ｇ／Ｌ程度の界面活性剤を含むエッチング剤を挙げることができる。 Next, the object to be processed is etched as necessary. By etching, a non-uniform natural oxide film on the surface of the aluminum-based material can be removed. Etching may be performed in accordance with a conventional method, for example, by using a highly alkaline solution based on sodium hydroxide and immersing the object to be processed in a moderately heated solution. Examples of the highly alkaline solution based on sodium hydroxide include an etching agent containing about 50 g / L sodium hydroxide and about 3 to 6 g / L surfactant.
さらに、エッチング後の被処理物を脱スマットする。脱スマットは、活性化ともいい、エッチングで生じたスマットを除去し、新たに薄い酸化膜を形成し、次の亜鉛置換反応を調整するための工程である。処理液として、硝酸を含有する水溶液が用いられる。 Further, the object to be processed after etching is desmutted. Desmutting is also called activation, and is a process for removing the smut generated by etching, forming a new thin oxide film, and adjusting the next zinc substitution reaction. An aqueous solution containing nitric acid is used as the treatment liquid.
上記のような前処理が行われた被処理物に対してジンケート（亜鉛置換）処理を行う。ジンケート処理は、アルミニウムとニッケルの中間のイオン化傾向を有する亜鉛の置換皮膜を形成することによって、ニッケルリンめっきの密着不良を防止するために行われる。ジンケート処理としては、公知のジンケート処理法を制限なく用いることができる。例えば、水酸化ナトリウムを１〜８ｍｏｌ／Ｌ、酸化亜鉛を０．１〜０．５ｍｏｌ／Ｌ、及び酒石酸ナトリウム等の錯化剤を０．１〜０．４ｍｏｌ／Ｌ含有する亜鉛置換液を用いて、処理温度１０〜４０℃、処理時間５〜６０秒という条件でジンケート処理することができる。さらに、このジンケート処理を２回以上繰り返し行ってもよい。本発明の方法では、密着性を向上させるために、ジンケート処理を２回行うこと（ダブルジンケート処理）が好ましい。 A zincate (zinc substitution) treatment is performed on the workpiece that has been pretreated as described above. The zincate treatment is performed in order to prevent poor adhesion of nickel phosphorus plating by forming a zinc replacement film having an ionization tendency intermediate between aluminum and nickel. As the zincate treatment, a known zincate treatment method can be used without limitation. For example, a zinc replacement solution containing 1 to 8 mol / L of sodium hydroxide, 0.1 to 0.5 mol / L of zinc oxide, and 0.1 to 0.4 mol / L of a complexing agent such as sodium tartrate is used. Thus, the zincate treatment can be performed under the conditions of a treatment temperature of 10 to 40 ° C. and a treatment time of 5 to 60 seconds. Further, this zincate treatment may be repeated twice or more. In the method of the present invention, in order to improve the adhesion, it is preferable to perform the zincate treatment twice (double zincate treatment).
ダブルジンケート処理の場合、第１ジンケート処理により、アルミニウム原子が溶出し、亜鉛原子が置換し、粗雑な亜鉛置換膜が析出する。 In the case of double zincate treatment, the first zincate treatment elutes aluminum atoms, substitutes zinc atoms, and deposits a rough zinc-substituted film.
第１ジンケート処理後に、硝酸水溶液で表面を洗浄することが好ましい。酸洗することにより、次の第２ジンケート処理で、粗雑な亜鉛置換膜が除去され、アルミニウム表面電位をシフトして、薄く均一で緻密な置換膜を得ることができる。 It is preferable to wash the surface with an aqueous nitric acid solution after the first zincate treatment. By pickling, a rough zinc-substituted film is removed by the next second zincate treatment, and the surface potential of the aluminum is shifted to obtain a thin, uniform and dense replacement film.
第２ジンケート処理の処理液としては、第１ジンケート処理と同じ液を使用する。第２ジンケート処理により、アルミニウム原子が溶出し、亜鉛原子が置換し、密着性のよい亜鉛置換膜が形成される。 As the processing solution for the second zincate treatment, the same solution as that for the first zincate treatment is used. By the second zincate treatment, aluminum atoms are eluted, zinc atoms are substituted, and a zinc-substituted film with good adhesion is formed.
本発明の方法では、ジンケート処理、ダブルジンケート処理の場合には第２ジンケート処理の後に、表面処理剤で表面調整処理を行うことが特徴である。表面調整処理により、ジンケート処理で形成された亜鉛層の溶出量をコントロールし、被処理物表面に残存する亜鉛の量を調整する。表面調整処理により溶出する亜鉛の量は、０．１〜０．９ｍｇ／ｄｍ２程度であることが好ましく、ジンケート処理後の被処理物表面には、亜鉛が０．４〜１．２ｍｇ／ｄｍ２程度残存していることが好ましい。被処理物表面に残存する亜鉛の量を上記の範囲内に調整することで、無電解ニッケルリンめっきの析出状態を変化させ、それにより密着強度を向上させることができる。 In the method of the present invention, in the case of a zincate treatment or a double zincate treatment, a surface conditioning treatment is performed with a surface treatment agent after the second zincate treatment. By surface adjustment treatment, the amount of zinc layer formed by zincate treatment is controlled, and the amount of zinc remaining on the surface of the object to be treated is adjusted. The amount of zinc eluted by the surface conditioning treatment is preferably about 0.1 to 0.9 mg / dm 2 , and zinc is 0.4 to 1.2 mg / dm on the surface of the workpiece after the zincate treatment. It is preferable that about 2 remain. By adjusting the amount of zinc remaining on the surface of the object to be processed within the above range, it is possible to change the deposition state of the electroless nickel phosphorus plating, thereby improving the adhesion strength.
表面調整剤として、有機酸の水溶液を使用する。有機酸は、めっき液に使用することができる有機酸であれば特に制限なく使用することができる。このような有機酸として、例えば、クエン酸、リンゴ酸、乳酸、コハク酸、酢酸等が挙げられる。処理液中の有機酸の濃度は、通常５〜５０ｇ／Ｌ程度、好ましくは１０〜３０ｇ／Ｌ程度である。表面調整剤は、特にｐＨを調整しなくても表面処理効果を奏し、ｐＨ４〜５．５に調整することでより安定した効果が得られる。ｐＨは、アンモニア水、水酸化ナトリウム等のアルカリ、又は硫酸、塩酸、硝酸等の酸で調整することができる。処理温度は、２０〜３０℃程度が好ましく、処理時間は、１０〜１８０秒間程度が好ましい。 An organic acid aqueous solution is used as the surface conditioner. The organic acid can be used without particular limitation as long as it is an organic acid that can be used in the plating solution. Examples of such organic acids include citric acid, malic acid, lactic acid, succinic acid, and acetic acid. The density | concentration of the organic acid in a process liquid is about 5-50 g / L normally, Preferably it is about 10-30 g / L. Even if it does not adjust pH in particular, a surface conditioning agent has a surface treatment effect, and the more stable effect is acquired by adjusting to pH 4-5.5. The pH can be adjusted with an alkali such as aqueous ammonia or sodium hydroxide, or an acid such as sulfuric acid, hydrochloric acid or nitric acid. The treatment temperature is preferably about 20 to 30 ° C., and the treatment time is preferably about 10 to 180 seconds.
その後に、無電解ニッケルリンめっき処理を行う。 Thereafter, an electroless nickel phosphorus plating process is performed.
無電解ニッケルリンめっき液としては、次亜リン酸塩を還元剤とする無電解ニッケルリンめっき液であれば、特に限定なく使用することができる。 As the electroless nickel phosphorus plating solution, any electroless nickel phosphorus plating solution containing hypophosphite as a reducing agent can be used without particular limitation.
無電解ニッケルリンめっき液として、例えば、ニッケル塩、次亜リン酸塩、及びオキシカルボン酸を含有する無電解ニッケルリンめっき液が挙げられる。ニッケル塩として、例えば、硫酸ニッケル、塩化ニッケル、炭酸ニッケル等が挙げられる。次亜リン酸塩として、例えば、次亜リン酸ナトリウム、次亜リン酸カリウム等が挙げられる。オキシカルボン酸として、例えば、乳酸、リンゴ酸、これらの塩（ナトリウム塩、カリウム塩、アンモニウム塩等）等が挙げられる。前記めっき液中の各成分の濃度としては、ニッケル塩は、５〜６０ｇ／Ｌ程度が好ましく、１５〜４０ｇ／Ｌ程度がより好ましい。次亜リン酸塩は、５〜６０ｇ／Ｌ程度が好ましく、２０〜４０ｇ／Ｌ程度がより好ましい。オキシカルボン酸は、５〜５０ｇ／Ｌ程度が好ましく、１０〜３０ｇ／Ｌ程度がより好ましい。 Examples of the electroless nickel phosphorus plating solution include an electroless nickel phosphorus plating solution containing nickel salt, hypophosphite, and oxycarboxylic acid. Examples of the nickel salt include nickel sulfate, nickel chloride, nickel carbonate, and the like. Examples of hypophosphites include sodium hypophosphite and potassium hypophosphite. Examples of the oxycarboxylic acid include lactic acid, malic acid, and salts thereof (sodium salt, potassium salt, ammonium salt, etc.). As a concentration of each component in the plating solution, the nickel salt is preferably about 5 to 60 g / L, and more preferably about 15 to 40 g / L. The hypophosphite is preferably about 5 to 60 g / L, more preferably about 20 to 40 g / L. The oxycarboxylic acid is preferably about 5 to 50 g / L, more preferably about 10 to 30 g / L.
めっき液のｐＨは、高硬度のめっき皮膜を得るという観点から、６以上であることが必要であり、６．５〜８程度が好ましい。ｐＨは、水酸化ナトリウム、アンモニア水等で調整することができる。処理温度は、８０〜１００℃程度が好ましく、８５〜９０℃程度がより好ましい。処理時間は、必要とする厚みのめっき皮膜が形成されるまでの時間であり、めっき皮膜の厚みに応じて適宜調整すればよい。 The pH of the plating solution needs to be 6 or more from the viewpoint of obtaining a high hardness plating film, and is preferably about 6.5 to 8. The pH can be adjusted with sodium hydroxide, aqueous ammonia or the like. The treatment temperature is preferably about 80 to 100 ° C, more preferably about 85 to 90 ° C. The treatment time is the time until a plating film having a required thickness is formed, and may be appropriately adjusted according to the thickness of the plating film.
上記のｐＨ６以上のめっき液を用いてアルミニウム系材料に無電解ニッケルリンめっきを行うことにより、高硬度、具体的には９００〜１１００Ｈｖ程度のビッカース硬度を有するニッケルリンめっき皮膜が得られる。なお、ビッカース硬度は、無電解ニッケルリンめっきを３０μｍ以上析出させ、マイクロビッカース硬さ試験機ＨＭ−２００（株式会社ミツトヨ製）を用いて荷重１００ｇｆにて測定した値である。また、該めっき皮膜は、以下の実施例で詳述するように、アルミニウム系材料との密着強度が良好である。 By performing electroless nickel phosphorus plating on an aluminum-based material using the above plating solution having a pH of 6 or more, a nickel phosphorus plating film having a high hardness, specifically, a Vickers hardness of about 900 to 1100 Hv is obtained. The Vickers hardness is a value measured by depositing electroless nickel phosphorus plating of 30 μm or more and using a micro Vickers hardness tester HM-200 (manufactured by Mitutoyo Corporation) at a load of 100 gf. The plating film has good adhesion strength with an aluminum-based material as described in detail in the following examples.
以上のように、本発明の方法によれば、アルミニウム系材料に対して、１回のめっき処理で、硬度の高いニッケルリン皮膜を良好な密着強度で形成することができる。従来の下地めっきを行った後にｐＨ６以上で無電解ニッケルリンめっきを行う方法では、２種類のめっき液を管理する必要があるのに対して、本発明の方法では１種類のめっき液を管理すればよいため、めっき液の管理にかかる煩雑さを軽減することができる。 As described above, according to the method of the present invention, a nickel phosphorus film having high hardness can be formed with good adhesion strength by a single plating process on an aluminum-based material. In the conventional method of performing electroless nickel phosphorous plating at a pH of 6 or higher after performing base plating, it is necessary to manage two types of plating solutions, whereas in the method of the present invention, one type of plating solution must be managed. Therefore, the complexity of managing the plating solution can be reduced.
以下、実施例及び比較例を示し、本発明をより具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.
実施例１
表１に記載のアルミニウム素材に対して、表１に記載した薬品を所定の条件で用いて以下の工程を行い、ニッケルリンめっき皮膜を得た。得られたニッケルリンめっき皮膜のビッカース硬度を、マイクロビッカース硬さ試験機ＨＭ−２００（株式会社ミツトヨ製）を用いて荷重１００ｇｆにて測定した。さらに、ニッケルリンめっき皮膜の密着強度を、試片を折り曲げた時の皮膜状態を目視により評価した。結果を表２に示す。
Example 1
The following processes were performed on the aluminum materials listed in Table 1 using the chemicals listed in Table 1 under predetermined conditions to obtain a nickel phosphorus plating film. The Vickers hardness of the obtained nickel phosphorus plating film was measured with a load of 100 gf using a micro Vickers hardness tester HM-200 (manufactured by Mitutoyo Corporation). Furthermore, the adhesion strength of the nickel phosphorus plating film was evaluated by visual observation of the film state when the specimen was bent. The results are shown in Table 2.
(1)アルカリ脱脂→水洗→(2)エッチング→水洗→(3)脱スマット→水洗→(4)第１ジンケート→水洗→(5)ジンケート剥離→水洗→(6)第２ジンケート→水洗→(7)表面調整 →水洗→(9)pH 6.5無電解ＮｉＰめっき(約30μm) (1) Alkaline degreasing → Washing → (2) Etching → Washing → (3) Desmutting → Washing → (4) First zincate → Washing → (5) Zincate peeling → Washing → (6) Second zincate → Washing → ( 7) Surface adjustment → Water washing → (9) pH 6.5 electroless NiP plating (about 30μm)
比較例１
以下の工程を行った以外は、実施例１と同様にしてニッケルリンめっき皮膜を製造し、密着強度を評価した。結果を表２に示す。
Comparative Example 1
A nickel phosphorus plating film was produced in the same manner as in Example 1 except that the following steps were performed, and the adhesion strength was evaluated. The results are shown in Table 2.
(1)アルカリ脱脂→水洗→(2)エッチング→水洗→(3)脱スマット→水洗→(4)第１ジンケート→水洗→(5)ジンケート剥離→水洗→(6)第２ジンケート→水洗→(9)pH6.5無電解ＮｉＰめっき(約30μm) (1) Alkaline degreasing → Washing → (2) Etching → Washing → (3) Desmutting → Washing → (4) First zincate → Washing → (5) Zincate peeling → Washing → (6) Second zincate → Washing → ( 9) pH6.5 electroless NiP plating (about 30μm)
比較例２
以下の工程を行った以外は、実施例１と同様にしてニッケルリンめっき皮膜を製造し、密着強度を評価した。結果を表２に示す。
Comparative Example 2
A nickel phosphorus plating film was produced in the same manner as in Example 1 except that the following steps were performed, and the adhesion strength was evaluated. The results are shown in Table 2.
(1)アルカリ脱脂→水洗→(2)エッチング→水洗→(3)脱スマット→水洗→(4)第１ジンケート→水洗→(5)ジンケート剥離→水洗→(6)第２ジンケート→水洗→(8)pH4.5無電解ＮｉＰめっき(約3μm)→(水洗)→ (9)pH6.5無電解ＮｉＰめっき(約30μm) (1) Alkaline degreasing → Washing → (2) Etching → Washing → (3) Desmutting → Washing → (4) First zincate → Washing → (5) Zincate peeling → Washing → (6) Second zincate → Washing → ( 8) pH4.5 electroless NiP plating (approx. 3μm) → (washing) → (9) pH6.5 electroless NiP plating (approx. 30μm)
表２より、実施例１の方法によれば、アルミニウム系材料に対して、１回のめっき処理で、硬度の高いニッケルリン皮膜を良好な密着強度で形成することができることがわかる。比較例１の方法では、ジンケート処理の後に表面調整処理を行っていないので、めっき皮膜の密着強度が低かった。比較例２の方法は、めっき工程を２回行う従来法である。 From Table 2, it can be seen that according to the method of Example 1, a nickel phosphorus film having high hardness can be formed with good adhesion strength by a single plating process on an aluminum-based material. In the method of Comparative Example 1, since the surface adjustment treatment was not performed after the zincate treatment, the adhesion strength of the plating film was low. The method of Comparative Example 2 is a conventional method in which the plating process is performed twice.
実施例２〜５
表面調整処理時間の影響を調べるために、表面調整処理時間を表３のように変えた以外は実施例１と同様にしてニッケルリンめっき皮膜を製造し、密着強度を評価した。結果を表３に示す。
Examples 2-5
In order to investigate the influence of the surface adjustment treatment time, a nickel phosphorus plating film was produced in the same manner as in Example 1 except that the surface adjustment treatment time was changed as shown in Table 3, and the adhesion strength was evaluated. The results are shown in Table 3.
表３より、表面調整処理は、３分以内の短い時間で効果を奏することがわかる。 From Table 3, it can be seen that the surface conditioning treatment is effective in a short time of 3 minutes or less.
実施例６〜９
表面調整液のｐＨの影響を調べるために、ｐＨを表４のように変えた以外は実施例１と同様にしてニッケルリンめっき皮膜を製造し、密着強度を評価した。結果を表４に示す。
Examples 6-9
In order to examine the influence of the pH of the surface conditioning solution, a nickel phosphorus plating film was produced in the same manner as in Example 1 except that the pH was changed as shown in Table 4, and the adhesion strength was evaluated. The results are shown in Table 4.
表４より、表面調整液のｐＨは、上記の酸性範囲で効果を奏することがわかる。 From Table 4, it can be seen that the pH of the surface conditioning solution is effective in the above acidic range.
実施例１０〜１３
工程
(1)アルカリ脱脂→水洗→(2)エッチング→水洗→(3)脱スマット→水洗→(4)第１ジンケート→水洗→(5)ジンケート剥離→水洗→(6)第２ジンケート→水洗→(7)表面調整(pH4.5、25℃、30sec) →水洗→(9)pH 6.5無電解ＮｉＰめっき(約30μm)
Examples 10-13
Process
(1) Alkaline degreasing → Washing → (2) Etching → Washing → (3) Desmutting → Washing → (4) First zincate → Washing → (5) Zincate peeling → Washing → (6) Second zincate → Washing → ( 7) Surface adjustment (pH 4.5, 25 ° C, 30 sec) → Washing → (9) pH 6.5 electroless NiP plating (approximately 30 μm)
この工程で１ｄｍ２／Ｌの処理を５０回、１００回、２００回、又は３００回連続して行った後に、実施例１と同様にめっき皮膜の密着強度を測定した。なお、ジンケート及び無電解ニッケルリンめっきは補給及び更新によって濃度を管理した。結果を表５に示す。 In this step, 1 dm 2 / L treatment was performed 50 times, 100 times, 200 times, or 300 times continuously, and then the adhesion strength of the plating film was measured in the same manner as in Example 1. The concentration of zincate and electroless nickel phosphorus plating was controlled by replenishment and renewal. The results are shown in Table 5.
表５より、表面調整液１Ｌ当たりの処理量を３００ｄｍ２まで増加させた場合にも、表面調整効果が持続することがわかる。これは、本発明のめっき方法において、表面調整液は長期間管理しなくても使用可能であることを示している。 From Table 5, it can be seen that even when the treatment amount per 1 L of the surface conditioning liquid is increased to 300 dm 2 , the surface conditioning effect is sustained. This indicates that in the plating method of the present invention, the surface conditioning liquid can be used without being managed for a long period of time.
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| JPS63259082A (en) * | 1987-04-15 | 1988-10-26 | Brother Ind Ltd | Plating method |
| JPH0310085A (en) * | 1989-06-07 | 1991-01-17 | Sony Corp | Surface treatment for substrate |
| JPH0423221A (en) * | 1990-05-18 | 1992-01-27 | Sony Corp | Surface treatment of substrate for hard disk |
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| JPH05230664A (en) * | 1991-12-25 | 1993-09-07 | C Uyemura & Co Ltd | Method for electroless nickel plating on aluminum or aluminum alloy |
| JPH0734254A (en) * | 1993-07-19 | 1995-02-03 | Okuno Chem Ind Co Ltd | Electroless plating method to aluminum material |
| JP2007023316A (en) * | 2005-07-13 | 2007-02-01 | Kobe Steel Ltd | Wear-resistant member and motive-power transmitting component |
| JP2017057486A (en) * | 2015-09-18 | 2017-03-23 | 三菱マテリアル株式会社 | Production of substrate for plated power module |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63259082A (en) * | 1987-04-15 | 1988-10-26 | Brother Ind Ltd | Plating method |
| JPH0310085A (en) * | 1989-06-07 | 1991-01-17 | Sony Corp | Surface treatment for substrate |
| JPH0423221A (en) * | 1990-05-18 | 1992-01-27 | Sony Corp | Surface treatment of substrate for hard disk |
| JPH05118458A (en) * | 1991-10-25 | 1993-05-14 | Aisin Aw Co Ltd | Manufacture of valve for automatic transmission |
| JPH05230664A (en) * | 1991-12-25 | 1993-09-07 | C Uyemura & Co Ltd | Method for electroless nickel plating on aluminum or aluminum alloy |
| JPH0734254A (en) * | 1993-07-19 | 1995-02-03 | Okuno Chem Ind Co Ltd | Electroless plating method to aluminum material |
| JP2007023316A (en) * | 2005-07-13 | 2007-02-01 | Kobe Steel Ltd | Wear-resistant member and motive-power transmitting component |
| JP2017057486A (en) * | 2015-09-18 | 2017-03-23 | 三菱マテリアル株式会社 | Production of substrate for plated power module |
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