JPH05156456A - Electroless plating pretreating agent for aluminum base material and electroless plating method using the same - Google Patents
Electroless plating pretreating agent for aluminum base material and electroless plating method using the sameInfo
- Publication number
- JPH05156456A JPH05156456A JP36155491A JP36155491A JPH05156456A JP H05156456 A JPH05156456 A JP H05156456A JP 36155491 A JP36155491 A JP 36155491A JP 36155491 A JP36155491 A JP 36155491A JP H05156456 A JPH05156456 A JP H05156456A
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- base material
- aluminum
- agent
- 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.)
- Granted
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミニウムおよびそ
の合金の無電解めっき前処理剤およびこれを用いた無電
解めっき方法に関する。より詳しくは、基材表面を強酸
および強アルカリ等を使用することなく、無電解めっき
を施すための前処理方法および前処理剤に係り、本発明
の処理に引きつずき無電解めっきを施したものは、磁気
ディスク、電子材料を始め装飾用機材として利用され
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment agent for electroless plating of aluminum and its alloys, and an electroless plating method using the same. More specifically, the present invention relates to a pretreatment method and a pretreatment agent for performing electroless plating on the surface of a base material without using strong acid or strong alkali. These products are used as decoration equipment including magnetic disks and electronic materials.
【０００２】[0002]
【従来技術】アルミニウムおよびその合金基材表面に接
着力の優れた金属皮膜を無電解めっき法により生成させ
ることは、アルミニウム表面の活性力の強さゆえにかな
り困難であり、通常、触媒付与処理に先立ってジンケー
ト処理を行っている。しかし、ジンケート処理法は、前
処理工程が長く複雑であるばかりでなく、苛性ソーダ、
硝酸、フッ酸等の強アルカリ、強酸を使用し基材表面を
侵食させるため、利用分野が限定される。また、合金の
種類によっては適用出来ないものもある。この他に陽極
酸化法、置換法、直接法等も有るが一長一短が有りジン
ケート処理法に勝るものではない。2. Description of the Related Art It is quite difficult to produce a metal film having excellent adhesive strength on the surface of aluminum and its alloy substrate by electroless plating, because of the strong activity of the aluminum surface. The zincate treatment is performed prior to the treatment. However, the zincate treatment method not only has a long and complicated pretreatment step, but also a caustic soda,
Since a strong alkali such as nitric acid or hydrofluoric acid or a strong acid is used to corrode the surface of the substrate, the field of use is limited. In addition, some alloys may not be applicable. In addition to this, there are anodizing method, substitution method, direct method, etc., but they have advantages and disadvantages and are not superior to the zincate treatment method.
【０００３】周知のように無電解めっきをするには、そ
の予備処理として、被めっき材料表面を塩化錫および塩
化パラジウム等を用いて処理し金属パラジウムを触媒核
として担持せしめることが必要であるが、アルミニウム
基材の場合には、苛性ソーダ水溶液による酸化膜の除
去、硝酸又はフッ酸−硝酸混液による表面調整、ジンケ
ート処理をへて塩化第一錫および塩化パラジウムの溶液
で順次、又は同時に処理し、無電解めっき前処理を行う
方法が採られている。As is well known, in order to carry out electroless plating, it is necessary to pretreat the surface of the material to be plated with tin chloride, palladium chloride or the like so that metallic palladium is supported as a catalyst nucleus. In the case of an aluminum base material, removal of an oxide film with a caustic soda solution, surface adjustment with nitric acid or hydrofluoric acid-nitric acid mixture, zincate treatment followed by treatment with stannous chloride and palladium chloride solutions, or simultaneously, A method of performing a pretreatment for electroless plating is adopted.
【０００４】しかしながら、この方法は前記したように
処理工程が長く複雑であり、強酸、強アルカリを使用す
るため鋳物製品には適用が困難である。また合金の種類
や、仕上がり表面の平滑度への要求により、硝酸および
フッ酸との配合比や濃度を変化させたり、苛性ソーダ溶
液への浸漬を省略させる必要がある。However, this method has a long treatment step and is complicated as described above, and it is difficult to apply it to a casting product because it uses a strong acid and a strong alkali. In addition, depending on the type of alloy and the demand for the smoothness of the finished surface, it is necessary to change the mixing ratio and concentration with nitric acid and hydrofluoric acid, or to omit immersion in a caustic soda solution.
【０００５】さらに、ジンケート処理後、生成した亜鉛
膜を酸で溶解剥離し、再びジンケート処理を行うことも
ある。いずれにせよ、アルミニウム基材に密着性の優れ
た無電解めっきを施すには、豊富な経験と熟練を必要と
する。Further, after the zincate treatment, the zinc film formed may be dissolved and peeled off with an acid, and the zincate treatment may be performed again. In any case, abundant experience and skill are required to perform electroless plating with excellent adhesion on an aluminum base material.
【０００６】また、アルミニウム基材に直接錫−パラジ
ウム処理を施し、引きつずき無電解めっきを行ったり、
又は置換法により無電解めっきを行っても金属皮膜は形
成されるが、極めて不均一であり、連続皮膜は形成され
ず、また、連続皮膜を形成するには、かなりの膜厚が要
求されることが実験的に確かめられている。Further, the aluminum base material is directly subjected to tin-palladium treatment, and is then subjected to scratch electroless plating.
Alternatively, a metal film is formed even if electroless plating is performed by the substitution method, but it is extremely non-uniform, a continuous film is not formed, and a considerable film thickness is required to form the continuous film. It has been confirmed experimentally.
【０００７】しかも、その皮膜は摩擦下の抵抗性は弱い
うえに、めっき金属粒子が粗く瘤状の表面を形成する可
能性が大きい。In addition, the coating has a low resistance to friction, and the plated metal particles are likely to be rough and form a bumpy surface.
【０００８】この理由は、めっき反応の律速となるパラ
ジウム触媒核が基材表面に不均質に、しかも巨大粒子状
に形成され、この核上に金属が形成され、島状に成長す
るためと考えられる。The reason for this is thought to be that the palladium catalyst nucleus, which is the rate-determining factor of the plating reaction, is formed inhomogeneously on the surface of the base material in the form of giant particles, metal is formed on this nucleus and grows like islands. Be done.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記のよう
な従来の複雑なめっき前処理とその欠点である不均質な
めっき皮膜を改善してより均質で強固な密着性と被覆力
を有する無電解めっきアルミニウム材料の製造を提供す
ることを目的として、鋭意研究を重ねた結果開発に成功
したものである。DISCLOSURE OF THE INVENTION The present invention has a more uniform and firm adhesion and covering power by improving the above-described conventional complicated plating pretreatment and its disadvantage, that is, the non-uniform plating film. With the aim of providing the manufacture of electroless plated aluminum materials, they have succeeded in development as a result of intensive research.
【００１０】[0010]
【課題を解決する手段】すなわち、本発明が提供しよう
とするアルミニウム系基材の無電解めっき前処理剤は、
アルミニウム基材の表面と結合能を有し、且つ貴金属イ
オンとキレート能を有する有機化合物を有効成分とする
ことを構成上の特徴とする。That is, the pretreatment agent for electroless plating of an aluminum-based substrate, which is to be provided by the present invention, is
The constitutional feature is that an organic compound having a binding ability with the surface of the aluminum base material and a chelating ability with a noble metal ion is used as an active ingredient.
【００１１】更に、本発明が提供しようとするアルミニ
ウム基材の無電解めっき方法は、アルミニウム基材を脱
脂洗浄、上記前処理剤で貴金属イオンを捕捉及び還元の
各処理を施す前処理工程と、次いで無電解めっき処理と
施すめっき工程とからなることを構成上の特徴とするも
のである。Further, the electroless plating method for an aluminum base material to be provided by the present invention comprises a pretreatment step of degreasing and washing the aluminum base material, capturing the noble metal ions with the pretreatment agent and reducing the pretreatment. Then, it is characterized in that it comprises an electroless plating process and a plating process to be applied.
【００１２】本発明に係わる前処理剤とは、アルミニウ
ム基材表面と結合または強固に接着し、かつ、貴金属イ
オンとキレート結合能を有する有機化合物である。The pretreatment agent according to the present invention is an organic compound which is bonded or strongly adhered to the surface of an aluminum substrate and has a chelate-bonding ability with a noble metal ion.
【００１３】係る化合物としては、アミノ基、アミド
基、イミド基等貴金属イオンとキレート結合能を有する
官能基を備え、かつアルミニウム基材表面に強固に接着
する有機化合物、または上記官能基を備え、かつアルミ
ニウム表面の酸化膜と化学的に結合する官能基を備えた
有機化合物であり、例えばアミン系硬化剤により硬化す
るエポキシ樹脂、ポリアクリルアミド、メラミン樹脂、
尿素樹脂、γーアミノプロピルトリエトキシシラン、Ｎ
−βーアミノエチルーγーアミノプロピルトリメトキシ
シラン、Ｎ−βーアミノエチルーγーアミノプロピルメ
チルジメトキシシラン等がある。As such a compound, an organic compound having a functional group having a chelate-bonding ability with a noble metal ion such as an amino group, an amide group or an imide group and firmly adhering to an aluminum substrate surface, or the above functional group, And an organic compound having a functional group chemically bonded to the oxide film on the aluminum surface, for example, epoxy resin, polyacrylamide, melamine resin, which is cured by an amine-based curing agent.
Urea resin, γ-aminopropyltriethoxysilane, N
Examples include -β-aminoethyl-γ-aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane.
【００１４】係る前処理剤は、水又は有機溶剤に溶解し
た液であり、その濃度は化合物の種類や前処理方法によ
って多少異なるが、多くの場合０．１〜１００ｇ／ｌ、
好ましくは、０．５〜１０ｇ／ｌである。０．１ｇ／ｌ
未満の場合は表面の均一な改質効果を与えるのに不十分
であり、一方１００ｇ／ｌを越えると改質効果はあるけ
れども経済的でない。The pretreatment agent is a liquid dissolved in water or an organic solvent, and its concentration varies depending on the kind of the compound and the pretreatment method, but in many cases 0.1 to 100 g / l,
It is preferably 0.5 to 10 g / l. 0.1 g / l
If it is less than 100 g / l, it is not sufficient to provide a uniform surface modification effect, while if it exceeds 100 g / l, there is a modification effect, but it is not economical.
【００１５】係る前処理剤は、化合物の性質に応じ貴金
属イオンを含む液を混合して予め貴金属イオンをキレー
ト捕捉したものであっても差し支えない。The pretreatment agent may be prepared by mixing a liquid containing a noble metal ion according to the property of the compound and capturing the noble metal ion with a chelate in advance.
【００１６】この場合、貴金属イオンの処理剤に対する
混合比は１／４〜１／１０モルの範囲が好ましい。尚、
必要に応じ、ｐＨ調整剤、界面活性剤等を配合させても
良い。In this case, the mixing ratio of the noble metal ion to the treating agent is preferably 1/4 to 1/10 mol. still,
If necessary, a pH adjuster, a surfactant and the like may be added.
【００１７】次に、本発明に係る無電解めっき方法につ
いて説明する。本発明にかかる方法は、上記めっき前処
理剤を用いる前処理工程にその特徴がある。Next, the electroless plating method according to the present invention will be described. The method according to the present invention is characterized by a pretreatment process using the plating pretreatment agent.
【００１８】まず、弱アルカリ脱脂剤でアルミニウム基
材表面を清浄にする。次いで、もし、表面が粗雑で密着
性の悪い酸化膜で覆われている場合は除去する必要があ
るが、緻密な酸化膜で覆われている場合はその必要はな
い。また、従来法では、酸化膜除去に引きつずき、合金
や成型方法の種類に応じ、硝酸またはフッ酸の配合を変
えて表面調整を行う必要があったが、その様な煩雑な酸
処理の必要はない。First, the surface of the aluminum substrate is cleaned with a weak alkaline degreasing agent. Next, if the surface is covered with an oxide film that is rough and has poor adhesion, it needs to be removed, but if it is covered with a dense oxide film, it is not necessary. Further, in the conventional method, it was necessary to perform the surface adjustment by changing the compounding of nitric acid or hydrofluoric acid depending on the type of alloy or molding method, which is caused by the oxide film removal. No need for
【００１９】次いで、 上記前処理剤をアルミニウム基
材を浸漬するか、又は塗布した後、乾燥する。乾燥は一
般の加熱乾燥で充分であり、１００〜１４０℃にて充分
乾燥する。この乾燥操作を省くと良好なめっき被膜の形
成はできない。Next, the above-mentioned pretreatment agent is dipped in or applied to the aluminum substrate, and then dried. General drying by heating is sufficient, and it is sufficiently dried at 100 to 140 ° C. If this drying operation is omitted, a good plating film cannot be formed.
【００２０】係る処理剤による表面処理は、貴金属イオ
ンを担持させることが必要であるが、本発明では表面処
理と同時に担持捕捉させる場合と、表面処理と捕捉処理
とを経時的に行う２つの形態がある。The surface treatment with such a treating agent requires supporting noble metal ions. In the present invention, there are two modes of carrying and capturing simultaneously with the surface treatment and performing the surface treatment and the capturing treatment over time. There is.
【００２１】同時処理は、前記のように貴金属イオンを
予め含有してキレート化した前処理剤を用いればよく、
経時的処理は乾燥後行うものであって、いずれの形態で
行うかは目的に応じ選択すれば良い。経時的貴金属イオ
ンの担持処理は、上記乾燥物を貴金属塩の希薄な水溶液
に浸漬し、貴金属イオンを捕捉させる。この場合、該溶
液濃度は０．０５〜０．５ｇ／ｌの範囲が好ましい。The simultaneous treatment may be performed by using a pretreatment agent containing a noble metal ion in advance and chelated as described above,
The treatment with time is performed after drying, and which form should be performed may be selected according to the purpose. In the noble metal ion supporting treatment with time, the dried product is immersed in a dilute aqueous solution of a noble metal salt to capture the noble metal ion. In this case, the solution concentration is preferably in the range of 0.05 to 0.5 g / l.
【００２２】基材表面に表面処理を施し貴金属イオンを
捕捉させたアルミニウム基材は、次に還元剤水溶液に浸
漬して、貴金属イオンを無電解めっき反応の触媒機能を
有する金属に還元させる。ここに使用される還元剤は、
次亜リン酸ソーダ、水素化ホウ素ナトリウム、ジメチル
アミンボラン等が使用される。還元剤の濃度は０．１〜
５ｇ／ｌの範囲が好ましい。また、この還元剤水溶液に
は錯化剤、界面活性剤が存在している方が好ましいが、
必ずしも不可欠のものではない。The aluminum base material having the surface of the base material surface-treated to capture the noble metal ions is then immersed in a reducing agent aqueous solution to reduce the noble metal ions to a metal having a catalytic function for the electroless plating reaction. The reducing agent used here is
Sodium hypophosphite, sodium borohydride, dimethylamine borane, etc. are used. The concentration of the reducing agent is 0.1
A range of 5 g / l is preferred. Further, it is preferable that a complexing agent and a surfactant are present in this reducing agent aqueous solution,
Not necessarily essential.
【００２３】尚、適用できる貴金属イオンとしては、パ
ラジウム、銀、金、白金等の金属イオンであるが、パラ
ジウムイオンが特に好適である。The applicable noble metal ions are metal ions such as palladium, silver, gold and platinum, but palladium ions are particularly preferable.
【００２４】上記の前処理剤により処理されたアルミニ
ウム基材表面には貴金属イオンとキレート結合する反応
基がくまなく全面に緻密に分布しており、次いで、貴金
属塩水溶液に浸漬することにより貴金属イオンとキレー
ト結合し、引きつずく還元処理により、貴金属イオンが
還元されて原子状の貴金属が生成する。On the surface of the aluminum substrate treated with the above-mentioned pretreatment agent, reactive groups chelating with noble metal ions are densely distributed all over the surface, and then the noble metal ions are dipped in an aqueous solution of noble metal salt. By chelate-bonding with, and by a reduction treatment, the precious metal ion is reduced to form an atomic precious metal.
【００２５】すなわち、アルミニウム基材全面に原子状
の触媒核が緻密に捕捉分布される。かかる処理を施した
基材に無電解めっきを行う事により、微細な金属粒子が
濃密で実質的な連続皮膜として沈積形成される。That is, the atomic catalyst nuclei are densely captured and distributed on the entire surface of the aluminum base material. By performing electroless plating on the substrate thus treated, fine metal particles are deposited as a dense and substantially continuous film.
【００２６】本発明において、かかる前処理を施した後
の無電解めっき処理は特に限定することなく幅広く適用
できる。即ち、めっき金属塩、キレート剤、ｐＨ調整
剤、還元剤よりなる基本組成のめっき液を建浴したもの
にめっき基材を浸漬して行うか、構成めっき液を２液以
上と分けて添加方式でめっき処理を施すか適宜選択すれ
ば良い。In the present invention, the electroless plating treatment after such pretreatment can be widely applied without particular limitation. That is, the plating base material is immersed in a bath containing a plating solution having a basic composition consisting of a plating metal salt, a chelating agent, a pH adjusting agent, and a reducing agent, or the constituent plating solution is divided into two or more addition methods. It suffices to carry out the plating treatment with or to select appropriately.
【００２７】めっき金属としては、ニッケル、銀、金、
銅、コバルト等めっきの外にこれらの２種以上の合金ま
た他の金属との合金めっきを単層又は積層したものであ
っても良い。As the plating metal, nickel, silver, gold,
In addition to copper, cobalt, etc. plating, a single layer or a laminate of alloys of two or more of these or alloys with other metals may be used.
【００２８】還元剤としては、次亜燐酸ソーダ、水素化
ホウ素化合物、ジアルキルアミノボラン、ヒドラジン、
ホルマリン等が用いられる。As the reducing agent, sodium hypophosphite, borohydride compound, dialkylaminoborane, hydrazine,
Formalin or the like is used.
【００２９】無電解めっき処理は公知であり、適宜薬品
を選定調液して常法に従い、常温又加温下で行う。The electroless plating treatment is publicly known, and it is carried out at ordinary temperature or under heating according to a conventional method by appropriately selecting and preparing chemicals.
【００３０】本発明に係るめっき被覆物は、前記したよ
うに特徴的な前処理の為めっき皮膜が濃密で実質的な連
続皮膜として形成されたものである。The plated coating according to the present invention is one in which the plating film is formed as a dense and substantially continuous film due to the characteristic pretreatment as described above.
【００３１】ここに、濃密と言うのは、均質で微細な金
属粒子が緻密な状態にあることを言い、また、実質的な
連続皮膜とは、基材表面に濃密な状態で一様に覆われて
基材表面が殆ど露出していない状態を言う。このような
沈積被覆の状態にあるか否かは、通常の顕微鏡又は電子
顕微鏡の観察によって、視覚的に捕らえることが出来
る。Here, "dense" means that homogeneous and fine metal particles are in a dense state, and "substantially continuous film" means that the surface of the substrate is uniformly covered in a dense state. It means that the substrate surface is barely exposed. Whether or not it is in such a deposited coating state can be visually recognized by observation with a normal microscope or an electron microscope.
【００３２】本発明に係るめっきアルミニウムは濃密で
実質的な連続皮膜として被覆されているのに比べ、従来
法によるめっきアルミニウムは、金属粒子が粗くかつ不
均質で、いずれも瘤状粒子が存在しているのみならず、
基材の露出面が認められて濃密で実質的な連続皮膜でな
いことが判る。In contrast to the plated aluminum according to the present invention which is coated as a dense and substantially continuous film, the plated aluminum according to the conventional method has coarse and inhomogeneous metal particles, and in both cases, bump-shaped particles are present. Not only
The exposed surface of the substrate is recognized, and it can be seen that it is not a dense and substantially continuous film.
【００３３】さらに、本発明に係わる無電解めっき皮膜
は被覆力が強固であるため、使用における摩擦下の抵抗
性が従来法により得られるめっき皮膜に比べ著しく大き
い。Further, since the electroless plating film according to the present invention has a strong covering power, the resistance under friction during use is remarkably higher than that of the plating film obtained by the conventional method.
【００３４】尚、本発明において適用できるアルミニウ
ム系基材としては、純アルミニウムを始め、ほぼ全ての
アルミニウム合金材料に適用可能であり、また、板、
条、管、押出成形材の様な展伸材、鋳造、ダイカストの
様な鋳物成形材にも適用出来る。As the aluminum base material applicable in the present invention, it is possible to apply to almost all aluminum alloy materials including pure aluminum, plate,
It can also be applied to wrought materials such as strips, pipes and extruded materials, and cast molding materials such as casting and die casting.
【００３５】[0035]
【実施例】以下、本発明を実施例に基づいて更に具体的
に説明する。 実施例１〜８ 弱アルカリ脱脂剤溶液に浸漬し脱脂、水洗した、表１に
示した各アルミニウム合金材料をアミノシランカップリ
ング剤（チッソ株式会社製、商品名Ｓ−３３０）０．５
ｇ／ｌ水溶液に５分間浸漬した後、１００〜１１０℃で
乾燥した。次いで、０．１ｇ／ｌの塩化パラジウム及び
０．１ｇ／ｌの塩酸から成る処理剤１リットルに該材料
を３分間浸漬し基材表面にパラジウムイオンを付与させ
た。次いで、常温の１ｇ／ｌの次亜リン酸ソーダ水溶液
に５分間浸漬しパラジウムイオンを還元し前処理を完結
させた。次いで、硫酸ニッケル２５ｇ／ｌ、次亜リン酸
ソーダ２５ｇ／ｌ、クエン酸ソーダ２５ｇ／ｌ酢酸ソー
ダ１０ｇ／ｌ及び酢酸鉛０．００１ｇ／ｌからなるｐＨ
４．５の液温９０℃の無電解めっき液に３０分間浸漬し
た。得られためっきアルミニウム材料を下記方法で評価
したところ、第１表の結果が得られた。EXAMPLES The present invention will be described in more detail below based on examples. Examples 1 to 8 Aminosilane coupling agents (manufactured by Chisso Corporation, trade name S-330) of the aluminum alloy materials shown in Table 1 which were immersed in a weak alkaline degreasing agent solution, degreased and washed with water 0.5
After dipping in a g / l aqueous solution for 5 minutes, it was dried at 100 to 110 ° C. Then, the material was immersed in 1 liter of a treating agent consisting of 0.1 g / l palladium chloride and 0.1 g / l hydrochloric acid for 3 minutes to impart palladium ions to the surface of the substrate. Then, it was immersed in a 1 g / l sodium hypophosphite aqueous solution at room temperature for 5 minutes to reduce palladium ions and complete the pretreatment. Then, a pH consisting of 25 g / l of nickel sulfate, 25 g / l of sodium hypophosphite, 25 g / l of sodium citrate and 10 g / l of sodium acetate and 0.001 g / l of lead acetate.
It was immersed for 30 minutes in an electroless plating solution of 4.5 at a liquid temperature of 90 ° C. When the obtained plated aluminum material was evaluated by the following method, the results shown in Table 1 were obtained.
【００３６】尚、めっき性の評価は、ＳＥＭ観察、剥離
テスト、外観等の総合観察を行い、下記の４段階法で表
した。 ◎… めっき表面が濃密で実質的に連続性の平滑な皮膜
を形成し、密着性が良好なもの ○… めっき表面が粗で濃密性を欠くが、密着性は良好
なもの △… めっき表面が粗で濃密性を欠くと共に、密着性が
やや不良なもの ×… めっき表面が荒れが目立ち、膨れ発生して濃密性
を欠き、且つ密着性不良なものFor the evaluation of the plating property, the SEM observation, the peeling test, and the general observation such as the appearance were conducted, and the following four-step method was used. ◎ ... A plating surface is dense and forms a substantially continuous smooth film with good adhesion. Good ... A plating surface is rough and lacks denseness, but adhesion is good. Coarse and lacking in denseness and slightly inferior in adhesiveness × ... Roughness of the plating surface is noticeable and swelling occurs, lacking in denseness and inferior in adhesiveness
【００３７】 第１表 合金の種類 形材 めっき性 （ＪＩＳ） 実施例１ １０８０ 板材 ◎ 実施例２ １１００ 線材 ◎ 実施例３ ３００３ 板材 ◎ 実施例４ ５０５６ 板材 ◎ 実施例５ ６０６３ Ｉ材 ◎ 実施例６ ７０７５ 管材 ◎ 実施例７ ＡＣ１Ａ 鋳造品 ◎ 実施例８ ＡＤＣ１２ ダイカスト品 ◎ Table 1 Types of alloy Shape material Platability (JIS) Example 1 1080 plate material ◎ Example 2 1100 wire material ◎ Example 3 3003 plate material ◎ Example 4 5056 plate material ◎ Example 5 6063 I material ◎ Example 6 7075 Pipe material ◎ Example 7 AC1A cast product ◎ Example 8 ADC12 die cast product ◎
【００３８】実施例９〜１２ 弱アルカリ脱脂剤溶液に浸漬し脱脂、水洗した１１００
（ＪＩＳ呼称）の板材を表２に示す各処理剤１リットル
で処理し、１００〜１１０℃で乾燥した。以下、実施例
１と同様にパラジウムイオンを付与し、次いで還元し、
前処理を行った後、次いで実施例１〜８と同様の組成の
めっき浴にて無電解ニッケルめっきを３０分間行った。
得られためっき製品につき同様に評価したところ第２表
の結果が得られた。Examples 9 to 12 1100 immersed in a weak alkaline degreasing agent solution, degreased and washed with water
A plate material of (JIS name) was treated with 1 liter of each treatment agent shown in Table 2 and dried at 100 to 110 ° C. Thereafter, palladium ions were added and then reduced in the same manner as in Example 1,
After performing the pretreatment, electroless nickel plating was then performed for 30 minutes in a plating bath having the same composition as in Examples 1 to 8.
When the plated product thus obtained was evaluated in the same manner, the results shown in Table 2 were obtained.
【００３９】 第２表 前 処 理 剤 溶液濃度（溶剤） めっき性 実施例９ エポキシ樹脂 ２．０ｇ／ｌ ◎ （エタノール） 実施例１０ ポリアクリルアミド ５．０ｇ／ｌ ◎ （ 水 ） 実施例１１ γーアミノフ゜ロヒ゜ルトリエトキシシラン ０．５ｇ／ｌ ◎ （ 水 ） 実施例１２ βーアミノエチルー １．０ｇ／ｌ ◎ γーアミノフ゜ロヒ゜ルトリメトキシシラン （エタノール） Table 2 Pre-treatment agent Solution concentration (solvent) Platability Example 9 Epoxy resin 2.0 g / l ◎ (ethanol) Example 10 Polyacrylamide 5.0 g / l ◎ (water) Example 11 γ- Aminopropyltriethoxysilane 0.5 g / l ◎ (water) Example 12 β-Aminoethyl-1.0 g / l ◎ γ-Aminopropyltrimethoxysilane (ethanol)
【００４０】実施例１３ 弱アルカリ脱脂剤溶液に浸漬し脱脂、水洗した１１００
（ＪＩＳ呼称）の板材を、予め塩化パラジウムにてパラ
ジウムイオンをアミノシランカップリング剤（チッソ株
式会社製、商品名Ｓ−３３０）に対し１／１０モルの割
合でキレート化させた０．５ｇ／ｌ水溶液１リットルに
５分間浸漬した後、１００〜１１０℃で乾燥した。次い
で実施例１と同様な方法で還元しした後、次いで実施例
１〜８と同様の組成のめっき浴にて無電解ニッケルを３
０分間行った。得られためっき製品は、濃密で平滑な連
続性のニッケル皮膜で覆われており、且つ密着性も良好
であった。Example 13 1100 which was immersed in a weak alkaline degreasing agent solution, degreased and washed with water
A plate material of (JIS name) was chelated in advance with palladium chloride at a ratio of 1/10 mol with respect to an aminosilane coupling agent (manufactured by Chisso Corporation, trade name S-330) at a rate of 0.5 g / l. After dipping in 1 liter of the aqueous solution for 5 minutes, it was dried at 100 to 110 ° C. Then, after reducing in the same manner as in Example 1, electroless nickel was added to the plating bath with the same composition as in Examples 1 to 8 in a plating bath.
It went for 0 minutes. The obtained plated product was covered with a dense and smooth continuous nickel film and had good adhesion.
【００４１】比較例１ 弱アルカリ脱脂剤溶液に浸漬し脱脂、水洗した１１００
（ＪＩＳ呼称）の板材を、無水炭酸ナトリウム２０ｇ／
ｌ、第３リン酸ナトリウム２５ｇ／ｌの７０℃に加温し
た混合溶液１リットルに１５分間浸漬し脱錆し、水洗し
た。次いで、常温の１：１硝酸溶液に５分間浸漬し表面
調整を行った後、水洗した。次いで、苛性ソーダ１２０
ｇ／ｌ、酸化亜鉛２０ｇ／ｌ、シアン化ニッケル２ｇ／
ｌ、シアン化第一銅１ｇ／ｌから成るジンケート溶液１
リットルに６０秒間浸漬した後、水洗した。次いで、常
温の１：１硝酸に５分間浸漬しジンケート膜を剥離し、
水洗した後再び上記と同組成のジンケート溶液に３０秒
浸漬した後、水洗した。次いで、実施例１と同様の組成
の無電解ニッケルめっき液に同一条件で３０分間浸漬し
てめっき処理を施した。得られためっき製品は、その表
面がやや荒れたニッケル皮膜で覆われて濃密な連続性皮
膜を構成しておらず、且つ密着性も不良であった。Comparative Example 1 1100 immersed in a weak alkaline degreasing agent solution, degreased and washed with water
(JIS name) plate material, anhydrous sodium carbonate 20g /
1 and 1 g of a mixed solution of 25 g / l trisodium phosphate heated to 70 ° C. for 15 minutes for derusting and washing with water. Then, the surface was adjusted by immersing it in a 1: 1 nitric acid solution at room temperature for 5 minutes and then washing with water. Then caustic soda 120
g / l, zinc oxide 20 g / l, nickel cyanide 2 g /
1, a zincate solution 1 consisting of cuprous cyanide 1 g / l
It was immersed in liter for 60 seconds and then washed with water. Then, it is immersed in 1: 1 nitric acid at room temperature for 5 minutes to remove the zincate film,
After washing with water, it was again immersed in a zincate solution having the same composition as above for 30 seconds, and then washed with water. Then, the electroless nickel plating solution having the same composition as in Example 1 was immersed for 30 minutes under the same conditions to perform plating treatment. The obtained plated product did not form a dense continuous film with its surface covered with a slightly rough nickel film, and had poor adhesion.
【００４２】比較例２〜８ 弱アルカリ脱脂剤溶液に浸漬し脱脂、水洗した表３に示
す各アルミニウム合金板材を苛性ソーダ５０ｇ／ｌの常
温の溶液１リットルに５分間浸漬し、脱錆した、水洗し
た。次いで、表３に示した各アルミニウム合金材に対応
する表面調整液１リットルに５分間浸漬し表面調整を行
った。引きつずき水洗し、比較例１と同一組成のジンケ
ート処理液１リットルに夫れ々れ６０秒間浸漬した後、
水洗した。次いで続いて実施例１と同様組成の無電解ニ
ッケルめっき液に３０分間同一条件で浸漬してニッケル
めっき処理を施した。得られためっき製品につき同様に
評価したところ、第３表の結果が得られた。Comparative Examples 2 to 8 Each aluminum alloy plate material shown in Table 3 which was immersed in a weak alkaline degreasing agent solution, degreased and washed with water was immersed in 1 liter of a caustic soda 50 g / l room temperature solution for 5 minutes to be derusted and washed with water. did. Next, the surface was adjusted by immersing it in 1 liter of the surface adjusting liquid corresponding to each aluminum alloy material shown in Table 3 for 5 minutes. After rinsing with water and dipping for 60 seconds in 1 liter of the zincate treatment liquid having the same composition as in Comparative Example 1,
Washed with water. Then, subsequently, the nickel plating treatment was performed by immersing in an electroless nickel plating solution having the same composition as in Example 1 for 30 minutes under the same conditions. When the plated product thus obtained was evaluated in the same manner, the results shown in Table 3 were obtained.
【００４３】 第３表 合金の種類 調整液組成 めっき性 （ＪＩＳ） 比較例２ １０８０ １：１硝酸 ○ 比較例３ ３００３ １：１硝酸 × 比較例４ ５０５６ ２５容量％硫酸 ○ 比較例５ ６０６３ ２５容量％硫酸 △ 比較例６ ７０７５ 硝酸３：フッ化水素酸１ × 比較例７ ＡＣ１Ａ 硝酸３：フッ化水素酸１ × 比較例８ ＡＤＣ１２ 硝酸３：フッ化水素酸１ × Table 3 Types of alloys Adjustment liquid composition Platability (JIS) Comparative example 2 1080 1: 1 nitric acid ○ Comparative example 3 3003 1: 1 nitric acid × Comparative example 4 5056 25% by volume sulfuric acid ○ Comparative example 5 6063 25 volumes % Sulfuric acid Δ Comparative example 6 7075 Nitric acid 3: Hydrofluoric acid 1 × Comparative example 7 AC1A Nitric acid 3: Hydrofluoric acid 1 × Comparative example 8 ADC12 Nitric acid 3: Hydrofluoric acid 1 ×
【００４４】[0044]
【発明の効果】本発明の前処理剤を使用すれば、基材表
面を強酸および強アルカリ等を使用することがないの
で、前処理に引きつずき無電解めっきを施したものは、
従来の欠点である不均質なめっき皮膜を改善してより均
質で強固な密着性と被覆力を有する無電解めっきアルミ
ニウム材料を提供することができる。EFFECTS OF THE INVENTION When the pretreatment agent of the present invention is used, the surface of the substrate is free from strong acids and strong alkalis.
It is possible to provide an electroless plated aluminum material having a more uniform and firm adhesion and covering power by improving the conventional disadvantage of non-uniform plating film.
Claims (4)
し、且つ貴金属イオンとキレート能を有する有機化合物
を有効成分とすることを特徴とするアルミニウム基材の
無電解めっき前処理剤。1. A pretreatment agent for electroless plating of an aluminum base material, which comprises an organic compound capable of binding to the surface of the aluminum base material and having a chelating ability with a noble metal ion as an active ingredient.
し、且つ貴金属イオンとキレート能を有する有機化合物
はアミノ基置換オルガノシラン系カップリング剤、アミ
ン系硬化剤で硬化するエポキシ樹脂、ポリアクリルアミ
ド、メラミン樹脂又は尿素樹脂から選ばれた１種又は２
種以上である請求項１記載のアルミニウム系基材の無電
解めっき前処理剤。2. An organic compound having a binding ability with the surface of an aluminum base material and having a chelating ability with a noble metal ion is an amino group-substituted organosilane coupling agent, an epoxy resin curable with an amine curing agent, or polyacrylamide. 1 or 2 selected from melamine resin or urea resin
The pretreatment agent for electroless plating of an aluminum-based substrate according to claim 1, which is one or more kinds.
キレート捕捉したものである請求項１または２記載のア
ルミニウム系基材の無電解めっき前処理剤。3. The pretreatment agent for an electroless plating of an aluminum-based substrate according to claim 1, wherein the pretreatment agent for electroless plating is a chelate-capturing noble metal ion.
１，２又は３いずれか記載の前処理剤で貴金属イオンを
捕捉及び還元の各処理を施す前処理工程と、次いで無電
解めっきを施すめっき工程とからなることを特徴とする
アルミニウム基材の無電解めっき方法。4. A pretreatment step of degreasing and washing an aluminum-based substrate, performing a treatment of capturing and reducing noble metal ions with the pretreatment agent according to claim 1, or 2 and then performing electroless plating. A method of electroless plating an aluminum base material, which comprises a plating step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3361554A JP3071286B2 (en) | 1991-11-29 | 1991-11-29 | Pretreatment agent for electroless plating of aluminum base material and electroless plating method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3361554A JP3071286B2 (en) | 1991-11-29 | 1991-11-29 | Pretreatment agent for electroless plating of aluminum base material and electroless plating method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05156456A true JPH05156456A (en) | 1993-06-22 |
| JP3071286B2 JP3071286B2 (en) | 2000-07-31 |
Family
ID=18474050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3361554A Expired - Fee Related JP3071286B2 (en) | 1991-11-29 | 1991-11-29 | Pretreatment agent for electroless plating of aluminum base material and electroless plating method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3071286B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002237497A (en) * | 2001-02-09 | 2002-08-23 | Citizen Watch Co Ltd | Electrode forming method of semiconductor element |
| WO2003002780A1 (en) * | 2001-06-28 | 2003-01-09 | Nikko Materials Co., Ltd. | Surface treatment agent, article surface-treated therewith and method of nickel plating using the agent |
| JP2003041374A (en) * | 2001-07-31 | 2003-02-13 | Nikko Materials Co Ltd | Surface treatment agent and surface treated article therewith |
| JP2007262495A (en) * | 2006-03-28 | 2007-10-11 | Nippon Chem Ind Co Ltd | Electroconductive electroless-plated powder and production method therefor |
| JP2017031476A (en) * | 2015-08-03 | 2017-02-09 | 東京応化工業株式会社 | Silane coupling agent aqueous solution, method for manufacturing monomolecular film and plating molding method |
-
1991
- 1991-11-29 JP JP3361554A patent/JP3071286B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002237497A (en) * | 2001-02-09 | 2002-08-23 | Citizen Watch Co Ltd | Electrode forming method of semiconductor element |
| WO2003002780A1 (en) * | 2001-06-28 | 2003-01-09 | Nikko Materials Co., Ltd. | Surface treatment agent, article surface-treated therewith and method of nickel plating using the agent |
| JP2003041374A (en) * | 2001-07-31 | 2003-02-13 | Nikko Materials Co Ltd | Surface treatment agent and surface treated article therewith |
| JP2007262495A (en) * | 2006-03-28 | 2007-10-11 | Nippon Chem Ind Co Ltd | Electroconductive electroless-plated powder and production method therefor |
| WO2007119417A1 (en) * | 2006-03-28 | 2007-10-25 | Nippon Chemical Industrial Co., Ltd | Conductive powder plated by electroless plating and process for producing the same |
| TWI419996B (en) * | 2006-03-28 | 2013-12-21 | Nippon Chemical Ind | Conductive electroless plating powder and its manufacturing method |
| JP2017031476A (en) * | 2015-08-03 | 2017-02-09 | 東京応化工業株式会社 | Silane coupling agent aqueous solution, method for manufacturing monomolecular film and plating molding method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3071286B2 (en) | 2000-07-31 |
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