JP2734020B2 - Manufacturing method of copper-plated resin molded product - Google Patents
Manufacturing method of copper-plated resin molded productInfo
- Publication number
- JP2734020B2 JP2734020B2 JP27939488A JP27939488A JP2734020B2 JP 2734020 B2 JP2734020 B2 JP 2734020B2 JP 27939488 A JP27939488 A JP 27939488A JP 27939488 A JP27939488 A JP 27939488A JP 2734020 B2 JP2734020 B2 JP 2734020B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- molded product
- resin molded
- molded article
- temperature
- 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 - Lifetime
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、熱変形劣化温度が165℃より高い耐熱性の
繊維強化或いは未強化の熱可塑性又は熱硬化性樹脂成形
品に均一な銅被膜を形成する新規な方法に関するもので
あり、本製造法による銅メッキ成形品は、特別の前処理
をすることなく銅が強固に均一に溝、孔等にも付着した
ものであり、しかもハロゲンなどの腐食性を有する元素
を全く含まないものであるので、そのままで或いは更に
銅その他の金属をメッキなどの下地として各種用途に好
適に使用されるものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat-resistant fiber-reinforced or unreinforced thermoplastic or thermosetting resin molded article having a heat deformation deterioration temperature higher than 165 ° C. The present invention relates to a novel method of forming a copper-plated product, in which copper is firmly and uniformly attached to grooves, holes, etc. without special pretreatment, and furthermore, halogen, etc. Since it does not contain any corrosive elements, it is preferably used as it is or further with copper or other metal as a base for plating or the like for various uses.
通常、熱可塑性樹脂成形品に、銅被膜を形成する方法
としては、無電解メッキ法、蒸着法、圧接法、接着剤に
よる接着などがある。In general, as a method for forming a copper film on a thermoplastic resin molded product, there are an electroless plating method, a vapor deposition method, a pressure welding method, adhesion with an adhesive, and the like.
無電解メッキ法は、最も一般的であり低温メッキが可
能であることから優れた方法であるが、通常は特別の前
処理を必須とするものである。この前処理工程を省いた
り簡略化するためにジエン系ゴム等を予め配合してなる
組成物からの成形品を使用する方法があるが、樹脂本来
の性能が劣化する場合が多い。また、ガラス繊維等の強
化材を配合した樹脂成形品の場合、強化材表面も同時に
強固に密着した良好なメッキをすることは困難であるこ
とから、強化材が成形品の表面に露出した部分が容易に
剥離するなどの欠点があった。The electroless plating method is the most common and is an excellent method because low-temperature plating is possible, but usually requires a special pretreatment. In order to omit or simplify the pretreatment step, there is a method of using a molded article from a composition in which a diene rubber or the like is previously compounded, but the original performance of the resin is often deteriorated. Also, in the case of a resin molded product containing a reinforcing material such as glass fiber, it is difficult to perform good plating in which the surface of the reinforcing material is also firmly adhered to at the same time. However, there was a defect such as easy peeling.
蒸着法は、蒸着のための特別の設備を必須とし、また
物品の種類によっては接着性を向上させるための前処理
が必要であった。更に、圧接法、接着剤による接着など
適宜使用されるものであるが、圧着不可能であったり、
成形品の形状が限定されたり、接着剤を使用する場合、
接着層が厚くなり、接着層の物性が得られた物品の物性
を劣化させるなどの欠点があるものであった。The vapor deposition method requires special equipment for vapor deposition, and depending on the type of article, requires a pretreatment to improve adhesiveness. Furthermore, it is used as appropriate, such as pressure welding, bonding with an adhesive,
If the shape of the molded product is limited or if an adhesive is used,
There were drawbacks such as an increase in the thickness of the adhesive layer and deterioration in the physical properties of the article obtained with the physical properties of the adhesive layer.
更に、蟻酸銅を物品に塗布し、非酸化性の雰囲気中で
加熱処理すると銅被膜が付着した物品が得られることは
知られている。しかし、従来この方法を熱可塑性樹脂や
熱硬化性樹脂の成形品に適用した例はなく、また、多量
生産に適した方法もなく、実用化されるに至っていな
い。Further, it is known that when copper formate is applied to an article and heat-treated in a non-oxidizing atmosphere, an article having a copper film adhered thereto can be obtained. However, heretofore, there is no example of applying this method to a molded article of a thermoplastic resin or a thermosetting resin, and there is no method suitable for mass production, and the method has not been put to practical use.
本発明は、上記の事情に鑑み、簡便な方法により、経
済的で高品質の銅膜の形成された樹脂成形品を提供する
方法について検討した結果、完成したものである。In view of the above circumstances, the present invention has been completed as a result of studying a method for providing an economical and high-quality resin molded product having a copper film formed thereon by a simple method.
すなわち、本発明は、変形劣化温度が165℃より高い
樹脂成形品の所望部に、蟻酸銅を溶解或いは分散した溶
液を塗布し130℃以下の温度で乾燥して蟻酸銅を付着さ
せ、非酸化性雰囲気中或いは減圧下で、165℃以上で該
成形品の変形劣化温度以下の範囲の所定温度に、温度13
0℃〜該所定温度の間を1deg/分以上の速度で昇温し保持
することを特徴とする銀メッキ樹脂成形品の製造法であ
り、蟻酸銅の付着量を0.005g/cm2以上とすること、付着
に用いる蟻酸銅の溶液として無水蟻酸銅粉末を沸点200
℃以下の有機溶媒に分散させた溶液を使用すること、蟻
酸銅を付着させた該成形品の近傍に追加の蟻酸銅を共存
させること、さらに蟻酸銅を付着させた該成形品多数個
を容器に収納するか或いは配置用具に配置して加熱処理
することからなる銅メッキされた樹脂成形品を製造する
方法である。That is, according to the present invention, a solution in which copper formate is dissolved or dispersed is applied to a desired portion of a resin molded product having a deformation deterioration temperature higher than 165 ° C., dried at a temperature of 130 ° C. or less, and adhered with copper formate, and non-oxidized. In a neutral atmosphere or under reduced pressure, the temperature is raised to a predetermined temperature in the range of 165 ° C or higher and the deformation / deterioration temperature of the molded article.
A method for producing a silver-plated resin molded article characterized in that the temperature is raised and maintained at a rate of 1 deg / min or more between 0 ° C and the predetermined temperature, and the amount of copper formate attached is 0.005 g / cm 2 or more. To a solution of copper formate used for the adhesion, anhydrous copper formate powder having a boiling point of 200
Using a solution dispersed in an organic solvent at a temperature of not more than ℃, adding additional copper formate in the vicinity of the molded article to which copper formate is adhered, and further adding a large number of the molded article to which copper formate is adhered to a container This is a method of producing a copper-plated resin molded product, which is housed in a container or placed in a placement tool and heat-treated.
以下、本発明について説明する。 Hereinafter, the present invention will be described.
本発明の変形劣化温度が165℃より高い樹脂成形品と
は、通常、射出成形、圧縮成形、トランスファー成形、
その他手段で成形してなる通常、溝、孔等を有する立体
形状の成形品であり、耐熱性の熱可塑性樹脂や熱硬化性
樹脂からなるものである。The resin molded article having a deformation deterioration temperature higher than 165 ° C. of the present invention is usually injection molding, compression molding, transfer molding,
Usually, it is a three-dimensional molded product having grooves, holes, and the like formed by other means, and is made of a heat-resistant thermoplastic resin or thermosetting resin.
ここに熱可塑性樹脂としては、ナイロン−６、ナイロ
ン−66、ナイロン−6/66、ナイロン−11、ナイロン−
３、メタキシリレンジアミンと脂肪族ジカルボン酸類か
ら誘導されるMXD6、MXD6/10などのポリアミド樹脂、ポ
リブチレンテレフタレート、ポリエチレンテレフタレー
トなどの結晶性ポリエステル樹脂などの汎用エンジニア
リングプラスチック類;P−ヒドロキシ安息香酸、フタル
酸、ビスフェノールなどを主要モノマーとする全芳香族
ポリエステルやこれらにポリエチレンテレフタレート等
をグラフトしてなる芳香族ポリエステル液晶ポリマー、
ポリエーテルイミド、ポリスルホン、ポリサルホン、ポ
リエーテルサルホン、ポリエーテルエーテルケトン、ポ
リフェニレンエーテル、ポリフェニレンサルファイド等
のエンジニアリングプラスチック並びにこれらのポリマ
ーの繊維、ミネラル、その他充填材強化物等が挙げら
れ、これらの中でも、上記した変形劣化温度が190℃以
上のものは好ましく、特に繊維強化したものにも好適に
適用される。また、熱硬化性樹脂としては、フェノール
樹脂、ジアリルフタレート樹脂、エポキシ樹脂、ポリア
ミン−ビスマレイミド樹脂、ポリマレイミド−エポキシ
樹脂、ポリマレイミド−イソシアネート樹脂、シアナト
樹脂、シアネート−エポキシ樹脂、シアネート−ポリマ
レイミド樹脂、シアネート−エポキシ−ポリマレイミド
樹脂等の通常の熱硬化性樹脂類；上記の熱硬化性樹脂類
とポリアミド（ナイロン）、芳香族ポリエステル、ポリ
エーテルイミド、ポリエーテルエーテルケトン、ポリサ
ルホン、ポリフェニレンエーテルなどのエンジニアリン
グプラスチックとを配合し、さらに適宜触媒類を付加し
てなる熱硬化性の所謂「IPN」；ポリエチレンなどのポ
リオレフィン、1,2−ポリブタジエンなどの樹脂に架橋
剤としての有機過酸化物に、更に適宜ラジカル重合性の
多官能性の化合物、熱硬化性樹脂などを配合してなる架
橋硬化性の樹脂類など、並びにこれらにガラス、炭素、
アルミナ、その他の繊維、繊維織布、粉体、その他充填
材を配合した強化物等が挙げられる。Here, as the thermoplastic resin, nylon-6, nylon-66, nylon-6 / 66, nylon-11, nylon-
3, MXD6 derived from meta-xylylenediamine and aliphatic dicarboxylic acids, general-purpose engineering plastics such as polyamide resins such as MXD6 / 10, crystalline polyester resins such as polybutylene terephthalate and polyethylene terephthalate; P-hydroxybenzoic acid; Phthalic acid, a wholly aromatic polyester having a main monomer such as bisphenol, or an aromatic polyester liquid crystal polymer obtained by grafting polyethylene terephthalate or the like onto these,
Polyetherimide, polysulfone, polysulfone, polyethersulfone, polyetheretherketone, polyphenyleneether, engineering plastics such as polyphenylenesulfide and the fibers of these polymers, minerals, and other filler-reinforced materials, among others, Those having the above-mentioned deformation deterioration temperature of 190 ° C. or more are preferable, and are particularly suitably applied to fiber-reinforced ones. Further, as the thermosetting resin, phenol resin, diallyl phthalate resin, epoxy resin, polyamine-bismaleimide resin, polymaleimide-epoxy resin, polymaleimide-isocyanate resin, cyanate resin, cyanate-epoxy resin, cyanate-polymaleimide resin And ordinary thermosetting resins such as cyanate-epoxy-polymaleimide resin; and the above thermosetting resins and polyamide (nylon), aromatic polyester, polyetherimide, polyetheretherketone, polysulfone, polyphenyleneether and the like. Thermosetting so-called "IPN" obtained by blending engineering plastics and further adding catalysts as appropriate; polyolefins such as polyethylene, and organic peroxides as cross-linking agents for resins such as 1,2-polybutadiene. Suitable Radically polymerizable polyfunctional compounds, crosslinking curable resins obtained by blending and thermosetting resins such as, as well as glass to, carbon,
Alumina, other fibers, fiber woven fabric, powder, and reinforced materials containing other fillers may be used.
本発明の蟻酸銅を溶解或いは分散した溶液とは無水蟻
酸銅、蟻酸銅四水和物或いはこれらの混合物などの蟻酸
第二銅化合物を蟻酸銅と実質的に反応しない比較的沸点
の低い溶媒に溶解或いは粉末を均一分散させた溶液であ
り、好適な溶媒としては水、アルコール、脂肪族炭化水
素、芳香族炭化水素、その他の好適には沸点200℃以下
のものが例示され、特に、無水蟻酸の場合には、水を含
まない有機溶媒、例べば、ヘプタン、ヘキサン、シクロ
ヘキサン、オクタン、プロパノール、ブタノール、ヘプ
タノール、ベンゼン、トルエン、キシレンなどと蟻酸銅
微粉末とを混練してなる分散溶液を用いるのが好適であ
る。なお、印刷用のインキ組成物等と同様に使用する場
合にはより高沸点の溶媒を選択して、減圧で乾燥する方
法も使用できるものである。The solution in which the copper formate of the present invention is dissolved or dispersed means a cupric formate compound such as anhydrous copper formate, copper formate tetrahydrate or a mixture thereof in a solvent having a relatively low boiling point which does not substantially react with copper formate. A solution obtained by dissolving or uniformly dispersing a powder. Examples of suitable solvents include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, and other suitable solvents having a boiling point of 200 ° C. or lower, especially formic anhydride. In the case of, a water-free organic solvent, for example, heptane, hexane, cyclohexane, octane, propanol, butanol, heptanol, benzene, toluene, xylene, etc. and a dispersion solution obtained by kneading a fine powder of copper formate. It is preferred to use. When the ink composition is used in the same manner as the printing ink composition, a method of selecting a solvent having a higher boiling point and drying it under reduced pressure can also be used.
上記した成形品の所望部に上記の蟻酸銅の溶液が塗布
し、乾燥、付着させる。塗布の方法は、刷毛塗、ディピ
イング、スプレーコート、バーコート、ロールコート、
印刷などその他の塗布手段が例示され、又、乾燥は蟻酸
銅の分解開始温度以下、通常、130℃以下、特に110℃以
下の温度で加熱或いは減圧乾燥する。ここに、所望面の
略全面に蟻酸銅が付着していればよく、多少のバラツキ
は特に問題とはならない。例えば、溝、穴などが蟻酸銅
の粉体或いは結晶状物で閉塞されていても通常１μｍ程
度以下の銅膜が溝、穴等の壁面に生成して溝、穴などを
閉塞することはないものである。また、成形品の全面で
はなく、一部分に銅メッキをするには所望部にのみ塗布
する方法や所望部以外を剥離性のレジスト類等を用い被
覆しておき、全面に塗布し、そのまま或いはレジストを
剥離する方法による。The above-mentioned copper formate solution is applied to a desired portion of the above-mentioned molded article, dried and adhered. The method of application is brush coating, depiring, spray coating, bar coating, roll coating,
Other coating means such as printing are exemplified, and drying is performed by heating or drying under reduced pressure at a temperature lower than the decomposition start temperature of copper formate, usually 130 ° C or lower, particularly 110 ° C or lower. Here, it is sufficient that copper formate adheres to substantially the entire desired surface, and slight variation does not cause any particular problem. For example, even if the grooves and holes are closed with copper formate powder or crystalline material, a copper film having a thickness of about 1 μm or less usually does not form on the walls of the grooves and holes and does not close the grooves and holes. Things. In addition, to apply copper plating only to a desired portion, not to the entire surface of the molded product, to apply copper only to a desired portion, or to coat a portion other than the desired portion with a releasable resist or the like, apply the entire surface, and then apply the resist as it is or as a resist. By the method of peeling off.
上記で得た蟻酸銅付着成形品を、非酸化性雰囲気中或
いは減圧下で165℃以上で該成形品の変形劣化温度以下
の範囲の所定温度に、温度130℃〜該所定温度の間を1de
g/分以上の速度で昇温し保持することにより、銅メッキ
成形品を得る。The molded product obtained by attaching copper formate obtained above is heated to a predetermined temperature in a range of 165 ° C. or more and a deformation deterioration temperature of the molded product in a non-oxidizing atmosphere or under reduced pressure, and a temperature between 130 ° C. and the predetermined temperature is 1 de.
By raising and maintaining the temperature at a rate of g / min or more, a copper-plated molded product is obtained.
加熱機器としては、赤外線、電子線、マイクロ波など
の放射線加熱、電気炉、オーブン、オイル加熱、加圧蒸
気加熱、その他の手段を適宜選択する。バッチ式又は被
加熱物品の導入部、加熱部、冷却取り出し部を持った連
続式加熱機など何れでもよい。また、樹脂成形品の変形
劣化温度によっては、加熱処理温度と変形劣化温度とが
近接する場合があるので設定温度のバラツキの小さいも
のとする。As the heating device, radiation heating such as infrared rays, electron beams, and microwaves, an electric furnace, an oven, oil heating, pressurized steam heating, and other means are appropriately selected. It may be any of a batch type or a continuous type heating machine having an introduction section, a heating section, and a cooling take-out section for articles to be heated. In addition, depending on the deformation deterioration temperature of the resin molded product, the heat treatment temperature and the deformation deterioration temperature may be close to each other.
加熱方法は、実質的に非酸化性雰囲気下或いは減圧下
で165℃以上で該成形品の変形劣化温度以下の範囲の所
定温度に、温度130℃〜該所定温度の間を1deg/分以上の
速度で昇温し保持することを除き特に限定はないが、16
5℃以上で該成形品の変形劣化温度以下の範囲の所定温
度に設定された加熱部として熱盤を持った加熱機器に投
入する方法は、昇温速度を速くできる。また、昇温速度
１〜35℃／分、特に２〜20℃／分で所定温度まで加熱
し、同温度に保持するのがよい。又、加熱時間は３時間
以下、好ましくは１〜60分間である。昇温速度が１℃／
分未満では得られるメッキ膜が不均一となったり、接着
強度が劣ったものと成ったりし易いので好ましくなく、
余りに速いと多数の成形品を同時に処理する場合に生じ
る接触部にも銅メッキが連続的に生成し、接触部を隔離
のための銅粉末の生成が妨げられたので好ましくない。The heating method is performed under a substantially non-oxidizing atmosphere or under a reduced pressure to a predetermined temperature in a range of 165 ° C. or more and a deformation degradation temperature of the molded article, and a temperature between 130 ° C. and the predetermined temperature of 1 deg / min or more. There is no particular limitation except that the temperature is raised and maintained at a speed, but 16
A method in which a heating unit set to a predetermined temperature within a range of 5 ° C. or higher and a temperature equal to or lower than the deformation deterioration temperature of the molded product is introduced into a heating device having a hot plate can increase a heating rate. Further, it is preferable to heat to a predetermined temperature at a heating rate of 1 to 35 ° C./min, particularly 2 to 20 ° C./min, and to maintain the same temperature. The heating time is 3 hours or less, preferably 1 to 60 minutes. Heating rate is 1 ℃ /
Less than a minute is not preferred because the resulting plating film is non-uniform or tends to have poor adhesive strength,
If the speed is too high, copper plating is continuously formed also on the contact portions generated when a large number of molded articles are processed at the same time, which hinders the generation of copper powder for isolating the contact portions.
非酸化性雰囲気とする方法は公知の、N2,Ar,CO2,CO,H
2などのガスを導入する方法、成形品を入れた加熱機器
内部の容積を小さくして実質的に蟻酸銅の分解ガス雰囲
気とする方法が例示され、特に連続式の加熱機器を用い
る場合には、加熱部への入口と出口の開口面積を小さく
することにより、不活性ガスを使用することなく容易に
分解ガス雰囲気に保持される。また、減圧とする方法
は、減圧可能な加熱器を用いる方法、被メッキ成形品を
減圧可能な容器内に収納し容器内のみ減圧とする方法又
は特に連続式加熱機器を用い、被メッキ成形品の導入部
と取り外し部を減圧室を配置する方法などが例示され、
減圧度は400Torr以下、特に200Torr以下とすることが好
ましい。Non-oxidizing atmosphere can be obtained by a known method such as N 2 , Ar, CO 2 , CO, H
Examples of the method of introducing a gas such as 2, a method of reducing the volume inside the heating device containing the molded product and substantially setting the gas atmosphere to a decomposition gas atmosphere of copper formate, particularly when using a continuous heating device By reducing the opening area of the inlet and the outlet to the heating section, it is possible to easily maintain the decomposition gas atmosphere without using an inert gas. The method of reducing the pressure may be a method using a heater capable of reducing the pressure, a method of storing the article to be plated in a container capable of reducing the pressure and reducing the pressure only in the container, or a method of forming the article to be plated using a continuous heating device. Examples of the method of arranging the decompression chamber for the introduction part and the removal part of the
The degree of pressure reduction is preferably 400 Torr or less, particularly preferably 200 Torr or less.
以上の方法により本発明の銅メッキ成形品を製造する
が、上記に一部触れたように本発明においては蟻酸銅を
付着させた樹脂成形品を収納し加熱処理するための容器
或いは配置用具を用いて、加熱機器への被メッキ用の樹
脂成形品を投入、取り出しの効率を高め、かつ、メッキ
条件のムラを小さくできるので好ましく、特に商業的に
多量生産を行う場合には好適である。Although the copper-plated molded product of the present invention is manufactured by the above method, as mentioned above, in the present invention, a container or an arrangement tool for storing and heat-treating a resin molded product to which copper formate is attached is provided. It is preferable because it can increase the efficiency of loading and unloading a resin molded product to be plated into a heating device and can reduce unevenness in plating conditions, and is particularly suitable for commercial mass production.
ここに、上記の容器、配置用具としては、処理温度に
耐える材質ができたものであれば、金属、樹脂、その他
特に限定はないが、通常はアルミニウム、鉄、銅、その
他の金属製のものである。容器或いは配置用具は成形品
を複数個、より密に配置し、かつ、投入、取り出し操作
を容易とするように成形品の形状、用いる加熱機器等に
応じて適宜最適な形を選択或いは設計する。なお、前記
した無水蟻酸銅粉末の揮発性の有機溶媒分散液を使用す
る好ましい方法の場合には必ずしも必要としないが、成
形品の形状、特に高さによっては、容器上部或いは蓋、
配置用具の上部に追加の蟻酸銅配置部を設けそこに配置
するのが、上下によるメッキ厚みのバラツキをより小さ
くできるので好ましい。Here, the above-mentioned container and the disposing tool are not particularly limited as long as they are made of a material that can withstand the processing temperature, but are not particularly limited, but are usually made of aluminum, iron, copper, and other metals. It is. For the container or the placement tool, a plurality of molded products are arranged more densely, and an optimal shape is appropriately selected or designed according to the shape of the molded product, the heating equipment to be used, etc. so as to facilitate the loading and unloading operations. . In the case of the preferred method of using a volatile organic solvent dispersion of the above-described copper formate anhydride powder, the method is not necessarily required. However, depending on the shape of the molded product, particularly the height, a container upper portion or a lid,
It is preferable to provide an additional copper formate arranging portion on the upper portion of the arranging tool and arrange it there, since the variation in plating thickness due to the vertical direction can be further reduced.
以上の方法で加熱処理した後、室温に冷却して、所望
部が銅メッキされ、かつ、被膜形成に関与しなかった蟻
酸銅から生成した銅粉末で接触部が隔離された銅メッキ
成形品を得る。この銅粉体は成形品を軽く拭く方法、空
気を吹きつける方法、その他の手段で容易に除去され
る。取り出された銅メッキ成形品は、必要に応じて公知
の防錆処理を施すこと、更に、公知の銅、ニッケル、金
その他金属の無電解メッキ或いは電解メッキなど適宜施
す。After the heat treatment by the above method, cooled to room temperature, a copper-plated molded product in which a desired portion is copper-plated, and a contact portion is isolated by a copper powder generated from copper formate which did not participate in film formation. obtain. The copper powder is easily removed by lightly wiping the molded article, blowing air, or other means. The taken-out copper-plated molded product is subjected to a known rustproofing treatment, if necessary, and further appropriately subjected to a known electroless plating or electrolytic plating of copper, nickel, gold or other metals.
ここに、この余分の銅粉末が生成しない場合には、成
形品相互間、成形品と容器或いは補助具間を隔離する特
別の手段を講じることが必須となるが、この手段を実現
するには多大の人手を必要としたり、２回以上の処理を
必須とするものとなるものであり、生産性の点から必要
なメリットとなるものである。Here, if this excess copper powder is not generated, it is necessary to take special measures to isolate the molded articles from each other, or between the molded article and the container or the auxiliary tool. This requires a great deal of manpower or requires two or more processes, which is a necessary merit in terms of productivity.
以下，実施例、比較例によって本発明をさらに具体的
に説明する。尚、実施例、比較例中の部は特に断らない
限り重量基準である。Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Parts in Examples and Comparative Examples are based on weight unless otherwise specified.
実施例１ 無水蟻酸銅粉末100部とブチルアルコール50部とを混
練して無水蟻酸銅粉末が均一に分散した分散溶液（以
下、処理液１という）を得た。Example 1 100 parts of anhydrous copper formate powder and 50 parts of butyl alcohol were kneaded to obtain a dispersion solution in which the anhydrous copper formate powder was uniformly dispersed (hereinafter referred to as treatment liquid 1).
炭素繊維強化メタキシリレンジアミンとアジピン酸と
からのナイロンMXD6を射出成形して得た厚さ3mm、幅140
mm、高さ55mmのやや湾曲したメガネフレーム成形品を用
い、この成形品に処理液１を塗布した後、100℃で乾燥
して無水蟻酸銅を全面に付着させた。Thickness 3mm, width 140 obtained by injection molding nylon MXD6 from carbon fiber reinforced meta-xylylenediamine and adipic acid
Using a slightly curved spectacle frame molded product having a height of 55 mm and a height of 55 mm, the treatment liquid 1 was applied to the molded product, and then dried at 100 ° C. to adhere anhydrous copper formate to the entire surface.
縦200mm、横300mm、高さ55mmのアルミニウム製で、横
部にガス注排出用のコック付ノズルを設けた蓋付の箱を
用意し、この箱に、前記で得たメガネフレーム30個の収
納配置し、N2をノズルから箱内に吹き込みつつ蓋をし、
N2吹き込みパイプをはずした後、これを減圧可能な上下
に加熱盤を有する。230℃に予熱した加熱器の加熱盤間
に入れ、加熱器内を数Torrまで減圧し、そのまま30分間
保持した。なお、箱内の昇温速度は７℃／分であった。Prepare a box with a lid of 200 mm in length, 300 mm in width and 55 mm in height and provided with a nozzle with a cock for gas injection and discharge in the horizontal part, and this box stores the 30 eyeglass frames obtained above Place, cover while blowing N 2 from the nozzle into the box,
After removing the N 2 blowing pipe, it has a heating plate above and below that can depressurize it. It was placed between the heating plates of the heater preheated to 230 ° C., the pressure inside the heater was reduced to several Torr, and the temperature was maintained for 30 minutes. The rate of temperature rise in the box was 7 ° C./min.
減圧を止め、箱を取り出し、室温に放冷して、銅メッ
キされたメガネフレームを得た。The decompression was stopped, the box was taken out, and allowed to cool to room temperature to obtain a copper-plated eyeglass frame.
得られたメガネフレームには銅膜が均一にフレーム同
士の接触部や容器内壁との接触部にも密着しており、接
触部での銅メッキ層の連続化による接着は全く無く、溝
部分にも過剰の銅膜の生成はなく、炭素繊維の跡も全く
見られなかった。In the obtained eyeglass frame, the copper film is evenly adhered to the contact part between the frames and the contact part with the inner wall of the container, and there is no adhesion due to the continuation of the copper plating layer at the contact part, and the groove part No excessive copper film was formed, and no trace of carbon fiber was observed.
又、この銅膜の厚みは0.2〜0.5μｍで、表面抵抗0.05
〜0.5Ω／□、セロハンテープによるクロスカットテス
トをした結果は100/100であった。The thickness of this copper film is 0.2 to 0.5 μm, and the surface resistance is 0.05
0.50.5Ω / □, the result of a cross cut test using cellophane tape was 100/100.
このフレームを用い、電解銅メッキをした結果均一な
光沢ある銅メッキメガネフレームが得られた。As a result of performing electrolytic copper plating using this frame, a uniform glossy copper-plated eyeglass frame was obtained.
実施例２ 実施例１において、加熱器に実施例１と同様の蓋をし
た箱を入れ、N2をノズルから箱内に吹き込みつつ蓋を
し、加熱器内を減圧としない他は同様として、実施例１
と同様の均一に銅メッキされたメガネフレームを得た。Example 2 In Example 1, a box with the same lid as in Example 1 was placed in the heater, and the lid was closed while blowing N 2 from the nozzle into the box. Example 1
An eyeglass frame uniformly plated with copper was obtained.
実施例３ 実施例１において、処理液１にかえて、蟻酸銅を飽和
させた水溶液を使用したものを用いる他は同様として全
面に銅メッキされたメガネフレームを得た。なお、銅メ
ッキ厚さは0.2〜1.0μｍであり、外観はやや不均一であ
った。Example 3 An eyeglass frame plated with copper was obtained in the same manner as in Example 1, except that an aqueous solution saturated with copper formate was used instead of the treatment liquid 1. The copper plating thickness was 0.2 to 1.0 μm, and the appearance was slightly uneven.
実施例４ 実施例１において、メガネフレームにかえて、直径約
35mm、高さ約10mmの歯車を用いる他は同様にして表面の
み銅メッキされた歯車を得た。尚、銅メッキ厚さは0.2
〜0.5μｍであった。Example 4 In Example 1, instead of the glasses frame, the diameter was about
A copper-plated gear was obtained in the same manner except that a gear having a height of about 35 mm and a height of about 10 mm was used. The copper plating thickness is 0.2
0.50.5 μm.
実施例５ モデル成形品として、片面に幅2mm及び1mmの角溝、Ｖ
字溝、並びに直径5mm、3mm及び1mmのドリル穴を形成
し、他面は平滑である厚み3mm、幅40mm、長さ145mmの下
記に記載した樹脂製の成形品を準備した。Example 5 As a model molded product, a square groove having a width of 2 mm and 1 mm on one side, V
A resin-made molded product described below having a groove having a thickness of 3 mm, a width of 40 mm, and a length of 145 mm, in which drill holes having diameters of 5 mm, 3 mm, and 1 mm were formed and the other surface was smooth, was prepared.
．成形品1:炭素繊維強化メタキシリレンジアミンとア
ジピン酸とからのナイロンMXD6 （商品名；レニー1022、三菱瓦斯化学（株）製） ．成形品2:ガラス繊維強化メタキシリレンジアミンと
アジピン酸とからのナイロンMXD6 （商品名；レニーＥ−40、三菱瓦斯化学（株）製） ．成形品3:炭素繊維強化ナイロン6/66共重合体 ．成形品4:ポリアリレート． （商品名,Uポリマー、ユニチカ（株）製） ．成形品5:ポリサルホン． （商品名；ユーデルポリサルフォン、アモコケミカル
ズ（株）製） ．成形品6:20重量％ガラス繊維強化ポリエーテルサル
ホン （三井東圧（株）製） ．成形品7:ポリエーテルイミド （商品名；ウルテム、GE社製） ．成形品8:ポリエーテルエーテルケトン （商品名；ビクトレックス、英国ICI社製） ．成形品9:ガラス繊維強化ポリエチレンテレフタレー
ト樹脂 ．成形品10:ガラス繊維強化ポリカーボネート樹脂． （商品名；ユーピロン、三菱瓦斯化学（株）製） ．成形品11:ガラス繊維強化ポリフェニレンサルファ
イド樹脂． また、配置用の補助具として厚み0.3mmのアルミニウ
ムシートを折り曲げて、折り曲げ面に対して垂直方向か
ら見た断面が5mm間隔で高さ10mmの高さの突起部のある
櫛状物を準備した。. Molded article 1: Nylon MXD6 from carbon fiber reinforced meta-xylylenediamine and adipic acid (trade name: Reny 1022, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded product 2: Nylon MXD6 from glass fiber reinforced meta-xylylenediamine and adipic acid (trade name: Reny E-40, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded article 3: Carbon fiber reinforced nylon 6/66 copolymer. Molded article 4: polyarylate. (Product name, U-Polymer, manufactured by Unitika Ltd.) Molded article 5: polysulfone. (Product name: Udel Polysulfone, manufactured by Amoco Chemicals Co., Ltd.). Molded product 6: 20% by weight glass fiber reinforced polyether sulfone (manufactured by Mitsui Toatsu Co., Ltd.). Molded product 7: polyetherimide (trade name; Ultem, manufactured by GE) Molded product 8: Polyetheretherketone (trade name: Victrex, manufactured by ICI, UK). Molded product 9: Glass fiber reinforced polyethylene terephthalate resin. Molded product 10: Glass fiber reinforced polycarbonate resin. (Product name: Iupilon, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded article 11: glass fiber reinforced polyphenylene sulfide resin. In addition, as a placement aid, a 0.3 mm-thick aluminum sheet was folded to prepare a comb-like material having a projection with a height of 10 mm at intervals of 5 mm at a cross section viewed from a direction perpendicular to the bent surface. .
これら成形品及び補助具を処理液１に浸漬し、乾燥し
た。These molded articles and auxiliary tools were immersed in the treatment liquid 1 and dried.
ついで、これら成形品を上記の補助具を用いて実施例
１と同様の箱中に２個づつ配置収納し、第１表に記載の
処理条件でメッキした結果を第１表に示した。Next, two of these molded articles were placed and stored in the same box as in Example 1 by using the above-mentioned auxiliary tool, and plated under the processing conditions shown in Table 1. The results are shown in Table 1.
なお、銅膜外観は目視観察によるものであり、○は均
一密着銅膜の生成を示し、△は成形品の変形を示す。The appearance of the copper film was determined by visual observation. ○ indicates the formation of a uniformly adhered copper film, and △ indicates deformation of the molded product.
実施例６ 実施例５において、成形品１〜10に代えて、下記の熱
硬化性樹脂の成形品を使用する他は同様とした。結果を
第２表に示した。 Example 6 Example 5 was the same as Example 5 except that molded articles of the following thermosetting resin were used instead of molded articles 1 to 10. The results are shown in Table 2.
．成形品12:ガラス繊維強化エポキシ樹脂 （三菱瓦斯化学（株）製） ．成形品13:キシリレンジアミンとエピクロルヒドリ
ンとより合成される四官能エポキシ樹脂 （三菱瓦斯化学（株）製）、商品名：エトラッドＸ）
を用いたガラス繊維強化品 ．成形品14:炭素繊維強化シアン酸エステル−マレイ
ミド−エポキシ系樹脂 （三菱瓦斯化学（株）製） 〔発明の作用および効果〕 以上の如くである本発明の製造法によれば、従来は特
別の前処理を施した後でなければ、無電解メッキなどで
密着性に優れた銅膜を形成することが困難であった樹脂
成形品に極めて簡単な手段により容易に密着性に優れた
銅膜が形成された成形品が製造できる。. Molded product 12: Glass fiber reinforced epoxy resin (Mitsubishi Gas Chemical Co., Ltd.). Molded article 13: tetrafunctional epoxy resin synthesized from xylylenediamine and epichlorohydrin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Etrad X)
Glass fiber reinforced product using. Molded article 14: Carbon fiber reinforced cyanate-maleimide-epoxy resin (Mitsubishi Gas Chemical Co., Ltd.) [Functions and Effects of the Invention] According to the manufacturing method of the present invention as described above, a copper film with excellent adhesion is formed by electroless plating or the like unless conventionally subjected to a special pretreatment. It is possible to easily produce a molded article having a copper film having excellent adhesion on a resin molded article which has been difficult to perform by extremely simple means.
しかも、多量に一括処理しても相互が微粉末状の銅に
より隔離されて銅メッキにより接着されることがないも
のであるので容易に多量生産ができるものである。In addition, even if a large amount is processed at a time, the particles are separated from each other by copper in the form of fine powder and are not bonded by copper plating, so that mass production can be easily performed.
この銅メッキ樹脂成形品の銅メッキ層は電気メッキ、
無電解メッキ、その他の手段により銅、ニッケル、クロ
ム、銀、金、その他のメッキを容易に均一にできるもの
であることから、そのまま或いはこれらメッキした製品
の安価な下地処理として好適に使用されるものである。The copper plating layer of this copper plating resin molded product is electroplated,
It can be easily and uniformly plated with copper, nickel, chromium, silver, gold, and other materials by electroless plating or other means. Therefore, it is suitably used as it is or as an inexpensive undercoating for these plated products. Things.
Claims (5)
の所望部に、蟻酸銅を溶解或いは分散した溶液を塗布し
130℃以下の温度で乾燥して蟻酸銅を付着させ、非酸化
性雰囲気中或いは減圧下で165℃以上で該成形品の変形
劣化温度以下の範囲の所定温度に、温度130℃〜該所定
温度の間を1deg/分以上の速度で昇温し保持することを
特徴とする銅メッキ樹脂成形品の製造法．1. A solution in which copper formate is dissolved or dispersed is applied to a desired portion of a resin molded product having a deformation deterioration temperature higher than 165 ° C.
It is dried at a temperature of 130 ° C. or less, and copper formate is adhered thereto. A method for producing a copper-plated resin molded product, wherein the temperature is raised and maintained at a rate of 1 deg / min or more.
請求項１記載の銅メッキ樹脂成形品の製造法．2. The method for producing a copper-plated resin molded article according to claim 1, wherein the amount of the copper formate attached is 0.005 g / cm 2 or more.
下の有機溶媒に分散させた溶液である請求項１記載の銅
メッキ樹脂成形品の製造法．3. The process for producing a copper-plated resin molded article according to claim 1, wherein said solution is a solution in which copper formate anhydride powder is dispersed in an organic solvent having a boiling point of 200 ° C. or lower.
の蟻酸銅を共存させる請求項１記載の銅メッキ樹脂成形
品の製造法．4. The method for producing a copper-plated resin molded article according to claim 1, wherein additional copper formate is present in the vicinity of the molded article to which copper formate is adhered.
に収納するか或いは配置用具に配置して加熱処理する請
求項１記載の銅メッキ樹脂成形品の製造法．5. The method for producing a copper-plated resin molded article according to claim 1, wherein a large number of said molded articles having copper formate adhered thereon are housed in a container or placed in a placement tool and heat-treated.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27939488A JP2734020B2 (en) | 1988-11-07 | 1988-11-07 | Manufacturing method of copper-plated resin molded product |
| KR1019890016012A KR0137370B1 (en) | 1988-11-07 | 1989-11-06 | Process for the preparation of plastic product plated with cupper |
| EP89120578A EP0368231B1 (en) | 1988-11-07 | 1989-11-07 | Process of producing copper plated resin article |
| DE68916180T DE68916180T2 (en) | 1988-11-07 | 1989-11-07 | Process for the production of copper-clad plastic articles. |
| US07/432,811 US5106462A (en) | 1988-11-07 | 1989-11-07 | Process of producing copper plated resin article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27939488A JP2734020B2 (en) | 1988-11-07 | 1988-11-07 | Manufacturing method of copper-plated resin molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02129380A JPH02129380A (en) | 1990-05-17 |
| JP2734020B2 true JP2734020B2 (en) | 1998-03-30 |
Family
ID=17610512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27939488A Expired - Lifetime JP2734020B2 (en) | 1988-11-07 | 1988-11-07 | Manufacturing method of copper-plated resin molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2734020B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131394A (en) * | 2005-11-09 | 2007-05-31 | Sanwa Tekki Corp | Hoisting accessory for container conveyance |
-
1988
- 1988-11-07 JP JP27939488A patent/JP2734020B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02129380A (en) | 1990-05-17 |
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