JPH11124681A - Plating method for polycarbonate or (and) abs resin molded goods - Google Patents

Plating method for polycarbonate or (and) abs resin molded goods

Info

Publication number
JPH11124681A
JPH11124681A JP30803897A JP30803897A JPH11124681A JP H11124681 A JPH11124681 A JP H11124681A JP 30803897 A JP30803897 A JP 30803897A JP 30803897 A JP30803897 A JP 30803897A JP H11124681 A JPH11124681 A JP H11124681A
Authority
JP
Japan
Prior art keywords
fluorine
plating
polycarbonate
abs resin
concn
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.)
Pending
Application number
JP30803897A
Other languages
Japanese (ja)
Inventor
Tsuguo Hashimoto
嗣夫 橋本
Hirohisa Kikuyama
裕久 菊山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
STELLA KEMIFUA KK
Original Assignee
STELLA KEMIFUA KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by STELLA KEMIFUA KK filed Critical STELLA KEMIFUA KK
Priority to JP30803897A priority Critical patent/JPH11124681A/en
Publication of JPH11124681A publication Critical patent/JPH11124681A/en
Pending legal-status Critical Current

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  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

PROBLEM TO BE SOLVED: To reform the surfaces of resin molded goods and to impart hydrophilicity thereto by bringing the molded goods into contact with fluorine for a specific time under an atmosphere of a specific fluorine concn. and specifying the contact angle of the surfaces to a specific value or below. SOLUTION: The polycarbonate or ABS resin molded goods are brought into contact with the fluorine for 1 to 30 minutes, more preferably 1 to 15 minutes under an atmosphere of 0.1 to 10% in the fluorine concn. If the long- time treatment is executed with the gaseous fluorine of the excessively high concn. in this case, the direction of water repellence is resulted and, therefore, such treatment is disadvantageous. As a result, the contact angle is confined to <=80 deg. by imparting hydrophilicity to the contact surfaces. The fluorine concn. refers to the content of the fluorine in a gaseous mixture composed of the gaseous fluorine and another inert gas. N2 , Ar, He, CO2 , etc., are used as the inert gas. The surfaces of the resins fluorinated by this treatment are made flat and plating is adhered thereto by the high polar force imparted by the fluorine. Ordinary electroless plating is applied to the plating.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明はポリカーボネート又は
(及び)ABS樹脂成形品のメッキ方法に関し、更に詳
しくは、極めて簡単な方法で従来困難とされてきたポリ
カーボネートやABS樹脂成形品のメッキを容易に行い
うる方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of plating a molded article of polycarbonate or (and) ABS resin, and more particularly, to a method of plating a molded article of polycarbonate or ABS resin which has been conventionally difficult by a very simple method. Regarding possible methods.

【0002】[0002]

【従来の技術】ポリカーボネートやABS樹脂の表面は
疎水性が大きくそのままではメッキすることが非常に困
難である。ポリカーボネートやABS樹脂表面にメッキ
を施すためには、クロム−硫酸液によるエッチングで極
性化と表面に凹凸を付ける方法が知られている。
2. Description of the Related Art The surface of polycarbonate or ABS resin has a large hydrophobicity, and it is very difficult to perform plating as it is. In order to perform plating on the surface of a polycarbonate or ABS resin, a method is known in which the surface is made polar by etching with a chromium-sulfuric acid solution.

【0003】しかし、この方法によるポリカーボネート
やABS樹脂の処理では、エッチング剤のクロム硫酸の
処理が難しく、環境対策に重大な問題を有していた。
[0003] However, in the treatment of polycarbonate or ABS resin by this method, it is difficult to treat chromic sulfuric acid as an etching agent, which has a serious problem in environmental measures.

【0004】[0004]

【発明が解決しようとする課題】本発明はフッ素を用い
て容易にポリカーボネートやABS樹脂の表面を改質
し、親水性を付与し、その上にメッキ、好ましくは無電
解メッキを施す方法を開発することにある。
SUMMARY OF THE INVENTION The present invention has developed a method of easily modifying the surface of a polycarbonate or ABS resin using fluorine to impart hydrophilicity, and then plating, preferably electroless plating thereon. Is to do.

【0005】[0005]

【課題を解決するための手段】この課題は、ポリカーボ
ネート又は(及び)ABS樹脂成形品を、フッ素濃度
0.1〜10%の雰囲気下で1〜30分、好ましくは1
〜15分間接触せしめて、表面の接触角を80度以下に
なし、次いで常法に従ってメッキを行うことにより解決
される。
The object of the present invention is to provide a molded article of polycarbonate or (and) ABS resin in an atmosphere having a fluorine concentration of 0.1 to 10% for 1 to 30 minutes, preferably 1 to 30 minutes.
The problem can be solved by contacting for about 15 minutes to reduce the contact angle of the surface to 80 degrees or less, and then performing plating according to a conventional method.

【0006】本発明者は既にポリプロピレン成形品につ
いて、フッ素と接触させてその表面を親水化させると、
その表面にうまくメッキ出来ることを見いだし、既に出
願(特開平8−302039号)した。
The present inventor has already found that when a polypropylene molded article is brought into contact with fluorine to make its surface hydrophilic,
It was found that the surface could be plated well, and an application was already filed (JP-A-8-302039).

【0007】[0007]

【発明の作用】本発明者は引き続く研究に於いて、ポリ
プロピレンと同様にメッキの極めて困難なポリカーボネ
ートやABS樹脂についても、ポリプロピレンとは化学
常識上全く異なった樹脂ではあるが、実に驚くべきこと
に、フッ素と接触させ、次いでメッキを行うとうまくメ
ッキができることを見出した。即ち、希薄なフッ素濃度
で、短時間通常1〜30分間、常温でポリカーボネート
やABS樹脂成形品の表面を処理すると、その表面の水
に対する接触角が低下し、80度以下、著しい場合は7
0度以下にまで低下し、次いでこの上に常法に従ってメ
ッキを行うと、うまくメッキが行えることを見出したも
のである。本発明はこの新しい知見に基づいて完成され
ている。
In the following research, the present inventor has found that polycarbonate and ABS resin, which are extremely difficult to be plated like polypropylene, are completely different from polypropylene due to chemical common sense. It has been found that plating can be performed well by contacting with fluorine and then plating. That is, when the surface of a polycarbonate or ABS resin molded product is treated with a dilute fluorine concentration for a short period of time, usually 1 to 30 minutes, at room temperature, the contact angle of the surface with water decreases, and is 80 ° or less, and in the case of a remarkable 7 ° C.
It has been found that when the temperature is reduced to 0 degrees or less, and then plating is performed on this in accordance with a conventional method, plating can be performed successfully. The present invention has been completed based on this new finding.

【0008】ポリカーボネート及びABS樹脂に対する
フッ素化を10分間、フッ素濃度を変化させて行い、接
触角への影響を調べた。結果を表1に示した。
The fluorination of polycarbonate and ABS resin was performed for 10 minutes while changing the fluorine concentration, and the effect on the contact angle was examined. The results are shown in Table 1.

【0009】[0009]

【表1】 [Table 1]

【0010】フッ素濃度が濃くなると接触角が大きくな
っていくことが認められた。フッ素濃度を2%にしてフ
ッ素化時間による影響を調べた結果を表2に示した。時
間が長くなると接触角が大きくなることが認められた。
It has been found that as the fluorine concentration increases, the contact angle increases. Table 2 shows the results of examining the effect of the fluorination time at a fluorine concentration of 2%. It was observed that the contact angle increased with increasing time.

【0011】[0011]

【表2】 [Table 2]

【0012】但し表1は室温で、ポリカーボネート及び
ABS樹脂成形品を使用したものであり、又表2は表1
に於いてフッ素濃度2%の場合について、そのフッ素化
時間だけを変えたものである。
However, Table 1 shows the results obtained by using molded products of polycarbonate and ABS resin at room temperature.
In the case where the fluorine concentration is 2%, only the fluorination time is changed.

【0013】ポリカーボネート及びABS樹脂の表面を
フッ素化の前後で電子顕微鏡写真を撮り、表面の状態を
調べたが、表面の荒れには差が認められなかった。
Electron micrographs were taken of the surfaces of the polycarbonate and ABS resin before and after fluorination, and the surface condition was examined. No difference was found in the surface roughness.

【0014】本発明の処理方法により、フッ素化された
ポリカーボネートやABS樹脂の表面は平坦である。従
ってフッ素により発現された強い極性力によりメッキが
付着するものと考えられる。濃い濃度のフッ素ガス又は
長時間処理すると撥水性の方向になるのでフッ素ガス濃
度0.1〜10%、好ましくは0.5〜5%で1〜30
分、好ましくは1〜15分、特に好ましくは1〜10分
の処理で親水化させるのが良い。
The surface of the fluorinated polycarbonate or ABS resin obtained by the treatment method of the present invention is flat. Therefore, it is considered that the plating adheres due to the strong polar force exerted by fluorine. If the treatment is performed at a high concentration of fluorine gas or for a long time, water repellency is obtained.
Minutes, preferably 1 to 15 minutes, particularly preferably 1 to 10 minutes.

【0015】ポリカーボネートやABS樹脂の表面をフ
ッ素で処理後、無電解メッキし、その表面をJISH8
630の方法で剥離テストを行った。その結果接触角が
80度以下のものは全然剥離しなかった。80度を越え
るとメッキが付かなかった。この結果接触角が80度以
下でないとメッキの付着性に好結果は得られない。
After the surface of polycarbonate or ABS resin is treated with fluorine, it is subjected to electroless plating, and the surface is subjected to JIS 8
A peel test was performed by the method of 630. As a result, those having a contact angle of 80 degrees or less did not peel at all. When it exceeded 80 degrees, no plating was applied. As a result, good results cannot be obtained for the plating adhesion unless the contact angle is not more than 80 degrees.

【0016】本発明に於けるフッ素濃度0.1〜10%
はフッ素ガスと他の不活性ガスとの混合ガス中にフッ素
が0.1〜10%含有されているものを指し、この際の
不活性ガスとしては、たとえばN2、アルゴンヘリウ
ム、炭酸ガス等が使用される。この際該濃度が0.1%
未満の場合は所期の効果が得難く、又10%より高くな
ると既に述べた通り接触角を80度以下とすることは出
来ない。
The fluorine concentration in the present invention is 0.1 to 10%.
Indicates a gas containing 0.1 to 10% of fluorine in a mixed gas of fluorine gas and another inert gas. Examples of the inert gas include N 2 , argon helium, carbon dioxide gas and the like. Is used. At this time, the concentration is 0.1%
If it is less than 10%, the desired effect is hardly obtained, and if it exceeds 10%, the contact angle cannot be reduced to 80 degrees or less as already described.

【0017】接触せしめる手段は特に制限されず、要は
ポリカーボネートやABS樹脂成形品表面が全面均一に
接触する手段であれば良い。
The means for making the contact is not particularly limited, and any means may be used as long as the entire surface of the polycarbonate or ABS resin molded article is in uniform contact.

【0018】メッキを施すに際しては、従来のメッキ方
法に従ってメッキを施せば良く、通常無電解メッキが適
用される。
When plating is performed, plating may be performed according to a conventional plating method, and usually, electroless plating is applied.

【0019】[0019]

【実施例】以下に実施例を示して本発明を更に具体的に
説明する。
The present invention will be described more specifically with reference to the following examples.

【0020】[0020]

【実施例1】表1で得られたフッ素濃度2%の各サンプ
ルに、ニッケルの無電解メッキを行った。サンプルの表
面を超純水で洗浄後、塩化すず(SnCl2:40g/
L,HCl(37%):40mL/L)の溶液に室温で
3分間浸漬した。水洗後塩化パラジウム(PdCl2
0.2g/L,HCL(37%):3mL/L)の溶液
に室温で3分間浸漬した。水洗後ニッケルメッキ浴(次
亜燐酸ニッケル:26.7g/L、ほう酸:12.0g/
L、硫酸アンモニウム:2.6g/L、硫酸ナトリウ
ム:4.9g/L)に25〜30℃で1時間浸漬してメ
ッキした。メッキした試験片を60℃、1時間安定化処
理してから、その表面に1mm間隔で切り目を入れ、粘
着テープを張り付け、引きはがして100個の格子のう
ちメッキ皮膜の剥がれた数を評価値とした。テスト結果
を表3に示した。剥離度は全然剥がれなかった場合が0
%である。但し、BLはブランクで、BL−1はフッ素
処理を施していないポリカーボネートを、またBL−2
は同じくABS樹脂を示す。
Example 1 Each sample having a fluorine concentration of 2% obtained in Table 1 was subjected to electroless plating of nickel. After washing the surface of the sample with ultrapure water, tin chloride (SnCl 2 : 40 g /
L, HCl (37%): 40 mL / L) at room temperature for 3 minutes. After washing with water, palladium chloride (PdCl 2 :
It was immersed in a solution of 0.2 g / L, HCL (37%): 3 mL / L) at room temperature for 3 minutes. After washing with water, nickel plating bath (nickel hypophosphite: 26.7 g / L, boric acid: 12.0 g /
L, ammonium sulfate: 2.6 g / L, sodium sulfate: 4.9 g / L) and plated at 25-30 ° C. for 1 hour. After stabilizing the plated test piece at 60 ° C for 1 hour, make a cut at 1mm interval on the surface, attach adhesive tape, peel off and evaluate the number of peeled plating film out of 100 grids. And The test results are shown in Table 3. The degree of peeling was 0 when no peeling occurred.
%. However, BL is blank, BL-1 is polycarbonate not treated with fluorine, and BL-2 is
Denotes an ABS resin.

【0021】[0021]

【表3】 [Table 3]

【0022】[0022]

【実施例2】実施例1で得られたサンプルに銅の無電解
メッキを行った。サンプルの表面を超純水で洗浄後、塩
化すず(SnCl2:40g/L,HCl(37%):4
0mL/L)の溶液に室温で3分間浸漬した。水洗後塩
化パラジウム(PdCl2:0.2g/L,HCL(37
%):3mL/L)の溶液に室温で3分間浸漬した。水
洗後銅メッキ浴(硫酸銅:12.0g/L、ロッセル
塩:30.0g/L、36%ホルマリン液:40mL/
L,チオ尿素:1mg/L,pH=12.5)に50〜
70℃で1時間浸漬してメッキした。メッキした試験片
を60℃、1時間安定化処理してから、その表面に1m
m間隔で切り目を入れ、粘着テープを張り付け、引きは
がして100個の格子のうちメッキ皮膜の剥がれた数を
評価値とした。テスト結果を表4に示した。剥離度は全
然剥がれなかった場合が0%である。また、BL−1及
びBL−2は表3に同じ。
Example 2 The sample obtained in Example 1 was subjected to copper electroless plating. After washing the surface of the sample with ultrapure water, tin chloride (SnCl 2 : 40 g / L, HCl (37%): 4)
(0 mL / L) at room temperature for 3 minutes. After washing with water, palladium chloride (PdCl 2 : 0.2 g / L, HCL (37
%): 3 mL / L) at room temperature for 3 minutes. After washing with water, copper plating bath (copper sulfate: 12.0 g / L, Rossel salt: 30.0 g / L, 36% formalin solution: 40 mL /
L, thiourea: 50 mg / L, pH = 12.5)
It was immersed at 70 ° C. for 1 hour for plating. Stabilize the plated test piece at 60 ° C for 1 hour, then apply 1m
Cuts were made at intervals of m, an adhesive tape was stuck, the sheet was peeled off, and the number of peeled plating films out of 100 grids was used as an evaluation value. The test results are shown in Table 4. The degree of peeling was 0% when no peeling occurred. BL-1 and BL-2 are the same as in Table 3.

【0023】[0023]

【表4】 [Table 4]

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】ポリカーボネート又は(及び)ABS樹脂
成形品をフッ素濃度0.1〜10%の雰囲気に1〜30
分接触させて、その表面を親水化させ、接触角を80度
以下になし、次いで常法によりメッキすることを特徴と
するポリカーボネート又は(及び)ABS樹脂成形品の
メッキ方法。
1. A polycarbonate or (and) ABS resin molded product is exposed to an atmosphere having a fluorine concentration of 0.1 to 10% in an atmosphere of 1 to 30%.
A method for plating a molded article of polycarbonate or (and) ABS resin, which comprises contacting each other to hydrophilize the surface thereof, setting the contact angle to 80 degrees or less, and then performing plating by a conventional method.
JP30803897A 1997-10-21 1997-10-21 Plating method for polycarbonate or (and) abs resin molded goods Pending JPH11124681A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP30803897A JPH11124681A (en) 1997-10-21 1997-10-21 Plating method for polycarbonate or (and) abs resin molded goods

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP30803897A JPH11124681A (en) 1997-10-21 1997-10-21 Plating method for polycarbonate or (and) abs resin molded goods

Publications (1)

Publication Number Publication Date
JPH11124681A true JPH11124681A (en) 1999-05-11

Family

ID=17976148

Family Applications (1)

Application Number Title Priority Date Filing Date
JP30803897A Pending JPH11124681A (en) 1997-10-21 1997-10-21 Plating method for polycarbonate or (and) abs resin molded goods

Country Status (1)

Country Link
JP (1) JPH11124681A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008081838A (en) * 2006-08-28 2008-04-10 Daicel Polymer Ltd Plated resin-molded body
JP2010150460A (en) * 2008-12-26 2010-07-08 Takamatsu Teisan Kk Method of modifying surface of polymer compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008081838A (en) * 2006-08-28 2008-04-10 Daicel Polymer Ltd Plated resin-molded body
JP2010150460A (en) * 2008-12-26 2010-07-08 Takamatsu Teisan Kk Method of modifying surface of polymer compound

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