JPH06235169A - Method of metallizing surface of polyester fiber - Google Patents
Method of metallizing surface of polyester fiberInfo
- Publication number
- JPH06235169A JPH06235169A JP1870493A JP1870493A JPH06235169A JP H06235169 A JPH06235169 A JP H06235169A JP 1870493 A JP1870493 A JP 1870493A JP 1870493 A JP1870493 A JP 1870493A JP H06235169 A JPH06235169 A JP H06235169A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- polyester fiber
- polyester
- electroless plating
- immersed
- 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
Links
Landscapes
- Chemically Coating (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面を金属で被覆したポ
リエステル繊維の製造方法に関する。得られた密着性の
高い金属被膜を有するポリエステル繊維は帯電防止用繊
維として衣料用途或いは工業用途に利用することができ
る。或いはテレビジョン、コンピュ−タ−等の放射線遮
蔽材等に利用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyester fiber whose surface is coated with a metal. The obtained polyester fiber having a highly adherent metal coating can be used as an antistatic fiber for clothing or industrial applications. Alternatively, it can be used as a radiation shielding material for televisions, computers and the like.
【０００２】[0002]
【従来の技術】一般にポリエステル繊維の表面を金属化
するに際し、無電解メッキ法が実用化されている。アル
カリ溶液などでエッチング処理を行い表面を粗面化し、
先ず塩化第一スズなどの比較的還元性の強い剤を繊維表
面に吸着させ、次いでパラジウムなどの貴金属イオンを
含む触媒溶液に浸漬させ、繊維表面に貴金属を析出させ
る。その後、公知の方法で無電解メッキ（化学メッキ）
を行うが、湿式の工程が複雑であり処理剤の浴中への持
ち込みなどで処理液の寿命が短く改善が待たれていた
（特開昭５８−１７１４１９号公報、特開昭６０−９９
０７１号公報等）。2. Description of the Related Art Generally, an electroless plating method has been put into practical use when metalizing the surface of polyester fibers. Roughening the surface by etching with an alkaline solution,
First, a relatively strongly reducing agent such as stannous chloride is adsorbed on the fiber surface, and then immersed in a catalyst solution containing a noble metal ion such as palladium to deposit the noble metal on the fiber surface. After that, electroless plating (chemical plating) by a known method
However, the wet process is complicated and the service life of the processing solution is short due to the carry-in of the processing agent into the bath, and the improvement has been awaited (JP-A-58-171419, JP-A-60-99).
071, etc.).
【０００３】[0003]
【発明の目的】本発明は以上の事情を背景としてなされ
たものであり，本発明の目的は従来より簡便なポリエス
テル繊維表面金属化方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for metallizing the surface of polyester fiber which is simpler than conventional methods.
【０００４】[0004]
【発明の構成】すなわち本発明は「 ポリエステル繊維
に２４８ｎｍの波長を有する紫外線パルスレーザー光
を、パルスエネルギー（フルエンス５０〜１５０mJ/c
m2) の条件下で２０〜５０パルス照射した後、洗浄し、
しかるのちに活性化処理を行い、次いで無電解メッキ処
理を施すことを特徴とするポリエステル繊維の表面金属
化法。」である。すなわちポリエステル繊維に２４８ｎ
ｍの波長を有する紫外線パルスレーザー光を照射し、ポ
リエステル繊維表面に化学変化及び結晶配向変化などを
伴う微細な凹凸構造を形成させ、ついでその表面を洗浄
して表面電位をプラス電位としパラジウムを含むマイナ
ス電位を有する溶液で活性化処理を行ったのち従来の無
電解メッキ処理を行いポリエステル繊維表面を金属化す
るものである。DETAILED DESCRIPTION OF THE INVENTION According to the present invention, "a polyester fiber is irradiated with an ultraviolet pulsed laser beam having a wavelength of 248 nm by a pulse energy (fluence of 50 to 150 mJ / c).
m 2 ), irradiation for 20 to 50 pulses, washing,
A method for surface metallizing polyester fibers, which is characterized by performing an activation treatment and then an electroless plating treatment. It is. That is, 248n for polyester fiber
Ultraviolet pulsed laser light having a wavelength of m is irradiated to form a fine concavo-convex structure on the surface of the polyester fiber, which is accompanied by a chemical change and a crystal orientation change, and then the surface is washed to make the surface potential a positive potential and contain palladium. After the activation treatment is performed with a solution having a negative potential, the conventional electroless plating treatment is performed to metallize the polyester fiber surface.
【０００５】本発明でいうポリエステルとは下記の一般
式（化１）で表される繰り返し単位を主たる構成成分と
するポリエステルが好ましく用いられ、特にエチレング
リコール及びテトラメチレングリコールを主たるグリコ
ール成分とするポリエステルが好ましく用いられる。The polyester referred to in the present invention is preferably a polyester having a repeating unit represented by the following general formula (Formula 1) as a main constituent component, and particularly a polyester having ethylene glycol and tetramethylene glycol as a main glycol component. Is preferably used.
【０００６】[0006]
【化１】 [Chemical 1]
【０００７】本発明でいう紫外線レーザー光とは２４８
ｎｍの波長を有するＫｒＦレーザーである。レーザー光
の照射方法には特に限定はない。照射は空気中，不活性
ガス中，加圧下，又は真空中の何れで実施しても良い。
照射に際しての温度は常温から１００℃までの範囲が望
ましい。照射条件として重要なのは照射フルエンス及び
照射ショット数である。照射フルエンスは通常１０〜３
００ｍＪ／ｃｍ2／パルスの範囲が望ましいが、特に好
ましいのはポリエステルの場合５０〜１５０ｍＪ／ｃｍ
2／パルスである。低フルエンスで照射するのが物性−
表面改質のバランスから見て望ましい。The ultraviolet laser light referred to in the present invention is 248.
KrF laser having a wavelength of nm. There is no particular limitation on the laser light irradiation method. Irradiation may be carried out in air, in an inert gas, under pressure, or in vacuum.
The temperature during irradiation is preferably in the range of room temperature to 100 ° C. Irradiation fluence and the number of irradiation shots are important as irradiation conditions. Irradiation fluence is usually 10-3
A range of 00 mJ / cm 2 / pulse is desirable, but particularly preferred is 50 to 150 mJ / cm for polyester.
2 / pulse. Physical properties of irradiation with low fluence
It is desirable from the viewpoint of surface modification balance.
【０００８】洗浄の方法は従来公知のいかなる方法を用
いてもよい。例えばベンゼン／メタノ−ル或いはアセト
ン／メタノ−ルなどの混合溶媒による洗浄或いは通常の
界面活性剤による洗浄などの方法を用いることができ
る。活性化処理の方法は例えば硫酸銅とアンモニア水或
いは苛性ソ−ダとアンモニア水或いは白金、金、パラジ
ウムからなる群から選ばれたいずれかの金属の酸性溶液
に繊維を含浸するか該溶液をスプレ−する方法などを用
いることができる。As a cleaning method, any conventionally known method may be used. For example, it is possible to use a method such as washing with a mixed solvent of benzene / methanol or acetone / methanol, or washing with a usual surfactant. The activation method is, for example, impregnating the fiber with an acidic solution of copper sulfate and ammonia water, caustic soda and ammonia water, or an acidic solution of any metal selected from the group consisting of platinum, gold and palladium, or spraying the solution. It is possible to use a method such as
【０００９】無電解メッキ処理の方法は電解メッキ処理
の方法と異なり化学反応によりメッキ処理を施す方法で
あるが、無電解メッキ処理に用いる化学メッキ用組成物
は従来公知のいかなる組成物でもよい。処理の方法は、
まず化学メッキのための触媒賦与を行う。触媒賦与の方
法としてはセンシタイジング−アクチベ−テイングの方
法とキヤタリスト−アクセレ−タ−の方法とがある。前
者の方法では、まず塩化第１スズ、次亜リン酸、塩化ヒ
ドラジン等の比較的強い還元剤を繊維表面に吸着させ、
次いで金、銀、パラジウム等の貴金属イオンを含む触媒
溶液に浸漬して繊維表面に貴金属を析出させて触媒とし
てもよいし、或いは先に貴金属イオンを含む触媒溶液に
浸漬して貴金属イオンを吸着させておき、次いで還元剤
溶液中で還元せしめ繊維表面に貴金属を析出させて触媒
としてもよい。後者の方法はスズ−パラジウム系の混合
触媒溶液に繊維を浸漬した後、塩酸、硫酸等の酸で活性
化し繊維表面にパラジウムを析出させることで代表され
る方法である。上述した方法で触媒賦与した後、化学メ
ッキを行うが化学メッキには一般に金属塩、還元剤、Ｐ
Ｈ調整剤等の成分からなる公知の化学メッキ液を使用す
ることが可能である。メッキ可能な金属としては銅、ニ
ッケル、銀、スズ、コバルト等である。銅、ニッケルが
溶液の安定性、繊維と金属被膜との固着性などの見地か
ら好ましい。The electroless plating method differs from the electrolytic plating method in that it is a chemical reaction, but the chemical plating composition used in the electroless plating may be any conventionally known composition. The processing method is
First, a catalyst is applied for chemical plating. As a method of imparting a catalyst, there are a sensitizing-activating method and a catalyst-accelerator method. In the former method, first, a relatively strong reducing agent such as stannous chloride, hypophosphorous acid and hydrazine chloride is adsorbed on the fiber surface,
Then, it may be immersed in a catalyst solution containing a noble metal ion such as gold, silver, or palladium to deposit the noble metal on the fiber surface as a catalyst, or it may be immersed in a catalyst solution containing noble metal ions first to adsorb the noble metal ion. Then, the catalyst may be reduced in a reducing agent solution and a noble metal may be deposited on the surface of the fiber to form a catalyst. The latter method is represented by immersing the fiber in a tin-palladium-based mixed catalyst solution and then activating it with an acid such as hydrochloric acid or sulfuric acid to precipitate palladium on the fiber surface. After applying the catalyst by the above-mentioned method, chemical plating is performed. Generally, metal salts, reducing agents, P
It is possible to use a publicly known chemical plating solution composed of components such as an H adjuster. The metal that can be plated is copper, nickel, silver, tin, cobalt, or the like. Copper and nickel are preferable from the standpoint of solution stability, adhesion between the fiber and the metal coating, and the like.
【００１０】[0010]
【発明の作用効果】本発明はポリエステル繊維の表面金
属化法において、ポリエステル繊維に予め紫外線パルス
レーザー光を照射することで、従来からなされている感
応性付与処理工程を省略し、しかも従来より密着性に優
れた金属被膜を有するポリエステル繊維を形成させるこ
とができる。すなわち紫外線パルスレーザー光を照射し
たポリエステルは微細な凹凸形状を有する表面に変化す
る。しかも洗浄した後の表面電位は＋（プラス）とな
る。そこで無電解メッキ（化学メッキ）時の活性化触媒
となるパラジウムを−（マイナス）の電位を有する水溶
液とすると、パラジウムと繊維表面とが電気化学的に結
合する。従って無電解メッキ液に浸漬し金属化したとき
に金属の析出・固着がより強固になされるものと推定さ
れる。また感応性付与処理が不要となるので薬品の使用
量を低減することができる。INDUSTRIAL APPLICABILITY According to the present invention, in the surface metallizing method of polyester fiber, the polyester fiber is previously irradiated with the ultraviolet pulsed laser beam, thereby eliminating the conventional process for imparting a sensitivity to the polyester fiber and further adhering it more closely than before. A polyester fiber having a metal coating having excellent properties can be formed. That is, the polyester irradiated with the pulsed ultraviolet laser light changes to a surface having fine irregularities. Moreover, the surface potential after cleaning becomes + (plus). Therefore, when palladium serving as an activation catalyst during electroless plating (chemical plating) is used as an aqueous solution having a-(minus) potential, palladium and the fiber surface are electrochemically bound. Therefore, it is presumed that the metal is more strongly deposited and fixed when it is immersed in an electroless plating solution and metallized. Further, since the sensitivity imparting process is unnecessary, the amount of chemicals used can be reduced.
【００１１】以下、実施例により本発明を具体的に説明
する。The present invention will be specifically described below with reference to examples.
【００１２】[0012]
【実施例 １〜５、比較例 １〜４】極限粘度〔η〕
０．６０、カルボキシル基末端濃度４５、７５デニ−ル
／５０フイラメントのポリエチレンテレフタレート繊維
（帝人株式会社製）を用い、目付１００ｇ／ｍ2の平織
り織物を製織した。Examples 1-5, Comparative Examples 1-4 Intrinsic viscosity [η]
A plain weave fabric having a basis weight of 100 g / m 2 was woven using polyethylene terephthalate fiber (manufactured by Teijin Limited) having a denier of 0.60 and a carboxyl group terminal concentration of 45 and 75 denier / 50 filament.
【００１３】上記のポリエステル織物サンプルにフルエ
ンス１０〜１５０ｍＪ／ｃｍ2，パルス幅は半値全幅で
２０ｎｓの条件で織物表面に均一に紫外線パルスレーザ
ー光を直接照射した。紫外線パルスレーザー光発生には
ラムダフィジック社製エキシマレーザー発生装置（ＬＰ
１２０ｃｃｉ）、ＫｒＦ（発振波長２４８ｎｍ）を用
い，繰り返し周波数は５Ｈｚとした。The above polyester woven fabric sample was directly irradiated with ultraviolet pulsed laser light uniformly on the woven fabric surface under the conditions of fluence of 10 to 150 mJ / cm 2 and full width at half maximum of 20 ns. Excimer laser generator (LP
120 cci) and KrF (oscillation wavelength 248 nm) were used, and the repetition frequency was 5 Hz.
【００１４】ついで紫外線パルスレーザー光を照射した
ポリエステル織物を脱イオン水中に浸漬、洗浄した。次
いで下記の塩化パラジウム水溶液でマイナスイオン性を
有する溶液に浸漬し、脱水後、引き続き下記の無電解メ
ッキ溶液に浸漬し金属を析出させた。 ＜塩化パラジウム水溶液＞塩化パラジウム１ｇ、塩酸２
０ｃｃ、水１０００ｃｃ ＜無電解メッキ溶液＞硫酸ニッケル８０ｇ、塩化アンモ
ン４０ｇ、硝酸ソーダ１０ｇ、次亜リン酸ソーダ４０
ｇ、水１０００ｃｃ 比較例として従来の塩化第一スズによる感応性付与処理
を行ったもの、エキシマレーザー照射条件を変更したも
の、活性化処理を省略したものを入れ性能を比較した。
結果を表１に示した。Then, the polyester fabric irradiated with the pulsed ultraviolet laser light was immersed in deionized water and washed. Then, it was immersed in a solution having a negative ionicity with the following palladium chloride aqueous solution, dehydrated, and subsequently immersed in the following electroless plating solution to deposit a metal. <Palladium chloride aqueous solution> Palladium chloride 1 g, hydrochloric acid 2
0 cc, 1000 cc of water <Electroless plating solution> Nickel sulfate 80 g, ammonium chloride 40 g, sodium nitrate 10 g, sodium hypophosphite 40
g, 1000 cc of water As comparative examples, the ones which were subjected to the conventional sensitivity imparting treatment with stannous chloride, the ones in which the excimer laser irradiation conditions were changed, and those in which the activation treatment was omitted were put and the performances were compared.
The results are shown in Table 1.
【００１５】[0015]
【表１】 [Table 1]
Claims (1)
有する紫外線パルスレーザー光をパルスエネルギー（フ
ルエンス５０〜１５０mJ/cm2) の条件下で２０〜５０パ
ルス照射した後、洗浄し、しかるのちに活性化処理を行
い、次いで無電解メッキ処理を施すことを特徴とするポ
リエステル繊維の表面金属化法。1. A polyester fiber is irradiated with 20 to 50 pulses of ultraviolet pulsed laser light having a wavelength of 248 nm under the condition of pulse energy (fluence 50 to 150 mJ / cm 2 ), followed by washing and then activation treatment. And then electrolessly plating the surface of the polyester fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1870493A JPH06235169A (en) | 1993-02-05 | 1993-02-05 | Method of metallizing surface of polyester fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1870493A JPH06235169A (en) | 1993-02-05 | 1993-02-05 | Method of metallizing surface of polyester fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06235169A true JPH06235169A (en) | 1994-08-23 |
Family
ID=11979037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1870493A Pending JPH06235169A (en) | 1993-02-05 | 1993-02-05 | Method of metallizing surface of polyester fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06235169A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328289A (en) * | 1999-05-17 | 2000-11-28 | Fuji Xerox Co Ltd | Formation of electrodeposited film, formation of electrode and electrodeposited film forming device |
| JP2010522829A (en) * | 2007-03-30 | 2010-07-08 | ダンマルクス テクニスケ ウニベルシテット | Preparation of polymer products for selective metallization |
| JP2014237900A (en) * | 2013-06-06 | 2014-12-18 | 日本電信電話株式会社 | Method and apparatus for manufacturing conductive fiber |
| WO2016152938A1 (en) * | 2015-03-24 | 2016-09-29 | オーエム産業株式会社 | Method for producing plated article |
-
1993
- 1993-02-05 JP JP1870493A patent/JPH06235169A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328289A (en) * | 1999-05-17 | 2000-11-28 | Fuji Xerox Co Ltd | Formation of electrodeposited film, formation of electrode and electrodeposited film forming device |
| JP2010522829A (en) * | 2007-03-30 | 2010-07-08 | ダンマルクス テクニスケ ウニベルシテット | Preparation of polymer products for selective metallization |
| US8628831B2 (en) | 2007-03-30 | 2014-01-14 | Danmarks Tekniskie Universitet | Preparation of a polymer article for selective metallization |
| JP2014237900A (en) * | 2013-06-06 | 2014-12-18 | 日本電信電話株式会社 | Method and apparatus for manufacturing conductive fiber |
| WO2016152938A1 (en) * | 2015-03-24 | 2016-09-29 | オーエム産業株式会社 | Method for producing plated article |
| JPWO2016152938A1 (en) * | 2015-03-24 | 2017-10-12 | オーエム産業株式会社 | Manufacturing method of plated products |
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