JPS6332913B2 - - Google Patents
Info
- Publication number
- JPS6332913B2 JPS6332913B2 JP55113728A JP11372880A JPS6332913B2 JP S6332913 B2 JPS6332913 B2 JP S6332913B2 JP 55113728 A JP55113728 A JP 55113728A JP 11372880 A JP11372880 A JP 11372880A JP S6332913 B2 JPS6332913 B2 JP S6332913B2
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- plating
- fiber
- noble metal
- 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.)
- Expired
Links
- 239000000835 fiber Substances 0.000 claims description 46
- 229910000510 noble metal Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 238000007747 plating Methods 0.000 claims description 25
- 238000007772 electroless plating Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- 229920000914 Metallic fiber Polymers 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 238000001994 activation Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、合成繊維あるいはセラミツクス繊維
などのような非金属繊維上に無電解メツキ法によ
り金属メツキを生成する方法に関する。
従来、電気伝導性のない非金属物品の表面に無
電解メツキ法にて、金属メツキを生成させるに
は、物品の表面を粗化、感受性化ついで活性化の
工程を経たのち、無電解メツキする方法が採用さ
れている。例えばプラスチツクス等の非金属物品
の無電解メツキの工程は下記の通りである。
The present invention relates to a method for producing metal plating on non-metallic fibers such as synthetic fibers or ceramic fibers by electroless plating. Conventionally, in order to generate metal plating on the surface of a non-metallic article with no electrical conductivity using an electroless plating method, the surface of the article is roughened, sensitized, and activated, and then electroless plating is performed. method has been adopted. For example, the process for electroless plating of non-metallic articles such as plastics is as follows.
【表】
↓
[Table] ↓
【表】
こゝで、感受性化（センシタイジング）とは、
被メツキ材の表面を脱脂後比較的強い還元剤たと
えば塩化第一スズと塩酸の混合液を表面に吸着さ
せる工程であり、また活性化（アクチベーシヨ
ン）とは、貴金属イオンを含んだ液、たとえば塩
化パラジウムと塩酸の混合水溶液中に感受性化し
た被メツキ材を浸漬し、感受性化により吸着され
ている還元物たとえば第１スズイオンの作用によ
つて、貴金属イオンを表面に還元析出させ、この
析出貴金属の触媒的作用によりメツキの析出をお
こなわせ、メツキ層の密着をよくするための工程
である。前記の方法は、貴金属イオンの還元析出
の反応が完結しないことが多いため、感受性化か
ら活性化の工程を２〜３回繰り返して、活性化を
確実なものにしている。しかし、多数回繰り返し
ても貴金属の析出が不充分なことが多く、従つて
活性化ののち、還元性溶に浸してから再び、貴金
属塩の浴に浸漬して、触媒能のある貴金属を還元
して付着させる方法が提案されている。
（例えば特開昭50−148238号）この方法の工程
は下記の通りである。[Table] Here, what is sensitizing?
After degreasing the surface of the material to be plated, a relatively strong reducing agent such as a mixed solution of stannous chloride and hydrochloric acid is adsorbed onto the surface. Activation is a process in which a liquid containing noble metal ions, For example, a sensitized material to be plated is immersed in a mixed aqueous solution of palladium chloride and hydrochloric acid, and noble metal ions are reduced and precipitated on the surface by the action of the adsorbed reductant, such as stannous ions, due to the sensitization. This is a process for depositing plating using the catalytic action of precious metals and improving the adhesion of the plating layer. In the above method, since the reaction of reduction and precipitation of noble metal ions is often not completed, the steps from sensitization to activation are repeated two or three times to ensure activation. However, even if repeated many times, the precipitation of precious metals is often insufficient. Therefore, after activation, immersion in a reducing solution and then immersion in a bath of noble metal salts is performed to reduce the catalytic noble metals. A method has been proposed in which it is attached by (For example, JP-A-50-148238) The steps of this method are as follows.
【表】
↓
[Table] ↓
【表】
これ等の方法を非金属繊維の無電解メツキに適
用すると、例えば前記特開昭50−148238号の方法
による場合、貴金属の折出にムラが生じ、繊維の
全周にムラなくしかも厚さの均一なメツキを生成
することはできない。また上述のいずれの方法も
液中でのイオンの還元反応を利用するため表面が
平滑なガラス繊維、アルミナ質繊維等の非金属繊
維に適用するには、イオンの吸着を容易にするた
めに繊維の表面粗化を強く行わねばならない。し
かし表面粗化を強く行うと、特にセラミツク繊維
の場合、繊維強度が著しく低下するという問題が
ある。
本発明者らは、これらの問題を解決すべく、活
性化工程における貴金属の付着方法について鋭意
検討の結果、活性化を与えうる貴金属の化合物を
繊維表面上で加熱分解させ、貴金属あるいは貴金
属の低次酸化物を繊維上に強固に付着もしくは結
合させることにより、しかも該貴金属化合物の水
溶液あるいは低沸点溶媒の溶液に繊維を浸漬し乾
燥することにより、各繊維の表面にムラなく貴金
属化合物を付着でき、加熱分解後の貴金属あるい
は貴金属の低次酸化物もムラなく付着もしくは結
合でき、従つてムラなく均一な厚みをもつた強固
なメツキを生成させることができることを見出し
本発明を完成させるに至つた。
即ち、本発明は非金属繊維の表面に無電解メツ
キを生成する方法において、触媒能のある貴金属
化合物の溶媒中に非金属繊維を浸漬、乾燥後加熱
処理することにより、貴金属あるいは貴金属の低
次酸化物を繊維上に強固に付着もしくは結合させ
てから、該金属あるいは該合金の無電解メツキ浴
に浸漬させ、該金属あるいは該合金のメツキ層を
生成することを特徴とする非金属繊維上に金属メ
ツキを生成する方法を提供するものである。
以下に本発明を更に詳しく説明する。
本発明方法は通常の方法で脱脂および湿潤化し
た非金属繊維を貴金属化合物の溶液に浸漬し、乾
燥後、加熱処理し、通常の無電解メツキにより非
金属繊維上に金属メツキを生成しようとするもの
であり、本発明方法の工程は下記の通りである。[Table] When these methods are applied to electroless plating of non-metallic fibers, for example, when using the method disclosed in JP-A-50-148238, the precipitation of precious metals becomes uneven, and evenly spreads over the entire circumference of the fibers. It is not possible to produce plating with uniform thickness. In addition, since all of the above methods utilize the reduction reaction of ions in the liquid, in order to apply them to non-metallic fibers with smooth surfaces such as glass fibers and alumina fibers, it is necessary to The surface must be roughened strongly. However, if the surface is too roughened, especially in the case of ceramic fibers, there is a problem in that the fiber strength is significantly reduced. In order to solve these problems, the present inventors have conducted intensive studies on the method of adhering noble metals in the activation process, and as a result, we have developed a method for thermally decomposing noble metal compounds that can provide activation on the fiber surface. By firmly adhering or bonding the secondary oxide onto the fibers, and by immersing the fibers in an aqueous solution of the noble metal compound or a solution of a low boiling point solvent and drying, the noble metal compound can be evenly attached to the surface of each fiber. The inventors discovered that noble metals or lower oxides of noble metals after thermal decomposition can be evenly attached or bonded, and that a strong plating with an even and uniform thickness can be produced, leading to the completion of the present invention. . That is, the present invention provides a method for producing electroless plating on the surface of nonmetallic fibers, in which the nonmetallic fibers are immersed in a solvent containing a noble metal compound having catalytic ability, dried, and then heat-treated. On non-metallic fibers, the oxide is firmly attached or bonded to the fibers and then immersed in an electroless plating bath of the metal or the alloy to form a plating layer of the metal or the alloy. A method of producing metal plating is provided. The present invention will be explained in more detail below. In the method of the present invention, non-metallic fibers that have been degreased and moistened in a conventional manner are immersed in a solution of a noble metal compound, dried, and then heat treated to produce metal plating on the non-metallic fibers by conventional electroless plating. The steps of the method of the present invention are as follows.
【表】
本発明方法において使用する触媒能のある貴金
属としてはパラジウム、白金、金などを例示する
ことができる。貴金属化合物の形態としては、水
又は低沸点の溶剤にとけやすく、比較的低温で分
解して金属あるいはその低次酸化物に変化するこ
とが好ましく、塩化物、硝化物、水酸化物などが
好ましい。
本発明で用いられる非金属繊維とは、耐熱温度
が少なくとも300℃以上の繊維であればいかなる
材質の繊維にも適用できる。たとれば、炭素繊
維、シリコンカーバイド繊維、アルミナ質繊維、
ガラス繊維などには特に有効な方法である。ま
た、被処理繊維の形態としては、連続繊維、長繊
維あるいは短繊維のいずれであつてもよく、編織
物、不織布などの状態にあつてもよい。されに、
これらの非金属繊維の繊維径、繊維束中のフイラ
メント数には限定なく、本発明を適用することが
できる。
本発明方法においては、これ等の繊維束を上記
貴金属化合物の溶液に浸漬したのち、乾燥し、そ
の後空気中又は窒素、アルゴンなどの雰囲気中で
300〜800℃好ましくは300〜600℃の温度域で加熱
処理し、貴金属あるいは貴金属の低次酸化物を繊
維上に分解・析出させる。加熱処理温度の下限
300℃は、浸漬により付着させた貴金属化合物を
加熱処理によつて、貴金属あるいは、貴金属の低
次酸化物となし、メツキ時にメツキ浴中に溶けだ
さないように、不溶化するための温度である。よ
つて、分解温度の高い化合物を選定したときに
は、加熱処理温度を高くしなければならない。ま
た、800℃を越えると、貴金属の酸化が進行し、
安定な酸化物になるため、触媒活性が著しく低下
することになる。したがつて、加熱処理温度を高
くするときは、焼成時の雰囲気の酸素濃度を低く
する必要がある。
本発明方法における貴金属あるいは貴金属の低
次酸化物の付着量は貴金属化合物溶液の濃度によ
り変えることができる。貴金属化合物は焼成工程
によつて繊維表面上に0.01〜0.5μ程度の粒子状と
なつて均一に分散して付着するが貴金属化合物の
付着量としては、この粒子の全表面積が繊維の表
面の0.5％以上を占めるものであればよい。付着
粒子の占める表面積が0.5％未満の場合は、メツ
キの析出反応が局所化し、均一な厚みをもつた金
属メツキが実現できない。
このように処理した繊維を無電解メツキ浴に浸
漬することによつて、該繊維上に均一に分散して
付着もしくは結合された貴金属あるいは貴金属の
低次酸化物が活性点となつて、各部で同時に析出
反応が生じ、被覆ムラのない均一な厚さをもつた
金属メツキが生成する。
従来の方法では、活性点の形成にムラがあるた
めメツキムラができたり、繊維の集合体にメツキ
される欠点があつたが、本発明はこれらの欠点を
なくし、同時に感受性化工程が省略され、連続的
に繊維上に無電解メツキを施すことができるとい
う利点を有している。したがつて、本発明によれ
ば、大量生産が可能となり、かつ工程の管理が容
易なため、繊維上に均一にしかもメツキ厚さをコ
ントロールしながら処理できる。
次に本発明を実施例で詳細に説明するが、本発
明は、これらによつて限定されるものではない。
実施例 １
繊維径16μｍ、フイラメント数2000本のガラス
繊維束（Ｅガラス繊維・日本硝子繊維(株)製）を
400℃の電気炉にて１分間加熱して、集束剤を揮
散させたのち、硝酸パラジウムの0.1wt％水溶液
に浸し、余分の付着溶液をローラーで絞つて風乾
後、再度400℃の電気炉で400℃、30秒間加熱して
パラジウムあるいはパラジウムの低次酸化物を繊
維上に焼付けた。この繊維に無電解メツキ法によ
りニツケルをメツキした。ニツケルの無電解メツ
キは、浴組成がNiCl2・6H2O30ｇ／、エチレ
ンジアミン60ｇ／、NaOH40ｇ／、
NaBH40.5〜0.6ｇ／、TlNO30.1ｇ／のメツ
キ浴にパラジウムあるいはパラジウムの低次酸化
物を焼付けた繊維をPH14、浴温90℃で30秒間浸漬
させたところ繊維上にニツケルが0.2μｍの厚さで
均一にメツキできた。
実施例 ２
繊維径15μｍ、フイラメント数200本の特公昭
51−12736号、特公昭51−13768号に記載されたア
ルミナ質繊維を、硝酸パラジウムの0.05wt％水溶
液に浸し、余分の付着溶液をローラーで絞り、乾
燥後、600℃の電気炉中に30秒間通し、パラジウ
ムあるいはパラジウムの低次酸化物を焼付けてか
ら、浴組成がCuSO40.05mol／ｌ、EDTA（エチ
レンジアミン四醋酸）0.12mol／、
NaCN0.008mol／、NaBH480mg／のメツキ
浴に上記の処理をしたアルミナ質繊維を25℃、30
秒間浸漬したところ、繊維上に厚さ0.5μｍの銅を
被覆できた。
一方、従来通りの方法を用いて、アルミナ質繊
維の表面に銅メツキするため、本明細書の最初に
示した工程にしたがつて感受性化、活性化の工程
を２回繰り返しておこなつてから、上記組成浴に
25℃、３分間浸漬したところ、メツキの析出は局
所化して、一部は厚く被覆されているにもかかわ
らず、一部は全く被覆されていなかつた。すなわ
ち活性点が均一に付着されていないと、局所的な
析出反応が進行し、均一なメツキが得られないこ
とが判明した。[Table] Examples of noble metals with catalytic ability used in the method of the present invention include palladium, platinum, and gold. As for the form of the noble metal compound, it is preferable that it is easily dissolved in water or a low boiling point solvent, decomposes at a relatively low temperature, and changes into a metal or its lower oxide, and chlorides, nitrides, hydroxides, etc. are preferable. . The non-metallic fibers used in the present invention may be fibers of any material as long as they have a heat resistance temperature of at least 300°C or higher. For example, carbon fiber, silicon carbide fiber, alumina fiber,
This method is particularly effective for glass fibers. The fibers to be treated may be in the form of continuous fibers, long fibers, or short fibers, and may be in the form of knitted fabrics, nonwoven fabrics, or the like. However,
The present invention can be applied without any limitation to the fiber diameter of these nonmetallic fibers or the number of filaments in the fiber bundle. In the method of the present invention, these fiber bundles are immersed in a solution of the noble metal compound, dried, and then placed in air or an atmosphere of nitrogen, argon, etc.
Heat treatment is performed at a temperature range of 300 to 800°C, preferably 300 to 600°C, to decompose and precipitate noble metals or lower oxides of noble metals on the fibers. Lower limit of heat treatment temperature
300℃ is the temperature at which the noble metal compound deposited by immersion is heated to become a noble metal or a lower oxide of a noble metal, and is insolubilized so that it does not melt into the plating bath during plating. . Therefore, when a compound with a high decomposition temperature is selected, the heat treatment temperature must be increased. In addition, when the temperature exceeds 800℃, oxidation of precious metals progresses.
Since it becomes a stable oxide, the catalytic activity will be significantly reduced. Therefore, when increasing the heat treatment temperature, it is necessary to lower the oxygen concentration in the atmosphere during firing. The amount of deposited noble metal or lower oxide of noble metal in the method of the present invention can be changed by changing the concentration of the noble metal compound solution. The noble metal compound is uniformly dispersed and attached to the fiber surface in the form of particles of about 0.01 to 0.5μ during the firing process, but the amount of the noble metal compound attached is such that the total surface area of these particles is 0.5 of the surface of the fiber. % or more. If the surface area occupied by the adhered particles is less than 0.5%, the plating precipitation reaction will be localized, making it impossible to achieve metal plating with a uniform thickness. By immersing the fibers treated in this way in an electroless plating bath, the noble metals or lower oxides of noble metals that are uniformly dispersed and attached or bonded to the fibers become active sites, and each part becomes active. At the same time, a precipitation reaction occurs, producing metal plating with uniform thickness and no uneven coating. In the conventional method, there was a drawback that the formation of active sites was uneven, resulting in the formation of plating spots or plating on fiber aggregates, but the present invention eliminates these drawbacks, and at the same time, the sensitization step is omitted. It has the advantage that electroless plating can be applied continuously on fibers. Therefore, according to the present invention, mass production is possible and the process is easy to manage, so that the plating thickness can be uniformly applied to the fibers while controlling the plating thickness. EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Example 1 A glass fiber bundle (E glass fiber, manufactured by Nippon Glass Fiber Co., Ltd.) with a fiber diameter of 16 μm and 2000 filaments was used.
After heating in an electric furnace at 400℃ for 1 minute to volatilize the sizing agent, it was immersed in a 0.1wt% aqueous solution of palladium nitrate, the excess adhering solution was squeezed out with a roller, air-dried, and then heated in an electric furnace at 400℃ again. Palladium or a lower oxide of palladium was baked onto the fiber by heating at 400°C for 30 seconds. This fiber was plated with nickel using an electroless plating method. Nickel's electroless plating has a bath composition of NiCl 2 6H 2 O 30g/, ethylenediamine 60g/, NaOH 40g/,
When fibers baked with palladium or lower oxides of palladium were immersed in a plating bath containing 0.5 to 0.6 g of NaBH 4 and 0.1 g of TlNO 3 for 30 seconds at pH 14 and bath temperature of 90°C, 0.2 μm of nickel was deposited on the fibers. I was able to plate it evenly with a thickness of . Example 2 Fiber diameter 15μm, number of filaments 200 Tokkosho
The alumina fibers described in No. 51-12736 and Japanese Patent Publication No. 51-13768 were soaked in a 0.05wt% aqueous solution of palladium nitrate, the excess adhering solution was squeezed out with a roller, and after drying, the fibers were placed in an electric furnace at 600℃ for 30 minutes. After baking palladium or a lower oxide of palladium, the bath composition was CuSO 4 0.05 mol/l, EDTA (ethylenediaminetetraacetic acid) 0.12 mol/l,
The alumina fibers treated as above were placed in a plating bath containing 0.008 mol of NaCN and 80 mg of NaBH 4 at 25℃ for 30 minutes.
When immersed for a second, the fibers were coated with copper to a thickness of 0.5 μm. On the other hand, in order to plate the surface of alumina fiber with copper using a conventional method, the sensitization and activation steps were repeated twice according to the steps shown at the beginning of this specification. , in the above composition bath
When immersed at 25°C for 3 minutes, plating precipitation was localized, and although some parts were thickly coated, some parts were not coated at all. That is, it has been found that if the active sites are not uniformly attached, local precipitation reactions proceed and uniform plating cannot be obtained.
Claims (1)
属あるいは合金のメツキを生成する方法におい
て、触媒能のある貴金属化合物の溶液中に非金属
繊維を浸漬、乾燥後加熱処理することにより、貴
金属あるいは貴金属の低次酸化物を繊維上に強固
に付着もしくは結合させてから、該金属あるいは
該合金の無電解メツキ浴に浸漬させ、該金属ある
いは該合金のメツキ層を生成することを特徴とす
る非金属繊維上に金属メツキを生成する方法。1. In a method of producing metal or alloy plating on the surface of nonmetallic fibers by electroless plating method, the nonmetallic fibers are immersed in a solution of a noble metal compound with catalytic ability, dried, and then heat-treated. Alternatively, a lower oxide of a noble metal is firmly adhered or bonded to the fiber, and then the fiber is immersed in an electroless plating bath of the metal or the alloy to form a plating layer of the metal or the alloy. A method of producing metal plating on non-metallic fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11372880A JPS5739284A (en) | 1980-08-18 | 1980-08-18 | Forming of metal plating on non-metal fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11372880A JPS5739284A (en) | 1980-08-18 | 1980-08-18 | Forming of metal plating on non-metal fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5739284A JPS5739284A (en) | 1982-03-04 |
| JPS6332913B2 true JPS6332913B2 (en) | 1988-07-01 |
Family
ID=14619628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11372880A Granted JPS5739284A (en) | 1980-08-18 | 1980-08-18 | Forming of metal plating on non-metal fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5739284A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6077151A (en) * | 1983-09-30 | 1985-05-01 | Asahi Glass Co Ltd | Metal-coated glass fiber, production thereof and frp product using said fiber |
| US4738896A (en) * | 1986-09-26 | 1988-04-19 | Advanced Technology Materials, Inc. | Sol gel formation of polysilicate, titania, and alumina interlayers for enhanced adhesion of metal films on substrates |
| KR20000059156A (en) * | 2000-07-19 | 2000-10-05 | 손태원 | Skin-core short fiber comprising metal and cellulose |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51116300A (en) * | 1974-11-27 | 1976-10-13 | Chugoku Marine Paints | Surface treated inorganic fiber or article and surface treating method |
-
1980
- 1980-08-18 JP JP11372880A patent/JPS5739284A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51116300A (en) * | 1974-11-27 | 1976-10-13 | Chugoku Marine Paints | Surface treated inorganic fiber or article and surface treating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5739284A (en) | 1982-03-04 |
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