JP2003183980A - Metal coated fiber body and method for producing the same - Google Patents
Metal coated fiber body and method for producing the sameInfo
- Publication number
- JP2003183980A JP2003183980A JP2001382054A JP2001382054A JP2003183980A JP 2003183980 A JP2003183980 A JP 2003183980A JP 2001382054 A JP2001382054 A JP 2001382054A JP 2001382054 A JP2001382054 A JP 2001382054A JP 2003183980 A JP2003183980 A JP 2003183980A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- fiber
- coating
- coated
- coated fiber
- 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
Links
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、繊維体に設けた金
属被覆の密着性および耐腐蝕性に優れると共に軽量であ
って低価格で製造でき、しかも人の皮膚への影響も少な
い金属被覆繊維体とその製造方法に関する。TECHNICAL FIELD The present invention relates to a metal-coated fiber which is excellent in adhesion and corrosion resistance of a metal coating provided on a fibrous body, is lightweight and can be produced at a low price, and has little influence on human skin. The present invention relates to a body and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】ナイロン繊維やポリエステル繊維などの
高分子材料からなる合成繊維表面に金属薄膜をコーテン
グした導電性繊維ないし導電性糸が従来から知られてお
り、金属コーテング膜の密着性を高めるために種々の方
法が試みられている。例えば、硫化銅をコーテングする
場合に、銅イオン捕捉基を有する染料で高分子材料を前
処理し、これに銅イオンを結合させた後に硫化する方法
(特公平01-37513号)や、アルカリ処理して粗面化した繊
維表面に銅イオン捕捉基を付着させた後にこれに硫化銅
を結合させる方法(特開平06-298973号)などが知られて
いる。また、アラミド繊維などのように金属メッキを施
し難いものについては、ポリビニルピロリドン(ＰＶＰ)
を利用して金属イオンを付着させ、これを還元して金属
メッキを形成する方法(特表平06-506267号)などが知ら
れている。2. Description of the Related Art A conductive fiber or conductive thread in which a metal thin film is coated on the surface of a synthetic fiber made of a polymer material such as nylon fiber or polyester fiber has been known in the past, in order to improve the adhesion of the metal coating film. Various methods have been tried. For example, in the case of coating copper sulfide, a method of pretreating a polymer material with a dye having a copper ion-trapping group, binding copper ions to the polymer material, and then sulfiding
(Japanese Patent Publication No. 01-37513) and a method of attaching copper ion-trapping groups to the surface of the fiber roughened by alkali treatment and then binding copper sulfide thereto (Japanese Patent Laid-Open No. 06-298973) and the like. ing. In addition, polyvinylpyrrolidone (PVP) is used for materials that are difficult to apply metal plating such as aramid fiber.
There is known a method of depositing metal ions by utilizing, and reducing the metal ions to form metal plating (Japanese Patent Laid-Open No. 06-506267).
【０００３】[0003]
【発明が解決しようとする課題】ところが、上記ＰＶＰ
を利用するメッキ方法は繊維の種類が限られるので一般
的ではない。また、銅イオン捕捉基を導入するコーテン
グ方法は金属被覆が銅やその化合物に限られ、しかも金
属被覆の付着強度が必ずしも十分ではないと云う問題が
ある。なお、繊維をアルカリ処理して粗面化すれば概ね
金属被覆の付着強度を高めることができるが、粗面化の
程度と金属被覆の状態が適切でないと十分な効果が得ら
れない。しかも、金属被覆繊維を衣類等に使用する場合
には洗濯や摩耗などの過酷な使用条件に耐える必要があ
る。さらに、導電性の観点からは、金属被覆の部分的剥
離によっても断線状態を招くので金属被覆は信頼性の高
い密着強度を有することが求められる。また、金属被覆
繊維とりわけ銀被覆繊維は大気中に酸化物や洗剤等によ
って表面腐食や変色を生じる問題がある。However, the above-mentioned PVP
The plating method using is not common because the types of fibers are limited. Further, the coating method of introducing a copper ion-trapping group has a problem that the metal coating is limited to copper or its compound and the adhesion strength of the metal coating is not always sufficient. Although the adhesion strength of the metal coating can be generally increased by roughening the fibers by treating them with an alkali, a sufficient effect cannot be obtained unless the degree of roughening and the state of the metal coating are appropriate. Moreover, when the metal-coated fiber is used for clothing or the like, it is necessary to withstand severe use conditions such as washing and abrasion. Further, from the viewpoint of conductivity, even if the metal coating is partially peeled off, a disconnection state is caused. Therefore, the metal coating is required to have a highly reliable adhesion strength. Further, metal-coated fibers, especially silver-coated fibers, have a problem that surface corrosion and discoloration occur in the atmosphere due to oxides, detergents, and the like.
【０００４】本発明は従来の金属被覆繊維における上記
問題を解決したものであって、優れた耐食性と被覆強度
を有する金属被覆繊維体を提供する。一般に金属被覆繊
維体は塩素や硫化物による表面腐食が多く見られる。こ
れを防止するため、下地の金属被覆の上側に防食用金属
被覆を設ける二重金属被覆繊維体があるが、これは金属
量が多く、コスト高を招くことが懸念される。本発明は
金属被覆表面にフッ素化合物被覆を設けることによっ
て、被覆金属量が少なく、耐腐食性に優れ、皮膚への刺
激も少ない金属被覆繊維体を提供するものである。The present invention solves the above-mentioned problems in conventional metal-coated fibers, and provides a metal-coated fiber body having excellent corrosion resistance and coating strength. Generally, metal-coated fibrous materials are often surface-corroded by chlorine and sulfide. In order to prevent this, there is a double metal-coated fiber body in which an anticorrosive metal coating is provided on the upper side of the underlying metal coating, but this has a large amount of metal, and there is a concern that this will lead to higher costs. The present invention provides a metal-coated fiber body having a small amount of coated metal, excellent corrosion resistance, and less irritation to the skin, by providing a fluorine compound coating on the metal-coated surface.
【０００５】[0005]
【課題を解決する手段】本発明は、金属被覆を有する繊
維体において、繊維体表面に設けた金属被覆を下地と
し、その上にフッ素化合物の表面被覆を設けたものであ
り、下地に導電性金属被覆を設けることによって優れた
導電性を有すると共に表面のフッ素化合物被覆によって
耐腐食性を高め、皮膚への刺激が少なく比較的軽量であ
って製造コストも低い金属被覆繊維体を提供する。According to the present invention, in a fibrous body having a metal coating, a metal coating provided on the surface of the fibrous body is used as a base, and a surface coating of a fluorine compound is provided thereon, and the base has a conductive property. (EN) Provided is a metal-coated fiber body which has excellent conductivity by providing a metal coating and which has a fluorine compound coating on the surface to enhance corrosion resistance, is less irritating to the skin, is relatively lightweight, and has a low manufacturing cost.
【０００６】すなわち、本発明は以下の構成からなる金
属被覆繊維体とその製造方法に関する。
（１）基体繊維の表面に下地の金属被覆を有し、さらに
その上にフッ素化合物被覆を有することを特徴とする金
属被覆繊維体。
（２）金属被覆を設けた後に基体繊維が結晶化温度以上
であって融解温度未満の温度で加熱処理されている上記
(1)の金属被覆繊維体。
（３）フッ素化合物被覆が繊維体重量の０.０１〜５％
である上記(1)または(2)に記載の金属被覆繊維体。
（４）基体繊維がアクリル繊維、ナイロン繊維、ポリエ
ステル繊維、高強度ナイロン系繊維、ポリフェニレンサ
ルファイド系繊維、ポリカーボネート系繊維、またはア
ラミド系繊維である上記(1)、(2)または(3)に記載する金
属被覆繊維体。
（５）下地の金属被覆が金、銀、銅、ニッケル、錫また
はこれらの合金の一種または二種以上からなる導電性金
属被覆である上記(1)〜(4)の何れかに記載する金属被覆
繊維体。
（６）下地の金属被覆がオレンジピールを有し、その上
側にフッ素化合物被覆をし、さらにパラフィン処理また
はワックス処理されている上記(1)〜(5)の何れかに記載
する金属被覆繊維体。That is, the present invention relates to a metal-coated fiber body having the following constitution and a method for producing the same. (1) A metal-coated fiber body characterized in that a base metal has a metal coating on the surface thereof, and further has a fluorine compound coating thereon. (2) The base fiber is heat-treated at a temperature equal to or higher than the crystallization temperature and lower than the melting temperature after the metal coating is provided.
The metal-coated fiber body of (1). (3) 0.01 to 5% of the weight of the fibrous body is covered with the fluorine compound.
The metal-coated fiber body according to (1) or (2) above, which is (4) The above (1), (2) or (3), wherein the base fiber is an acrylic fiber, nylon fiber, polyester fiber, high strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber or aramid fiber A metal coated fiber body. (5) The metal as described in any one of (1) to (4) above, wherein the underlying metal coating is a conductive metal coating made of one or more of gold, silver, copper, nickel, tin or alloys thereof. Coated fiber body. (6) The metal-coated fiber body according to any one of (1) to (5) above, wherein the underlying metal coating has orange peel, a fluorine compound coating is provided on the upper side, and the paraffin treatment or wax treatment is further performed. .
【０００７】さらに、本発明は以下の製造方法に関す
る。
（７） 基体繊維の表面に金属被覆を設けた後に、これ
を基体繊維の結晶化温度以上であって融解温度未満の温
度で加熱処理し、次いで、この金属被覆表面にフッ素化
合物被覆を基体繊維の結晶化温度以下で形成する金属被
覆繊維体の製造方法。
（８） フッ素系化合物被覆の形成溶液として、有機フ
ッ素系界面活性剤またはアルコキシシラン系フッ素化合
物溶液を用いる上記(7)に記載する金属被覆繊維体の製
造方法。Furthermore, the present invention relates to the following manufacturing method. (7) After the metal coating is provided on the surface of the base fiber, it is heat-treated at a temperature higher than the crystallization temperature of the base fiber and lower than the melting temperature, and then the base compound fiber is coated with a fluorine compound. A method for producing a metal-coated fiber body which is formed below the crystallization temperature. (8) The method for producing a metal-coated fiber body according to the above (7), wherein an organic fluorine-based surfactant or an alkoxysilane-based fluorine compound solution is used as the solution for forming the fluorine-based compound coating.
【０００８】[0008]
【発明の実施の態様】以下、本発明を実施態様に基づい
て具体的に説明する。本発明の金属被覆繊維体は、基体
繊維の表層に下地の金属被覆とその上にフッ素化合物被
覆を有することを特徴とするものである。なお、本発明
において繊維体とは短繊維(ステープル)、長繊維(フィ
ラメント)、これらの繊維からなる各種の加工糸(フィラ
メント糸、紡績糸など)を云い、これらを広く含めて繊維
体と云う。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on embodiments. The metal-coated fiber body of the present invention is characterized by having an underlying metal coating on the surface layer of the base fiber and a fluorine compound coating thereon. In the present invention, the term "fibrous body" refers to short fibers (staples), long fibers (filaments), and various processed yarns (filament yarns, spun yarns, etc.) made of these fibers, and is broadly referred to as a fibrous body. .
【０００９】本発明の金属被覆繊維体の基体となる繊維
（基体繊維と云う）としては、ポリエステル、ポリアミ
ド、アクリル、ポリオレフィン、ナイロンなどの高分子
材料を主成分とした合成繊維、木綿などの天然繊維、レ
ーヨンなどのセルロース系繊維、これらの有機繊維のほ
かにガラスファイバーなどの無機繊維、またはこれらの
複合繊維体などが挙げられる。これらの繊維体は二種以
上を混紡したものでも良く、合成繊維と天然繊維を混紡
したものでも良い。As the fibers (referred to as substrate fibers) as the substrate of the metal-coated fiber body of the present invention, synthetic fibers mainly composed of polymer materials such as polyester, polyamide, acrylic, polyolefin and nylon, natural fibers such as cotton, etc. Fibers, cellulosic fibers such as rayon, in addition to these organic fibers, inorganic fibers such as glass fibers, or composite fibrous bodies thereof may be mentioned. These fiber bodies may be a mixture of two or more kinds, or a mixture of synthetic fibers and natural fibers.
【００１０】さらに、本発明は基体繊維として高強度ナ
イロン系繊維、ポリフェニレンサルファイド系繊維、ポ
リカーボネート系繊維、またはアラミド系繊維を用いた
ものを含む。高強度ナイロン系繊維とはザイロンの商品
名で市販されている高重合ナイロン繊維などである。こ
れらの繊維は高重合体であり溶融温度が高く耐熱性に優
れており、この基体繊維を用いた金属被覆単繊維を配合
した導電性樹脂は高温環境下での使用に適する。Further, the present invention includes those using high-strength nylon fibers, polyphenylene sulfide fibers, polycarbonate fibers, or aramid fibers as the base fibers. The high-strength nylon fiber is, for example, a highly polymerized nylon fiber marketed under the trade name of Zylon. These fibers are high polymers, have a high melting temperature, and are excellent in heat resistance, and the conductive resin containing the metal-coated single fiber using this base fiber is suitable for use in a high temperature environment.
【００１１】基体繊維の表面に設ける下地の金属被覆
は、例えば、金、銀、銅、ニッケル、錫、またはこれら
の合金の一種または二種以上からなる導電性金属被覆が
好ましい。なお、被覆方法ないし手段は限定されない。
電解メッキや化学(無電解)メッキ、あるいは真空蒸着な
どを利用することができる。基体繊維表面に電解メッキ
あるいは化学メッキなどによって上記金属の被覆を設け
ると良い。なお、金属被覆を設ける際に、予め繊維体表
面をアルカリ等によってエッチング処理し、粗面化すれ
ば被覆されるメッキ金属がこの繊維体表面の粗面に入り
込んでアンカー効果を発揮するので好ましい。この金属
被覆は一層でも二層以上でも良い。The underlying metal coating provided on the surface of the base fiber is preferably a conductive metal coating made of one or more of gold, silver, copper, nickel, tin, or alloys thereof. The covering method or means is not limited.
Electrolytic plating, chemical (electroless) plating, vacuum deposition or the like can be used. It is preferable to provide a coating of the above metal on the surface of the base fiber by electrolytic plating or chemical plating. When the metal coating is provided, it is preferable that the surface of the fibrous body is previously subjected to an etching treatment with an alkali or the like to roughen the plated metal to enter the roughened surface of the fibrous body and exert an anchor effect. This metal coating may be a single layer or two or more layers.
【００１２】上記金属被覆は、その表面にオレンジピー
ルを有するものが好ましい。金属被覆がオレンジピール
を有することによって密着強度が向上する。オレンジピ
ール(orange peel)とはオレンジの皮に似た状態であっ
て、表面粗さが概ね０.０１〜１μmの表面状態を云い、
ユズ肌ないし梨地肌と称されている。金属被覆の層厚が
概ね数百ナノメータ(nm)以下であるとき、金属被覆がオ
レンジピールを有するものは被覆の裏側まで粗面状態に
なっており、基体繊維の表面がこの粗面状態の金属被覆
裏面に入り込んでアンカー効果を発揮するので基体繊維
と金属被覆との接着強度が向上する。さらに、金属被覆
表面がオレンジピールを有することにより、その上側の
フッ素化合物被覆との接着強度も向上する。The metal coating preferably has orange peel on its surface. Since the metal coating has orange peel, the adhesion strength is improved. Orange peel is a state similar to orange peel and has a surface roughness of about 0.01 to 1 μm.
It is called yuzu skin or satin skin. When the layer thickness of the metal coating is approximately several hundreds of nanometers (nm) or less, the metal coating having orange peel is roughened to the back side of the coating, and the surface of the substrate fiber is a metal in this roughened state. Since it enters the back surface of the coating and exerts an anchor effect, the adhesive strength between the base fiber and the metal coating is improved. Further, since the metal coating surface has orange peel, the adhesive strength with the fluorine compound coating on the upper side is also improved.
【００１３】本発明の金属被覆繊維体は上記金属被覆の
表面にフッ素化合物被覆を有する。金属被覆繊維体にお
けるフッ素系化合物被覆の量は５重量％以下、好ましく
は０.０１〜５重量％が適当である。このフッ素化合物
被覆によって優れた撥水が得られる。長期間持続的な撥
水性を有するにはフッ素化合物被覆の量は０.５重量％
以上が好ましい。なお、この被覆量が５重量％を上回っ
ても撥水性は大きく変わらないので、被覆量は５重量％
以下が適当である。The metal-coated fiber body of the present invention has a fluorine compound coating on the surface of the metal coating. The amount of the fluorine compound coating in the metal-coated fiber body is 5% by weight or less, preferably 0.01 to 5% by weight. Excellent water repellency is obtained by this fluorine compound coating. To have long-lasting water repellency, the amount of fluorine compound coating is 0.5% by weight
The above is preferable. Even if the coating amount exceeds 5% by weight, the water repellency does not change significantly, so the coating amount is 5% by weight.
The following are appropriate:
【００１４】このフッ素化合物被覆は有機フッ素系界面
活性剤、あるいはアルコキシシラン系フッ素化合物など
を用いて形成すると良い。例えば、上記化合物を含む溶
液を金属被覆表面に塗布し、あるいはこれらの溶液に金
属被覆繊維体を浸して金属被覆表面にフッ素化合物溶液
を付着させ、これを乾燥し加熱処理してフッ素系界面活
性剤を反応させ、あるいはアルコキシシコンの加水分解
などにより金属被覆表面にフッ素化合物被覆を形成す
る。The fluorine compound coating may be formed by using an organic fluorine type surfactant or an alkoxysilane type fluorine compound. For example, a solution containing the above compound is applied to a metal-coated surface, or a metal-coated fiber body is dipped in these solutions to adhere a fluorine compound solution to the metal-coated surface, which is dried and heat-treated to give a fluorine-based surface active agent. A fluorine compound coating is formed on the surface of the metal coating by reacting the agent or by hydrolyzing the alkoxysilicone.
【００１５】フッ素化合物溶液としては市販のフッ素系
界面活性剤を用いることができる。この一例として、１
〜１０％濃度のフッ素系界面活性剤、０.１〜１％濃度
のメラミン樹脂、および０.０５〜１％の触媒化合物を
混合した水溶液が知られている。なお、フッ素系界面活
性剤の濃度が１０％より濃いと金属被覆繊維体の表面が
茶色に変色するので好ましくない。また、この濃度が１
％未満であると撥水効果が低く、塩素や硫黄化合物に対
する変色防止効果も低くなる。As the fluorine compound solution, a commercially available fluorine type surfactant can be used. As an example of this, 1
An aqueous solution in which a fluorinated surfactant having a concentration of -10%, a melamine resin having a concentration of 0.1 to 1%, and a catalyst compound of 0.05 to 1% are mixed is known. If the concentration of the fluorine-based surfactant is higher than 10%, the surface of the metal-coated fiber body will be discolored to brown, which is not preferable. Also, this concentration is 1
If it is less than%, the water repellent effect is low and the discoloration preventive effect against chlorine and sulfur compounds is also low.
【００１６】本発明の金属被覆繊維体は、その表面にフ
ッ素系化合物被覆を有し、これが下地の金属被覆の保護
層となるので耐腐蝕性が向上する。具体的には、例え
ば、この金属被覆繊維体を塩素系洗浄剤で洗濯した場
合、この表面被覆によって塩素系洗浄剤の浸透を防止す
るので塩素系洗浄剤に対する耐腐蝕性に優れる。また、
塵埃や汗などに含まれる硫化物等による硫化反応、ある
いは空気中での酸化反応等による腐食に対しても優れた
耐食性を示す。さらに、下地の金属被覆が外部に露出し
ないので皮膚に対する刺激が殆どなく、金属アレルギー
などを生じる虞がない。また、これらフッ素化合物被覆
は透明性が高いので適度な膜厚下において下地の金属被
覆の色調が被覆表面に表れる。従って、白色系の導電性
金属被覆を設けることにより、耐腐食性に優れ、かつ金
属アレルギーを生じない白色導電性繊維体を得ることが
できる。The metal-coated fiber body of the present invention has a fluorine-based compound coating on its surface, which serves as a protective layer for the underlying metal coating, so that the corrosion resistance is improved. Specifically, for example, when the metal-coated fiber body is washed with a chlorine-based cleaning agent, the surface coating prevents penetration of the chlorine-based cleaning agent, and thus the corrosion resistance to the chlorine-based cleaning agent is excellent. Also,
It also has excellent corrosion resistance against sulfide reactions caused by sulfides contained in dust and sweat, and corrosion caused by oxidation reactions in air. Furthermore, since the underlying metal coating is not exposed to the outside, there is almost no irritation to the skin and there is no risk of metal allergy or the like. Further, since these fluorine compound coatings have high transparency, the color tone of the underlying metal coating appears on the coating surface under an appropriate film thickness. Therefore, by providing the white conductive metal coating, it is possible to obtain a white conductive fiber body which is excellent in corrosion resistance and does not cause metal allergy.
【００１７】本発明の金属被覆繊維体はフッ素系化合物
被覆の表面にさらに表面処理を施したものを含む。表面
処理としては、パラフィンやワックスによる防錆処理な
いしオイル処理(オイリング)などを施すことができる。
なお、この防錆処理によって白色度の経時的な低下や密
着性(剥離強度)の低下を防止することができる。また、
オイル処理を施すことにより繊維体表面の滑り性が向上
する。このオイル処理は繊維体を織機や編機によって加
工する際にその滑りを良くするので金属被覆の密着性の
保護にもなる。金属被覆繊維体は実際に使用する際に、
摩擦、剪断力、曲げ等の物理的な力を受け、その強さや
頻度によって金属被覆の剥離や欠落が生じる。それらの
度合いは直接的には金属被覆と繊維体との密着強度に基
づくが、上記表面処理を施すことによって摩擦や剪断力
などが緩衝され、その結果として金属被覆の剥離が防止
される。The metal-coated fiber body of the present invention includes a surface of a fluorine-based compound coating which is further surface-treated. As the surface treatment, rust prevention treatment with paraffin or wax or oil treatment (oiling) can be applied.
It should be noted that this rust-prevention treatment can prevent a decrease in whiteness over time and a decrease in adhesion (peel strength). Also,
The oil treatment improves the slipperiness of the surface of the fibrous body. This oil treatment improves the slippage of the fibrous body when it is processed by a loom or a knitting machine, and thus protects the adhesion of the metal coating. When the metal coated fiber body is actually used,
When subjected to physical forces such as friction, shearing force, and bending, the metal coating is peeled off or missing depending on its strength and frequency. Although their degree is directly based on the adhesion strength between the metal coating and the fibrous body, the above surface treatment buffers friction, shearing force, etc., and consequently prevents the metal coating from peeling.
【００１８】本発明の金属被覆繊維体は短繊維や長繊
維、あるいは紡績糸や加工糸など各種の糸にして用いら
れる。また、金属被覆繊維を単独に用いる他に、合成繊
維や天然繊維、あるいは合成繊維と天然繊維の混合繊維
に混紡した混合繊維として用いることができる。さら
に、本発明の金属被覆繊維体は織布または不織布などの
布地材料や編物材料などとして用いることができる。こ
の場合、銀やスズ、ニッケルなどを用いたものは高い白
色度を有するので染色した際に発色性に優れ、テキスタ
イルや衣料品の布材に適する。さらに、銀などをコーテ
ングしたものは抗菌繊維体および抗菌衣料として利用す
ることができる。具体的な用途としては、抗菌性の靴
下、下着、上着、白衣、寝具、シーツ、ナプキン、手
袋、シャツ、ズボン、絨毯、マット、カーテンあるいは
作業衣などが挙げられる。The metal-coated fiber body of the present invention is used as various fibers such as short fibers and long fibers, spun yarns and processed yarns. In addition to using the metal-coated fiber alone, it can be used as a mixed fiber obtained by mixing and spinning a synthetic fiber, a natural fiber, or a mixed fiber of a synthetic fiber and a natural fiber. Further, the metal-coated fiber body of the present invention can be used as a fabric material such as a woven fabric or a non-woven fabric, a knitting material, or the like. In this case, those using silver, tin, nickel, etc. have a high whiteness and therefore have excellent coloring properties when dyed, and are suitable for textile materials and cloth materials for clothing. Further, those coated with silver or the like can be used as an antibacterial fiber body and an antibacterial clothing. Specific applications include antibacterial socks, underwear, outerwear, lab coats, bedding, sheets, napkins, gloves, shirts, pants, rugs, mats, curtains or work clothes.
【００１９】また、本発明の金属被覆繊維体は布地材料
等に限らず、その導電性を利用して電磁波シールド材、
無塵服、手袋、靴、カバー、作業衣などの静電防止材
料、あるいは電極や電線の軽量化を図る代替材料などに
用いることができる。さらに、有機材料との混錬による
複合導電材料や繊維体強化プラスチックの導電性補強材
などに用いることができる。Further, the metal-coated fiber body of the present invention is not limited to a fabric material and the like, but its electric conductivity is utilized to provide an electromagnetic wave shielding material,
It can be used as an antistatic material such as dust-free clothes, gloves, shoes, covers, work clothes, or an alternative material for reducing the weight of electrodes and electric wires. Further, it can be used as a composite conductive material obtained by kneading with an organic material, a conductive reinforcing material for fibrous body reinforced plastic, and the like.
【００２０】なお、本発明の金属被覆繊維体を製造する
手段として、基体繊維をチーズ巻の状態でタンク内に設
置し、チーズ巻の内側から外側に向かってメッキ液が流
れるようにしてメッキすると良い。具体的には、タンク
内に基体繊維を支える軸を設け、軸の周面にはメッキ液
が流れ出す多数の小孔を設け、軸にはメッキ液の導入管
を接続する。この軸にチーズ巻の基体繊維を差し込み、
メッキ液を供給する。メッキ液は軸の内部を流れて小孔
から外部に流れ出し基体繊維を内側から外側に向かって
通過する。このような製造手段によれば、繊維の間隙が
メッキ液によって外側に押し広がられた状態となり、繊
維相互の細部にまでメッキ液が浸透するので、チーズ巻
きの状態でも繊維体の表面に金属メッキが均一に形成さ
れる。As a means for producing the metal-coated fiber body of the present invention, when the base fiber is placed in a tank in a state of cheese roll and the plating solution is flowed from the inside to the outside of the cheese roll, plating is performed. good. Specifically, a shaft for supporting the base fibers is provided in the tank, a large number of small holes through which the plating solution flows out are provided on the peripheral surface of the shaft, and a pipe for introducing the plating solution is connected to the shaft. Insert the cheese-wound base fiber into this shaft,
Supply plating solution. The plating solution flows inside the shaft, flows out from the small holes to the outside, and passes through the substrate fibers from the inside toward the outside. According to such a manufacturing means, the gap between the fibers is spread outward by the plating solution, and the plating solution penetrates into the details of the fibers, so that even when cheese is wound, the metal on the surface of the fibrous body remains. Plating is formed uniformly.
【００２１】金属被覆(メッキ)を施した後にこの繊維体
を乾燥し、上記温度範囲の加熱処理を施す。この加熱処
理はメッキ槽内に加圧水蒸気を導入して行っても良い。
またはメッキ槽から巻糸体を取り出して、電気炉などに
移して加熱処理しても良い。なお、加熱処理雰囲気は空
気中でも良いが、金属被覆の酸化による変色を防止する
ためには窒素やアルゴン等の不活性雰囲気下で加熱処理
を行うと良い。また、金属被覆(メッキ)、加熱処理を終
えた繊維体を再びメッキ工程のタンクに入れ、フッ素系
化合物溶液を循環して接触させた後に、加圧水蒸気を導
入し、乾燥、加熱処理を施すことによって金属被覆の上
層に均一にフッ素化合物を被覆することができる。After applying the metal coating (plating), the fibrous body is dried and subjected to heat treatment within the above temperature range. This heat treatment may be performed by introducing pressurized steam into the plating tank.
Alternatively, the wound body may be taken out of the plating tank and transferred to an electric furnace or the like for heat treatment. The heat treatment atmosphere may be air, but in order to prevent discoloration due to the oxidation of the metal coating, it is preferable to perform the heat treatment under an inert atmosphere such as nitrogen or argon. In addition, metal coating (plating), put the fibrous body that has been subjected to heat treatment again in the tank of the plating process, circulate the fluorine-containing compound solution to make contact, then introduce pressurized steam, and perform drying and heat treatment. Thus, the fluorine compound can be uniformly coated on the upper layer of the metal coating.
【００２２】[0022]
【実施例】以下、本発明を実施例によって具体的に示
す。前述のメッキ手段を用い、基体繊維(１５０テ゛ニール)
をメッキ槽に入れ、以下の処理工程(イ)〜(ホ)を経て金
属被覆繊維体を得た。
(イ)脱脂処理：脱脂液(エースクリーンA-220:奥野製薬工業社製
品)の５wt％溶液を５５℃でメッキ槽に５分間循環させ
た後、イオン交換水を通じて十分に洗浄した。
(ロ)アルカリ処理：脱脂処理後に２０wt％水酸化ナトリ
ウム溶液を７０℃でメッキ槽に２０分間循環させ、さら
にイオン交換水を通じて十分に洗浄した後に５wt％濃塩
酸溶液を室温でメッキ槽に２分間循環させた。
(ハ)活性化処理：アルカリ処理後に濃塩酸溶液と塩化パ
ラジウム混合溶液(キャタリストC:輿野製薬工業社製品)をメッ
キ槽に室温で３分間循環させた後にイオン交換水を通じ
て十分に洗浄した。さらに１０wt％硫酸溶液をメッキ槽
に４５℃で３分間循環させて活性化した。
(ニ)第一層金属被覆の形成：以上の前処理によって繊維
体表面に触媒を付着させた後に、この基体繊維を銀、ニ
ッケル、銅の各メッキ液に浸し、無電解メッキによって
下地の第一層金属被覆を形成した。
(ホ)加熱処理：以上の工程を経て製造した金属被覆繊維
体の一部を電気炉に装入し、基体繊維の結晶化温度以上
および融解温度未満の温度条件で加熱冷却処理した。EXAMPLES The present invention will be specifically described below with reference to examples. Base fiber (150 denier) using the plating means
Was placed in a plating tank, and a metal-coated fiber body was obtained through the following treatment steps (a) to (e). (A) Degreasing treatment: A 5 wt% solution of a degreasing liquid (A-screen A-220: product of Okuno Chemical Industries Co., Ltd.) was circulated in a plating tank at 55 ° C. for 5 minutes, and then thoroughly washed with ion-exchanged water. (B) Alkaline treatment: After degreasing treatment, a 20 wt% sodium hydroxide solution was circulated in the plating tank at 70 ° C. for 20 minutes, further thoroughly washed with ion-exchanged water, and then a 5 wt% concentrated hydrochloric acid solution was added to the plating tank at room temperature for 2 minutes. Circulated. (C) Activation treatment: After alkali treatment, a concentrated hydrochloric acid solution and a palladium chloride mixed solution (Catalyst C: a product of Akashino Pharmaceutical Co., Ltd.) were circulated in the plating tank at room temperature for 3 minutes, and then thoroughly washed with ion-exchanged water. . Further, a 10 wt% sulfuric acid solution was circulated in the plating tank at 45 ° C. for 3 minutes for activation. (D) Formation of first-layer metal coating: After the catalyst is attached to the surface of the fibrous body by the above pretreatment, the base fiber is dipped in each plating solution of silver, nickel, and copper, and electroless plating is used to form a base layer. A single layer metallization was formed. (E) Heat treatment: A part of the metal-coated fiber body produced through the above steps was charged into an electric furnace and heat-cooled at a temperature above the crystallization temperature of the base fiber and below the melting temperature.
【００２３】〔実施例１〕上記(イ)〜(ホ)の工程によっ
て得た金属被覆繊維体を、フッ素系界面活性剤(０.０５
％濃度、１％濃度、３％濃度、５％濃度)、メラミン樹
脂(０.３％濃度)、有機アミン(０.１％濃度)を含む水溶
液に浸漬し、取り出して乾燥後、４時間加熱処理した。Example 1 The metal-coated fiber body obtained by the above steps (a) to (e) was treated with a fluorosurfactant (0.05).
% Concentration, 1% concentration, 3% concentration, 5% concentration), immersed in an aqueous solution containing melamine resin (0.3% concentration), organic amine (0.1% concentration), taken out, dried and heated for 4 hours Processed.
【００２４】〔実施例２〕上記(イ)〜(ホ)の工程によっ
て得た金属被覆繊維体を、アルコキシシラン系界面活性
剤(０.０５％濃度、１％濃度、３％濃度、５％濃度)、
酢酸(０.１％濃度)を含む水溶液に浸漬し、取り出して
乾燥後、４時間加熱処理した。Example 2 A metal-coated fiber body obtained by the above steps (a) to (e) was treated with an alkoxysilane-based surfactant (0.05% concentration, 1% concentration, 3% concentration, 5%). concentration),
It was immersed in an aqueous solution containing acetic acid (0.1% concentration), taken out, dried, and heat-treated for 4 hours.
【００２５】これらの金属被覆繊維体について、白色度
および塩素漂白試験を行い腐蝕の有無を調べた。塩素漂
白試験は塩素水溶液(商品名ハイター５０％を含む水溶
液)１００ccの中に試料の銀被覆繊維を室温下で１０分
間浸し、発生する気泡を観察して３段階評価を行った。
白色度は室温で大気下に放置(１ヶ月、３ヶ月)した後、
ハンターの式に基づいてＬ値を求めた。これらの結果を
表１に示した。また、比較例としてフッ素化合物被覆を
形成しない繊維体を対比して示した。With respect to these metal-coated fibrous bodies, whiteness and chlorine bleaching tests were conducted to examine the presence or absence of corrosion. In the chlorine bleaching test, a sample silver-coated fiber was immersed in 100 cc of an aqueous chlorine solution (an aqueous solution containing 50% of product name Higher) at room temperature for 10 minutes, and bubbles generated were observed to make a three-stage evaluation.
Whiteness is left at room temperature in the atmosphere (1 month, 3 months), then
The L value was calculated based on Hunter's formula. The results are shown in Table 1. In addition, as a comparative example, a fibrous body not coated with a fluorine compound is shown in comparison.
【００２６】この結果に示すように、本発明の好ましい
範囲に属する金属被覆繊維体は何れも塩素腐蝕に対して
優れた耐食性を有しており、さらに耐変色性も高く、銀
被覆においては白色度も高い。一方、比較例は何れも塩
素による腐食がみられ、また白色度も低下した。As shown in these results, all of the metal-coated fiber bodies which belong to the preferred range of the present invention have excellent corrosion resistance against chlorine corrosion, have high discoloration resistance, and are white in silver coating. The degree is also high. On the other hand, in each of the comparative examples, corrosion due to chlorine was observed, and the whiteness also decreased.
【００２７】[0027]
【発明の効果】本発明の金属被覆繊維体は耐腐食性に優
れると共に被覆強度が大きい。具体的には、塩素漂白試
験において優れた耐塩素腐蝕性を有している。さらに、
大気中に放置しても変色せずに白色度を保つ。また、加
熱下でも伸縮率が小さく、外力に対する耐久性に優れ
る。従って、これまでは金属被覆の密着性や耐変色性が
十分でないために適用できなかった分野にも本発明の金
属被覆繊維体を用いることできる。The metal-coated fiber body of the present invention has excellent corrosion resistance and high coating strength. Specifically, it has excellent chlorine corrosion resistance in a chlorine bleaching test. further,
Maintains whiteness without discoloration even when left in the atmosphere. Further, the expansion and contraction rate is small even under heating, and the durability against external force is excellent. Therefore, the metal-coated fiber body of the present invention can also be used in the fields that could not be applied until now because the adhesion and discoloration resistance of the metal coating were insufficient.
【００２８】[0028]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 古谷 暢男 秋田県秋田市茨島３丁目１番６号 株式会 社ジェムコ第一事業所内 (72)発明者 前田 雄亮 秋田県秋田市茨島３丁目１番６号 株式会 社ジェムコ第一事業所内 Ｆターム(参考） 4L031 AA13 AA17 AA18 AA20 AA21 AB01 BA04 BA11 CA01 CB12 DA14 DA15 4L033 AA05 AA07 AA08 AA10 AC06 AC15 CA59 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Nobuo Furuya Stock Market Association, 3-1, 6 Ibaraki, Akita City, Akita Prefecture Company Gemco No. 1 Office (72) Inventor Yusuke Maeda Stock Market Association, 3-1, 6 Ibaraki, Akita City, Akita Prefecture Company Gemco No. 1 Office F-term (reference) 4L031 AA13 AA17 AA18 AA20 AA21 AB01 BA04 BA11 CA01 CB12 DA14 DA15 4L033 AA05 AA07 AA08 AA10 AC06 AC15 CA59
Claims (8)
し、さらにその上にフッ素化合物被覆を有することを特
徴とする金属被覆繊維体。1. A metal-coated fiber body comprising a base fiber and a base metal coating on the surface of the base fiber, and further a fluorine compound coating thereon.
温度以上であって融解温度未満の温度で加熱処理されて
いる請求項１の金属被覆繊維体。2. The metal-coated fiber body according to claim 1, wherein after the metal coating is provided, the base fiber is heat-treated at a temperature not lower than the crystallization temperature and lower than the melting temperature.
１〜５％である請求項１または２に記載の金属被覆繊維
体。3. The fluorine compound coating is 0.0 in the weight of the fibrous body.
It is 1-5%, The metal-coated fiber body of Claim 1 or 2.
維、ポリエステル繊維、高強度ナイロン系繊維、ポリフ
ェニレンサルファイド系繊維、ポリカーボネート系繊
維、またはアラミド系繊維である請求項１、２または３
に記載する金属被覆繊維体。4. The base fiber is an acrylic fiber, a nylon fiber, a polyester fiber, a high strength nylon fiber, a polyphenylene sulfide fiber, a polycarbonate fiber or an aramid fiber.
The metal-coated fiber body as described in 1.
ル、錫またはこれらの合金の一種または二種以上からな
る導電性金属被覆である請求項１〜４の何れかに記載す
る金属被覆繊維体。5. The metal coating according to claim 1, wherein the underlying metal coating is a conductive metal coating made of one or more of gold, silver, copper, nickel, tin or alloys thereof. Fibrous body.
し、その上側にフッ素化合物被覆をし、さらにパラフィ
ン処理またはワックス処理されている請求項１〜５の何
れかに記載する金属被覆繊維体。6. The metal-coated fiber body according to claim 1, wherein the underlying metal coating has orange peel, a fluorine compound coating is provided on the upper side, and the paraffin treatment or wax treatment is further performed.
に、これを基体繊維の結晶化温度以上であって融解温度
未満の温度で加熱処理し、次いで、この金属被覆表面に
フッ素化合物被覆を基体繊維の結晶化温度以下で形成す
る金属被覆繊維体の製造方法。7. After providing a metal coating on the surface of the base fiber, this is heat-treated at a temperature higher than the crystallization temperature of the base fiber and lower than the melting temperature, and then the surface of the metal coating is coated with a fluorine compound. A method for producing a metal-coated fiber body which is formed at a crystallization temperature of a base fiber or lower.
有機フッ素系界面活性剤またはアルコキシシラン系フッ
素化合物溶液を用いる請求項７に記載する金属被覆繊維
体の製造方法。8. A solution for forming a fluorine compound coating,
The method for producing a metal-coated fiber body according to claim 7, wherein an organic fluorine-based surfactant or an alkoxysilane-based fluorine compound solution is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001382054A JP3972127B2 (en) | 2001-12-14 | 2001-12-14 | Metal-coated fiber body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001382054A JP3972127B2 (en) | 2001-12-14 | 2001-12-14 | Metal-coated fiber body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003183980A true JP2003183980A (en) | 2003-07-03 |
| JP3972127B2 JP3972127B2 (en) | 2007-09-05 |
Family
ID=27592550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001382054A Expired - Fee Related JP3972127B2 (en) | 2001-12-14 | 2001-12-14 | Metal-coated fiber body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3972127B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006085915A (en) * | 2004-09-14 | 2006-03-30 | Railway Technical Res Inst | Linear body whose thermal expansion is small and manufacturing method therefor |
| US7166354B2 (en) * | 2000-12-26 | 2007-01-23 | Mitsubishi Materials Corporation | Metal coated fiber and electroconductive composition comprising the same and method for production thereof and use thereof |
| JP2010510403A (en) * | 2006-11-21 | 2010-04-02 | ミリッツ デトレフ | Method for metallizing polyester and metallized polyester |
| CN101363189B (en) * | 2007-08-06 | 2010-12-08 | 四川得阳化学有限公司 | Technique for coating inorganic strengthening layer on polyphenyl thioether fabric surface |
| CN103668944A (en) * | 2013-12-16 | 2014-03-26 | 天诺光电材料股份有限公司 | Silvered aramid conductive fiber and preparation method thereof |
| CN105200761A (en) * | 2015-10-13 | 2015-12-30 | 四川大学 | Palladium-free activation chemical nickel-plating method for electromagnetic shielding polyphenylene sulfide fiber |
| JP6980145B1 (en) * | 2021-03-31 | 2021-12-15 | ナガセケムテックス株式会社 | Dough coating composition |
| WO2022030399A1 (en) * | 2020-08-04 | 2022-02-10 | ナガセケムテックス株式会社 | Laminate and fabric coating composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106381689B (en) * | 2016-08-31 | 2019-03-08 | 浙江益南纤维科技有限公司 | A kind of preparation process of the metal wool composite fibre with electro-magnetic screen function |
-
2001
- 2001-12-14 JP JP2001382054A patent/JP3972127B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7166354B2 (en) * | 2000-12-26 | 2007-01-23 | Mitsubishi Materials Corporation | Metal coated fiber and electroconductive composition comprising the same and method for production thereof and use thereof |
| JP2006085915A (en) * | 2004-09-14 | 2006-03-30 | Railway Technical Res Inst | Linear body whose thermal expansion is small and manufacturing method therefor |
| JP4708748B2 (en) * | 2004-09-14 | 2011-06-22 | 公益財団法人鉄道総合技術研究所 | Method for producing low thermal expansion linear body |
| JP2010510403A (en) * | 2006-11-21 | 2010-04-02 | ミリッツ デトレフ | Method for metallizing polyester and metallized polyester |
| CN101363189B (en) * | 2007-08-06 | 2010-12-08 | 四川得阳化学有限公司 | Technique for coating inorganic strengthening layer on polyphenyl thioether fabric surface |
| CN103668944A (en) * | 2013-12-16 | 2014-03-26 | 天诺光电材料股份有限公司 | Silvered aramid conductive fiber and preparation method thereof |
| CN103668944B (en) * | 2013-12-16 | 2015-11-25 | 天诺光电材料股份有限公司 | A kind of aramid fiber Conductive Silver-Coated PET Fibers and preparation method thereof |
| CN105200761A (en) * | 2015-10-13 | 2015-12-30 | 四川大学 | Palladium-free activation chemical nickel-plating method for electromagnetic shielding polyphenylene sulfide fiber |
| WO2022030399A1 (en) * | 2020-08-04 | 2022-02-10 | ナガセケムテックス株式会社 | Laminate and fabric coating composition |
| JP6980145B1 (en) * | 2021-03-31 | 2021-12-15 | ナガセケムテックス株式会社 | Dough coating composition |
| JP2022156228A (en) * | 2021-03-31 | 2022-10-14 | ナガセケムテックス株式会社 | Fabric coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3972127B2 (en) | 2007-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100808322B1 (en) | Metal-coated fiber and electroconductive composition comprising the same, and method for production thereof and use thereof | |
| KR100639093B1 (en) | Conductive fiber, manufacturing method therefor, apparatus, and application | |
| JP2003183980A (en) | Metal coated fiber body and method for producing the same | |
| WO2006047607A2 (en) | Method for improved dyeing of difficult to dye items, yarns, fabrics or articles | |
| WO2003070004A1 (en) | Anti-microbial utility and kitchen wipe utilizing metallic silver as an oligodynamic agent | |
| JP4560750B2 (en) | Metal-coated fibers and their applications | |
| US4283452A (en) | Polyester textile material having improved opacity | |
| JP4329105B2 (en) | Metal-coated fiber body and method for producing the same | |
| JP3906903B2 (en) | Metal-coated fiber body and method for producing the same | |
| US20040258914A1 (en) | Enhanced metal ion release rate for anti-microbial applications | |
| JP4524725B2 (en) | Metal-coated fiber body | |
| JP4789081B2 (en) | Metal-coated fiber body and method for producing the same | |
| JP4543356B2 (en) | Metal-coated fiber body, its use and production method | |
| US4420507A (en) | Process for improving opacity of polyester textile materials | |
| JP7014414B2 (en) | Plating fiber and electric wire | |
| JP5803057B2 (en) | Dyed fiber material and method for producing the same | |
| JP4161287B2 (en) | Conductive resin composition and production method and use thereof | |
| JP2007063704A (en) | Electroconductive fiber | |
| JPH10280270A (en) | Antimicrobial and deodorizing fiber and its production | |
| JPS62299567A (en) | Production of metal coated fiber | |
| JPH0749627B2 (en) | Method for producing metal-coated fiber cloth | |
| JP3919965B2 (en) | Chlorine-resistant silver-coated fiber structure and manufacturing method thereof | |
| JP3712310B2 (en) | Polymer molding having antibacterial properties | |
| TWM549701U (en) | Metal textile yarn with metal oxide ceramic coating layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041210 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050221 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20061207 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20061219 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Effective date: 20070211 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20070306 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070427 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Effective date: 20070522 Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Effective date: 20070524 Free format text: JAPANESE INTERMEDIATE CODE: A61 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100622 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100622 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 3 Free format text: PAYMENT UNTIL: 20100622 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100622 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100622 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110622 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20120622 |
|
| LAPS | Cancellation because of no payment of annual fees |