JP2008031507A - Silver-plated fibrous material - Google Patents
Silver-plated fibrous material Download PDFInfo
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- JP2008031507A JP2008031507A JP2006204548A JP2006204548A JP2008031507A JP 2008031507 A JP2008031507 A JP 2008031507A JP 2006204548 A JP2006204548 A JP 2006204548A JP 2006204548 A JP2006204548 A JP 2006204548A JP 2008031507 A JP2008031507 A JP 2008031507A
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本発明は、銀めっきを付着した繊維、繊維束や糸などの繊維材料の技術に関する。 The present invention relates to a technique of a fiber material such as a fiber, a fiber bundle, or a thread to which silver plating is attached.
銀めっきを付着した繊維、繊維束や糸などの繊維材料は、抗菌性や防臭性、導電性や電磁波遮蔽性があって機能性に優れている。また、外観が銀白色であって意匠性に優れている。各種の性能が高い。衣類、浄化材、導電材、静電気除去材、電磁波遮蔽材や装飾材など多方面において用いられる。 Fiber materials such as fibers, fiber bundles and yarns with silver plating attached have excellent antibacterial and deodorizing properties, electrical conductivity and electromagnetic wave shielding properties, and excellent functionality. In addition, the appearance is silver white and the design is excellent. Various performances are high. It is used in various fields such as clothing, purification materials, conductive materials, static electricity removal materials, electromagnetic wave shielding materials and decoration materials.
銀めっき付き繊維材料は、特許文献1に例示されているように、繊維材料に銀の無電解めっきを施して製造される。この銀めっき付き繊維材料は、外周面に銀めっきをほぼ均一に付着し、外周を銀めっき膜で覆っている。銀めっき膜は、厚さが数分の一μm程度である。 As exemplified in Patent Document 1, the fiber material with silver plating is manufactured by applying silver electroless plating to the fiber material. This fiber material with silver plating adheres silver plating almost uniformly on the outer peripheral surface and covers the outer periphery with a silver plating film. The silver plating film has a thickness of about 1 / μm.
[背景技術の課題]
銀めっき付き繊維材料は、銀めっき用の銀塩、高価な銀を原料としている。銀の使用量が多くなると、原料費が高くなる。そこで、高価な銀を節約するため、銀の使用量を減らし、繊維材料に付着する銀めっき膜を薄くすることが考えられる。
[Issues of background technology]
The fiber material with silver plating is made from silver salt for silver plating and expensive silver. As the amount of silver used increases, the raw material costs increase. Therefore, in order to save expensive silver, it is conceivable to reduce the amount of silver used and to thin the silver plating film attached to the fiber material.
ところが、銀めっき付き繊維材料は、外周面に付着している銀めっき膜が薄くなると、銀イオンの溶出が不活発になって、抗菌性や防臭性が低下する。また、電気抵抗が増加して、導電性や電磁波遮蔽性が低下する。また、外観が銀白色にならず、濁った色になることがあり、意匠性が低下する。即ち、銀めっき膜を薄くすると、性能が低下する。銀めっき膜を薄くしても、性能が維持されることが望まれる。 However, when the silver plating film adhering to the outer peripheral surface of the fiber material with silver plating becomes thin, elution of silver ions becomes inactive, and the antibacterial and deodorizing properties decrease. In addition, the electrical resistance increases, and the electrical conductivity and electromagnetic wave shielding properties decrease. Moreover, the external appearance does not become silvery white and may become a cloudy color, and the designability is lowered. That is, when the silver plating film is thinned, the performance is lowered. Even if the silver plating film is thinned, it is desired that the performance is maintained.
[課題を解決するための着想]
銀めっき付き繊維材料において、外周面に付着する銀めっき膜を薄くしても、性能を低下させないため、薄くした銀めっき膜の下に他の金属めっき膜を介在することにした。そして、その下地の金属めっき膜は、銅又は銅合金のめっき膜にすることにした。銅又は銅合金は、銀より安価なことが多い上、銀ほどではないが、抗菌性や防臭性、導電性や電磁波遮蔽性に優れている。しかも、銀との付着性や繊維材料との付着性に優れている。
[Idea for solving problems]
In the fiber material with silver plating, even if the silver plating film adhering to the outer peripheral surface is thinned, the performance is not lowered. Therefore, another metal plating film is interposed under the thinned silver plating film. The underlying metal plating film is a copper or copper alloy plating film. Copper or a copper alloy is often less expensive than silver and, although not as good as silver, is excellent in antibacterial properties, deodorization properties, conductivity and electromagnetic wave shielding properties. In addition, it has excellent adhesion to silver and fiber material.
銀めっき付き繊維材料は、外周面を銅又は銅合金のめっき膜で覆い、その銅めっき膜又は銅合金めっき膜の外周面を銀めっき膜で覆うことにした。銀めっき膜は、その内周面に銅又は銅合金のめっき膜が積層する。内周層の銅めっき膜又は銅合金めっき膜と外周層の銀めっき膜の内外2層によって、抗菌性や防臭性、導電性や電磁波遮蔽性などの性能が発揮される。外周層の高価な銀めっき膜は、薄くしても、性能がほぼ維持される。 In the fiber material with silver plating, the outer peripheral surface was covered with a copper or copper alloy plating film, and the outer peripheral surface of the copper plating film or the copper alloy plating film was covered with the silver plating film. The silver plating film has a copper or copper alloy plating film laminated on the inner peripheral surface thereof. The inner and outer layers of the copper plating film or copper alloy plating film of the inner peripheral layer and the silver plating film of the outer peripheral layer exhibit performances such as antibacterial properties, deodorization properties, conductivity, and electromagnetic wave shielding properties. Even if the expensive silver plating film of the outer peripheral layer is thin, the performance is substantially maintained.
1)繊維、繊維束や糸などの繊維材料は、外周面に銅めっき又は銅合金めっきを付着して外周面を銅めっき膜又は銅合金めっき膜で覆い、その銅めっき膜又は銅合金めっき膜の外周面に銀めっきを付着して銅めっき膜又は銅合金めっき膜の外周面を銀めっき膜で覆い、銀めっき膜の内周面に銅又は銅合金めっき膜を積層していることを特徴とする銀めっき付き繊維材料。 1) For fiber materials such as fibers, fiber bundles and threads, copper plating or copper alloy plating is attached to the outer peripheral surface, and the outer peripheral surface is covered with a copper plating film or copper alloy plating film, and the copper plating film or copper alloy plating film The silver plating film is attached to the outer peripheral surface of the copper plate, the outer peripheral surface of the copper plating film or the copper alloy plating film is covered with the silver plating film, and the copper or copper alloy plating film is laminated on the inner peripheral surface of the silver plating film. A silver-plated fiber material.
2)上記の銀めっき付き繊維材料において、
繊維材料は、ポリエステル繊維、ナイロン繊維、アクリル繊維やアラミド繊維などの合成繊維、合成繊維の束や糸であることを特徴とする。
2) In the above silver plated fiber material,
The fiber material is a synthetic fiber such as polyester fiber, nylon fiber, acrylic fiber or aramid fiber, or a bundle or thread of synthetic fiber.
3)上記の銀めっき付き繊維材料において、
銅合金めっき膜は、銅−銀合金めっき膜であることを特徴とする。
3) In the above silver plated fiber material,
The copper alloy plating film is a copper-silver alloy plating film.
4)繊維、繊維束や糸などの繊維材料は、銅又は銅合金の無電解めっきを施し、その後、銀の無電解めっきを施し、請求項1、2又は3に記載の銀めっき付き繊維材料を得ることを特徴とする製造方法。 4) Fiber materials such as fibers, fiber bundles and threads are subjected to electroless plating of copper or copper alloy, and then subjected to electroless plating of silver, and the fiber material with silver plating according to claim 1, 2 or 3 The manufacturing method characterized by obtaining.
銀めっき付き繊維材料は、その外周面に銅めっき膜又は銅合金めっき膜が付着し、その銅めっき膜又は銅合金めっき膜の外周面に銀めっき膜が付着している。外周層の銀めっき膜と内周層の銅めっき膜又は銅合金めっき膜の2層によって、抗菌性や防臭性、導電性や電磁波遮蔽性などの性能が発揮される。高価な銀めっき膜は、薄くして銀の使用量を減らしても、性能がほぼ維持される。 In the fiber material with silver plating, a copper plating film or a copper alloy plating film adheres to the outer peripheral surface, and a silver plating film adheres to the outer peripheral surface of the copper plating film or copper alloy plating film. Performances such as antibacterial properties, deodorization properties, electrical conductivity and electromagnetic wave shielding properties are exhibited by the two layers of the outer peripheral layer silver plating film and the inner peripheral layer copper plating film or copper alloy plating film. Even if an expensive silver plating film is thinned to reduce the amount of silver used, the performance is almost maintained.
実施形態における繊維材料は、ポリエステル繊維、ナイロン繊維、アクリル繊維やアラミド繊維などの合成繊維の糸である。合成繊維の糸は、繊度が28〜1100〔dTex〕で、フィラメント数が3〜192〔本〕である。 The fiber material in the embodiment is a yarn of synthetic fiber such as polyester fiber, nylon fiber, acrylic fiber or aramid fiber. The yarn of the synthetic fiber has a fineness of 28 to 1100 [dTex] and a filament number of 3 to 192 [pieces].
実施形態の銀めっき付き合成繊維糸を製造する場合は、上記の合成繊維糸に、最初に、銅又は銅合金の無電解めっきを施し、次に、銀の無電解めっきを施す。この銀めっき付き合成繊維糸は、外周面に銅又は銅合金のめっきを付着して外周面を銅めっき膜又は銅合金めっき膜で覆い、その銅めっき膜又は銅合金めっき膜の外周面に銀めっきを付着して銅めっき膜又は銅合金めっき膜の外周面を銀めっき膜で覆っている。銀めっき膜は、その内周面に銅又は銅合金めっき膜が積層している。 When manufacturing the synthetic fiber yarn with silver plating of embodiment, the electroless plating of copper or a copper alloy is first given to said synthetic fiber yarn, and then the electroless plating of silver is given. This synthetic fiber yarn with silver plating adheres copper or copper alloy plating to the outer peripheral surface, covers the outer peripheral surface with a copper plating film or copper alloy plating film, and silver on the outer peripheral surface of the copper plating film or copper alloy plating film. Plating is attached and the outer peripheral surface of the copper plating film or copper alloy plating film is covered with a silver plating film. The silver plating film has a copper or copper alloy plating film laminated on the inner peripheral surface thereof.
銅又は銅合金の無電解めっきと銀の無電解めっきは、それぞれ、糸を前処理し、次に、本処理を行う。前処理は、前処理液に糸を浸漬し、接触中の前処理液と糸とを相対的に移動させる。本処理は、めっき液に糸を浸漬し、接触中のめっき液と糸とを相対的に移動させる。 In the electroless plating of copper or copper alloy and the electroless plating of silver, the yarn is pretreated and then the main treatment is performed. In the pretreatment, the yarn is immersed in the pretreatment liquid, and the pretreatment liquid and the yarn that are in contact are relatively moved. In this treatment, the yarn is immersed in the plating solution, and the plating solution and the yarn in contact are moved relatively.
銀めっき付き合成繊維糸の実施例は、次の通りである。
[第1例]
合成繊維糸は、ポリエステル繊維の糸で、繊度が66〔dTex〕、フィラメント数が4〔本〕である。このポリエステル繊維糸は、最初に、銅の無電解めっきを施す。銅の無電解めっきの前処理は、脱脂処理、エッチング処理、中和処理、表面調整処理、触媒付与処理とアクセレータ処理を順次行う。エッチング処理は、カセイソーダ水溶液を使用する。中和処理は、塩酸水溶液を使用する。表面調整処理は、界面活性剤の水溶液を使用する。触媒付与処理は、塩化パラジウム、塩化第1スズなどの触媒と塩酸の水溶液を使用する。アクセレータ処理は、硫酸水溶液を使用する。
Examples of synthetic fiber yarns with silver plating are as follows.
[First example]
The synthetic fiber yarn is a polyester fiber yarn having a fineness of 66 [dTex] and a filament count of 4 [pieces]. The polyester fiber yarn is first subjected to copper electroless plating. As a pretreatment for the electroless plating of copper, a degreasing treatment, an etching treatment, a neutralization treatment, a surface conditioning treatment, a catalyst application treatment and an accelerator treatment are sequentially performed. The caustic soda aqueous solution is used for the etching process. The neutralization treatment uses an aqueous hydrochloric acid solution. The surface conditioning treatment uses an aqueous solution of a surfactant. The catalyst application treatment uses a catalyst such as palladium chloride or stannous chloride and an aqueous solution of hydrochloric acid. The accelerator treatment uses a sulfuric acid aqueous solution.
銅めっき液の組成は、次の通りである。なお、Lはリットルを表す。
銅 塩:硫酸銅 10g/L
錯化剤:酒石酸カリウムナトリウム(ロッセル塩) 40g/L
還元剤:ホルムアルデヒド 10g/L
pH調整剤:カセイソーダ 8〜10g/L
安定剤:微 量
また、銅めっき液は、
pH:12.5
温 度:25℃
である。めっき時間は、5分である。
The composition of the copper plating solution is as follows. L represents liters.
Copper salt: Copper sulfate 10g / L
Complexing agent: potassium sodium tartrate (Rossel salt) 40 g / L
Reducing agent: formaldehyde 10 g / L
pH adjuster: caustic soda 8-10g / L
Stabilizer: Small amount Copper plating solution
pH: 12.5
Temperature: 25 ° C
It is. The plating time is 5 minutes.
ポリエステル繊維糸は、外周面に銅めっき膜が均等に付着する。ポリエステル繊維糸の外周面は、銅めっき膜で被覆される。銅めっき膜は、厚さが0.1μm位である。この銅めっき膜は、付着力テープテストで剥離しなかった。 The polyester fiber yarn has a copper plating film uniformly attached to the outer peripheral surface. The outer peripheral surface of the polyester fiber yarn is covered with a copper plating film. The copper plating film has a thickness of about 0.1 μm. This copper plating film was not peeled off by the adhesive tape test.
なお、銅めっき膜の厚さは、銅めっき時間の長短で増減する。例えば、銅めっき時間を10分にすると、銅めっき膜の厚さが0.2μm位になる。 Note that the thickness of the copper plating film varies depending on the length of the copper plating time. For example, when the copper plating time is 10 minutes, the thickness of the copper plating film is about 0.2 μm.
銅めっき膜が付着したポリエステル繊維糸は、次に、銀の無電解めっきを施す。銀の無電解めっきの前処理は、銅の無電解めっきのそれとほぼ同様である。 Next, the electroless plating of silver is applied to the polyester fiber yarn to which the copper plating film is adhered. The pretreatment of the electroless plating of silver is almost the same as that of the electroless plating of copper.
銀めっき液の組成は、次の通りである。なお、mlはミリリットルを表す。
銀 塩:硝酸銀 3g/L
錯化剤:エタノールアミン 10ml/L
安定剤:チオリンゴ酸 0.5g/L
還元剤:蟻 酸 15g/L
また、銀めっき液は、
pH:12
温 度:20℃
である。めっき時間は、30分である。
The composition of the silver plating solution is as follows. Ml represents milliliters.
Silver salt: Silver nitrate 3g / L
Complexing agent: ethanolamine 10ml / L
Stabilizer: Thiomalic acid 0.5g / L
Reducing agent: Formic acid 15g / L
The silver plating solution
pH: 12
Temperature: 20 ° C
It is. The plating time is 30 minutes.
ポリエステル繊維糸は、外周面を被覆した銅めっき膜の外周面に銀めっき膜が均等に付着する。銅めっき膜の外周面は、銀めっき膜で被覆される。銀めっき膜は、厚さが0.1μm位である。この銀めっき膜は、付着力テープテストで剥離しなかった。 In the polyester fiber yarn, the silver plating film uniformly adheres to the outer peripheral surface of the copper plating film covering the outer peripheral surface. The outer peripheral surface of the copper plating film is covered with a silver plating film. The silver plating film has a thickness of about 0.1 μm. This silver plating film was not peeled off by the adhesive tape test.
なお、銀めっき膜の厚さは、銀めっき時間の長短で増減する。例えば、銀めっき時間を45分にすると、銀めっき膜の厚さが0.15μm位になる。 Note that the thickness of the silver plating film varies depending on the length of the silver plating time. For example, when the silver plating time is 45 minutes, the thickness of the silver plating film is about 0.15 μm.
本例のポリエステル繊維糸は、外周面に銅めっき膜と銀めっき膜が内外に厚さ0.1μm位ずつ積層している。内周層と外周層のめっき膜によって導電性がある。長さ1cm当りの電気抵抗値が10Ω以下である。外周層が銀めっき膜であり、外観が銀白色である。この銀白色は、洗濯テストで変色しなかった。洗濯耐久性がある。 In the polyester fiber yarn of this example, a copper plating film and a silver plating film are laminated on the outer peripheral surface in thicknesses of about 0.1 μm each. The inner peripheral layer and the outer peripheral layer have conductivity due to the plating film. The electrical resistance value per 1 cm length is 10Ω or less. The outer peripheral layer is a silver plating film, and the appearance is silver white. This silver white color did not change in the washing test. Washable durability.
銅めっき膜と銀めっき膜が内外に厚さ0.1μm位ずつ付着したポリエステル繊維糸は、厚さ0.2μm位の銀めっき膜のみが付着した場合に比較して、抗菌性や防臭性、導電性や電磁波遮蔽性などの性能と意匠性がほぼ同じである。銀の使用量は、ほぼ半減している。 The polyester fiber yarn with copper plating film and silver plating film attached to the inside and outside each about 0.1 μm thick has antibacterial and deodorizing properties compared to the case where only the silver plating film with thickness of about 0.2 μm is attached. The performance and design properties such as conductivity and electromagnetic shielding properties are almost the same. The amount of silver used is almost halved.
[第2例]
本例は、第1例における内周層の銅の無電解めっきに代えて、銅合金の銅−銀合金の無電解めっきを施す。その他の点は、第1例におけるのと同様である。
[Second example]
In this example, instead of the electroless plating of copper in the inner peripheral layer in the first example, electroless plating of a copper-silver alloy of a copper alloy is performed. Other points are the same as in the first example.
銅−銀合金の無電解めっきの前処理は、第1例における内周層の銅の無電解めっきのそれとほぼ同様である。
銅−銀合金めっき液の組成は、次の通りである。
銅 塩:酢酸銅 5g/L
銀 塩:硝酸銀 2.5g/L
錯化剤:エチレンジアミン 10ml/L
還元剤:水酸化ヒドラジン 0.2ml/L
安定剤:少 量
また、銅−銀合金めっき液は、温度が30℃である。めっき時間は、10分である。
The pretreatment of the electroless plating of the copper-silver alloy is substantially the same as that of the electroless plating of the inner peripheral layer copper in the first example.
The composition of the copper-silver alloy plating solution is as follows.
Copper salt: Copper acetate 5g / L
Silver salt: Silver nitrate 2.5g / L
Complexing agent: ethylenediamine 10ml / L
Reducing agent: hydrazine hydroxide 0.2 ml / L
Stabilizer: Small amount The temperature of the copper-silver alloy plating solution is 30 ° C. The plating time is 10 minutes.
ポリエステル繊維糸は、外周面に銅−銀合金めっき膜が均等に付着する。ポリエステル繊維糸の外周面は、銅−銀合金めっき膜で被覆される。銅−銀合金めっき膜は、厚さが0.1μm位である。この銅−銀合金めっき膜は、付着力テープテストで剥離しなかった。 The polyester fiber yarn has a copper-silver alloy plating film uniformly attached to the outer peripheral surface. The outer peripheral surface of the polyester fiber yarn is covered with a copper-silver alloy plating film. The copper-silver alloy plating film has a thickness of about 0.1 μm. This copper-silver alloy plating film was not peeled off by the adhesive tape test.
なお、銅−銀合金めっき膜の厚さは、銅−銀合金めっき時間の長短で増減する。例えば、銅−銀合金めっき時間を20分にすると、銅−銀合金めっき膜の厚さが0.2μm位になる。 Note that the thickness of the copper-silver alloy plating film varies depending on the length of the copper-silver alloy plating time. For example, when the copper-silver alloy plating time is 20 minutes, the thickness of the copper-silver alloy plating film is about 0.2 μm.
銅−銀合金めっき膜が付着したポリエステル繊維糸は、次に、第1例におけるのと同様に、銀の無電解めっきを施す。このポリエステル繊維糸は、外周面を被覆した銅−銀合金めっき膜の外周面に銀めっき膜が均等に付着する。銅−銀合金めっき膜の外周面は、銀めっき膜で被覆される。銀めっき膜は、厚さが0.1μm位である。この銀めっき膜は、付着力テープテストで剥離しなかった。 Next, the polyester fiber yarn to which the copper-silver alloy plating film is adhered is subjected to silver electroless plating in the same manner as in the first example. In this polyester fiber yarn, the silver plating film uniformly adheres to the outer peripheral surface of the copper-silver alloy plating film covering the outer peripheral surface. The outer peripheral surface of the copper-silver alloy plating film is covered with a silver plating film. The silver plating film has a thickness of about 0.1 μm. This silver plating film was not peeled off by the adhesive tape test.
本例のポリエステル繊維糸は、外周面に銅−銀合金めっき膜と銀めっき膜が内外に厚さ0.1μm位ずつ積層している。内外層のめっき膜によって導電性がある。長さ1cm当りの電気抵抗値が10Ω以下である。外周層が銀めっき膜であり、外観が銀白色である。この銀白色は、洗濯テストで変色しなかった。洗濯耐久性がある。 In the polyester fiber yarn of this example, a copper-silver alloy plating film and a silver plating film are laminated on the outer peripheral surface by a thickness of about 0.1 μm. The inner and outer layer plating films are conductive. The electrical resistance value per 1 cm length is 10Ω or less. The outer peripheral layer is a silver plating film, and the appearance is silver white. This silver white color did not change in the washing test. Washable durability.
銅−銀合金めっき膜と銀めっき膜が内外に厚さ0.1μm位ずつ付着したポリエステル繊維糸は、厚さ0.2μm位の銀めっき膜のみが付着した場合に比較して、抗菌性や防臭性、導電性や電磁波遮蔽性などの性能と意匠性がほぼ同じである。銀の使用量は、減少している。 Polyester fiber yarns with a copper-silver alloy plating film and a silver plating film attached to the inside and outside by about 0.1 μm each have antibacterial and antibacterial properties compared to the case where only a silver plating film with a thickness of about 0.2 μm is attached. Performance and design properties such as deodorization, conductivity and electromagnetic wave shielding are almost the same. Silver usage is declining.
本発明は、抗菌性や防臭性電磁波遮蔽性や静電気除去性のある繊維製品の素材、抗菌性や防臭性の浄化材、導電性物品の素材、装飾物品の素材などに利用される。 INDUSTRIAL APPLICABILITY The present invention is used as a material for textiles having antibacterial and deodorant electromagnetic wave shielding properties and static electricity removal, an antibacterial and deodorizing purification material, a material for conductive articles, a material for decorative articles, and the like.
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KR101057025B1 (en) | 2008-08-23 | 2011-08-16 | 김동현 | Gold and silver plating method on conductive fiber |
JP2011231382A (en) * | 2010-04-28 | 2011-11-17 | Nagoya Plating Co Ltd | Plating liquid for polymer fiber, method for plating polymer fiber using the same, and method for producing the same |
CN112941442A (en) * | 2019-01-30 | 2021-06-11 | 浙江华达新型材料股份有限公司 | Preparation process of steel plate surface coating based on heat treatment |
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