JP6502104B2 - Elastic wire - Google Patents

Description

  The present invention relates to a wire having stretchability, and more particularly to a stretchable wire suitable for wiring such as a robot or wearable electronic device that requires stretchability, or an electromagnetic wave shielding material.

  An ordinary electric wire has a structure in which a metal wire is used as a core and the outer periphery is covered with an insulator, so it has almost no stretchability. On the other hand, as an electric wire having stretchability, there is a curled cord which can be expanded and contracted by forming the electric wire in a coil form, and is widely used in fixed telephones and the like. However, there are various problems such as being thick and heavy in general, and curled cords being easily entangled with each other.

  Therefore, as a technique related to a high strength and stretchable wire having stretchability in the wire itself, for example, in Patent Document 1, the outer periphery of a core yarn formed by winding an inelastic yarn in a state in which an elastic yarn is stretched about twice In addition, a stretchable wire is disclosed, in which a copper foil is spirally wound and is covered with a polyurethane or vinyl tube. However, copper foil is weak to friction, etc., and has a problem that it is easily broken when it is bent.

  Further, Patent Document 2 discloses a stretchable electric wire in which a plurality of core wires in which conductive wires are disposed on the outer periphery of a core material made of stretchable elastic yarn are covered with a false twisting yarn. Furthermore, in Patent Document 3, the core portion is an elastic cylindrical body composed of an elastic body that can expand and contract and an intermediate layer covering the outer periphery, and a conductor is wound around the core portion to form a conductor portion, and the conductor portion A stretchable wire is disclosed, the outer periphery of which is coated with an insulator. The stretchable wire described in these patent documents is a wire having a structure in which a copper foil or a copper wire is wound around an elastic yarn such as polyurethane so as not to lose stretchability.

  However, the elastic yarns, copper foils, copper wires, etc., used here for conventional stretchable electric wires all have low mechanical properties such as tensile strength, and such stretchable electric wires give tension and bending many times. When used for the purpose of being used, there was a problem that it was easy to break.

Japanese Patent Application Laid-Open No. 61-290603 JP 2004-134313 A International Publication No. 2008/078780 Brochure

  An object of the present invention is to provide a stretchable wire having excellent tensile strength and bending fatigue properties.

The elastic electric wire of the present invention is an aromatic polyamide fiber comprising an elastic fiber having an elongation of 100% or more and a metal-coated fiber having a strength of 2.5 cN / dtex or more, and the metal-coated fiber is metal-plated Uses both electroless plating and electroplating, and a lubricant is applied to the metal-coated fiber, the lubricant is an aliphatic ester or mineral oil lubricant, and the metal-coated fiber is around the elastic fiber. It is characterized by being arranged.
Furthermore, the metal-coated fiber is wound and / or braided around the elastic fiber, the metal-coated fiber is a twisted multifilament, and the metal-coated fiber is metal-plated aromatic polyamide fiber Is preferred.
In another method of producing an elastic wire according to the present invention, a metal-coated fiber having a strength of 2.5 cN / dtex or more is disposed around the elastic fiber having an elongation of 100% or more , and the metal-coated fiber is metal plated Aromatic polyamide fiber, metal plating uses both electroless plating and electroplating, and metal coated fiber is coated with lubricant, and lubricant is aliphatic ester type or mineral oil type lubricant A method characterized by

  According to the present invention, a stretchable wire having excellent tensile strength and bending fatigue property is provided.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
The stretchable wire of the present invention comprises elastic fibers having an elongation of 100% or more and metal-coated fibers having a strength of 2.5 cN / dtx or more, and metal-coated fibers are disposed on the outer periphery of the elastic fibers. Furthermore, it is preferable that the outermost part of the elastic intermediate made of elastic fiber and metal-coated fiber is covered with an insulator.

  The elastic fiber used for the stretchable wire of the present invention may be a stretchable cable with an elongation of 100% or more, and the type of the polymer is not particularly limited. For example, polyurethane-based elastic fiber, polyolefin-based elastic fiber, polyester-based elastic fiber, polyamide-based elastic fiber, natural rubber-based elastic fiber, synthetic rubber-based elastic fiber, and composite rubber-based elastic fiber of natural rubber and synthetic rubber, etc. it can.

  Among them, polyurethane-based elastic fibers are optimally used in the present invention as elastic fibers because they have high elongation and excellent durability. Natural rubber fibers are characterized in that the stress per cross sectional area is small compared to other elastic fibers, but they tend to be slightly deteriorated, and it tends to be somewhat difficult to maintain stretchability over a long period of time. Synthetic rubber elastic fibers are excellent in durability, but tend to be difficult to obtain those with high elongation.

  Here, as an elastic fiber used in the present invention, a monofilament or a multifilament may be used, and a long fiber or a spun yarn may be used. The fiber diameter of each single yarn is preferably in the range of 1.5 to 50 dtex, and the fiber diameter of the elastic fiber portion in the core portion of the stretchable wire is preferably in the range of 20 to 4000 dtex. In particular, the elongation is preferably an elastic fiber in the range of 150 to 1000%.

The stretchable wire of the present invention uses a stretchable intermediate composed of such elastic fibers and metal-coated fibers. And, the metal coated fiber is the conductor of electricity.
Here, the metal-coated fiber constituting the stretchable wire needs to have a strength of 2.5 cN / dtx or more, and preferably in the range of 3.0 to 25.0 cN / dtex. The metal-coated fiber is preferably an organic fiber having excellent flexibility. The fiber strength before metal coating is preferably in the range of 7.0 to 40.0 cN / dtex. Furthermore, as the fiber to be coated with metal, it is preferable to be an organic fiber that is more excellent in tensile strength, such as aromatic polyamide fiber (hereinafter referred to as "aramid fiber"), wholly aromatic polyester fiber, polybenzobisoxazole fiber, etc. . In particular, among the above organic fibers, aramid fibers are preferred. Aramid fibers are excellent in heat resistance, bending fatigue properties of the fibers themselves, and cut resistance, and are very useful for improving the physical properties of the resulting stretchable wire. For example, when the metal-coated fiber has high heat resistance, it is possible to adopt a general processing means such as soldering the conductor portion (metal-coated fiber) of the stretchable wire after peeling the coating resin. Become.

  Examples of aramid fibers include meta-aramid fibers and para-aramid fibers. More specifically, preferred examples of aramid fibers include poly-metaphenylene isophthalamide fibers (Teijin Limited, Inc.) as meta-aramid fibers. Product name "Cornex (registered trademark)". Moreover, as para-aramid fiber, for example, poly-p-phenylene terephthalamide fiber (made by Teijin Ltd., trade name "Twaron (registered trademark)") and copoly-p-phenylene-3,4'-oxydiphenylene terephthalamide fiber (For example, Teijin Limited, "Technola (registered trademark)") and the like are exemplified.

  The fineness of the metal-coated fiber to be a conductor can be appropriately designed by changing it according to the required characteristics such as required strength and conductivity or depending on the application. For example, in the case of a conductor used for communication cables such as a robot cable, earphone, headphone cable, USB cable such as a mouse of a personal computer, or electromagnetic shielding, the range of single fiber fineness 0.5 to 20 dtex is preferable, 1 to 5 dtex The range is more preferred. And it is preferable that it is a fiber bundle which those single fibers gathered, as a total fineness, 10-5000 dtex is preferable, and also speaking, the range of 100-4000 dtex is preferable. The number of single fibers in the fiber bundle is preferably 40 to 1,500. By using a fiber assembly composed of such fine fine fibers of single fibers, it is possible to make the wire more excellent in flexibility and flexibility and high in strength.

  The metal-coated fiber used in the present invention is a fiber to which the surface of the high-strength fiber as described above is coated with a metal to which conductivity is imparted. As a method of obtaining the metal-coated fiber which becomes the conductor part of such an elastic wire of the present invention, for example, a method of covering the fiber with a metal wire or metal foil, a conductive metal powder, etc. There is a method of adhering to the fiber surface by the above method, or a method of directly coating the surface of the yarn by electroless plating, sputtering, vacuum deposition or the like. At this time, the method of coating the conductive material on the fiber surface directly is preferable from the viewpoint of bending resistance. As a method of coating the fiber surface directly, electroless plating is preferable in terms of mass productivity. If it is necessary to increase the thickness of the metal coating to further enhance the conductivity, it is also a preferred embodiment to further carry out electroplating after electroless plating. The metal to be plated may be any metal such as copper, nickel, silver and gold, but copper is most preferable in terms of electric resistance, price and the like. In addition, other metals alone or their alloys may be used.

The metal coating amount may be set in accordance with the required conductivity. However, if the metal coating per single fiber becomes thick, peeling and cracking of the coating are likely to occur during bending, so the fineness of the single yarn (single fiber) or the yarn may be reduced according to the required electrical resistance value. It is preferable to make the metal coating thinner while securing the same conductivity by increasing the number of single yarns constituting (fiber bundle) and increasing the surface area.
Moreover, in order to form a metal coating efficiently, it is preferable to implement electroless plating and to electroplate after providing conductivity to an organic fiber thread. Since it takes time to metal-cover such as 0.1 μm or more in electroless plating, it is an effective means to use electroplating together in this way.

The thickness of the coating (plating) of the metal-coated fiber is preferably 0.05 to 5.0 μm, and more preferably 0.1 to 3.0 μm. When the thickness is 3.0 μm or more, the metal coating amount increases, and the fiber yarn tends to be hard or lose its flexibility.
Moreover, it is preferable to use the metal-coated fiber used for the elastic wire of the present invention by twisting as needed. As a twist number, it is preferable that the twist coefficient shown below exists in the range of 0.5-3.0.
Twist factor (TM) TM = T × √ D / 1055
[Wherein, TM; twist coefficient, T; twist number (turns / m), D: total denier (tex) of organic fiber yarn raw yarn] ]

  The twist coefficient is preferably around 1.0 from the viewpoint of the tensile strength of the fiber. Further, as the twist is applied, the conductivity is improved and the electric resistance tends to be lowered. It is inferred that this is because the contact resistance is reduced because the metal surfaces of the metal coated on each single yarn adhere to each other by strong twisting by twisting. Furthermore, twisting also has the effect of canceling the defects caused by the dropouts and cracks of the plating. By twisting in this way, it is possible to reduce the electrical resistance value, but if it is twisted too much, the tensile strength will decrease, so it is necessary to determine according to the application, and in general The twist coefficient is preferably in the range of 1.0 to 2.0.

  In addition, a lubricant is applied to the metal-coated fiber in order to prevent oxidation of the surface and to prevent corrosion, or to reduce the friction coefficient between single fibers of the fiber and the insulation coating resin, and to improve the bending fatigue property. Is preferred. Wire cords using ordinary hard metal-coated single yarns have high friction between single yarns and single yarns, and bending is repeated during processing and use, so that metal coating plating may fall off or crack Was apt to occur. In such a thing, the electric resistance value rose and it was difficult to use as a wire cord. When the above-mentioned lubricant adheres between single yarns as in the preferred embodiment of the present invention, the friction between single yarns is reduced, and more stable performance can be exhibited during the manufacturing process and use. It becomes.

  Furthermore, when such a lubricant is present, since a lubricant having a high decomposition temperature is present on the surface of the metal-coated fiber disposed on the outer periphery of the elastic fiber, the interior thereof may be impregnated with an insulating resin or the like. It will also be possible to block effectively. When the elastic fiber portion is impregnated with the insulating resin or the like, the constituting single yarns are converged, and not only the stretchability but also the flexibility and the bending fatigue property tend to be impaired.

  As the lubricant to be applied, aliphatic ester type and / or mineral oil type lubricants are preferable. Furthermore, you may use it in combination with a normal rust inhibitor. Examples of aliphatic ester lubricants include ester compounds of aliphatic monocarboxylic acids and aliphatic monohydric alcohols such as lauryl oleate, isooctyl stearate, butyl stearate and isotridecyl stearate, neopentyl glycol dilaurate Ester compounds of aliphatic monocarboxylic acids and aliphatic polyhydric alcohols such as 1,6-hexanedioldiolate, trimethylolpropane triherragonate, etc., di (2-ethylhexyl) azelate, dioleyl adipate, diisostearylthio Examples thereof include ester compounds of aliphatic polycarboxylic acids such as dipropionate and diisostearyl sebacate with aliphatic monohydric alcohols and the like. Moreover, as a mineral oil type lubricant, various liquid paraffin, vaseline, ceresin, solid paraffin, etc. are mentioned, and it can emulsify in water and can apply | coat them as needed.

  The lubricant used as a preferred embodiment in the present invention is preferably a non-silicon or non-fluorinated lubricant as described above. When a silicone or fluorine lubricant is used, the decomposition temperature is too high, which may inhibit the solderability of the obtained wire cord, or may cause an extremely small amount of contamination in the subsequent processing process. There is a tendency. The decomposition temperature of the lubricant used in the present invention is preferably 150 ° C. or higher, and more preferably in the range of 150 to 350 ° C.

  In the stretchable wire of the present invention, metal-coated fibers are arranged on the outer periphery of the above-mentioned elastic fibers. Here, being disposed on the outer periphery means that the length of the metal-coated fiber on the outer peripheral portion is larger than the length of the elastic fiber at the central portion and is disposed on the outer peripheral portion as a comparison. Therefore, the metal-coated fiber in the outer peripheral portion is not always always disposed at the outermost side, and in part, the elastic fiber in the central portion may be disposed at the outer side.

  And in order to arrange the metal-coated fiber outside in this way, in the stretchable wire of the present invention, it is preferable that the metal-coated fiber is wound and / or braided on the outer periphery of the elastic fiber. More specifically, as a method of winding and / or braiding a metal-coated fiber to be a conductor to an elastic fiber of a core, for example, an elastic fiber to be an elastic core to be between two pairs of rollers In the stretched state, a method in which one or a plurality of spirally wound and / or braided conductor portions which are coated with a single conductor portion made of a metal-coated fiber or an insulating resin on the outer periphery of the elastic core portion is mentioned Be In order to facilitate the development of stretchability, the conductive core and the conductor wire are preferably stretched in a state of preferably 1% or more, more preferably 10% or more, still more preferably 50% or more, particularly preferably 100% or more. A method of winding and / or braiding the metal-coated fiber can be employed. Further, in this manner, the elastic fiber is doubled with the metal-coated fiber in a stretched state, and the method of shrinking the elastic fiber to the original length is the outer circumference of the elastic fiber of the core by remaining the metal-coated fiber length. It will also be arranged metal-coated fibers in the part.

Furthermore, as a method of winding and / or braiding the metal-coated fiber, for example, a method of winding and / or braiding the metal-coated fiber (conductor portion) using a covering machine can also be adopted. At this time, in order to increase the pullout resistance between the stretchable core portion and the conductor portion, it is preferable that the conductor wire be wound and / or braided with an appropriate tension.
The stretchable wire of the present invention uses a stretchable intermediate composed of the elastic fiber and the metal-coated fiber as described above. The outer diameter of the stretchable intermediate before covering with this insulator is preferably a diameter in the range of 0.2 to 2.0 mm.

  Furthermore, it is preferable that the stretchable wire of the present invention has the outermost part covered with an insulator. The outer diameter of the wire after the insulation coating is preferably 0.5 to 5.0 mm, and the weight per length is preferably in the range of 1.0 to 10.0 g / m. Further, the elongation to break is preferably in the range of 50 to 500% although it depends on the degree of winding of the metal-coated fiber and the like.

  The covering with the insulator at the outermost part of this stretchable wire is, for example, as a method of covering with the specific insulator, (1) coating the metal coated fiber which is a conductor first with an insulator, and then A method of obtaining an elastic wire by winding and / or braiding elastic fibers in the core, (2) after winding and / or braiding metal-coated fibers in the elastic fibers of the core, the conductor section It is possible to adopt a method in which both the core and the core part are covered with an elastic insulator. In the case of the former method (1), the insulator is not particularly limited, but in the case of the latter method (2), the insulator is preferably an elastic body. The former method (1) is a method of the latter method (2) because the coating with the insulator may be damaged in the step of winding and / or braiding the insulation coated conductor portion to the elastic fiber of the core portion. Particularly preferred. As another method, it is also preferable to use a method of covering an insulating fiber around as an insulator.

The insulator covering the outer layer of the wire is preferably an elastic body, and the properties desired further include stretchability, water resistance and aging resistance. From such a point of view, it is preferable to use a synthetic rubber elastic body as the insulator. More specifically, examples of synthetic rubber elastomers include acrylic rubber, nitrile rubber, butadiene rubber, styrene butadiene rubber, chlorosulfonated polyethylene rubber, urethane rubber, ethylene vinyl acetate Rubber, isoprene rubber, epichlorohydrin rubber, polysulfide rubber, fluorine rubber, silicone rubber, ethylene / propylene rubber, chloroprene rubber and butyl rubber are preferable. More preferably, they are butyl rubbers, polysulfide rubbers, and silicone rubbers which are excellent in stretchability and water resistance.
Such a stretchable electric wire of the present invention is a conductor having high stretchability, and is excellent in tensile strength and bending fatigue resistance, and in particular, robots, wearable electronic devices, and electromagnetic wave shielding materials which require stretchability. Etc. are suitably used for wiring such as

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, the evaluation method used in the Example is as follows.
(1) Electric resistance value The electric resistance value between 1 m of electric wire cords was measured with resistance value measuring device (made by Hioki Co., Ltd. milliohm high tester 3540-02A).
(2) Fineness Measured according to JIS-L1013.
(3) Electric resistance value after bending fatigue By the method described in JIS P 8115, after bending the stretchable wire 1000 times, the electric resistance value between 1 m of electric wire cords was measured by the method of (1).

Example 1
(Metal coated fiber)
Copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber having a total fineness of 440 dtex and a single fiber number of 267 (copolymer aramid fiber, manufactured by Teijin Limited, "Technola (registered trademark)" tensile strength; 24.5 cN / Dtex (long fiber yarn) was subjected to metal coating treatment (copper plating treatment) according to the following method to obtain a conductor.
First, a surfactant ("Cataposit 1501 PREDIP", manufactured by Rohm and Haas Electronic Materials Co., Ltd. (hereinafter, the agent in this treatment is a product of the same company, and therefore will not be described)) 0.05% aqueous solution, about 40 After soaking for about 1 minute at ° C, it is immersed in a treatment solution containing Pd as a catalyst ("OMNISHIELD ACTIVATOR 1572" 0.2% + concentrated hydrochloric acid 0.8% solution) for 1 minute at room temperature to adsorb Pd, Washing with water was performed to remove excess Pd. After that, the treatment liquid containing copper ("OMNISHIELD ELECTROLESS COPPER 1598M" 4.8%, "OMNISHIELD ELECTROLESS COPPER 1598A" 1.0%, "OMNISHIELED ELECTROLESS COPPER 1598R" 0.2%, "CUPOSIT Y" 1.4%, Electroless copper plating was performed by immersing in “CUPOSIT Z” 2.2%, “OMNISHIELD 1120SR COPPER REPLENISHER” 0.16% solution). Thereafter, copper sulfate _{(CuSO 4 · 5H 2 O)} 20%, carried out copper electroplating 5.0% solution in sulfuric acid, to give copper coated fiber of the plating thickness 1.5μm (the conductor).
Thereafter, as a lubricant, a fatty acid ester, diisostearyl adipate, was used in an amount of 1.0 wt. After being applied, a twist with a twist coefficient of 2.0 was applied to obtain a metal-coated fiber (conductor). The strength of this metal-coated fiber was 3.8 cN / dtex.

(Elastic wire)
Next, using a covering machine, cored with polyurethane denier of 3740 dtex and 288 single fibers (manufactured by Asahi Kasei Fibers Co., Ltd., “Leuca”, elongation 800%), using a covering machine, 2.0 times ( The above copper-plated aramid fiber (metal-coated fiber) was wound under an elongation of 100% to obtain an elastic intermediate. The obtained intermediate was composed of elastic fibers 3740 dtex and metal-coated fibers 2300 dtex of the conductor portion in terms of fineness.
Subsequently, the obtained stretchable intermediate was passed through a 0.5 mm-thick silicone rubber tube to obtain a stretch electric wire in which silicone rubber was formed as an insulating coating layer at the outermost part. When the tensile test was conducted, at the time of elongation of 150%, almost no change was observed in the elastic fiber in the central portion and the insulation coating layer of the outermost layer, but the metal-coated fiber in the outer peripheral portion was completely stretched, It was cut after that. The evaluation results are shown in Table 1.

Example 2
A flexible wire was obtained in the same manner as in Example 1 except that the lubricant was not applied to the metal-coated fiber after metal plating. The obtained evaluation results are shown together in Table 1.

Comparative Example 1
The experiment was carried out in the same manner as in Example 1 except that 14 copper wires of 0.040 mm in diameter (the elastic fibers 3740 dtex and the copper wires 1600 dtex of the conductor portion were included in terms of fineness) were used instead of metal coated fibers. I got a stretchable wire. The obtained evaluation results are shown together in Table 1.

Claims (4)

An aromatic polyamide fiber consisting of elastic fibers with an elongation of 100% or more and metal-coated fibers with a strength of 2.5 cN / dtex or more, and metal-coated fibers are metal-plated, and metal plating uses electroless plating and electroplating In addition, a lubricant is applied to the metal-coated fiber, the lubricant is an aliphatic ester or mineral oil lubricant, and the metal-coated fiber is disposed on the outer periphery of the elastic fiber. Stretchable wire.   The stretchable wire according to claim 1, wherein the metal-coated fiber is wound and / or braided around the periphery of the elastic fiber.   The stretchable wire according to claim 1 or 2, wherein the metal-coated fiber is a twisted multifilament. A metal-coated fiber having a strength of 2.5 cN / dtex or more is disposed on the outer periphery of an elastic fiber having an elongation of 100% or more , and the metal-coated fiber is an aromatic polyamide fiber plated with metal. in combination with electroplating, and more metal coated fibers are coated is lubricant method for producing a stretchable wire lubricant, wherein Rukoto der aliphatic ester or mineral oil-based lubricants.