JP5941317B2 - Metal coated fiber - Google Patents

Description

  The present invention relates to a metal-coated fiber that can be used for applications such as a center line, a signal line, and a shield line of an electric wire.

  Copper wires are used for conventional electric wires and shield wires, and are used in automobiles, electronic devices, audio devices and the like. However, in applications where bending and twisting are frequently applied, there is a problem that the copper wire is likely to break due to metal fatigue. Further, there is a problem that the copper wire is easily broken due to the tension during the mounting process.

  In order to solve these problems, Patent Document 1 proposes a metal foil wound around the surface of an organic fiber substrate, and Patent Documents 2 to 4 propose a material obtained by performing metal plating on the surface of an organic fiber substrate. .

JP-A-01-107415 JP 2000-096431 A JP 2010-059532 A JP 2009-242839 A

  However, in Patent Document 1, since an organic fiber base material is used, flexibility and tensile strength are improved as compared with a metal wire such as a copper wire, but a metal foil is spiraled around the outer periphery of the organic fiber base material. When the interval of winding in the shape is narrow, there is a problem that the flexibility is insufficient.

  Further, in Patent Documents 2 and 3, by treating (etching) the surface of the organic fiber substrate with an acid / alkali solution, fine irregularities are formed on the surface of the organic fiber substrate and the adhesion is improved by the anchor effect. be able to. However, since fine irregularities are formed on the surface of the organic fiber substrate, there is a problem that the strength of the organic fiber substrate is lowered. Moreover, although the method of plasma-processing an organic fiber base material using nitrogen or argon gas was also examined, there also existed a problem which the intensity | strength of an organic fiber base material also falls here.

  Further, in Patent Document 4, a supercritical fluid containing an organometallic complex is brought into contact with an organic fiber substrate, and then an activation treatment is performed, so that the surface of the organic fiber substrate is not uneven, and metal plating is performed. Adhesion can be improved. However, this method is complicated because it is necessary to set the temperature and pressure to high with dedicated equipment. Furthermore, since the organometallic complex to be used is expensive, there is a problem that productivity is low and cost is high.

  Therefore, the present invention is excellent in adhesion with a metal plating film provided on the surface of the organic fiber base material, and has a small decrease in tensile strength of the organic fiber base material itself after the plating treatment, and also has excellent flexibility. The object is to provide fibers.

The metal-coated fiber of the present invention is a plating base layer composed of a polymer compound layer having a heterocyclic ring and a metal salt that functions as an oxidizing agent and has an electroless plating catalytic ability on the surface of an organic fiber substrate. A metal-coated fiber in which a metal plating film is provided on the plating base layer by an electroless plating method, and the organic fiber base material has a twist coefficient k of the following formula 1 in the range of 500 to 3146, and a metal The tensile strength of the coated fiber is maintained at 90 to 100% when the tensile strength of the organic fiber base material is set to 100% before providing the plating base layer and the metal plating film by the electroless plating method. To do. (Expression 1) k = T × √D (T = number of twisted yarns (T / m), D = total fineness (dtex))

  The metal-coated fiber of the present invention has excellent adhesion to the metal plating film provided on the surface of the organic fiber substrate, and after the plating treatment, the decrease in the tensile strength of the organic fiber substrate itself is small and the flexibility is excellent. Is.

It is a figure explaining the metal-coated fiber which provided the metal plating film by the metal-plating base layer and the electroless-plating method in the organic fiber base material of the twist yarn coefficient k <= 4200. It is a figure explaining the metal coating fiber which provided the metal plating film by the metal-plating base layer and the electroless-plating method in the organic fiber base material whose twist yarn coefficient k exceeds 4200.

The present invention will be described in detail.
The present invention provides, on the surface of an organic fiber base material, a plating base layer composed of a polymer compound layer having a heterocyclic ring and a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating, A metal-coated fiber in which a metal plating film is provided on a plating base layer by an electroless plating method, and the organic fiber base material has a twist coefficient k of the following formula 1 in a range of 500 to 3146 .
(Expression 1) k = T × √D (T = number of twisted yarns (T / m), D = total fineness (dtex))
Moreover, since the metal-plating base layer and a metal plating film osmose | permeate the inside of an organic fiber base material as shown in FIG. 1, the metal-coated fiber obtained becomes low in resistance of metal coating fiber. Furthermore, it is excellent also in the adhesiveness of an organic fiber base material and a metal plating film. In addition, the tensile strength of the resulting metal-coated fiber is 90 to 100% when the tensile strength of the organic fiber substrate before the plating base layer and the metal plating film by the electroless plating method are taken as 100%. Hold.

(1) Organic fiber substrate The organic fiber substrate used in the present invention has a twisting coefficient k of the following formula 1 in the range of 500 to 3146 . (Expression 1) k = T × √D (T = number of twisted yarns (T / m), D = total fineness (dtex))
Thus, “twisted yarn coefficient k” is a value obtained by multiplying T = twisted yarn count by √D = total fineness. Further, an organic fiber base material obtained by twisting an organic fiber having a specific D = total fineness (dtex) at a specific T = twisting number of yarns (T / m) so that the twisting coefficient k is a value of 500 to 3146 is used. . When the twisting coefficient k exceeds 3146 , the plating base layer and the metal plating film do not penetrate into the inside of the organic fiber base as shown in FIG. 2, and the resistance of the resulting metal-coated fiber is increased. The adhesion between the material and the metal plating film is also poor. If the twisted yarn coefficient k is less than 500, the tensile strength may be lowered when the organic fiber substrate is immersed in an alkaline solution. In addition, the tensile strength of the metal-coated fiber obtained using the organic fiber base material having a twisting coefficient k of 500 to 3146 is the tensile strength of the organic fiber base material before providing the plating base layer and the metal plating film by the electroless plating method. It is easy to keep 90% or more when the strength is 100%.

  Further, “D = total fineness (dtex)” here represents the thickness of the yarn. Since the cross-section of the thread is not a perfect circle, but can have various shapes, the thickness is expressed by the ratio of length to weight. In the case of a filament yarn, “decitex (dtex)” is used. Decitex is the number of grams per 10,000 m.

  Further, “T = twisted yarn number (T / m)” here is the number of twists per 1 m.

  The material of the organic fiber base material of the present invention is not particularly limited, but materials having high strength properties such as aramid fiber, aromatic polyester fiber, polyparaphenylene benzobisoxazole fiber are desirable.

In addition, the organic fiber substrate of the present invention may be subjected to a hydrophilic treatment on the surface of the substrate before forming the plating base layer. By subjecting the surface of the base material to a hydrophilic treatment, the compound layer having a heterocyclic ring can be hydrogen-bonded with a functional group generated from the surface of the base material, thereby improving adhesion. Moreover, it becomes easy to form a plating underlayer (= a layer containing a compound having a heterocyclic ring and a metal salt), and the deposition and adhesion of the metal plating film by the electroless plating method are improved.
Any appropriate method can be adopted as a method for hydrophilizing the substrate surface. The hydrophilic treatment may be, for example, a dry treatment or a wet treatment. Examples of the dry treatment include discharge treatment such as corona discharge treatment, plasma treatment (excluding plasma treatment using nitrogen or argon gas) and glow discharge treatment; ozone treatment; UV ozone treatment; ultraviolet ray treatment and electron beam treatment. Examples include ionizing active ray treatment. Examples of the wet treatment include ultrasonic treatment using a solvent such as water and acetone; alkali treatment; anchor coat treatment. These processes may be performed independently or in combination of two or more.

(2) Plating underlayer The plating underlayer of the present invention is composed of a polymer compound layer having a heterocyclic ring and a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating.

  Examples of the compound having a heterocyclic ring used in the present invention include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl- 3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethylaminopyrrole 3-diethylaminopyrrole, 3-diphenylaminopyrrole Pyrrole derivatives such as 3-methylphenylaminopyrrole and 3-phenylnaphthylaminopyrrole; thiophene, 3-methylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n-hexylthiophene, 3-n- Heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n-decylthiophene, 3-n-undecylthiophene, 3-n-dodecylthiophene, 3-methoxythiophene, 3-naphthoxythiophene and Examples include thiophene derivatives such as 3,4-ethylenedioxythiophene, preferably pyrrole, thiophene, and 3,4-ethylenedioxythiophene, and more preferably pyrrole.

  The treatment temperature for polymerizing the compound having a heterocyclic ring is appropriately selected depending on the type of the compound having a heterocyclic ring used in the present invention, and is preferably 10 ° C to 130 ° C.

  Examples of the metal salt that functions as an oxidizing agent used in the present invention and has the electroless plating catalytic ability include, for example, silver nitrate, silver acetate, silver sulfate, silver perchlorate, silver fluoride, silver nitrite, silver chloride, Silver bromide, silver propionate, silver tartrate, silver methyl ethyl acetate, silver trimethyl acetate, silver carbonate, silver oxalate, silver thrombate; copper nitrate, copper sulfate, copper chloride, copper chlorate, perchloric acid Copper salts such as copper, copper bromide, copper acetate, copper carbonate, copper oxalate; nickel salts such as nickel nitrate, nickel sulfate, nickel chloride, nickel bromide, nickel acetate, nickel carbonate, nickel oxalate; palladium sulfate, Examples thereof include palladium salts such as palladium nitrate, palladium acetate, palladium chloride, palladium bromide, palladium iodide and the like. Among these, halides are preferable, and palladium chloride is particularly preferable.

As a method for forming the plating underlayer of the present invention (consisting of a polymer compound layer having a heterocyclic ring and a metal salt having electroless plating catalytic ability adsorbed on the layer), the following (a) to ( Any of c) can be adopted.
(A) a step of immersing the organic fiber base material in an aqueous solution containing (i) a compound having a heterocyclic ring and (ii) a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating, and then pulling up (B) a method comprising: immersing the organic fiber substrate in an aqueous solution containing the compound having a heterocyclic ring; and immersing the pulled material in an aqueous solution containing the metal salt (c) the organic fiber A method comprising the steps of immersing a substrate in an aqueous solution containing the metal salt and contacting the pulled material with a vapor containing the compound having a heterocyclic ring. Each method utilizes means known to those skilled in the art. Can be done.

In the method (a), when an aqueous solution containing the compound having a heterocyclic ring and a metal salt is prepared, the concentration ratio of the compound having a heterocyclic ring and the metal salt (= compound having a heterocyclic ring / metal salt) is 0. It is 1-80, Preferably it is 0.1-40. When the concentration ratio is less than 0.1, the oxidation state and polymerization of the compound having a heterocyclic ring are insufficient, and the reduction state of the metal salt is also insufficient, so that it can act as a catalyst for electroless plating. It becomes difficult. On the other hand, if the concentration ratio is greater than 80, the metal salt cannot be uniformly deposited on the material, so that the metal plating film may not be formed uniformly in the subsequent plating process.
The treatment temperature in the step of immersing the material in the aqueous solution containing the compound having a heterocyclic ring and the metal salt is 10 ° C. to 130 ° C., and the treatment time is 0.1 minute to 120 minutes, preferably 20 minutes. ~ 60 minutes.

In the method (b), the concentration of the aqueous solution containing the compound having a heterocyclic ring is 5 × 10 −4 to 0.9M, preferably 0.01 to 0.5M.
Further, the treatment temperature of the step of immersing the material in the aqueous solution containing the compound having a heterocyclic ring is 10 ° C. to 130 ° C., and the treatment time is 0.1 minute to 50 minutes, preferably 1 minute to 40 minutes. It is.

In the methods (b) and (c), a preferable aqueous solution containing the metal salt is 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3).
The treatment temperature in the step of immersing the material in the aqueous solution containing the metal salt is 10 ° C. to 130 ° C., and the treatment time is 0.1 minute to 50 minutes, preferably 1 minute to 40 minutes.

In the method (c), the vapor containing the compound having a heterocyclic ring may be a vapor obtained by vaporizing an aqueous solution containing the compound having a heterocyclic ring, but preferably the compound itself having a heterocyclic ring is vaporized. Steam.
The treatment temperature in the step of contacting with the vapor containing the compound having a heterocyclic ring is 10 ° C. to 130 ° C., the treatment time is 0.1 minutes to 40 minutes, preferably 1 minute to 30 minutes, The pressure may be normal pressure or reduced pressure.

(3) Metal Plating Film The metal plating film of the present invention is provided on the plating base layer by an electroless plating method.
That is, in the method of (a) to (c) above, the surface of the organic fiber base material provided with the plating underlayer is immersed in a plating solution for depositing a metal, thereby using an electroless plating method. A metal plating film is formed.
The plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. That is, as a metal that can be used for electroless plating, for example, copper, gold, silver, nickel, chromium, and the like can be applied, but copper is preferable. Specific examples of the electroless plating bath include ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) and the like.
The treatment temperature for electroless plating is 20 ° C. to 50 ° C., preferably 30 ° C. to 40 ° C., and the treatment time is 10 minutes to 40 minutes, preferably 15 minutes to 30 minutes.

  Moreover, it is preferable that the thickness of the metal plating film formed by the electroless plating method is 0.3 to 3 μm. When the thickness of the metal plating film exceeds 3 μm, the flexibility may be lowered, and when the thickness is less than 0.3 μm, for example, the metal plating film may not function as a center line, a signal line, or a shielding material of the electric wire.

  Alternatively, hot tin plating or electroplating may be performed on a metal plating film formed by an electroless plating method. In particular, when an organic fiber base material having high heat resistance is used, hot-dip tin plating is effective.

The metal coated fibers of the present invention, the center lines and signal lines of the electric wire, when used as a shield material, but it may also be added to twist as needed.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.

[Example 1]
<Plating underlayer formation method>
Pyrrol monomer 6.5 mM, palladium chloride aqueous solution 0.25 mM, and hydrochloric acid 10 mM were added to ion-exchanged water, and this aqueous solution was mixed. Then, a base material made of aramid fibers (Kevlar Toray DuPont Co., Ltd.) having D: total fineness of 110 dtex, T: number of twisted yarns of 100 T / m, that is, k: twisting factor of 1048, is added to this mixed solution. Immersion at 30 ° C. for 30 minutes, followed by washing with ion-exchanged water and drying to form a plating underlayer.
<Electroless plating>
Next, the base material made of aramid fibers on which the plating base layer is formed is immersed in an electroless plating bath (Melplate CU5100P bath, manufactured by Meltex Co., Ltd.) at 50 ° C. for 20 minutes to form a copper film, Metal-coated fibers were obtained.

[Example 3]
D: Total fineness is 110 dtex, T: Twisted yarn count is 300 T / m, that is, k: The same operation as in Example 1 is used except that a base material made of aramid fiber having a twist yarn coefficient of 3146 is used. Formed.
Thereafter, electroless plating was performed in the same manner as in Example 1 to form a copper film, and metal coated fibers were obtained.

[Comparative Example 1]
(Pretreatment of organic fiber substrate: Etching)
D: Total fineness of 110 dtex, T: Twisting yarn number of 100 T / m, that is, k: Substrate made of aramid fiber having a twisting coefficient of 1048 is immersed in a basic fiber cleaning-surfactant solution at 25 ° C. for 3 minutes. And washed with ion-exchanged water. Next, it was immersed in a 90% sulfuric acid solution at 30 ° C. for 30 seconds and washed with ion-exchanged water.
(Catalyst added)
The pretreated aramid fiber substrate was immersed in a 35% hydrochloric acid aqueous solution containing Sn—Pd colloid for 3 minutes at 30 ° C. and washed with water.
(activation).
Next, it was immersed in a 98% sulfuric acid solution 100 mL / L for 3 minutes at 40 ° C. and washed with water.
(Electroless plating)
A base material made of aramid fibers subjected to catalyst application and activation is immersed in an electroless plating bath (Melplate CU5100P bath Meltex Co., Ltd.) for 20 minutes at 50 ° C. to form a copper film, and metal coated fibers Got.

[Comparative Example 2]
(Pretreatment of organic fiber substrate: Plasma)
D: Total fineness is 110 dtex, T: Twist yarn number is 100 T / m, that is, k: Plasma treatment (voltage: 15 kV, voltage) on a substrate made of aramid fiber with a twist coefficient of 1048 Nitrogen gas: 25 L / min, treatment time: 10 seconds).
(Catalyst added)
The pre-treated aramid fiber substrate was immersed in a 35% aqueous hydrochloric acid solution containing Sn—Pd colloid for 3 minutes at 30 ° C. and washed with water.
(activation).
Next, it was immersed in a 98% sulfuric acid solution 100 mL / L for 3 minutes at 40 ° C. and washed with water.
(Electroless plating)
A base material made of aramid fibers subjected to catalyst application and activation is immersed in an electroless plating bath (Melplate CU5100P bath Meltex Co., Ltd.) for 20 minutes at 50 ° C. to form a copper film, and metal coated fibers Got.

[Comparative Example 3]
D: Total fineness is 110 dtex, T: Twisted yarn count is 450 T / m, that is, k: The same procedure as in Example 1 is used except that a base material made of aramid fiber having a twist coefficient of 4720 is used, and the plating underlayer is formed. Formed.
Thereafter, electroless plating was performed in the same manner as in Example 1 to form a copper film, and metal coated fibers were obtained.

[Reference example]
A bundle of 10 copper wires having a diameter of 0.1 mm was used.

Various evaluation tests were performed on the metal-coated fibers of Examples 1 and 3 and Comparative Examples 1 to 3 manufactured above, and the results are summarized in Table 1. In addition, the copper wire of the reference example was subjected to an evaluation test of resistance value and flexibility. The evaluation test items, evaluation methods and evaluation criteria are as follows.

<Resistance value>
About the obtained metal-coated fiber, the distance between two terminals was set to 1 m using a digital tester (CUSTOM CDM-2000D), and the resistance was measured.

<Adhesion>
A tape was affixed to the obtained metal-coated fiber, and pressure-bonded with a roller having a load of 2 kg. Thereafter, the tape was peeled off, and the migration of the plating film to the tape was evaluated. The evaluation criteria were as follows.
○: No transfer of plating film to tape ×: Transfer of plating film to tape

<Tensile strength>
The obtained metal-coated fiber was subjected to a tensile test according to the JIS L1013 chemical fiber filament yarn test method. In addition, the tensile strength of the organic fiber base material before providing a plating base layer and the metal plating film by the said electroless-plating method was set to 100%, and the tensile strength of the obtained metal-coated fiber was evaluated relatively.

<Flexibility>
(Before test)
Before the bending test, the resistance of the metal-coated fiber obtained was measured using a digital tester (CUSTOM CDM-2000D) with a distance between two terminals of 0.1 m.
(After test)
Using the MIT folding resistance tester (Tester Sangyo Co., Ltd.), the obtained metal-coated fiber was loaded under the conditions of a load of 2.9 N, a bending angle of 270 °, a bending radius of 0.38 mm, and a bending speed of 175 times / minute. After bending 100 times, the resistance was measured using a digital tester (CUSTOM CDM-2000D) with the distance between the two terminals being 0.1 m.

Claims (1)

On the surface of the organic fiber base material, a plating base layer composed of a polymer compound layer having a heterocyclic ring and a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating is provided. A metal-coated fiber provided with a metal plating film by an electroless plating method,
The organic fiber base material has a twist coefficient k of the following formula 1 in the range of 500 to 3146,
The tensile strength of the metal-coated fiber is maintained at 90 to 100% when the tensile strength of the organic fiber base material is 100% before providing the plating base layer and the metal plating film by the electroless plating method. Metal coated fiber.
(Expression 1) k = T × √D (T = number of twisted yarns (T / m), D = total fineness (dtex))