KR20100023646A - Manufacturing method of electroconductive fabric for electromagnetic interference(emi) shielding by using tin plating - Google Patents

Abstract

PURPOSE: A manufacturing method of conductive fabric for electromagnetic interference(EMI) shielding is provided to improve productivity by reducing manufacturing costs and processing time while minimizing environmental loading substances. CONSTITUTION: A manufacturing method of conductive fabric for electromagnetic interference(EMI) shielding includes the following steps: inputting a fiber material(S100); performing a degreasing, an etching, a neutralization, an acid treatment and an activation processes(S200); performing nickel or tin plating with the tin plating or substitution tinning plating(S300); and performing a discoloration preventing process(S400).

Description

Manufacturing method of electroconductive fabric for electromagnetic interference (EMI) shielding by using tin plating

The present invention relates to a method for manufacturing a conductive fiber, and more particularly, to a method for manufacturing a conductive fiber for electromagnetic shielding by tin plating method which can improve productivity by minimizing environmental load material and reducing manufacturing cost and processing time. It is about.

In general, small portable devices such as mobile phones and PDAs tend to become smaller and thinner in order to secure ease of movement as they become household items, and efforts are being made to reduce concerns about electromagnetic wave emission. Plastics, which are used as housing materials for most electronic products, lack the ability to shield electromagnetic waves, so that methods such as forming conductive layers through surface processing, painting conductive paints, vacuum deposition of metal particles, and laminating metal thin films are used. However, considering the light and thin design, the use of conductive fibers is preferred.

According to Korean Patent No. 0421787, a solution containing a salt of a conductive metal selected from the group consisting of nickel and copper and an electroless solution consisting of a reducing solution of the conductive metal are added and mixed to a paper material on which pulp fibers have been beaten. A process for reducing precipitation of the conductive metal directly on the beaten pulp fibers is disclosed.

According to Korean Patent Laid-Open Publication No. 2001-0026385, copper and nickel are sequentially electroless double-plated on a fiber substrate including synthetic fibers to maintain the inherent flexibility of the fibers and to provide conductivity and improve oxidation resistance, corrosion resistance and abrasion resistance. Provided is a conductive fiber that can be usefully used as an electromagnetic wave shielding agent.

 However, as the dependence on the electroless plating method increases, not only toxic substances such as formaldehyde are discharged, but also the plating time becomes longer and the chemical requirements increase, resulting in lower productivity.

Literature Information of the Prior Art

[Document 1] Korean Registered Patent No. 0421787 “Method of manufacturing conductive paper using electroless plating method”

[Patent 2] Korean Unexamined Patent Publication No. 2001-0026385 “Conductive Fiber for Electromagnetic Interception and Method for Manufacturing the Same”

Accordingly, the present invention is to fundamentally solve the conventional problems as described above, the electromagnetic wave shielding conductive fiber by the tin plating method that can improve productivity by minimizing the environmental load material and eco-friendly and reduced manufacturing cost and processing time Its purpose is to provide a method of manufacturing.

In order to achieve the above object, the present invention provides a method for plating to impart conductivity on a fiber, comprising: a first step of introducing a fiber material; A second step of degreasing, etching, neutralizing, acidifying, and activating the fiber material of the step; A third step of simultaneously performing at least electro tin plating or substituted tin plating on the fiber material of the step; And a fourth step of performing a discoloration prevention treatment on the fiber material of the step.

In the present invention, the second step includes a degreasing and etching process for ultrasonic treatment in a caustic soda solution, a neutralization treatment with a hydrochloric acid solution, an acid treatment with a hydrochloric acid solution, and palladium chloride, tin chloride and hydrochloric acid. And a step of catalyzing with a catalyst solution and a step of activating with a sulfuric acid solution.

In addition, the third step of the present invention is selectively performed in the order of electroless nickel plating process, electroless copper plating process, electro copper plating process, substituted tin plating process, electro tin plating process, more specifically such a The third step of the present invention can be implemented in eleven embodiments.

On the other hand, the terms or words used in the present specification and claims are not to be construed as limiting the ordinary or dictionary meanings, the inventors should use the concept of the term in order to explain the invention in the best way. Based on the principle that it can be properly defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configuration shown in the drawings are only the most preferred embodiments of the present invention, and do not represent all of the technical ideas of the present invention, and various alternatives may be substituted at the time of the present application. It should be understood that there may be equivalents and variations.

As described in the above configuration and operation, the present invention provides an effect that can be environmentally friendly to minimize the environmental load material and to reduce the production cost and processing time to improve productivity.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1 is a process flow diagram showing a manufacturing method according to a first embodiment of the present invention, Figure 2 is a process flow diagram showing a manufacturing method according to a second embodiment of the present invention, Figure 3 is a flow chart according to a ninth embodiment of the present invention The process flow chart which shows a manufacturing method.

The present invention relates to a method of plating to impart conductivity on a fiber, the first step of injecting a fiber material (S100); A second step (S200) of degreasing, etching, neutralizing, acidifying, and activating the fiber material of the step; A third step of subjecting the fiber material of the step to at least nickel or copper plating and then performing electro tin plating or substituted tin plating in parallel; And a fourth step (S400) of performing a discoloration prevention treatment on the fiber material of the step.

Polyester fiber is appropriate in the first step (S100) of injecting the fiber material, but is not limited thereto. Subsequently, a second step (S200) including a degreasing / etching step, a neutralization step, an acid treatment step, a catalysis step, and an activation step is performed.

In the degreasing and etching process, 80 to 120 g / L of caustic soda solution is used, followed by ultrasonic treatment at 40 to 80 ° C. for 0.5 to 10 minutes, followed by washing with water to two to three steps. In the plating process, if oil, dust or other impurities are adsorbed on the surface of the plated body, problems such as unplating, plating stains and poor adhesion are likely to occur. Therefore, the organic solvent or alkaline degreasing solution is used for removal. To perform the process. In plating on polyester fibers, degreasing is possible by dipping the fibers in a high concentration of sodium hydroxide or potassium hydroxide solution. In this process, the polyester is hydrolyzed in alkaline solution to break down into water-soluble sodium terephthalate and ethylene glycol and the fiber surface is etched. After this process, it is necessary to wash with water sufficiently in order to completely remove the water-soluble sodium terephthalate and the like adsorbed on the fiber surface. When ultrasonic waves are applied in this process, fats, dusts, or impurities adsorbed on the surface of the fiber are easily desorbed, and the liquid easily penetrates between the fillers of the fiber, so that the plating film is evenly deposited on the fiber filler in the subsequent plating process. And desorption of ethylene glycol with hydrolyzed, water-soluble sodium terephthalate.

In the neutralization step, 20 to 150 ml / L solution of 35 to 36% hydrochloric acid is used, and 0.5 to 2 minutes is carried out at 20 to 45 ° C, followed by 2 to 3 steps of washing with water. The neutralization step is a step of neutralizing the alkaline liquid adsorbed on the fiber surface during the degreasing and etching process, in which sodium hydroxide on the fiber surface is neutralized by hydrochloric acid as shown in the following equation.

NaOH + HCl → NaCl + H2O

In the acid treatment step, a 20-150 mL / L solution of 35-36% hydrochloric acid is used and carried out at 20-45 ° C. for 0.5-2 minutes. The acid treatment process needs to be supplemented with Cl- ions in order to prevent aggregation of the colloidal particles in the palladium colloidal liquid used in the subsequent catalysis process. When the concentration of Cl- ions in the palladium colloidal solution is lowered, the colloid aggregates, which lowers the stability of the catalyst solution and causes unplating and plating unevenness in continuous plating.

In the catalysis step, Pd colloidal catalyst solution containing palladium chloride, tin chloride, and hydrochloric acid is used for 30 seconds to 5 minutes at 20 to 45 ° C, followed by washing with water to two to three stages. The catalysis process forms a palladium catalyst layer to selectively deposit metal only on the surface of the plated body. The palladium particles adsorbed here act as a catalyst for the oxidation reaction of the reducing agent in the plating liquid. The palladium catalyst solution contains palladium chloride, tin chloride and hydrochloric acid and may contain dispersants, stabilizers and other metal ions, if necessary. In this solution, divalent tin is oxidized to tetravalent tin, and the electrons emitted are received by divalent palladium ions and reduced to palladium metal.

Sn2 + + Pd2 + → Sn4 + + Pd0

In the activation step, it is carried out at 15 to 60 ° C. for 30 seconds to 5 minutes using a 10% to 100 ml / L solution of 98% sulfuric acid. The activation process is a process of fixing the palladium catalyst nucleus on the surface of the plated body to improve the catalytic activity. The Pd-Sn colloidal particles adsorbed in the catalysis step are converted into Sn (OH) 2 or Sn (OH) 4 by hydrolysis in the washing step after the catalysis step. The activation process removes the Sn (OH) 2 or Sn (OH) 4 layer to form a high catalytic activity palladium catalyst layer.

The third step (S300) of the present invention is an electroless nickel plating process (S320), an electroless copper plating process (S340), an electro copper plating process (S350), a substituted tin plating process (S360), an electro tin plating process (S380) Optionally, but the third step (S300) of the present invention may be implemented in 11 embodiments as shown in Table 1, but is not limited thereto, and select various combinations according to the use. Can be.

In detail, the electroless nickel plating process (S320) includes nickel sulfate hexahydrate 0.02 to 0.2 mol / L + citric acid or sodium citrate dihydrate 0.02 to 0.2 mol / L + hypophosphoric monohydrate 0.02 to 0.2 mol / L + Ammonia water was added to the plating liquid containing a small amount of stabilizer to carry out in the range of pH 8.0 to 10.0, and the electroless copper plating process (S340) was 0.03 to 0.07 mol / L copper sulfate, 0.3 to 0.21 mol / L complexing agent, and form Aldehyde 0.03-0.07 mol / L, caustic soda 0.1-0.4 mol / L, using a solution containing a small amount of stabilizer, the electro-copper plating process (S350) is copper sulfate pentahydrate 0.03-0.7 mol / L, sulfuric acid 0.1 Using an electrolytic copper plating solution containing ˜2.0 mol / L and a stabilizer, 30 seconds to 10 minutes at a current density of 0.5 to 20 A / dm 2 at 15 to 60 ° C. was performed. 50 g / L methanesulfonic acid, 2-2.5 g / L tin ions, 2-75 g / L thiourea, 20-120 g / L sodium gluconate, 1-60 g / L Iroquinone and a plating solution containing a small amount of stabilizer were used, and the electro tin plating process (S380) was carried out using 50 to 150 g / L methanesulfonic acid, 2 to 2.5 g / L tin ion, and a small amount of stabilizer. It is carried out using a plating solution containing.

In the present invention, the following process illustrates the following Examples 1, 2, and 9, but the same manner as in the remaining examples.

Example 1 Conductive Fiber by Electro Tin Plating

In electroless nickel plating process, nickel sulfate hexahydrate 0.02-0.2 mol / L + citric acid or sodium citrate dihydrate 0.02-0.2 mol / L + hypophosphoric monohydrate 0.02-0.2 mol / L + small amount of stabilizer After adding ammonia water to a plating liquid and adjusting pH to the range of 8.0-10.0, plating is performed for 1 to 10 minutes at 35-60 degreeC, and washing with water is performed 2-3 steps.

In the electroplating process, use a plating solution containing 50 to 150 g / L methanesulfonic acid, 2 to 2.5 g / L tin ions (added as methanesulfonic acid tin) and a small amount of stabilizer at 15 to 60 ° C. Plating is carried out at a current density of 0.5 to 20 A / dm 2 for 1 to 10 minutes, followed by washing with water to 2 to 3 steps.

Finally, the conventional discoloration prevention treatment step (S400) is performed, followed by washing with water and two to three steps, followed by drying.

Example 2 Manufacturing Process of Conductive Fiber by Substituted Tin Plating

In electroless nickel plating process, nickel sulfate hexahydrate 0.02-0.2 mol / L + citric acid or sodium citrate dihydrate 0.02-0.2 mol / L + hypophosphoric monohydrate 0.02-0.2 mol / L + small amount of stabilizer After adding ammonia water to a plating liquid and adjusting pH to the range of 8.0-10.0, plating is performed for 1 to 10 minutes at 35-60 degreeC, and washing with water is performed 2-3 steps.

In the electroless copper plating process, a solution containing 0.03 to 0.07 mol / L copper sulfate, 0.3 to 0.21 mol / L complexing agent, 0.03 to 0.07 mol / L formaldehyde, 0.1 to 0.4 mol / L caustic soda and a small amount of stabilizer is used. Then, plating is carried out at 35 to 60 ° C. for 2 to 15 minutes, followed by washing with water to 2 to 3 steps.

In the substituted tin plating process, 5 to 50 g / L methanesulfonic acid, 2 to 2.5 g / L tin ions (added as tin methanesulfonic acid tin), 2 to 75 g / L thiourea, and 20 to 120 g / L glue Plating is performed at 25 to 60 ° C. for 1 to 10 minutes using a plating solution containing sodium chorate, 1 to 60 g / L hydroquinone, and a small amount of stabilizer, followed by washing with water to two to three stages.

Finally, after performing the conventional discoloration prevention treatment process (S400) and performing the water washing 2-3 stages, the dehydration process (S500) and the drying process (S600).

Such substitution plating is used only in certain industrial fields and the film thickness is kept very thin.

Example 9 Manufacturing Process of Conductive Fiber by Electro Tin Plating Method after Electroless Copper Plating

In the electroless copper plating process, a solution containing 0.03-0.07 mol / L copper sulfate, 0.3-0.21 mol / L complexing agent, 0.03-0.07 mol / L formaldehyde, 0.1-0.4 mol / L caustic soda, and a small amount of stabilizer Using it, plating is performed at 35-60 degreeC for 2 to 15 minutes, and water washing 2-3 steps are performed.

15 to 60 ° C using a plating solution containing 50 to 150 g / L methanesulfonic acid, 2 to 2.5 g / L tin ions (added with methanesulfonic acid tin) and a small amount of stabilizer in the electroplating process Plating is performed for 1 to 10 minutes at a current density of 0.5 to 20 A / dm 2, followed by two to three steps of washing with water.

Finally, after performing the conventional discoloration preventing treatment process (S400) and performing the water washing 2-3 stages, the dehydration process (S500) and the drying process (S600).

According to this method, it is possible to produce a conductive fiber having excellent flexibility, and when used in the electromagnetic shielding gasket and tape, the contact area is improved to improve the shield characteristics. By minimizing the use of nickel or using nickel-free (Ni-Free), it is easy to establish the nickel allergy countermeasure from the manufacturing site of the conductive fiber and the user.

It is apparent to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations will have to belong to the claims of the present invention.

1 is a process flow diagram showing a manufacturing method according to the first embodiment of the present invention.

Figure 2 is a process flow diagram showing a manufacturing method according to a second embodiment of the present invention.

Figure 3 is a process flow diagram showing a manufacturing method according to a ninth embodiment of the present invention.

Explanation of symbols on the main parts of the drawings

S100: first step S200: second step

S300: third step (first embodiment) S300: third step (second embodiment)

S300: third step (ninth embodiment) S400 fourth step

S500: Dehydration Process S600: Drying Process

Claims (14)

In a method of plating to impart conductivity on a fiber: A first step (S100) of injecting a fiber material; A second step (S200) of degreasing, etching, neutralizing, acidifying, and activating the fiber material of the step; A third step of performing nickel or copper plating on the fiber material in the above step and performing at least electro tin plating or substituted tin plating in parallel; And Method for producing a conductive fiber for electromagnetic shielding by tin plating method characterized in that it comprises a; a fourth step (S400) to perform a discoloration prevention treatment for the fiber material of the step. The method of claim 1, The second step (S200) includes a degreasing and etching process for ultrasonic treatment in a caustic soda solution, a neutralization treatment with a hydrochloric acid solution, an acid treatment with a hydrochloric acid solution, and palladium chloride, tin chloride and hydrochloric acid. A method for producing conductive fibers for electromagnetic wave shielding by a tin plating method, comprising a step of catalyzing a catalyst solution and a step of activating a sulfuric acid solution. The method of claim 1, The third step (S300) of the electroless nickel plating process (S320), electroless copper plating process (S340), electro copper plating process (S350), substituted tin plating process (S360), electro tin plating process (S380) of Optionally in order, Electroless nickel plating process (S320) contains nickel sulfate hexahydrate 0.02-0.2 mol / L + citric acid or sodium citrate dihydrate 0.02-0.2 mol / L + hypophosphoric monohydrate 0.02-0.2 mol / L + small amount of stabilizer Ammonia water was added to the plating solution to carry out in the range of pH 8.0-10.0, The electroless copper plating process (S340) contains 0.03-0.07 mol / L copper sulfate, 0.3-0.21 mol / L complexing agent, 0.03-0.07 mol / L formaldehyde, 0.1-0.4 mol / L caustic soda, and a small amount of stabilizer. Using a solution, The electro-copper plating process (S350) uses an electrolytic copper plating solution containing 0.03 to 0.7 mol / L of copper sulfate pentahydrate, 0.1 to 2.0 mol / L of sulfuric acid, and a stabilizer, at 0.5 to 20 A / dm 2 at 15 to 60 ° C. 30 seconds to 10 minutes at full density, Substituted tin plating process (S360) includes 5-50 g / L methanesulfonic acid, 2-2.5 g / L tin ions, 2-75 g / L thiourea, 20-120 g / L sodium gluconate, 1-60 g / L hydroquinone, and a plating solution containing a small amount of stabilizer, Electroplating process (S380) is performed by tin plating method using a plating solution containing 50 to 150 g / L methanesulfonic acid, 2 to 2.5 g / L tin ions, and a small amount of stabilizer. The manufacturing method of the conductive fiber for shielding. The method of claim 3, The third step (S300) is a manufacturing method of the conductive fiber for electromagnetic shielding by the tin plating method, characterized in that it comprises an electroless nickel plating step (S320) and an electro tin plating step (S380). The method of claim 3, The third step (S300) is a conductive fiber for electromagnetic shielding by the tin plating method characterized in that it comprises an electroless nickel plating process (S320), an electroless copper plating process (S340), a substituted tin plating process (S360). Manufacturing method. The method of claim 3, The third step (S300) is a conductive fiber for electromagnetic shielding by the tin plating method characterized in that it comprises an electroless nickel plating process (S320), an electroless copper plating process (S340), an electro tin plating process (S380). Manufacturing method. The method of claim 3, The third step (S300) of the conductive fiber for electromagnetic shielding by the tin plating method characterized in that it comprises an electroless nickel plating step (S320), an electrocopper plating step (S350), a substituted tin plating step (S360). Manufacturing method. The method of claim 3, The third step (S300) of the conductive fiber for electromagnetic shielding by the tin plating method characterized in that it comprises an electroless nickel plating process (S320), an electro copper plating process (S350), an electro tin plating process (S380). Manufacturing method. The method of claim 1, The third step (S300) is characterized in that it comprises an electroless nickel plating process (S320), an electroless copper plating process (S340), an electro copper plating process (S350), a substituted tin plating process (S360) The manufacturing method of the conductive fiber for electromagnetic wave shielding by the plating method. The method of claim 1, The third step (S300) is characterized in that it comprises an electroless nickel plating process (S320), an electroless copper plating process (S340), an electro copper plating process (S350), an electro tin plating process (S380) The manufacturing method of the conductive fiber for electromagnetic wave shielding by the plating method. The method of claim 1, The third step (S300) is an electroless copper plating process (S340), substituted tin plating process (S360) comprising the method of manufacturing a conductive fiber for electromagnetic shielding by tin plating method, characterized in that it comprises. The method of claim 1, The third step (S300) is a manufacturing method of the conductive fiber for electromagnetic shielding by tin plating method, characterized in that it comprises an electroless copper plating step (S340), electro tin plating step (S380). The method of claim 1, The third step (S300) of the conductive fiber for electromagnetic shielding by the tin plating method characterized in that it comprises an electroless copper plating step (S340), an electro copper plating step (S350), a substituted tin plating step (S360). Manufacturing method. The method of claim 1, The third step (S300) of the conductive fiber for electromagnetic shielding by the tin plating method characterized in that it comprises an electroless copper plating process (S340), an electro copper plating process (S350), an electro tin plating process (S380). Manufacturing method.

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