KR101178568B1 - Method of manufacturing acrylic conductive fibers using latent catalyst - Google Patents

Abstract

The present invention relates to a method for producing an acrylic conductive fiber to uniformly form the copper sulfide compound inside the fiber by controlling the production rate of the copper sulfide compound using a latent catalyst. In the method of manufacturing acrylic conductive fiber according to the present invention, after mixing acrylic fiber, a copper compound containing copper having an oxidation number of +2, and a reducing agent for reducing the copper compound, adsorbing copper monovalent ions to the acrylic fiber, A sulfur compound containing sulfur and an acidic latent catalyst are added to the treatment bath to adsorb copper sulfide to the acrylic fiber.

Description

Method for manufacturing acrylic conductive fibers using latent catalyst

The present invention relates to a method for producing an acrylic conductive fiber, and more particularly, to an acrylic conductive fiber manufacturing method for uniformly forming a copper sulfide compound inside the fiber by controlling the production rate of the copper sulfide compound using a latent catalyst. .

In order to impart conductivity to the acrylic fiber, a method of forming a copper sulfide compound inside the acrylic fiber is used. There are two methods for forming the copper sulfide compound in the acrylic fiber.

One is a method of imparting conductivity to an acrylic fiber by adsorbing copper ions into the acrylic fiber and then adding sulfur molecules to form a copper sulfide compound in the acrylic fiber. In this method, copper divalent ions are reduced to copper monovalent ions, and then copper ions are adsorbed into the acrylic fiber through coordinating with nitrile groups of the acrylic fiber, and then sulfur molecules are added to the copper ions to combine with sulfur. To form a copper sulfide compound inside the acrylic fiber.

To this end, a complex is first formed by coordinating the nitrile group of the acrylic fiber with copper monovalent ions. In addition, the copper sulfide compound is formed by combining with copper monovalent ions and sulfur, and the bonding strength between the copper monovalent ions and the nitrile group of the acrylic fiber is weak, while the copper monovalent ions are combined with sulfur to form the copper sulfide compound. A large proportion of copper sulfide compounds desorb from acrylic fibers. A powdery precipitate is produced by the copper sulfide compound desorbed in this way, and this powdery precipitate has a problem of contaminating the fiber surface and the processing apparatus. And the copper monovalent ions that did not produce the copper sulfide compound is reduced to metal copper, the reduced metal copper has a problem that severely contaminate the inner wall of the processing apparatus.

Alternatively, there is a method of forming the copper sulfide compound in the acrylic fiber by generating the copper sulfide compound in the treatment bath and then adsorbing the acrylic sulfide in the acrylic fiber. However, the production rate of the copper sulfide compound produced in the treatment bath is so fast that there is a problem that the copper sulfide compound is unevenly adsorbed on the acrylic fiber, the copper sulfide compound not adsorbed on the acrylic fiber forms a powdery precipitate. Powdery deposits have the problem of contaminating the fiber surface and the processing apparatus.

The technical problem to be solved by the present invention is to provide a method for producing an acrylic conductive fiber to uniformly form the copper sulfide compound inside the fiber by controlling the production rate of the copper sulfide compound using a latent catalyst.

In order to solve the above technical problem, the acrylic conductive fiber manufacturing method according to the present invention is mixed with an acrylic fiber, a copper compound containing copper having an oxidation number of +2 and a reducing agent for reducing the copper compound in the treatment bath, A copper ion adsorption step of adsorbing copper monovalent ions to the fiber; And a copper sulfide adsorption step of adsorbing copper sulfide to the acrylic fiber by adding a sulfur compound including sulfur and an acidic latent catalyst in the treatment bath.

The copper ion adsorption step may be performed by adding an acidic latent catalyst to the treatment bath.

The copper compound may be at least one compound selected from cupric sulfate, cupric acetate, and cupric chloride. And the copper compound may be set in the range of 5 to 50% by weight relative to the acrylic fiber.

The sulfur compound including sulfur may be at least one compound selected from sodium thiosulfate, sodium hydrogen sulfite, sodium hyposulfite and sodium formaldehyde sulfoxylate. And the sulfur compound containing sulfur may be set in the range of 5 to 50% by weight relative to the acrylic fiber.

The acidic latent catalyst may be at least one compound selected from magnesium chloride, ammonium chloride and zinc acetate. And the acid-based latent catalyst added in the copper sulfide adsorption step may be set in the range of 0.5 to 4% by weight relative to the acrylic fiber, the acid-based latent catalyst added in the copper ion adsorption step is 0.05 to compared to the acrylic fiber It can be set in the range of 2% by weight.

The acrylic fiber may be an acrylic fiber having an acrylonitrile content of 85% or more.

According to the present invention, since a large amount of copper sulfide compound can be uniformly formed inside the acrylic fiber, low electrical resistance is exhibited. In addition, since powdery precipitates are not formed when the conductive acrylic fibers are manufactured, contamination of the fibers and contamination of the inner wall of the processing apparatus due to the powdery precipitates can be prevented. In addition, the acrylic fiber produced according to the present invention hardly changes the electrical conductivity before and after washing, and is excellent in washing resistance.

1 is a flow chart showing a process of performing a preferred embodiment of the acrylic conductive fiber manufacturing method according to the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the acrylic conductive fiber manufacturing method using a latent catalyst according to the present invention. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention and to those skilled in the art to fully understand the scope of the invention. It is provided to inform you.

1 is a flow chart showing a process of performing a preferred embodiment of the acrylic conductive fiber manufacturing method according to the present invention.

Referring to FIG. 1, in the acrylic conductive fiber manufacturing method according to the present invention, first, an acrylic fiber, a copper compound, a reducing agent and a first acidic latent catalyst are mixed in a treatment bath to adsorb copper monovalent ions to the acrylic fiber ( S110). Copper ion adsorption step (S110) to adsorb the copper monovalent ions may be carried out at a temperature in the range of 40 to 90 ℃. The copper ion adsorption step (S110) is performed by maintaining a predetermined time at a first temperature, and then heating the temperature to a temperature higher than the first temperature and maintaining a predetermined time at a second temperature to thereby adsorb copper monovalent ions to the acrylic fiber. Can be. For example, the first temperature may be 55 ° C and the second temperature may be 90 ° C. At this time, the copper monovalent ions are adsorbed to the acrylic fiber in such a way that the covalent bonds with the nitrile group of the acrylic fiber.

Acrylic fibers refer to synthetic fibers having an acrylonitrile content of at least 35% in the fiber structure. Acrylic fibers are classified into acrylic fibers and modacryl fibers, wherein acrylic fibers have an acrylonitrile content of 85% or more and modacryl fibers have an acrylonitrile content of 35 to 85%. In the present embodiment, the content of acrylonitrile of the acrylic fiber is not particularly limited, but preferably acrylic fiber having an acrylonitrile content of 85% or more is used.

The copper compound is a compound including copper having +2 oxidation, and may be cupric sulfate, cupric acetate, cupric chloride, or a combination thereof. At this time, the copper compound may be set in the range of 5 to 50% by weight compared to the acrylic fiber. If the copper compound is set to less than 5% by weight relative to the acrylic fiber, conductivity is not imparted to the acrylic fiber. And when the copper compound is set larger than 50% by weight compared to the acrylic fiber, the precipitate is generated in the treatment bath.

The reducing agent reduces the copper compound. As long as the copper divalent ion can be reduced to the copper monovalent ion, the kind of the reducing agent is not particularly limited, and hydroxyamine sulfate may be used. The reducing agent may be set in the range of 1 to 20% by weight based on the acrylic fiber.

The first acidic latent catalyst may be an inorganic metal salt, an ammonium salt, preferably magnesium chloride, ammonium chloride, zinc acetate, or a combination thereof. The first acidic latent catalyst slowly decomposes to adjust the pH in the treatment bath to control the rate at which copper ions are adsorbed onto the acrylic fiber. If a general acid catalyst other than the first acidic latent catalyst is used, copper ions are adsorbed to the acrylic fiber too quickly and copper ions are not uniformly adsorbed to the acrylic fiber. The first acidic latent catalyst may be set in the range of 0.05 to 2% by weight relative to the acrylic fiber. When the first acidic latent catalyst is set to less than 0.05% by weight relative to the acrylic fiber, it does not serve as a catalyst. When the first acidic latent catalyst is set larger than 2% by weight of the acrylic fiber, copper ions are rapidly adsorbed to the acrylic fiber and copper ions are non-uniformly adsorbed to the acrylic fiber.

Next, a sulfur compound and a second acidic latent catalyst are added to the treatment bath to adsorb copper sulfide to the acrylic fiber (S120). Copper sulfide adsorption step (S120) for adsorbing copper sulfide to the acrylic fiber may be performed for 30 minutes to 5 hours at a temperature set in the range of 40 to 100 ℃. The copper sulfide adsorption step (S120) may be performed by maintaining a predetermined time at a third temperature, and then heating the temperature to a temperature higher than the third temperature to maintain a predetermined time at a fourth temperature, thereby adsorbing the copper sulfide to the acrylic fiber. . For example, the third temperature may be 40 ° C, and the fourth temperature may be 60 ° C.

The sulfur compound is a compound containing sulfur and may be composed of sodium thiosulfate, sodium hydrogen sulfite, sodium hyposulfite, sodium formaldehyde sulfoxylate, and combinations thereof. The sulfur compound reduces copper ions adsorbed to the acrylic fiber or copper ions remaining in the treatment bath to form copper sulfide. The copper sulfide thus formed is adsorbed onto the acrylic fiber, thereby providing conductivity to the acrylic fiber.

Like the first acidic latent catalyst, the second acidic latent catalyst may be an inorganic metal salt or an ammonium salt, preferably magnesium chloride, ammonium chloride, zinc acetate, or a combination thereof. The second acidic latent catalyst slowly decomposes to adjust the pH in the treatment bath to control the rate at which sulfur molecules are produced from the sulfur compound. Sulfur compounds such as sodium thiosulfate, sodium bisulfite and sodium hyposulfite are produced by decomposition under high temperature and strong acidic conditions. Therefore, by adjusting the pH in the treatment bath using the second acid-based latent catalyst it is possible to control the rate at which sulfur molecules are generated from the sulfur compound. Since sulfur molecules generated from the sulfur compound are very rapidly bonded to copper to form copper sulfide, the rate of formation of copper sulfide is controlled by using a second acidic latent catalyst.

If the rate at which the copper sulfide is not produced is not controlled, that is, if the production rate of copper sulfide is high, a powdery precipitate is generated in the treatment bath, and copper sulfide is not uniformly adsorbed to the acrylic fiber. As described above, copper ions are coordinately bonded to the nitrile group of the acrylic fiber. When the bonding force is considerably weak and the production rate of copper sulfide is high, the copper ions are desorbed from the acrylic fiber to generate a powdery precipitate. In addition, the bonding force between the nitrile group and the copper ions is weak, so that a large amount of copper ions remain in the treatment bath. When the production rate of copper sulfide is high, the copper sulfide generated in the treatment bath is not adsorbed to the acrylic fiber and powdery precipitate. Will occur. And copper sulfide adsorbed on the acrylic fiber is also not uniformly adsorbed due to the high production rate of copper sulfide.

 However, when the second acidic latent catalyst is used, the temperature in the treatment bath can be controlled so that sulfur molecules can be gradually produced, thereby making it possible to control the rate at which copper sulfide is produced. As a result, copper ions, which are coordinated with the acrylic fiber, are uniformly bonded with sulfur, thereby allowing copper sulfide to be uniformly adsorbed on the acrylic fiber. In addition, since copper ions remaining in the treatment bath may be gradually bonded with sulfur, copper sulfide generated as the copper ions and sulfur are combined is gradually adsorbed to the acrylic fiber so that the copper sulfide may be uniformly bonded to the acrylic fiber.

The second acidic latent catalyst may be set in the range of 0.5 to 4% by weight relative to the acrylic fiber. If the second acidic latent catalyst is set to less than 0.5% by weight relative to the acrylic fiber, it will not serve as a catalyst. And when the second acid-based latent catalyst is set larger than 4% by weight compared to the acrylic fiber, the rate of bonding copper ions and sulfur is fast, the powdery precipitate is formed as described above or non-uniform adsorption of copper sulfide occurs.

As a result, by using the second acidic latent catalyst, powdery precipitates are not formed during manufacture, thereby preventing fiber contamination and contamination of the treatment bath, thereby making the manufacturing process stable and uniforming of copper sulfide to acrylic fibers. It can be adsorbed easily, exhibits low electrical resistance, and enables the production of high-performance conductive acrylic fibers with durability against external friction.

Example  One

First, an aqueous solution containing 100 g of acrylic fiber having an acrylonitrile content of 85% or more, 50 g of cupric sulfate, 5 to 20 g of hydroxyamine sulfate, and 0.1 g of magnesium chloride was prepared. And after processing for 30 minutes in the state which kept the temperature of this aqueous solution at 55 degreeC, the temperature of the aqueous solution was heated to 90 degreeC and processed for 30 minutes. Next, after lowering the temperature of the aqueous solution to 40 ° C., 50 g of sodium thiosulfate and 3 g of magnesium chloride were added to the aqueous solution. And after processing for 2 hours while maintaining the temperature of the aqueous solution at 60 ℃, the temperature of the aqueous solution was heated to 90 ℃ was treated for 30 minutes. At this time, the liquid ratio was set to 1:10. The specific resistance of the fiber of Example 1 prepared in this manner was measured by a volume resistivity measurement method, and the specific resistance was measured after washing 20 times with the JIS L 1013 A method for the same fiber.

Example  2

First, an aqueous solution containing 100 g of acrylic fiber having an acrylonitrile content of at least 85%, cupric sulfate 40g, 5-20 g of hydroxyamine sulfate and 0.1 g of magnesium chloride was prepared. And after processing for 30 minutes in the state which kept the temperature of this aqueous solution at 55 degreeC, the temperature of the aqueous solution was heated to 90 degreeC and processed for 30 minutes. Next, after lowering the temperature of the aqueous solution to 40 ° C, 40 g of sodium thiosulfate and 3 g of magnesium chloride were added to the aqueous solution. And after processing for 2 hours while maintaining the temperature of the aqueous solution at 60 ℃, the temperature of the aqueous solution was heated to 90 ℃ was treated for 30 minutes. At this time, the liquid ratio was set to 1:10. The specific resistance of the fiber of Example 2 prepared in this manner was measured in the same manner as in Example 1, after washing in the same manner as in Example 1, the specific resistance was measured.

Example  3

First, an aqueous solution containing 100 g of acrylic fiber having an acrylonitrile content of 85% or more, 30 g of cupric sulfate, 5 to 20 g of hydroxyamine sulfate, and 0.1 g of magnesium chloride was prepared. And after processing for 30 minutes in the state which kept the temperature of this aqueous solution at 55 degreeC, the temperature of the aqueous solution was heated to 90 degreeC and processed for 30 minutes. Next, after lowering the temperature of the aqueous solution to 30 ° C, 40 g of sodium thiosulfate and 3 g of magnesium chloride were added to the aqueous solution. And after processing for 2 hours while maintaining the temperature of the aqueous solution at 60 ℃, the temperature of the aqueous solution was heated to 90 ℃ was treated for 30 minutes. At this time, the liquid ratio was set to 1:10. The specific resistance of the fiber of Example 3 prepared in this manner was measured in the same manner as in Example 1, after washing in the same manner as in Example 1, the specific resistance was measured.

Example  4

First, an aqueous solution containing 100 g of acrylic fiber having an acrylonitrile content of 85% or more, 20 g of cupric sulfate, 5 to 20 g of hydroxyamine sulfate, and 0.1 g of magnesium chloride was prepared. And after processing for 30 minutes in the state which kept the temperature of this aqueous solution at 55 degreeC, the temperature of the aqueous solution was heated to 90 degreeC and processed for 30 minutes. Next, after lowering the temperature of the aqueous solution to 40 ° C., 20 g of sodium thiosulfate and 3 g of magnesium chloride were added to the aqueous solution. And after processing for 2 hours while maintaining the temperature of the aqueous solution at 60 ℃, the temperature of the aqueous solution was heated to 90 ℃ was treated for 30 minutes. At this time, the liquid ratio was set to 1:10. The specific resistance of the fiber of Example 4 prepared in this manner was measured in the same manner as in Example 1, and after washing in the same manner as in Example 1, the specific resistance was measured.

Example  5

First, an aqueous solution containing 100 g of acrylic fiber having an acrylonitrile content of 85% or more, 10 g of cupric sulfate, 5 to 20 g of hydroxyamine sulfate, and 0.1 g of magnesium chloride was prepared. And after processing for 30 minutes in the state which kept the temperature of this aqueous solution at 55 degreeC, the temperature of the aqueous solution was heated to 90 degreeC and processed for 30 minutes. Next, after lowering the temperature of the aqueous solution to 40 ° C, 10 g of sodium thiosulfate and 3 g of magnesium chloride were added to the aqueous solution. And after processing for 2 hours while maintaining the temperature of the aqueous solution at 60 ℃, the temperature of the aqueous solution was heated to 90 ℃ was treated for 30 minutes. At this time, the liquid ratio was set to 1:10. The specific resistance of the fiber of Example 5 prepared in this manner was measured in the same manner as in Example 1, and after washing in the same manner as in Example 1, the specific resistance was measured.

Comparative example

First, an aqueous solution containing 100 g of acrylic fiber having 30% or more of acrylonitrile and 30 g of cupric sulfate was prepared. And it processed for 30 minutes, maintaining the temperature of this aqueous solution at 100 degreeC. Next, 30 g of sodium thiosulfate and 3 g of sulfuric acid were added to the aqueous solution. And it processed for 2 hours, maintaining the temperature of aqueous solution at 90 degreeC. At this time, the liquid ratio was set to 1:10. The specific resistance of the fiber of the comparative example prepared in this manner was measured in the same manner as in Example 1, after washing in the same manner as in Example 1, the specific resistance was measured.

Table 1 shows specific resistance values before and after washing the fibers of Examples 1 to 5 and Comparative Examples.

[Table 1]

Looking at Table 1, it can be seen that the specific resistance values of the fibers of Examples 1 to 5 are quite small. Comparing the specific resistance values of the fibers of Examples 1 to 5 with the specific resistance values of the Comparative Examples, it was found that the specific resistance values of the fibers of Examples 1 to 5 were significantly smaller than those of the comparative examples by about 1/20 to 1/100. Can be. And before and after washing, the fibers of Examples 1 to 5 hardly changed the resistivity value, whereas the fibers of the comparative example showed that the resistivity value increased by three times before and after washing. From this, it can be seen that the washing resistance of the fibers of Examples 1 to 5 is very excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation in the embodiment in which said invention is directed. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

Claims (6)

A copper ion adsorption step of adsorbing copper monovalent ions to the acrylic fiber by mixing a acrylic fiber, a copper compound containing copper having an oxidation number of +2, and a reducing agent for reducing the copper compound in a treatment bath; And
And a copper sulfide adsorption step of adsorbing copper sulfide to the acrylic fiber by adding a sulfur compound containing sulfur and an acidic latent catalyst in the treatment bath.
The acid-based latent catalyst added in the copper sulfide adsorption step is an acrylic conductive fiber manufacturing method, characterized in that at least one compound selected from magnesium chloride, ammonium chloride and zinc acetate. The method of claim 1,
Copper ion adsorption step is an acrylic conductive fiber manufacturing method, characterized in that performed by adding an acid-based latent catalyst in the treatment bath. The method according to claim 1 or 2,
The copper compound is at least one compound selected from cupric sulfate, cupric acetate and cupric chloride,
The copper compound is an acrylic conductive fiber manufacturing method, characterized in that set in the range of 5 to 50% by weight relative to the acrylic fiber. The method according to claim 1 or 2,
The sulfur compound is at least one compound selected from sodium thiosulfate, sodium hydrogen sulfite, sodium hyposulfite and sodium formaldehyde sulfoxylate,
The sulfur compound is an acrylic conductive fiber manufacturing method, characterized in that set in the range of 5 to 50% by weight relative to the acrylic fiber. The method according to claim 1 or 2,
The acid-based latent catalyst added in the copper sulfide adsorption step is an acrylic conductive fiber manufacturing method, characterized in that it is set in the range of 0.5 to 4% by weight relative to the acrylic fiber. The method of claim 2,
The acid-based latent catalyst added in the copper sulfide adsorption step is an acrylic conductive fiber manufacturing method, characterized in that set in the range 0.05 to 2% by weight compared to the acrylic fiber.

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