JPH0726332B2 - Method for producing conductive fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing electrically conductive fibers.

[Conventional technology]

Conventionally, in the IC manufacturing factory and the place where flammable substances are handled, if the clothing is charged with static electricity, the IC may be damaged by the discharge of static electricity, or the sparks of the discharge may ignite the flammable substance and cause an explosion accident or fire. There is a danger. Therefore, in an IC manufacturing factory or a place where flammable substances are handled, workers usually wear conductive clothes so as not to be charged with static electricity.

Conventionally, to give conductivity to textile products such as clothes, for example, an ultrafine stainless fiber having a diameter of about 10 to 15 μm is folded into the fiber or a diameter of 15 to 15 is obtained by coating the surface of the fiber with copper sulfide.
A method of using an acrylic fiber of about 30 μm is known.

However, a fiber product woven with ultrafine stainless fiber has excellent durability in a non-bent state, but weaving is complicated, and the body bendability is poor. On the other hand, a product made of an acrylic fiber coated with copper sulfide has a hue There was a problem of being limited.

Therefore, as a conventional technique for solving these problems, there is, for example, a conductive fiber described in Japanese Patent Application No. 2-46832 filed by the applicant of the present application.

This is made by polymerizing a pyrrole compound (monomer capable of forming an electron-conjugated polymer) on polyamide-containing fiber such as 6-nylon or 6,6 nylon, which has strong hydrophilicity, to form a composite with the fiber. It is what gave sex.

[Problems to be Solved by the Invention]

By the way, even if the technical idea filed by the applicant of the present application is simply applied to acrylic fibers having excellent chemical resistance, which can be expected to be commercialized for various items, acrylic fibers are generally fibers having good hydrophobicity. Therefore, it was not possible to simply polymerize the pyrrole compound to form a composite with the acrylic fiber as in the case of the polyamide-containing fiber.

The present invention has been made against the background of such a conventional technique, and an object thereof is to provide a method for producing an acrylic fiber having excellent durability and conductivity.

[Means for Solving the Problems]

The conductive fiber of the present invention, after the acrylic fiber is dyed with a cationic dye, is immersed in a treatment liquid containing a monomer capable of forming an electron-conjugated polymer and an oxidative polymerization agent, and the electron-conjugated polymer is added to the acrylic fiber. The present invention provides a method for producing a conductive fiber that is composited.

As the acrylic fiber used in the present invention, for example, a dyeable acrylonitrile-based polymer fiber can be used. Here, as the polymerization of this acrylonitrile,
Aqueous suspension polymerization using a redox catalyst is often used. In order to enhance the dyeability and bulkiness of the fiber, a copolymer with a small amount of other components is generally used as a fiber raw material.

Styrene sulfonic acid, allyl or methallyl sulfonic acid is used as the dyeing seat for the cationic dye, and methyl vinyl pyridine is used for the acid dye. Further, the copolymerization with methyl acrylate, methyl methacrylate, vinyl acetate, etc. promotes the diffusion of the dye into the fiber.

Wet spinning and dry spinning are used for spinning, and most of them are staples.

Further, as the fiber form of the acrylic fiber, any form such as staple fiber, multifilament, spun yarn, woven fabric, non-woven fabric, knitted fabric and the like can be used. The nonwoven fabric may be obtained by any of the needle punching method, the spun bond method, the melt blow method, the stitch bond method, and the papermaking method.

Further, the acrylic fiber may be a fiber composed of nylon, polyethylene terephthalate, cationic dyeable polyester, vinylon, cellulose, wool, silk, cotton, polyethylene, polypropylene, etc., in addition to the acrylic fiber alone. , It is necessary to contain acrylic, especially acrylic fiber content is 50% by weight
The above is preferable. Furthermore, even if the form of the fiber itself is a single composition fiber, sea-island type fiber, heart-sheath type fiber,
It may be a composite fiber such as a split-type fiber, a side-by-side type fiber, or an alternate arrangement type fiber.

In addition to the acrylic fiber, the fiber which is the object of the present invention can be a fiber dyeable with a cationic dye, and therefore the present invention can be applied to a cationic dyeable polyester fiber. .

On the other hand, as the cationic dye used in the present invention, CI
42025 (CIBasic Blue 1) or CI42555 (CIBasi
Triarylmethane dyes such as c Violet 3), CI46005
Acridine dyes such as (CIBasic Orange 14), CI5
0240 (CIBasic Red 2) or CI12210 (CIBasic
Adin dyes such as Blue 16), CI52015 (CIBasic Bl
ue 9) and other thiazine dyes, CI48070 (CIBasic Red
12) or methine and polymethine dyes such as CI48065 (CIBasic Yellow 11), CI41000 (CIBasic V
iolet 10) and others, as well as Aizen Cathil
on (Hodogaya), Astrazon L (FBy), Basacryl (BAS
F), Calocozine Acrylic (CCC), Deorlene (Ciba),
Diacrul Supara (Mitsubishi), Genacryl (G), Maxilon (G
y): Nikalon (Nippon Kagaku), Sevron (DuP), Sumiacryl
(Sumitomo) and the like.

Dyeing with a cationic dye is performed by adjusting the pH of the treatment liquid to an acidic side with acetic acid or the like.

As the acid used for adjusting the pH, for example, hydrochloric acid, acetic acid, formic acid, p-toluenesulfonic acid, salicylic acid, perchloric acid or the like can be used, and the dye concentration in the treatment liquid of the cationic dye is 0.001 to 0.2% by weight. %, And the pH of the treatment liquid is preferably 3 to 7. The dyeing conditions are not particularly limited and may be the same as the usual dyeing conditions, but it is preferable that a predetermined amount is exactly and uniformly exhausted to the fibers.

A thermal dissociation type cationic dye can also be used as the other cationic dye. Examples of the thermal dissociative cationic dye include Karacryl ED (manufactured by Nippon Kayaku Co., Ltd.), AIZEN C
ATHILON DP (manufactured by Hodogaya Chemical Co., Ltd.) and the like can be mentioned.

The conductive fiber of the present invention is obtained by bringing an acrylic fiber dyed with a cationic dye as described above into contact with a monomer capable of forming an electron conjugated polymer, and polymerizing the monomer in the presence of an oxidative polymerization agent. It is a complex product.

The monomer capable of forming the electron-conjugated polymer is a substance having a conjugated double bond in the molecular structure and causing polymerization by oxidation.

A typical example thereof is a 5-membered heterocyclic compound. Preferable examples of the 5-membered heterocyclic compound used in the present invention include pyrrole, thiophene, furan,
Indole or a derivative thereof, for example, N-methylpyrrole, 3-methylpyrrole, 3-methylthiophene, 3-methylfuran, 3-methylindole, etc., is not limited thereto.

These monomers are polymerized by contacting with an oxidative polymerization agent, preferably in the presence of a dopant.

As the dopant, any commonly used acceptor dopant can be used.

As the acceptor dopant, halogens such as chlorine, bromine and iodine; Lewis acids such as phosphorus pentafluoride; protonic acids such as hydrogen chloride and sulfuric acid; transition metal chlorides such as ferric chloride; silver perchlorate , Transition metal compounds such as silver boron fluoride, and the like.

Further, as the oxidative polymerization agent, permanganic acid or permanganic acid (salt); chromic acid such as chromium trioxide,
Nitrate such as silver nitrate; Halogen such as chlorine, bromine and iodine; Hydrogen peroxide, benzoyl peroxide and other oxidants; Peroxodisulfuric acid, potassium peroxodisulphate, etc., Bell oxo acids, per oxo salts; Hypochlorous acid Acids, oxygen acids such as potassium hypochlorite and potassium hypochlorite, oxyacid salts; transition metal chlorides such as ferric chloride, cupric chloride, stannic chloride and potassium chloride; silver oxide Metal oxides such as Among these oxidative polymerization agents, halogens, peroxo acids (salts), transition metal chlorides and the like have an action as a dopant, and therefore when these are used as oxidative polymerization agents, other dopants are Although it is not necessary to use it together, the conductivity can be further improved by using it together with the dopant. In addition, as the oxidative polymerization agent, for example, ammonium persulfate, potassium persulfate, sodium persulfate, cupric perchlorate, ferric perchlorate and the like can be used, and these can be used alone or in combination.

The amount of the oxidative polymerization agent used with respect to the monomer capable of forming the electron-conjugated polymer is preferably 2 to 3 times, especially about 2 times.

In the present invention, an acrylic fiber dyed with a cationic dye is immersed in the treatment liquid, and a monomer capable of forming an electron-conjugated polymer and an oxidative polymerization agent are brought into contact with each other in the treatment liquid.

Examples of the method of treating the acrylic fiber with the treatment liquid include, for example, a method of immersing the acrylic fiber in the treatment liquid containing a monomer, an oxidative polymerization agent and, if necessary, a dopant before the monomer is substantially polymerized, an oxidative polymerization agent. And if necessary a treatment liquid containing a dopant, a method of sequentially immersing the acrylic fiber in a treatment liquid containing a monomer, after immersing the acrylic fiber in a treatment liquid containing an oxidative polymerization agent and a dopant as necessary, Examples include a method of adding a monomer to this treatment liquid.

According to this method, the processing time can be shortened.
Since the oxidative polymerization agent has a lower permeability to the acrylic fiber than the monomer, a method of separately performing the treatment with the monomer-containing treatment liquid and the dipping treatment with the oxidative polymerization agent-containing treatment liquid is adopted as in the method. It is preferable that the dipping treatment with the treatment liquid containing the oxidative polymerization agent is performed first. Since the amount of the oxidative polymerization agent impregnated into the acrylic fiber is increased in this case, the composite of the electron conjugated polymer and the acrylic fiber is formed. Promoted, resulting in better and more durable conductivity.

When the monomer and the oxidative polymerization agent capable of forming these electron-conjugated polymers are liquids, these can be used as they are as the treatment liquid, but when the monomer and the oxidative polymerization agent are used as they are, especially the oxidative polymerization with the monomer is performed. In the method of immersing the acrylic fiber in the treatment liquid mixed with the agent, the formation of the polymer in the treatment liquid is rapid and the formation of the composite of the acrylic fiber and the polymer is hindered, so that sufficient conductivity cannot be obtained. Therefore, it is preferable to dilute the monomer and the oxidative polymerization agent with an appropriate solvent before use.

As this solvent, water or a commonly used organic solvent can be used, and examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, t-butyl alcohol and i-butyl alcohol. Aliphases such as acetone and methyl ethyl ketone; Ethers such as diethyl ether and tetrahydrofuran; Halogenated hydrocarbons such as methylene chloride and chloroform; Esters such as ethyl acetate and butyl acetate; Aromatic such as toluene and benzene Hydrocarbons; Aliphatic hydrocarbons such as hexane; Nitrogen-containing compounds such as acetonitrile and benzonitrile, or a mixture thereof, which are appropriately selected from these solvents according to the monomer, dopant, oxidative polymerization agent and acrylic fiber. To use. The monomer concentration and the oxidative polymerization agent concentration in the treatment liquid vary depending on the material of the acrylic fiber and the desired conductivity, but the monomer concentration is preferably about 5 × 10 ⁻³ to 1 molar concentration. Polymerization agent concentration is 1 ×
It is preferably about 10 ⁻³ to 1 molar concentration. The monomer concentration is preferably about 0.01 to 5% by weight per acrylic fiber.

The dopant concentration is preferably about 1 × 10 ⁻⁴ to 1 × 10 ⁻² molar concentration.

The treatment liquid temperature when the acrylic fiber is immersed in the treatment liquid is preferably −20 to 30 ° C., and particularly preferably −20 to 5 ° C., in order to improve the imparted conductivity. Further, the immersion time of the acrylic fiber varies depending on the material of the acrylic fiber and the desired degree of conductivity, but is usually about 1 minute to 4 hours.

[Action]

In the conductive fiber of the present invention, first, acrylic fiber is dyed with a cationic dye.

After that, the dyed acrylic fiber is immersed in a treatment liquid containing a monomer capable of forming an electron-conjugated polymer and an oxidative polymerization agent to complex the electron-conjugated polymer with the acrylic fiber.

By doing so, the monomer is easily adsorbed on the acrylic fiber which is dyed with a cationic dye in advance and the microstructure of the fiber is loose, and the fiber and the polymer are combined by polymerizing the monomer. A conductive fiber having durability is obtained.

〔Example〕

Hereinafter, examples of the present invention will be described in detail.
It is not limited to these examples.

Example 1 A 180 g / m ² non-woven fabric obtained by needle punching an acrylic fiber having a single yarn of 1.5 de and a fiber length of 51 mm was mixed with Di of 2 g / concentration.
It is a cationic dye after thoroughly washing with an adavin EWN (manufactured by Bayer AG) at 60 ° C to completely remove antistatic agents, oil agents and the like.

Karacryl Red GRL-ED (manufactured by Nippon Kayaku Co., Ltd.) was dipped in a dyeing solution containing 0.1% by weight and 0.25% by weight of acetic acid at 105 ° C. for 60 minutes to obtain a red nonwoven fabric.

Next, this non-woven fabric was thoroughly washed with ion-exchanged water and then dried at 120 ° C.

Next, after dipping for 240 minutes in an aqueous solution containing pyrrole 0.01 mol / kg and ferric chloride 0.03 mol / kg (liquid temperature 7 ° C.), it was thoroughly washed with water and dried at 60 ° C.

The resulting nonwoven fabric was dark red.

The surface resistance of the non-woven fabric after the treatment was 380 Ω, and the surface resistance after the light resistance test (black panel temperature 63 ° C.) for 100 hours was 15 kΩ.

Comparative Example 1 A nonwoven fabric was obtained in the same manner as in Example 1 except that the acrylic fiber was not dyed with a cationic dye.

The surface resistance of the obtained non-woven fabric after treatment is 17 kΩ,
After performing a light resistance test (black panel temperature 63 ° C.) for 100 hours, the surface resistance value was 15 × 10 ⁶ Ω.

〔The invention's effect〕

In the present invention, after the acrylic fiber is dyed with a cationic dye in this manner, it is immersed in a treatment liquid containing a monomer capable of forming an electron-conjugated polymer and an oxidative polymerization agent, and the acrylic fiber is mixed with the electron-conjugated polymer. Since it is a conductive fiber that is made into a resin, it is possible to obtain an acrylic fiber having excellent durability and conductivity.

Claims (1)

[Claims] 1. An acrylic fiber is dyed with a cationic dye and then dipped in a treatment liquid containing a monomer capable of forming an electron-conjugated polymer and an oxidative polymerization agent to complex the electron-conjugated polymer with the acrylic fiber. A method for producing a conductive fiber, comprising: