JPH03294579A - Electrically conductive fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to fibers having electrical conductivity.

[Conventional technology]

Traditionally, in IC manufacturing factories and other places where flammable materials are handled, if clothing is charged with static electricity, the static electricity discharge can damage the IC, or the sparks from the discharge can ignite the flammable materials, causing explosions and fires. There is a danger that this may occur.

For this reason, in IC manufacturing plants or places where flammable substances are handled, workers usually wear conductive clothing to prevent static electricity from building up.

Conventionally, in order to impart conductivity to textile products such as clothing, for example, ultra-fine stainless steel fibers with a diameter of about 10 to 15 μm were folded into the fibers, or acrylic fibers with a diameter of about 15 to 30 μm coated with copper sulfide were used. There are known methods such as using

However, although textile products woven with ultra-fine stainless steel fibers have excellent durability when not bent, they are complicated to weave and have poor body flexibility; on the other hand, those made of acrylic fibers coated with copper sulfide are The problem was that it was limited.

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

This material is, for example, highly hydrophilic 6-nylon, 6.6
Conductivity is imparted to polyamide-containing fibers such as nylon by polymerizing a pyrrole compound (monomer capable of forming an electronically conjugated polymer) and compositing the fibers with the fibers.

(Problems to be Solved by the Invention) By the way, even if we simply try to apply the technical concept proposed by the applicant as described above to acrylic fibers with excellent chemical resistance that can be expected to be commercialized into a wide variety of products, Since acrylic fibers have good hydrophobicity, it was not possible to simply polymerize a pyrrole compound and form a composite with acrylic fibers, as is the case with polyamide-containing fibers.

The present invention was made against the background of such conventional technology, and an object of the present invention is to provide an acrylic fiber having excellent durability and conductivity.

[Means to solve the problem]

The conductive fiber of the present invention is produced by dyeing an acrylic fiber with a cationic dye and then immersing it in a treatment solution containing a monomer capable of forming an electronically conjugated polymer and an oxidative polymerization agent to dye the acrylic fiber with an electronically conjugated polymer. The present invention provides a composite conductive fiber.

As the acrylic fibers used in the present invention, for example, fibers made of a dyeable acrylonitrile polymer can be used. Here, the polymerization of acrylonitrile is as follows:
Aqueous suspension polymerization using redox catalysts is often used. In order to improve the dyeability, bulkiness, etc. of fibers, copolymers with small amounts of other components are generally used as fiber raw materials.

Styrene sulfonic acid, allyl or methallyl sulfonic acid, etc. are used as a dyeing seat for cationic dyes, and methyl vinyl pyridine and the like are used for acid dyes. Furthermore, copolymerization with methyl acrylate, methyl methacrylate, vinyl acetate, etc. facilitates the diffusion of the dye into the interior of the fiber.

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

Further, the acrylic fiber may be in any form, such as stable fiber, multifilament, spun yarn, woven fabric, nonwoven fabric, or knitted fabric. The nonwoven fabric may be obtained by any of the needle punching method, spun bonding method, melt blowing method, stitch bonding method, and paper making method.

Furthermore, in addition to being composed of acrylic alone, the acrylic fiber may also contain fibers such as nylon, polyethylene terephthalate, cationically dyeable polyester, vinylon, cellulose, wool, silk, cotton, polyethylene, and polypropylene. , it is necessary to contain acrylic, and it is particularly preferable that the content of acrylic fiber is 50% by weight or more. Furthermore, the form of the fiber itself may be a single composition fiber, or a composite fiber such as a sea-island type fiber, a core-sheath type fiber, a split type fiber, a side-by-side type fiber, or an alternating arrangement type fiber.

In addition to the above-mentioned acrylic fibers, the fibers to which the present invention is applied can also include fibers that can be dyed with cationic dyes, and therefore, the present invention can also be applied to cationically dyeable polyester fibers. .

On the other hand, the cationic dye used in the present invention is C8
1,42025 (C0I, Bas 1cBlue 1
) or C01,42555 (C0I, Ba5ic
Triallylmethane dyes such as Violet 3), C
, 1,46005 (C0I.

Acridine dyes such as Ba5ic Orange 14), C, 1,50240 (C0I.

Ba5ic Red 2) or C8I.

12210 (C0I, Ba5ic Blue
e16), C,1,52015 (C,
1, Ba5ic Blue 9), thiazine dyes such as C,1,48070 (C,I.

Ba5ic Red 12) or C01°480
Methine and polymethine dyes such as 65 (C0I, Ba5ic Yellowll), C,I, 41000
(C, 1, Ba5icViolet 10), etc., as well as Aizen Cathilo
n (Hodogaya), Astrazon L (FBy),
Ba5acryl (BASF), Ca1ocozine Acrylic (CCC),
Deorlene (Ciba), Diacrul
5upara (Mitsubishi), Genacryl (G)
, Maxilon (Gy): N1ka Ion (Nippon Kagaku), 5evron (DuP), Sumiacr
Examples include yl (Sumitomo).

Staining with a cationic dye is performed by adjusting the pH of the treatment solution to the acidic side using acetic acid or the like.

Examples of acids used for the preparation of p) include hydrochloric acid,
Sulfuric acid, formic acid, P-)luenesulfonic acid, salicylic acid, perchloric acid, etc. can also be used, and the dye concentration in the cationic dye treatment solution is preferably about 0.001 to 0.2% by weight, and the pH of the treatment solution is preferably 3 to 7. The dyeing conditions are not particularly limited and may be the same as normal dyeing conditions, but it is preferable that a predetermined amount is accurately and uniformly exhausted onto the fibers.

Note that thermally dissociable cationic dyes can also be used as other cationic dyes. Examples of the thermally dissociable cationic dye include Karacryl ED (manufactured by Nippon Kayaku), A
Examples include IZEN CATHILON DP (manufactured by Hodogaya Chemical Co., Ltd.).

The conductive fiber of the present invention is produced by bringing the acrylic fiber dyed with a cationic dye as described above into contact with a monomer capable of forming an electronically conjugated polymer, and polymerizing this monomer in the presence of an oxidative polymerization agent. It is made by combining products.

A monomer capable of forming an electronically conjugated polymer is a substance that has a conjugated double bond in its molecular structure and undergoes polymerization upon oxidation.

Representative examples include 5-membered heterocyclic compounds, and examples of the 5-membered heterocyclic compounds preferably used in the present invention include virol, thiophene, furan, indole, and derivatives thereof, such as N-methylpyrrole, 3-methylvirol, 3-methylthiophene,
These include, but are not limited to, 3-methylfuran and 3-methylindole.

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

As this dopant, all commonly used acceptor dopants can be used.

Acceptor dopants include 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 boron silver fluoride, and the like.

In addition, examples of oxidative polymerization agents include permanganic acid or permanganic acids (salts); chromic acids such as chromium trioxide;
Nitrates such as silver nitrate; halogens such as chlorine, bromine, and iodine; oxides such as hydrogen peroxide and benzoyl peroxide; peroxo acids and peroxo acid salts such as peroxonisulfate and potassium peroxonisulfate; hypochlorous acid, Oxygen acids and acid salts such as potassium hypochlorite and potassium hypochlorite; ferric chloride, cupric chloride, tin chloride,
Examples include transition metal chlorides such as potassium chloride; metal oxides such as silver oxide. Among these oxidative polymerization agents, halogens, peroxo acids (salts), transition metal chlorides, etc. act as dopants, so when they are used as oxidative polymerization agents, they are especially sensitive to other dopants. Although it is not necessary to use them together, the conductivity can be further improved when used together with a dopant. In addition, as other oxidative polymerization agents, for example, ammonium persulfate, -rum, potassium persulfate, sodium persulfate, cupric perchlorate, ferric perchlorate, etc. can be used, and these can be used alone or in combination. .

The amount of the oxidative polymerization agent to be used is preferably about 2 to 3 moles, particularly about 2 moles, relative to the monomer capable of forming the electronically conjugated polymer.

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

Examples of methods for treating acrylic fibers with a treatment solution include: (1) immersing the acrylic fiber in a treatment solution containing a monomer, an oxidative polymerization agent, and, if necessary, a dopant before the monomer is substantially polymerized; (2) A method of sequentially immersing acrylic fibrils in a treatment solution containing an oxidative polymerization agent and, if necessary, a dopant, and a treatment solution containing a monomer; Examples include a method in which a monomer is added to the treatment liquid after the treatment liquid is immersed in the treatment liquid.

According to method (2), processing time can be shortened.

In addition, since oxidative polymerization agents have lower permeability into acrylic fibers than monomers, it is recommended to perform treatment with a monomer-containing treatment solution and immersion treatment with an oxidation polymerization agent-containing treatment solution separately, as in methods ① and ②. It is preferable to first perform a dipping treatment with a treatment solution containing an oxidative polymerizing agent.This increases the amount of oxidizing polymerizing agent impregnated into the acrylic fibers, so it is difficult to combine the electronically conjugated polymer with the acrylic fiber. oxidation is promoted, resulting in better and more durable conductivity.

When the monomers and oxidative polymerization agents that can form these electronically conjugated polymers are liquid, they can be used as they are as the treatment liquid. In the method of immersing acrylic fibers in a treatment solution mixed with a treatment agent, the formation of polymer in the treatment solution is rapid, preventing the formation of a composite between the acrylic fibers and the polymer, making it impossible to obtain sufficient conductivity. Therefore, it is preferable to dilute the monomer and oxidative polymerization agent with an appropriate solvent.

As this solvent, water or a commonly used organic solvent can be used. Examples of the organic solvent include methanol, ethanol, n-propanol, i-propanol, and t-propanol.
Aliphatic alcohols such as butyl alcohol and i-butyl alcohol; Aliphatic ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as methylene chloride and chloroform; ethyl acetate and acetic acid Examples include esters such as butyl, aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as hexane; nitrogen-containing compounds such as acetonitrile and benzonitrile, or mixtures thereof; monomers,
It is appropriately selected and used depending on the dopant, oxidative polymerization agent, and acrylic fiber. The monomer concentration and oxidative polymerization agent concentration in the treatment solution vary depending on the material of the acrylic fiber and the desired conductivity, but the monomer concentration is 5 x 10-3 ~
The concentration of the oxidative polymerization agent is preferably about 1 molar, and the concentration of the oxidative polymerization agent is preferably about I x 10-3 to 1 molar. In addition, the monomer concentration is 0.0% per acrylic fiber.
The amount is preferably about 0.01 to 5% by weight.

In addition, the dopant concentration is lXl0-'~1x10-2
A molar concentration level is preferred.

The temperature of the treatment liquid when immersing the acrylic fibers in the treatment liquid is -20 to 30°C in order to further improve the given conductivity.
is preferable, and particularly preferably -20 to 5°C. The immersion time for the acrylic fibers varies depending on the material of the acrylic fibers and the desired degree of conductivity, but is usually about 1 to 1 hour.

[Function] To prepare the conductive fiber of the present invention, first, acrylic fiber is dyed with a cationic dye.

Thereafter, the dyed acrylic fibers are immersed in a treatment liquid containing a monomer capable of forming an electronically conjugated polymer and an oxidative polymerization agent, thereby compounding the electronically conjugated polymer onto the acrylic fibers.

By doing this, the monomer is easily adsorbed to the acrylic fiber, which has been dyed with a cationic dye in advance and has a loose microstructure, and by polymerizing the monomer, the fiber and polymer are composited. Durable conductive fibers are obtained.

[Examples] Examples of the present invention will be described in detail below.
The invention is not limited to these examples.

Example 1 Acrylic fiber with a single yarn of 1.5 de and fiber length of 51 mm was
A 180 g/rrf nonwoven fabric obtained by needle punching was heated to 2 gllet degree Diadavin EWN (B
ayer A, G, Inc.) at 60°C to completely remove antistatic agents, oils, etc., and then a cationic dye Karacryl Red GRL-ED (Nippon Kayaku ■) was applied. 1 containing 0.1% by weight and 0.25% by weight of acetic acid
A red nonwoven fabric was obtained by dyeing by immersing it in a dyeing solution at 05°C for 60 minutes.

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

Next, pyrrole 0.01 mol/kg, ferric chloride 0.0
After being immersed in an aqueous solution containing 3 mol/kg (liquid temperature 7°C) for 240 minutes, it was thoroughly washed with water and dried at 60°C.

The obtained nonwoven fabric was dark red.

The surface resistance value of the nonwoven fabric after treatment was 380Ω, and the surface resistance value after conducting a double light test (black panel temperature 63°C) for 100 hours was 15Ω.

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

The surface resistance value of the obtained nonwoven fabric after treatment was 17Ω, and the double light test (black panel temperature 63°C) was 100Ω.
The surface resistance value after the test was 5×10”Ω.

〔Effect of the invention〕

In the present invention, after dyeing acrylic fibers with a cationic dye, the acrylic fibers are immersed in a treatment solution containing a monomer capable of forming an electronically conjugated polymer and an oxidative polymerization agent to composite the electronically conjugated polymer onto the acrylic fibers. Since the acrylic fiber is a conductive fiber obtained by converting the acrylic fiber into a polyurethane, it is possible to obtain an acrylic fiber with excellent durability and conductivity.

Claims (1)

[Claims] (1) After dyeing acrylic fibers with a cationic dye, the acrylic fibers are immersed in a treatment solution containing a monomer capable of forming an electronically conjugated polymer and an oxidative polymerization agent to compound the electronically conjugated polymer onto the acrylic fibers. conductive fiber.