JPH09111666A - Electric conductive fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electroconductive fiber having a short half life and a low voltage in a frictional electric charge and suitable for a cloth such as a sweater by imparting a compound containing a polyether on the surface of the electroconductive fiber having a electric conductivity at a specific value or higher. SOLUTION: This electroconductive fiber is obtained by imparting 1-20wt.% compound containing a polyether structure on the surface of an electroconductive sheath core composite fiber of which sheath part of a core part consisting of an acrylonitrile- based polymer, is arranged in a cross sectional ratio of (5/95)-(60/40), containing 15-70vol.% electroconductive fine particles such as titanium oxide having >=10<-3> s/cm resistivity and <=3μm mean particle diameter in the core part, or another electroconductive fiber having >=10<-6> s/cm electroconductivity obtained by forming a membrane of a metal or a metallic compound such as copper sulfide and copper iodide having 0.1-10μm membrane thickness on the surface of the fiber. The compound containing the polyether structure is obtained by reacting a compound obtained by reacting an alkyleneoxide adduct polyetherpolyol with a polyvalent isocyanate compound and blocking the unreacted isocyanate groups with a compound obtained by reacting a polyetherpolyol with an epihalohydrin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an excellent conductive fiber which can be widely used in the field of clothing such as sweaters.

[0002]

2. Description of the Related Art Generally, synthetic fibers are electrically insulating, and static electricity generated by contact or friction does not easily leak. As a result, various problems such as (1) clinging to clothes, (2) adhesion of dirt, (3) flammable gas caused by static electricity charged on clothes, ignition of dust, explosion, and (4) malfunction of electronic devices cause. Especially, with the spread of electronic devices such as personal computers, the obstacle (4) has been highlighted in recent years. As a technology to impart antistatic property to spun yarn,
By mixing conductive fine particles such as carbon black or metal (compound) into the spinning dope, and blending a small amount of the spun fiber with ordinary fiber, good antistatic property can be imparted, and further, the dyeing property, the texture, etc. Since it does not impair the original characteristics of processed textile products, it is beginning to be used in the market.

However, when electrically conductive fibers are mixed, the frictional electrification voltage shows a low value due to the neutralization of electric charges by corona discharge with a small amount of mixing, but the leakage of electric charges is less likely to occur due to a small amount of mixing, and the charge half-life is reduced. Has a disadvantage of being longer than 120 seconds. In addition, the conductive fibers obtained by composite spinning of these conductive fine particles are generally expensive, and the manufacturing cost is significantly higher than the cost of ordinary spun yarns, limiting the fields of application. is the current situation.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and to provide an inexpensive conductive fiber having a short charge half-life and a low friction electrification voltage.

[0005]

The present invention has a conductivity of 10%.
^The above problem is solved by a conductive fiber in which a compound containing a polyether is present in an amount of 1 to 20% by weight on the surface of the conductive fiber of ^-6 S / cm or more.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of earnestly analyzing the mechanism of manifestation of antistatic property when a conductive fiber is mixed with a normal fiber, the present inventors have conventionally conducted antistatic treatment to shorten the charge half-life. Dozens of fibers or fibers mixed with antistatic agents
% It was necessary to mix it with ordinary fibers, but it was found that by giving ionic conductivity to the surface of the conductive fibers, conductive fibers having a short charge half-life can be obtained during mixing.

At present, it is not clear about this mechanism, but generally, the mechanism of manifesting antistatic property in the conductive fiber mixture is presumed as follows. That is, the lines of electric force are collected from the charged object charged by friction to the conductive fibers and an unequal strong electric field is formed in the vicinity thereof. For this reason, ion pairs of air are generated in the vicinity of them, so-called corona discharge occurs, and ions of the opposite polarity to the charged object move to the charged object, and ions of the same polarity diffuse to the air or move to the grounded body. . As a result, the static electricity of the charged object is neutralized. As a result, the conductive fiber causes a self-discharge by the electric field formed by the charged body itself to eliminate the electric charge (Static Handbook, First Edition, P816, The Institute of Static Electricity, Ohmsha).
When neutralizing by ion pairs generated by corona discharge, the line of electric force weakens from the charged object and the corona discharge does not occur in the static elimination by the conductive fiber.Therefore, the decay of the charge is hardly observed and the charge half-life is shortened. It will be longer (published by Ohmsha, Electrostatics Handbook, 1st edition, P815, Japan Electrostatic Society).

However, when an ion conductive substance of a compound containing a polyether structure is attached to the surface of the conductive fiber,
Surprisingly, the decay of charge after corona discharge was observed. The mechanism of this phenomenon is not clear at present, but it is estimated as follows. That is, of the ion pairs generated in the vicinity of the conductive fibers, the ions having the same polarity as the charged object diffuse into the air or recharge the fiber surface near the conductive fibers. In the case of ordinary core-sheath type conductive fibers, the surface of the conductive fibers near the conductive fibers is recharged. It remains in the fiber. Also,
In the case of a conductive fiber having a metal or a metal compound attached to its surface, the charge recharged to the conductive fiber itself leaks, but the charge recharged to the fiber near the conductive fiber remains. However, due to the action of the ion conductive substance of the compound containing the polyether structure on the surface of the conductive fiber, not only the electric charge recharged on the conductive fiber itself but also the bleed-out of the ion conductive substance adheres to the fiber near the conductive fiber. It is presumed that the charge half-life is shortened because the effect of the effect is that the fibers near the conductive fibers also rapidly leak the charge.

As the polymer constituting the conductive fiber used in the present invention, a heat-meltable polymer typified by polyester, nylon, polyethylene, polypropylene, etc., a solvent typified by polyacrylonitrile, rayon, polyurethane, etc. Soluble polymer or natural fiber,
Ceramic fibers or the like can be used. Further, other polymers, compounds, additives and the like may be used depending on the case in order to improve spinnability, conductivity, and other functionalities.

As the conductive fiber, a fiber having a metal or metal compound present on the fiber surface in a film thickness of 0.01 to 10 μm is preferably used, and as the metal and the metal compound, gold,
Examples thereof include metals represented by silver, copper, palladium, aluminum, iron, nickel and the like, and oxides, sulfides and carbonyl salts thereof, but copper sulfide and copper iodide are particularly preferable. The above metals may be used alone or in combination of two or more.

Examples of the method for forming a metal or metal compound coating on the fiber surface include a vacuum deposition method, a sputtering method, an ion plating method, a plating method and a chemical fixing method. In addition, after forming a coating for protecting the coating of a metal or a metal compound, a polyamide-based, polyester-based, polyolefin-based, polyether-based, acrylonitrile-based, phenol-based, urethane-based, or epoxy-based polymer may be coated. It is possible.

As another conductive fiber, the ratio of the core portion and the sheath portion is the core portion / the sheath portion = 5/95% to 60/40%, preferably 10/90% to 50/50%. Has a specific resistance of 1
A conductive core-sheath composite fiber made of a polymer containing 15 to 70% by volume of conductive fine particles having a density of 0 ^-3 S / cm or more is also suitably used. When the proportion of the core portion is less than 5%, the conductive performance is not sufficient even if the conditions described later are satisfied, and when it exceeds 60%, the conductivity is saturated and at the same time, the present invention. The economic merit, which is one of the purposes, will not be obtained.

Examples of the polymer constituting the core component and the sheath component include a heat-melting polymer represented by polyester, nylon, polyethylene, polypropylene and the like, and a solvent-soluble polymer represented by acrylic, rayon, polyurethane and the like. However, an acrylonitrile polymer is preferably used.

The acrylonitrile-based polymer may be an acrylonitrile-based polymer which is usually used in the production of acrylic fibers, but the monomer composition must contain at least 50% by weight of acrylonitrile. . Of the monomer composition, the acrylonitrile composition ratio is 50
If it is less than wt%, the resulting fiber does not exhibit the original properties of the acrylic fiber.

Monomers copolymerizable with acrylonitrile include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid 2
-Ethylhexyl, 2-hydroxyethyl acrylate,
Acrylic esters typified by hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, methacrylic acid Methacrylic acid esters represented by cyclohexyl, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and further acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, styrene, vinyl Examples thereof include toluene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride and vinylidene fluoride.

Further, p-sulfophenyl methallyl ether, methallyl sulfonic acid, acrylonitrile polymer,
Copolymerization of allyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and alkali salts thereof is preferable for improving dyeability.

The molecular weight of the acrylonitrile polymer is not particularly limited, but a molecular weight of 100,000 or more and 1,000,000 or less is desirable. If the molecular weight is less than 100,000, the spinnability tends to decrease, and at the same time, the yarn quality of the raw yarn tends to deteriorate. Molecular weight 10
If it exceeds 0,000, the concentration of the polymer giving the optimum viscosity of the spinning dope will be low, and the productivity will tend to be low.

Examples of the solvent for the acrylonitrile polymer include nitric acid (aqueous solution), zinc chloride aqueous solution, rhodan salt aqueous solution, dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate, γ-butyrolactone and acetone.

In the conductive core-sheath composite fiber, the amount of conductive fine particles contained in the core component is 15 to 70% by volume with respect to the core portion. When the content is less than the above range, the electroconductivity is insufficient, and when the content exceeds the above range, the electroconductivity is saturated, and at the same time, the economic merit, which is one of the objects of the present invention, cannot be obtained.

The conductive fine particles have a powdery conductivity of 10 ^−3.
S / cm or more is required. If the conductivity is less than 10 ⁻³ S / cm, the conductivity performance will be insufficient. As the conductive material, metals typified by iron, copper, aluminum, lead, tin, gold, silver, nickel and their oxides, sulfides, carbonyl salts, ITO (indium tin oxide), ATO Conductive metal oxides such as (antimony / tin oxide) and zinc oxide, and non-metal conductive materials obtained by coating these with carrier fine particles of barium sulfate, titanium oxide, potassium titanate, and aluminum, furnace black,
Carbon black type conductive materials typified by channel black, thermal black, acetylene black, and conductive polymer compounds typified by polyacetylene, polypyrrole, polyaniline, tetracyanoparaquinodimethane (TCNQ) and tetrathiafulvalene (TTF). And an organic conductive compound represented by a complex or the like.

The particle size of the conductive fine particles is determined by the filtration step of the stock solution,
From the viewpoint of stability in the spinning process, the average particle size is preferably 3 μm or less.

The ratio of the core portion to the sheath portion is the core portion / sheath portion = 5/95.
% To 60/40%, more preferably 10/90% to 50/50%. When the proportion of the core portion is less than 5%, the conductive performance is not sufficient even if the conditions described later are satisfied. On the other hand, if it exceeds 60%, a complete core-sheath structure cannot be obtained and the core portion is exposed to the fiber surface in many portions, which is not preferable.

The conductivity of the conductive fiber used in the present invention must be 10 ^-6 S / cm or more. If the conductivity of the conductive fiber is less than 10 ^-6 S / cm, no concentration is observed from the charged object charged by friction to the conductive fiber of the line of electric force, and the unequal strong electric field required for corona discharge is present in the vicinity. Cannot be formed. Therefore, it becomes difficult to realize the antistatic property of the spun yarn.

As the compound having a polyether structure used in the present invention, a compound (C) obtained by reacting the following compound (A) and compound (B) is preferably used. Compound (A): a polyether polyol compound obtained by adding an alkylene oxide to a compound having two or more active hydrogens in a molecule is reacted with a polyvalent isocyanate compound to obtain a compound having an unreacted isocyanate group, A compound obtained by blocking unreacted isocyanate groups of a compound with an acidic sulfite. Compound (B): Active hydrogen obtained by reacting the same polyether polyol compound used to produce compound (A) with epihalohydrin and then with a polyalkylenepolyamine, and having an amine bond in the molecule. Compound (C) obtained by reacting a reaction product having at least two of the above with epihalohydrin in the presence of water.

The compound (A) is obtained by reacting a compound obtained by reacting a polyether polyol compound with a polyvalent isocyanate compound with an acidic sulfite to block unreacted isocyanate groups. That is, when the compound (A) reacts the polyether polyol compound with the polyvalent isocyanate compound, at least one isocyanate group of the polyvalent isocyanate compound is reacted with the polyether polyol compound, and the other at least one isocyanate group is reacted. It is obtained by subjecting a compound having a chemical structure in which a group remains unreacted to an acidic sulfite reaction.

The term "blocking" used herein means to react an unreacted isocyanate group with an acidic sulfite to temporarily block the isocyanate group so that the isocyanate group does not react with active hydrogen. The compounds (A) and (B) In the reaction (1), the blocking acidic sulfite is released and the reaction proceeds to obtain the compound (C).

The compound having an unreacted isocyanate group is a polyether polyol compound and a polyvalent isocyanate compound in the presence or absence of a solvent in the range of 80 to 130.
It is obtained by reacting at a temperature of preferably 100 to 110 ° C. for 1 to 5 hours, and optionally removing the solvent. For the reaction between the polyether polyol compound and the polyvalent isocyanate compound, it is preferable to react 1.5 to 6 moles of the polyvalent isocyanate compound with respect to 1 mole of the polyether polyol compound, and the reaction mole number of the polyvalent isocyanate compound is 1. If it is less than 5 mol, the viscosity of the product increases and it becomes difficult to handle. On the other hand, if the amount exceeds 6 mol, a large amount of polyvalent isocyanate compound remains unreacted, which discolors the fiber and reduces the dyeing fastness. The blocking reaction of the compound having an unreacted isocyanate group is carried out by adding 1 to 1.5 molar amount of acid sulfite to 1 molar equivalent of the remaining unreacted isocyanate group and heating at 30 to 50 ° C. for 1 to 3 hours. Then do. 20 to 5 for acid sulfite in blocking
It is preferably used as a 0% by weight aqueous solution, whereby the compound (A) can be obtained as an aqueous solution.

As the polyether ester compound used for the compound (A), polyhydric alcohol, bisphenol,
Examples of the polyalkylene polyamide, sorbitan alkyl monoester, sorbitan alkyl diester, castor oil, hydrogenated castor oil, and the like, include compounds obtained by adding an alkylene oxide to a compound having two or more active hydrogens. The above compound having two or more active hydrogens, in the presence or absence of a catalyst, 150 to
It is obtained by addition-polymerizing an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide or the like at 190 ° C., or by randomly or block-adding two or more kinds of alkylene oxides. The addition mole number of alkylene oxide is 20 to
200 mol is preferred. Among the compounds that add alkylene oxide, polyhydric alcohols include ethylene glycol, polyethylene glycol, butanediol, propylene glycol, polypropylene glycol, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, and bisphenol. Examples of the polyalkylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetraamine, terotaethylenepentamine, polyethyleneimine and the like. Examples of the sorbitan alkyl ester include monoesters or diesters of sorbitan and fatty acids, and fatty acids constituting the ester include lauric acid, oleic acid, stearic acid, palmitic acid, myristic acid, coconut oil fatty acid, and beef tallow fatty acid. Etc.

Examples of the polyvalent isocyanate compound used for producing the compound (A) include methylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate. Examples thereof include isocyanate, nitrodiphenyl diisocyanate, diphenylmethane sulfone diisocyanate, nitrodiphenyl methane diisocyanate, diphenyl sulfone diisocyanate, full orange isocyanate, chrysene diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, dimethoxy biphenyl diisocyanate and triphenylmethane triisocyanate.

Examples of the acidic sulfite used for producing the compound (A) include acidic sodium sulfite and acidic potassium sulfite.

The compound (B) is obtained by reacting a polyether polyol compound with epihalohydrin and then with a polyalkylene polyamine (hereinafter referred to as [reaction product (b)]) in the presence of water. The reaction product (b) obtained as an intermediate raw material, which is obtained by reacting epihalohydrin below, is a reaction product having a chemical structure in which a polyether polyol compound and a polyalkylene polyamine are crosslinked with epihalohydrin. That is, the reaction product (b) is an addition reaction of one mole of epihalohydrin to each of the OH groups with respect to two or more hydroxyl groups (hereinafter referred to as [OH group]) of one molecule of the polyether polyol compound. Then, 1 mol of each of the halohydrin groups formed in the molecule of the addition reaction product is reacted with 1 mol of a polyalkylene polyamine, and then the reaction product (b) is reacted with active hydrogen bonded to nitrogen in the molecule. The reaction product (b) is obtained by adding and reacting with epihalohydrin in a molar number corresponding to.

The compound (B) can be produced, for example, as follows. First, 2 to 7 mol of epihalohydrin was added to 1 mol of the polyether polyol compound,
The reaction is carried out at -80 ° C for 1 to 2 hours to obtain an epihalohydrin adduct of a polyether polyol compound, and 2 to 7 mol of polyalkylene polyamine is further added to 120 to 1
By reacting at 30 ° C. for 3 to 5 hours, a compound in a form in which a polyether polyol compound and a polyalkylene polyamine are crosslinked with epihalohydrin is obtained. The reaction amount of the polyalkylene polyamine is preferably 2 to 7 mol, and if it is less than 2 mol, the viscosity of the reaction product (b) increases and it becomes difficult to handle, and if it exceeds 7 mol, the polyalkylene polyamine becomes excessive and unreacted. It remains as it is and causes coloring.

The relationship between the reaction molar ratio of epihalohydrin and polyalkylene polyamine to the polyether polyol compound is O in the polyether polyol compound molecule.
It depends on the number of H groups. That is, when the number of OH groups is 2, it is preferable to react 2 to 2.5 mol of epichlorohydrin with 1 mol of the polyether polyol compound, and then react 2 to 2.5 mol of polyalkylene polyamine. Further, when the number of OH groups is 32, it is preferable to react the polyether polyol compound epihalohydrin and the polyalkylene polyamine at a molar ratio of 1: 3 to 3.5: 3.5, respectively. When the number of O groups is 1: 4 to 4.5: 4 to 4.5, when the number of O groups is 5, each is from 1: 5 to 5.5: 5 to 5.5, and when the number of OH groups is 6, It is preferable to react at a molar ratio of 1: 6 to 6.5: 6 to 6.5.

Next, the reaction product (b) obtained above
To 50 to 60 by adding epihalohydrin in the presence of water.
The reaction is carried out at 0 ° C. for 5 to 10 hours to obtain an aqueous solution of the compound (B), and the addition amount of epihalohydrin to the reaction product (b) is preferably 2 to 20 mol per 1 mol of the reaction product (b).

Since the above reaction is fast and easily gels,
It is preferable to carry out in the presence of water, and the amount of water added is preferably such that the concentration of the compound (B) becomes 20 to 50% by weight.
As the polyether polyol compound and the polyalkylene polyamine used for producing the compound (B), the same polyether polyol compound and polyalkylene polyamine as those used for producing the compound (A) can be used, and epichlorohydrin is used as the epihalohydrin. ,
Epibrom hydrin etc. are mentioned.

The compound (A) and the compound (B) obtained as described above are added to an aqueous solution containing 1 mol of the compound (A), and an aqueous solution containing 1 to 4 mol of the compound (B) is added.
Reaction is carried out at 0-60 ° C for 5-10 hours to give compound (C)
To obtain an aqueous solution of. Compound (C) thus obtained
Aqueous solution as it is or if necessary, water, p
An H-preparing agent, a softening agent, a water repellent, a hard finishing agent, and a leveling agent are added and used as a treating agent.

The compound having a polyether structure used in the present invention needs to be attached to the conductive fibers in an amount of 1 to 20% by weight. If it is less than 1% by weight with respect to the conductive fiber, sufficient antistatic property cannot be obtained, and if it exceeds 20% by weight, problems such as deterioration of dyeability, deterioration of dyeing fastness, and texture hardening become remarkable. .

In order to obtain an antistatic spun yarn using the conductive fiber of the present invention, it is necessary to mix the conductive fiber in an amount of 0.1 to 10% by weight. If the mixing ratio is less than 0.1% by weight, sufficient antistatic property cannot be obtained. If the mixing ratio exceeds 10% by weight, the antistatic effect is saturated and at the same time, no economic merit is obtained.

[0039]

The present invention will be described more specifically with reference to the following examples. The conductivity of the fiber, the core / sheath ratio, the coating thickness of the metal and the metal compound, and the antistatic performance were evaluated by the following methods.

[Conductivity of Fiber] A single fiber was taken out from the fiber bundle, cut into exactly 1 cm, and the end portion was bonded to a metal terminal with silver paste (Dotite manufactured by Fujikura Kasei Co., Ltd.). A DC voltage of 1000 V was applied between the terminals at 20 ° C. and a relative humidity of 40 RH%, and the resistance value R (Ω) between the terminals was measured by a super insulation meter (SM-8210 Toa Denpa Kogyo Co., Ltd.). From this, the conductivity σ (S / c
m) was calculated by the following equation. σ = 1 / (1.11 × 10 ⁻⁶ × R × (d / ρ)) where d is the fineness and ρ is the specific gravity of the fiber.

[Core / sheath ratio, coating thickness of metal and metal compound] The cross section of 10 fibers was measured from a transmission electron micrograph and determined as an average value.

[Evaluation of Antistatic Performance] The conductive fiber obtained was spun into a knitted fabric having a basis weight of 300 g (10 cm × 20 cm).
After knitting, 100 parts of the knitted fabric was dipped in 5000 parts of a refining liquid (score roll concentration of 1 g / liter aqueous solution), and an oil removing process was performed at 70 ° C. for 20 minutes. Dip in 5000 parts of dyeing solution [BLUE-KGLH (Dye manufactured by Hodogaya Chemical Co., Ltd.) 0.5 part, acetic acid 2 parts, sodium acetate 0.5 part], and take 100 minutes for 30 minutes.
After heating to 100 ° C. and heating at 100 ° C. for 60 minutes, the knitted fabric was taken out and air-dried to obtain a sample for measuring antistatic performance.

In the case of permanent antistatic property evaluation, a fully automatic washing machine for home use was used, and 50000 parts of washing liquid (detergent: aqueous solution of Kao bio-beads concentration of 1 gram / liter) per 100 parts of knitted fabric. And was washed at 40 ° C. The washed knitted fabric was dried at 70 ° C. for 60 minutes and repeatedly washed 10 times to obtain a permanent antistatic evaluation sample.

The obtained evaluation sample was completely dried at 130 ° C. for 60 minutes, cooled in a silica gel-sealed desiccator, and then in a constant temperature and constant humidity atmosphere (temperature 20 ° C., relative humidity 40%).
The humidity was controlled for 24 hours or more. The static halftone meter (made by Shishido trading company) measures the charge half-life, and the Kyoto University chemical research rotary static tester (made by Koa trading company) measures the frictional electrification voltage and the amount of charged electric charge.
-L-1094-1980 (Test method for electrostatic properties of woven and knitted fabrics)
A reference test was performed based on the amount of triboelectric charge, and the antistatic performance was evaluated.

Static Honest Meter Usage conditions Applied voltage 1000 V Application time 30 seconds Sample rotation speed 1000 rpm Rotary static tester Usage conditions Drum rotation speed 400 rpm Friction time 60 seconds Friction cloth Cotton Measurement conditions of charged amount of friction Friction cloth 10 times Friction cloth Nylon, Acrylic knit, etc. Antistatic agent (compound (C)) processing conditions Bath ratio by immersion method 1:30 Processing conditions 60 ° C × 20 minutes Squeezing rate 30% Drying 95 ° C × 30 minutes

(Examples 1, 2, 3 Comparative Examples 1, 2, 3)
The average molecular weight obtained by adding ethylene oxide to polypropylene glycol having an average molecular weight of 2000 is 30.
23 parts of hexamethylene diisocyanate was added to 200 parts of the polyether polyol compound of 00, and the reaction was carried out at 100 to 110 ° C. for 1 hour under a nitrogen stream to obtain a product containing 2.3% of free isocyanate groups. . To the total amount of this product, 65 parts of a 20% aqueous sodium sulfite solution was added, reacted at room temperature for 1 hour, and 944 parts of water was further added.
A transparent aqueous solution of compound (A) was obtained.

Next, to 200 parts of the same polyether polyol compound as used above, 0.4 part of boron trifluoride etherate was added, and 12.3 parts of epichlorohydrin were gradually added while maintaining at 70 to 80 ° C., and added. After 90-1
React at 00 ° C for 1 hour, then diethylenetriamine 1
3.9 parts was added and the reaction was performed at 120 to 130 ° C. for 3 hours to obtain a reaction product (b). 30 parts of water and epichlorohydrin 12.3 were added to the total amount of the obtained reaction product (b).
Parts, and reacted at 50-60 ° C. for 3 hours, and then water 95
4 parts were added to obtain a reddish brown transparent aqueous solution of the compound (B).

50 parts of the compound (A) and 50 parts of the compound (B) obtained above were mixed and reacted at 50 to 60 ° C. for 5 hours to prepare an aqueous solution of the urethane compound (C) (concentration: 20%, 25%).
A viscosity of 330 CPS at pH C, pH 6.3) was obtained.

Conductivity 10 S / cm, copper sulfide film thickness 0.
Conductivity of 15 μm, 2d × 51 mm acrylic conductive fibers (manufactured by Japan Silkworm Co., Ltd .: trade name Thunderon) using an aqueous solution of the compound (C) containing a polyether structure as described above while changing the adhesion amount. Fiber is normal acrylic fiber 2
The mixing ratio with d × 51 mm was variously changed to form a spun yarn of 1/52 meter count, and a flat knitted fabric was knitted with two 18 gauges to evaluate the antistatic performance. The results are shown in Table 1.

[0050]

[Table 1]

Examples 5, 6, 7 and Comparative Example 4 Acrylonitrile polymer (molecular weight: 93.5% by weight of acrylonitrile, 6.0% by weight of methyl acrylate, 0.5% by weight of sodium methallylsulfonate) 160,000) was dissolved in dimethylformamide to obtain a spinning dope (E) having a polymer concentration of 30% by weight. Furthermore, spinning is performed by variously changing the addition amount of granular conductive titanium oxide (ET-500W manufactured by Ishihara Sangyo Co., Ltd.) having a particle size of 0.2 to 0.3 μ, a powder conductivity of 2 to 5 S / cm, and a specific gravity of 4.6. Stock solution 100 having the same composition as stock solution (E)
The solution was dispersed in parts by weight to prepare a spinning dope (F). (F) was used as the spinning dope for forming the core and (E) as the spinning dope for forming the sheath.

After heating the spinning dope separately to 130 ° C.,
It was discharged into an inert gas at 230 ° C. using a core-sheath spinneret having 400 holes and a hole diameter of 0.2 mmφ. The discharge ratio of the spinning dope was variously changed so that the volume ratios of the core part and the sheath part of the unstretched yarn were respectively predetermined ratios. The obtained undrawn yarn was continuously drawn 3.75 times in hot water at 100 ° C.
It was washed in hot water at 5 ° C. The obtained fiber bundle was dried under a relative tension of 40% and a temperature of 150 ° C. under a non-tensioned state, subjected to a relaxation treatment, and contracted by 20% to obtain a conductive fiber (D). The fineness of the obtained conductive fiber (D) was 3 denier. This conductive fiber (D) was cut into 51 mm, and then the conductive fiber treated with the above-mentioned aqueous solution of the compound (C) containing a polyether structure at an adhesion amount of 5% by weight was used as a normal acrylic fiber 2d × The mixing ratio with 51 mm was variously changed to form a spun yarn of 1/52 meter count, and a flat knitted fabric was knitted with two 18 gauge yarns to evaluate the antistatic performance. Table 2 shows the results.
It was shown to.

[0053]

[Table 2]

(Examples 8, 9, 10, 11, 12) Conductive fibers treated with the aqueous solution of the compound (C) containing the polyether structure used in Example 6 at an adhesion amount of 5% by weight ( D) Using 3d × 51 mm and various synthetic fibers (H),
A mixed yarn of 3% by weight was used to form a spun yarn of 1/52 meter count, and a flat knitted fabric was knitted with two 18-gauge yarns, and the antistatic performance was evaluated. Table 3 shows the results. The abbreviations in the table mean the following. [Note] PP polypropylene fiber PET polyester fiber AN acrylic fiber R rayon fiber W wool

[0055]

[Table 3]

[0056]

According to the present invention, an excellent conductive fiber having a short charge half-life and a low friction electrification voltage can be provided at a low cost.

Claims (6)

[Claims] 1. A compound containing a polyether is contained in an amount of 1 to 20 on the surface of a conductive fiber having an electric conductivity of 10 ⁻⁶ S / cm or more.
Conductive fiber present by weight%. 2. The conductive fiber having an electric conductivity of 10 ⁻⁶ S / cm or more has a metal or metal compound content of 0.01 to 5 on the fiber surface.
The conductive fiber according to claim 1, which is a fiber having a film thickness of 10 μm. 3. The conductive fiber having an electric conductivity of 10 ⁻⁶ S / cm or more has a cross-sectional ratio of the core part and the sheath part of the core part / sheath part = 5/9.
5 to 60/40, and the core has a specific resistance of 10 ^-3 S / cm
The conductive fiber according to claim 1, which is a core-sheath composite fiber made of a polymer containing 15 to 70% by volume of the above conductive fine particles. 4. The conductive fiber according to claim 2, wherein the metal compound is copper sulfide or copper iodide. 5. The conductive fiber according to claim 3, wherein the polymer constituting both the core-sheath component is an acrylonitrile polymer. 6. The conductive fiber according to claim 1, wherein the compound having a polyether structure is a compound (C) obtained by reacting the following compound (A) and compound (B). Compound (A): a polyether polyol compound obtained by adding an alkylene oxide to a compound having two or more active hydrogens in a molecule is reacted with a polyvalent isocyanate compound to obtain a compound having an unreacted isocyanate group, A compound obtained by blocking unreacted isocyanate groups of a compound with an acidic sulfite. Compound (B): Active hydrogen obtained by reacting the same polyether polyol compound used to produce compound (A) with epihalohydrin and then with a polyalkylenepolyamine, and having an amine bond in the molecule. A compound obtained by reacting a reaction product having at least two of the above with epihalohydrin in the presence of water.