JPH0978354A - Electroconductive acrylic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electroconductive acrylic fiber having excellent electroconductivity and electric charge half-life and excellent also in whiteness and process passing. SOLUTION: This fiber is a core-sheath conjugate fiber having a cross-sectional area ratio of the core part to the sheath part of 5/95-80/20. The core part is composed of an acrylonitrile polymer containing 15-70vol.% of electroconductive fine particles having a specific resistance of >=10<-3> S/cm, and the sheath part is composed of a mixture of an acrylonitrile polymer and a compound containing a polyether structure, whose weight ratio is 95/5 to 70/30. Further, the content of the compound, containing a polyether structure, in the total of the electroconductive acrylic fiber is >=1wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive acrylic fiber having excellent conductivity, whiteness and yarn strength, 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. In particular, acrylic fibers have a drawback that they are more likely to be charged with static electricity than other fibers, and are likely to cause the above-mentioned various problems. Therefore, acrylic fibers are required to have particularly high antistatic properties.

As a technique for imparting conductivity to acrylic fibers, fibers obtained by mixing carbon black in a spinning dope and spinning the fibers have been proposed, but for clothing applications where hue and whiteness and color development are required. Is difficult to adapt.

Further, as a method for improving these hues to a white color, there is a method using a metal oxide typified by tin oxide, and an example of application to acrylic fibers is JP-A-59-2.
No. 23309, Japanese Patent Laid-Open No. 57-39213 and the like. In the technology disclosed in JP-A-59-223309, in which an acrylonitrile polymer solution and an elastic polymer solution in which conductive fine particles are dispersed are mixed and spun, the conductive fine particles phase-separated from the acrylonitrile polymer are contained. High conductivity can be obtained because the elastic polymer that is exposed to the surface of the fiber, but conductive fine particles adhere to the spinning nozzle in the spinning process, resulting in uneven fineness and defective ejection direction of the nozzle, and from spinning to spinning. In all the processes, there is a problem that peeling of the polymer, abrasion of the guide, and dropping of the conductive fine particles are caused.

Further, it is said that the mechanism of antistatic property when the conductive fiber is mixed is neutralization of electric charge by corona discharge (Electrostatic Handbook, First Edition, P815).
Published by Ohmsha, Japan Electrostatic Society). The friction electrification voltage shows a low value due to the neutralization of the electric charge by corona discharge with a small amount of the mixed cotton, but there is a disadvantage that the leakage of the electric charge is less likely to occur and the charge half-life is longer than 120 seconds due to the small amount of the mixed cotton. As a method of reducing the charge half-life, a method of applying an oil agent having an antistatic ability, and a method of adding an antistatic agent to a spinning dope and mixing the spun cotton are common, but do not mix a large amount. Is not observed, and there is a problem that the original properties of the fiber-processed product such as dyeability and texture are impaired.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a conductive acrylic fiber having excellent conductivity and charge half-life, and having excellent whiteness and process passability. Is an issue.

[0007]

The present invention is a core-sheath composite fiber having a cross-sectional area ratio of the core portion to the sheath portion of 5/95 to 80/20, and the core portion has a specific resistance of 10 ^-3 S / cm or more. Made of an acrylonitrile-based polymer containing 15 to 70% by volume of conductive fine particles, the sheath having a weight ratio of the acrylonitrile-based polymer to the compound containing a polyether structure of 95/5 to 70/3.
This problem is solved by a conductive acrylic fiber which is composed of a mixture of 0 and in which the content of the compound containing a polyether structure in all fibers is 1% by weight or more.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have made a diligent analysis of a mechanism of developing antistatic property when a conductive raw cotton is mixed with a normal raw cotton, and as a result, the core-sheath type conductive fiber has a ionic conductivity in the sheath portion. It was found that the addition of the conductive fiber gives a conductive fiber having a short charge half-life when mixed. At this point,
Although this mechanism is not clear, it is estimated as follows.

That is, in general, the mechanism of manifesting the antistatic property in the conductive fiber mixed cotton is that electric lines of force are collected from the charged object charged by friction to the conductive fiber and an unequal strong electric field is formed in the vicinity thereof. For this reason, an ion pair of air is generated in the vicinity of it, so-called corona discharge occurs, and ions of the opposite polarity to the charged object move to the charged object, ions of the same polarity move to the air or move to the grounded body. To do. As a result, the static electricity of the charged object is neutralized. As a result, it is said that the conductive fiber causes self-discharge by the electric field formed by the charged body itself and eliminates the charge (Static Handbook, First Edition, P816, published by Ohmsha, Ed. Also, in neutralization by ion pairs generated by corona discharge in the static elimination by conductive fiber, the line of electric force from the charged object weakens and the corona discharge does not occur, so that the subsequent decay of the charge is hardly observed, It is said that the half-life will increase (Electrostatic Handbook, First Edition, P815
Published by Ohmsha, Japan Electrostatic Society). However, when the core-sheath type conductive fiber was added with an ion-conductive substance of a compound containing a polyether structure in the sheath portion, it was also observed that the charge was attenuated after corona discharge. In other words, of the ion pairs generated in the vicinity of the conductive fiber, the ions of the same polarity as the charged object have a surface close to that of an insulator in the case of a normal core-sheath conductive fiber, so that they cannot move to the grounding body through it. Almost nothing, and recharged or concentrated near the core-sheath type conductive fiber rather than diffused into the air, and the charge is leaked promptly by the action of the antistatic agent kneaded in the sheath, so the charge is halved. It is estimated that the period will be shortened.

In the present invention, the acrylonitrile-based polymer constituting the core component and the sheath component may be any acrylonitrile-based polymer used in the usual production of acrylic fibers. Further, the acrylonitrile-based polymers constituting the core component and the sheath component may have the same composition or different compositions, but the constitution of the monomer is such that at least 50% by weight of acrylonitrile is contained. is necessary. When the acrylonitrile composition ratio is less than 50% by weight in the monomer composition, the obtained fiber does not exhibit the original characteristics of the acrylic fiber and is not suitable for the purpose of the present invention.

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.

As a method for polymerizing the acrylonitrile copolymer, any polymerization method may be used, and examples thereof include random, block and graft copolymerization methods. The production method may be any method, but examples thereof include bulk, solution, aqueous suspension and emulsion polymerization, and continuous polymerization or batch polymerization may be used.

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.

In the present invention, the degree of polymerization of the acrylonitrile polymer is not particularly limited, but 0.1 g of the polymer is dissolved in 100 ml of dimethylformamide, and the specific viscosity measured at 25 ° C. is in the range of 0.1 to 0.2. Preferably there is.

The conductive fine particles contained in the core component have a powdery specific resistance of 10 ^-3 S / cm or more. Examples of such conductive fine particles include iron, copper, aluminum, lead,
Metals typified by tin, gold, silver, nickel and their oxides, sulfides, carbonyl salts, and conductive materials such as ITO (indium tin oxide), ATO (antimony tin oxide), and zinc oxide. Metal oxides and barium sulphate, tin oxide, zinc oxide and titanium oxide whose surface is coated with tin oxide or zinc oxide are mentioned, and antimony oxide is added to tin oxide as an additive to enhance conductivity. A combination of zinc, aluminum, potassium, indium, germanium, tin, and other metal oxides can be used, and a conductive polymer compound represented by polyacetylene, polypyrrole, polyaniline, or the like, tetracyanoparaquinodimethane (TCNQ) And an organic conductive compound represented by a complex of tetrathiafulvalene (TTF).

The average particle diameter of the conductive fine particles is preferably 3 μm or less from the viewpoint of stability in the filtration and spinning steps of the stock solution, and from the viewpoint of improving conductivity, the aspect ratio is more than that of granular particles. Needles with a large diameter are preferred. The content of the conductive fine particles varies depending on the form and type of the fine particles and the required conductive performance.
~ 70% by volume, 15% for the core in the case of needles
70% by volume. When the content is less than the above range, the electroconductivity is insufficient, and when it exceeds the above range, spinning stability and drawability in the subsequent step are deteriorated and sufficient yarn quality cannot be obtained.

As the sheath component in the present invention, it is necessary to use a mixture of an acrylonitrile polymer and a compound having a polyether structure. Examples of the compound having a polyether structure include polyfunctional polyether ester, polyfunctional polyether, polyfunctional polyether amide, polyfunctional polyether ester amide, random, block and graft of acrylonitrile with a monomer having a polyether structure. Examples thereof include polymers. Any polyfunctional polyether ester may be used, for example, the following formula (1) or formula (2)

[0018]

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[0019]

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Those obtained by polycondensation of the block-type polyether represented by and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid ester are used. The average molecular weight is preferably 5,000 to 100,000, and 10,000 to 5
0000 is more preferable. When the average molecular weight is less than 5,000, the solubility in water is increased, the dye bleaching, etc., and further, it easily comes off during washing, and it is impossible to achieve sufficiently permanent attenuating property, while the average molecular weight is 100,000. Crossing,
When preparing a spinning dope, the solubility in a solvent decreases, which is not preferable.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid and isophthalic acid. Further, examples of the aromatic dicarboxylic acid ester include dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, bis (2-hydroxyethyl) terephthalate, dimethyl isophthalate, diethyl isophthalate, dibutyl isophthalate and the like.

As the monomer containing a polyether structure,
Any type may be used, for example, the following formula (3)

[0023]

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Polyalkylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate and the like represented by are used. These may be used alone or in combination of two or more depending on the purpose.

In the present invention, it is necessary that the content of the compound having a polyether structure in all the fibers is 1% by weight or more. If the content is less than 1% by weight, the ability to leak charges is insufficient.

Further, in order to obtain excellent antistatic performance, it is desirable that the compound containing the polyether structure of the sheath portion is arranged in the acrylonitrile polymer in the fiber direction in the form of streaks.
It is preferable that the high density portion of polyfunctional polyether ester has a diameter of 0.1 to 5 μm and a length of 1 μm or more. When the diameter is less than 0.1 or the length is less than 1 μm, antistatic performance is obtained. Is not sufficient, and if the diameter exceeds 5 μm, the spinnability is remarkably reduced. This streak formation is affected by the miscibility between the type of acrylonitrile polymer and the polyfunctional polyether ester, the compatibility or the mixing method of both components at the time of preparing the dope, further the dope temperature, the nozzle hole diameter, There is no particular limitation as long as the above-mentioned streak arrangement conditions are satisfied.

To prevent oxidative deterioration of the compound containing a polyether structure, a phenol-based, phosphite-based, or thioether-based antioxidant can be added, and a hindered amine-based or benzotriazole-based UV absorber can be added to improve light stability. .

In the conductive acrylic fiber of the present invention, in the fiber cross section, the area ratio of the core part and the sheath part is 5/9.
It is necessary to be 5 to 80/20, and 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, and when it exceeds 80%, a complete core-sheath structure cannot be obtained and the core portion is a fiber. It is not preferable because many parts are exposed on the surface. In the present invention, it is important that the core is not exposed on the fiber surface. When exposed to the fiber surface like a side-by-side type composite fiber, generally in each process from spinning to spinning, although high conductive performance is obtained, abrasion of various guides and fluffing of the fiber, and further, conductive fine particles from the fiber Problems such as falling off occur and it becomes difficult to industrially produce stably.

The conductive acrylic fiber of the present invention can be manufactured, for example, by the following method. First, the spinning dope for forming the core is prepared so that the conductive fine particles are 10 to 30% by weight and the acrylonitrile polymer is 5 to 20% by weight, and the spinning dope for forming the sheath contains a polyether structure. Separately prepared are 1 to 20% by weight of compound and 20 to 40% by weight of acrylonitrile polymer. The solvent used at this time is not particularly limited, but for example, organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and acetone are preferably used.

Further, for the purpose of improving various performances of the final fiber, titanium dioxide or the like is added to a spinning solution for forming a sheath portion for improving whiteness, or phenol-based or phosphite is used for preventing oxidative deterioration of polyfunctional polyether ester. -Based, thioether-based antioxidants, hindered amine-based and benzotriazole-based UV absorbers to improve light stability, and hydrophilic compounds and rubber-like components added to the core to further improve conductivity. You can

The two spinning stock solutions for forming the core portion and the sheath portion are formed into a fiber form by a dry method, a wet method or a dry-wet method using an ordinary core-sheath composite spinneret to obtain an undrawn yarn. The unstretched yarn is stretched 2 to 7 times in hot water at 70 ° C. or higher and desolvated, then dried and relaxed by heat treatment to 5
Shrink more than%. If the temperature of hot water during drawing is less than 70 ° C, a sufficient draw ratio cannot be obtained, and as a result, sufficient yarn quality cannot be obtained. Similarly, if the draw ratio is less than 2 times, sufficient yarn quality cannot be obtained, and if it exceeds 7 times, yarn breakage frequently occurs and the core portion is cut off, which lowers the conductive performance, which is not preferable. The above-mentioned drying and relaxation heat treatment can be carried out individually or in combination with drying by a heat roll or a net process and relaxation methods such as annealing, hot plate relaxation and steam relaxation, which have been conventionally used for producing acrylic fibers. The shrinkage ratio in the relaxation heat treatment is 5% or more, preferably 10% or more in order to secure good dyeability or yarn quality required for spinning and knitting.

[0032]

The present invention will be described more specifically with reference to the following examples. In the examples, the measurement of the electrical conductivity of the fiber and the evaluation of the antistatic performance were performed by the following methods.

(Measurement of Conductivity of Fiber) Single fibers were taken out from the fiber bundle, accurately separated by 1 cm, and bonded to a metal terminal with silver paste (Dotite manufactured by Fujikura Kasei Co., Ltd.). At a temperature of 20 ° C and a relative humidity of 40RH%, a DC voltage of 1000V is applied between these terminals, and the resistance value R between the terminals is R.
(Ω) was measured with a super insulation meter (SM-8210 Toa Denpa Kogyo Co., Ltd.). From this conductivity σ (S / cm)
Was calculated by the following formula. σ = 1 / (1.11 × 10 ⁻⁶ × R × (d / ρ) ^1/2 ), where d is the fineness, and ρ is the specific gravity of the fiber.

(Evaluation of Antistatic Performance) A conductive yarn and ordinary acrylic fiber were formed into a spun yarn of 1/52 meter count at a predetermined mixing ratio, and a 18-gauge double-knitted fabric was used to knit a plain knitted fabric.
Soak 100 parts of the knitted fabric in 5000 parts of a scouring solution (aqueous solution having a score roll concentration of 1 g / l), and
The oil was removed for 20 minutes at 0 ° C, and then the knitted fabric 10
To 0 part, 0.5 part of dyeing solution [BLUE-KGLH (Dye manufactured by Hodogaya Chemical Co., Ltd.), 2 parts of acetic acid, 0.5 parts of sodium acetate.
Part] It was immersed in 5000 parts, heated to 100 ° C. for 30 minutes, heated at 100 ° C. for 60 minutes, taken out of the knitted fabric, and air-dried to obtain an antistatic sample.

In the case of the evaluation of permanent antistatic property, 50,000 parts of washing liquid (detergent: aqueous solution of bio-beads manufactured by Kao Co., Ltd., 1 g / l) was used for 100 parts of the knitted fabric using a household automatic washing machine. 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 an antistatic evaluation sample. The obtained evaluation sample was cooled in a desiccator filled with silica gel,
2 in a constant temperature and humidity atmosphere (temperature 20 ° C, relative humidity 40%)
Humidified for 4 hours. The charge half-life measurement using a static Honest meter (manufactured by Shishido Trading Co., Ltd.), the friction electrification voltage measurement using the Kyoto University Chemical Research Institute Rotary Static Tester (manufactured by Koa Trading Co., Ltd.), and the measurement of the amount of electrified charge are JIS-
The antistatic performance was evaluated based on L-1094-1980 (reference test method for charging property of woven and knitted materials).

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 electrostatic charge amount Friction cloth 10 times Friction cloth Nylon, Acrylic knit fabric

Comparative Example 1 Acrylonitrile polymer (specific viscosity 0.16) consisting of 93.5% by weight of acrylonitrile, 6.0% by weight of methyl acrylate and 0.5% by weight of sodium methallyl sulfonate was added to dimethylformamide. To obtain a spinning dope (A) having a polymer concentration of 30% by weight.
Further, the particle size is 0.2 to 0.3 μm, and the powder resistance value is 2 to 5 S /
cm granular conductive titanium oxide (ET manufactured by Ishihara Sangyo Co., Ltd.
(500 W) 15 parts by weight was dispersed in 100 parts by weight of a spinning dope having the same composition as the spinning dope (A) to prepare a spinning dope (B). In addition, 1 part by weight of a polyfunctional polyether ester (in formula 1, a block-type polyether ester of m = n = 73 and dimethyl terephthalate are condensed, having an average molecular weight of 25,000) has the same composition as the spinning solution (A). A spinning dope (K) was prepared by dispersing in 100 parts by weight of the spinning dope. (B) was used as the spinning dope for forming the core, and (K) was used 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 for forming the core and the sheath was 50/50 (volume ratio). The undrawn yarn thus obtained was subsequently drawn 3.75 times in hot water of 100 ° C. and further washed in hot water of 95 ° C. The obtained fiber bundle had a relative humidity of 4 under no tension.
It was dried at 0% and a temperature of 150 ° C., subjected to a relaxation treatment, and shrank by 20%. The fineness of the obtained fiber was 3 denier, and the conductivity and charge half-life of the fiber were evaluated and are shown in Table 1.

(Examples 1, 2 and 3) 90 parts by weight of granular conductive titanium oxide (ET-500W manufactured by Ishihara Sangyo Co., Ltd.) was dispersed in 100 parts by weight of a spinning dope having the same composition as the spinning dope (A) and spun. Stock solution (C) was prepared. Further, 4 parts by weight of the same polyfunctional polyether ester used in Comparative Example 1 was dispersed in 100 parts by weight of a spinning dope having the same composition as the spinning dope (A) to prepare a spinning dope (L). The spinning dope (C) is used as the spinning dope for forming the core part, the spinning dope (L) is used as the spinning dope for forming the sheath part, and the discharge ratio (volume ratio) of the spinning dope for the core and the sheath is 10/90, 25/75, 50/5
A fiber having a fineness of 3 denier was obtained in the same manner as in Comparative Example 1 except that 0 was used. The conductivity and charge half-life of the resulting fiber were evaluated and are shown in Table 1.

[0040]

[Table 1]

(Comparative Example 2) Long axis 2.
A spinning stock solution (D) was prepared by dispersing 18 parts by weight of needle-shaped conductive titanium oxide (FT-2000 manufactured by Ishihara Sangyo Co., Ltd.) having 9 μ and an aspect ratio of 13 in 100 parts by weight of a spinning stock solution having the same composition as the spinning stock solution (A). Prepared. A fiber having a fineness of 3 denier was obtained in the same manner as in Comparative Example 1 except that the spinning dope (D) was used instead of the spinning dope (B) as the spinning dope for forming the core. The conductivity and charge half-life of the resulting fiber were evaluated and are shown in Table 2.

(Examples 4, 5 and 6) As conductive fine particles, 30 parts by weight of needle-shaped conductive titanium oxide (FT-2000 manufactured by Ishihara Sangyo Co., Ltd.) having a major axis of 2.9 μm and an aspect ratio of 13 was used as a spinning stock solution (A). A spinning dope (E) was prepared by dispersing 100 parts by weight of the spinning dope having the same composition as the above). Spinning stock solutions (E) and (L) are used in place of the spinning stock solutions (B) and (K) instead of the spinning stock solutions that form the core and the sheath, and the spinning stock solutions of the core and the sheath are discharged (volume ratio). Was changed to 5/95, 25/75, and 50/50, and fibers having a fineness of 3 denier were obtained in the same manner as in Comparative Example 1. The conductivity and charge half-life of the resulting fiber were evaluated and are shown in Table 2.

[0043]

[Table 2]

Example 7 An acrylonitrile polymer (specific viscosity 0.16) consisting of 93% by weight of acrylonitrile, 6.5% by weight of vinyl acetate and 0.5% by weight of sodium methallylsulfonate was dissolved in dimethylacetamide. A spinning dope (F) having a polymer concentration of 25% by weight was obtained. Furthermore, granular conductive titanium oxide having a particle diameter of 0.2 to 0.3 μ and a powder resistance value of 2 to 5 Ω · cm (ET-500 manufactured by Ishihara Sangyo Co., Ltd.
A spinning stock solution (G) was prepared by dispersing 75 parts by weight of W) in 100 parts by weight of the spinning stock solution (F). Further, 3 parts by weight of the same polyfunctional polyether ester used in Comparative Example 1 was dispersed in 100 parts by weight of a spinning dope having the same composition as the spinning dope (F) to prepare a spinning dope (M).

An eccentric type core having a hole diameter of 0.15 mm and 60 holes using the spinning dope (G) as the spinning dope for forming the core part and the spinning dope (M) as the spinning dope for forming the sheath part. Approximately 7m from the sheath spinneret once discharged into the air
After traveling in the m space, it was introduced into a 70% by weight dimethylacetamide aqueous solution coagulating bath at 35 ° C. to coagulate. The coagulated yarn is taken from this coagulation bath at a speed of 60 m / min, and 6
Washed in 0 ° C hot water, stretched 3 times in 95 ° C hot water, applied an oil agent, dried on a 140 ° C heating roll, and relaxed 10% by using a 260 ° C hot plate, 180 denier / 60 filaments An acrylic filament having a round cross section was obtained. The conductivity and charge half-life of the resulting fibers were evaluated and are shown in Table 3.

Example 8 An acrylonitrile polymer (specific viscosity 0.16) consisting of 96% by weight of acrylonitrile and 4% by weight of vinyl acetate was dissolved in dimethylacetamide to prepare a spinning solution (H) having a polymer concentration of 25% by weight. ) Got.
Furthermore, particle size 0.2-0.3μ, powder resistance value 2-5Ω · c
m conductive granular titanium oxide (ET-made by Ishihara Sangyo Co., Ltd.
A spinning stock solution (I) was prepared by dispersing 75 parts by weight of 500 W) in 100 parts by weight of the spinning stock solution (H). Further, 3 parts by weight of the same polyfunctional polyether ester used in Comparative Example 1 was dispersed in 100 parts by weight of a spinning dope having the same composition as the spinning dope (H) to prepare a spinning dope (N).

Using the spinning dope (I) as the spinning dope for forming the core part and the spinning dope (N) as the spinning dope for forming the sheath part, a core-sheath spinneret having a hole diameter of 0.075 mm and 400 holes Then, it was introduced into a coagulation bath at 40 ° C. and 55 wt% dimethylacetamide aqueous solution to coagulate. The coagulated yarn was taken out from the coagulation bath at a speed of 40 m / min, washed in boiling water, stretched 5 times, applied with an oil agent, dried, and subjected to heat and moisture relaxation treatment. The fineness of the obtained fiber was 3 denier. The conductivity and charge half-life of the resulting fibers were evaluated and are shown in Table 3.

[0048]

[Table 3]

(Examples 9, 10, 11) Acrylonitrile polymer (specific viscosity 0.16) consisting of 93.5% by weight of acrylonitrile, 6.0% by weight of methyl acrylate and 0.5% by weight of sodium methallylsulfonate. ) And lauroxy polyethylene glycol (in formula 3, R ₁ = H, R ₂ =
C ₁₂ H ₂₅ , n = 30) 20.0% by weight, acrylonitrile 73.0% by weight, vinyl acetate 7.0% by weight and a mixing ratio with an antistatic acrylonitrile polymer (specific viscosity 0.18). It was dissolved in dimethylformamide with various changes to prepare a spinning solution (J) having a polymer concentration of 30% by weight. A fiber having a fineness of 3 denier was obtained in the same manner as in Comparative Example 1 except that (J) was used as the spinning stock solution forming the sheath and the discharge ratios of the spinning stock solutions forming the core and the sheath were changed. It was The conductivity and charge half-life of the resulting fiber were evaluated and are shown in Table 4.

[0050]

[Table 4]

[0051]

EFFECT OF THE INVENTION The conductive acrylic fiber of the present invention has excellent conductivity, whiteness, yarn strength, and process passability, and can be widely used for clothing such as sweaters.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akemi Kitani 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Office

Claims (3)

[Claims] 1. A cross-sectional area ratio of the core portion to the sheath portion is 5/95 to 8
It is a 0/20 core-sheath composite fiber, and the core has a specific resistance of 10 ⁻³ S
/ Cm or more made of acrylonitrile polymer containing 15 to 70% by volume of conductive fine particles, and the sheath has a weight ratio of 95/5 to 70/30 of the acrylonitrile polymer and the compound containing a polyether structure. Consisting of a mixture,
The content of compounds containing polyether structure in all fibers is 1
Conductive acrylic fiber characterized by being more than weight%. 2. The conductive acrylic fiber according to claim 1, wherein the compound having a polyether structure is a polyfunctional polyether ester, a polyfunctional polyether, a polyfunctional polyether amide, or a polyfunctional polyether ester amide. 3. The conductive acrylic fiber according to claim 1, wherein the compound having a polyether structure is a copolymer with acrylonitrile, acrylate, or methacrylate.