JP3046501B2 - Conductive composite fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive conjugate fiber having excellent conductivity. More specifically, the present invention relates to a novel conductive conjugate fiber having extremely low whiteness, which has very little coloring, has good spinning properties, and can be stably produced.

[0002]

2. Description of the Related Art As is well known, synthetic fibers such as polyester fibers and polyamide fibers are not conductive, so that static electricity is liable to be charged due to friction, and various obstacles are caused by adhesion of dust and discharge. There is.

In order to solve such a problem, there has been proposed a method of using a fiber containing a white conductive substance in a fiber product. In this case, as the conductive substance, a substance in which a conductive film mainly composed of tin oxide is provided on the surface of white or colorless inorganic fine particles has attracted attention.

For example, Japanese Patent Publication No. 58-39175 discloses an antistatic polymer composition in which 3 to 20% by weight of titanium oxide fine particles coated with stannic oxide are dispersed in a melt-moldable synthetic polymer. Things have been suggested. However, in this case, the conductivity of stannic oxide alone is insufficient, and it is necessary to add an appropriate doping agent in order to obtain a satisfactory conductive fiber.

Japanese Patent Publication No. 62-29526, Japanese Patent Publication No. 1-2365, Japanese Patent Application Laid-Open No. 2-289108, and Japanese Patent Application Laid-Open No. 5-51811 disclose, in the conductive layer component, the surface of titanium oxide particles. Conductive composite fibers containing conductive particles formed with a conductive film made of a metal oxide containing a doping agent have been proposed. But,
The specifically disclosed conductive coatings are only zinc oxide using aluminum oxide as a dopant and stannic oxide using antimony oxide as a dopant, and thus satisfy both whiteness and conductive performance at the same time. It cannot be improved to the level that it can. Therefore, in reality, whiteness is sacrificed to some extent in order to satisfy the conductive performance.

On the other hand, Japanese Patent Application Laid-Open No. 4-153305 proposes conductive fibers containing indium oxide particles as conductive particles. However, the specifically disclosed conductive particles are those using tin oxide as a doping agent, which not only presents a pale yellow color, but also is extremely easily agglomerated, so that it is uniformly dispersed in the thermoplastic polymer. It is difficult to disperse and it is difficult to stably produce yarn.

Japanese Patent Application Laid-Open No. Sho 60-110920 proposes a conductive composite fiber containing, in a conductive layer component, a conductive substance having a conductive film formed on the surface of metal oxide particles. Is a variety of metal oxides such as tin oxide, zinc oxide, copper oxide, indium oxide, zirconium oxide, and tungsten oxide on the surface of inorganic fine particles such as tin oxide, zinc oxide, titanium oxide, magnesium oxide, silicon oxide, and aluminum oxide. Particles having a conductive film formed thereon are exemplified as conductive particles, and it is disclosed that a small amount of a second component is added to the conductive film to enhance conductivity at the same time. However, the conductive particles specifically disclosed are those in which tin oxide containing a small amount of antimony oxide is coated on the surface of the titanium oxide particles as a conductive film, and the appearance is close to white but pale gray blue. A conductive particle satisfying both the conductive performance and the whiteness at the same time has not been known.

[0008]

SUMMARY OF THE INVENTION The present invention has been made on the background of the above-mentioned prior art, and an object of the present invention is to provide a novel white conductive conjugate fiber having little coloring and excellent conductive properties. .

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the surface of metal oxide particles can be converted from indium oxide containing tin oxide via a tin oxide layer. The conductive particles provided with a conductive layer are excellent in whiteness, and furthermore, when dispersed in a thermoplastic polymer, exhibit appropriate dispersibility and cohesiveness. The inventors have found that a conductive conjugate fiber can be obtained, and have reached the present invention.

That is, according to the present invention, there is provided a conductive conjugate fiber comprising a non-conductive layer component A composed of a fiber-forming polymer and a conductive layer component B composed of a thermoplastic polymer containing a conductive substance. The conductive substance is a conductive particle having a multi-layered film composed of a tin oxide layer and an upper layer containing indium oxide containing tin oxide on the surface of the metal compound particles, and an average particle diameter of the conductive particles. Is 0.1 ~
Provided is a conductive conjugate fiber having a particle size distribution ratio γ of 1.0 μm or less and 2.0 or less. [However, the particle size distribution ratio γ is represented by D ₃₀ when the cumulative weight of the settled particles by the centrifugal sedimentation method is 30% of the total particle weight, and D ₇₀ when the accumulated weight is 70% of the total particle weight. Γ = D ₃₀ / D ₇₀

Hereinafter, the present invention will be described in detail. As the thermoplastic polymer used as one component (conductive layer component B) of the conjugate fiber of the present invention, any known thermoplastic polymer can be used. Examples of such a polymer include polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene, nylon 6, nylon 6,6, polyethylene terephthalate, polybutylene terephthalate, and the like, in which a copolymer component is copolymerized. And, if necessary, a mixture of two or more thereof.

In the conductive conjugate fiber of the present invention, the conductive particles contained in the conductive layer component B have the greatest characteristics. That is, it is important that the surface of the metal compound particles contain conductive particles having a multi-layered film composed of a tin oxide layer as a lower layer and an indium oxide layer (conductive film) containing tin oxide as an upper layer.

The metal compound particles are optional as long as they have a high whiteness per se. Examples thereof include titanium oxide, aluminum oxide, zinc oxide, silicon oxide, zinc sulfide, barium sulfate, zirconium phosphate, and titanium. Metal compound particles such as potassium acid and silicon oxide / aluminum oxide composite oxide are used. Among them, titanium oxide or aluminum oxide, particularly aluminum oxide, is preferable because the whiteness level of the obtained fiber is good and the dispersibility in the thermoplastic polymer and the cohesion for forming the conductive structure are balanced. . In the case of aluminum oxide,
The purity is desirably 99% or more. If the purity is less than 99%, it becomes difficult to form a tin oxide layer or a tin oxide-containing indium oxide layer, and it becomes difficult to obtain particles having conductive properties described later. .

The amount of the conductive particles coated with the tin oxide layer is preferably in the range of 0.5 to 50% by weight, particularly 1.5 to 40% by weight, based on the metal compound particles of the substrate. The coating of the contained indium oxide layer tends to be non-uniform, and the volume resistance of the powder tends to increase under the influence of the metal compound particles of the substrate. Conversely, if the content is too large, the amount of tin oxide that does not adhere to the surface of the metal compound particles of the substrate increases, and the whiteness and conductive performance of the conductive particles tend to decrease. On the other hand, the coating amount of the indium oxide layer containing tin oxide is 5 to 20 with respect to the metal compound particles of the substrate.
0 wt%, in particular 8-150% by weight range are preferred, also 0.1 to 20 wt% as SnO ₂ content of tin oxide relative to indium oxide, is particularly from 2.5 to 15 wt% preferred . If the coating amount of the indium oxide layer is too small, the conductive performance tends to decrease. Conversely, if the coating amount is too large, the conductive performance is not further improved and disadvantageous in cost. If the amount of tin oxide added is too large or too small, the conductive performance tends to be insufficient. In particular, those having a volume resistance value of 10 Ωcm or less are preferable for obtaining excellent conductive performance.

[0015] Such conductive particles, for example, by uniformly coating a hydrate of 0.5 to 50 wt% of tin oxide as SnO ₂ in the metal compound particle surface, a hydrate of tin oxide Sn
A hydrate of indium oxide as O ₂ containing 0.1 to 20 wt% an In ₂ O ₃ as a covering 5 to 200 wt%, then obtained by heat treatment at three hundred and fifty to seven hundred and fifty ° C. in a non-oxidizing atmosphere.

Here, there are various methods for forming a film of tin oxide hydrate. For example, after adding a tin salt or stannate solution to an aqueous suspension of metal compound particles, a method of adding an alkali or an acid, separately adding a tin salt or a stannate and an alkali or an acid in parallel There is a method of adding and coating. In order to uniformly coat the surface of the metal compound particles with the hydrated tin oxide, the latter parallel addition method is more suitable.
It is more preferable to keep the temperature at ℃. In addition, the pH when tin salt or stannate and alkali or acid are added in parallel
Is 2 to 9. The isoelectric point of tin oxide hydrate is pH = 5.5.
Therefore, preferably, pH = 2 to 5 or pH 6 to
It is important to maintain the value of 9, so that the reaction product of tin can be uniformly deposited on the surface of the metal compound particles.

As the tin salt, for example, tin chloride, tin sulfate,
Tin nitrate or the like can be used. As the stannate, for example, sodium stannate, potassium stannate and the like can be used. As the alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, aqueous ammonia, ammonia gas, etc., and as the acid, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, etc. can be used. .

There are various methods for forming a film of indium oxide hydrate containing an oxide. However, since the previously coated tin oxide hydrate film is not dissolved, a tin salt and an indium salt are used. More preferably, a mixed solution of the above and an alkali are separately added in parallel to form a film. At this time, it is more preferable to heat the aqueous suspension to 50 to 100 ° C. Further, the pH when the mixed solution and the alkali are added in parallel is 2 to 9, preferably 2 to 5, or
It is important to maintain a pH of 6 to 9, which allows the reaction products of tin and indium to be uniformly deposited.

As a raw material of tin, for example, tin chloride, tin sulfate, tin nitrate and the like can be used. As a raw material of indium, for example, indium oxide, indium sulfate, or the like can be used.

In the present invention, when the above-described conductive particles are mixed with a thermoplastic polymer to impart conductivity, the conductive particles efficiently and continuously exhibit excellent conductivity in a matrix. Requires that the size of the conductive particles be small to some extent. However, if the particle size is too small, the cohesion becomes strong, so that the continuity of the particles is reduced and the conductive performance becomes insufficient. Become. On the other hand, if the particle size is too large, the cohesiveness of the particles is reduced and it becomes difficult to form a continuous structure of the particles, so that the conductive performance becomes insufficient. Therefore, the average particle size of the conductive particles is 0.1 to 1.0 μm.
It is necessary to

Further, since the conductive particles according to the present invention have relatively large particle aggregating properties, if the particle size distribution is wide, the influence of the small particle size portion becomes large and the particles are easily aggregated.
As a result, not only the conductivity of the particles becomes poor due to a decrease in the continuous arrangement of the particles, but also the yarn breakage is liable to occur during the spinning. Therefore, the particle size distribution ratio γ defined below is 2.0 or less,
Preferably, it is required to be 1.7 or less. Particle size distribution ratio γ
In order to obtain conductive particles having a particle size of 2.0 or less, the conductive particles prepared by the above-described method may be subjected to a classification treatment according to a standard method.

The average particle size and the particle size distribution ratio γ are as follows:
It is measured by the method described above. (1) Average particle size of conductive particles can be measured using a centrifugal particle size measuring device (CP-50 manufactured by Shimadzu Corporation).
It was calculated based on the obtained centrifugal sedimentation curve. That is,
Sedimentation for particle size and total particle weight based on centrifugal sedimentation curve
From the cumulative weight particle size distribution curve representing the particle weight,
Particle size whose particle weight is equivalent to 50% by weight based on the total particle weight
And this value was taken as the average particle size. (2) Particle size distribution ratio of conductive particles γ of settled particles obtained in the measurement of average particle size of conductive particles
From the cumulative weight particle size distribution curve, the total weight of
Particle size corresponding to 30% by weight (D₃₀)
70% by weight of the total weight of the falling particles
The corresponding particle size (D ₇₀) Is read and calculated by the following equation. γ = D₃₀/ D₇₀ The smaller the value of γ, the sharper the particle size distribution of the conductive particles becomes.
Become

The conductive layer component B of the conductive particles described in detail above
The blending amount in the properties of the thermoplastic polymer to be blended,
It varies depending on the type, crystallinity, particle continuity (chain-shaped performance), etc., but is 50 to 80% by weight, preferably 60 to 75% by weight.
% By weight. When the amount is less than 50% by weight, the hue is good, but the level of the conductive performance is often insufficient. On the other hand, when the amount exceeds 80% by weight, not only mixing becomes difficult, but also the fluidity becomes poor. There is also a tendency that the yarn formability is reduced and the yarn formability is also deteriorated.

The conductive layer component B may contain, if necessary, a coupling agent, a dispersant (eg, waxes, polyalkylene oxides, various surfactants, organic electrolytes, etc.), a pigment, a stabilizer, and a fluidity improver. And other additives can be added.

Next, the fiber-forming polymer constituting the other component (the non-conductive layer component A) of the conductive conjugate fiber of the present invention is arbitrary as long as it can be melt-spun. Specific examples of such a polymer include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon 6,6, and polyolefins such as polyethylene and polypropylene. Merged or mixed polymers can also be used. Furthermore, if necessary, any additives such as a matting agent, a coloring agent, an oxidation stabilizer, a dyeability improving agent, an antistatic agent and the like may be contained. Above all, when the nonconductive layer component A is an antistatic polymer containing an antistatic agent at a ratio of 10 ⁸ to 10 ¹² Ωcm, the nonconductive layer component A is a sheath, and the conductive layer component B is It is preferable to use a conjugate fiber disposed on the core since a fiber having both good electrical conductivity between the fiber surfaces and good dust resistance can be obtained.

The antistatic agent preferably used is a polymer having a polyoxyethylene polyether chain, for example, a block copolymer having a polyoxyethylene block as a main chain component (polyetherester, polyetheresteramide, etc.). And polyoxyethylene-based polyethers (polyoxyethylene glycol, non-random copolymerized polyoxyethylene-based polyethers in which a long-chain olefin oxide is added to the end of a polyoxyethylene glycol chain), and organic sulfonate compounds such as Examples thereof include an alkylbenzenesulfonate and an alkylsulfonate, and it is particularly preferable to use a polyoxyethylene-based polyale and an organic sulfonate in combination.

Among them, a non-random copolymerization type represented by the following general formula (I) is a polyoxyethylene-based polyether, in which a polyoxyethylene block is used as a main chain component and a long-chain olefin oxide is added to a molecular chain terminal. It is preferable to use a polyoxyethylene-based polyether from the viewpoint of improving the washing performance of the conductive performance between the fiber surfaces.

[0028]

Embedded image Z [(CH ₂ CH ₂ O) _m (R ¹ O) _n R ² ] _k (I) In the above formula, Z is a molecular weight of 30 having 1 to 6 active hydrogens.
0 or less, and R ¹ has 6 to 50 carbon atoms.
An alkylene group, R ² is a hydrogen atom, and has 1 to 40 carbon atoms.
A monovalent hydrocarbon group or a monovalent acyl group having 2 to 40 carbon atoms,
k is an integer of 1 to 6, m is an integer such that k × m is 70 or more,
n is an integer of 1 or more.

In such a polyoxyethylene-based polyether, the hydrophobic R ¹ O unit is present in at least one of the polyoxyethylene molecular chain terminals in one or two or more blocks, so that the washing performance of the conductive property is high. The property becomes good.

The average molecular weight of the polyoxyethylene polyether represented by the above formula (I) is 5,000 to 1,
It is preferably in the range of 6000, particularly in the range of 5500 to 14000. Outside this range, the dispersion state in the sheath component tends to deteriorate and the effect of improving the inter-fiber surface conductivity tends to decrease.

Specific examples of such polyoxyethylene-based polyethers are preferably those described in, for example, JP-A-2-269762, and some of them are shown in Table 1 below.

[0032]

[Table 1]

The content of the above-mentioned polyoxyethylene polyether in the sheath component is 0.5 to 10% by weight, preferably 1 to 5% by weight. When the content is less than 0.5% by weight, the conductive performance between the fiber surfaces tends to decrease. On the other hand, if it exceeds 10% by weight, the effect of improving the conductivity between the fiber surfaces is saturated, and the mechanical properties, heat resistance, light resistance and the like of the fibers are rather impaired.

Examples of the organic sulfonic acid salts include, for example, sodium, sodium dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid, hexadecylsulfonic acid, and dodecylsulfonic acid. An alkali metal salt such as potassium or a quaternary phosphonium salt is preferably used. Among them, sodium dodecylbenzenesulfonate having an average carbon number of about 1
Preferred is a mixture of 4 sodium alkyl sulfonates.

These organic sulfonates may be used alone or in combination of two or more, but the content in the sheath component is from 0.1 to 5%.
% By weight, preferably 0.1 to 3% by weight. When the content is less than 0.1% by weight, the volume resistivity of the non-conductive layer component A does not decrease sufficiently, and it is impossible to impart sufficient inter-fiber surface conductivity to the obtained conjugate fiber. If this amount exceeds 5% by weight, the yarn is liable to be broken during the production of the conjugate fiber, and the mechanical properties of the fiber are liable to be impaired.

Next, the composite structure of the non-conductive layer component A and the conductive layer component B of the conductive composite fiber of the present invention can have any structure, and may be any of a side-by-side type and a core-sheath type. Also, the cross-sectional shape of the conductive layer component can be any shape, and the number thereof can be any number of one or more. Among them, a core-sheath composite fiber in which the conductive layer component B is disposed in the core portion is preferable because the dust generation resistance is improved. At this time, the non-conductive layer component A is preferably an anti-static polymer containing an anti-static agent, as described above, from the viewpoint of improving the conductive performance between the fiber surfaces.

The ratio between the non-conductive layer component A and the conductive layer component B in the cross section of the fiber can be made extremely wide. However, if the ratio of the conductive component is too large, the strength of the obtained conductive composite fiber decreases. Therefore, the area ratio of the conductive component in the fiber cross section is preferably 50% or less. On the other hand, the lower limit of this conductive layer component is only required that the conductive layer component is continuous along the fiber axis direction, and is usually 1% or more, particularly preferably 3% or more of the fiber cross-sectional area.

It is not necessary to employ any particular method and conditions for producing such conductive conjugate fibers. It can be appropriately selected from the known spinning methods and spinning conditions for producing a bicomponent composite fiber.

[0039]

The conductive conjugate fiber of the present invention is different from the conventional conductive particles having a conductive film containing tin oxide as a main component, in that the oxidized fiber contains tin oxide via a tin oxide layer. Since the conductive particles having the multi-layered film composed of the indium layer are blended, the whiteness can be remarkably improved.
Moreover, since the conductive particles have an appropriate average particle size and a particle size distribution ratio, it is presumed that it is easy to form a continuous structure in the fiber axis direction by being appropriately aggregated in the conjugate fiber. Exhibits excellent conductive performance.

Therefore, the conjugate fiber of the present invention is extremely suitable for producing white or light-colored fiber products, and when imparting antistatic properties to fiber products by mixing with other chargeable fibers,
The conductive fiber has such a feature that it is less noticeable than before.

The composite structure is a core-sheath type having a non-conductive layer component as a sheath, and an anti-static polymer containing an anti-static agent as the non-conductive component (volume resistance value of 10 ⁸ to 10 ¹² Ωc).
By using m), not only the conductivity between the fiber cross-sections, but also the conductivity between the fiber surfaces can be set to an excellent level, and at the same time, troubles of dust generation due to frictional detachment of the conductive layer components can be reduced. It can be suppressed.

[0042]

The present invention will be described in more detail with reference to the following examples. In addition, each evaluation item in an Example was measured by the following method. (1) Volume resistance value of conductive particles and nonconductive component A (unit: Ωcm) 10 g of conductive particles are packed in a cylinder having a diameter of 1 cm, and a pressure of 200 kg is applied from above by a piston to form a compact. A direct current (1 KV) is applied to the compact to measure the volume resistance of the conductive particles. On the other hand, the volume resistivity of the non-conductive component A is determined by spinning a yarn of 30 denier / 3 filaments from this, and calculating the volume resistivity from the cross-sectional resistance of 100 fibers. The resistance measurement conditions were 20 ° C and 40% R.
H.

(2) Color difference of conductive particles (brightness index L value,
(Chromaticness index b value) The powdery conductive particles are converted into L particles using a Hunter type color difference meter.
The value and the b value are measured. (3) Average particle size and particle size distribution ratio γ Using a centrifugal particle size measuring device (CP-50, manufactured by Shimadzu Corporation)
Calculated based on the obtained centrifugal sedimentation curve. That is,
From the cumulative weight particle size distribution curve representing the settling particle weight with respect to the particle size and the total particle weight based on the centrifugal settling curve,
The particle size corresponding to 50% by weight of the sedimentation particle weight based on the total particle weight was read, and this value was defined as the average particle size. On the other hand, the particle diameters (D ₃₀ , D ₇₀ ) corresponding to 30% by weight and 70% by weight of the settled particles with respect to the total particle weight were determined, and γ = D ₃₀ /
_D70 was calculated.

(4) Cross-sectional resistance value of conjugate fiber (unit: Ω / c)
m) The cross-sectional resistance value is an electric resistance value between cross sections per 1 cm length of a single fiber. For the measurement, a single fiber is cut into a length of 1 cm, placed on a Teflon film, and both cut surfaces (both ends) are coated with a conductive paint (Doitite) and measured with a resistance meter (DC 1 KV). The measurement conditions are a temperature of 20 ° C. and a humidity of 30% RH.

(5) Surface resistance value of conjugate fiber (unit: Ω / c)
m) The surface resistance value is an electric resistance value per 1 cm surface interval of a single fiber. The measurement is performed by directly placing a detection end on the fiber surface at an interval of 1 cm and using a resistance meter (DC 1 KV). The measurement conditions were a temperature of 20 ° C. and a humidity of 30% RH.

REFERENCE EXAMPLE 1 100 g of rutile-type titanium dioxide (KR-310 manufactured by Titanium Kogyo Co., Ltd.) was dispersed in 1 liter of water to form an aqueous suspension. This suspension was kept warm at 70 ° C. Stannic chloride prepared separately (SnCl ₄ · 5H ₂
O) A solution prepared by dissolving 11.6 g in 100 ml of 2N hydrochloric acid and 12% by weight aqueous ammonia were added simultaneously over about 40 minutes so as to maintain the pH of the suspension at 7 to 8. Indium chloride (InCl ₃ ) 3 prepared separately
6.7g and stannic chloride (SnCl ₄ · 5H ₂ O)
A solution prepared by dissolving 5.4 g in 450 ml of 2N hydrochloric acid and 12% by weight aqueous ammonia were simultaneously added dropwise for about 1 hour so that the pH of the suspension was maintained at 7 to 8. After the completion of the dropwise addition, the treated suspension was filtered and washed, and the obtained cake of the treated pigment was dried at 110 ° C. The dried powder is heat-treated at 500 ° C. for 1 hour in a stream of nitrogen gas (1 liter / minute),
Conductive particles were obtained. Dry classifying the obtained conductive particles,
The conductive particles described in Table 2 (Example 1) were prepared.

Reference Example 2 Dimethyl terephthalate 100
Parts, ethylene glycol 60 parts, calcium acetate monohydrate 0.06 parts (0.066 parts based on dimethyl terephthalate)
Mol%) and cobalt acetate tetrahydrate 0.0
09 parts (0.007 mol% based on dimethyl terephthalate) were charged into a transesterification vessel, and the temperature was increased from 140 ° C. to 220 ° C. over 4 hours in a nitrogen gas atmosphere, and methanol produced was distilled out of the system. A transesterification reaction was performed while performing the reaction. After the transesterification reaction, 0.058 parts of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) as a stabilizer and 0.024 parts of dimethylpolysiloxane as an antifoaming agent were added. Then, 10 minutes later, 0.04 parts of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added, and at the same time, the temperature was raised to 240 ° C. while removing excess ethylene glycol, and then transferred to a polymerization reactor. did. Then 760 mmHg over 1 hour
And 1 mmHg, and at the same time, the temperature was raised from 240 ° C. to 285 ° C. over 1 hour and 30 minutes. 2 hours after the start of pressure reduction

[0048]

Embedded image

(Where j is an integer of 18 to 28 and 2 on average)
1, m is an average value of about 115, and n is an average value of 3). A polyoxyethylene polyether having an average molecular weight of 7106 in a molten state so as to have the content shown in Table 3, and dodecylbenzene Sodium sulfonate was made into a 50% ethylene glycol solution and added under reduced pressure to the content shown in Table 3. When polymerization was further performed for 1 hour under reduced pressure of 1 mmHg or less under stirring, Cyanox 1790 (American
0.1 parts and Mark AO-41
0.3 parts of 2S (manufactured by Adeka Argus Chemical Co., Ltd.) was added under reduced pressure, and the mixture was further polymerized for 20 minutes to give an intrinsic viscosity of 0.6.
A polymer having a softening point of 40 to 0.660 and a softening point of 261.5 to 263 ° C. was obtained. This polymer was formed into chips by a conventional method.
Table 3 shows the volume resistance value of this product.

[Examples 1 to 7, Comparative Examples 1 to 7] The conductivity shown in Table 2 obtained by changing the titanium oxide particles, the tin oxide layer coating amount and the indium oxide layer coating amount in the above production method. 250 parts by weight of particles and 100 parts by weight of polyethylene are sufficiently mixed by heating with a kneading machine, and the obtained composition is used as a core, and a concentric core-sheath composite having polyethylene terephthalate containing 2.5% by weight of titanium oxide as a sheath. The fiber is spun using a spinning machine, stretched 4 times at 100 ° C., heat-set at 160 ° C., and a composite of a fiber cross section having a core / sheath area ratio of 1: 6 and a fiber configuration of 60 denier / 3 filaments. Fiber was obtained. Table 2 shows the results. Example 7 is the result of using conductive particles having a tin oxide layer and an indium oxide layer containing tin oxide on the surface of aluminum oxide (purity 99.9%) particles, and Comparative Example 7 was a result of using titanium oxide particles. It is a result of using conductive particles having a tin oxide layer containing antimony oxide on the surface.

[0051]

[Table 2]

[Examples 8 to 17] 250 parts by weight of the conductive particles shown in Table 3 obtained by changing the coating amounts of the metal compound particles and the indium oxide layer used in Reference Example 1 above,
100 parts by weight of polyethylene is sufficiently heated and mixed in a kneader,
The obtained composition was used as a core, while in Reference Example 2 above,
A polyester obtained by changing the blending amounts of the polyoxyethylene-based polyether and the organic sulfonate used as shown in Table 3 was used as a sheath and spun using a concentric core-sheath composite spinning machine, and quadrupled at 100 ° C. After drawing, the resultant was heat-set at 160 ° C. to obtain a composite fiber having an area ratio of a core portion and a sheath portion of a fiber cross section of 1: 6 and a fiber configuration of 60 denier / 3 filaments. Table 3 shows the results.

[0053]

[Table 3]

[Embodiments 18 and 19]
Instead of polyethylene terephthalate used for the sheath component,
Average molecular weight 2 as polyoxyethylene polyether
4% by weight of polyethylene glycol of 0000, and sodium dodecylsulfonate as an organic sulfonate in 2%
The procedure was performed in the same manner as in Example 8 except that polyethylene terephthalate (volume resistance 1 × 10 ¹⁰ Ωcm) blended by weight% was used and the content of the conductive particles in the core component was changed as shown in Table 4. The results are shown in Table 4.

[0055]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D01F 8/00-8/18

Claims (5)

(57) [Claims] 1. A conductive conjugate fiber comprising a non-conductive layer component A composed of a fiber-forming polymer and a conductive layer component B composed of a thermoplastic polymer containing a conductive substance,
The conductive substance is a conductive particle having a multi-layered film composed of a tin oxide layer and an upper layer containing indium oxide containing tin oxide on the surface of the metal compound particles, and an average particle diameter of the conductive particles. Is 0.1 to 1.0 μm, particle size distribution ratio γ
Is 2.0 or less.
[However, the particle size distribution ratio γ is D ₃₀ , the particle size when the cumulative weight of the settled particles by the centrifugal sedimentation method becomes 30% of the total particle weight.
When the particle diameter when the same was 70% expressed in D _70, gamma =
Represented by D ₃₀ / D _70] 2. The conductive conjugate fiber according to claim 1, wherein the metal compound particles are metal oxide particles made of titanium oxide or aluminum oxide. 3. The composite fiber having the non-conductive layer component A as a sheath,
2. A core-sheath type composite fiber having a conductive layer component B as a core.
The conductive conjugate fiber according to the above. 4. The non-conductive layer component A has a volume resistivity of 1
4. The conductive conjugate fiber according to claim 3, wherein the conductive conjugate fiber contains an antistatic agent at a ratio of from 0 ⁸ to 10 ¹² Ωcm. 5. An antistatic agent comprising a polyoxyethylene polyether and an organic sulfonate, wherein the content of each is 0.5 to 10% by weight based on the weight of the non-conductive layer component A, and 5. The composition according to claim 4, wherein the amount of the latter is 0.1 to 5.0% by weight.
The conductive conjugate fiber according to the above.