JPH0345714A - Electrically conductive conjugate fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber capable of providing antistatic textile products, good in coloring properties and excellent in fashionability by joining an electrically conductive layer composed of an organic polymer fine particle- containing thermoplastic polymer having a specific electrically conductive film to an electrically nonconductive layer composed of a fiber-forming polymer. CONSTITUTION:The objective fiber, obtained by joining (A) an electrically conductive layer composed of a thermoplastic polymer, containing organic polymer fine particles having an electrically conductive film composed of an inorganic oxide-based (e.g. tin oxide) and/or inorganic halide-based electrically conductive substance and having 0.01-10mum, preferably 0.1-3mum average particle diameter to (B) an electrically nonconductive layer composed of a fiber-forming polymer (e.g. nylon 6 or polyethylene terephthalate) and having <=10<12>OMEGA/cm electrical resistance value at 1kV DC voltage.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a conductive composite 111M, and more specifically, a conductive coating comprising an inorganic oxide-based and/or inorganic halide-based conductive material as conductive fine particles. The present invention relates to a novel conductive composite fiber containing organic polymer fine particles having the following properties.

[Prior Art] In general, synthetic Ili@ and natural fibers are easily charged with static electricity, so when used in clothing, they tend to cause problems such as discomfort when the charged static electricity is discharged. In order to eliminate these obstacles, various methods have been used to impart conductivity to mM. One of the effective methods is
There is a method of incorporating conductive carbon black as a conductive substance into synthetic fibers. However, l1ff products containing carbon black are colored black or gray, which limits their use in applications that require fashionability.

In order to improve the defects caused by such coloring, a method using cuprous iodide as a conductive substance (Japanese Patent Application Laid-Open No. 57-1692
0), a method using tin oxide (Japanese Unexamined Patent Publication No. 57-11)
212), a method using zinc oxide (Japanese Unexamined Patent Publication No. 57-1988),
5919) and a method using titanium oxide having a tin oxide film (Japanese Unexamined Patent Publication No. 53-92854). However, textile products obtained using these conductive substances still have the drawbacks that they still retain coloration due to the coloring of the conductive substance, and that the color development due to dyeing is reduced.

[Problems to be Solved by the Invention] The present inventors conducted studies with the aim of providing a conductive conjugate fiber that has excellent color tone and color development, which could not be achieved with the techniques described above, and has an excellent electromagnetic effect. As a result, we discovered that this can be achieved by providing an S conductive layer made of a thermoplastic polymer containing organic polymer fine particles (hereinafter sometimes simply referred to as conductive fine particles) having a specific conductive coating. be.

[Means for Solving the Problems] The object of the present invention is to provide an organic polymer having an average particle diameter of 0.01 to 10 μm and having a conductive coating made of an inorganic oxide-based and/or inorganic halide-based conductive material. A conductive layer made of a thermoplastic polymer containing fine particles and a non-conductive layer made of a fiber-forming polymer are bonded to each other.
This can be achieved by using conductive composite fibers whose electrical resistance value at DC voltage is 1012 Ω/cm or less.

The organic polymer fine particles constituting the conductive fine particles used in the present invention are not particularly limited as long as they have adhesive properties with a coating of an inorganic oxide-based and/or inorganic halide-based conductive substance. Polystyrene, styrene-divinylbenzene copolymer, polymethyl acrylate,
Methyl acrylate-styrene copolymer, benzoguanamine-formaldehyde copolymer, polyphenyl ester, polyphenylene oxide, crosslinked polyphenylene oxide, silicone resin, etc. are preferably used, and these particles are used alone or in combination of two or more types. be able to. In addition, in order to improve the adhesion of the conductive coating to the organic polymer fine particles, functional groups that are highly reactive with the conductive coating on the surface of the organic polymer fine particles, such as hydroxyl groups,
It is also preferable to provide carboxyl groups or the like, or to provide appropriate irregularities on the surface of the organic polymer fine particles.

Inorganic oxide-based conductive substances forming the conductive film of the conductive fine particles used in the present invention include tin oxide, zinc oxide,
Examples include indium oxide, tungsten oxide, niobium oxide, etc., and may be combined with one or more suitable additives to roughly improve conductivity or color tone. In addition, examples of inorganic halide conductive substances include cuprous iodide,
Examples include niobium chloride, which may be combined with one or more suitable additives to roughly improve conductivity or color tone.

It is preferable that the film made of a conductive substance covering the surface of the organic polymer fine particles completely covers the surface of the fine particles, but if the surface coverage of the film is 50% or more, it will not be effective as the objective of the present invention. You can get sex. The thickness of the conductive film when completely covering the surface of the fine particles is 0.5μ
m or less is preferable, 0.2 μm or less is more preferable, 0
．． A thickness of 1 μm or less is generally preferred. The thickness of the conductive film is 0
．． If it exceeds 5 μm, the obtained conjugate fiber will have a dull color tone and the color development will be reduced, which is not preferable. Conventionally, to form a conductive film on the surface of organic polymer fine particles,
Any method known as a method for forming a conductive film on the surface of inorganic fine particles, a polymer film, etc. can be employed.

The specific resistance of the organic polymer fine particles having a conductive coating thus obtained in a powder state is preferably 109Ω·c.
m or less, more preferably 10 6 Ω·cm or less, and most preferably 10 4 Ω·cm or less. If it exceeds 109 Ω·cm, it is not preferable because the electromagnetic effect of the composite fiber made using it will decrease.

The average particle diameter of the conductive fine particles must be 0.01 to 10 μm, preferably 0.05 to 5 μm, and 0.1 to 3 μm.
μm is more preferable. If the average particle diameter is less than o, oi μm, the handling of the organic polymer fine particles deteriorates, making it difficult to form a conductive film on the surface of the organic polymer fine particles, while if it exceeds 10 μm, Unless the particle blending ratio is increased, conductivity will not be exhibited and the melt viscosity of the conductive layer will increase, making it impossible to satisfy both silk-spinning properties and conductivity.

The thermoplastic polymer constituting the conductive layer is not particularly limited as long as it has thermal stability that does not cause decomposition at the melt spinning temperature and can be melt extruded. It may not have the ability to form. and,
Specific examples thereof include polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polyethylene and polypropylene.

The conductive layer is formed by containing conductive fine particles in the thermoplastic polymer described above, and the content of the conductive fine particles in the conductive layer can be selected as appropriate depending on the training performance required of the composite fiber obtained, but it is 10 to 10. 50% by volume is preferred, 15-4
0% by volume is more preferred. If the content of conductive fine particles in the conductive layer is less than 10% by volume, the antistatic properties of the composite fiber obtained will be insufficient, and if the content exceeds 50% by volume, the viscosity of the conductive layer will increase, resulting in poor spinning properties. decreases, which is not desirable. In addition, the conductive layer may contain additives such as conventionally known conductive substances, dispersants, ionic conductive agents, colorants, pigments, ferroelectrics, various stabilizers, and fluidity improvers, to the extent that they do not deviate from the purpose of the conductive layer. can be blended.

The fiber-forming polymer constituting the non-conductive layer is not particularly limited as long as it has fiber-forming ability, and specific examples include polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, Examples include polyolefins such as polyethylene and polypropylene, or blends and copolymers thereof, and may be the same polymer as the thermoplastic polymer used for the conductive layer or a different type of polymer. In addition, the non-conductive layer may include conventionally known conductive substances, dispersants, ionic conductive agents, colorants, pigments, ferroelectrics, various stabilizers, fluidity improvers, etc., without departing from the purpose of the present invention. Additives can be added.

The conductive composite fiber of the present invention has a conductive layer and a non-conductive layer joined together, and although many types of joining are possible, it is preferable that the conductive layer is continuous in the imt* direction. . Typical joining types include core-sheath type, side-by-side type, multilayer type, and multicore type. In the case of core-sheath type, a conductive layer is provided on the core component, and a part of the core component is lubricated.
A shape in which the Li fiber surface is exposed can also be adopted. Further, the cross-sectional shape of the conductive composite fiber may be circular or non-circular.

The area fraction occupied by the conductive layer in the fiber cross section of the conductive composite fiber can take a wide range, but from the viewpoint of maintaining the strength of the fiber, it is preferably 80% or less, and the conductive layer is continuous in the fiber axis direction. 3% or more is preferable from the point of view of
More preferably 5 to 60%.

The electrical resistance of the conductive composite fiber of the present invention at 1 kV DC voltage must be 1012 Ω/cm or less, and 10
If it exceeds 12 Ω/cm, the training effect aimed at by the present invention cannot be achieved.

Any conventionally known method can be used for spinning and drawing to obtain the conductive conjugate fiber of the present invention.

The conductive composite fiber of the present invention can be obtained in the form of a continuous filament or a staple by mixing it with other fibers. It is possible to impart antistatic properties to products.

[Example] The invention will be described in detail below with reference to Examples.

Note that the characteristic values in the examples were determined according to the following method.

(A) Average particle diameter of conductive fine particles Determined by electron micrographs of particles.

(8) Specific resistance diameter of conductive fine particles in powder state: 1 cm
10 grams of particles are packed into an insulating cylinder, and a pressure of 2 degrees kilograms is applied from the top with a piston.
It was determined by applying a DC voltage of 1 to 1000 volts.

(C) Specific resistance of conductive resin (conductive layer) The conductive resin was molded into a lot shape with a diameter of 2 mm and a length of 61 cm, and a current voltage of 0.1 to 1,000 volts was applied to determine the specific resistance.

(D) Electrical resistance value of fiber A linear mm cut into a length of 60 m is pasted on a polyethylene terephthalate film, including the ends of the fiber. A measurement sample was prepared by applying a conductive resin paint (trade name: Dotite 5-1) manufactured by Genji Kasei Co., Ltd. to #5 on both ends of tip 1 and drying it. This sample
The electrical resistance value was determined by applying a 1 kV DC voltage at 0'C and 30% R and dividing the electrical resistance value by the length of 5 cm.

Example 1 After dissolving 40 parts by weight of stannous chloride and 10 parts by weight of antimony trichloride in 1000 parts by weight of water, 50 parts by weight of divinylbenzene-styrene copolymer particles having an average particle diameter of 0.9 μm were dispersed. I let it happen. Thereafter, water was evaporated by heating the dispersion to coat the particle surfaces with stannous chloride and antimony trichloride. After drying, the particles were oxidized in air at 250° C. for 6 hours to obtain conductive fine particles having a conductive oxide film. The conductive fine particles had an average particle diameter of 1.0 μm and were uniformly covered with an oxide film. In addition, the specific resistance in powder form is 1.2X103
It was Ωcm.

By kneading 175 parts by weight of the conductive fine particles (true specific gravity: 2.5y/d) and 79.8 parts by weight of nylon 6 powder (ratio ffl: 1.14) in an extruder, 3
Conductive resin pellets containing 0% by volume of conductive fine particles were obtained. The specific resistance of this pellet is 3.0X103Ω・C
mteatted.

A core-sheath type composite material with this conductive resin as a core component and polyethylene terephthalate with a number average molecular weight of 20,000 as a sheath component, in which titanium oxide particles with an average particle diameter of 0.4 μm are dispersed in 0.5 parts as a matting agent. A drawn yarn (core/sheath area ratio = 10/90) was obtained by a conventional melt spinning method. This undrawn yarn was stretched 2.5 times at 130° C. to obtain a drawn yarn of 32 denier/4 filaments. . The electrical resistance value of this single yarn was 1.1×10 10 Ω/cm, which was found to be at a level that showed excellent electrical conductivity.

When the above-mentioned drawn yarn was dyed for 98° Cl2O minutes at a bath ratio of 1:100 using a Neido Blue disperse dye manufactured by Terra Seal, it was found that it exhibited a deep blue tint.

Comparative Example 1 Conductive titanium oxide fine particles were obtained in the same manner as in Example except that titanium oxide fine particles having an average particle diameter of 0.3 μm were used instead of the divinylbenzene-styrene copolymer particles. The obtained fine particles had an average particle diameter of 0.4 μm and were uniformly coated with an oxide film. The specific resistance of the fine particles in a powder state was 3.7×10 3 Ω·cm.

This conductive titanium oxide fine particle (true specific gravity: 4゜7g/d)
A conductive resin pellet containing 30% by volume of conductive titanium oxide fine particles was obtained by kneading 329 parts by weight and 79.8 parts by weight of nylon 6 powder using an extruder. The specific resistance of this pellet is 3.7X103Ω・cm
Met.

A drawn yarn was obtained in the same manner as in Example 1 using this conductive resin as a core component. The electrical resistance value of this single yarn is 6.6X
It was found that the resistance was 10''Ω/ctn, which is a level that indicates excellent training properties.

However, when it was dyed using the same method as in Example 1, it was only dyed pale blue.

Example 2 10 parts by weight of divinylbenzene-styrene copolymer particles with an average particle size of 0.9 μm were dispersed in a 70°C aqueous solution in which 460 parts by weight of iodine and 500 parts by weight of potassium iodide were dissolved in 1000 parts by weight of water. I let it happen. The dispersion was stirred for 1 hour, washed with water, filtered, and air-dried overnight to obtain 13.5 parts by weight of iodine-adsorbed fine particles. 40 parts by weight of cuprous chloride and 85 parts by weight of ammonium chloride were dissolved in 1000 parts by weight of water, and 13.5 parts by weight of iodine-adsorbing fine particles were dispersed in an aqueous solution at 55°C in which 10 parts by weight of copper wire was submerged. . The dispersion was stirred for 1 hour under a nitrogen atmosphere, and then dispersed for 30 minutes in 1000 parts by weight of boiling water to which 2 parts by weight of Score 400 (manufactured by Kao Atlas Co., Ltd.) and 20 parts by weight of ammonium chloride were added. The dispersion was washed with water, filtered, and dried to obtain conductive fine particles whose surfaces were coated with cuprous iodide.The obtained conductive fine particles had an average particle diameter of 1.0 from an electron micrograph.
The copper iodide coating was uniformly coated in micrometers. Also,
The specific resistance was 22Ω·cm.

Conductive fine particles obtained by the above method (true specific gravity: 2゜Og/m
l') 60 parts by weight and low density polyethylene powder (specific gravity: 0
．． 92>64.4 parts by weight were kneaded using an extruder to obtain conductive resin pellets containing 30% by volume of conductive fine particles. The specific resistance of this pellet is 50Ω・
It was cm.

A stretched system was obtained in the same manner as in Example 1 using this conductive resin as a core component. The electrical resistance value of this single yarn is 7.1X
It was found that the resistance was 109Ω/cm, which is a level that indicates excellent training properties.

When the above-mentioned drawn yarn was dyed in the same manner as in Example 1, it was found that it exhibited a deep blue tint.

Comparative Example 2 Conductivity was obtained in the same manner as in Example 1, except that divinylbenzene-styrene copolymer particles having an average particle diameter of 01OO5 μm were used instead of the divinylbenzene-styrene copolymer particles used in Example 1. The oxide was coated.

When the obtained particles were observed under an electron microscope, it was found that the divinylbenzene-styrene copolymer particles were hardly coated with the conductive oxide. Further, when the specific resistance of the powder was measured, it exceeded 1015 Ω·cm and had no conductivity.

Comparative Example 3 Conductive fabrication was performed in the same manner as in Example 1, except that divinylbenzene-styrene copolymer particles having an average particle size of 28 μm were used instead of the divinylbenzene-styrene copolymer particles used in Example 1. Conductive fine particles having a conductive film were obtained. The conductive fine particles have an average particle diameter of about 29 μm,
The oxide film was uniformly coated. Further, the specific resistance in the powder state was 6.3×10 3 Ω·cm.

Using these conductive fine particles, conductive resin pellets were obtained in the same manner as in Example 1, but the specific resistance was 1015Ω.
cm, and had no conductivity.

[Effects of the invention] The conductive composite fiber according to the present invention contains inorganic oxide and/or
Alternatively, it contains organic polymer fine particles with a conductive film that is better than inorganic halide conductive materials, and has good coloring properties, making it possible to provide electrically conductive textile products with excellent fashionability, and its industrial value is extremely high. It is something.

Claims (1)

[Claims] Average particle diameter of 0.01 to 0.01 with a conductive coating made of an inorganic oxide-based and/or inorganic halide-based conductive material
A conductive layer made of a thermoplastic polymer containing 10 μm organic polymer fine particles and a non-conductive layer made of a fiber-forming polymer are bonded together, and the electrical resistance value at 1 kV DC voltage is 10^1^2Ω/ A conductive composite fiber having a thickness of cm or less.