JPH11117178A - Electrically conductive fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrically conductive fiber having antistatic property to suppress static damage in low-humidity atmosphere and exhibiting heat- resistance and flexibility by forming a conductive layer composed of a specific conductive composition on the surface of a fiber. SOLUTION: An electrically conductive fiber holding a conductive layer and having a surface resistivity of 10<6> to 10<12> Ω/(square) at 25 deg.C and 15% RH, a charge attenuation time of <=2 sec and a surface resistivity variation ratio of <=5.0 after heating at 250 deg.C for 1 min is produced by preparing an electrically conductive composition composed of a conductive polymer such as a polyaniline or its derivative, preferably a sulfonated polyaniline, e.g. aminoanisole sulfonic acid, a water-soluble or water-dispersible thermoplastic resin containing anionic group such as a copolymerized polyester containing 1-10 mol.% of a group selected from sulfonic acid group and its alkali metal salt group such as sodium 5-sulfoisophthalate unit and a surfactant and applying the conductive composition to the surface of fiber such as thread or sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to conductive fibers, and more particularly, to fibers having excellent antistatic properties and conductivity even under low humidity. The present invention relates to a sheet-like material such as a yarn, a knitted woven fabric or a non-woven fabric which is composed of the two.
Specific examples include clothing such as antistatic work clothes, uniforms and white coats, interior textile products such as carpets, curtains and chair coverings, hats and bags, and textile products for industrial materials.

[0002]

2. Description of the Related Art Conventionally, fibers are excellent in flexibility, heat resistance, dimensional stability, mechanical strength, and the like. -It is used in large quantities and in a wide range as a substrate. In particular, synthetic fibers have been widely used in recent years because of their excellent uniformity and processability. Since synthetic fibers are generally hydrophobic, static electricity tends to be generated on the surface of the fibers, and dust and the like easily adhere to the surface, causing various troubles. Generally, a surfactant is used as an antistatic agent for fibers and the like. However, a surfactant having a sufficient surface resistance (1) to suppress adhesion of dust, dust, and the like.
0 ¹⁰ Ω / □ or less), and the antistatic ability tends to change under the influence of ambient moisture and moisture. In particular, there is a disadvantage that the surface resistance of the fiber, which has been reduced by the surfactant, is greatly increased under low humidity, and the desired antistatic ability cannot be obtained. As a result, dust adheres to the fiber surface, causing various troubles. In today's high-tech environment, there is a demand for fibers free from static electricity in low-humidity environments. For this reason, the appearance of antistatic agents that provide a surface resistance of 10 ¹⁰ Ω / □ or less under low humidity is desired. I have.
Conductive polymers such as polyaniline and polypyrrole are known as materials giving such a low surface resistance value. All of them are soluble in a specific organic solvent, but they are water or a water / alcohol mixed solvent. Since the system was insoluble or indispensable, a method of bonding a sulfonic acid group to an aromatic ring was performed, and a method of mixing a water-soluble or water-dispersible resin alone was not used because sufficient film characteristics were not obtained. Has been done.
However, when a resin having good compatibility with sulfonated polyaniline is used, a predetermined surface resistance value is not obtained. Conversely, when a predetermined surface resistance value is obtained, the surface becomes cloudy and the original transparency of the fiber is impaired. The problem had arisen.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of earnest research focusing on the above-mentioned problems, and an object of the present invention is to make use of the excellent characteristics of the original fiber and to obtain the same even under low humidity. Has sufficient antistatic ability to overcome electrostatic damage,
It is another object of the present invention to provide an inexpensive fiber that has heat resistance and does not lose flexibility and transparency.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a conductive fiber having a conductive layer laminated on the surface of the fiber.
The surface resistance value in a 5 ° C., 15% RH atmosphere is 10 ⁶ to 1
0 ¹² Ω / □, and a charge decay time of 2 seconds or less, and a rate of change in surface resistance of the conductive layer after heating at 250 ° C. for 1 minute is within 5.0. It is about fibers.

The fibers used in the present invention include polyesters, polyamides, polyacrylonitriles, acetates, polyolefins such as polyethylene and polypropylene, polyphenylene sulphites, polyimides, meta-aramids, paraamides and polybenzoxaoxanes. Synthetic fibers such as zole, semi-synthetic fibers such as rayon, polynosic, and promix, and natural fibers such as cotton, hemp, and wool, or blends, cross-wovens, cross-knits, and non-woven fabrics thereof You can use anything you like.

The conductive polymer according to the present invention is applicable to the present invention as long as it is soluble in water or an organic solvent.
Examples include polyaniline and its derivatives, preferably water-soluble sulfonated polyaniline, and organic solvents-soluble polypyrrole, that is, polypyrrole having a long-chain alkyl group substituent, polythiophene and its derivatives. Further, a polyaniline solution obtained by adding an inorganic acid or a sulfonic acid group-containing compound to a dispersion of polyaniline or a copolymer thereof is exemplified. At this time, the inorganic acid includes hydrochloric acid, perchloric acid, sulfuric acid, nitric acid and the like, and the sulfonic acid group-containing compound includes benzenesulfonic acid, naphthalenesulfonic acid and polystyrenesulfonic acid. Among them, sulfonated polyaniline is suitable for the present invention because of its good solubility in water.

[0007] As the sulfonated polyaniline, a sulfonated aniline copolymer containing an alkoxy group-substituted aminobenzenesulfonic acid as a main component is suitable as a basic material of the conductive composition of the present invention. It is suitable. Furthermore, in terms of improving the coating properties, spreadability, and hardness of the coated body of the conductive composition of the present invention, the 5-
It is more preferable to use the copolymerized polyester containing a sulfoisophthalic acid unit in an amount of 1 mol% or more and 10 mol% or less.

Here, specific examples of aminoanisolesulfonic acids include 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, and 2-aminoanisole-sulfonic acid. 6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-aminoanisole-6-sulfonic acid, 4-aminoanisole- Examples thereof include 2-sulfonic acid and 4-aminoanisole-3-sulfonic acid.

The methoxy group of anisole is an ethoxy group, i
It is also possible to use a compound substituted with an alkoxy group such as a so-propoxy group. However, 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid,
-Aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-
Sulfonic acid and 3-aminoanisole-6-sulfonic acid are preferably used.

As described above, the sulfonated polyaniline copolymer used in the present invention has a sulfonic acid group content of 70% or more, preferably 80% or more, more preferably 100%, based on the aromatic ring. In addition, there is no problem for the purpose of the present invention, even if aromatic rings containing a sulfonic acid group and aromatic rings not containing a sulfonic acid group are mixed or alternately arranged. If the sulfonic acid group content of the sulfonated polyaniline copolymer is less than 70%, the solubility or dispersibility of the copolymer in water, alcohol or a mixed solvent system thereof becomes insufficient, and as a result, The coatability and spreadability to the fiber are deteriorated, and the conductivity of the obtained coating film tends to be significantly reduced. The sulfonated polyaniline copolymer used in the present invention has a number average molecular weight of 300 to 500,000, and preferably 1,000 or more in terms of solubility in the solvent and strength of the coating film.

The use ratio of the sulfonated polyaniline copolymer is 0.01-10 parts by weight, preferably 0.1-2 parts by weight, per 100 parts by weight of the solvent. When the use ratio of the sulfonated polyaniline copolymer is less than 0.01 part by weight, the long-term storage property of the solution is deteriorated, pinholes are easily generated on the surface coat layer, and the conductivity of the coated surface is significantly deteriorated. On the other hand, if the use ratio exceeds 10 parts by weight, the solubility and dispersibility of the copolymer in water or a water / organic solvent system and the coatability of the coat layer tend to deteriorate, which is not preferable.

As the solvent, any organic solvent can be used as long as it does not dissolve or swell the fibers such as polyester. However, use of a mixed solvent with water or an organic solvent such as water / alcohol is more preferable in terms of the use environment. Not only is preferred, but also the coating properties on the support and the conductivity may be improved. Organic solvents include alcohols such as methanol, ethanol, propanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; propylene glycols such as methyl propylene glycol and ethyl propylene glycol. And amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone are preferably used. These are used by being mixed with water at an arbitrary ratio. Specific examples of this include water / methanol, water / ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol, and the like. The ratio used is preferably water / organic solvent = 1/10 to 10/1.

The thermoplastic resin used in the present invention preferably has a hydrophilic group. Among them, an ionic group and / or a carboxyl group and / or a hydroxyl group and / or a sulfonic group and / or an amide group and / or It preferably has an acid anhydride group and / or a glycidyl group and / or a chloro group and / or a polyalkylene glycol. In particular, it is preferably a water-soluble or water-dispersible resin containing an anion group, and is preferably a copolymerized polyester to which at least one group selected from the group consisting of a sulfonic acid group and an alkali metal base thereof is bonded.
A copolymerized polyester having at least one group selected from the group consisting of a sulfonic acid group and an alkali metal base thereof (hereinafter, referred to as a sulfonic acid group-containing copolymerized polyester) refers to a dicarboxylic acid component and / or a glycol component. A polyester partially bonded to at least one group selected from the group consisting of a sulfonic acid group and an alkali metal base thereof, and among them, at least one group selected from the group consisting of a sulfonic acid group and an alkali metal base thereof The copolymerized polyester prepared by using an aromatic dicarboxylic acid component containing a group of 1 to 10 mol% with respect to the total acid component is preferable in that the surface hardness of the conductive laminated film of the present invention is high. . As an example of such a dicarboxylic acid, 5-sodium sulfoisophthalic acid is preferred.

Other dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid,
4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid, cyclohexane-1,
4-dicarboxylic acid and the like. From the viewpoint of improving the surface hardness of the conductive laminated film of the present invention, terephthalic acid and isophthalic acid are preferred.

As the glycol component for preparing the copolymerized polyester, ethylene glycol is mainly used, and in addition, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, and ethylene oxide adduct of bisphenol A are also used. , Polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol and the like can be used. Among them, when ethylene glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexane dimethanol, or the like is used as a copolymer component, the compatibility with the sulfonated polyaniline is improved, and the surface resistance, strength, and transparency of the coating film surface are improved. This is preferred in terms of improving the properties.

Further, transparency and adhesion can be further improved by graft polymerization of a vinyl monomer having a hydrophilic group on the side chain of the polyester. Examples of the vinyl-based monomer having a hydrophilic group that can be grafted on the polyester include a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, and the like, an acid anhydride group as a group that can be converted into a hydrophilic group, Those containing a glycidyl group, a chloro group and the like can be mentioned. Among them, those having a carboxyl group are most preferred.

For example, monomers containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n
Alkyl acrylates such as -butyl acrylate and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-
Alkyl methacrylate such as butyl methacrylate, 2
Hydroxy-containing monomers such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N -Methoxymethyl methacrylamide, N, N-dimethylolacrylamide,
Examples include amide group-containing monomers such as N-phenylacrylamide, and epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate. Other monomers having a hydrophilic group include, for example, monomers containing an epoxy group such as allyl glycidyl ether, styrene sulfonic acid, monomers containing a sulfonic acid group or a salt thereof such as vinyl sulfonic acid and salts thereof, crotonic acid, Monomers containing a carboxyl group or a salt thereof such as itaconic acid, maleic acid, fumaric acid and salts thereof, and monomers containing an acid anhydride such as maleic anhydride and itaconic anhydride are exemplified. These can be used in combination with other monomers. Examples of other monomers include, for example, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride, and the like. Copolymerization can be carried out using two or more kinds. The ratio of the monomer having a hydrophilic group to the other monomer is preferably in the range of 30/70 to 100/0 in molar ratio. When the ratio of the monomer having a hydrophilic group is 30
If it is less than mol%, the effect of increasing the transparency of the coating film cannot be sufficiently exhibited.

As a method for grafting a monomer having a hydrophilic group to the polyester, a known graft polymerization method can be used. The following method is mentioned as a typical example. For example, a radical polymerization method in which radicals are generated in a polyester of a main chain by light, heat, radiation, or the like, and then a monomer is graft-polymerized, or AlCl3,
There are a cation polymerization method in which cations are generated using a catalyst such as TiCl4, and an anion polymerization method in which anions are generated using metal Na, metal Li, or the like. Further, there is a method in which a polymerizable unsaturated double bond is previously introduced into the polyester of the main chain, and a vinyl monomer is reacted with the polymerizable unsaturated double bond. Examples of the monomer having a polymerizable unsaturated double bond used therein include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. be able to. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid. Further, there is a method of reacting a main-chain polyester having a functional group introduced into a side chain with a branch polymer having a group that reacts with the functional group at the terminal. For example, a polymer substance having a hydrogen-donating group such as -OH group, -SH group, -NH2 group, -COOH group -CONH2 group in a side chain;
One end is -N = C = O group, -C = C = O group,

[0019]

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[0020]

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And the like, and a reaction in the reverse combination. The weight ratio of the main chain polyester of the present invention to the grafted vinyl monomer is 40 / 60-9.
5/5, more preferably 55 / 45-9.
3/7, most preferably in the range of 60/40 to 90/10. When the weight ratio of the polyester in the main chain is less than 40%, the properties such as heat resistance and processability of the conventional polyester are impaired because the graft-polymerizable vinyl monomer remains completely unreacted. On the other hand, when the weight ratio of the main chain polymer substance exceeds 95%, the effect of improving conductivity and transparency, which is the object of the present invention, cannot be sufficiently exhibited.

In addition, the copolymer component may contain a small amount of a dicarboxylic acid component or a glycol component containing an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like. It is also possible to bond acrylic acid, methacrylic acid, styrene sulfonic acid, acrylamide, or the like to the main chain of the polyester in the form of graft copolymerization.

Further, in order to improve the surface hardness of the coating film obtained by applying the obtained conductive layer of the present invention to fibers, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride It is also possible to use a polycarboxy group-containing monomer such as the above as a copolymer component of the polyester in a proportion of 5 mol% or less. If it exceeds 5 mol%, the resulting sulfonic acid group-containing copolymerized polyester becomes thermally unstable and easily gelates,
It is not preferable as a component of the conductive layer of the present invention.

The above-mentioned sulfonic acid group-containing copolymerized polyester can be subjected to a transesterification reaction, a polycondensation reaction, and the like, using, for example, the above-mentioned dicarboxylic acid component, the above-mentioned glycol component, and if necessary, the above-mentioned polycarboxylic acid-containing monomer. It is obtained by performing a reaction or the like. The obtained sulfonic acid group-containing copolymerized polyester is heated and stirred with a solvent such as n-butyl cellosolve, and can be used as an aqueous solution or aqueous dispersion by gradually adding water while stirring.

The content of the above-mentioned sulfonic acid group-containing copolymerized polyester is preferably from 50 to 2,000 parts by weight, more preferably from 50 to 2,000 parts by weight, based on 100 parts by weight of the sulfonated polyaniline, in view of the conductivity and mechanical properties of the obtained conductive laminated film. Is from 100 to 1500 parts by weight, most preferably 2
It is 00 to 1000 parts by weight.

The conductive layer of the present invention is usually dissolved or dispersed in a solvent and applied to a desired fiber surface. As the solvent used here, any organic solvent can be used as long as it does not dissolve or swell the fiber base material (for example, polyester fiber or the like). The use of water or a mixed solvent of water and an organic solvent is not only preferable in terms of use environment, but also sometimes improves the antistatic property of the obtained conductive fiber of the present invention.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; methyl propylene glycol; Propylene glycols such as propylene glycol, amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone are preferably used. These organic solvents can be used by being mixed with water at an arbitrary ratio.

Examples of mixing include water / methanol, water /
Ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol and the like can be mentioned. The mixing ratio is
Water / organic solvent = 1/10 to 10/1 is preferred.

The proportion of the solvent used is not particularly limited, but is usually 10 parts by weight based on 100 parts by weight of the sulfonated polyaniline.
It is 00 to 20000 parts by weight. When the amount of the solvent used is extremely large, the applicability of the obtained conductive laminated film of the present invention may be deteriorated. Therefore, pinholes are easily generated in the conductive layer, and the conductivity of the conductive fiber may be significantly reduced, that is, the antistatic property may be reduced. When the amount of the solvent used is extremely small, the solubility or dispersibility of the sulfonated polyaniline in the solvent may be insufficient, and the surface of the obtained conductive layer may not be easily flat.

The conductive layer of the present invention is excellent in coating properties and spreadability by using only the above-mentioned components, and has a good surface hardness of the obtained conductive layer. By further using a polymer compound, it becomes possible to apply the composition to a fiber surface having poor wettability.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan fatty acid ester, and fluoroalkyl carboxylic acids, perfluoroalkyl carboxylic acids, and the like. Fluorinated surfactants such as perfluoroalkylbenzenesulfonic acid, perfluoroalkylquaternary ammonium, and perfluoroalkylpolyoxyethyleneethanol are used, but are not limited thereto.

The amount of the surfactant used in the present invention is 0.00 0.00 part by weight of the sulfonated polyaniline.
1 part by weight or more and 10 parts by weight or less.

When the amount of the surfactant exceeds 10 parts by weight, the surfactant in the coat layer is set off on the non-coated surface, causing a problem in secondary processing or the like.

Examples of the high molecular compound which can be contained in the conductive layer of the conductive fiber of the present invention include water-soluble resins such as polyacrylamide and polyvinylpyrrolidone, and water-soluble or water-dispersible compounds containing a hydroxyl group or a carboxylic acid group. Acrylic resins such as polymerized polyester, polyacrylic acid and polymethacrylic acid, acrylate resins such as polyacrylate and polymethacrylate, polyethylene terephthalate, polybutylene terephthalate,
Such as ester resins, polystyrene, poly-α-methylstyrene, polychloromethylstyrene, polystyrenesulfonic acid, styrene resins such as polyvinylphenol,
Vinyl ether resins such as polyvinyl methyl ether and polyvinyl ethyl ether, polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, and phenol resins such as novolak and resol may be used. Among them, water-soluble or water-dispersible copolymerized polyesters and polyvinyl alcohols containing a hydroxyl group or a carboxylic acid group from the viewpoint of compatibility with the above-mentioned sulfonated polyaniline, and from the viewpoint of adhesion to a fiber base material such as polyester. preferable.

The amount of the polymer compound is preferably from 0 to 100 parts by weight based on 100 parts by weight of the sulfonated polyaniline.
0 parts by weight, more preferably 0 to 500 parts by weight. When the amount of the polymer compound is 1000 parts by weight or more, the conductivity of the sulfonated polyaniline does not appear, and the original antistatic function is not exhibited.

The conductive layer of the conductive laminate of the present invention includes
In addition, various additives may be included. Such additives
As TiO_Two, SiO_Two, Kaolin, CaC
O_Three, Al_TwoO_Three, BaSO_Four, ZnO, talc, my
Inorganic particles such as mosquitoes and composite particles;
Organic particles composed of related or cross-linked products thereof
And the like. To further improve conductivity
And SnO_Two, (Tin oxide), ZnO (zinc oxide) powder
Finally, the inorganic particles (TiO2)_Two, BaSO _Four
Etc.), carbon black, graphite, carbon fiber, etc.
It is also possible to add a carbon-based conductive filler
is there. The content of the above additives is determined by sulfonated polyaniline.
At a ratio of 4000 parts by weight or less to 100 parts by weight
Preferably. If it exceeds 4000, the conductive layer
May cause uneven coating due to increased viscosity.
You.

As a method of laminating a conductive layer on the surface of the fiber yarn, there are a method of laminating an aqueous or oil-based emulsion by a guide roll after melt spinning, and a method of dipping in a liquid. Further, as a method of laminating the conductive layer on the surface of the sheet-like material, a back coating method, a dipping method, a spraying method and the like can be mentioned.

Function and Effect When the conductive fiber of the present invention is used as a fiber, it is possible to provide an antistatic property even under low humidity while maintaining high surface strength, flexibility and transparency.

Examples Next, examples and comparative examples of the present invention will be described, but the present invention is not limited to these examples. The evaluation method used in the present invention is shown below.

1) Presence / absence of whitening of the conductive layer The surface of the conductive layer was irradiated with light with bromolite, and the presence / absence of whitening was evaluated as follows. -There is no whitening part on the conductive layer surface. : A part of the surface of the conductive layer is whitened. : ×

2) Surface resistance value Applied voltage 500 V, 25
C., 15% RH and 60% RH.

3) Charge decay time Using a static decay meter manufactured by ETS, USA,
The sample is sandwiched between the electrodes in an atmosphere of 25 ° C. and 15% RH, and a voltage of 5.0 KV is applied. When the applied voltage reaches 5.0 KV, the electrodes are grounded. Under measurement of time t99 until becomes.

4) Evaluation of Adhesion of Conductive Layer to Nonwoven Fabric and Woven Fabric The cellophane tape was peeled off from the surface of the conductive layer, and whether the conductive layer was peeled off from the nonwoven fabric and woven fabric was evaluated as follows. -The conductive layer does not peel off and does not adhere to the cellophane tape at all. : ○-The conductive layer slightly peeled off and adhered to the cellophane tape. : △ ・ The conductive layer is completely peeled off and adheres to cellophane tape. : ×

5) Water resistance The surface of the conductive layer was wiped 10 times at a constant pressure using a commercially available tissue paper impregnated with water. Δ, x when completely wiped off.

6) Heat resistance The conductive laminated film and the nonwoven fabric are manufactured by ESPEC HIG.
Using H-TEMP OVEN PHH-1, 250
After heating at 1 ° C. for 1 minute, the surface resistance before and after that was measured by the same method as in 2) above, and the ratio was calculated. 1 at 250 ° C
Change rate of surface resistance value of conductive layer after heating for one minute Change rate (times) = (B) / (A) (A): Surface resistance value of conductive layer at 25 ° C. and 60% RH atmosphere (B): 25 ° C, 60% RH after heating at 250 ° C for 1 minute
Surface resistance value of conductive layer under atmosphere

(Synthesis Example 1) Preparation of sulfonic acid group-containing polyaniline coating solution 2-aminoanisole-4-sulfonic acid 100 mmol
Was stirred and dissolved in a 4 mol / l aqueous ammonia solution at 23 ° C., and ammonium peroxodisulfate (100 mmol) was dissolved.
l of aqueous solution was added dropwise. After the addition, the mixture was further stirred at 23 ° C. for 10 hours, and the reaction product was separated by filtration, washed, and dried to obtain 13 g of a powdery copolymer. The volume resistivity of this copolymer was 12.3 Ω · cm. 3 parts by weight of the above polymer was stirred and dissolved at room temperature in 100 parts by weight of a 0.3 mol / l sulfuric acid aqueous solution to prepare a conductive composition. At this time, the content of the sulfonic acid group of the sulfonated polyaniline is 100
%Met. 2.0 parts by weight of the sulfonated polyaniline was dissolved in 50 parts by weight of water and 50 parts by weight of isopropanol.

(Synthesis Example 2) Synthesis of Polyester (A) and Preparation of Its Water / Alcohol Dispersion (Aaq) First, a sulfonic acid group-containing polyester was synthesized by the following method, and further its dispersion was prepared. Dimethyl terephthalate 46 mol%, dimethyl isophthalate 47 mol% and sodium 5-sulfoisophthalate 7 mol% are used as dicarboxylic acid components, and ethylene glycol 50 mol% and neopentyl glycol 5 are used as glycol components.
Using 0 mol%, a transesterification reaction and a polycondensation reaction were carried out by a conventional method. The glass transition temperature of the obtained sulfonic acid group-containing polyester was 69 ° C. The sulfonic acid group-containing polyester (300 parts) and n-butyl cellosolve (150 parts) were heated and stirred to form a viscous solution, and 550 parts of water was gradually added with further stirring to obtain a uniform pale white solid having a solid content of 30% by weight. Was obtained. This dispersion was further added to a mixture of equal amounts of water and isopropanol to prepare (Aaq) an aqueous dispersion of a sulfonic acid group-containing polyester having a solid content of 8% by weight.

(Synthesis Example 3) Synthesis of Acrylic Graft Polyester (B) and Preparation of Aqueous Dispersion (Baq) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 5 mol of dimethyl terephthalate and dimethyl 4.5 moles of isophthalate, 6.5 moles of ethylene glycol, 3.5 moles of neopentyl glycol
Mol and 0.002 mol of tetra-n-butyl titanate, and transesterification was performed at 160 to 220 ° C. for 4 hours. Then, 0.5 mol of fumaric acid was added, the temperature was raised to 200 to 220 ° C. over 1 hour, and the pressure of the reaction system was gradually reduced. Then, the reaction was carried out at a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester (B0). I got

Next, the above polyester B0300 was placed in a reactor equipped with a stirrer, thermometer, reflux device and metering dropping device.
Parts, 360 parts of methyl ethyl ketone and 120 parts of isopropyl alcohol, and heated and stirred to dissolve the resin under reflux. After the resin is completely dissolved, a mixture of 35 parts of acrylic acid and 65 parts of ethyl acrylate, 1.5 parts of octyl mercaptan, and 6 parts of azobisisobutyronitrile are dissolved in a mixture of 90 parts of methyl ethyl ketone and 30 parts of isopropyl alcohol. The resulting solution was added dropwise to the polyester solution over 1.5 hours, and further reacted for 3 hours to obtain a graft polymer (B) solution. After the graft polymer solution was cooled to room temperature, 59 parts of triethylamine was added and neutralized, and then 800 parts of ion-exchanged water was added and stirred for 30 minutes. Thereafter, the solvent remaining in the solvent is distilled off by heating to form an aqueous dispersion, and this dispersion is further added to a mixed solution of an equal amount of water and isopropanol, and an alcohol / water dispersion having a solid content of 8% by weight (Baq ).

(Preparation of base nonwoven fabric) 0.4% by weight of sodium alkylbenzenesulfonate and 0.1% of titanium oxide were used.
A polyethylene terephthalate having an intrinsic viscosity of 0.63, containing 0.4% by weight, is melted at 290 ° C., extruded from a nozzle by a conventional method, placed on a net-shaped conveyor, and then pressure-bonded with an embossing roll and wound up. A non-woven fabric was produced.

(Preparation of raw yarn and conductive fabric) Polyethylene terephthalate containing 0.3% by weight of sodium alkylbenzenesulfonate and 0.03% by weight of titanium oxide and having an intrinsic viscosity of 0.62 was melted at 290 ° C. The coating solution was extruded from the nozzle by a conventional method, and the coating solution was applied to the surface of the yarn using a guide roll, and then wound at a speed of 1500 m / min.
Thereafter, the undrawn filament was subjected to a drawing heat treatment at a drawing temperature of 90 ° C. and a heat treatment temperature of 150 ° C., and was wound up to obtain a conductive fiber. The obtained conductive fiber was used as a plain woven fabric to prepare a predetermined conductive woven fabric.

(Example 1) A solid content ratio of the sulfonated polyaniline obtained in Synthesis Example 1 and the sulfonic acid group-containing polyester obtained in Synthesis Example 2 was 10/90, and a surfactant was prepared. Dip coating was performed on a coating solution in which Emulgen 810 (manufactured by Kao) was added so as to have a ratio of 8/100 to the sulfonated polyaniline, to prepare a conductive nonwoven fabric of the present invention.

Example 2 A conductive nonwoven fabric was produced in the same manner as in Example 1 except that the solid content ratio of the sulfonated polyaniline and the sulfonic acid group-containing polyester was changed to 20/80.

Example 3 A conductive nonwoven fabric was produced in the same manner as in Example 1 except that the dispersion of Synthesis Example 3 was used instead of the dispersion of Synthesis Example 2.

Example 4 A conductive nonwoven fabric was produced in the same manner as in Example 1 except that the concentration of the coating solution was changed to 1%.

(Comparative Example 1) As a coating solution, an anionic antistatic agent, "Chemistat SA-" manufactured by "Sanyo Chemical Industries" was used.
A conductive nonwoven fabric was produced in the same manner as in Example 1 except that No. 9 was used.

(Comparative Example 2) As a coating solution, a cationic antistatic agent, Chemistat 630 manufactured by Sanyo Chemical Industries, Ltd. was used.
Except having used 0-H, it carried out similarly to Example 1 and produced the conductive nonwoven fabric.

(Comparative Example 3) The nonwoven fabric of the substrate was evaluated as it was without applying the coating liquid.

Table 1 shows the above results. As shown in Table 1, all of the examples had low surface resistance at low humidity, sufficient antistatic properties, and excellent heat resistance. On the other hand, in Comparative Example 1, the heat resistance was good, but the surface resistance at low humidity was large and the antistatic property was insufficient. In Comparative Example 2, the surface resistance was slightly increased at low humidity, the antistatic property was insufficient, and the heat resistance was not sufficient. Further, Comparative Example 3 had no antistatic property at all.

(Example 5) The conductive woven fabric obtained by applying the coating solution used in Example 1 was evaluated.

Example 6 A conductive fabric was produced in the same manner as in Example 5, except that the solid content ratio of the sulfonated polyaniline and the sulfonic acid group-containing polyester was changed to 20/80.

Example 7 A conductive fabric was produced in the same manner as in Example 5, except that the dispersion of Synthesis Example 3 was used instead of the dispersion of Synthesis Example 2.

Example 8 An electrically conductive fabric was produced in the same manner as in Example 5, except that the concentration of the coating solution was changed to 1%.

(Comparative Example 4) As a coating solution, an anionic antistatic agent, Chemistat SA- manufactured by Sanyo Chemical Industries, Ltd. was used.
Except for using No. 9, the same procedure was performed as in Example 5 to prepare a conductive woven fabric.

(Comparative Example 5) As a coating solution, a cationic antistatic agent, Chemistat 630 manufactured by Sanyo Chemical Industries, Ltd. was used.
Except having used 0-H, it carried out similarly to Example 5 and produced the conductive textile.

Comparative Example 6 A conductive woven fabric was prepared in the same manner as in Example 5, except that a woven fabric was prepared from the original yarn without applying the coating solution.

Table 2 shows the results. As shown in Table 2, all of the examples had low surface resistance at low humidity, had sufficient antistatic properties, and were excellent in heat resistance. On the other hand, Comparative Example 4 had good heat resistance, but had a large surface resistance at low humidity and insufficient antistatic properties. In Comparative Example 5, the surface resistance increased at low humidity, the antistatic property was insufficient, and the heat resistance was not sufficient. Comparative Example 6 had no antistatic property at all.

[0068]

As is clear from the above description, the conductive fiber of the present invention has excellent transparency and exhibits excellent antistatic properties even under low humidity. Furthermore, heat resistance is sufficient. The conductive fiber of the present invention is suitable for clothing such as antistatic work clothes, uniforms and white coats, interior fiber products such as carpets, curtains and chair coverings, hats and bags, and textile products for industrial materials. is there.

[0069]

[Table 1]

[0070]

[Table 2]

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Claims (14)

[Claims] 1. A conductive fiber in which a conductive layer is laminated on the surface of a fiber, wherein the conductive layer has a surface resistance value of 10 ⁶ to 10 ¹² Ω / □ in an atmosphere of 25 ° C. and 15% RH, and a charge decay time. Is 2 seconds or less, and the rate of change in surface resistance of the conductive layer after heating at 250 ° C. for 1 minute is within 5.0. 2. A conductive fiber, wherein the conductive layer according to claim 1 contains a conductive polymer. 3. The conductive fiber according to claim 1, wherein the conductive layer contains a thermoplastic resin. 4. The conductive fiber according to claim 1, wherein the conductive layer contains a surfactant. 5. The conductive fiber according to claim 1, wherein the fiber is a yarn and / or a sheet. 6. A conductive fiber, wherein the conductive polymer according to claim 2 is polyaniline or a derivative thereof. 7. A conductive fiber, wherein the thermoplastic resin according to claim 3 has a hydrophilic group. 8. The thermoplastic resin according to claim 3, having at least one of an ionic group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, an acid anhydride group, a glycidyl group, a chloro group, and a polyalkylene glycol. A conductive fiber characterized by the above-mentioned. 9. A conductive fiber, wherein the thermoplastic resin according to claim 3 is a water-soluble or water-dispersible resin containing an anionic group. 10. The conductive fiber according to claim 3, wherein the thermoplastic resin is a copolyester in which at least one group selected from the group consisting of a sulfonic acid group and an alkali metal base thereof is bonded. . 11. The thermoplastic resin according to claim 3, wherein
A conductive fiber comprising 1 to 10 mol% of a sulfoisophthalic acid unit. 12. A conductive fiber, wherein the polyaniline or the derivative thereof according to claim 6 is a polyaniline containing a sulfonic acid group. 13. A conductive fiber, wherein the polyaniline or the derivative thereof according to claim 6 contains an alkoxy-substituted aminobenzenesulfonic acid. 14. A conductive laminate, wherein the polyaniline or the derivative thereof according to claim 6 contains aminoanisolesulfonic acid.