JP2000096346A - Heat-storing and conductive fiber and yarn and fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-storing and conductive fiber not colored and having both a heat-storing property and a conductive property, and to provide a fiber product comprising the heat-storing and conductive fibers. SOLUTION: This heat-storing and conductive fiber comprises a sheath-core conjugate fiber whose core portion contains white conductive ceramic particles, and has an electric conductivity of >=10-6 S/cm. The white conductive ceramic particles exist as aggregates having an average diameter of 0.5-5 μm, and are contained in the core portion in a concentration of 15-70 vol.%. A yarn and a fabric comprise the fibers, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat storage and conductive fiber having both heat storage and conductivity, and to a fiber product such as a yarn or a cloth made of the heat storage and conductive fiber.

[0002]

2. Description of the Related Art Hitherto, as a fiber material in the field of winter clothing or sports clothing, heat storage fibers in which carbide-based ceramic fine particles are kneaded by adding carbide-based ceramic fine particles to a spinning solution in order to enhance heat retention have been proposed. However, such fiber material, the fiber is colored,
It is unsuitable when whiteness and coloring are required for clothing.

[0003] In general, synthetic fibers are electrically insulative, and are easily charged with static electricity generated by contact or friction.
There is a problem that the charged static electricity causes clinging of clothes, adhesion of dirt, ignition of combustible gas and dust, explosion, and malfunction of electronic devices. As a means for solving the problem of static electricity of the synthetic fiber, there is a method of kneading fine particles of a conductive substance represented by carbon black into the fiber, and there is also a method of core-sheath composite spinning as a kneading method. Since the conductive fibers are colored, there is a drawback that the applications for which the conductive fibers are used are limited.

In order to solve the problem of coloring of the heat storage fiber or the conductive fiber, indium tin oxide,
A method has been proposed in which white ceramic fine particles having conductivity, such as antimony and tin oxide, are disposed on the core of the core-sheath composite fiber. In this method, although conductivity and heat storage are obtained, the method is not practical. A large amount of white ceramic fine particles is required in order to secure sufficient heat storage to exhibit heat retention.

[0005]

DISCLOSURE OF THE INVENTION The present invention is based on the object of using an electrically conductive fine particle, particularly a white ceramic fine particle having conductivity, if such a fine particle is present in a specific agglomerated state at the core of the conjugate fiber. It has been found that a fiber which is free from coloring and has both heat storage properties and conductivity can be obtained within the range of a typical use amount. SUMMARY OF THE INVENTION An object of the present invention is to provide a heat storage and conductive fiber which is not colored and has both heat storage and conductivity, and a fiber product comprising the heat storage and conductive fiber.

[0006]

The gist of the present invention is to provide a fiber in which white conductive ceramic fine particles are arranged on the core of a core-sheath composite fiber, and the ceramic fine particles have an average diameter of 0.1 mm.
A heat storage and conductive fiber which is present as an aggregate of 5 to 5 μm, is contained in an amount of 15 to 70% by volume in the core, and has a conductivity of 10 ⁻⁶ S / cm or more.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The heat storage and conductive fibers of the present invention
It is necessary that the white conductive ceramic fine particles be disposed on the core of the core-sheath composite fiber, and if the white conductive ceramic fine particles are disposed on the sheath, processing passability in a processing step such as a spinning process is poor. Also, when used for clothing or the like, the feeling of wearing becomes poor.

In the present invention, the white conductive ceramic fine particles may have a conductivity of 1% without imparting coloring to the fiber.
In order to exhibit good conductivity and heat storage of 0 ^-6 S / cm or more, it is desirable that the white color and the conductivity be 10 ^-3 S / cm or more, preferably indium tin oxide , Antimony-tin oxide, conductive titanium oxide, etc., but are not limited to these as long as they are white and have a conductivity of 10 ⁻³ S / cm or more. The white conductive ceramic fine particles have a particle size of 0.1.
It is preferably at least 01 μm and less than 5 μm. If the particle size exceeds 5 μm, no agglomerate is formed, and the spinning nozzle pressure for obtaining fibers increases, resulting in poor spinnability.
If it is less than 01 μm, handling becomes difficult.

In the heat storage and conductive fiber of the present invention,
It is necessary that the white conductive ceramic fine particles disposed on the core of the core-sheath composite fiber exist as an aggregate having an average diameter of 0.5 to 5 μm. The mechanism by which the aggregates of white conductive ceramic particles are formed is not clear, but the process in which the substrate polymer solidifies during fiber formation in the spinning process, i.e., in the case of melt spinning, a wet process is performed in a polymer melt. In the case of solution spinning such as spinning, it is understood that, in a polymer solution, ceramic fine particles agglomerate due to phase separation from a polymer dense phase as the polymer solidifies.

[0010] Thermal conductivity and conductivity are generated by the formation of heat and electron paths formed by a series of conductive ceramic fine particles. The polymer phase between the conductive ceramic fine particles and the conductive ceramic fine particles is formed in the path. And acts as a defect point to hinder the transfer of heat and electrons. Therefore,
The heat conduction performance and the conduction performance depend on the number of passes and the number of defect points in the passes. In the heat storage and conductive fibers of the present invention, the conductive ceramic fine particles are present as aggregates, the contact interface between the aggregates in the path is increased, and the number of defect points in the path is reduced, so that the light energy is reduced to the ceramic fine particles. The heat absorbed and converted into heat energy is efficiently transferred to the entire fiber, and is stored in the entire fiber to enhance the heat retention, improve the conductive performance, and easily discharge static electricity.

The presence of aggregates of white conductive ceramic fine particles in the core is determined by cutting out the fiber longitudinal section of the core-sheath composite fiber, subjecting the exposed longitudinal section of the core to ion plasma etching, and scanning the treated surface with a scanning type. It can be confirmed by observing with an electron microscope. The size of the aggregate, that is, the diameter, can be calculated as an average diameter by performing image processing on an image with a scanning electron microscope.

The larger the diameter of the aggregate of the white conductive ceramic fine particles is, the more advantageous it is.
If it exceeds m, the number of passes becomes relatively small, and it becomes difficult to obtain fine fibers having good heat storage properties and conductivity. The number of passes depends on the total amount of the white conductive ceramic fine particles contained in the core, and in the heat storage and conductive fiber of the present invention, the total amount of the white conductive ceramic fine particles is 15 to 70% by volume in the core. , Preferably 20 to 60% by volume. When the amount of the white conductive ceramic fine particles is less than 15% by volume, heat storage and conductivity are insufficient or unevenness occurs, and
If the content exceeds 0% by volume, the spinnability may be deteriorated, and the core may be cut to lose heat storage and conductive functions.

The heat storage and conductive fiber of the present invention is a core / sheath composite fiber, and the volume ratio of the core / sheath is not particularly limited, but the volume ratio of the core / sheath is preferably 10/90. ~
It is preferably 50/50. Examples of the core and sheath components of the core-sheath composite fiber constituting the heat storage and conductive fiber of the present invention include polyester, nylon, polyethylene, polypropylene, acrylonitrile-based polymer, polyurethane, rayon, and the like. The components may be combinations of different or similar polymers.

Particularly, in the heat storage and conductive fiber of the present invention, the core and sheath components of the core-sheath composite fiber are preferably acrylonitrile-based polymers, and when the core and sheath components are acrylonitrile-based polymers, The heat storage and conductive fibers of the present invention are excellent in texture, appearance, and coloring, and are suitably used for sweaters and the like.

The acrylonitrile-based polymer is a polymer containing 50% by weight or more of acrylonitrile, and may be a homopolymer of acrylonitrile, but is preferably an acrylonitrile copolymer. When the content of acrylonitrile is less than 50% by weight, the properties as acrylic fibers are lost, which is not preferable.
In the case of an acrylonitrile copolymer, an unsaturated monomer copolymerizable with acrylonitrile is copolymerized within a range containing 50% by weight or more of acrylonitrile. Examples of the unsaturated monomer copolymerizable with acrylonitrile include: Of the monomer.

That is, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
Acrylic esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, methacrylic acid Methacrylates such as cyclohexyl, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, N-methylolacrylamide, diacetone Monomers such as acrylamide, styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, and vinylidene fluoride Further, in the case of the purpose of dyeability improvement, p- sulfophenyl methallyl ether, methallyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2
-Acrylamide-2-methylpropanesulfonic acid and alkali metal salts thereof.

The molecular weight of the acrylonitrile-based polymer is not particularly limited, but is preferably from 100,000 to 1,000,000 in terms of spinnability, yarn quality and productivity. Fiber properties tend to decrease, and if it exceeds 1,000,000, productivity tends to decrease.

The heat storage and conductive fibers of the present invention can be obtained by blending white conductive ceramic fine particles with a polymer or a polymer solution serving as a core component in core-sheath composite spinning, and then performing core-sheath composite spinning. Core-sheath composite spinning is a melt spinning method,
Dry spinning, wet spinning or dry-wet spinning may be used.However, when the core and sheath components are acrylonitrile-based polymers, it is necessary to increase the size of the aggregate of white conductive ceramic fine particles. , Dry spinning method,
Dry-wet spinning is preferably employed.

The heat storage and the method of obtaining conductive fibers when the core and sheath components are acrylonitrile-based polymers will be further described. The acrylonitrile-based polymers may be converted to dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate, γ- A solution is prepared by dissolving in a solvent of acrylonitrile-based polymer such as butyrolactone, rodan salt aqueous solution, zinc chloride aqueous solution, nitric acid aqueous solution, and the like. Is prepared, and a core-sheath composite spinning is performed using a solution to which the white conductive ceramic fine particles are not added as a spinning solution for the sheath.

The heat storage and conductive fibers of the present invention may have any fineness, but in consideration of being used for clothing, the fineness is 1 to 1 in terms of processability such as spinning and knitting and weaving. 3
It is preferably 0 denier. The heat storage and conductive fiber of the present invention may be in the form of a filament yarn or a spun yarn, but in particular, a spun yarn has more space inside than a filament yarn, and the heat stored in the fiber. It has little heat dissipation and excellent heat retention, and is preferable as a yarn form. The spinning method for spinning the heat storage and conductive fibers of the present invention is not particularly limited, and includes cotton spinning, hemp spinning, 2-inch spinning, and spinning.
Inch spinning, worsted spinning, wool spinning, open-end spinning, jet spinner, and the like are used.

The heat storage and conductive fiber of the present invention may be a woven fabric, a knitted fabric or a non-woven fabric in a yarn form or not in a yarn form. Is excellent in heat insulation and free of static electricity.

Further, the heat storage and conductive fibers of the present invention can be used alone, and can be used in combination with other fibers to provide heat retention and reduce static electricity damage.
Other fibers that can be mixed include vegetable fibers such as cotton and hemp, animal fibers such as silk, wool and mohair, recycled fibers such as rayon and cupra, acetate fibers, vinylon fibers, polyester fibers, nylon fibers, and acrylic fibers. And synthetic fibers such as polyethylene fibers and polypropylene fibers. The mixing method may be any method such as blending, blending, weaving, and knitting.

[0023]

The present invention will be described below in more detail with reference to examples. The evaluation items in the examples were measured by the following methods.

[Electrical Conductivity of Fiber] A single fiber taken out of a fiber bundle is adhered between two metal terminals separated by 1 cm with a silver paste and attached at a temperature of 20 ° C. and a relative humidity of 40 RH%. A DC voltage is applied, and the resistance value R (Ω) between metal terminals is measured by a super insulation meter SM-8 manufactured by Toa Denpa Co., Ltd.
The conductivity σ (S / cm) was calculated by the following equation. Conductivity σ (S / cm) = 1 / (1.11 × 10 ⁻⁶ × R ×
(D / ρ)) where d is fineness (denier) and ρ is specific gravity of fiber

[Friction charge voltage] 300 g in weight, length 20
cm, a knitted fabric of 10 cm in width is scoured with a nonionic surfactant, dyed and air-dried to obtain a sample.
Friction band voltage (V) was measured with a Kyoto University Chemical Research Type rotary static tester (produced by Koa Shokai) based on L1094-1980 (a method for testing the chargeability of a woven or knitted fabric). The rotation speed of the drum was 400 rpm, the friction time was 60 seconds, and cotton cloth was used as the friction cloth.

[Heat storage property of fiber] Weight 300g, length 2
After irradiating a knitted fabric having a size of 0 cm and a width of 10 cm with a black and white reflex lamp (500 W) for 30 minutes from a position 1.5 m away from the knitted ground under an atmosphere of 20 ° C. and 60 RH%, the surface temperature of the knitted fabric (° C.) Was measured with a thermoviewer (infrared sensor manufactured by JEOL Ltd.).

(Examples 1 to 8 and Comparative Examples 1 to 3) As the core spinning solution, 93.5% by weight of acrylonitrile, 6.0% by weight of methyl acrylate and 0.5% by weight of sodium methallylsulfonate were used. Acrylonitrile-based polymer (A) having a molecular weight of 160,000 and conductive titanium oxide having a particle size of 0.2 μm and conductivity of 5 × 10 ⁻¹ S / cm (WP manufactured by Mitsubishi Materials Corporation) (B) Was added to dimethylformamide at a mixing ratio (weight) shown in Table 1 and mixed.
It was prepared by dispersion treatment in a ball mill for about 20 hours. Also,
As a spinning dope for the sheath, an acrylonitrile-based polymer having a molecular weight of 150,000 consisting of 93.1% by weight of acrylonitrile and 6.9% by weight of vinyl acetate was used at a polymer concentration of 30% by weight.
Was prepared by dissolving in dimethylformamide.

Each spinning dope is heated to 130 ° C. and the number of holes is reduced to 40.
0, 230 using a core-sheath composite spinneret having a pore diameter of 0.2 mm
The spinning solution was discharged into an inert gas at a temperature of 0 ° C. while changing the discharge ratio of each spinning solution so that the core / sheath volume ratio shown in Table 1 was obtained.
2. The obtained undrawn yarn is then continuously placed in hot water at 100 ° C.
The film was stretched 75 times and further washed in hot water at 95 ° C. Subsequently, the fiber bundle was dried and relaxed at 150 ° C. and 40 RH% under no tension and contracted by 20% to obtain a fiber bundle having a single fiber fineness of 3 denier. Table 1 shows the average diameter, the occupied volume ratio (vol%), and the conductivity of the fiber of the conductive titanium oxide aggregate at the core of the obtained fiber. Also, a mixture of raw cotton 3d × 51 mm obtained by cutting the obtained fiber bundle into a length of 51 mm and ordinary acrylic fiber raw cotton 2d × 51 mm is mixed at a ratio of 10% by weight / 90% by weight.
Into a 1/52 meter count spun yarn, knitted into a flat knitted fabric with two 18 gauge strands using this spun yarn, and evaluated the antistatic performance and heat storage properties. The results are shown in Table 1. Indicated.

[0029]

[Table 1]

[0030]

The heat storage and conductive fibers of the present invention can be used economically because fine particles of conductive material, especially white fine ceramic particles having conductivity, are present in a specific agglomerated state at the core of the composite fiber. In the range of the amount, there is no coloring, and is a fiber having both heat storage and conductivity, the yarn of the heat storage and conductive fiber of the present invention, preferably a woven or knitted or non-woven fabric composed of spun yarn, Since it has heat retention and reduces static electricity damage, it is extremely useful as a material for textile products such as winter clothing and sports clothing.

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Claims (4)

[Claims] 1. A fiber in which white conductive ceramic fine particles are arranged in a core portion of a core-sheath composite fiber, wherein the ceramic fine particles exist as an aggregate having an average diameter of 0.5 to 5 μm and occupy the core portion. A heat storage and conductive fiber, wherein the heat storage and the conductive fiber have a conductivity of 10 ⁻⁶ S / cm or more. 2. The heat storage and conductive fiber according to claim 1, wherein the core and sheath components are made of an acrylonitrile-based polymer and have a fineness of 1 to 30 denier. 3. A yarn spun from the heat storage and conductive fibers according to claim 1, 2 or 3. 4. A fabric comprising the heat storage and conductive fibers according to claim 1, 2 or 3.