JPH08113819A - Netlike structure-having antistatic fiber and its production - Google Patents

Abstract

PURPOSE: To obtain an ultra-fine antistatic fiber having netlike structure and retaining hydrophilic properties of an ethylene-vinyl alcohol copolymer and characteristic properties of an ester polymer. CONSTITUTION: This fiber is composed of mixed fibers containing at least an ethylene-vinyl alcohol copolymer and an ester polymer, and has a three dimensional netlike structure. The fiber is extremely fibrillated and excellent in antistaticity, soil-proofing properties and bacterial. barrier properties and has high strength and dyeability. Accordingly, the fiber can be used as woven cloth, knit cloth or nonwoven cloth, and it is applicable in a wide range of usage, such as clothes, warm-keeping material, artificial leather, absorbent for sanitary product, protection clothes, curtain, sheet, wiper, filter and house wrap.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic fiber having an ultrafine network structure and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for producing ultrafine fibers, a so-called melt blown method has been known in which a molten polymer is extruded from a spinning nozzle and drawn by a heating fluid to be finely drawn. However, although the melt blown method can surely obtain extremely fine fibers, it has a drawback that the fibers obtained are extremely weak because the fibers are thinned at the stage of the molten polymer, so that the stretch orientation and crystallization are small.

On the other hand, there is a so-called flash spinning method as a method for obtaining an ultrafine fiber which is superior in strength to the ultrafine fiber obtained by the melt blown method. The flash spinning method involves extruding a solution of a low boiling solvent and a polymer through a spinning nozzle, as described in U.S. Pat.
The solvent is instantly vaporized. However, although conventional fibers obtained by such flash spinning can be made into high-strength ultrafine fibers, they do not have antistatic property, so that they are electrically charged and various troubles occur when they are used as they are.

On the other hand, as for the antistatic fiber, a manufacturing method utilizing a general melt spinning method is known, and blending a polyalkylene oxide component into the fiber has antistatic durability. It is known to be the most suitable for obtaining the antistatic yarn. However, no attempt has been made in the flash spinning method. It is considered that there is a problem that the polyalkylene oxide component is eluted in the solvent and a fiber having an antistatic property cannot be formed. Therefore, in the case of the flash spinning method, it is general to apply an antistatic agent to impart antistatic property as an auxiliary process after forming fibers into a fabric. However, there is a problem that the antistatic property does not have durability, such as an increase in incidental processing cost and a decrease in antistatic property over the course of use due to peeling of the antistatic agent from the fabric. Therefore, the inventors of the present invention have made diligent studies, and in Japanese Patent Application No. 6-71180, Japanese Patent Application No. 6-71177, and Japanese Patent Application No. 6-71178,
An antistatic reticulated fiber, a nonwoven fabric thereof, and a manufacturing method thereof have been proposed.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, particularly paying attention to the hydrophilicity of an ethylene-vinyl alcohol-based polymer, and making use of the original properties of an ester-based polymer. The present invention is intended to provide an antistatic reticulated structure fiber.

[0006]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention provides (1) at least ethylene-
An antistatic network-structured fiber comprising a mixed fiber containing a vinyl alcohol-based copolymer and an ester-based polymer and having a three-dimensional network structure, and (2) at least an ethylene-vinyl alcohol-based copolymer The polymer and the ester-based polymer are mixed, a spinning mixed solution of the mixture and the solvent is formed, and thereafter, flashing under autogenous pressure or higher pressure to a temperature and pressure region substantially lower than that. Spinning, and at that time, the concentration of the polymer in the spinning mixed solution is 5 to 30% by weight, the spinning temperature is 160 to 220 ° C., and the dissolution time of the polymer is 90 minutes or less. A method for producing an electrically conductive network-structured fiber is provided.

According to the present invention, since the ethylene-vinyl alcohol copolymer improves hydrophilicity, antistatic property is imparted. Furthermore, the ester-based polymer is
A block copolymer ester containing a polyalkylene oxide component exhibits an extremely good antistatic effect due to the hydrophilic properties of both polymers. Although the reason is not clear, it is considered that the vinyl alcohol component and the polyalkylene oxide component have hygroscopicity, and the synergistic effect enhances the antistatic property.

Next, the present invention will be described in detail. The reticulated structure fiber according to the present invention refers to a fiber group in which fibril fibers corresponding to 0.01 to 10 μm are formed in a three-dimensional reticulated state, and the reticulated state is endless in the longitudinal direction of the yarn. .

An ethylene-vinyl alcohol copolymer is required as one of the polymer components constituting the fiber of the present invention. The ethylene-vinyl alcohol-based copolymer refers to a crystalline polymer made of a known random copolymer of ethylene and vinyl alcohol. The amount of the copolymerization is not particularly limited, but it is preferable that the proportion of the repeating unit composed of ethylene is 20 to 70 mol%. The remainder is preferably vinyl alcohol alone, but may be composed of repeating units of vinyl alcohol and other vinyl monomers. The proportion of the repeating unit composed of ethylene is more preferably 30 to 50 mol%.
When the proportion of ethylene units in the copolymer is less than 20 mol%, that is, the proportion of vinyl alcohol units is 7
When it is more than 0 mol%, the obtained reticulated fiber lacks flexibility. On the other hand, when the proportion of ethylene units exceeds 70 mol%, the proportion of vinyl alcohol units, that is, hydroxyl groups is inevitably small, and the affinity of the nonwoven fabric for water is lowered. It can be obtained by saponifying the vinyl acetate portion of the ethylene-vinyl alcohol copolymer, and the saponification degree in that case is preferably about 95% or more. When the saponification degree is low, the crystallinity of the copolymer is lowered, so that the copolymer is likely to be softened, which causes a trouble in the subsequent thermocompression bonding step. In addition,
As the ethylene-vinyl alcohol copolymer, it is preferable to use one having an average molecular weight of about 8,000 to 30,000.

The other polymer component constituting the fiber of the present invention is an ester polymer, and examples of the ester polymer include polyethylene terephthalate and polybutylene terephthalate. Furthermore, with these as the main components, isophthalic acid, sebacic acid, terephthalic acid,
Dicarboxylic acid components such as phthalic acid, glutaric acid, adipic acid, 5-sodium sulfoisophthalic acid and naphthalic acid, and ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanediene It is also possible to use those containing a diol component such as methanol or xylylene glycol as a copolymerization component in a range of up to 40 mol%. In this case, the viscosity is the mixing ratio of tetrachloroethane and phenol of 1/1 (weight ratio), 2
The relative viscosity measured at 0 ° C. and a concentration of 0.5% by weight is 1.3 to
It can be applied from fiber grade of about 1.6 to high viscosity resin (relative viscosity 1.7) produced by solid state polymerization. The higher the viscosity of the polymer, the stronger the strength of the nonwoven fabric, which is the preferred direction.

Among the ester-based polymers constituting the fiber of the present invention, the use of a block copolymer ester containing a polyalkylene oxide component may further enhance the antistatic effect. In this case, the block copolymer means polyethylene oxide, polypropylene oxide, and ethylene oxide-propylene oxide copolymer.

Specifically, when a polyester is synthesized, a polyalkylene oxide compound having one or more (preferably two) ester functional groups such as a hydroxyl group, a carboxyl group, an alkoxycarbonyl group and an amino group is added. What is obtained by this is suitable. The polyalkylene oxide component has a molecular weight of 400 to 20.
000, preferably 800 to 10,000. The content of the polyalkylene oxide component in the block copolymerized ester is 10 to 50% by weight, preferably 2
0-40% by weight is preferred.

The content of the polyalkylene oxide component in the fiber is preferably 0.3 to 35% by weight.
If the amount is less than 0.3% by weight, the amount of polyalkylene oxide component in the fiber is small, so that it becomes unsatisfactory when higher antistatic performance is required. On the other hand, if it exceeds 35% by weight,
Although it is sufficiently satisfactory in terms of antistatic performance, the antistatic property is saturated, the strength of the fiber is reduced, and the heat resistance is also reduced. Furthermore, the performance of the three-dimensional reticulated fiber is deteriorated and the cost is increased, which is not preferable. Therefore, 0.5-2
It is more preferable to contain 0% by weight, and 1 to 10% by weight
Is most preferable.

As the polyalkylene oxide, a modified polyalkylene oxide, for example, a compound obtained by adding alkylene oxide to bisphenols such as bisphenol A and bisphenol S is preferable from the viewpoint of improving heat resistance and antistatic property. . Further, a hydrophilic component such as 5-alkali metal sulfoisophthalic acid or N, N'-bis (amino-n-propyl) piperazine is used as a polyester-forming component, or an organic or inorganic electrolyte or other ionic compound is used as a block copolymer. Compounding is particularly preferable because it has the advantage of increasing the antistatic activity of the block copolymer.

When the ester polymer is a polyalkylene oxide component-containing block copolymer ester, the hydrophilic properties of both the block copolymer and the ethylene-vinyl alcohol copolymer are very good. Shows the effective antistatic effect. The reason for this is not clear, but it seems that the vinyl alcohol component and the polyalkylene oxide component have hygroscopicity, and the synergistic effect enhances the antistatic property.

In the present invention, the proportion of the ethylene-vinyl alcohol copolymer in the mixed fiber is preferably 5 to 95% by weight. If this proportion exceeds 95% by weight, the contribution of the ester-based polymer is reduced, but the characteristics of this ester-based polymer are lost, although the antistatic performance is good, and the modulus of the fiber is reduced, and If you do so, you will lose the waist, use, and feeling of wearing, which is not good.
The ratio of ethylene-vinyl alcohol copolymer is 5
If it is less than weight%, the antistatic performance is deteriorated. Therefore 1
Most preferably, it is from 0 to 90% by weight.

In the present invention, in addition to the ethylene-vinyl alcohol-based copolymer and the ester-based polymer, other crystalline polymer may be contained to the extent that the present invention is not excluded. For example, an olefin polymer such as polyethylene or polypropylene may be contained.

As described above, the fiber according to the present invention is a mixture of at least ethylene-vinyl alcohol copolymer and ester polymer, but these are basically incompatible with each other. , Fibrillation can be promoted. This incompatibility with each other means that the mixed polymer components are present independently and have the essential fiber properties of the individual polymers. As is generally known that mixed fibers of polymers which are not compatible with each other are easily divided into components by physical force,
Since the fibers of the present invention are incompatible with each other, extremely fine fibril fibers of a simple polymer are mainly constituted.

Next, a method for producing the reticulated structure fiber of the present invention will be described. However, it goes without saying that the present invention is not limited to this method. In order to produce the fiber of the present invention, a generally known flash spinning method can be applied. That is, a mixed polymer of an ethylene-vinyl alcohol-based copolymer and an ester-based polymer is used, and a solvent which does not dissolve in these polymers at a low temperature but dissolves at a high temperature and a high pressure is used to Dissolve under high temperature and high pressure to form one bath phase. Then, the polymer and the solvent can be produced by spinning from a nozzle in a state of phase separation.

Examples of the solvent include generally known aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as butane, pentane and isomers and homologs thereof, and alicyclic hydrocarbons such as cyclohexane. Unsaturated hydrocarbons, halogenated hydrocarbons such as trichloromethane, methylene chloride, carbon tetrachloride, chloroform, 1,1
-Dichloro-2,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane, methyl chloride, ethyl chloride, etc., alcohols, ethers, ketones, nitriles, amides, fluorocarbons, and these Examples thereof include a mixture of solvents. In recent years, the use of solvents that deplete the ozone layer must be avoided as global environmental issues have been clamored for. Including this environmental problem, preferable solvents for the present invention include methylene chloride, 1,1-dichloro-2,2-difluoroethane, 1,2-dichloro-1, and
1-difluoroethane and the like can be mentioned.

The concentration range of the polymer cannot be unconditionally limited depending on the degree of polymerization of this polymer, the kind of solvent and the pressure state, but in the present invention, the concentration of the polymer in the spinning mixed solution is 5 to 30% by weight. It is preferable that When the concentration of the polymer is less than 5% by weight, it is difficult to obtain continuous long fibers. On the other hand, if it exceeds 30% by weight, it becomes a tubular fiber which is not fibrillated and contains bubbles, and it becomes impossible to obtain a reticulated fiber having an ultrafine high strength fibril.

On the other hand, the solvent concentration is preferably 70 to 95% by weight. If the solvent concentration is less than 70% by weight, the viscosity of the spinning mixed solution becomes too high and the dissolution of the polymer is less likely to be uniform, and ultrafine fibril fibers do not tend to be formed, but fibers having voids tend to be formed. On the other hand, if it exceeds 95% by weight, the reticulated structure fibers made of fibril fibers do not become continuous, which is not preferable.

It is very desirable to add and inject nitrogen, represented by an inert gas, carbon dioxide, etc. before or after preparing the spinning mixed solution in order to increase the spinning pressure. In particular, adding an inert gas before the temperature rise prevents the deterioration of the polymer, promotes the temperature rise property, promotes the solubility of the polymer in a solvent, improves the productivity of extremely fine fibril network fibers, etc. From the viewpoint of.

In producing the reticulated structure fiber of the present invention, the stretching and orientation of the fiber are made by the explosive force associated with the vaporization of the solvent, and the strength of the fiber is determined by whether the fiber is sufficiently stretched and oriented. Often. This explosive force is the vaporization force due to the instantaneous speed, and the solvent vaporizes at once in a time of 0.1 seconds or less, and in the process, the concentration of the polymer increases in the short time, and finally the mixture is mixed. Only the polymer precipitates. Although the mixed polymer precipitated by the evaporation of the solvent is cooled, the strength of the fiber is most important in this cooling process, and in order to obtain a high-strength fiber, cooling with a flash flow and stretching depending on its speed are required. The orientation must be sufficient. In the present invention, since it is composed of mixed fibers of ethylene-vinyl alcohol-based copolymer and ester-based polymer which are not compatible with each other, fibrillation is sufficiently promoted by this flush flow, and extremely fine fibril fibers are obtained. it can.

In the present invention, since the polymers are incompatible with each other, the polymers are easily separated from each other even if the polymers are dissolved in the solvent. Therefore, it is preferable to add a surface active agent. This surface active agent is effective for keeping the spinning mixed solution stable in an emulsified state, and generally, a nonionic surface active agent can be applied. For example,
Examples include monoesters of lauric acid, stearic acid, and oleic acid, and polyoxyethylene adducts of lauryl alcohol, stearyl alcohol, and oleyl alcohol. The more uniform the mixed solution, the more extremely fine fibril network fibers can be obtained.

The melting and spinning temperature of the spinning mixture for obtaining the fiber of the present invention must be 160 to 220 ° C. In particular, the ester polymer has a large decrease in viscosity in the presence of a solvent, and among them, the polyalkylene oxide component-containing block copolymer ester has a large decrease in viscosity in the presence of a solvent, and the polyalkylene oxide component is easily eluted in the solvent. Therefore, if the temperature exceeds 220 ° C., coloring of the fibers may be observed, decomposition may be promoted, and fibers having high strength and antistatic property may not be obtained, which is not preferable.
On the other hand, if it is less than 160 ° C., it is not preferable because it does not become an ultrafine fibril fiber but a tubular fiber having a hollow portion.

Generally, the dissolution time of a polymer in flash spinning cannot be unconditionally limited because there is a trade-off between dissolution and spinning temperature. That is, when the temperature is high, the dissolution time needs to be as short as possible, and when the temperature is relatively low, the dissolution time may be long.

The dissolution time of the spinning mixture for obtaining the fibers according to the invention is preferably within 90 minutes and as short as possible. When the dissolution time of the spinning mixture exceeds 90 minutes, the polyalkylene oxide component-containing block copolymer ester or ethylene-vinyl alcohol copolymer may be colored or thermally decomposed, or the fiber strength may be reduced. Further, if the dissolution time is too short, the dissolution of the polymer becomes insufficient, which may cause problems such as clogging in the filter and problems in producing uniform fibers.

The pressure during spinning of the mixed solution in which the polymer is dissolved is not limited to any particular value depending on the amount of the solvent, the concentration of the polymer, and the amount of the inert gas added, but it is usually preferably 50 kg / cm ² or more. When it is less than 50 kg / cm ² , the explosive force at the time of flash spinning is lowered, the orientation of the fibers is lowered, and high strength fibers cannot be obtained. In addition, there is a problem in that the discharge becomes uneven and stable fibers cannot be spun out in a high fibril state. The upper limit pressure is not particularly limited, but it is necessary to carry out spinning at a pressure not higher than the boundary pressure for two-phase separation between the polymer and the solvent.

At the time of spinning, the spinning mixed solution is flash-spun from under autogenous pressure or higher pressure through a pressure drop chamber to a temperature and pressure region substantially lower than that.
A generally known nozzle can be applied to the spinning nozzle.

In the polymer or the spinning mixed solution, a matting agent, a lightproofing agent, a heatproofing agent, a pigment, an opening agent, a weatherproofing agent, an ultraviolet absorber, a heat storage agent, a stabilizer usually used for fibers. Etc., if the effect of the present invention is not impaired,
Can be added.

[0032]

EXAMPLES Next, the present invention will be specifically described based on Examples. In addition, measurement and evaluation of various characteristics in the following examples were performed by the following methods. (Melting point of polymer) The melting point was defined as the temperature at which the extremum of the melting absorption curve was measured using a differential scanning calorimeter DSC-2 type manufactured by Perkin Elmer Co., Ltd. at a temperature rising rate of 20 ° C / min. (Fine fineness) The true fineness was determined according to JIS L-1090. (Strength and Elongation of Fiber) Tensilon UTM-4-1-100 manufactured by Toyo Baldwin Co., Ltd. was used, and the sample length was 10 cm.
Twisting was performed 20 times / 5 cm with a gripping interval of 5 cm, and the strength and elongation were measured at a pulling speed of 5 cm / min. The strength obtained was divided by the above-mentioned fineness to obtain the strength of the fiber. In each of these formulations, the number of measurements was 20 and the average value was used for evaluation. (Modulus of Fiber) When measuring the strength and elongation of the above-mentioned fiber, “7.10” specified in JIS L-1013 is used.
According to "Measurement of initial tensile resistance", the initial tensile resistance (g / denier) was defined as the modulus value. (Specific surface area) "BELSORP2" manufactured by Bell Japan
8 "was used to measure the specific surface area of the fiber by the BET nitrogen adsorption method, and the specific surface area was determined in m ² / g. (Antistatic property) According to JIS L-1094 A method, 4.5
5 pieces of 5 cm × 4.5 cm sample pieces were prepared, pre-dried at 70 ° C. for 1 hour, and then 20 ° C. × 40% R.S. H. The sample was adjusted by leaving it at room temperature for one day. Then, it was attached to a static Honest meter, the half-life time (second) was measured under the following conditions, and the average value was shown.

Discharge voltage between electrodes: 10000 V Distance between electrodes: 20 mm for power reception, 20 mm for discharge Turntable number of revolutions: 1730 rpm Discharge time: 30 seconds (fiber dyeability) After the following dispersion dyeing was carried out, the following reduction dyeing was carried out. After further washing with water and drying, the dyeability of the fiber was evaluated as follows.

◎ Extremely good ○ Good △
Slightly good × poor (dispersion dyeing) Disperse dye Blue E-FBL (Sumitomo Chemical) 1%
owf, dispersant Disper-TL (manufactured by Meisei Chemical Co., Ltd.) of 1 g / liter, formic acid of 0.1 g / liter as an auxiliary agent, and a bath ratio of 1:50 were used to perform boil dyeing for 60 minutes. (Reduction dyeing) As a refining agent, 1 mol / liter of Sanmor FL-100 (manufactured by Nichika Chemical Co., Ltd.), 2 g / liter of hydrosulfite, 1 g / liter of caustic soda, and a bath ratio of 1:50 at 80 ° C for 20 minutes. Processed. Examples 1-7, Comparative Examples 1-2 64 parts by weight of an oligomer (number average degree of polymerization: 4) obtained by the esterification reaction of terephthalic acid and ethylene glycol, and an ethylene oxide adduct of bisphenol [A] (average molecular weight: 6000). ) 33 parts by weight, 3 parts by weight of bisethylene glycol ester of 5-sodium sulfoisophthalic acid, and 0.02 part by weight of antimony trioxide (used as a 2% solution of ethylene glycol) were charged to a reactor, and 0.1 ton was charged. Polycondensation was carried out at 270 ° C. for 4 hours to obtain a block copolymer ester polymer.

This block copolymer has a melting point of 1
An ethylene-vinyl alcohol-based copolymer in which ethylene is copolymerized at a temperature of 65 ° C., a density of 1.14 g / cm ³ , a melt index value of 3.5 g / 10 minutes and a saponification degree of 98%, and a melting point. Is 256 ° C, the mixing ratio of tetrachlorethane and phenol is 1/1 (weight ratio), and 2
The relative viscosity ηrel measured at 0 ° C. and a concentration of 0.5% is 1.
Polyethylene terephthalate, which is 38, was mixed.

Then, the mixing ratio of these block copolymers, ethylene-vinyl alcohol copolymer, and polyethylene terephthalate was changed as shown in Table 1, and 300 g of methylene chloride as a solvent was always added to 500 cc.
These were used and filled in an autoclave.

At this time, the concentration of the mixed polymer in the solution was 18
The solvent concentration in the solution was adjusted to 82% by weight. Further, as the surface active agent, lauryl ether containing 3 mol% of polyoxyethylene and tridecyl stearate were added in an amount of 0.2% by weight to each of the mixed polymers.

After closing the autoclave, nitrogen was injected into the autoclave so that the pressure became 50 kg / cm ² , stirring was started at an appropriate speed, and heating was started. It took 25 minutes to reach the temperature of 200 ° C. after reaching the temperature of 80 ° C., and stirring was continued for 10 minutes after reaching the temperature of 200 ° C. to obtain a uniform solution. At this time, the dissolution time was 35 minutes, and the pressure was a gauge pressure of 95 kg / cm ² . Next, using a high-pressure gas applying device, a pressure of 95 kg /
Immediately open the valve while circulating nitrogen gas of cm ² into the autoclave, and have a pressure drop chamber with a hole diameter of 0.70 m.
It was spun into the air through a nozzle of mφ and L / D = 1.

The obtained fiber is opened to form a non-woven web, which is then heat calendered with a calender roll group to give 50 g.
A non-woven fabric corresponding to / m ² was produced. Table 1 shows the antistatic performance of the obtained non-woven fabric and the result of dyeing it with a disperse dye.
Shown in

[0040]

[Table 1]

In Examples 1 to 3 and 7, the obtained fibers had a very good fibril state, no coloring of the fibers, high fiber strength and high specific surface area, antistatic performance and dyeing with a disperse dye. It was excellent in sex. Further, even if home laundry was repeated 10 times for this nonwoven fabric, the performance hardly changed. In particular, since it contained a polyalkylene oxide component, the antistatic performance was extremely excellent. In Example 4, since the content of the ethylene-vinyl alcohol-based copolymer is small,
Although it had antistatic properties, it was not expensive. In Example 5, although the ethylene-vinyl alcohol copolymer content was high, the antistatic property was saturated. In Example 6, since the polyalkylene oxide component was contained, the electrostatic performance was slightly improved as compared with Example 4.

In Comparative Example 1, since the ester polymer was not contained at all, the antistatic performance was obtained, but the fibril state was poor and the specific surface area of the fiber was reduced. Moreover, the dyeability of the obtained fiber was also lowered. In Comparative Example 2, since no ethylene-vinyl alcohol copolymer was contained in the fiber, satisfactory antistatic performance was not obtained. Comparative Examples 3 to 4 Compared to Example 3, the polymer concentration in the solution was changed. Otherwise, flash spinning was performed under the same conditions as in Example 3. The results are shown in Table 2.

[0043]

[Table 2]

In Comparative Example 3, since the polymer concentration in the solution was too low, only short fibers containing powdery fibers could be produced. In Comparative Example 4, since the polymer concentration in the solution was too high, the solution viscosity was increased, the fibrillation did not occur, and a tubular fiber having a hollow portion was formed. For this reason, the specific surface area of the fibers was reduced. Examples 8-11, Comparative Examples 5-7 Compared to Example 3, the spinning temperature and dissolution time were changed to the conditions shown in Table 2. Otherwise, flash spinning was performed under the same conditions as in Example 3. In addition, those which can be formed into a sheet were made into a non-woven fabric in the same manner as in Example 3 and the performance thereof was evaluated. Table 3 shows the results.

[0045]

[Table 3]

In Examples 8 and 9, the obtained fibers had an extremely good fibril state, no coloring of the fibers, high fiber strength and high specific surface area, and both antistatic performance and dyeability with disperse dyes. It was excellent. Further, even if home laundry was repeated 10 times for this nonwoven fabric, the performance hardly changed. In Example 10, although the spinning temperature was relatively low, although it was partially in the fibril state,
Most of the fibers became hollow fibers with cavities. Therefore, the specific surface area of the fiber was slightly reduced, but there was no problem in terms of physical properties of the fiber. In Example 11, since the spinning temperature was relatively high and the dissolution time was relatively long, the ethylene-vinyl alcohol-based copolymer tended to decompose, and some coloring of the fibers was observed. Therefore, the fiber strength was slightly lowered.

In Comparative Example 5, since the spinning temperature was too low,
It was not fibrillated, and became a tubular fiber with a cavity.
As a result, the specific surface area of the fiber was reduced. In Comparative Example 6, since the spinning temperature was too high, the polymer component was decomposed to give a strange odor and only colored fibers were obtained. The fiber had a great decrease in strength and could not be used. In Comparative Example 7, the spinning temperature was relatively high, and the dissolution time of the polymer was too long. Therefore, the polymer was decomposed, the entire yarn exhibited a pale yellow color, and some yellow fibers were mixed. . Therefore, the fiber strength was reduced. From the above, in Comparative Examples 6 to 7, it was not possible to evaluate the fibers.

[0048]

EFFECTS OF THE INVENTION According to the present invention, it is composed of an ethylene-vinyl alcohol copolymer and an ester polymer, and has a network structure composed of an extremely high degree of extremely fine fibril fiber which has never been obtained before. It has excellent electrical performance, antifouling properties, printability, and gas barrier properties, and has high strength and high modulus. Therefore, it should be suitable for general-purpose applications such as woven, knitted, and non-woven fabrics, heat insulating materials, artificial leather, absorbent materials for sanitary materials, protective clothing, curtains, sheets, wipers, filters, house wraps, etc. You can Further, since it contains an ester polymer, it has a great effect that not only coloring with a pigment but also appropriate dyeing in a later step can be performed.

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Claims (6)

[Claims] 1. An antistatic network-structured fiber comprising a mixed fiber containing at least an ethylene-vinyl alcohol-based copolymer and an ester-based polymer and having a three-dimensional network structure. 2. The antistatic network-structured fiber according to claim 1, wherein the proportion of the ethylene-vinyl alcohol copolymer in the mixed fiber is 5 to 95% by weight. 3. The ester-based polymer is a block copolymerized ester containing a polyalkylene oxide component, and the proportion of the polyalkylene oxide component in the fiber is 0.3 to 35% by weight. The antistatic reticulated structure fiber according to 2. 4. At least an ethylene-vinyl alcohol-based copolymer and an ester-based polymer are mixed to form a spinning mixed solution of this mixture and a solvent, and thereafter, under autogenous pressure or higher pressure. Flash spinning to a temperature and pressure range substantially lower than that, at that time, the concentration of the polymer in the spinning mixed solution was 5 to 30% by weight, the spinning temperature was 160 to 220 ° C., and the dissolution of the polymer. 90 hours
A method for producing an antistatic network-structured fiber, characterized in that the time is within minutes. 5. The mixing weight ratio of the ethylene-vinyl alcohol copolymer and the ester polymer is 95/5 to 5
/ 95, The method for producing an antistatic reticulated structure fiber according to claim 4. 6. The ester polymer is a block copolymerized ester containing a polyalkylene oxide component, and the ratio of the polyalkylene oxide component in the mixed polymer is 0.3 to 3.
The method for producing an antistatic reticulated structure fiber according to claim 4 or 5, characterized in that the content is 5% by weight.