JPS59157323A - Manufacture of artificial fiber - Google Patents

Abstract

PURPOSE:To manufacture an extremely strong fiber from an ultra-high molecular weight polymer which has hitherto been difficult to spin, without causing the agglutination of filaments, by extruding a solution of an organic polymer through a spinnerette, solidifying the extruded filament by cooling, etc., applying a surface active agent, etc. to the solidified fiber, and removing the solvent from the fiber. CONSTITUTION:A solution of an organic polymer (e.g. polyethylene) is extruded through a spinnerette, solidified mainly by cooling, and formed to a fiber by removing the solvent therefrom. In the above process, at least one substance selected from a surface active agent, fine powder essentially insoluble in the solvent, and an oily substance which does not swell the organic polymer, is applied to the extruded filament prior to the completion of the solvent removal, and the then solvent is removed from the filament in a drying chamber, etc. to obtain the objective fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing man-made fibers from organic polymers, and particularly for producing extremely high-strength fibers from polymers with small molecular weights that have undergone spinning difficulties due to conventional methods. , relates to a method for reducing denier unevenness, cross-sectional morphology unevenness, and adhesion between single fibers.

In the case of a solid, the molecular chain end of an organic polymer is a kind of micro-a
It can be considered a structural defect. Therefore, when manufacturing artificial fibers from organic polymers, it is expected that a polymer with fewer molecular chain ends, or in other words, a polymer with a small molecular weight, will be able to produce strong fibers.

However, in the final fiber JR production process, when the molecular weight increases beyond a certain level, a non-uniform structure occurs inside the fiber and the arc degree tends to decrease. Furthermore, as the molecular weight increases, the viscosity increases rapidly, making spinning operations difficult. For example, when trying to melt-spun a polymer with a molecular weight of about 1 million, the melt viscosity ranges from several million to several billion voids, making it difficult to thin the yarn during spinning, and the advantage of melt-spinning is high speed. I also lost it. To solve the problem of high viscosity, when dry spinning is performed by dissolving in a solvent, the concentration of the solution must be lower than that for ordinary molecular weight polymers, which makes drying difficult and unstable spinning. Become. Even when wet spinning, uniform coagulation becomes difficult.

- As a method of making fibers from polymers with very large molecular weights, there is a method using a solvent that solidifies without removing the solvent by just cooling the solution. This is disclosed in Japanese Patent No. 44-26409.

This method is an excellent method for stably spinning fibers from a dilute polymer solution. Polyethylene fiber gold with a molecular weight still spun by this method, 25% of the solvent
Tensile strength is 31/d when stretched with Arashi remaining above the tension.
Above, the elastic modulus is 900? It is stated in JP-A-55107506 that fibers with a particle diameter of /ci or more can be obtained.

The disadvantage of this method is that the morphology of the spun fibers is more unstable than that obtained by conventional dry spinning. As a result, during the solvent removal process, there is a noticeable increase in fiber unevenness, *flattening and increase in variation in fiber cross-sectional morphology, and occurrence of adhesion between single fibers, resulting in uneven gloss, rough texture, and The IA is presumed to be responsible for unfavorable properties such as low tear frequency and low impact resistance.

As a result of various studies by the present inventors to reduce and eliminate the drawbacks of the method of JF Makon et al., the solvent was removed from the gel-like ultrafine material obtained by cooling and solidifying the organic polymer bath liquid extruded from the spinneret. After the atomization after extrusion from the die is practically completed, but before the removal of the solvent is completed, the surfactant, the fine powder virtually insoluble in the solvent, and the polymer are preliminarily removed. selected from the group of oily substances that do not swell n
It has been found that it is effective to completely deposit one or more ``? It has very high strength with few irregularities in the cross-sectional shape of single fibers, and it prevents adhesion between single fibers.
"It is possible to obtain fibers that do not contain L.

First, the surfactant used in the method of the present invention does not have the ability to dissolve the polymer to be made into fibers at a temperature below the temperature at which the spinning solution containing the polymer is cooled and solidified;
More preferably, the polymer has virtually no ability to swell. For example, for the production of polyolefin fibers, oxyethene groups, oxypropylene groups, oxybutylene groups, etc.
derivatives with groups, anionic activators such as higher carboxylic acid salts, cationic activators such as alkylpyridinium salts, polyethylene glycol alkyl ether,
Polyols such as polyethylene glycol fatty acid esters (monoesters and diesters), polyethylene glycol propylene glycol block-xi compounds, polyethylene glycol argylphenyl ethers, polyethylene glycol fatty acid esters, pentaerythritol, and low-F-positive carbohydrates. Nonionic surfactants such as fatty acid esters, alkyl esters, alkyl sulfate esters, and amines such as ethylene oxide or probyne oxide can be used; The stronger the better. As lipophilic groups, aromatic ones are better than aliphatic long-chain ones. Furthermore, in the case of polyester, polyamide, polyacrylonitrile, and polyvinyl alcohol, generally those with a good balance of hydrophilicity and lipophilicity, and those with slightly strong lipophilicity also give excellent results. As lipophilic groups, aliphatic groups, polypropynon glycol, and polybutylene glycol are better than aromatic groups. The amount of surfactant used is 0.005 to 5i per gel-like fiber cooled and solidified after spinning! -% is preferred. Here, if the adhesion layer, which is preferable in the steps up to the removal of the solvent, is excessively removed in step 8 after the stretching photon or in the processing step into the product, a surfactant washing step is provided after the stretching photon. Is possible. The surfactant may be one that is submersible with respect to the solvent contained in the spinning solution. When liquid cooling is performed after the surfactant attachment step, it is preferable that the surfactant is not soluble in the liquid used for the liquid cooling.

Next, it is used in the method of the present invention. It is safe that the fine powder, which is practically insoluble in the solvent that is sweetened with the spinning solution, has a particle size smaller than the diameter of the gel-like fiber when cooled and solidified after spinning. Although it is preferable that the particle size is smaller than the fiber diameter of the stretched fibers, there is no need to worry if the particle size is too small. Regarding the shape of the particles, those in which the ratio of the major axis to the minor axis is relatively 1 are preferable, and those in the shape of a hole or flaky are preferable, and acicular particles are not preferable. Fine particles include colloidal silica with a diameter of several 101 TIμ, colloidal alumina rirui Vi @ titanium oxide with a diameter of several 100 μμ, and spherical particles of calcium carbonate (cal-height type crystals). Shows preventive effect. In addition, silica gel, calcium carbonate, crystalline calcium chloride, and the like, which are spherical or irregularly shaped particles with a diameter of several microns to about 10 microns, have an immediate anti-scaly effect. Flake-like particles such as Merck, clay, mica, graphite, molybdenum sulfide, etc., with a major axis of 20μ or less are not allowed.
L shows excellent rust prevention effect. - Needle-shaped particles such as carbonate crystals (Arabite type crystals), carbide whiskers, quantified silicon whiskers, titanium and potassium have poor rust prevention effects. The amount of fine powder used is 0.01 per gel-like fiber that has been cooled and solidified after spinning.
~10% storm volume is preferable.

Furthermore, the oily substance used in the method of the present invention, which does not wet the organic polymer, has a vapor pressure so low that its evaporation is virtually undetectable when left in the spinning solution. It is a liquid substance at the temperature at which it solidifies upon cooling. There is no problem even if it is solid at room temperature.

For example, in polyolefin fiber, polyoxyethylene with a molecular weight of about 4,000 or more, polyoxypropylene, etc., co-compounds, accumulated oils and fats, and purple pigments. These include high-boiling paraffin and high-boiling point silicone oil. VC for polyester, polyamide, polyacrylonitrile, polyvinyl alcohol
In addition to these, paraffin, oil, wax, and polybutene oligomers from Tsutsuna point can also be used. These oily substances should be ones that do not substantially swell the polymer to be made into fibers, but it is preferable that the oily substances are not vulgar when it comes to the hidden secrets contained in the spinning solution. The amount of oil to be used is preferably 0.05 to 5% by weight based on the gel-like fibers spun and solidified after spinning.

1' used in the method of the present invention! Surfactants, fine powders, and oils such as those mentioned above must be used alone.
(iJ' i stop, but it is 5J ability to use it in combination of two or more in the division of sonzo n,9, and it is possible to use it in combination of two or more of the middle blades and ra in the true division. It is also possible.

These items can also be attached alone.
It can be applied in one go, but it is preferable to disperse it in fine particles in the air, or to dissolve or disperse it in a diluting agent such as water and then apply it. If a liquid bath is used for cooling, the adhering process f4 is dissolved or dispersed in the liquid bath, or if a treatment is performed subsequent to the liquid bath, it is dissolved or dispersed in the liquid bath. Preferably, it is treated. When cooling is effected by airflow and cooling rollers, it is preferred to deposit the film directly in front of the cooling rollers. However, the process of layering and stirring is a great effort if the electrolyte is removed before photons are removed.
TV can be placed. The adhesion process can be divided into two or more stages, and different processing agents can be applied to each layer.

The method of the present invention has a particularly pronounced effect when the polymer used has a curative strength of less than 10%. When the concentration of the bath solution is less than 5%, it, - is particularly noticeable, and the conventionally known methods can only produce threads with four sides, such as threads made from film.

The polymer that can be used in the method of the present invention preferably has an average molecular weight of 400,000 or more, and can efficiently produce fibers with extremely high strength and uniformity by an unconventional method.

Next, the invention will be explained with reference to examples.

Example I A polyester having an average molecular weight of 2,000,000 M'A was dissolved in white kerosene to obtain a 3.5% bath liquid. This bath solution is spun into the air from a spinneret kept at 130°C with a spinning hole of 0.5 mm in diameter, and introduced into a 25°C oil bath equipped with a VC 15 cm below the spinneret and cooled. It is fibrous.

Is there 3 degrees of lauryl 7-osphate salt in the oil bath? /1
．． Polyglobilenoxide Ethylene oxide block copolymer (molecular weight 2,500) 50? /l was dissolved. Next, the fibrous material that came out of the oil bath was heated to 50°C.
The film was dried with gradual stretching in a drying machine kept at a temperature between 90°C and 90°C. The total processing expansion ratio is 4.0
The solvent content after drying was 9.6%, and the yarn speed was 24 m/min. Note that the passage time through the drying chamber was 8 minutes.

8. The obtained fibers were further heated in air at 140°C. Stretched 7 times. The stretching time was 20 minutes. The obtained fiber had a strength of 33 f/d, an elongation of 4.7 inches, and a Young's modulus of 480?
/d1 u% by Worcester Evenness tester 1.8
%, the cross-sectional shape of the single fibers was an oval shape with minute irregularities on the surface, and the length/breadth axis ratio was 1:0.6 to 0.7.

Comparative Example 1 Among the spinning and drawing conditions of Example 1, when only water was used as the liquid in the oil bath, no difference was observed in the drawability of the obtained fibers.
However, the U% was 4.5%, and the cross-sectional shape of the single fiber was a flat oval shape with a length ratio of 1:0.07 to 0.25. The stalemate was noticeable and rare.

When the oil was not applied in this way, the fluff was often wrapped around the roller, so the oiling locations were changed to the location where the oil exited the cooling bath, the center of the drying room, and the location where the product exited the drying room. After applying the same oil as in Example 1, the roller curling was almost completely eliminated in the case of chair n.

The twisted fibers were treated in almost the same manner as in Example 1, after being oiled after leaving the cooling bath. The ones that were oiled in the center of the drying chamber had an oval shape with a length ratio of 1:0.4 to 0.5 and were slightly flattened, but the U% was small and there was no problem of sticking of short fibers. When lubricated after leaving the drying room, the U% was 3.3%, the cross-sectional shape was a flat oval with a length ratio of 1:0.12 to 0.30, and there was considerable adhesion between the single fibers. was.

Example 2 Polyethene having a weight average molecular weight of 1.9 million was dissolved in decalin to prepare a 4.8% bath solution. This solution was spun from a spinneret maintained at 132°C with a spinning hole with a diameter of 0.75 m into a spinning tube with an upper end of 100°C and a lower end of 30°C.
The fibers were introduced into a 25° C. water bath provided directly below the spinning cylinder and cooled to form a fiber.

Next, this fiber is passed through a drying room at 60°C for 4 minutes for 1.
The yarn was stretched 8 times, then passed through a drying room at 85° C. for 4 minutes to be further stretched 2.2 times, and sent to a drawing furnace at a yarn speed of 28 m/min. The solvent content after drying was 9.2%. The drawing furnace stretched the film by a factor of 9.0 at room temperature. The length of time for one stretch is 18
It took a minute.

Under these conditions, polydimethylsiloxane having a viscosity of 80 centivoids at 20 DEG C. was sprayed and adhered to the fibers.

The attachment position is as follows: Immediately before the cooling bath in L1, 1 page after the cooling bath,
Immediately after drying at 60°C, immediately after drying at 85°C, and immediately after drawing oven, the yarn quality was examined. When the layering position was immediately after drying and stretching at 85°C, the U-chi was too thin and the single fibers were stuck together, but when the layer was applied at other positions, the U%
It was small, and I could hardly admit to seeing it this way. -1
The shape of the surface was more circular as the deposition position was closer to the spinneret.

There was almost no difference in strength and elongation between each attachment position.

Implementation 13 All para-xylene VC with a weight average molecular weight of 4 million was decomposed to obtain a 2.0% bath liquid. This bath liquid has a diameter of 0.4
It was spun from a spinneret kept at 128°C with sequential spinning holes, and placed 25m below the spinneret. When a 0.8% aqueous dispersion of colloidal silica was placed in a cooling bath and the wheat was cooled and solidified in the bath, it was dried and stretched in the same manner as in Example 1. I have the honor of not wearing anything.'n-1.

Example 4 Highly crystalline boriflobin having an average molecular weight of 340 was dissolved in decalin to form a 2.5% solution. This solution was kept at 135'G through a spinning hole with a diameter of 0.5 mm.
Spun into the air from a spinneret, 30 cm from 10K gold.
A cooling bath was placed at the bottom, and a 25'C aqueous oil solution was placed in the cooling bath to cool the spun yarn to form fibers. Is there senal sulfonate potash 40 in the oil bath? /l, 2 moles of oleylphos7ate ethylene oxide 351/l, polyethylene glycol dilaurate) 30 f/l, polyethylene glycol monolauryl ether 15? /d has been misunderstood. After solidifying the spun yarn in the oil bath, it was dried in the same manner as in Example 1. The fibers produced in the drying process had a solvent content of 8.7% and a yarn speed of 16 m/min.

Note that the drying step took 12 minutes to complete.

The resulting combed fibers were drawn 4.8 times in air at 155'G. The stretching time was 20 minutes. The obtained fiber had a strength of 21 y/d, an elongation of 6.2%, a Young's modulus of 280 f/d,
The cross-sectional shape of the u% 1.9% single fiber was a round shape with minute irregularities on the optical surface, and the length/breadth axis ratio was 0.6 to 0.7.

Example 5 Polyethylene having an N shield average molecular weight of 1.7 million was bath dissolved in white kerosene to obtain a 3% bath liquid. This molten g is completely straight 0.4 degree spinning hole k
The material was spun into air kept at 40°C from a spinneret kept at 130°C, and then introduced into a treatment bath equipped with a VC 7.5 cm below the spinneret, where it was cooled and made into a fiber. Table 1 shows the results of examining the pink-up amount 2 of the treatment solution and the treatment effect by changing the fineness of the treatment bath. 2. Pick-up is the effect of the active ingredient of the treatment agent on the M-roof of the swollen fibers.

Procedural Amendment (Spontaneous) March 25, 1980, Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office], Indication of Case Patent Application No. 58-29958 2 Name of Invention Method for Manufacturing Artificial Fibers 1621 Sakazu, Kurashiki City (10g) Co., Ltd. ri Ra Ray Hou 99 Ueno et al. - 4, Agent Telephone: Tokyo 03 (277) 3182 5, Claims and Detailed Description of the Invention in the specification to be amended, 6, Amendment Contents 1) The scope of claims in lines 5 to 13 of page [Specification box] will be corrected as shown in the attached sheet.

2) On page 4, line 3 of the same page, [-1 is deleted after the refinement is virtually completed.

3) Insert the following text between pages 16 and 17.

Example 6 Polyethylene with a weight average molecular weight of 1.9 million was dissolved in white kerosene to make a 3.5% solution. This solution was pressed through a spinneret to form a surfactant (lauryl ether of polyethylene glycol with a molecular t1.500). ) was spun into a dispersed nitrogen stream, and a pair of cooling rollers with a surface temperature of 5°C was placed 1.5 m below the nozzle, and after being wound 7 times, the winding speed was 1.2 m/min. The amount of surfactant attached was 0.05 q per rolled gel fiber (polymer content 4 times).
It was 6. This gel-like fiber did not cause sticking between single fibers during the subsequent drying and stretching steps.

Example 7 When colloidal silica (spherical particles with an average particle diameter of 30 mμ) was used in place of the surfactant in Example 6, similarly excellent anti-sticking effects were exhibited.

Example 8 When silicone oil (Shin-Etsu Chemical Co., Ltd. KF-95, viscosity: 10 centimeters) was used in place of the surfactant in Example 6, it similarly exhibited an excellent anti-sticking effect. "1) When producing fibers by extruding an organic polymer solution from a spinneret and solidifying it mainly by cooling, and then removing the solvent, spinning A method for producing an artificial fiber, characterized in that the surfactant and the solvent are virtually non-adherent to the yarn.

Claims (1)

[Claims] 1) When a solution of an organic polymer is extruded from a spinneret, solidified mainly by cooling, and then the solvent is removed to produce mechanical fibers, after the thread thinning after extrusion from the spinneret is virtually completed. 2, before the solvent removal is completed, the spun yarn is treated with at least one substance selected from the group of surfactants, fine powders virtually insoluble in the medium, and oily substances that do not swell the organic polymer. A method for producing artificial fibers, which comprises attaching a seed substance.