KR101856501B1 - Fibrillated cellulose filament preparation method thereof - Google Patents

Abstract

The present invention relates to a method for producing microcellulose long fibers using liquid crystals of microfibrous cellulose, and a microcellulose long fiber produced by the production method. Since the microcellulose long fiber has high mechanical strength and is an environmentally friendly material, thereby being applicable to various fields.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a microcrystalline cellulose filament and a method for producing the same.

The present invention relates to a process for producing microcellulose filaments having high mechanical strength and being environmentally friendly, and microcellulose filaments prepared by the process.

Cellulose is one of the most common natural polymers found on the earth, found in most plants such as wood, cotton, and shrub, as well as in animals with dry epidermis such as muddock and urchins, 1-4 glucosidic linkages and has a molecular weight of 4.6 × 10 ⁵ to 1.7 × 10 ⁶ . Cellulose is a structural unit that forms the skeleton of plants and is a key component of the cell membrane of all higher plant cells, and plants, especially wood, play a key role in maintaining high strength.

Cellulosic molecules having an effective diameter of about 6 to 7 angstroms are regularly bonded through hydrogen bonding and are strongly bonded to form microfibrillated or nanofibrillated cellulose having a diameter of 2 to 5 nm. To form cellulose long fibers.

Natural cellulose is present in amorphous or crystalline form. Since the strength of cellulosic fibers depends on the presence and direction of cellulose crystals, a process for obtaining microcellulose filaments having a high concentration of crystallized cellulose and excellent mechanical properties is required.

Accordingly, an object of the present invention is to provide a method for producing environmentally friendly microcellulose filaments having a high mechanical strength by using a liquid crystal of microfibrous cellulose, and a method for producing microcrystalline cellulose filaments prepared by the above- will be.

In order to achieve the above object,

(a) preparing a liquid crystal solution in which microfibrous cellulose is partially oriented;

(b) injecting the liquid crystal solution into the inlet of the spin chuck;

(c) orienting the microfibrous cellulose in the uniaxial direction while passing the liquid crystal solution in the direction of the uniaxial axis of the spin chuck;

(d) injecting the unidirectionally oriented microfibrous cellulose into the coagulation bath through the discharge portion of the radial channel;

(e) coagulating and fibrillating the microfibrous cellulose while water in the microfibrous cellulose oriented in the uniaxial direction in the coagulation bath is desorbed by diffusion;

(f) separating the coagulated long-fiberized microfibrous cellulose in a coagulation bath; And

(g) drying the separated long fibrous microfibrous cellulose. The present invention also provides a method for producing microcrystalline cellulose filaments.

In addition, one embodiment provides microcellular filamentous fibers prepared according to the method.

According to the method for producing microcrystalline cellulose filaments according to the present invention, there is no deterioration of the physical properties of the microfibrous cellulose, and since it contains water as a solvent, it is eco-friendly.

The microcellulose filament produced by the above method has high mechanical strength such as high tensile strength, elongation at break and tensile elastic modulus due to strong hydrogen bonding between the cellulose.

In addition, since the microcellulose filament is a biodegradable natural material, it is more environmentally friendly than conventional polymer synthetic fibers or carbon fibers.

Furthermore, the microcellulose filaments can be used for protecting materials such as automobile and airplane interior and exterior structures, bulletproof clothing and bulletproof helmets, information and communication materials such as exposed parts of optical cables and radar dome structural materials, ski boards and tennis rackets It can be applied to various fields such as sporting goods.

1 is a schematic view showing a method and an apparatus for producing microcrystalline cellulose filaments according to the present invention.
2 is a schematic view showing a liquid crystal solution passing through a radial channel and a radial channel in an apparatus for producing microcellulose filament according to the present invention.

Hereinafter, the present invention will be described in detail by way of examples. The embodiments can be modified into various forms as long as the gist of the invention is not changed.

As used herein, " comprising "means that other elements may be included unless otherwise specified.

The present invention provides a process for producing microcellulose filaments and a microcellulose filament produced by the process.

[ Microcellulose Long-fiber  Manufacturing method]

According to one embodiment of the present invention, there is provided a method for producing a microcellulose filament,

(a) preparing a liquid crystal solution in which microfibrous cellulose is partially oriented;

(b) injecting the liquid crystal solution into the inlet portion 21 of the radial channel;

(c) orienting the microfibrous cellulose in a uniaxial direction while passing the liquid crystal solution in a direction of one axis of the radiation channel (20);

(d) injecting the unidirectionally oriented microfibrous cellulose into the coagulation bath (30) through the discharge part (22) of the radiation channel;

(e) coagulating and fibrillating the microfibrous cellulose while water in the microfibrous cellulose oriented in the uniaxial direction in the coagulation tank (30) is desorbed by diffusion;

(f) separating the coagulated long-fiberized microfibrous cellulose from the coagulation bath (30); And

(g) drying the separated long fibrous microfibrous cellulose.

The steps (a) to (g) may be sequentially performed to produce the microcrystalline long fibers.

To prepare the microcrystalline cellulose filament, first, a liquid crystal solution in which microfibrous cellulose is partially oriented is prepared (step (a)).

The microfibrous cellulose used for producing the microcrystalline long fibers is obtained by fibrillating cellulose.

The cellulose is not particularly limited, and one derived from a cellulose-containing material can be used. For example, pulp, chemical pulp, mechanical pulp, recycled pulp, cellulose powder or a mixture thereof can be used. Examples of the cellulose-containing material include cellulosic fibers such as cellulosic fibers and cellulose acetate produced by plants or bacteria that are natural fibers, chitin derivatives such as chitin and chitosan contained in crustaceans such as sea urchins, shrimp and crabs, , And the like, but the present invention is not limited thereto. In addition, the cellulose fiber-containing material containing plant as a raw material may be wood such as coniferous or hardwood, cotton, hemp, or sheep. Cellulosic fibers obtained from wood such as coniferous trees and broad-leaved trees are very finely structured and have high strength and are the most distributed biomass on the planet.

The cellulose may have a diameter of 10 to 1,000 mu m and a length of 0.1 to 100 mm. Specifically, the cellulose used may have a diameter of 10 to 500 mu m and a length of 0.1 to 50 mm, but is not limited thereto.

The microfibrillated cellulose obtained by fibrillating the cellulose is microfibrillated cellulose or nanofibrillated cellulose.

The microfibrous cellulose has a diameter of 5 nm to 100 nm. Specifically, the diameter of the microfibrous cellulose may be 5 nm to 50 nm, more specifically 5 nm to 10 nm, but is not limited thereto.

The length of the microfibrous cellulose is 100 nm to 500 탆. Specifically, the length of the microfibrous cellulose may be 100 nm to 100 탆, more specifically, 100 nm to 10 탆, but is not limited thereto.

The diameter and length of the microfibrous cellulose are obtained by thinly casting a microfibrous cellulose dispersion on a substrate and drying the microfibrous cellulose dispersion, measuring the average length of the plurality of fibers and the diameter measured by AFM (Atomic Force Microscope) do.

As the aspect ratio of the microfibrous cellulose is larger and the diameter is smaller, it is advantageous for use in the production method. Particularly, when the diameter and the length of the microfibrous cellulose are within the above ranges, it is advantageous to form a liquid crystal solution of the microfibrillated cellulose.

The microfibrous cellulose has a liquid crystal in which particles are arranged by themselves in a specific concentration range. A liquid crystal solution in which the microfibrous cellulose is partially oriented is produced by using the properties of the microfibrous cellulose.

The liquid crystal solution includes the microfibrous cellulose and water, and the liquid crystal solution includes 0.1 to 13% by weight of microfibrous cellulose based on the total weight of the liquid crystal solution.

When the content of the microfibrous cellulose in the liquid crystal solution is in the above range, the microfibrous cellulose in the liquid crystal solution becomes liquid crystalline and the viscosity of the liquid crystal is appropriate, so that the microfibrous cellulose is smoothly conveyed in the radial channel, And thus excellent microcellulose long fibers having excellent mechanical properties can be produced.

In the liquid crystal solution, the microfibrous cellulose is partially oriented.

Next, the liquid crystal solution is injected into the inlet 21 of the spin chan- nel (step (b)).

The liquid crystal solution in which the microfibrous cellulose is partially oriented is put into the inlet portion 21 of the radiation channel.

The radiation channel 20 used at this time has such a shape that the cross-sectional area of a cross section perpendicular to the traveling direction of the radiation channel becomes smaller as it goes from the inflow portion 21 of the radiation channel toward the discharge portion 22 of the radiation channel 1).

For example, the cross-sectional area of the radial channel inlet may be 10 ⁶ to 10 ¹⁶ times the cross-sectional area of the radial channel outlet. Specifically, the cross-sectional area of the radial channel inlet may be 10 ¹⁰ to 10 ¹⁴ times the cross-sectional area of the radial channel discharger, but is not limited thereto.

As another example, the cross section of the radial channel may be circular, the diameter of the cross section of the inlet section of the radial channel may be between 10 and 10 ⁶ mm, the diameter of the cross section of the discharge section of the radial channel may be between 0.01 and 0.5 mm .

When the cross section of the radiation channel is circular, the diameter of the inlet section of the radiation channel may be 10 ³ to 10 ⁸ times the diameter of the outlet section of the radiation channel. Specifically, the diameter of the inlet section of the radial channel may be 10 ⁵ to 10 ⁷ times the diameter of the outlet section of the radial channel.

Next, the microfibrous cellulose is oriented in the uniaxial direction while passing the liquid crystal solution in the direction of the uniaxial axis of the radiation channel 20 (step (c)).

The liquid crystal solution is allowed to pass from the inflow portion 21 of the radial channel toward the discharge portion 22 of the radial channel, that is, in a direction uniaxial to the traveling direction of the radial channel.

In the inflow portion of the radiation channel having a relatively large cross-sectional area and space, as the liquid crystal solution in which the microfibrous cellulose is partially oriented passes along the uniaxial direction of the direction of the radiation channel, as the cross-sectional area and space gradually become narrower, The microfibrous cellulose is uniaxially oriented.

As the microfibrous cellulose is oriented in the uniaxial direction, it is strongly bonded to the microfibrous cellulose which is oriented in the uniaxial direction by the hydrogen bond and the van der Waals attractive force, and the microcellulose sheet having excellent mechanical strength such as tensile strength and elastic modulus Fibers can be produced.

Next, the microfibrous cellulose oriented in the uniaxial direction is injected into the coagulation bath 30 through the discharge part 22 of the radiation channel (step (d)). Next, in the coagulation bath 30, water in the unidirectionally oriented microfibrous cellulose is desorbed by diffusion to solidify the microfibrillated cellulose to form a long fiber (step (e)).

A coagulating solution is stored in the coagulation bath 30, and the microfibrous cellulose oriented in the uniaxial direction is introduced into the coagulation bath stored in the coagulation bath.

The coagulation liquid is a liquid mixture of water and ethanol or _{NaOH, KOH, BaCl 2, PbCl} 2, Ba (NO 3) 2, Pb (NO 3) 2, Ca (NO 3) 2, CaCl 2, FeCl 2, FeCl 3 , and CuSO ₄ , and the like, but is not limited thereto.

In the mixture of water and ethanol, the volume ratio of ethanol to water is 1: 2 to 1: 5. Specifically, the volume ratio of ethanol to water may be 1: 2 to 1: 4, more specifically 1: 3.

It is also possible to select the group consisting of NaOH, KOH, BaCl ₂ , PbCl ₂ , Ba (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ , CaCl ₂ , FeCl ₂ , FeCl ₃ and CuSO ₄ The concentration of the at least one aqueous solution may be from 3% by weight to 10% by weight, in particular from 3% by weight to 7% by weight, and more particularly 5% by weight.

When the coagulating solution is in the above composition and concentration range, water in the microfibrous cellulose is advantageous to desorption by diffusion. Specifically, when the coagulating solution is in the above composition and concentration range, it is economical and suitable for causing a solidification reaction.

The water in the microfibrous cellulose is desorbed by the diffusion due to the difference in concentration, the mechanical strength of the microfibrous cellulose is improved by the hydrogen bonding between the -OH groups existing in the cellulose, and the microfibrous cellulose coagulates and solidifies It becomes advantageous. The microfibrous cellulose gradually aggregates and coagulates and becomes filamentous.

Further, in step (e), a crosslinking agent may be further added.

The cross-linking agent may be selected so that the cross-linking agent is at least one selected from the group consisting of 2,4-methylenediphenyl diisocyanate (MDI), 4,4'-methylenediphenyl diisocyanate (MDI), xylylene diisocyanate (XDI), m-tetramethyl xylylene diisocyanate (TMXDI), p-tetramethyl xylylene diisocyanate (TMXDI), toluylene diisocyanate (TDI), di-alkyldiphenylmethane diisocyanate, tetra-alkyldiphenylmethane diisocyanate, 3,3'- Diisocyanate (TODI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, naphthalene diisocyanate (NDI), 4,4'-dibenzyl diisocyanate, hydrogenated MDI ), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, -2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diiso Diisocyanate (HDI), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, and ethylene diisocyanate , And specifically may be at least one selected from the group consisting of 2,4-methylenediphenyl diisocyanate.

By adding the cross-linking agent, it is possible to produce microcellulose filaments which are strongly bonded to each other by hydrogen bond and van der Waals attraction between the microfibrillated cellulose molecules oriented in the uniaxial direction, and have excellent mechanical strength such as tensile strength and elastic modulus.

Next, the coagulated fibrous microfineous cellulose is separated from the coagulation bath 30 (step (f)).

Alternatively, after separating the long fiberized microfibrous cellulose from the coagulation bath 30, the separated long fiberized microfibrous cellulose may be poured into the washing tank 40 and washed with a washing solvent (see FIG. 1) .

The cleaning solvent may be at least one solvent selected from the group consisting of water, methanol, ethanol and acetone, but is not limited thereto.

By the step of washing the separated long fibrous microfibrous cellulose, it is possible to produce a long fibrous microfibrous cellulose free from impurities.

Then, the separated long fibrous microfibrous cellulose is dried (step (g)).

The separated long fibrous microfibrous cellulose may be dried using a hot air drying method, but the present invention is not limited thereto.

In the hot air drying, the drying temperature may be 100-150 ° C, and the drying time may be 1 to 30 minutes, but is not limited thereto.

The microcytic cellulose filaments can be produced through the above-mentioned steps. For a description of microcellulose filaments, refer to the description given below in [Microcellulose filaments].

Through the above-described method for producing microcircular cellulose filaments, microcellulose filament fibers having high mechanical strength such as high tensile strength, elongation at break and tensile elastic modulus and being environment-friendly are applicable to various fields.

[ Microcellulose Long fiber ]

The microcellulose filament is prepared according to the method for producing the microcellulose filament.

The diameter of the microcellulose filament is 10 to 800 nm. Specifically, the diameter of the microcellulose filament may be 10 to 700 nm, more specifically, 20 to 600 nm, but is not limited thereto.

The microcrystalline long fibers include 50 to 100% of crystallized cellulose. Specifically, the microcellulose filament may include 80 to 100% of crystallized cellulose, but is not limited thereto.

When the microcellulose long fibers include the crystallized cellulose in the above range, the mechanical strength of the prepared microcellulose long fibers can be increased.

The tensile strength of the microcellulose filament may be 3 to 15 MPa. Specifically, the tensile strength of the microcellulose filament may be 4 to 14 MPa, more specifically, 5 to 14 MPa, but is not limited thereto.

When the tensile strength of the microcellulose filament is in the above range, the prepared microcellular filament can maintain a suitable mechanical strength.

The elongation at break of the microcellulose filament may be 1.5 to 10%. Specifically, the elongation at break of the microcellulose filament may be from 1.5 to 7.5%, more specifically from 2 to 5%, but is not limited thereto.

When the elongation at break of the microcrystalline cellulose filaments is in the above range, the prepared microcellulose filaments can maintain a suitable mechanical strength.

The tensile elastic modulus at a elongation of 0.5% of the microcellulose filament may be 1.5 to 10 Gpa. Specifically, the tensile elastic modulus at a elongation of 0.5% of the microcellulose filament may be 1.5 to 7.5 GPa, more specifically, 2 to 7 GPa, but is not limited thereto.

The tensile elastic modulus when the elongation percentage of the microcellulose filament is 2.0% may be 2 to 15 Gpa. Specifically, the tensile elastic modulus when the microcellulose filament elongation is 2.0% elongation may be 2.5 to 12 GPa, more specifically, 4 to 12 GPa, but is not limited thereto.

When the tensile modulus of elasticity of the microcylulose long fibers is in the above range, the prepared microcellulose long fibers can maintain a suitable mechanical strength.

The above contents will be described in more detail by the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the examples.

[ Example ]

Example  One

The microfibrous cellulose aqueous dispersion solution containing 0.1 wt% was introduced into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into a coagulation tank of an aqueous solution of ethanol of 25 vol% through the discharging portion of the spinning channel, and the microfibrillated cellulose which was solidified in the coagulation bath to take up the long fibrous cellulose was taken. The solidified fibrous microfine cellulose was washed and dried.

Example  2

The microfibrous cellulose aqueous dispersion solution containing 5 wt% of water was put into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into a coagulation tank of an aqueous solution of ethanol of 25 vol% through the discharging portion of the spinning channel, and the microfibrillated cellulose which was solidified in the coagulation bath to take up the long fibrous cellulose was taken. The solidified fibrous microfine cellulose was washed and dried.

Example  3

The microfibrous cellulose aqueous dispersion solution containing 7 wt% was introduced into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into a coagulation tank of an aqueous solution of ethanol of 25 vol% through the discharging portion of the spinning channel, and the microfibrillated cellulose which was solidified in the coagulation bath to take up the long fibrous cellulose was taken. The solidified fibrous microfine cellulose was washed and dried.

Example  4

The microfibrous cellulose aqueous dispersion solution containing 13 wt% was introduced into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into a coagulation tank of an aqueous solution of ethanol of 25 vol% through the discharging portion of the spinning channel, and the microfibrillated cellulose which was solidified in the coagulation bath to take up the long fibrous cellulose was taken. The solidified fibrous microfine cellulose was washed and dried.

Example  5

The microfibrous cellulose aqueous dispersion solution containing 13 wt% was introduced into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into a coagulation tank of a mixed solution containing 25 vol% aqueous ethanol solution and 0.054 weight% of 2,4-methylenediphenyl diisocyanate through the discharge portion of the spin chuck, So as to take a microfibrous cellulose having a long fiber. The solidified fibrous microfine cellulose was washed and dried.

Example  6

The microfibrous cellulose aqueous dispersion solution containing 13 wt% was introduced into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into the coagulation tank of a mixed solution containing 25 vol% aqueous ethanol solution and 0.175 weight% of 2,4-methylenediphenyl diisocyanate through the discharge portion of the spinning channel, So as to take a microfibrous cellulose having a long fiber. The solidified fibrous microfine cellulose was washed and dried.

Comparative Example  One

The microfibrous cellulose aqueous dispersion solution containing 14 wt% was introduced into the inlet of the spin chuck at a flow rate of about 8 ml / h, and the microfibrous cellulose was uniaxially oriented while passing the solution in the uniaxial direction of the spin chuck. The microfibrous cellulose oriented in the uniaxial direction was introduced into a coagulation tank of an aqueous solution of ethanol of 25 vol% through the discharging portion of the spinning channel, and the microfibrillated cellulose which was solidified in the coagulation bath to take up the long fibrous cellulose was taken. The solidified fibrous microfine cellulose was washed and dried.

Evaluation example  1: tensile strength

The tensile strengths of the microcellulose filament yarns prepared in Examples 1 to 6 and Comparative Example 1 were measured at 25 ° C and 65% relative humidity using an Instron tester (Instron Engineering Corp., Canton, Mass.) According to the ASTM D885 method The specimens were stretched until the specimens were broken at a tensile rate of 300 mm / min for a sample length of 250 mm in the humidity condition. The strength at the breaking point was determined, and the test was carried out 10 times or more.

Evaluation example  2: Break Elongation

The elongation at break of the microcellulose filaments prepared in Examples 1 to 6 and Comparative Example 1 was measured using an Instron tester (Instron Engineering Corp., Canton, Mass.) At a temperature of 25 ° C and a relative humidity of 65% The elongation at the breaking point was obtained by tensile test at a tensile speed of 300 mm / min for the sample length, and the elongation at break was obtained.

Evaluation example  3: Seal Modulus of elasticity

The tensile strengths of the microcellulose filament yarns prepared in Examples 1 to 6 and Comparative Example 1 were measured at 25 ° C and 65% relative humidity using an Instron tester (Instron Engineering Corp., Canton, Mass.) According to the ASTM D885 method The slope of the stress / strain curves was measured at a tensile elongation of 0.5% and 2.0% at a tensile rate of 300 mm / min for a sample length of 250 mm in a humidity condition. The slope of the stress / strain curve was measured 10 times or more, Respectively.

Table 1 below shows the microfibrous cellulose concentration, the content of the crosslinking agent, and the results according to Examples 1 to 3 of Examples 1 to 6 and Comparative Example 1.

Example Comparative Example One 2 3 4 5 6 One Concentration (wt%) of microfibrous cellulose 0.1 5 7 13 13 13 14 Content (wt%) of crosslinking agent (2,4-methylenediphenyl diisocyanate) - - - - 0.054 0.175 - Tensile Strength (MPa) 5.7 6.4 8.5 10.8 11.4 13.2 0.8 Elongation at break (%) 2.1 2.4 2.7 3.1 3.7 4.8 0.7 Tensile modulus (GPa) at elongation of 0.5% 2.1 2.8 3.7 4.8 5.2 6.7 0.2 The tensile modulus (GPa) at an elongation of 2.0% 4.9 5.8 7.5 8.2 9.4 10.9 0.5

As can be seen from the above Table 1, it was confirmed that Examples 1 to 6 had better mechanical properties such as tensile strength, elongation at break and tensile elastic modulus than Comparative Example 1.

20: Radiation channel
21: inlet of the radiation channel
22: discharge part of the radiation channel
30: Coagulation bath
40: Washing tank

Claims (14)

(a) preparing a liquid crystal solution in which microfibrous cellulose is partially oriented;
(b) injecting the liquid crystal solution into the inlet of the spin chuck;
(c) orienting the microfibrous cellulose in the uniaxial direction while passing the liquid crystal solution in the direction of the uniaxial axis of the spin chuck;
(d) injecting the unidirectionally oriented microfibrous cellulose into the coagulation bath through the discharge portion of the radial channel;
(e) coagulating and fibrillating the microfibrous cellulose while water in the microfibrous cellulose oriented in the uniaxial direction in the coagulation bath is desorbed by diffusion;
(f) separating the coagulated long-fiberized microfibrous cellulose in a coagulation bath; And
(g) drying the separated long fibrous microfibrous cellulose,
The liquid crystal solution prepared in the step (a) comprises the microfibrous cellulose and water,
Wherein the liquid crystal solution comprises 0.1 to 13% by weight of microfibrous cellulose based on the total weight of the liquid crystal solution. The method according to claim 1,
Wherein the microfibrous cellulose has a diameter of 5 nm to 100 nm and a length of 100 nm to 500 탆. delete The method according to claim 1,
Sectional area of the cross-section perpendicular to the uniaxial direction of the radial channel decreases from the inflow portion of the radial channel toward the discharge portion of the radial channel. The method according to claim 1,
The coagulation liquid is stored bath the coagulation liquid mixture of water and ethanol or _{NaOH, KOH, BaCl 2, PbCl} 2, Ba (NO 3) 2, Pb (NO 3) 2, Ca (NO 3) 2, CaCl 2, FeCl 2, FeCl _3, and CuSO ₄ , in an aqueous solution of the microcrystalline cellulose. 6. The method of claim 5,
The volume ratio of ethanol to water in the mixture of water and ethanol is 1: 2 to 1: 5,
And one kind selected from the group consisting of NaOH, KOH, BaCl ₂ , PbCl ₂ , Ba (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ , CaCl ₂ , FeCl ₂ , FeCl ₃ and CuSO ₄ By weight of the aqueous solution is from 3% by weight to 10% by weight. The method according to claim 1,
In the step (e), a crosslinking agent is further added,
Wherein the cross-linking agent is selected from the group consisting of 2,4-methylenediphenyl diisocyanate (MDI), 4,4'-methylenediphenyl diisocyanate (MDI), xylylene diisocyanate (XDI), m-tetramethyl xylylene diisocyanate (TMXDI) p-tetramethyl xylylene diisocyanate (TMXDI), toluylene diisocyanate (TDI), di-alkyl diphenyl methane diisocyanate, tetra-alkyl diphenyl methane diisocyanate, 3,3'-dimethyl diphenyl- Diisocyanate (TODI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, naphthalene diisocyanate (NDI), 4,4'-dibenzyl diisocyanate, hydrogenated MDI (H12MDI), 1 Diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2, 4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, Diisocyanate, hexane-1,6-diisocyanate (HDI), dimeric fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate and ethylene diisocyanate Wherein the microcrystalline cellulose is at least one selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol. The method according to claim 1,
After step (f) and before step (g)
And washing the separated long fibrous microfibrous cellulose with at least one solvent selected from water, methanol, ethanol and acetone. A microcellular filamentous fiber produced according to the method of claim 1. 10. The method of claim 9,
Wherein the microcrystalline cellulose filaments have a diameter of 10 nm to 800 nm. 10. The method of claim 9,
The tensile strength of said microcellular filamentous fibers measured according to the ASTM D885 method is 3 to 15 MPa. 10. The method of claim 9,
Wherein the elongation at break of the microcellulose filament is 1.5 to 10%. 10. The method of claim 9,
Wherein the tensile elastic modulus at the elongation of 0.5% of the microcellulose filament as measured according to the ASTM D885 method is 1.5 to 10 GPa. 10. The method of claim 9,
Wherein the tensile elastic modulus at a elongation of 2.0% of the microcellulose filament as measured according to the ASTM D885 method is 2 to 15 GPa.

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