KR890000128B1 - Polyamide fiber and it's film making method and apparatus - Google Patents

Abstract

A method comprises (i) extruding pre-polymer soln. (polymerized amides solvent contg. dissolution accelator with aromatic diamine and aromatic diesidchloride, intrinsic viscosity 1.0-4.0) through a die at the velosity of 50-250 m/sec, (ii) passing into mol.-orientation feed rollers and mol.-orientation discharge rollers for mol.- orientation by velosity difference of the rollers, (iii) spraying polymn.-accelation-solvent i.e. tamines solvent or a mixt. of t- amines and amides solvent from upper, lower, right and left sides of the rollers at the velosity of 2-50 m/sec to complete polymg. and (iv) washing, drying and winding.

Description

Method for producing wholly aromatic polyamide fiber and film and apparatus therefor

1 and 2 schematically show a process for producing a conventional polyamide fiber and film,

3 is a view schematically showing a process for producing a polyamide fiber and a film of the present invention,

4 is an enlarged schematic view of the molecular alignment roller according to the present invention of FIG.

* Explanation of symbols for main parts of the drawings

1: radial block 2: detention and die

3: Molecular orientation feed roller 3 ': Molecular orientation feed roller

4: molecular polymerization accelerator 5: molecular polymerization accelerator injection machine

6: prepolymer solution in liquid crystal state 7: guide

8: washing device 9: drying device

10: winding machine 11: coagulation bath

11 ': Molecular polymerization accelerator container 12: Coagulation bath supply pipe

12 ': molecular polymerization accelerator supply plate 13: coagulation bath

14: radiation pipe 15: air supply pipe

16: air and coagulation liquid discharge pipe 17: neutralization roller and outlet

18: neutralizing device 19: fiber and film

20: dope

The present invention relates to a method and a device for producing a wholly aromatic polyamide fiber and a film, and more particularly, to spun the prepolymer solution and the molecular polymerization accelerator at a suitable speed to enhance the degree of molecular polymerization and at the same time the molecular orientation feed roller The present invention relates to a method and a device for producing a wholly aromatic polyamide fiber and a film having high orientation as well as high strength and high elasticity by using the linear velocity difference of the molecular orientation delivery roller.

In general, fibers, short fibers, and films made of wholly aromatic polyamides are not only light in weight, but also have high strength and high elasticity. They also have heat resistance, abrasion resistance, or electrical insulation, which are inherent to the aircraft, automobile industry, composite materials, and construction materials. It is usefully used not only for special industries such as but also for leisure sports.

Due to this usefulness, various studies have been conducted on the preparation of polyamide filament islands or films. For example, US Pat. Nos. 3,869,429 and 3,869,430 separate polyamides polymerized in an amide solvent, and It describes that polyamide fibers or films are prepared by spinning a solution dissolved in a sulfuric acid solvent into water or methanol through detention, and US Pat. Nos. 4,298,565, 4,070,431 and 4,048,279. In this case, a solidification bath is used to form an air layer at the lower end of the detention, and the fiber and the film are sucked into the radiation tube, and then must be passed through the neutralizing device (see attached drawings 1 and 2).

However, this method is complicated by separating and washing the polymer, washing with water, and drying it back into sulfuric acid solution, which is difficult to control the polymerization reaction, and also increases the cost, and increases the risk due to the use of sulfuric acid solvent. There are disadvantages.

In addition, there is a difficulty in post-treatment problems such as Na ₂ SO ₄ produced as a by-product, and it is difficult to obtain a synergistic effect of intrinsic viscosity because water is used as a precipitation solvent in the spinning process, and due to the residual acid and alkaline substances in the fiber After a long time, the physical properties of the polymer were weakened, and sometimes the cumbersome action of injecting air prevented the unstretched polymer from being cut or blocked by the radiation tube during the initial spinning, making continuous production impossible.

Therefore, the present inventors have repeatedly conducted research for a long time in order to solve such a conventional problem, and as a result of remodeling the most important spinning device in the production of polyamide fibers, an aromatic polyamide fiber and a film having superior physical properties have been produced. In other words, the present invention is a high-aromatic, high elastic modulus and highly oriented polyaromatic poly that is capable of continuous winding while shortening the process by simultaneously spinning and ejecting the prepolymer solution and the molecular polymerization accelerator at a high speed simultaneously. It is an object of the present invention to provide a method for producing amide fibers and films, and an apparatus thereof.

Hereinafter, the present invention will be described in detail.

The present invention is a method for producing a wholly aromatic polyamide fiber and a film, a preliminary viscosity of 1.0 to 4.0 in which the aromatic diamine and the radial dieside chloride is polymerized in a mixture obtained by dissolving an inorganic salt as a solvent promoter in an amide solvent. The polymer solution is ejected at a rate of 50 to 250 m / min through the confinement and passed through the molecular orientation feed roller and the molecular orientation delivery roller, so that molecular orientation occurs at the linear speed difference of the roller, while tertiary amine solvent Molecular polymerization promoter, which is a single or tertiary amine solvent and a mixed solvent of amide solvent, is dispersed at the upper and lower sides of the molecular orientation roller at a rate of 2 to 50 m / sec to completely polymerize it, and then washed in a conventional manner. It is a method of manufacturing a wholly aromatic polyamide fiber and a film by winding after drying and drying.

In addition, the present invention is a device for producing a wholly aromatic polyamide fiber and film, the spin block is formed with a die and a die for ejecting the prepolymer solution, and at the lower end of the molecular orientation feed roller for inducing the polymer; Molecular serpentine feed rollers are installed up and down, but the first stage is provided with a molecular orientation supply roller, the second stage is provided with at least one pair of molecular orientation delivery rollers, respectively, the injection amount of the molecular polymerization promoter on the left and right sides of the molecular orientation roller. The appropriate number of molecular polymerization promoting solvent ejectors to spray the solvent while controlling them are installed at each roller or up and down so as to spray each other on the left and right sides on the horizontal center line of the molecular orientation roller, and the molecular polymerization on the left and right sides. The facilitating solvent injection machines are located on the same vertical line on the left and right sides of the roller. It is a device for producing a wholly aromatic polyamide fiber and film, characterized in that made by being connected to each of the molecular polymerization promoting solvent receiving container and the molecular polymerization promoting solvent re-supply pipe located at the lower end.

Hereinafter, the present invention will be described in more detail.

The prepolymer solution in the liquid crystal state characterized by the present invention is obtained by solution polymerization of an aromatic diamine and an aromatic dieside chloride in a solution in which an inorganic salt is dissolved in an amide solvent, wherein N-methylpi is used as the amide solvent. Ralidone (NMP), hexamethylphosphoramide (HMPA), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMOS), N, N, N ' Any one of, N'-tetramethylurea (TMO) is selected and used as an inorganic salt, either lithium chloride (LiCl) or calcium chloride (CaCl ₂ ).

The amount of the inorganic salt added to the amide solvent is preferably about 5 to 11% by weight based on the amide solvent.

On the other hand, for example, P-phenyldiamine and terephthaloyl chloride may be used as the polymer of the aromatic diamine and the aromatic dieside chloride, and when these are added to the amide solvent in which the inorganic salt is dissolved, the following general formula (I) Polyphenylene terephthalamide having the unit of is repeatedly obtained as the liquid crystal prepolymer solution according to the present invention.

Herein, in order to obtain a high molecular weight polymer having undergone many studies, the present inventors have good impurity of 0.03% or less, and the polymerization of the monomers should be performed almost equivalently.

In the present invention, the intrinsic viscosity of the prepolymer solution obtained by the above polymerization method may be 1.0 to 4.0, more preferably 2.0 to 3.0, and the polymer content of the prepolymer solution is 4 to 12 weight based on the polymerization solvent. It is good to let it be about%.

Here, if the content of the polymer solution is less than 4% by weight, the intrinsic viscosity of the final polymer is sharply lowered, so that the yield of fibers or films is greatly reduced, on the contrary, the content of the polymer solution is more than 12% by weight. In this case, it is very difficult to control the process due to rapid polymerization.

On the other hand, the molecular polymerization promoter according to the present invention serves to promote the polymerization reaction of the prepolymer solution and at the same time enhance the degree of polymerization. At this time, a tertiary amine solvent may be used as the molecular polymerization promoter, and for example, pyridine, quinoline, pyrazine, triethylamine, picoline, acrylidine and quinoxaline A mixed solvent of a tertiary amine and an amide solvent may be used alone or by selecting any one of the amide solvents described above.

Hereinafter, a method for preparing an aromatic polyamide according to the present invention and a process for preparing fibers and films will be described in detail with reference to the accompanying drawings.

First, the inorganic salt is dissolved in the amide solvent as a dissolution accelerator, and the aromatic diamine is completely dissolved while slowly stirring, and then, while cooling to low temperature, the aromatic dieside chloride is added while stirring rapidly in the presence of a nitrogen atmosphere.

In this state, when the appropriate time passes, the composition of the prepolymer solution is transferred from optical isotropic to optically anisotropic as the polymerization proceeds.

The optically anisotropic prepolymer solution obtained here represents a liquid crystal state immediately before the polymer solution is solidified. When the optically anisotropic prepolymer solution in the liquid crystal state is transferred to the radiation block 1 of FIG. In 2) radiation occurs. The liquid crystal prepolymer solution thus radiated is oriented by the linear velocity difference due to the rotation of the molecular alignment supply roller 3 and the molecular alignment delivery roller 3 'installed at the lower end of the die and the die 2. At the same time, the molecular polymerization promoter 4 is injected from the left and right sides of the liquid crystal prepolymer solution to be emitted through the molecular polymerization accelerator injection machine 5. At this time, the polymerization rate and the degree of polymerization of the liquid crystal prepolymer solution 6 are rapidly increased by the molecular polymerization promoter 4, and the reaction by the reaction promoting action is completed, and the degree of polymerization and the degree of molecular orientation are enhanced.

For example, the liquid crystal prepolymer solution 6 is first quantitatively supplied to the spinning block 1 via a gear pump (not shown in the figure) to provide a suitable L / D (detention and diameter of the cap for the capillary length in the die). When it is ejected through the mold and the die (2) having a), it passes through the molecular orientation feed roller (3) and the molecular orientation feed roller (3 '), and then through the guide (7) to wash the amide solvent, inorganic salt and polymerization byproduct. The washing apparatus 8 and the drying apparatus 9 and the winder 10 to which the fibers and the film are dried are wound.

In the present invention, L / D is not absolute but preferably in the range of 0.5 to 10, more preferably in the range of 1 to 5, so that the liquid crystal prepolymer solution passes through the die and the die (2). The blowing rate (the volume of the liquid crystal prepolymer solution passing through the die and the die and the average speed in the capillary capillary calculated from the slits of the die and the die) is preferably 10 m / min to 400 m / min. More preferably, it is suitable to be about 50 m / min to 250 m / min. On the other hand, it is preferable that the linear velocity of the molecular alignment supply roller 3 is about 2 to 5 times higher than the discharge rate of the liquid crystal prepolymer solution, and the linear velocity of the molecular alignment supply roller 3 'is the molecular orientation supply roller 3. It is appropriate to be in the range of 2 to 10 times the linear velocity. If the linear velocity of the molecular orientation feed roller 3 is less than twice the ejection velocity of the liquid crystal prepolymer 6, the polymer solution accumulates and becomes impossible to supply. In this state, the supply of the continuous prepolymer solution becomes impossible.

On the contrary, if the increase is more than 5 times, the polymer is not drawn to the feed roller as it is pulled at a high speed before completion of the polymerization reaction of the liquid crystal prepolymer to be ejected, but also causes a great cause of cut.

Furthermore, when the linear velocity of the molecularly oriented feeding roller (3 ') is lower than twice the linear velocity of the molecularly oriented feeding roller (3), the orientation of the polymer becomes poor and the intrinsic viscosity is an absolute function of the thickness of the fiber and film. On the principle that the relationship is maintained, the acceleration of the polymerization reaction is slowed down, and the physical properties of the fiber and the film are weakened, which makes it difficult to stably and continuously produce the product during winding. On the contrary, when the linear velocity is increased by 10 times or more, the polymer may be out of the limit of the orientation of the polymer and may be cut before the long fiber or the film is formed.

Therefore, the linear velocity of the molecular orientation feed roller 3 is preferably in the range of 2 to 5 than the linear velocity of the liquid crystal prepolymer ejected from the die and die 2, and the linear orientation of the molecular orientation delivery roller 3 ' It is preferable to keep the molecular orientation feed roller 2 to 10 times the linear velocity.

On the other hand, the thickness (D) of the molecular orientation supply roller (3) and the molecular orientation delivery roller (3 ') shown in FIG. 4 is the molecular orientation supply roller (3) and the molecular orientation delivery roller (3'). It is appropriate that all of them are about 20 to 70 mm. If the thickness (D) of the molecular alignment feed roller (3) and the molecular alignment feed roller (3 ') is reduced to 20 mm or less, the fibers and the film are mutually aligned in the polymer orientation. It becomes slippery and difficult to obtain a product having a uniform and excellent orientation, and when it is made larger than 70 mm, the fiber is fused to the supply roller so that the fiber is not separated from the roller and thus high strength and high elastic fiber are not obtained.

In addition, it is preferable that the appropriate number of stages of the molecular alignment feed roller 3 and the molecular alignment feed roller 3 'be about 2 to 5 stages, and the positions of the molecular alignment feed roller 3 and the molecular alignment feed roller 3'. Must satisfy the following equation (see Figure 4).

[d ₃ = 3D-10D] = [d ₁ , d ₂ 1 (5D≥d ₁ ≥1 / 2D) + (9D≥d ₂ ≥2D) Here, the singular is the molecular orientation feed roller (3) and the molecule. It refers to the number of layers of the orientation feed roller (3 '), and if the number of stages is less than two stages, the stability decreases when inducing a prepolymer solution or winding fibers and films. Not only is it complicated, but the operation is confusing and cumbersome.

More preferably, it is good to set it as 2 to 3 steps.

On the other hand, as shown in Figure 4 of the accompanying drawings, the position of the molecular orientation feed roller (3) and the molecular orientation transport roller (3 ') may be installed in a suitable place to guide and orient the polymer, that is, the molecular orientation transport roller ( 3 ') is installed where the distance (d ₃ = d ₁ + d ₂ ) from the center to the bottom of the die and the die is 3D to 10D as described above, d ₁ is 1 / 2D to 5D, and d ₂ is Only when the roller is installed in the limited range of 2D to 9D, the polymer can be induced into the molecular orientation supply roller (3) and the molecular orientation delivery roller (3 '), and the accumulation of polymer on the roller and the phenomenon of cutting It can be prevented, and the orientation of the polymer can be increased within a certain distance.

For example, by maintaining the positions of the molecular alignment supply roller 3 and the molecular alignment delivery roller 3 'within the above ranges, the orientation of the polymer can be uniformly increased, and the liquid crystal prepolymer at the time of spraying the molecular polymerization promoting solvent. The degree of polymerization of the solution can be sufficiently enhanced to produce fibers or films of high orientation and high elasticity as well as high orientation.

The liquid crystal prepolymer solution (6) supplied to the roller passes through the molecular alignment supply roller (3) and the molecular orientation delivery roller (3 '). At this time, the molecular polymerization accelerator container (11') and the molecular polymerization promotion are carried out. The molecular polymerization promoter 4 continuously supplied from the solvent resupply pipe 12 'is injected from the molecular polymerization accelerator injection machine 5 on the left and right sides.

At this time, the injection speed and the injection amount of the molecular polymerization promoter can be freely controlled by the injectors attached to the left and right sides, and the molecules are changed by the linear velocity difference between the molecular orientation supply roller 3 and the molecular orientation delivery roller 3 '. At the point when the chain develops into a fully oriented state, high orientation, high strength, and high elasticity are obtained by promoting the reaction and increasing the degree of polymerization as appropriate injection of the molecular polymerization promoter.

On the other hand, the vertical position of the molecular polymerization accelerator injection machine (5) can be installed above or below the horizontal center line of the molecular alignment roller, the vertical position of the left and right injection machine is installed on the vertical line, the distance between the left and right is the molecular orientation roller diameter ( It is preferable to make it about 2 to 5 times of D).

The number of such injectors can be changed as the number of molecular orientation rollers increases or decreases. However, as a result of many studies by the present inventors, as a factor that greatly affects the increase in the degree of polymerization of the fiber and the film, the solvent and the injection rate and the injection speed of the molecular polymerization It was found that these were proportional to the discharge amount of the prepolymer solution.

For example, the injection speed of the injection polymerization accelerator is preferably in the range of 2 to 50 m / sec, and the injection amount is suitably in the range of 1 to 10 times (V / V) of the supplied prepolymer solution. If the injection speed and the injection amount are out of the above range, the weakening of the reaction promotion and the increase of the polymerization degree are remarkably decreased, and excellent physical properties of high orientation, high elasticity and high strength cannot be expected, and stable and continuous production is difficult.

Since the prepolymer solution (prepolymer solution) in the liquid crystal state has a relatively low molecular weight and low concentration, the reaction is promoted quickly to enhance the degree of molecular polymerization and at the same time as the linear velocity difference of the molecular orientation roller, high orientation and high elasticity are achieved. As a result of obtaining the fibers and films of the polymer, the final polymers thus obtained have intrinsic viscosity of not less than 4.50, breaking strength of not less than 20 g / d, initial elastic modulus of not less than 500 kg / cm 2, and breakdown voltage of not more than 230 KV / mm. The angle was obtained within 23 °, and the heat treatment was carried out after spinning to improve the cutting strength and elastic modulus easily.

That is, the present invention is a method for obtaining a polyamide fiber and a film that is easy to operate and stable, and a shortened process in which spinning is completed at the same time as polymerization is completed without using a conventional sulfuric acid dope using a molecular polymerization promoter. Excellent polyamide fibers with high strength, high modulus, and high orientation as well as instantaneous polymerization due to the linear velocity difference of the molecular orientation roller in the improved spinning apparatus and the reaction promoting action of the spray polymerization accelerator. You can get a film.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 (Comparative Example 1)

The four-necked flask of 51 was sufficiently removed from the dryer, 2400 ml of NMP or DMAc solution was added thereto, and the temperature was raised. Then, 54.0 g of calcium chloride or 45.0 g of lithium chloride were added and mixed to dissolve completely in a nitrogen stream.

49.0 g of PPD was added to the mixture, and then completely dissolved. Lower the temperature with cold water, and add 1.0 g of TPA, and react with stirring well (3,000 RPM). The prepolymer solution thus obtained is jetted through the L / D tri-population, and the injection rate is adjusted to be 5 times that of the prepolymer solution jetted while the injection speed of the rich polymerization catalyst is 30 m / sec.

At this time, the linear velocity of the molecular orientation feed roller is the same as the linear velocity of the prepolymer solution discharged, and the linear velocity of the molecular orientation feed roller is about 10 times faster than the linear velocity of the molecular orientation feed roller. Pass through to obtain the final islands and the film at a winding speed of 1500 RPM.

At this time, the intrinsic viscosity of the final fiber is measured while changing the polymerization temperature and the polymerization time in addition to the conditions as smooth.

Example 2 (Comparative Example 2)

The same procedure as in Example 1 was carried out in the reaction process to change only the polymer content of the L / D and the polymerization solvent and the inorganic chloride content of the organic amide solvent to prepare the final fiber and film. The solvent used was NMP, the inorganic salt was calcium chloride, the monomers were TCP and PPD, and the results of measuring the final polymer intrinsic viscosity were as shown in Table 2 below.

Table 1

[Table 2]

In Table 2, A (%) is the polymer content (W / V) for the polymerization solvent, B (%) is the inorganic salt content (W / V) for the organic amide solvent, and Evaluation is expressed as good, normal, or poor.

Example 3 (Comparative Example 3)

In the same manner as in Example 1 but in the polymerization and spinning process, the molecular polymerization solvent is changed as shown in Table 3, and the content rate is changed as shown in Table 2 to prepare the final fiber and film. The measurement results of the physical properties are shown in Table 3 below.

Table 3

Example 4 (Comparative Example 4)

Into a sufficiently dried 51 four-necked flask, 200 ml of NMP was added under a nitrogen stream, the internal temperature was raised, and 49.6 g of calcium chloride was added to dissolve completely.

Then, 49.0 g of PPD was completely dissolved, and the temperature was lowered to 20 ° C. or lower. Then, 91.9 g of TPC was added to the mixture, which was then stirred at 3000 RPM for 5 minutes to prepare a prepolymer solution. Through the spinning process under the conditions as shown in Table 4 through to produce the final fiber and film. The measurement results of the physical properties of the fibers and films thus prepared are shown in Table 5 below.

Table 4

* ㆍ Molecular polymerization solvent injection rate (m / sec), D: diameter of molecular orientation roller (30mm).

ㆍ Molecular polymerization solvent injection amount (times: #): Drainage of the prepolymer solution discharged.

ㆍ Molecular orientation feed roller linear velocity (times: #): multiple of the prepolymer solution velocity discharged.

ㆍ Molecular orientation delivery roller linear velocity (times: #): Multiple of linear velocity of molecular orientation supply roller.

Table 5

Claims (15)

In the method for producing a wholly aromatic polyamide fiber and a film, a prepolymer solution having an intrinsic viscosity of 1.0 to 4.0 is polymerized in a mixture obtained by dissolving an inorganic salt as a dissolution accelerator in an amide solvent. While sputtering at 50 to 250m / min through a molecular orientation feed roller and a molecular orientation feed roller, molecular orientation occurs at the linear velocity difference of the roller, while tertiary amine solvent alone or 3 Molecular polymerization promoter, which is a mixed solvent of amine-based solvent and amide-based solvent, is sprayed from the upper, lower, left, and right sides of the molecular orientation roller at a speed of 2 to 50 m / sec to completely polymerize, and then washed and dried in a conventional manner. Winding method for producing wholly aromatic polyamide fibers and films. The method of claim 1, wherein the imide solvent is N-methylpyrrolidone, hexamethylphosphoramide, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N, N, N ', By selecting at least one of N'-tetramethylurea. The method of claim 1, wherein the inorganic salt is selected by selecting at least one of lithium chloride and calcium chloride. The method according to claim 1, wherein the polymer content is 4 to 12% by weight based on the polymerization solvent. The method according to claim 1, wherein the linear velocity of the molecular orientation supply roller is made to be 2 to 5 times the discharge linear velocity of the prepolymer solution discharged from the detention. The method according to claim 1, wherein the linear velocity of the molecular alignment feed roller is set to be 2 to 10 times the linearity of the molecular alignment feed roller. The method of claim 1, wherein the tertiary amine solvent is selected from pyridine, quinoline, pyrazine, trimethylamine, picoline, acriridine, and quinoxaline. The method according to claim 1, wherein the injection amount of the molecular polymerization promoter is about 1 to 10 times the prepolymer solution and the injection speed is 2 to 50 m / sec. In the apparatus for producing the wholly aromatic polyamide fiber and the film, the spinning block (1) is formed with a detention and die (2) for ejecting the prepolymer solution, and induces the prepolymer solution at the lower end thereof. Molecular orientation supply roller (3) and molecular orientation delivery roller (3 ') are installed up and down, the first stage is a molecular orientation supply roller (3), the second stage or less at least one molecular orientation delivery roller (3') is a pair And a suitable number of injection polymerization promoters for injecting the solvent (4) while controlling the injection amount of the molecular polymerization promoter (4) on the left and right sides of the molecular alignment rollers (3,3 ') (5). , 5 ') is provided for each roller (3, 3') so as to be sprayed facing each other on the horizontal center line or left and right of the molecular orientation roller (3, 3 '), the molecular polymerization accelerator injection In the left and right sides of the roller (3, 3 ') The wholly aromatic polyamide fiber and the film (19), characterized in that formed in the same vertical line and connected to each of the molecular polymerization accelerator receiving container (11 ') and the molecular polymerization accelerator solvent supply pipe (12') located at the lower end thereof (19). ) Device for manufacturing. 10. Device according to claim 9, characterized in that the detention and the size (L / D) of the die (2) are about 1-5. 10. The device according to claim 9, wherein the molecular orientation rollers (3, 3 ') have a diameter (D) of 20 to 70 mm and are formed in two to five stages. 10. The device according to claim 9, wherein the molecular orientation supply roller (3) is installed at a distance (d ₁ ) whose center is about 1D to 5D from the lower end of the detention (2). 10. The apparatus according to claim 9, wherein the molecular orientation delivery roller (3 ') is installed at a distance (d ₂ ) from the center of the molecular orientation delivery roller (3) to the center of the molecular orientation supply roller (3). 10. The device according to claim 9, wherein the molecular orientation delivery feed roller (3 ') is installed at a distance (d ₃ ) whose center is about 3D to 10D from the lower end of the detention (2). 10. The apparatus according to claim 9, wherein the center distance between the left and right sides of the pair of molecular alignment rollers (3, 3 ') is 2D to 9D with respect to the roller diameter (D).

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