WO2020045161A1

WO2020045161A1 - Acrylic yarn package

Info

Publication number: WO2020045161A1
Application number: PCT/JP2019/032407
Authority: WO
Inventors: 大島郁人; 川本貴史; 村上哲也
Original assignee: 東レ株式会社
Priority date: 2018-08-29
Filing date: 2019-08-20
Publication date: 2020-03-05
Also published as: TW202012295A; JPWO2020045161A1; CN112533850A; EP3845477A1; KR20210049790A; US20210323786A1; EP3845477A4

Abstract

In order to provide an acrylic yarn package which, when an acrylic yarn having a high total fineness is wound around a core bobbin, prevents winding collapse during transfer, this acrylic yarn package comprises an acrylic yarn having a total fineness of 8000 dtex or more and wound around a bobbin, and the acrylic yarn on the package has a width of 0.22 mm/1000 dtex or more and a hardness of 60 or more.

Description

Acrylic yarn package

The present invention relates to an acrylic yarn package having a good winding shape and having less trouble during transportation and unwinding. In particular, the present invention is suitable as an acrylic precursor yarn package used for carbon fiber production.

Polyacrylonitrile-based long fibers are used not only for clothing but also in recent years as precursors for carbon fibers.Therefore, many improvement techniques have been used to obtain carbon fibers with excellent performance and to increase their productivity. It has been disclosed.

The carbon fiber is once wound in a spinning process of spinning an acrylonitrile-based fiber yarn as a precursor, and then sent to a firing process, where the fiber is heated and fired in an air atmosphere at 200 to 300 ° C. to be converted to an oxidized fiber. And a carbonization process of further heating to 300 to 3000 ° C. in an inert atmosphere such as nitrogen, argon, helium, etc., and carbonizing it. Widely used for general industrial applications.

In general, carbon fibers are composed of filaments having a single yarn number of 1000 or more, and multifilaments are used as one yarn unit. However, acrylic yarn as a raw material is produced in a firing process as a subsequent process. Due to the difference in the yarn speed, it is general that the yarn is once wound in a yarn-making process and then sent to a firing process. In order to increase the productivity in the firing step, it is effective to increase the amount of acrylic yarn that can be processed at one time, but the acrylic yarn is usually wound around a core bobbin, so that one bobbin is used. If a large amount of yarn is wound up, the bobbin will drop vertically when transported to the firing process, or the swelling of the end face will increase, resulting in poor unwinding during the firing process. May occur.

In an acrylic yarn package for a carbon fiber precursor, Patent Document 1 describes a technique for defining winding conditions such as a twill angle and a winding tension in order to obtain a good winding shape at the time of winding. However, there is no description of collapse during transport. Patent Document 2 discloses a technique for obtaining a good winding shape by taking a specific yarn width and a yarn deviation ratio for a thick acrylic yarn of 33,000 dtex or more. Unless the convergence is improved by adding water, the deterioration of the winding shape and the trouble at the time of unwinding cannot be completely prevented. It has been a problem that it is not suitable for long-distance movement because of the increase in mass and mass.

Further, in order to prevent collapse during transport, techniques for defining the hardness of the package for fibers having a total fineness of about several tens to several hundreds dtex are described in

Patent Documents

3 and 4, but 1000 dtex is used. However, it cannot be directly applied to an acrylic yarn package for a carbon fiber precursor having a large total fineness.

JP-A-11-263534 JP-A-2002-3081 JP-A-51-23322 JP 2005-273106 A

The present invention is to solve such a problem of the prior art, and when winding an acrylic yarn having a large total fineness around a core bobbin, to provide an acrylic yarn package that does not collapse during transportation. Make it an issue.

The present invention employs the following means in order to solve such problems. That is, the acrylic yarn package of the present invention is a package in which an acrylic yarn having a total fineness of 8000 dtex or more is wound around a bobbin, and the yarn width of the acrylic yarn on the package is 0.22 mm / 1000 dtex. As described above, the acrylic yarn package has a hardness of 60 or more.

According to the present invention, when winding an acrylic yarn having a high total fineness around a core bobbin, it is possible to provide an acrylic yarn package having a good winding shape which does not collapse even when transported to the next step.

FIG. 1 is a schematic view showing an acrylic yarn package. FIG. 2 is a schematic view showing an acrylic yarn package in which a warp occurs in the center.

The present invention, the above-described problem, when winding an acrylic yarn having a high total fineness on a core bobbin, a keen examination of a carbon fiber precursor acrylic thick yarn package having a good winding shape that does not collapse even during conveyance, The inventors have sought to solve such a problem by setting the yarn width and hardness of the package to a certain value or more.

The carbon fiber precursor acrylic yarn used in the present invention is composed of a so-called acrylic polymer, for example, a polymer obtained by polymerizing a comonomer of preferably 90% by mass or more and less than 10% by mass of acrylonitrile. Is what it is. Such comonomers include acrylic acid, methacrylic acid, itaconic acid, or their methyl esters, ethyl esters, propyl esters, butyl esters, alkali metal salts, ammonium salts, or allyl sulfonic acid, methallyl sulfonic acid, or these. At least one selected from alkali metal salts and the like can be used.

Such acrylic polymers are obtained by using known polymerization methods, for example, polymerization methods such as emulsion polymerization, suspension polymerization, and solution polymerization.Further, when producing acrylic fibers from these polymers, for example, dimethylacetamide A polymer solution containing a solvent selected from dimethylsulfoxide (hereinafter, referred to as DMSO), dimethylformamide, nitric acid, zinc chloride, and an aqueous solution of rhodan soda is used as a spinning yarn and spun by a wet spinning method or a dry spinning method.

The spun yarn is then subjected to drawing in a bath, and the drawing in the bath may be performed directly on the spun yarn, or may be performed after the spun yarn is washed once with water and the solvent is removed. Good. The stretching in the bath is preferably performed about 2 to 6 times in a stretching bath at 50 to 98 ° C. After the stretching, an oil agent is preferably applied, dried and densified by a hot roller or the like, and then steamed. After being subjected to stretching, it is wound around a core bobbin to form a package.

At the time of winding into such a package, a plurality of yarns may be combined into several yarns and then wound. In order to improve the productivity of carbon fibers, it is effective to fire the multifilament yarns at once. Therefore, the total fineness of the yarn wound in the present invention is 8000 dtex or more. Further, the moisture content of the yarn is preferably 3% or less in order to avoid an increase in mass during transportation. The total amount of the acrylic yarn obtained by subtracting the bobbin mass and the water content from the mass of the entire package is preferably larger in order to reduce the number of the acrylic yarn threading operations in the firing step and to make the work more efficient, and preferably 120 kg. Above, more preferably, it is wound up to 200 kg or more.

(4) In order to eliminate the collapse during transport, it is important that the hardness of the bobbin end measured by a durometer is 60 or more. If the hardness is less than 60, the package is likely to be loosened, and it is easy for the package to collapse during transport and to have a shed when unwinding. The hardness of 60 or more can be achieved by setting the tension of the yarn at the time of winding to an appropriate value. When winding a large amount of yarn, it is general to gradually reduce the tension from a large tension and wind it, but the value should be an appropriate value according to the fineness of the yarn and the number of filaments Can be.

In the acrylic yarn package of the present invention, it is necessary to wind the acrylic yarn on the package so that the yarn width is 0.22 mm / 1000 dtex or more. When the yarn width is smaller than 0.22 mm / 1000 dtex, the thickness of the yarn becomes large, a gap is generated between adjacent yarns, and the yarn is liable to collapse during transportation. On the other hand, if the yarn width is larger than 0.54 mm / 1000 dtex, the convergence of the yarn becomes poor, and troubles such as twill drop and winding of a single yarn may occur at the time of unwinding in the firing step. It is preferable that the width of the acrylic yarn is in the range of 0.22 mm to 0.54 mm / 1000 dtex. The method for setting the yarn width on the package to the above range is not particularly limited, but when winding the yarn with a winding machine, a method of winding after passing a free roller group for convergence for a certain amount or more is preferably used. .

In the acrylic yarn package of the present invention, if the static friction coefficient of the acrylic yarn is less than 0.13, even if the yarn width and hardness are controlled to specific conditions to prevent winding collapse, even when winding, Since swelling of the end face may occur, it is preferable that the static friction coefficient be 0.13 or more by applying an appropriate type and amount of an oil agent.

{Also, in the acrylic yarn package of the present invention, it is preferable to set the yarn misalignment ratio to 15 to 59% and the twill angle on the package to 6 to 14 °. The yarn deviation ratio is a ratio of the yarn deviation amount S to the yarn width T in two yarns passing in parallel at the closest position on the package. That is, this yarn deviation ratio is determined by (S / T) × 100 shown in FIG. When this is conceptually described with reference to FIG. 1, the acrylic yarn 4 is a yarn that passes in parallel with the acrylic yarn 3 on a position closest to the acrylic yarn package 1, This is the ratio of the yarn deviation S between the acrylic yarn 3 and the acrylic yarn 4 to the yarn width T. The yarn width T and the yarn deviation amount S are values measured by a method described later.

As shown in FIG. 1, the twill angle is an angle (θ) between a straight line perpendicular to the axis of the core bobbin 2 (line α perpendicular to the core bobbin axis direction) and the direction of the acrylic yarn 4 to be wound. ).

The yarn deviation ratio and the twill angle can usually be controlled by setting the winding speed of the winder spindle per one yarn traverse, that is, the so-called wind ratio, to an appropriate value. If the wind ratio is an integer, the yarn passes through exactly the same yarn path before and after one traverse. By setting the decimal portion of the wind ratio to an appropriate value, the yarn path before and after one traverse is shifted, The deviation ratio can be controlled. Also, by setting the size of the entire wind ratio including the integer part to an appropriate value, the helix angle can be controlled. If the yarn deviation ratio is less than 15%, the package will have large undulations, and even if the winding tension is increased, the hardness may decrease, and the winding tends to collapse during transportation. Further, when the yarn deviation ratio is larger than 59%, the contact surface between the inner layer yarn and the outer layer yarn becomes smaller, so that the inner layer yarn slips and is pushed out by the pressing of the outer layer yarn at the time of winding, so that the end face is removed. It will swell. Therefore, it is preferable to set the yarn deviation ratio in the range of 15% to 59% since both the hardness and the end face shape can be set to favorable numerical values.

If the twill angle is smaller than 6 °, the twill drop during unwinding is liable to occur, and if the twill angle is larger than 14 °, the end face bulges larger, so that the twill angle is in the range of 6 to 14 °. It is preferred that When winding at a constant wind ratio, the twill angle decreases linearly as the diameter of the package wound on the core bobbin increases, so change the wind ratio during winding according to the amount of yarn wound. Thus, winding can be performed while keeping the twill angle within a certain range. For example, by making the spindle drive and traverse drive independent, detecting the spindle rotation speed, calculating to achieve the set wind ratio, and then controlling the traverse drive rotation speed, the winding in the winding process The wind ratio can be set freely according to the amount.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The measuring methods used in the examples and comparative examples will be described below.

<Total fineness>
A sample yarn of 20 m was collected from the package to be measured, and the total fineness was determined by a method according to JIS L1013: 2010.

<Static friction coefficient>
1.5 m of a sample yarn was collected from the package to be measured, and wound around the package after collection. At this time, it was wound around the center of the package along the circumferential surface of the package. After winding the sample yarn so that the contact angle with the package was 540 °, a 150 g weight was attached to each end of the sample yarn. Thereafter, the mass of the weight at one end of the yarn was increased, and the mass at which the yarn started slipping on the separate roll was measured, and the mass was determined by the following equation.
Static friction coefficient (μs) = 3 / π × Ln (T1 / 150)
π: Pi T1: Mass (g) of the weight when slipping starts.

<Thread width>
The yarn width of the acrylic yarn on the package is measured using a caliper with a point within 2 cm from the package ends (hereinafter referred to as both ends), the center, and a total of 5 points between the ends and the center, and divided by the total fineness. The value obtained was taken as the yarn width.

<Yarn deviation ratio>
For the two yarns passing in parallel on the closest part on the package, the amount of yarn deviation (S) shown in FIG. 1 was determined by using calipers at both ends of the package, the center, and a total of 5 between the both ends and the center. The points were measured, and the value obtained by dividing the average value by the yarn width was defined as the yarn deviation ratio.

<Twill angle range>
While unwinding the wound package, the angle between the straight line (α) perpendicular to the axial direction of the core bobbin 2 shown in FIG. 1 and the direction of the wound yarn 4 at every 10 kg until all the yarns are exhausted. (Θ) was measured at the center of the package, and the range of the measured values was defined as the twill angle range.

<Hardness>
Using a Hardness Tester “Type C” (for Cellular Rubber & Yarn Package) manufactured by Kobunshi Keiki Co., Ltd., two places 2 cm inside from both ends of the package are measured, and the average value is taken as a yarn package. Hardness.

<Crash during transport>
The acrylic yarn package was passed through a carriage with a spindle, and a transport vibration test according to JIS Z0232: 2004 was performed once for each acrylic yarn package, and the presence or absence of winding collapse was determined at the following two levels. .
：: There was no increase in end face bulge of 5.0 mm or more and no increase of warpage of 10 mm or more.
X: The end face swelling increased by 5.0 mm or more, and the warpage increased by 10 mm or more.

From the straight line 5 connecting both ends of the upper part of the package shown in FIG.

<End face bulge>
With respect to the yarn traverse width (L) at the outermost surface of the package shown in FIG. 1, the end surface swelling amount (k1, k2) which is the height of the point where the side surface of the package bulges outmost is the both side surfaces of the package. , And the average value was taken as the bulge at the end face.

<Trouble during unwinding>
When the package was set on a creel and the entire amount was unwound, no bleeding or no single yarn wrapping occurred.

(Example 1)
A 19% DMSO solution of an acrylic polymer having an intrinsic viscosity [η] of 1.96, which is composed of 99.6% by mass of acrylonitrile and 0.4% by mass of itaconic acid, was used as a stock solution for spinning. % And 70% water in a coagulation bath at 8 ° C. to obtain a coagulated yarn. The coagulated yarn is stretched 2.8 times in hot water while washing with water, and the remaining DMSO is further washed with water until the amount becomes 0.01% or less in the yarn. For dry densification. Subsequently, the film was dried again after being stretched 4.3 times in pressurized steam. Two 6000 filament yarns are plied, and a 12,000 filament yarn having a total fineness of 13300 dtex is wound by a winder on a core bobbin made of FRP having an outer diameter of 145 mm. Then, the acrylic yarn obtained by subtracting the mass of the bobbin and the amount of water from the mass of the entire package was wound up to 120 kg. The water content was determined by sampling about 12 m of the yarn to be wound in advance, measuring the water content by a method according to JIS L1013: 2010, and multiplying by the amount of the wound yarn.

As shown in Table 1, the result was a good package with no collapse during transport.

(Examples 2 to 5, Comparative Examples 1 to 4)
In the same manner as in Example 1 except that the total amount of the acrylic yarn obtained by subtracting the bobbin mass and the water content from the mass of the entire package was 240 kg, the yarn width at the time of winding, the wind ratio and the tension of the winding machine were changed. The yarn was changed and wound in the yarn width, yarn deviation ratio and twill angle ranges shown in Table 1.

As shown in Table 1, as shown in Table 1, the packages of Examples 2 to 5 were good packages with no winding collapse during transportation, but Example 4 had a yarn misalignment ratio of 60% or more during winding. Since the surface in contact with the inner layer yarn and the outer layer yarn becomes smaller, the outer layer yarn presses the inner layer yarn at the time of winding, and the inner layer yarn slides and is pushed out, so that a package having a large end face bulge is obtained. In Example 5, since the yarn width was as large as 0.55 mm / 1000 dtex or more and the convergence of the yarn was poor, the shedding and single yarn winding occurred during unwinding in the firing step. Comparative Examples 1 to 3 had a hardness of less than 60 as compared with Example 2, and collapsed during transport. In Comparative Example 4, the yarn width was less than 0.22 mm / 1000 dtex as compared with Example 2, and winding collapse occurred during transportation.

(Examples 6 and 7)
Winding was performed in the same manner as in Example 2 except that the amount of oil applied was adjusted to change the coefficient of static friction of the yarn, with the yarn width and yarn deviation ratio shown in Table 1. As a result, as shown in Table 1, it was a good package without collapse during transportation. In Example 6, the static friction coefficient was as low as less than 0.13, and the side slippage of the yarn occurred at the time of winding, resulting in a package having a large end face bulge.

(Example 8)
A yarn having 24,000 filaments and a total fineness of 26,600 dtex was wound in the same manner as in Example 2 except that four 6000 filament yarns were plied.

(Example 9)
A 24,000 filament and a total fineness of 29,100 dtex were wound at a yarn width and a yarn deviation ratio shown in Table 1, in the same manner as in Example 8, except that the draw ratio in the pressure steam was 3.9.

(Example 10)
In the same manner as in Example 2 except that six 6000 filament yarns having a single yarn fineness of 0.74 dtex were combined, 36000 filaments and a total fineness of 26,600 dtex were wound at a yarn width and a yarn deviation ratio shown in Table 1. .

1: Acrylic yarn package 2: Core bobbin 3: Acrylic yarn 4: Acrylic yarn 5: Straight line connecting both ends of the upper part of the package 6: Curve L following the upper part of the package L: Yarn traverse width k1, k2: End face Swelling amount S: Yarn deviation amount T: Yarn width U: Warp θ: Twill angle α: Line perpendicular to core bobbin axis direction

Claims

A package comprising an acrylic yarn having a total fineness of 8000 dtex or more wound on a bobbin, wherein the acrylic yarn on the package has a yarn width of 0.22 mm / 1000 dtex or more and a hardness of 60 or more. package.
The acrylic yarn package according to claim 1, wherein the total amount of the acrylic yarn is 120 kg or more.
The acrylic yarn package according to claim 1 or 2, wherein the acrylic yarn has a static friction coefficient of 0.13 or more.
The yarn according to any one of claims 1 to 3, wherein the acrylic yarn on the package has a yarn width of 0.22 to 0.54 mm / 1000 dtex, a yarn deviation ratio of 15 to 59%, and a twill angle of 6 to 14 °. Acrylic yarn package.