JPS5818408A - Water-absorbing acrylic fiber showing antistatic properties - Google Patents

Abstract

PURPOSE:A specific water-absorbing resin and antistatic polymer are selected and added to improve both of the properties, water-absorption and antistatic property, synergetically and give the fiber having both of satisfactory properties by adding a small amount of them. CONSTITUTION:A water-absorbing resin of less than 0.5 micron particle size in absolute dry and of 10-300cc/g water absorption and an antistatic polymer of an acrylonitrile copolymer containing 30-85wt% copolymer coponents of formulaIor II are added by less than 10wt%, preferably 1.5-8wt%, to give a composition containig more than 90wt% acrylonitrile polymer. The resultant composition is subjected to wet spinning to form fiber that has pores of more than 0.2 micron major axis in the cross section, less than 10 seconds of charge half-life measured at 20 deg.C and 65% HR and more than 20% water retention. The amounts of the water-absorbing resin and the antistatic polymer are 0.5- 7.0wt% and 1.0-7.5wt% respectively. The water-absorbing polymer is preferably a copolymer of acrylonitrile containing less than 30% crosslinking monomers such as acrylic diester and other vinyl monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-absorbing r-cryl fiber with antistatic properties, and more specifically, it is made by blending a specific water-absorbing resin and an antistatic polymer, and has dyeability. This invention relates to a novel acrylic fiber that has excellent spinnability, processability such as strength and elongation, and practical performance, as well as antistatic properties and water absorption properties.

Conventional acrylic fibers, like other synthetic fibers such as polyamide and polyester, have poor water absorption and hygroscopicity, so they are used for underwear, V-shirts, etc.
BACKGROUND OF THE INVENTION In most cases, blended fabrics with cotton, rayon, etc. are used as materials for clothing, such as sportswear, 5R11, etc., to ensure comfort.

Many studies have been made to improve the water absorption and hygroscopic properties of this acrylic fiber, but nothing with satisfactory performance has yet been proposed.

For example, when producing acrylic am consisting of a single fiber by a wet spinning method, an acrylic fiber exhibiting water absorption properties can be obtained by fixing the porous structure of the swollen gel-like thread. The micropores are unstable and easily disappear during the subsequent drying process or ironing, resulting in decreased water absorption, resulting in the absorption of extremely large amounts of spinning oil and poor dye fastness. It has inherent disadvantages.

In addition, many proposals have been made regarding means for forming pores inside the fiber by removing the added substance after spinning a spinning dope to which specific substances such as free** or organic substances have been added. Such a method can hardly be said to be an industrially advantageous method since it causes essential problems such as contamination of the solvent by the substance, deterioration of the working environment, and complication of the manufacturing process such as recovery of the substance. Several techniques have been proposed for imparting water absorption and hygroscopic properties to 7-cryl fibers by partially hydrolyzing them, but such fibers with large amounts of carboxyl groups introduced onto their surfaces have poor physical properties and color fastness. The decrease was remarkable, and when water was absorbed, 'ltf 6 < r =/ 1g tJH
t 6 Ch d−ゝ′. (1) This is not a satisfactory method.

Under these circumstances, the inventors of the present invention have conducted extensive research in order to eliminate the drawbacks listed above and provide industrially advantageous water-absorbing acrylic fibers with excellent practical performance. It was discovered in 1982 that it was possible to make acrylic fibers with practical performance and nine water-absorbing properties without problems such as nozzle clogging, thread breakage, winding melting, and tearing during the manufacturing process.
17860 was proposed. However, this prior invention also suffers from static disturbances (i.e., disturbances of fabrics and electric shocks during the drying process after dyeing process, rectifying sewing process, etc.)
! There are inherent problems such as lubricants, clinging when worn, and discharge sparks when undressing, and further recasting is desired from these points of view.In light of such circumstances, the present three authors are excellent. As a result of intensive research to provide a new porous water-absorbing acrylic fiber that has processability, practical performance, and no electrostatic damage, by selecting and blending a specific water-absorbing resin and antistatic polymer, The present invention was achieved by discovering that the synergistic effect between the two is remarkable, and that even a small amount added can dramatically improve water absorbency and water retention as well as antistatic properties compared to conventional porous acrylic fibers.

In other words, the object of the present invention is to have stable water absorption performance that does not easily deteriorate due to heat treatment, etc., as well as excellent practical performance such as physical properties such as strength and elongation, dyeing fastness, and spinnability, and which is suitable for use in porous U&W. 2. The purpose of Ike is to provide a new water-absorbing acrylic fiber that does not have particularly noticeable static electricity damage, and is free from nozzle clogging, thread breakage 1, wrapping, and @a Xiu's manufacturing process 1, and is free from additive substances. Another object of the present invention is to provide an industrially advantageous structural means for water-permeable acrylic fibers that does not cause problems such as recovery of water, deterioration of the working environment, and does not have a sticky feeling when water is absorbed. It will become clear from the following description that the water-absorbing acrylic fiber with electrostatic properties that achieves the purpose of the present invention is a acrylic fiber of 90 points @ 96 or higher (hereinafter referred to as AN , 1-t) i polymer and a water absorbing, 81 mm, and antistatic polymer of less than 10% by weight, and! It has pores with a major axis of 0.2.14 or more in the cross section of 8 fibers, and has a half-life of 2.
0, 10 seconds or less under 65*RH, and the water retention rate is 20. The water-absorbing resin has a particle size of 0.5 mm or less in an absolute dry state, and a particle size of 10 to 800 mm.
The antistatic polymer is an AN copolymer containing 80 to 85% by weight of a copolymer component represented by the following general formula (1) or (2). be.

O CHx=CCHz 0-(CzH40)l-(CsHa
O) BH (2) The present invention will be described in detail below. First, the AN polymer of the present invention may be any one that is not used in the production of conventionally known γ-cryl fibers, and is not limited in any way. However, from the viewpoint of fiber properties, dyeability, etc., it is desirable to use a copolymer of AN of preferably 80 fold pupil % or more, more preferably 85g6 or more, and the balance being other vinyl monomers. 50 Next, a detailed description will be given of the water-absorbing resin blended into the AN-based polymer.

Such a resin has a particle size of 0.5, a or less, preferably 0.2, a or less in an absolutely dry state, and a lo~800
cc/9, preferably 2o~150 cc/
It has a water swelling degree of 9 and is insoluble in water and AN polymer solvents! ! It can be adopted as long as it is IiI fat.
It is necessary to set the particle size of the fat and the water expansion per 1 m degree within the recommended range of the present invention, and excellent practical performance can only be achieved by selecting a water-absorbing resin that satisfies these characteristics. The fiber can be produced industrially advantageously without the problems of manufacturing process E. In other words, the particle size and water swelling characteristics of the core 11 resin play an important role in the water absorption performance of the resulting fibers, and only when using the amount recommended in the present invention can improve the spinnability or the Himeji characteristic. The resulting fibers have satisfactory physical properties such as strength and elongation, as well as practical performance such as spinnability and dyeability.

In addition, the ratio of crosslinking (crosslinking density) of the resin is 1 to 15 per 400 polymer crosslinking units constituting the resin,
More preferably, by setting the number to 2 to 10, it is possible to further improve the spinnability of the resin-containing AN-based polymer spinning stock solution in combination with the particle size characteristics, thereby improving the nozzle packing and yarn. It is desirable because it allows the production of fibers with sufficient strength and elongation, water absorption, etc., without problems such as cutting f'L, etc. Also, regarding the method for producing such water absorption 1!1 resin,
There is no limitation as long as a resin that satisfies the E-grip properties recommended in the present invention can be obtained, but the following methods can be used, for example, in terms of industrially advantageous production of resins having such characteristics. The particle size is 0.5μ or less, preferably 0.2μ or less, and the single r! t1
For complete loss, preferably more than 50% by weight, more preferably more than 70% of AN, crosslinking monomers and A of a predetermined amount are used.
A cross-linked AN copolymer with another vinyl monomer copolymerizable with N or an aqueous dispersion of the polymer is added with 1 according to a conventional method.
By introducing a carboxyl group by the action of a caustic substance, 10 to aoocc7y, preferably 20 to 150
An aqueous dispersion of a resin or fat having a water swelling degree of CC/f can be produced industrially advantageously.

Examples of the crosslinkable monomer E include diesters, triesters, or tetraesters of acrylic acid or methacrylic acid, monolyl esters of unsaturated carboxylic acids, noacrylic esters of polyhydric carboxylic acids,
Divinyl-based AAS water products, divinyl sulfone, methylenebisacrylamide, or divinylbenzene, Part 1
Crosslinkable monomers having two or more copolymerizable double bonds in the molecule, such as alkyl or halogen-substituted monomers, and/or monomers such as carboxylic acids or unsaturated sulfonic acids.
By using a crosslinkable monomer that grows at least one epochita group in the molecule, such as diester or unsaturated G17S/diether, as the copolymerization component, crosslinking occurs during or after the polymerization is completed. Color is easily achieved, especially when two copolymerizable double bonds are present in the molecule.
Divinyl sulfone, which grows individually and has high alkali resistance.
It is desirable to use crosslinkable monomers such as methylenebisacrylamide and divinylbenzene as copolymerization components. The method for producing a crosslinked AN copolymer having a particle size of 1 am is described in, for example, Mochi II@51-24 by the present applicant.
The invention of No. 884 can be adopted and implemented advantageously.

First, by using a resin in which a crosslinked AN-based copolymer coexists as the water-absorbing resin, miscibility with the fiber-forming matrix polymer (AN-based polymer), spinnability, etc. are further improved. desirable. The method for producing a water-absorbing resin in which such a crosslinked AN copolymer coexists is not limited in any way, but includes, for example, the selection of a vinyl hexamer constituting the crosslinked AN copolymer or adjustment of hydrolysis conditions. For example, by partially hydrolyzing only the surface layer of the crosslinked AN-based copolymer particles to leave an unreacted core of the copolymer, or by further colloidizing the resin particles remaining in the core. mill,
It can be advantageously produced by a method such as grinding using a ball mill or the like to expose at least a portion of the crosslinked AN copolymer on the surface of the water absorbent resin.

Next, the control polymer blended into the AN-based polymer will be described.

Such a polymer contains 80 to 85% by weight, preferably 50 to 85% by weight of the copolymer component represented by the general formula (1) or (2) in F.
It is an AN copolymer containing 85% by weight, more preferably 70 to 85% by weight, and a small amount of the polymerizable unsaturated vinyl compound may be copolymerized.

(, ;1i2=niυ−0−(Cm Ha O)t (
Us Hs U)m “(1)CHs=C−C)b −
0-(Cz Ha O) t (Cs Hs O) mH
(2) When the copolymerization ratio of the compound represented by the general formula (1) or (■) satisfies the recommended range of the present invention, it exhibits the antistatic property-imparting effect aimed at by the present invention and has a water absorbency of 11
However, if the lower limit of the range is exceeded, the effect of imparting antistatic properties will be insufficient, and if the limit is exceeded, compatibility with the AN-based polymer may occur. O is undesirable because it causes problems such as decreased solubility or antistatic durability under paper.
Weight 11) and the proportion of the antistatic polymer (Y: weight), the total amount of X and Y is 10% by weight based on the total weight of the AN polymer, water absorbent resin, and antistatic polymer. It is necessary that the value is less than Excellent, and preferably it satisfies the following expressions (3) to (01.5≦X + Y <8 (8)0.
5≦X<7.0 (4)1.0≦
Y <7.5 (5) If the blending ratio of the water-absorbing resin and antistatic polymer is out of the recommended range of the present invention, problems such as nozzle clogging and yarn breakage may occur during spinning, and The resulting fiber cannot have sufficient physical properties, dyeability, etc., which is undesirable.Next, the method for producing the water-absorbing acrylic fiber according to the present invention will be described. Any method can be used as long as it yields fibers with the performance of
! In other words, the AN-based polymer is dissolved in a well-known solvent to prepare a spinning stock solution, and a water-absorbing resin and an antistatic polymer, preferably a mixed water dispersion thereof, are added to the spinning stock solution. After adding and mixing a predetermined amount of the material, wet spinning, water washing, and stretching are performed according to conventional methods. Next, the stretched gel yarn thus obtained is dried and densified if desired, then subjected to a moist heat relaxation treatment, and optionally subjected to a ** treatment, an oil treatment, etc., and then dried.

Here, as an aqueous dispersion of a water-absorbing resin and an antistatic polymer suitably blended in the above-mentioned spinning stock solution, 2 to 80% by weight,
More preferably, by using an aqueous dispersion with a concentration of 5 to 20 g6, S for preparing a spinning stock solution is further added to the aqueous dispersion.
Or some inorganic solvent and/or no other! Add salt (e.g. mirabilite, combined soda) etc.
It is desirable to use a material prepared to have a degree of 1000 ep or less because the dispersibility of the aqueous dispersion in the spinning stock solution, spinnability, etc. can be further improved.

In addition, the L-period thermal relaxation treatment conditions are conditions such that the water retention rate of the moist heat treated product increases by 1.5 times or more compared to the fiber that is not subjected to the moist heat treatment in an atmosphere of hot water, saturated steam, superheated steam, etc. It is desirable to perform moist heat treatment below. By performing such moist heat treatment, the pores existing in the fiber are enlarged and fixed, and the water absorption performance is improved due to the formation of pores outside the fiber, and physical properties such as strength and elongation, dyeing fastness, etc. are significantly improved. We can provide recast acrylic fibers. None, such moist heat treatment conditions vary depending on the AN polymer used as the material, the type of water-absorbing resin, spinning conditions, etc., and are difficult to define unambiguously.
In particular, by adopting skin temperature conditions of 110 or more, more preferably 120 or more in a saturated steam atmosphere, it is possible to achieve a 1lIIIF effect in a short time.
Delicious.

In addition, at least two kinds of spinning liquids, a water-absorbent-skin-containing spinning stock solution and a water-absorbing resin-free spinning stock solution, are used, and for example, at least a part of the water-absorbing resin-free AN-based polymer is exposed on the fiber surface. According to the calendar system, the following calendars are used: SEESUKO rJl, side T pie π side type, sandwich type, fundum il
It goes without saying that it is possible to perform IK composite spinning in shapes such as * type, sea-island type, etc. In addition, the antistatic polymer can also be blended on the side of the water-absorbing, fat-poor AN-based polymer,
By intensively blending the water-absorbing resin into the same spinning stock solution, it is possible to further exhibit a synergistic effect, which is desirable. The water-absorbing acrylic fiber according to the present invention produced in this way has a major diameter of 0.2μ in the fiber cross section. It is necessary to have pores of 511I or more and a water retention rate of 2O4 or more, preferably 25 or more, and for the first time, such a fiber has water absorption and water retention performance comparable to that of cotton. In addition, the fibers according to the present invention can be 20e, 65R
1 (It is necessary to have performance with a half-life of 1 to 0 at F, and a half-life of 80 seconds or less under 20'C, 404JRH. is preferable, and is the first such fiber to be used for underwear, sportswear, blankets,
In the form of products such as sheets, it is possible to eliminate discomfort caused by static electricity.

Here, although it is not clear why the acrylic fiber made by blending a small amount of the specific water-absorbing resin and anti-static polymer recommended in the present invention exhibits surprising water-absorbing behavior and anti-static performance, the water-absorbing Hydrophilic groups such as carbogycyl groups in the resin work together with hydrophilic groups in the antistatic polymer to improve antistatic performance, and are also dispersed in the AN polymer in a It is presumed that the antistatic polymer enhances the dispersion and arrangement of the water-absorbing resin and promotes the formation of voids, thereby providing a synergistic effect such as improving water absorption and water retention performance.

The acrylic fiber according to the present invention described above is free from problems such as nozzle clogging, thread breakage, etc. ! It does not have the F problem and has practical performance such as physical properties such as strength and elongation, color development, color fastness, and anti-resistance, and has satisfactory antistatic performance and water absorption performance. These are the noteworthy effects of the present invention. Manufacturing process and practical performance E The 1' grill fiber of the present invention, which has many initial points, can be used alone or with commercially available l
Underwear that is comfortable to wear by blending with various synthetic iron fibers such as polyester, poly-1-mide, poly-1-crylonitrile, modacrylic, cotton, wool, etc.
It has become possible to use it as a material for coolers, towels, sportswear, summer clothing, etc.

The effects of the present invention will be explained in more detail with reference to Examples below. In the examples, parts and percentages are expressed on a weight basis unless otherwise specified.

In the following examples, the water swelling/111t of the water-absorbing resin, the water retention rate and the half-life of the fibers were measured or calculated using the method described in F. Approximately 0.5g was immersed in pure water and after 24 hours at 25C,
The water-absorbing m fat with water swelling adjustment is sandwiched between P paper to remove the water between the fat particles.0 The weight of the sample prepared in this way
stomach). Next, the sample is dried in a vacuum dryer at 80'C until it becomes constant, and the weight (W2) is measured. Based on the measurement results of 0 to E, it is pumped out according to the following formula.

2 C) Water retention'' *(*) Immerse approximately 52 samples in pure water, and after 2 hours at 25-3'C, remove them using a centrifugal dehydrator (with a radius of 12 cm).
/W) at 2.00 rpm for 5 minutes to remove water between the fibers. The weight of the sample adjusted in this way (
”s).

Next, the sample is dried in a dry air dryer at 80C until it reaches tM, and 41 t (W2) is measured. Based on the above measurement results, it is calculated using the following formula.

2 (3) Half-life (seconds) Pour 40'c of washing liquid (neutral detergent: 29/l) & Bitsu@ (bath ratio: t/ao) into Kaiwash + JIi for household use 1,
After running for 10 minutes, rinse with rich warm water for 5 minutes twice, then drain and dehydrate. Repeat this operation 8 times (washing 8
The sample was dried for 80 minutes at 70'C in an air-drying oven, then dried for 1 hour at 70'C, and left overnight in a measurement chamber at 20'C adjusted to the measurement conditions. prepared.

The test piece was measured using a static winter meter (Shishido Mokai $
111) After applying an applied voltage of 10,000 V to the K for 80 cycles (sample rotation 1K: 10 G Or-p-m), measure the time for the amount of charge to reach half of the amount. Indicates good conductivity.

Example I AN7611. Methyl methacrylate (MMA) 20g6
, methylene bi, zycryl 1mide (MBA) 2m and p-styrene sulfone rll soda (spsS) 2%
A frame 41 consisting of a polymer particle size of 0.1 and a
An aqueous emulsion of an AN polymer was prepared, and it was subjected to an alkali treatment at 95° C. for 60 minutes with stirring in an 8% aqueous solution of caustic soda. The obtained water absorbency lll1 fat is 0.1μ
It also had a particle size of 99 cc/P and a water swelling rate of 99 cc/P.
30 mol) An antistatic polymer consisting of methacrylate 75q6 was prepared. A mixed aqueous dispersion of this water absorbing resin and antistatic polymer was prepared by 9
AN-based polymer A containing 0% AN, Q, 7ξ accumulation and 0.3% methallyl sulfone city soda (SMAS)
(Intrinsic viscosity in dimethylformamide solution of 80 t-
DA] = 1.8) 0 water-absorbing night fat and antistatic polymer were added to a spinning stock solution consisting of 10 parts and 90 parts of a 50g6 Rodan soda aqueous solution by changing the amount of the added amount. Disperses evenly in raw materials and liquids without agglomerating,
When the spinning dope was wet-spun using a 0.060jEIφ spinneret according to a conventional method, spinning, coagulation, water washing, and stretching could be performed satisfactorily without any problems such as nozzle clogging or yarn breakage. /Wet bulb temperature = 120υ/60υ×
After dry densification for 20 minutes, 125tX in grating steam
The fiber cross sections of 98 kinds of fibers were wet-treated for 5 minutes and dried for 10 minutes at 110 mm, and the cross-sections of the fibers were magnified 5000 times using a scanning electronic IJI imager, and the diameters were 0.2 μ or more. Table 1 also shows the results of measuring the number of pores and the water retention rate and antistatic property (half-life) of the obtained fibers.

Table 1 (Note) (1) Circle mark: Wooden invention product It is understood that water absorption and antistatic properties are significantly improved.Example 2 A N-P containing the AN-based polymer A described in Example 1 and 88% AN and 12% vinyl acetate. , using Polymer B, adding 8% each of a water-absorbing resin and an antistatic polymer to the spinning stock solution of Polymer B, and 1. ordinary side-by-side type composite #&fiber spinning. Wet composite spinning (A/B
=50150) W&M (Oni 9) was produced according to the recipe in Example 1 except for the following.

This fiber has 9 ftl of pores smaller than 0.2μ! It had a water retention rate of 8096, a half-life of 3 seconds at 20'c x 6596LHF, and 5 seconds at 20'c x 40*RH'F.

Example 8 A yarn of 58# metric count and 610 twists/m was made by spinning 4a fibers of 84 inclination of 1,5 steepness and 8 described in Example 1, and after dyeing with cheese. A double-sided skin blue was prepared and a wear test was conducted.The results are shown in Table 2.

As is clear from Table 2 E, it is understood that the present invention (=K 5 ) has no electrostatic damage and is excellent in comfort.

Example 4 The #It fiber of Example 1 Gourd 6 was blended with 4096 ordinary acrylic fibers exhibiting a shrinkage rate of 26, and double-sided underwear was prepared according to the method described in Example 8. The water retention rate of this underwear is 86%
, and the half-life is 6 seconds at 20t'X@l*RH, 20
It was fired in 17 seconds with 'cX40mRH. In addition, when I tested this underwear, I found almost no static electricity damage, and I didn't feel sticky when exercising while playing tennis.
Comparison 1. It has significantly superior heat retention and drying speed compared to cotton underwear used in

Claims (1)

[Claims] It consists of a 1-crylonitrile polymer weighing more than 1.90% by weight and a water-absorbing resin and an antistatic polymer weighing less than 10% by weight. is 10 seconds or less under 20 tl' and 65% RH, and has a water retention rate of 2OS or more. Here, the water absorbent resin has a particle size of 0.6 μ or less in an absolutely dry state and 1 lll of water with a particle size of 10 to 9 Q Q cc / f.
O 0 CHx, which is a resin having a degree of =C-CHs-0-(CzH40), (CsHs
O)-H(2)2, the water-absorbing acrylic fiber according to claim 1, f3, which has five or more pores with a major diameter of 0.2μ or more E in the cross section of the fiber. 8. The water-absorbing resin has polymer repeating units 4 constituting the resin.
2. The water-absorbing acrylic fiber according to claim 1, which is a resin having 1 to 15 per 00 fibers. The water-absorbing acrylic fiber according to claim 1, which has a half-life of 30 seconds or less at 20t', 40q6RHF.