DE2061213A1 - Novel acrylic fiber and process for making it - Google Patents

Description

"- Dipl.-Ing.Rofohsld Kramer 70/8756

Λί.Τ

SOOO Μοή :: tion 12
rEüte 1
Telephone eeo3 53

Mitsubishi Rayon Co. Ltd., Tokyo / Japan

Novel acrylic fiber and process for making it

(Claimed priorities:

December 11, 1969 Japan 99728/69

March 31, 1970 Japan 26553/70)

The invention relates to a novel acrylic fiber with excellent It also has excellent anti-static properties as a result of its ability to absorb moisture the invention a process for the production of said fiber.

Acrylic fibers generally have excellent properties, as far as their grip, their ability to be colored and their weathering properties takes into account here. As a result of these properties, this fiber established itself in the textile industry together with nylon and polyester fibers through very quickly. On the one hand, consumer interest in synthetic fibers is increasing

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because of their excellent properties, which are found in natural fibers not found, constantly on, but on the other hand you know very well that synthetic fibers have certain disadvantages that you have not found in any natural fiber. Their relatively low absorption capacity for moisture and the associated relatively poor antistatic properties are typical examples of these disadvantages of synthetic fibers. Similar to nylon and polyester fibers the acrylic fibers show a much poorer absorption capacity ^ ability for moisture than wool, cotton and regenerated fibers. In addition, these synthetic fibers tend to generate static charges, and this is precisely why their commercial value is reduced if they are used for the manufacture of Clothing to be used. The fact that the synthetic fibers have so far been used little for the manufacture of underwear relies to a large extent on their poor sweat absorption. It is therefore increasingly emerging the requirement to avoid the disadvantages mentioned in the production of textile fabrics from synthetic fibers.

According to the invention this is achieved by the new acrylic fiber, which is characterized by a mixed polymer A containing as Aggregate units

a) at least 10 percent by weight, preferably at least 40 percent by weight and most preferably at least 85 percent by weight Acrylonitrile,

b) 0.2 to 20 percent by weight, preferably 0.2 to 8 percent by weight

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Percent n-3-oxo-hydrocarbon-substituted acrylamide the structural formula (I):

OO

R _ c - R ¹ - Ii - S - C - GH ₀ (I)

H E "

where E and E "are members of the groups formed from hydrogen or lower alkyl groups with not more than ten carbon atoms and E ^{1 is} a member of the group formed from an ethylene group C and lower" alkyl-substituted ethylene groups with not more than 15 carbon atoms,

c) as the third aggregate unit, at least one monomer suitable for copolymerization from the group comprising vinyl acetate, Acrylic esters, methacrylic esters, monomers with a hydroxyl group, Monomers with a carboxyl group or their salts, monomers with a sulfo group or their salt, monomers with a Amide group, polyethylene glycol esters of acrylic or methacrylic acid and monomers with a polyethylene glycol group in their Side chain and

d) another monomer, which for copolymerization with one of the above-mentioned monomer components is suitable.

The new acrylic fiber shows an excellent absorption capacity for moisture and therefore excellent antistatic properties Properties. It is made from a solution of the above-mentioned mixed polymer in a suitable solvent with the aid of conventional wet or dry spinning processes or with the aid of the

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Dry jet-wet spinning process manufactured.

In the structural formula (I) listed above for the n-3-oxohydrocarbon-substituted acrylamide, the lower alkyl groups E, E "contain a maximum of 10 carbon atoms and can contain one cycloalkyl group. Examples of E, E" are the following groups; Methyl, ethyl, propyl, isopropyl, η-butyl, pentyl, cyclohexyl, cyclopentyl, isooctyl, n-decyl and 4-ethyl-2-hexyl groups. E "is preferably present as a hydrogen or methyl group. E ¹ can consist either of an ethylene group or of substituted ethylene groups in which a carbon atom bonded directly to the nitrogen atom of the acrylamide has at least one lower alkyl substituent two carbon atoms of the ethylene group are counted from the side of the nitrogen atom. That is, the carbon atom bonded directly to the nitrogen atom is designated as the first atom and another as the second atom. Using this numbering, R ¹ is denoted as ethylene, 1-methylethylene, 1 , 1-dimethylethylene, 1,1,2-trimethylethylene, 1-methyl-1-ethylethylene, 1-methyl-i-isobutylethylene, 1-ethyl-i-isopropylethylene, 1,2-dimethylethylene, 1,1-diisopropylethylene, 1-n-Butyl-in-Pentyläthylen and 1-Methyl-i-Cyclohexyläthylen illustri cht.

Typical examples of n-3-oxo-hydrocarbon-substituted Acrylamides are N-3-oxo-butyl acrylamide, N-3-oxo-1-1-methylbutyl

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acrylamide, N-3-Oxo-i -1 -Dimethylbutyl acryl amide, IT-3-Oxo-i -Methyl-1-Cyclohexylbutyl acrylamide, N-3-oxo-1-1-dimethyl-2-ethylbutyl acrylamide, ΪΓ-3-Οχο-Ι, ^ - Dimethyl-I-Isopropyl-Hexylacrylamid, N ^ -oxo-i-i-diisobutyl ^ -isopropyl - ^ - methylhexyl acrylamide, N-3-oxo-1 -i-Dibutyl-2-n-propylheptylacrylamide and F-3-Oxo-i -Methylbutyl- oL-methyl acrylamide.

On detailed study it was found that the copolymer of F-3-oxo-carbon-substituted acrylamide and acrylonitrile plays a special role (with regard to the absorption of moisture from the environment. A copolymerization of acrylonitrile with other hydrophilic monomers such as vinylpyrrolidone, acrylic acid , Methacrylic acid and vinyl pyridine do not ensure increased moisture absorption. The polymers made of any of the above-mentioned hydrophilic monomers such as polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and polyvinyl pyridine are water-soluble. On the other hand, a homopolymer formed from IT-3-0xo-1-1-dimethylbutyl acrylamide, ala typical example of an n-3-oxo- λ hydrocarbon-substituted acrylamides capable of swelling in water, but being water-insoluble .. The moisture absorption in percent of the homopolymer, although it depends on the molecular weight, is approximately 25%, based on d as weight of the homopolymer.

In view of these facts, it can be assumed that the hydrophilic property of 3-N-0xo ~ 1-1 ~ dimethylbutyl acrylamide

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is inferior to that of the hydrophilic monomers which form the above-mentioned water-soluble polymers.

Unexpectedly, it was found that the copolymer was made of Acrylonitrile and N-3-oxo-i-i-dimethylbutyl acrylamide one notable shows improved moisture absorption compared to the other acrylic copolymers. this is a Epoch-making discovery that can never be made on the basis of the previously known state of knowledge in the context of this technology could expect. It is believed that this is the reason for this effect is based on the fact that the internal intermolecular axane Hydrogen bonds in the monomer are broken in the presence of water will. This causes the hydrogen bonds to break but a large deformation of the molecular structure and an excessive swelling of the polymer molecule. This swelling can be directly related to the increase in the absorption capacity of moisture. The lifting of the One imagines hydrogen bonding as follows

R-C-C-N.

Ψ ο

CH2 H E E "O

I I I I Il

E-O-C-N-C-G-O-E

Il I I

0 E ¹ E

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The n-3-oxo-hydrocarbon-substituted ones lie in the dry state Acrylamide units in the copolymer in the form of a ring structure containing six members, due to the formation the intra-molecular hydrogen bond listed above. But if water penetrates the mixed polymer, then the Dissolved hydrogen bond, and that formed from six members Ring opens and increases its volume. It is also believed that hydrogen bonding occurs simultaneously with this dissolution the -C-O- or -HE group connects with the water molecules, so that the volume increases even further by swelling. In summary, it should therefore be stated that one believes the large swelling of the n-3-oxo-hydrocarbon-substituted ones caused by water Acrylamide units of the mixed polymer contribute in a remarkable way to the absorption capacity for increasing moisture of the mixed polymer.

This increase in the moisture absorption capacity of the mixed polymer is further enhanced by the absorption of a third aggregate unit formed by a monomer, namely a hydrophilic monomer such as acrylic acid, methacrylic acid, itaconic acid or hydroxyethyl acrylic acid * It is believed that the improvement the ability to absorb moisture through the combination of the hydrophilic swelling of the n-3-oxo-hydrocarbon-substituted Acrylamide with the high absorption capacity for moisture of the hydrophilic monomer is effected

Said third hydrophilic monomer can be a polymeric

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si'erbaren monomer with a -OH-, -COOH group or its salt, a -SO ^ H group or its salt or a -CON group. A typical example of such a monomer is found in the acrylate-containing group listed below? Sodium acrylate, methacrylates such as sodium methacrylate, itaconic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate. Acrylamide, sodium vinyl benzene sulfonate, and N-vinyl pyrrolidone. It is surprising to note that the Acrylnitrilmischpolymer with a remarkably increased capacity to absorb moisture ψ can be created due to the copolymerization with the above hydrophilic monomers.

In addition to the improvement in the ability to absorb moisture, the antistatic property of the resulting mixed polymer is also increased improved by copolymerization of the polyethylene glycol ester of the structural formula (2) listed below «

CH ₂ -C - (CH ₂ ) _m X

CY- (OH ₂ .CH ₂ .O) _n - R ₁ (2)

»

Here, X is hydrogen or groups of the 3 form -CY ¹ -

₂ CH ₂ O) _n R ₁ ¹ , Y is oxygen or an -NH group, R _{1 is} an alkyl group having 1 to 22 carbon atoms, a substituted phenyl group or an unsubstituted phenyl groupj Y ¹ and R ₁ ¹ are replaced by the same group as Y or .R ₁ formed! Y and Y 'and R ₁ and R ₁ ' can either be the same as one another or one another

- 9 -109826/1927

be different} m is full or a positive integer between 1 and 10, η is a positive integer between 1 and 200, and n ¹ is a positive integer between 1 and 200 and can either be the same as or different from η .

The proportion of the abovementioned polyethylene glycol ester is in the range between 0.5 % and 40%, based on the weight of the entire mixed polymer.

Needless to say, the acrylic copolymer of the present invention is used to improve its ability to be cured may also contain fourth monomers such as acidic or basic monomers. Some examples of such monomers that can be added for this purpose are listed in the following group: vinylbenzenesulfonic acid, methallylsulfonic acid, Allylsulfonic acid, sulfophenyl methacrylic ethers, salts of the above monomers, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and NjN-dimethylethyl acrylate.

The acrylic fiber of the invention can be spun from a solution of a mixture containing:

1. a copolymer with the aggregate units a) at least Weight percent acrylonitrile, b) 1 to 40 weight percent of the above-mentioned substituted acrylamides of structural formula (1) and c) in a counterbalancing form Amount of the above-mentioned third monomer> and

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2. a copolymer which as an aggregate unit contains at least 85 percent by weight of acrylonitrile.

If you use polyethylene glycol, you become the third Component of the mixed polymer A in a proportion between 5 and 89 percent by weight, preferably between 5 and 80 percent by weight, and use acrylonitrile in the base copolymer in an amount between 10 and 94 percent by weight. In in this case is to "prefer that the total content of the above Polyethylene glycol in the range between 0.5 and 40 percent by weight, is preferably between 1 and 20 percent by weight. In this case, the content of the substituted one is desirable Acrylamides of structural formula (1) in the fiber in the range between 0.2 and 8 percent by weight.

Because of its excellent ability to absorb moisture the acrylic fiber of the present invention is "especially for manufacturing suitable for underwear. In addition, however, the laundry is due to its excellent antistatic property prevented from being undesirably applied to the human body when worn. This is a particularly good one Solution to the problem of poor moisture absorbency and poor antistatic properties, which in general present in conventional acrylic fibers. If you apply the previously known methods of improving moisture Absorption capacity and the antistatic properties additionally still in the fiber according to the invention, then

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the properties obtained are even more improved.

In the following, the present invention is to be explained on the basis of exemplary embodiments. In these examples, the moisture capacity of the fiber is represented by a difference value between the weight content of moisture that is absorbed by the fiber when measured at 20 ⁰ C even in an atmosphere of 93% relative humidity and a relative another time at 65% humidity is present,

example 1

An acrylonitrile copolymer was made by copolymerizing a mixture of 90 percent by weight acrylonitrile, 7 percent by weight N-3-oxo-1,1-dimethylbutyl acrylamide and 3 percent by weight Produces ITsodium vinylbenzenesulfonate. The copolymers obtained showed a specific viscosity of 0.17 »that in a solution of 0.1 g / l of the mixed polymer in dimethylformamide at a Temperature of 25 ° C was determined · This measurement was also made at carried out the following examples in the same way.

The copolymer was dissolved in dimethylformamide to make a spinning solution with a concentration of the polymer of 24 percent by weight to obtain.

The spinning solution was spun by means of the wet spinning process,

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i pour the solution into an aqueous solidifying bath extruded a spinneret to produce filaments. i) The resulting undrawn filaments were at one draw ratio of 5 in boiling water while they were being rinsed, stretched. The drawn threads were then dried with the aid of a drying roller, and the dried threads were then dried

ο brought to relaxation in a steam atmosphere of 2.3 kg / cm pressure.

The value of the moisture absorption capacity of the acrylic fiber ^ was determined to be 9> 1 % . For comparison, the value of the moisture absorbency of the conventional acrylic fiber was also determined under the corresponding conditions. It was found to be 1.5 %. This proves that the moisture absorbency value of the acrylic fiber of the present invention was remarkably improved by using the method of the present invention.

Example 2 > Λ

An acrylonitrile copolymer with a specific viscosity of 0.168 was obtained by copolymerization of a mixture of 93 percent by weight of acrylonitrile and 3 percent by weight of N-3-0xo-1-1-dimethylbutyl acrylamide and generates 4 weight percent acrylic acid. A dimethylformamide solution of the mixed polymer obtained was prepared in the manner described in Example 1 by means of the wet spinning method spun. The undrawn threads were on a Draw ratio of 4.5 while being drawn at the same time

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were rinsed in boiling water · Then they were dried and then relaxed in a steam atmosphere of 2.5 kg / cm *

The obtained acrylic fiber had an excellent moisture absorbency, the value of which was 10.1 % .

Example 3

Dimethylacetamide was used for the solution of an acrylonitrile mixed polymer consisting of 93 percent by weight of acrylonitrile, 2.5 percent by weight of N-3-oxo-1-1 ~ dimethylbutyl acrylamide and 4.5 percent by weight of sodium acrylate. The spinning solution at a concentration of 23 percent by weight was spun with the aid of conventional wet spinning process * After spinning, the "thread was stretched at a Yerstreckverhältnis of 5 in boiling water and then dried. The acrylic fiber thus obtained showed a moisture capacity of 12.3% * The measurement of the antistatic property of the acrylic fiber was in the following manner performed ι the moisture content of a yarn sample was determined by placing the sample at least 20 hours aufbewährt relative humidity at 20 ⁰ O and 50%. After this conditioning, the sample to a voltage of 10,000 was " V charged for more than 5 seconds by rotating the sample at 1,000 revolutions / min. After charging, the half-life of the discharge was determined using a static charge meter. The received

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20 & 1213

The result is shown in Table 1 below together with the results for other types of laser.

Table 1

sample Half-life in seconds after this
To wash after this
To dye after ten times
like to wash
under use
dung one
Detergent invention
more appropriate
thread before the
To wash 14.0 15.0 25.0 conventional
Acrylic fiber less than
1.0 38.0 more than
60 more than
60 Viscose fiber dto. 1.2 1.4 1.3 Wool dto. 1.5 5.7 15.0 dto.

From the above results it can be seen that the inventive Acrylic fiber has a far better antistatic property than the conventional acrylic fiber and that it almost corresponds to that of wool fibers. The excellent antistatic property can be achieved using a conventional known antistatic agent can still be improved. With the actual Use of the textile product, for example underwear, produced from the fiber of the present invention could not be caused by the generation of electrical charges caused difficulties can be determined. Also one could not observe any particular pollution of the product, thus These facts lead to the finding that the fiber according to the invention with regard to its dirt repellency of

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- 15 -

conventional acrylic fiber is superior,

Example 4

For the production of a spinning solution with a concentration of Ί8 percent by weight became dimethyl sulfoxide for a solution of an acrylonitrile copolymer a specific viscosity of 0.162, containing 92 weight percent acrylonitrile, '$ weight percent N-3-Oxo-i-i-dimethylbutyl acrylamide and 5 weight percent Hydroxyethyl acrylate, is used. The resulting dope was made into filaments using the conventional wet spinning process spun.

The threads obtained were drawn to a "drawing ratio of 6" in a water bath at 100 ° C. containing 10 % dimethyl sulfoxide. After the subsequent rinsing process with boiling water to remove the remaining solvent in the fiber, the thread was dried The thread was gradually cooled in steam of 20 atmospheres pressure, and the moisture absorption capacity of the thread obtained was found to be 9 »6 % .

Example 5

For the production of a spinning solution with a concentration of

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28 percent by weight of dimethylformamide was used for the solution of an acirylnitrile polymer having a specific viscosity of 0.160, which contained 94 percent by weight of acrylonitrile, 3 percent by weight of N ^ -oxo-II-dimethyl-I-ethyrbutyl acrylamide and 3 percent by weight of N-vinylpyrrolidone. The spinning solution was spun into acrylic threads using the conventional Prock spinning process. The temperature of the spinning solution was 120 C. The flow rate of the air used for drying was 0.6 m / min. The temperature at the top of the spinning chamber was 24O ⁰ C and the bottom of the jSpinnkammer 120 ⁰ C, the withdrawal speed of the spun yarns was 300 m / min. The undrawn threads obtained were then subjected to a drawing process at a drawing ratio of 4 in a boiling water bath. After the drawing process, the drawn filaments to relax in an environment of 14O ⁰ C and 25% relative humidity were brought. The moisture absorbency of the acrylic fiber was 10.9%. The measurement of the antistatic property described in Example 3 was applied to the acrylic fibers obtained in this way. It was found that the half-life was 10 seconds even after washing the fiber ten times. From this result it can be concluded that an outstandingly improved antistatic property of the fibers can be achieved with the aid of the method according to the invention.

Example 6

To a spinning solution with a concentration of 24 percent by weight

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To obtain, an acrylonitrile copolymer having a specific viscosity of 0.172 was dissolved in dimethylacetamide. The copolymer consisted of 93 percent by weight of acrylonitrile, 5 percent by weight of NS-oxo-ii-dibutyl-nonylhydric acrylamide and 2 percent by weight of methyl acrylate. The acrylic fiber produced from this spinning solution using the method described in Example 1 showed a moisture absorbency of 8.6 %.

Example 7

An acrylic copolymer A with a specific viscosity of 0.14 was made from 61 percent by weight of acrylonitrile, 2 percent by weight of N-3-oxo-1-i-dimethylbutyl acrylamide, 30 weight percent polyethylene glycol ester of acrylic acid of the structural formula below

CH ₂ - CH

CO- (CH ₂ CH ₂ O) ₈₀ - C ₁₈ H ₃₇ 0

and 7 weight percent vinyl acetate.

Another acrylic copolymer B with a specific viscosity of 0.17 was made from 95 percent by weight acrylonitrile and 5 percent by weight vinyl acetate.

15 parts by weight of the mixed polymer A and 85 parts by weight of the Copolymers B were dissolved in dimethylformamide to make a spinning solution having a concentration of 21% by weight

10 9 8 2 6/1927 - 18 -

· The spinning solution thus prepared was poured into an aqueous Solidifying bath in the usual wet spinning process Way extruded. The undrawn thread became a 'drawing process at a draw ratio of 5 in a boiling water bath subject.

After the rinsing and drying process, the dried thread was relaxed in a steam atmosphere of 2.3 kg / cm pressure. The on this So treated threads were made into a knitted fabric using conventional spinning and knitting techniques. The resulting fabric was subjected to the bleaching and washing procedures set forth below. At every step in the process a measurement of the moisture absorbency, the antistatic property, the softness, the dirt repellency determined from a fabric sample.

1. The bleaching of the swatch was carried out under the following conditions performed:

Bleach: 2 g / l Sodium chloride 0.2 g / l acetic acid 0.2 g / l Sodium ac et at 1.5 g / l Auxiliary bleach HV (* 1) 1:50 Liquid ratio 98 ⁰ C temperature 60 minutes Time

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Note »(* 1) Trademark ink help« lead chiiitt els, manufactured by Hodogaya Chemical Industry ltd.

2. After the bleaching process, the bleached was dechlorinated Sample taken under the following conditions.

Sodium acid sulphite 1 g / l

Liquid ratio

temperature 7O ⁰ O

Time 15 minutes

3 · After the dechlorination, the fabric sample was washed under the treatment conditions listed below ·

ZABU (* 2) 3 g / l

Liquid ratio

! Temperature 40 ° 0

Time 20 minutes

Note: (* 2) Trademark of a detergent, manufactured

by Kao Soap Co.

4. The measurement of the softness was carried out in a known manner in the manner of the organoleptic grip test. The he The result was given in five classes.

Grade 5 remarkably soft
Class 4 soft
Class 5 a bit soft

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Class 2 somewhat stiff (a distinctive property similar to that of conventional acrylic fibers) Class 1 stiff

5. The measurement of the resistance to soiling was carried out in the following manner.

a) Oil pollution attempt

Composition of pollution materials:

0.3 g printer's ink

Beef fat 0.5 g

liquid paraffin 1.5 g

Carbon tetrachloride 4-00 ml

Liquid ratio 1i10Q

Temperature room temperature

Time 2 minutes

After the fabric was immersed in a bath of the above composition, it was rinsed with water and air dried. The dried swatch was then used to measure its whiteness a spectrophotometer measured in a conventional manner.

b) Dry pollution

Composition of dirt materialsχ Printing ink 1.75 g

Clay 17.0 g

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Cement 17.0 g

Silica 17, og

The above soil composition was placed in a ball mill along with 10 5 x 5 cm swatches and 30 balls introduced. After the ball mill 10 minutes had rotated lengthways, the excess dirt on the surfaces of the samples was removed, then the samples were measured as described above to determine their degree of whiteness.

The result is shown in Tables 2A and 2B. From the Results are seen to oppose the acrylic fiber of the present invention the conventional acrylic fibers an excellent, improved soft grip, resistance to dirt, having hygroscopic property, antistatic property and resistance to washing treatments. The following tables also show the results obtained with the conventional acrylic fibers.

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Table 2A

Test results when using the acrylic fibers according to the invention

Resilient
compared to Ver
dirty dry
Pollution
tongue
middle i / oak
; rad in
Qassen Hygroscopic
pish
characteristic
in % Anti-static
cal own
shaft, after this
bleaching Whiteness in % 67 4 to 5 10.5 Half-life
time in
Seconds after ten
malignant
Vaschen oily
Pollution
tongue
middle 67 4 to 5 9.8 4.5 61 4.4 63

Table 2B
Test results using conventional acrylic fibers

Resilient
compared to Ver
dirty dry
Pollution
tongue
middle Soft
srad in
Classen Hygroscopic
pish
Characteristic
in % Antistatic
cal own
shaft after this
bleaching Whiteness in % 58 2 1.8 Half-life
time in
Seconds after ten
malignant
To wash oily
Pollution
tongue
middle 61 2 1.7 longer than
60 49 longer than
60 54

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Example 9

Han used purified dimethylformamide to produce a 28% solution of a mixed polymer of 78% by weight Acrylonitrile, 7 percent by weight vinyl acetate, 3 percent by weight iN-J-Oxo-i-i-dimethylbutyl acrylamide and 12 percent by weight Polyethylene glycol methacrylate of the structural formula below s

GH _x
GJH ₂ -C

Me spinning solution was spun using the known dry spinning method in the presence of 220 ⁰ O at the nozzle openings 200 and ⁰ O in the lower region of the spinning chamber. After carrying out a stretching process, washing, peeling, drying, releasing, an acrylic fiber with excellent moisture absorption and antistatic properties, softness and resistance to soiling was obtained, as can be seen in Table 3 below.

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Table 3

Resistance to pollution

Whiteness in%

oily
Polluting
middle

dry dirt-itfeiche-

medication

grad in Qassen

Hygroscopic property in %

Antistatic property

Half-life in seconds

after this
bleaching

60

10.7

6.5

after ten times
To wash

62

10.4

5.1

Examples 9

To produce a spinning solution with a concentration of 24 % (percent by weight), 20 parts by weight of a mixed polymer A with a specific viscosity of 0.12 and 80 parts by weight of a further mixed polymer B were uniformly mixed with one another and dissolved in dimethylacetamide. The first-mentioned copolymer A consisted of 67 percent by weight of acrylonitrile, 8 percent by weight of N-3-oxo-i-methylbutyl- oL -methyl acrylamide and 25 percent by weight of polyethylene glycol of itaconic acid, which corresponded to the following structural formula:

CH - CH ₂ -

COO (CH ₂ CH ₂ O) ₁₅ C ₁₂ H ₂₅

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The second copolymer B consisted of 93) 5 percent by weight Acrylonitrile, 6 percent by weight methacrylate and 0.5 percent by weight Sodium vinyl benzene sulfonate. The spinning solution thus prepared was placed in an aqueous solidifying bath extruded according to the wet spinning process. After the stretching, washing, drying and relaxation process, one received an acrylic fiber with excellent properties shown in the table below.

Table 4

Resistance ge
gene pollution Dry
Polluting
tion material Degree of softness
Ln
Qassen Hygroscopi
cal own
shank in
% before the
dry Whiteness in% 66 4- to 5 12.1 after that
Drying (* 3) oily
dirty
material - 4 to 5 11.7 65 -

Notej (* 3>) The acrylic fiber was rated at 5% based on the

Paser weight, Deorlene Blue 5G (Trademark of a basic dye manufactured by Ciba).

Example 10

Parts by weight of a mixed polymer A were 80 parts by weight

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- 26 -

share another mixed polymer B mixed evenly to form an acrylic fiber with excellent moisture absorption, Maintain softness and resistance to pollution. As the manufacturing method, that in Example 1 specified procedures are used. The properties of the fibers obtained are shown in Table 5A below. That The former copolymer A consisted of 60 percent by weight Acrylonitrile, 10 weight percent N-3-0xo-1-1-dimethylbutyl acrylamide and 30 percent by weight of polyethylene glycol acrylamide the following structural formula:

CH ₀ - CH

C- ι

The second copolymer B consisted of 94- percent by weight of acrylonitrile and 6 Ge .Lei- ^ρ: ι -ζ vat methyl acrylic at.

For comparison, a uniform mixture of 20 parts by weight of a mixed polymer C with 80 parts by weight of a further mixed polymer D was processed in the same way as above. The copolymer C consisted of 63 percent by weight acrylonitrile, 7 percent by weight methacrylate and 0 percent by weight polyethylene glycol acrylamide of the structural formula already listed above, while the copolymer C was formed from 94 percent by weight acrylonitrile and 6 percent by weight methyl acrylate. The properties of the comparative fiber thus produced are shown in Table 5B. From the results it can be seen that the special properties of the fiber according to the invention by using the N ^ -ta ^ VA ^^ iW-kutylacrylamid existing

- 27 -

Component are conditional.

Table 5A.
Fiber, produced according to example IO

Resistance ge
gene pollution Dry
Polluting
tion file Degree of softness
in classes Hygroscopi
cal own
shank in % bite degree in % 67 4 to 5 12.3 pliges ver
dirty
material 68 4- to 5 12.1 after this
bleaching 69 after ten
malignant
Vaschen 68

Table 5B
Comparison fiber

Resistance ge
gene pollution Dry
Pollution
tongue material Degree of softness
in classes Hygroscopic
cal own
shank in% after this
bleaching Whiteness in % 63 4th 5.0 after ten
malignant
To wash oily ver
dirty
material 65 4- 4.7 66 63

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- 28 -

Example 11

A spinning solution having a concentration of 24 percent by weight was made by dissolving 30 parts by weight of an acrylonitrile copolymer A has a specific viscosity of 0.170 and 70 parts by weight of another mixed polymer B in dimethylacetamide generated. The mixed polymer A consisted of 80 percent by weight acrylonitrile, 15 weight percent N-3-oxo-i-i-dimethylbutyl acrylamide and 5 weight percent itaconic acid, while the other interpolymer B was formed from 93 percent by weight acrylonitrile and 7 percent by weight vinyl acetate. The spinning solution obtained was in an aqueous solidifying bath extruded according to the procedure described in Example 1. The thread received was drawn to a draw ratio of 5 in boiling water and at the same time cleaned in the water bath to be wound up on a drying roller. Subsequently, the

dried thread relaxed in a steam atmosphere of 2.3 kg / cm pressure. The moisture absorbency of the acrylic fiber thus obtained was found to be 11.9%.

Example 12

A spinning solution with a concentration of 23 »5 percent by weight was made by dissolving 40 parts by weight of an acrylonitrile copolymer A has a specific viscosity of 0.168 and 60 parts by weight of an acrylonitrile copolymer B a specific

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Viscosity of 0.17 produced in dimethylacetamide. The Acrylnitrilmischpolymer A consisted of 77 weight percent acrylonitrile ", 20 weight percent acrylic acid and 3 weight percent N-3-0xo-1-1-Dimethylbutylacrylamid while the Acrylnitrilmischpolymer B from 93 weight percent of acrylonitrile and 7 weight percent methyl acrylate was formed. The spinning solution was introduced into an aqueous solidifying bath extruded as described in Example 1. The thread obtained was drawn to a drawing ratio of 4.5 in boiling water. After drying, the thread was subjected to a relaxation treatment in a steam atmosphere of 2.5 kg / cm pressure obtained acrylic fiber was found to be 12.5%

Example 13

A spinning solution having a concentration of 23 percent by weight was prepared by dissolving 40 parts by weight of an acrylonitrile copolymer A of a specific viscosity of 0.15 "and 60 parts by weight of another mixed polymer B of a specific Viscosity of 0.16 produced in dimethylacetamide. The acrylonitrile copolymer A consisted of 80 percent by weight acrylonitrile, 5 percent by weight N-3-Oxo-i-1-dimethylbutyl acrylamide and 15 weight percent Acrylic acid, while the other copolymer B is formed from 94 percent by weight acrylonitrile and 60 percent by weight methacrylate was. The obtained spinning solution was extruded into a thread using the wet spinning method. The received

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- 30 -

Yarn was boiled to a draw ratio of 5 Water stretched and dried. The moisture absorbency of the acrylic fiber obtained was 12.9%. The result the measurement of their antistatic property is shown in Table 6. From Table 6 it can be seen that the Acrylic fiber produced according to the invention has a permanent antistatic property that of conventional acrylic fibers is far superior, and comes very close to that of viscose fibers. This antistatic property can still be achieved simultaneous use of the known antistatic agents improved will. Textiles, for example underwear, which were made from the acrylic fibers according to the invention, showed no problem in their electrostatic property. It was also found that the Fabric has excellent resistance to pollution

- 31 -109826/1927

Table 6

rehearse Antistatic property after this
Wash after this
To dye after tenma
ligem Vaschen Inventive
appropriate
Acrylic fiber Half-life in seconds 1.5 3.9 3.0 Conventional
Acrylic fiber untreated
delt 38.0 greater than
60 greater than
60 viscose
fibers fewer
than 1.0 1.2 1.4 1.3 Wool dto. 1.5 5.7 15.0 dto · dto ·

example

A spinning solution having a concentration of 18 percent by weight was prepared by dissolving 20 parts by weight of an acrylonitrile copolymer A of a specific viscosity of 0.162 and 80 parts by weight of a mixed polymer B of a specific viscosity of 0.17 generated in dimethyl sulf oxide. The acrylonitrile copolymer A consisted of 70 weight percent acrylonitrile, 15 weight percent N-3-0XO-1-1-dimethylbutyl acrylamide and 15 weight ·! percent hydroxyaryl acrylate, while the other copolymer B was formed from 97 percent by weight acrylonitrile and 3 percent by weight vinyl acetate. The spinning solution was made using the conventional Spun into threads using a wet spinning process. the

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filaments obtained were drawn to a draw ratio of 6 in a water bath at 10O ⁰ C, containing 10% dimethyl Bulfoxid. They were then rinsed in boiling water to remove the remaining solvent. After drying, the filaments were relaxed in a steam atmosphere of 2.0 atmospheres. The hygroscopic property of the acrylic fiber obtained was 9 »1%.

- 33 109826/1927

■ ν '■ ■■■ "■■ ■"" ^: """

Example 15

A spinning solution having a concentration of 28% was prepared by dissolving 45 parts by weight of an acrylonitrile mixed polymer A having a specific viscosity of 0 × 16 and 55 parts by weight of another mixed polymer B having a specific viscosity of 0.167 in dimethylformamide. The acrylonitrile copolymer A consisted of 77 percent by weight of acrylonitrile, 3 percent by weight of N-3-oxo-1-1-dimethyl-2-ethyl) utyl acrylamide and 20 percent by weight of vinyl pyrrolidone, while the other copolymer B consisted of 96 percent by weight of acrylonitrile and 4 The spinning solution obtained was spun with the aid of the conventional iron spinning process, the temperature of the solution being 120 ⁰ O, the flow rate of the drying air being 0.6 mjeimin, the temperature in the upper area of the spinning chamber being 240 ⁰ O, the Temperature in the lower area of the spinning chamber 120 ⁰ O, the withdrawal speed of the spun filaments was 300 m / min. The resulting unstretched filaments were en to a stretch ratio of 3 x 4 x stretched in boiling water and then the drawn filaments were relaxed without tension, wherein the environment having a temperature of 140 ⁰ O and 25% relative humidity. The moisture absorbency of the acrylic fibers obtained was 12.5%. The antistatic property of the sample was measured in the manner described in Example 3. The half-life after washing ten times was 2.5 S «k ·, a result which the

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remarkably improved permanent antistatic property made clear.

Example 16

A spinning solution with a concentration of 24% by weight was made by dissolving 30 parts by weight of an acrylonitrile- Mixed polymer A with a specific viscosity of 0.172 and

W 70 parts by weight of another mixed polymer B with a specific viscosity of 0.17 in dimethyl acetamide. The acrylonitrile copolymer A consisted of 80 percent by weight of acrylonitrile, 15 percent by weight of methyl acrylate and 5 percent by weight of N-3-oxo-1-1-dibutyl-2-n-propylheptyl acrylamide, while the other copolymer B of 97 percent by weight of acrylonitrile and 3 percent by weight of methyl acrylate was educated. The acrylic fiber obtained from this spinning solution by means of the method described in Example 1 showed an uptake

Fe ability for humidity of 11.0%.

Example 17

A spinning solution with a concentration of 24% by weight was made by dissolving 30 parts by weight of a mixed polymer A has a specific viscosity of 0.169 and 70 parts by weight of a mixed polymer B with a specific viscosity of

109826/1927 _ ₃₅ _

0.169 in Dime thylac et amid. Bas- first-mentioned mixed polymer A consisted of 77 weight percent acrylonitrile, 10 weight percent acrylic acid, 10 weight percent sodium vinyl benzene sulfonate and 5 percent by weight N-3-0X0-I-I-dimethylbutyl acrylamide, while the other copolymer B consists of 93 percent by weight acrylonitrile and 7 percent by weight vinyl acetate was educated. The dope was extruded into an aqueous solidification bath using the known wet spinning process. During the rinsing process, the filament became drawn to a draw ratio of 5 in boiling water. After drying, the filament was placed in a steamy atmosphere relaxed by 2.5 kg / cm. The acrylic fiber obtained showed a moisture absorbency of 12.7%. the other properties practically corresponded to those of the conventional one Acrylic fibers »

Example 18

A spinning solution with a concentration of 24 percent by weight was obtained by dissolving 8 parts by weight of a mixed polymer A having a specific viscosity of 0.159 and 92 parts by weight of another mixed polymer B with a specific viscosity of 0.169 dimethyl-ac et amide. The former copolymer A consisted of 65 weight percent acrylonitrile, 5 weight percent vinyl acetate and 50 weight percent H-3-oxo-1-1-dimethylbutyl Acrylamide, while the second copolymer B

109826/1927 - 36 -

from 89 percent by weight acrylonitrile, 6 percent by weight vinyl acetate and 5 percent by weight methacrylic acid was formed. The spinning solution was then made using the known wet spinning process processed. During the rinsing process, the thread was drawn to a draw ratio of 5 in. Boiling water. The thread was then dried and subjected to a sparging treatment subject. The obtained acrylic fiber showed a moisture absorbency of 13.1%.

Example 19

Five spinning solutions at a concentration of 24 percent by weight were prepared by dissolving 10 parts by weight of an ingredient which was selected from five acrylonitrile copolymers A, and 90 parts by weight of another mixed polymer B in Dimethylformamide produced. Each acrylonitrile copolymer A consisted of 65 weight percent acrylonitrile, 10 weight percent Methacrylic acid, 5 percent by weight vinyl acetate and 20 percent by weight of an N-3-oxo-hydrocarbon-substituted acrylamide the group listed in Table 7, while the other copolymer B of 95 percent by weight acrylonitrile and 7 percent by weight Vinyl acetate was formed and had a specific viscosity of 0.17. The spinning solutions obtained were spun in the manner described in Example 1. The moisture absorption capacity of the acrylic fibers obtained si «· listed in Table 7.

109826/1927 -37-

Table 7

N-3-oxo-hydrocarbon
substituted acrylamide Hygroscopic property
in % Kf-3-oxo-butyl acrylamide 12.1 N-3-oxo-methyl cyclohexyl-
butyl acrylamide 10.0 fr-3-0xo-1-1-dibutyl-2-.n-
propylhexyl acrylamide 7.5 N-3-oxo-.i-methylbutyl- ol -
methyl acrylamide 9.1 Ν-3-ΌΧΟ-1 -I-dimethylbutyl-
OL -butylacrylamide 7.9

Example 20

Six similar mixtures, each of which contained 15 parts by weight of an ingredient selected from 6 interpolymers A having a specific viscosity of 0.13 and 85 parts by weight of a copolymers B having a specific viscosity of 0.18, were prepared by dissolving in dimethylacetamide The first-mentioned copolymer JL consisted of 50 percent by weight of acrylonitrile, 10 percent by weight of Bf-3-oxo-1-1-dimethylbutyl acrylamide and 40 percent by weight of a component of the polyethylene glycol ethers listed in Table 8 , while the second copolymer B consisted of 94 percent by weight of acrylonitrile and 6 percent by weight of methyl acrylate was educated. Me from the spinning solutions produced in this way in the Aerylfaeera produced in the Veiae described in Example 1 showed excellent hygroscopic properties

109826/1927

and antistatic properties listed in Table 8 are.

Table 8

Mixed polymer A Polyethylene η -H y ^R 1 Hygro skopi see Antistatic
characteristic ßubstituenten von
glycol ester Cn of structural formula 2 50 -H -0- ⁰ I ₂ H ₂₅ Property in Half-life s ζ eit
in seconds
after this m 100 -H -0- ⁰ I ₂ H ₂₅ 10.1 χ Eu? υ en 0 30th -H -0- ⁰ S ¹¹ I ₇ 12.3 4, ₅ 0 30th -H -0- / 'j if 10.9 3.9 0 15th -H -0- C ₄ H ₉ 11.8 5.0 0 15th -0- 9.4 3.8 CM 9.0 9.4 4th 9.6

16 claims

109826/1927

Claims (10)

70/8756 Claims Λ j Acrylic fiber with improved moisture absorption, characterized by a mixed polymer A, containing units as aggregate a) at least 10 percent by weight of acrylonitrile, b) between 0.2 and 20 percent by weight of n-3-oxo-hydrocarbon-substituted Acrylamide of structural formula (1): 0 0
H - G - H ^f - H - C - C - GH «(D f I t ~ H E " where H and E "members of hydrogen and lower, respectively Alkyl groups do not contain more than 10 carbon atoms ό AT* formed group and H ^{1 is} a member / group formed from an ethylene group and lower alkyl-substituted ethylene groups having not more than 15 carbon atoms, and c) a third monomer suitable for copolymerization in an amount of the group which balances the weight, including vinyl acetate, acrylic esters, methacrylic esters, monomers with a hydroxyl group, monomers with a carboxyl group or their salts, monomers having a sulfo group or their salts, monomers having an amide group and 109826/1927 _ ₂ _ Polyethylene glycol esters of acrylic acid, methacrylic acid and Monomers with a polyethylene glycol side chain. 2. Acrylic fiber according to claim 1, characterized in that the proportion of acrylonitrile is at least 85 percent by weight and the proportion of substituted acrylamides of structural formula (1) in the range between 0.2 and 8 percent by weight. 3. Acrylic fiber according to claim 1, characterized that the proportion of acrylonitrile is at least 60 percent by weight, the proportion of the substituted Acrylamides of structural formula (1) is in the range between 0.2 and 20 percent by weight and the proportion of the third Monomers is between 0.5 and 40 percent by weight and off Polyethylene glycol ester of the structural formula (2) below consists of χ OH ₂ -O- CY- (CH ₉ CH-O). -IL
0
where Σ is a member of the group formed from hydrogen, and groups with the structural formula - C - T ¹ - (CH ₂ CH ₂ O) _n - R ^ ¹ , 0
T a member of the group formed from oxygen and a -HH group, E ^ a member of the group formed from alkyl groups with 1 to 22 carbon atoms, phenyl groups and substituted phenyl groups, Y ¹ and R ^ 'members of the same 109826/1927 ■ - 3 - \ ■ ■ '■ . Groups as listed for Y or R ^, where X and Y ¹ and R ^ and R _- ^ ^f can either be the same or different, β Hull or a positive integer between 1 and 10, η a positive one integer between 1 and 200 and n ^{1 is} a positive integer between 1 and 200, which either corresponds to or can be different from η, 4. Acrylic fiber according to claim 1, characterized that the third monomer is a member of the group formed from acrylic acid, methacrylic acid, itaconic acid, Sodium salts of the acids mentioned, methyl acrylate, methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methacrylate, Vinyl acetate, acrylamide, methacrylamide, sodium allyl sulfonate, Sodium methallyl sulfonate, sodium sulfophenyl methallyl ether, Sodium sulfophenyl allyl ether and vinyl pyrrolidone. Acrylic fiber according to Claim 1, characterized in that the mixed polymer A is mixed with a mixed polymer B which contains at least 85 percent by weight of acrylonitrile which is mixed with the said mixed polymer A as an aggregate component. 6. Acrylic fiber according to claim 5, characterized in that the copolymer A substituted as an aggregate at least 50 percent by weight of acrylonitrile, 1 to 50 percent by weight of dos mentioned 109826/1927 Acrylamide of structural formula (1) and said third Monomer in an amount "forming the weight balance" and that the proportion of the substituted acrylamide Structural formula (1) is present in the fiber in the range between 0.2 and 20% based on the fiber weight. 7. Acrylic fiber according to claim 5 »characterized in that the copolymer A is used as one Aggregate component a) between 10 and 94 percent by weight acrylonitrile, b) between 0.2 and 20 percent by weight of the substituted acrylamide of structural formula (1) and c) between 5 and 89 percent by weight of the polyethylene glycol ester structural formula (2) contains and the proportion of the substituted acrylamide of structural formula (1) in the fiber in a range between 0.2 and 8 # based on the fiber weight is present 8. Acrylic fiber according to claim 5 »characterized that the copolymer A as an aggregate component a) between 10 and 94 percent by weight acrylonitrile, b) between 0.2 and 20 percent by weight of said substituted Acrylamides of structural formula (1), c) between 5 and 80 percent by weight of said polyethylene glycol ester the structural formula (2) and d) in an amount equal to the weight of the building at least 109826/1927 one member of said third monomers contains, with the exception of the Pdlyäthylenglykolester of the structural formula (2), ■ where the proportion of the substituted acrylamides of the structural formula (1) in the fiber in the range between 0.2 and 8% based on the fiber weight, is present 9 · A method for producing the acrylic fiber according to any one of the claims 1 to 8, characterized by 1. Production of a mixed polymer A by copolymerizing a mixture of a) at least 10 percent by weight of acrylonitrile, b) between 0.2 and 20 percent by weight of n-3-oxo-hydrocarbon-substituted Acrylamide of the structural formula ⁽¹⁾ SS RCE ¹ -NCC-OH ₀ (1) HE " where E and E ^{w are} members of the group formed from hydrogen and lower alkyl groups, respectively, having not more than 10 carbon atoms, E ^{1 is} a member of the group formed from an ethylene group and lower alkyl-substituted ethylene groups having not more than 15 carbon atoms, and c) the monomer suitable for copolymerization in a proportion of the group that forms the weight balance, consisting of vinyl acetate, acrylic esters, methacrylic esters, monomers with a hydroxyl group, monomers with a Carboxyl group or its salts, monomers with a 109826/1927 ßulfogruppe or their salts, monomers with an amide group and polyethylene glycol esters of acrylic acid and Methacrylic acid, 2. Preparation of a spinning solution which contains the copolymer A dissolved in a solvent, and 3. Extruding the spinning solution into a solidification medium to form filaments. 10. The method according to claim 9 »characterized in that the proportion of acrylonitrile at least 85 percent by weight and the proportion of substituted acrylamides of structural formula (1) in the range between 0.2 and 8 percent by weight is 11. The method according to claim 9, characterized in that the proportion of acrylonitrile is at least 60 percent by weight, the proportion of substituted acrylamides of structural formula (1) in the range between 0.2 and 20 percent by weight and the proportion of the third monomer is between 0.5 and 40 percent by weight and off Polyethylene glycol esters of the following structural formula (2) consists: CJH ₂ »Ο- (0H ₂ ) _m I C-ϊ- (CHICH ₂ O) ₁₁₁ R ₁ (2) ti where X is a member of the group formed from hydrogen, and . "109826/1927 Groups ait der itrtüEturforasl * O * Y * - (GH Q X is a member of the group formed from oxygen and © in a member of the group, formed from alkyl groups Jiit 1 to 22 Schienet of f & toiiien, phenyl groups tmd substituted en Slieaylgiupptm, I "and R ^" members of the happy groups, like ßie fttr 1 and R ^ were listed, where t and X ¹ and S ^ uad S. ^ 'can either be the same or different, m Hull or a positive integer between 1 and 10, η a positive integer between 1 and 200 and n' a positive whole number between 1 and 200 * which can either correspond to or be different from η. 12 »Method according to claim 9, characterized as the third monomer is a bed end part the group consisting of acrylic acid, methacrylic acid, itaconic acid, sodium precipitates, four-mentioned acids, methyl acrylate, Methylme-baorylat ^ Syiiroxyathylacrylat, Hydroxyathylmetacrylat, Tinylacetat ^ Acrylamidetacrylaaiid, allylsulionAt, HfttriiiHaietliallyliulfOiAt, methallyl ether, "" LtriuAeulfophenylallyl ether and Yinylifet * Method according to Aaepruch 9, thereby ε β k β η a -Btichnet, dajö dl "SjpinalÖeung" ine Hiechung de * Miuchpolyiiere i and de · Miechpol ^ er * B, where »le • iae A «| fr ^ g».% TiÄh * it miadeeten * 85 weight »proaent * β m nitrile is present. 14. The method according to claim 13, characterized that the mixed polymer A to be mixed as an aggregate units at least 50 percent by weight of acrylonitrile and 1 to 40 percent by weight of the substituted acrylamide of structural formula (1) and in one the weight balance forming amount contains the third monomer and that the proportion of the mixed polymer A in the mixture is determined so that the content of the substituted acrylamide of structural formula (1) in the fiber is in a range from 0.2% to 20%, based on the fiber weight. 15 · The method according to claim 13, characterized in that the mixed polymer A to be mixed as Aggregate units a) 10 to 94 percent by weight acrylonitrile, b) 0.2 to 20 percent by weight of said substituted acrylamides of structural formula (1) and c) 5 to 89 percent by weight of said polyethylene glycol ester contains and that the proportion of the mixed polymer A in the mixture is determined ao} that the content * n substituted Acrylamide of structural formula (1) in the fiber in the area between 0.2 and 8%, based on the fiber weight, is present, 16. Procedure after. To claim 13, characterized marked 10 9826/1927 draws that the mixed polymer A to be mixed as Aggregate units a) 10 to 94 percent by weight acrylonitrile, b) 0.2 to 20 percent by weight of the substituted acralamide of structural formula (1), c) $ to 80 percent by weight of said polyethylene glycol ester and d) in a proportion determining the weight balance, at least one member of the third monomers mentioned, excepted the polyethylene glycol esters mentioned, and its proportion in the mixture mentioned is determined in such a way that the proportion of substituted acrylamide of structural formula (1) in the fiber is in the range between 0.2 and 8 % _t based on the fiber weight. 109826/1927