DE2009478A1 - Antistatic agent and method for the antistatic treatment of acrylic fibers - Google Patents

Description

The invention relates to an antistatic agent and a method for the antistatic treatment of acrylic fibers, in particular to a method for the antistatic treatment of acrylic fibers with an agent consisting of polymeric cationic antistatic agent, an anionic surface treatment agent and an agent for improving the feel of the fiber.

In this description, the expression "means for improving the grip property of the fiber" is intended to mean a dispersant, a plasticizer, a smoothing agent or a mixture of two or three of these agents can be understood.

Π Ο »β Λ 1

- 2 -

It is known that acrylic fibers tend to move during the Spinning, knitting or weaving or in the use of fiber products. In practice, charging has different functions Difficulties result. Due to the electrostatic charge on the fibers, they remain on the surface of the machine adhere and are repelled from one another during the textile process such as carding or stretching. Because . These difficulties can sometimes make acrylic fibers no compact Yarn are formed.

It is important for the practical use of acrylic fibers that the fibers have a frictional property suitable for the purpose and have sufficient flexibility. These characteristic properties can be obtained by smoothing or softening the fibers. Smoothness and softness The acrylic fibers are used to eliminate defects that occur in practice, such as incorrect winding of the fibers on one 'Roll in an aftertreatment process, faulty upsetting in a crimping chamber, breakage of the yarn due to mechanical Stress during fiber spinning, weaving, knitting, twisting and winding and the formation of pinholes and imperfections to prevent quilting and sewing and finally a break in the weaving and knitting process.

Numerous treatments have been proposed, which is also excellent antistatic

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Effect the property, smoothness and softness of the acrylic fibers. The known treatment agents are used in a dyeing or washing process however easily removed from the fiber. For a perfect implementation of the after-treatment of the fiber and the textile processing as well as for the proper use of fiber products, acrylic fibers are required, which are durable Have anti-static properties. As is known, synthetic fibers such as acrylic fibers, polyamide fibers and polyester fibers have one have a greater tendency to charge themselves electrically than natural fibers such as cotton, wool or silk. It is therefore practical very important to the problem of static electricity due to the electrifying property of synthetic fibers to solve.

The aim of this invention is a method for antistatic treatment of acrylic fibers, which gives the fibers high anti-static properties that make them durable opposed to wet treatment such as scrubbing, dyeing and washing. It is also an object of this invention to provide an antistatic agent to create that is suitable for this process. Through the process, the acrylic fibers should also have a high degree of permanent antistatic property as well as a great smoothness and softness are given.

The method according to the invention is characterized in that the acrylic fibers are treated with the following treatment agents

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will:

1. A polymeric cationic antistatic agent comprising at least 50 percent by weight of a monomeric unit of the formula

?1
OH ₉ -C ρ

000 (0H ₂ ) _n -N- E ₅ .OSO ₅ R ₅ ^ '

contains, where R ^, Rp »R ^» R /, and R ^ are each a component is selected from the group consisting of hydrogen atoms and lower alkyl groups, is selected and η is an integer not greater than 20;

2. An anionic surfactant of the formula

0
[> (OCH ₂ CH ₂ ) _k o] -LP- (OX) _m

wherein R is a selected from the group of saturated and unsaturated aliphatic hydrocarbon groups and X corresponds to a component selected from the group consisting of a hydrogen atom forming a salt with a tertiary amine and monovalent metallic atoms, k is zero or one integer between Λ and 100 and 1 and m each signify 1 or 2, taking into account the relationship 1 + m «3, and furthermore

0Q984 1/1702

5 · © in means for improving the grip property.

A preferred embodiment of the method according to the invention consists in that acrylic fibers produced from polyacrylonitrile, from an acrylonitrile copolymer or from a mixture thereof treated with an aqueous emulsion containing a solid composition consisting of 5 to 50 percent by weight, preferably 15 to 50 percent by weight of a water soluble one polymeric cationic antistatic agents, 5 "to 50 percent by weight, preferably 5 to 40 percent by weight of one phosphoric ester type anionic surfactant, 2 to 30% by weight of a dispersant, 5 to 40% by weight a smoothing agent for lowering the coefficient of friction and imparting extreme smoothness to the fiber and 10 to 40 percent by weight of a plasticizer.

Venn this composition in the manufacturing process of acrylic fibers is used, an antifoam agent, for example 1 to 6 percent by weight of one, may be used to improve the process conditions silicone-containing anti-foaming agents.

In a further embodiment of the invention, the acrylic fibers are cationic with a water-soluble polymer Antistatic agent and an anionic surfactant of the phosphoric acid ester type in a separate treatment bath treated. In this case, the order of treatments is

9U1 / 17Ö2 - ⁶ -

not mandatory, and it is preferred between the two Treatment stages a dry and heat treatment of the Fibers inserted. With a separate treatment system, a grip property improving agent in view of the Stability of the bath, the feasibility of the antistatic treatment and the spinnability of the obtained fibers with each Bath can be combined. The separate treatment system in which the acrylic fibers separately with the water-soluble polymeric cationic antistatic agent and the anionic surface active agent Phosphoric ester type agents are treated to fix the reaction product of the antistatic agent and the anionic surfactant on the surface and inside of the acrylic fiber so that a stable antistatic property and softness is achieved.

The invention is explained in detail below.

The polymeric cationic antistatic agent useful in the invention is a homopolymer or a copolymer with at least 50 percent by weight of a monomeric unit of the formula

CHp - σ ρ (ι)

² ' _Ν (+)? 2

COO (CHp) - N - E,. OSO;

₃ .

where R ,,, Rp, R ₃ , R ^, and R, - each represent a component selected from the group consisting of hydrogen atoms

ÖÖ98A1 / 17Θ2 - 7 -

and alkyl groups having 1 to 12 carbon atoms, which are different from each other or all the same, furthermore η means an integer not greater than 20.

For the copolymerization with the monomer of formula (I) is particularly a monomer is suitable which has the following formula:

CH ₉ -C (II)

COO (CH ₂ CH ₂ O)

where Rg denotes a component selected from the group consisting of hydrogen atoms and lower alkyl groups of Λ to 5 carbon atoms, IU denotes a component selected from the group consisting of hydrogen atoms, alkyl groups of 1 to 22 carbon atoms and substituted or unsubstituted phenyl groups, and η is an integer between 1 and 200.

Acrylic fibers with good antistatic properties can already be obtained if the fibers only with the polymer cationic antistatic agents are treated. They have anti-static properties however, the fibers are reduced by dyeing and repeated washing, since the antistatic agent is in Vasser is soluble and during staining and vashing from the Fibers are removed.

With a careful study of a method of prevention

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to remove the antistatic agent and to improve the laundry resistance of the antistatic agent, it has been found that by using the specific anionic surfactant together with the polymeric cationic antistatic agent the intended purpose is achieved.

Any anionic surfactant can be used with the polymeric kationi- ™ to improve antistatic resistance see antistatic agents are combined. However, some anionic surfactants have a tendency to remove the iron in the To absorb water, which causes the fibers to yellow

The yellowing of the strands is due to the absorption of iron is most noticeable when the fibers are treated only with the above-mentioned polymeric cationic antistatic agent. Yellowing can be reduced when an anionic surfactant is used together with the polymeric cationic Antistatic agent is used. Phosphorus components of the following formula are particularly suitable for preventing the yellowing of the

Prevent fibers:

) _k 0] ₁ P (0X) _m (III)

where E is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, X is a

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Hydrogen atom that forms a salt with a tertiary amine, or denotes a monovalent metal atom, k is zero or a positive integer between 1 and 100, 1 and m are the same 1 or 2, where the relation 1 + m ■ 3 must be fulfilled. The phosphorus components also increase the antistatic resistance of the fiber. For this purpose you can use one or more Types of anionic surfactants can be used. Usually the anionic surfactant likes consist of two or more anionic components.

By using the polymeric cationic antistatic agent together with the anionic surface active agent an acrylic fiber is obtained which has washable antistatic properties. However, neither can it be the polymer cationic antistatic agents nor the anionic surfactant are stably dispersed in the same bath because the Mixture or the reaction product of the components is insoluble in water is. A suitable dispersant is therefore required to stabilize the aqueous dispersion of both agents. The dispersants usable for this purpose are not limited when the reaction between both agents is not hindered.

Nonionic or amphoteric surfactants, in particular non-ionic agents of the polyethylene oxide ether type and block copolymer type nonionic agents

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from a propylene oxide unit and an ethylene oxide unit, such as they are mentioned in the following formula, in view of the stability of the dispersion and the unhindered reaction preferred between the anionic and cationic agents. The formula is:

'(° 3 ^H 6 °) _m

where I ¹ , m ¹ and n 'are an integer between 10 and 100. However, the dispersants which can be used are not limited to the compounds mentioned.

When the water-soluble polymeric cationic antistatic agent and the anionic surface active agent are des Phosphoric acid ester applied separately to the acrylic fibers, see above the addition of the dispersant is not necessary. As already mentioned, gives simultaneous or separate treatment of the acrylic fibers with the polymeric cationic antistatic agent and the anionic surface active agent Fibers have a substantially permanent antistatic property, these agents become the acrylic fibers during fiber manufacture then the fibers (tow or bundle of threads) become slightly sticky. The result is defects such as incorrect winding of the fibers on a roller. Sticky acrylic fibers also have poor carding properties in the fiber spinning process so that it is difficult to get a good one out of them

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Manufacture tissue. It is also very difficult to get out of the sticky acrylic fibers to produce a good, even yarn, and sometimes the spinning process cannot be carried out at all due to this stickiness.

Even if a textile product can be made from tacky acrylic fibers, the product has stickiness due to its stickiness Defects such as undesirable grip properties and easy soiling. The mentioned disadvantages also have textile products which are treated with the mixture of the two agents during the finish To avoid the disadvantages due to stickiness, it is necessary to adjust the coefficient of friction decrease between the fibers; because the disadvantages of polymer spinning and fiber spinning are due to the high coefficient of friction attributed to the sticky acrylic fiber. To meet this requirement, a smoothing agent is used together with the polymeric cationic antistatic agents or the anionic surfactant or the mixture of both are used.

The smoothing agents usable for this invention are not limited to any specific group. So can be used as a smoothing agent z. B. Esters of saturated or unsaturated carboxylic acids with 10 to 20 carbon atoms and alcohols such as anisole, sorbitol, glucose and glycols such as ethylene glycol, polyethylene glycol and propylene glycol can be used. In special cases

009841/1792

dimethylpolysiloxane and methylhydropolysiloxane are advantageous, to prevent the acrylic fibers from sticking together. The mentioned Esters have a good dispersion effect. The use of the ester together with the dispersant is therefore * suitable for a further stabilization of the treatment bath containing the cationic agent and the anionic agent.

It has been found that the antistatic agent with the polymeric cationic see w, the anionic surfactant, the dispersion means and said smoothing means treated product has a sufficient softness, while exhibiting at the same time resistant anti-static properties. Since, in particular, a fiber tow or thread bundle treated with the treatment agents in the polymer spunbond tends, owing to its brittleness, to be destroyed by a crimping machine, it is desirable that a plasticizer be used together with the treatment agents.

The usual plasticizers for acrylic fibers may be used as plasticizers, with the exception of those by means of which the coefficient of friction the fibers are greatly enlarged.

Preferred plasticizers are carbamyl derivatives of the formula:

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OR _c

Il I -

R ₈ -CN

O R,

Il I

-C-N

200 9478 B. Q V (CH ₂ ) _g - f. ^D 2 C -
I. NH I. C =
I.
I.

-A] - (CH ₂ ) _f -

¹ H.

where Rg and

^ -Different or identical alkyl groups having at least 6 carbon atoms and Rq, R ₁ Q, R ₁₁ and R _{12 are} each components selected from the group consisting of hydrogen atoms, alkyl groups having not more than 5 carbon atoms and hydroxyl radicals, R ₁₀ and R _{11 in} each case preferably denotes an acid amide chain which is derived from an acid and a polyamine, D ₁ and D _{2 are} each an oxygen atom, sulfur atom or an imidraic, c is zero or an integer between 1 and 3, A is an oxygen atom, sulfur atom, Amino radical having a simple alkyl or alkylol group of at least 5 carbon atoms, e.g. B. -NH ₂ H ^ OH or -NH ₂ Ht-- or a methylene group with methyl or a hydroxyl group, g and f each ^w 6il ^{s are} integers between 1 and 8, preferential prices between Λ and 3, h and e respectively Zero or an integer - cited 1 and 6, preferably zero or an integer between Λ and 3, i and d are each an integer between 1 and 6, preferably 2 or less, R _1Z , and R ₁ C are each Mean hydrogen atom or a methyl group and are equal to or from each other

00 98 A1 / 1792

are different, B is an alkyl group or a positive radical such as the cation of an acid residue, and Y is a negative radical such as an anion of a halogen or an acid residue.

When these treating agents are appropriately combined with each other, they have an appropriate amount of these treating agents Impregnated acrylic fibers have excellent permanent antistatic properties, good grip properties and can can be subjected to a polymer spinning process or a fiber spinning process without difficulty.

When the treatment agent is the acrylic fibers during the manufacturing process of the fibers are added, the treated fibers are required to have a coefficient of friction between the fibers is low enough to avoid the above-mentioned polymer or fiber spinning difficulties. For this purpose, the treated acrylic fibers are required to have a static coefficient of friction ε as) between the fibers does not exceed the value 0.55 and that the dynamic coefficient of friction ^ d) is at most 0.30. The coefficient of friction are determined by means of a Röder type coefficient of friction tester in accordance with JIS-L-1074 · (1965). If the coefficients of friction of the acrylic fibers are within the stated range, then polymer spinning occurs and fiber spinning does not pose any problems. Sometimes one is enough

009841/1792 - ^ -

■■ - ■ "■ - 15 - 2008478

suitable plasticizer the regulations for the coefficient of friction, without the need to add a smoothing agent. The invention therefore also includes methods in which the Requirements for smoothness and softness at the same time by only one surfactant or the requirements for dispersion and smoothness are simultaneously satisfied by only one surfactant.

The following is another example of a Procedure explained.

When the acrylic fibers with the treatment agents during fiber production are treated, the procedure is preferably carried out as follows:

1, Undried acrylic fiber with an aquagel filament structure are treated in one bath or in several baths that contain individual treatment agents, and

2. The treated swollen acrylic fibers are dried and heat treated ^ - ^ "

Through this process, acrylic fibers become substantially permanent Preserved anti-static properties.

The treating agents can also be applied to acrylic fibers

Ί6

009841/1792

that are not in the aquagel-lilament structure. Acrylic fiber products made from conventional acrylic fibers can therefore also be treated by the method according to the invention.

As is evident from the obxgen description is clear that loading can act of acrylic fibers by the process of this invention in each stage of the process between the polymer spinning and "final finishing to be applied. In the treatment, however, a vote of impregnating amount is each treatment agent required in the Relevant treatment stage to the aim of this invention, ie to achieve stable antistatic properties of the acrylic fibers.

Usually, the total absorption amount of the treating agents is 0.05 to 10%, preferably 0.1 to 2 %, of the weight of the acrylic fibers. If the method according to the invention is used in the polymer spinning process, the treatment agent according to the invention may be added to the acrylic fiber instead of the usual lubricant. If the process according to the invention is used in a process step after dyeing, the agent may be added in the usual way *

Since no special device is required for the method according to the invention is, it is industrially very advantageous «

0 Q 9 8 /. : / 1 7: 2

The acrylic fiber useful in the invention contains at least 40 percent by weight of a polymerized acrylonitrile and • can also contain a maximum of 60 percent by weight of one or more other monomeric units. The acrylic fiber can after the dry spinning process, wet spinning process or dry-wet spinning process are spun. The solvent to be used can be selected from those conventionally used for acrylic polymers to be selected.

Furthermore, the method according to the invention can be used with any fiber mixture which contains acrylic fibers.

Practical examples of the method according to the invention are given below.

example 1

A spinning solution was prepared from 25 percent by weight of a copolymer which consisted of 93 percent by weight of acrylonitrile and 7 percent by weight of methyl acrylate and had a specific viscosity of 0.16, and also of 75 percent by weight of dimethylformamide. The spinning solution was pressed into an aqueous bath at 40 ^° C. which contained 50 percent by weight of dimethylformamide and then stretched in a stretching ratio of 5. The fibers obtained had aquagel filament structure and

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contained an amount of weight corresponding to the weight of the thread inside Water. The Aquagel fibers were 5 to 10 seconds long impregnated in an aqueous dispersion that had 1.65 percent by weight of the following composition

Poly-y5 -Acrylyloxyäthyldiäthylmethyl-

ammonium methyl sulfate 30 percent by weight

P ³ 12 ^H 25 ^(0CH 2 ^CH 2 ⁾ 4 ⁰ ^ 2 ^p (°) ( ^0Na ) 21 »Emulgen 147 (dispersant of

Kao Soap Co., Japan) 12 ^w

O ^ , β -Dihydroxyäthyl- r> ', s · -di ( i - stearylamidäthyl) acetate urea 18 "Sorbitol monopalmitate 12"

Noran silicone plasticizer S (made by Dainihon Inki Co., Japan) 6 ^w Anti-foam silicone (made by Toshiba Co., Japan) 1 "

The impregnated fibers were squeezed by a pair of nip rollers so that they were 1.2 percent by weight of the Fiber weight of the composition mentioned. Then the fibers were dried at 140 ° 0 and JO minutes long in the relaxed state with saturated steam of heat-treated.

The received. From fiber to fiber, fibers had one

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static coefficient of friction Cus) of 0.419 and from fiber to fiber a dynamic coefficient of friction ^ cL) of 0.247. The fibers obtained could thus be spun into a yarn of good quality without difficulty under ordinary spinning conditions.

The obtained fibers were subjected to cleaning, dyeing and ten-fold waxing treatments according to the following conditions.

1. Cleaning

fScourol # 400 (from the company
Kao Soap Co., Japan

Cleaning supplies; 2 percent by weight

the fiber weight

.Sodium pyrophosphate 0.05 "

Liquid ratio 1:50

! Temperature 70 ⁰ C

Time 15 minutes

2. Coloring

/ Deorlene Blue 5G (more cationic

J dye from Ciba Co.) 5 "

<Acetic acid 0.5 "

Vj sodium acetate 0.5 "

Liquid ratio 1:50

Temperature 100 ⁰ C

Time 120 minutes

009841/1792 ² ° "

Soaping 1: O, 50 0 percent by weight
of the paser weight / Scourol # 400 50 ⁰ O ⁿ 25 (^ Ammonia 20th Minutes LIQUID RATIO temperature Time

_k 3. Vaschen ten times

Zab (no detergent manufactured by Kao Soap Co., Japan) 3 g / l

Liquid ratio 1:50 temperature 40 ⁰ C Time 20 minutes

Using a "Static Ilonestmeter" from Shishido Shokai Co., Japan, became the antistatic Properties of the original, cleaned, dyed and washed fibers were measured. The measurement results are detected by the half-life.

Measurement of the antistatic properties

It was measured by means of a "Static Honestneter" according to the conditions listed below from a fiber sample, ie for at least 2Ό hours under atmospheric conditions: ⁰ !! from

0098 ^ 1/1792 " ²¹ "

Was exposed to 20 ⁰ C and 50% relative humidity, the antistatic property was measured:

applied voltage

Duration of stress exposure

Speed of rotation of the sample

10,000 V at least 5 seconds 1,000 r.p.m.

The half-life was determined to be the time at which the voltage had dropped to half its value.

For comparison, conventional acrylic fiber, viscous rayon fiber, and wool fiber were the same antistatic measurement subjected. The results are recorded in Table 1.

Table 1

fiber Half-life t ,, / o (see) original cleaned colored washed Antistatic
Acrylic fiber according to
the invention 1.0> 1.4 3.7 5.0 conventional
Acrylic fiber 1.0> 38.0 60 < 60 < Vi sko s he ayon-
fiber 1.0> 1.2 1.4 1.3 Wool fiber 1.0> '1.5 15.7 15.0

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- 22

The table shows that with the antistatic agent of the invention treated acrylic fibers had a significantly higher non-static property than conventional acrylic fibers and that the antistatic property was intermediate between viscose rayon and wool fibers. The table also shows that the antistatic agents on the acrylic fibers were more resistant to cleaning, dyeing and washing.

The fabrics made from the aforementioned acrylic antistatic fibers had good wear properties, great ones Resistance to pollution and no electrostatic disadvantages.

Example 2

A spinning solution was prepared from 25 percent by weight of a polymer consisting of 90 percent by weight of acrylonitrile, 7 percent by weight of vinyl acetate and 3 percent by weight of vinyl bromide and having a specific viscosity of 0.15, and of 75 percent by weight of dimethylacetamide. The spinning solution was pressed into an aqueous spinning bath of 40 ⁰ G, which contained 50% dimethylacetamide, and stretched five times. The fibers obtained had an aquagel filament structure. The fibers were impregnated in the same treatment bath as described in Example 1 and squeezed out so that the

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Treatment emulsion was 1.1 percent by weight of the fiber weight. The fibers were then dried and relaxed Condition «it * treated saturated steam · You were in the in the same way as described in Example 1, subjected to a cleaning, dyeing and washing treatment. In Table 2 shows the antistatic properties of the fibers obtained and of the untreated fibers.

Table 2

fiber "Half-life t ^ y ₂ (see) original cleaned colored washed Antistatic
fiber 1.0> 1.4 6.2 Bra treated
fiber 1.0> 59.1 60 < 60 <

It is clear from Table 2 that the acrylic fiber treated according to the example has excellent permanent antistatic properties.

The antistatic fiber had a static coefficient of friction Cus) of 0.408 and a dynamic coefficient of friction Cud) of 0.240. She could get to one without any difficulty spun with good yarn and made into a good tufted carpet. The tufted carpet had some resistance against soiling which was higher than that of conventional carpets. It did not cause any electrostatic deficiency like

009841 / 17'9 2

an electrostatic shock or the like.

Example 3

A spinning solution was prepared from 25.5 percent by weight of a polymer consisting of 93 percent by weight acrylonitrile and 7 percent by weight vinyl acetate and having a degree of polymerization of 1,500, and from 76.5 percent by weight dimethylacetamide. The spinning solution was pressed by means of a spinneret with 20,000 openings 0.08 mm in diameter into an aqueous bath at 40 ° C., which contained 40 percent by weight of dimethylacetamide, and was drawn in a draw ratio of 5. The fiber obtained had an aquagel filament structure. It was impregnated in an aqueous solution containing 0.65 percent by weight of Sanstat No. 6 (anionic surfactant from Sanyo Kasei Co., Japan), squeezed by two nip rollers so that it was 0.65 percent by weight, based on the thread weight, from Sanstat Nr. \ , then dried for two minutes at 130 ° C on a cylinder dryer. The fibers treated in this way were also impregnated in an aqueous emulsion, which had the following addition

composition had:

Poly- / £ -acrylyloxyäthyldiäthylmethylammoniummethylsulfat

X, β -dihydroxyethyl-oL ¹ , /? '-diQ? stearylamide ethyl) acetate urea Noran silicone plasticizer S sorbitol monopalmitate

28 Weight
Percentages 24 Il 24 It 24 It

009841/1792 " ²⁵

The fiber was squeezed out by two nip rollers so that it contained 1.25 percent by weight, based on the weight of the thread, of the composition mentioned. Then, it was dried for 2 minutes at 13O ⁰ C.

The fibers treated in this way were heat-treated ^{with saturated steam up to 130 ° C. in the relaxed state.} The obtained fibers had a static coefficient of friction (juß) of 0.405 "and a dynamic coefficient of friction (^ d) of 0.272 Properties to test.

The half-life of the fibers obtained was 4.7 seconds.

Example 4

An aqueous suspension was prepared that was 2 percent by weight a solid composition of the following components contained:

Poly / 5 acrylyloxyethyl diethylmethylammonium methyl sulfate 34 weight

percentages

Sanstat Mr. 6 26 "

Emuigen 147 20 "

- 26 0 09841/1792

%,, · 5 -dihydroxyethyl- Φ ¹ , / · <'-di (,.> Stearylamidätnyl) -acetatiiarnstoff 20 percent by weight

The aqueous solution was added to fibers made of a copolymer were made, which consisted of 97 percent by weight acrylonitrile and 3 percent by weight vinyl acetate, and although in an amount that the fibers 0.1 percent by weight of the Fiber weight contained in this solid composition. the obtained fibers had a static coefficient of friction Cus) of 0.401 and a dynamic coefficient of friction (^ d) of 0.222. They were soft and exhibited suitable smoothness without undesirable sticking of adjacent fibers together.

The fibers obtained had a half-life of 5 to 7 seconds after dyeing and washing ten times. This shows, that they had sufficient antistatic resistance.

Example 5

An aqueous emulsion of the composition given in Example 1 was added to an undershirt made of acrylic fibers in an amount added that the shirt contained 1.5 percent by weight of the fiber weight of this solid composition.

The undershirt was very soft to the touch and showed no electrostatic disadvantages, while de? :: on and

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_ ₂₇ _ 200P478

Pull out. The advantage of the antistatic property was not lost even after washing ten times. Sa's undershirt showed resistance to water spots and Pollution. These results show that the undershirt had the properties suitable for practical use.

Example 6

It was a spinning solution of 27 weight percent of a copolymer, that of 93 percent by weight acrylonitrile and 7 percent by weight Vinyl acetate consisted and had a specific viscosity of 0.155, and 73 percent by weight Dimethylformamide produced.

The spinning solution was extruded through a spinneret which had a temperature of 105 ⁰ G into a spinning shaft, wherein the upper portion has a temperature of 230 ⁰ C and the lower portion had a temperature of 105 ° C. The fibers or filaments were drawn five times in boiling water. The fibers obtained had an aquagel filament structure. They were impregnated in an aqueous emulsion containing 1.3 percent by weight of the composition given below, then squeezed out so that the fiber contained 1.3 percent by weight of the fiber weight of this composition, and finally dried.

- 28 -0098 ^ 1/1792

Composition:

Copolymer consisting of 9 parts by weight of β- acrylyl-oxyäthyldäthylmethylammoniummethylsulfat and 1 part by weight of a condensation product of ethylene oxide and acrylic acid 34 percent by weight

Triethanolamine salt of a mixture containing 1 part of a compound of the formula: ₀

C ₈ H ₁₇ O (CH ₂ CH ₂ O) ₃ P (OH) ₂

and 1 part of a compound of the formula:

0
P (OH) 26 ^M.

Zontes TA.-43O (plasticizer from the company

Matsumoto Ushi Co., Japan) 20 "

Emuigen 14-7 20 "

The dried fibers were subjected to a thermal treatment

<
relaxed with saturated steam. The treated fibers had a static coefficient of friction of 0.387 and a dynamic coefficient of friction of 0.227, and also had suitable smoothness. In addition, the fibers had good antistatic resistance as shown below.

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200P478

fiber original after
Clean after.
To dye after ten times
Vaschen 1.0 1.4 2.3 4.2

The treated fibers show even after washing ten times has a half-life that is less than 5 seconds. The fibers could be spun, woven and knitted without difficulty will.

Example 7

Aquagel fibers according to Example 1 were in an aqueous Impregnated dispersion, the 0.65 percent by weight of a solid Composition with the following components contained:

Poly-β- methacrylyloxyethyl dimethylmethylammonium methyl sulfate

· ■ * «, β -dihydroxyethyl oil ', /' -diQ # - stearylamide ethyl) acetate urea

54 weight percentages 46

The impregnated fibers were squeezed out so far that they 0.65 percent by weight of the fiber weight of the composition mentioned and then dried at 135 ° O on a roller.

0098A1 / 1 792

- 30 -

The dried fibers were then impregnated in an aqueous solution, the 0.95 percent by weight of the following specified composition contained:

Γσ.ρΗοςΟ (GH, CH ₅ O) JF (OH) o.2N (CHoCH ₅ OH), 68 weight

L ¹ ^ *? ,. £ j c d. cL o percent

Noran silicone softener S 32 "

^ The impregnated fibers were squeezed out until they contained 0.95 percent by weight of the fiber weight of the composition mentioned, then they were heat-treated ^{with saturated steam at 140 ° C. in the relaxed state.}

The fibers obtained had a static coefficient of friction (yUß) of 0.1411 and a dynamic coefficient of friction C- ^ d) of 0.2 & 9. The half-life was 5-7 seconds.

Example 8

Aquagel fibers of Example 1 were with an aqueous Treated dispersion containing 0.65 percent by weight of a solid composition of the following components:

Poly-;) - acrylyl oxyäthylme thyl -

ammonium methyl sulfate 54- weight

percentages

d , β -dihydroxyethyl- χ · ,, 3 ^! - (ß stearylaaidäthyl) -acetatharnstöff 46 "

0098A1 / 1792

The impregnated fibers were squeezed out until they were 0.65 percent by weight of the fiber weight of the composition mentioned contained, then they were heated to 135 ° C Rolls dried. The fibers obtained had a static coefficient of friction Cms) of 0.380 and a dynamic coefficient of friction Cud) of 0.231

The fibers were spun into a yarn, knitted into a cloth and then impregnated in an aqueous solution that is 0.8 percent by weight an anionic surface-active agent of the formula:

£ (OH) ₂ .2N (CH ₂ CH ₂ OH)

contained. The impregnated fibers were squeezed until it contained 0.8 weight percent of the fiber weight of the anionic surface active agent, then for 10 minutes cleaned at 120 ⁰ C and dried under the same conditions as in Example 1, dyed and subjected to a ten-fold washing treatment ·

The fiber obtained had a half-life of 6.7 seconds.

009841/17 9-2

Compare example game

They were prepared in the same manner as in Example 1 Aquagel fibers so with an aqueous emulsion that is 1.0 percent by weight the composition given below, treated so that the content of this composition was 1.0 percent by weight of the fiber weight.

Poly- β -acrylyloxyäthyldiäthylmethyl-

ammonium methyl sulfate 46 percent by weight

36

Emuigen 147 18 "

The treated fibers had a static coefficient of friction (ytts) of 0.66 and a dynamic coefficient of friction G / d) of 0.42. They had a sticky feel and could not due to inadequate carding properties can be made into a good fabric.

10 claims

009841/1792

Claims (3)

PATENTANWALT SOOO Munich 12 70/8702 Maria-Blrnbaum-Straßel ■., 200P478 Telephone ββ OS S3 "**» "". Patent claims 1. A method for the antistatic treatment of acrylic fibers, characterized by the use of the following treatments: 1. a polymeric cationic antistatic agent which at least 50 percent by weight of a monomeric unit the lormel ^d ■ (- ") UÜU (.01I ₂ ^ ₁₁ - JN - K ^ .UbUjJX ^ where R, j, R ₂ , R ^, R ^ and Rc are each a member selected from the group consisting of hydrogen atoms and lower alkyl groups, and η is an integer not greater than. 20, is; 2. An anionic surfactant of the formula O
π W ^ ^ Jöl · * Jl m * where R is one from the group consisting of saturated and unsaturated - 2 009841/179 2 selected aliphatic hydrocarbon groups Is a constituent and X corresponds to a constituent selected from the group consisting of a with a tertiary amine consists of a salt-forming hydrogen atom and monovalent metallic atoms, k the value zero or an integer between 1 and and 1 as well as m 1 or 2 respectively, taking into account of the relation 1 + m «■ 3 mean, and further 3. a means for improving the grip property. 2. The method according to claim 1, characterized that the treatment agents (1, 2 and 3) before the addition of an antistatic composition be united. 3. The method according to claim 1, characterized 5 that the acrylic fiber first with the treatment agents 1 and 3 "and then with the Treatment agents 2 and 3 are treated. 4. The method according to claim 1, characterized in that the acrylic fibers first with the Treatment agents 2 and 3 and then treated with the treatment agent 1. 0 9 8 4 1/1792 5. The method according to claim 2, characterized in that that the proportions of treatment agents 1 and 2 in the antistatic composition each up to 50 percent by weight. 6. The method according to claim 1, characterized in that the treatment agent 1 further at least 50 percent by weight of a monomer of the formula OH ₀ -C C. ι COO (CH ₉ CHoO) -Rr ₇ contains, where Rg is a component that is derived from the Group is selected which consists of a hydrogen atom and alkyl groups having 1 to 5 carbon atoms, IU represents a component selected from the group which is composed of a hydrogen atom, alkyl groups having 1 to 22 carbon atoms and substituted or unsubstituted phenyl groups and j is one represents an integer between 1 and 200. 7. The method according to claim 1, characterized in that that the treatment agent 3 consists of 2 to 30 percent by weight of a dispersant, 10 to 40 percent by weight of a plasticizer and 5 to 009841/1792 ^ 200P478 40 percent by weight of a smoothing agent. 8. The method according to claim 5 or 4, characterized that the acrylic fibers are subjected to the first treatment, dried, heat-treated and then subjected to a second treatment. 9. The method according to claim 1, characterized in that | shows that the acrylic fibers have an aquagel Have pilamentous structure. 10. Antistatic agent for acrylic fibers, characterized by the following components: 1. A polymeric cationic antistatic agent comprising at least 50 percent by weight of a monomer of formula E ₁ \ CH ₂ -C φ? 2 C00 (CH ₂ ) _n -NE ₅ - OSO ₅ E ₅ ^ > contains, where 3L ·, Rp> - ^ 3 »^ 4 " ^ ³¹ ^ ^ 5 lower alkyl groups that are different from one another or the same and η is an integer not greater than ; 2. An anionic surfactant of the 009841/1792 - Sr- formula fl [H (OGH ₂ CH ₂ ) _k 0] _£ -P- (OX) _m where R is a saturated or unsaturated aliphatic ^ hydrocarbon group having 1 to 22 carbon atoms, Z corresponds to a component selected from the group consisting of hydrogen atoms forming a salt with a tertiary amine and monovalent metal atoms, k the value O or a integer between 1 and 100 and 1 and m each mean Ί or 2 taking into account the relationship 1 + m »3 and furthermore 3. a means for improving the grip properties of the fibers, wherein the treatment agents have such properties that they cause a static coefficient of friction of a maximum of 0.55 and a dynamic coefficient of friction of a maximum of 0.30 between the fibers when the fibers contain between 0.05 and percent by weight of the fiber weight of these components and the coefficients of friction according to through. _u . JIS-L-1074 · defined Röder method can be measured. 000041/179