DE1917410A1 - Antistatic Agents and Methods for Treating Hydrophobic Synthetic Fibers - Google Patents

Description

April 3, 1968 Japan No. 21420/68 October 1, 1968 Japan No. 70817/68

The invention relates to antistatic agents and methods for Treatment of hydrophobic synthetic fibers.

Synthetic fibers, e.g. B. fibers made of polyethylene terephthalate, Polyacrylonitrile or polyamide are used independently or in combination with natural fibers in a variety of ways. As these synthetic Fibers are generally hydrophobic, they have a tendency to become electrostatically charged when they are in the form of Clothing or flooring.

The static charge causes synthetic ones to adhere

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Clothes on the wearer's body, easy soiling and discharge noise when taking off clothes. the static charge is generated by repeated rubbing of fibers, threads or fabrics and prevents normal spinning, Stretching, twisting, weaving and knotting.

There are different methods of preventing static Charging and antistatic agents are known, however, to overcome the shortcomings of such hydrophobic synthetic fibers A useful antistatic agent is required to have three properties, namely, good antistatic properties, high resistance to washing and cleaning as well as excellent grip. However, it is very difficult to get an antistatic to find one that meets these requirements. For example, that described in British Patent Specification 852,299 Anti stat icurn with the general formula

RO
CH ₂ = CC- (OC _a H ₄ ) i- (OC ₃ H ₆ ) _iB -R

a great antistatic effect, but the disadvantage when Wash and clean to be removed easily. Another antistatic agent has the disadvantage of increasing the quality of the grip decrease or stain the fibers considerably. Λ

Methods for eliminating these disadvantages have become known, in which copolymers of the compounds mentioned above

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a functional group such as a compound containing a methylol group or an epoxy group or an acrylonitrile contains, be connected. However, the known method has the following disadvantages:

1. insufficient stability of the dispersion liquid,

2. a washing treatment must be carried out, 3 · the fibers discolour during drying,

4. The durability is insufficient.

Incidentally, the service life is a treatment after above method inadequate.

This invention aims to provide antistatic agents and a method of antistatic treatment which are hydrophobic Fibers incorporated greater and more permanent antistatic properties and improve the hand quality of the hydrophobic fibers without discoloring the fibers.

The inventors have found that antistatic compounds, which give the hydrophobic fibers better antistatic properties, greater durability and better grip Copolymerization of (I) alkoxy-polyalkylene glycol acrylate or alkoxy-polyalkylene glycol methacrylate and (II) diacrylate or Dimethacrylate can be obtained from polyalcohols.

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The component (I) of the antistatic agent according to the invention is a compound of the general formula

! f

CH ₂ . C-CidCgH ^ -ioCjHj ^ -Hj (1)

in which R. H, CH_ or C _O H_ represents j R-Ott, alkoxy radicals with no more than 18 carbon atoms, tfälogerie, alkyl sulfite radicals with no more than 18 carbon atoms, phenoxy radicals and naphthoxy radicals, and 1 and m satisfy the formulas Ö · <1 and O <m <1. Component (I) is produced by reacting lower alkyl monoethers of polyalkylene glycol and acid chlorides of acrylic or methacrylic acid in the presence of pyridine. A value of 1 above 10 and below 100, in particular above 20 and below 70, is important. The antistatic effect of a copolymer with a value of 1 under 10 is insufficient. Even if the value for 1 exceeds 100, the polymerizability is low and the durability is insufficient. The component (1) is hydrophilic and a cause of the antistatic property of the obtained copolymer.

Component (II) is a diacrylate or a dimethacrylate of polyalcohols such as methylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol. The component (II) ensures the three-dimensional structure of the copolymer, while the interlinking component is the resistance to Washing and cleaning improved.

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INSPECTED

The polymerization of components (I) and (II) is carried out by a conventional method, ie the two components are heated in water in the presence of a free radical polymerization catalyst such as. B. potassium, sodium or Aminoniunipersulfat or hydrogen peroxide or a redox polymerization such as. B. a mixture of the aforementioned oxidizing agent as a free radical catalyst and reducing agents such as sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, oxalic acid and iron II sulfate.

It is characteristic of the copolymer according to the invention that it can be obtained by copolymerization in water. If the copolymerization is carried out in organic solvents, z. B. dimethyl sulfoxide, dimethylformamide or dimethylacetamide, so it is necessary to add a dispersant, to distribute the obtained copolymer in the treatment bath. Fibers made this way also have the Disadvantage that the fiber does not have a grip, which is undesirable.

The treatment temperature is determined by the activity of the catalyst used. The copolymerization is carried out in a temperature range from room temperature to 100 C ₁ especially in the temperature range between 30 C and 60 C. It is necessary to prevent gelation in the above-mentioned two-component copolymerization reaction. Therefore, the temperature must be controlled very carefully. The gel formation in this copolymerization system depends on the type of

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Components and the ratio of their composition. The gel formation concentration of the copolymerization system is defined in this application as the smallest concentration, based on the weight of the entire polymerization mixture, which causes gel formation when approximately 20 ecm of a mixture of components (I) and (II) are dissolved in dimethyl sulfoxide and this is 0.2 g sulfuric acid / hour and 0.02 mol azo-bis-isobutylnitrile / hour are added; this reaction mixture is melted into an ampoule with an inner diameter of 18 mm and a length of approximately '- 120 mm and the copolymerization is carried out for 2k hours at 35 ° C. in a rotating heating bath (k revolutions / minute). The gelation concentration of the copolymerization system must be kept in a range of Ik to 30% by weight in order to obtain the copolymer of the present invention, that is, a copolymerization system is very unstable if the gelation concentration is below Ik% and it is difficult to make it economical. Even if the gelation concentration is over 30 % , the obtained copolymer is well soluble in water and hence it is easily removed in cleaning, dyeing and washing. A copolymer produced at a gel formation concentration of Ik to 30 % has the desired three-dimensional structure, is insoluble in water and organic solvents and furthermore has suitable dispersion properties and better adhesive properties to the fiber. As a result, the antistatic properties of textiles treated with such a copolymer have excellent washing and cleaning resistance.

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In particular, a copolymer of greater durability can be obtained from a copolymer system having a gelation concentration of 17 to 27 % .

The copolymer according to the invention can be further improved, if it contains acrylonitrile or vinyl esters of higher alcohols with more than 8 carbon atoms as component (III). Through this the grip and durability of the treated fiber is improved.

A copolymer containing acrylonitrile is also obtained by the above method, and its composition is 5 to 45% based on the total polymer weight. Also, a copolymer containing vinyl esters of higher alcohols is produced in an emulsion copolymerization system, and its composition is 20 to 6 %. The specific viscosity of a copolymer containing acrylonitrile is in the range from 0.3 to 1.0, and the optical transmittance of its one percent disperse solution should be above k5% .

The specific viscosity of the copolymer dispersion is obtained by measuring. The relative viscosity of the dispersion that the Contains copolymers in this amount of 1 percent by weight based on the weight of the dispersion, is in the Ostwald-Viskosiraeter measured at a temperature of 30 C and then calculated the specific viscosity from the relative.

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The optical transmission of the copolymer dispersion is also measured. The copolymer is dispersed in water with a mixture of Nonipol 70 (trademark of Sanyo Chemical Co. in Japan) and Sunmorine ÖT-70 (trademark of Sanyo Chemical Co. in Japan) in a ratio of 6: 1, so that the copolymer and the mixture contained in the dispersion is 0.25 or 0.025 percent by weight based on the weight of the dispersion. The dispersion of the copolymer is introduced in mm W a quartz cell having a width of 10; then the permeability of the dispersion in the cell is measured with a Hitachi-Perkin-Elmer 139 UV-VIS spectrometer.

Suitable vinyl esters for the copolymer according to the invention are Vinyl esters of higher alcohols with more than 8 carbon atoms such as acrylates or methacrylates of octyl, decyl, undecyl, Dodecyl, palmityl or stearyl alcohol.

If there are fewer than 8 carbon atoms, the copolymer obtained has a

^w poorer grip on the synthetic fibers and poorer resistance to washing.

The application of the copolymer according to the invention to the synthetic Fiber is carried out in such a way that one prepares an aqueous dispersion of the copolymer, the synthetic one Immersing the fiber in this dispersion, removing the excess moisture by pressing it out and then drying the fiber, The water dispersion contains 0.1 to 6 percent by weight

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Copolymers based on the weight of the dispersion.

It is desirable that on the textiles that have been dipped and pressed in the copolymer en-Disp er sion, 0.1 to 8 percent by weight of the copolymer based on the weight of the Fiber remain. If the remaining amount of copolymers exceeds 8 percent by weight, an unwanted one occurs Grip of the fiber, or the fibers stick to one another. On the other hand, if the remaining amount is less than 0.1 percent by weight, so the antistatic property is insufficient.

The pressed product should be dried at a temperature of 8o C to 200 C. It is not necessary that the invention Copolymers still need post-treatment after drying because they have a three-dimensional structure * Die Fibers cannot discolor even when heated to high temperatures. According to the method according to the invention can Polyacrylonitrile fibers, polyamide fibers, polyester fibers, polyvinyl alcohol fibers and polypropylene fibers, alone or in admixture with rayon or natural fibers such as Cotton or wool. Particularly suitable synthetic fibers for the process according to the invention are polyacrylonitrile fibers and fibers of acrylonitrile copolymers e.g. B. a copolymer of Acrylonitrile and at least one copolymer component such as methyl acrylatej Methyl methacrylate, sodium salt of sulfonated styrene, sodium methacrylate sulfonate, sodium acrylic sulfonate, 2-methyl-5-vinylpyridine, vinyl chloride and vinylidene chloride.

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These polyacrylonitrile fibers are spun using the wet process, d. H. in an organic solvent such as dimethyl sulfoxide, dirnethylacet amide, dimethylformamide or Acrylonitrile polymers dissolved in sodium thiocyanate are pressed from a spinneret into a Ktmgulationslösung, stretched and then washed with water. This washed fiber is an aquagel with a relatively large internal surface area. The polyacrylonitrile fiber to which the inventive. The method used is said to be an Aquasol with a inner surface area of 35 to 160 m / g. The inner surface area is measured as follows. The fiber is used to solidify their structure frozen by liquid nitrogen and then slowly dried in a vacuum at about -5 C. The dried fiber is then used for measurement by the BET method used, d. H. for the one developed by Brunnaer-Emmett-Teller Method whereby the amount of gas absorbed by the substance is determined.

Substance absorbed nitrogen Cross section of the absorbed molecule 1.62 χ 10 "* ⁹ m ² / molecule Absorption temperature -195.3 ° C

In general, the aquagel has the polyacrylonitrile fiber an internal surface area of 20 to 300 na / g. By drying the swollen acrylonitrile fiber, the fiber structure becomes denser and the inner surface smaller. With surface hardness greater than 16o m / g prepares the diffusion of the antistatic

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1 91 7 A1 O

Polymers in the Paser Difficulty. The durability of the The antistatic effect is then reduced. Fibers with a inner surface below 3 »-5 m / s is enough for practical Application does not work. An advantageous embodiment of the invention Process is in a steam treatment of the polyacrylonitrile laser impregnated with the dispersion at 90 C and to see subsequent drying. The steam treatment causes that the copolymer adheres firmly to the fiber and does not disappear during the spinning and winding of the treated fiber.

The invention is illustrated by means of the following examples.

example 1

Methoxy-polyoxyethylene glycol methacrylate (PEGM) was prepared from 1.2 mol of methacrylic chloride and 1.0 mol of methoxypolyethylene glycol with an average molecular weight of 1,100 in the presence of pyridine as a synthesis catalyst. Polyethylene glycol dimethacrylate (PIiGDM) was produced from 3 moles of methacrylic chloride and 1.0 mole of methoxypolyethylene glycol with an average molecular weight of 1,100 in the presence of sulfuric acid as a synthesis catalyst. The gel formation concentration of the methoxypolyethylene glycol methacrylate was 32 percent by weight, that of the polyethylene glycol dimethacrylate was k percent by weight. From the methoxypolyoxyethylene glycol methacrylate and the polyethylene glycol dimethacrylate 6 mixtures, M. to Mg, were prepared according to Table 1, from which the

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Mixing ratios and gelation concentrations are shown.

Table 1

Mixed
No. PEGM (weight
percent) PEGDM (weight
Percent) Gel formation
concentration
(%) ^M l 100 0 32 ^M 2 96.5 35 26th ^M 3 94 6th 22nd \ 92 8th 19th ^M 5 90 10 16 ^M 6 82 18th 12th

10 parts by weight of acrylonitrile and 90 parts by weight of a mixture according to Table 1 were dissolved in 90 parts by weight of ion-exchanged water, 0.3 part by weight of potassium persulfate and 0.1 part by weight of sodium hydrogen sulfite were added to this solution with stirring at a speed of 200 revolutions / min and the copolymerization was carried out ^ 0 ° C carried out for four hours. The six polymers obtained were given the designations A ₁ to Ag corresponding to the six mixtures M to Mg. For the polymer system that used the mixture Mg, however, I.300 parts by weight of ion-exchanged water were required because the copolymerization system due to the low gelation concentration of the mixture Mg is unstable. the

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Ί 91.74 10

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Gel formation in the copolymerization system using the mixture My, namely proceeds very slowly, so that a satisfactory copolymerization cannot take place.

Then, a polyacrylonitrile type antistatic fiber is included

a thread size of 3 den. by the following procedure. 22 parts by weight of a mixture consisting of 94.5 mol% of acrylonitrile, 5 mol% of the sodium salt of sulfonated styrene, 0.3 part by weight of azo-bis-isobutylnitrile dodecyl mercaptan, 1 part by weight of water and Ο, θ6 parts by weight of dodecyl mercaptan were dissolved in 76 parts by weight of dimethyl sulfoxide and adjusted to pH k with sulfuric acid. This mixture was polymerized with mechanical stirring for 40 hours at a temperature of 50 C. The polymer content of the polymer solution thus obtained was 20.2 percent by weight. This polymer solution was forced through a spinneret with a diameter of 0.07 ^m n> ^u * id and solidified in a 50 percent by weight aqueous solution of dimethyl sulfoxide. The product was stretched six times in a 30 percent strength by weight aqueous dimethyl sulfoxide solution at 98 ° C., and the fibers thus obtained were washed with water. The washed fibers, which are in the aquagel form, were then immersed in the aforementioned five polymer solutions A ₁ to A ₁ . (Copolymer content 0.8 percent by weight), pressed with compression rollers up to 100 % moisture content based on the weight of the fiber and dried the fibers for three minutes at 170 ° C,

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The five kinds of treated acrylonitrile type fiber and the untreated fiber became six knitted products K

processed to K ^ and K ₀ and in an electric wash 5 "

machine washed five times under the following conditions:

Washing liquor

Fluid behavior temperature

Time

3 g / L surfactant (anion active) 1:40
40 ° C

Wash 40 minutes, rinse 5 minutes

The moisture content of the washed knitted product was then adjusted to 40 % relative humidity at 20 ° C. for 72 hours in a conditioning scanner and the static charge caused by friction and the half-life with a test device manufactured by Koa Shokai , measured. The results are summarized in Table 2.

Table 2

knitted
Product No. Monomer
according to no. static
Charge (V) Half-life
time (see) ^K l ^M l 4800 25.0 ^K 2 ^M 2 1900 5.2 S. M ₃ 1500 3.7 H M ₄ 1300 5.5 S. ^W 5 1500 3.2 ^K B - 83OO 30Q «s £ ·

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Fibers which had been treated with a polymer which did not contain a diester of a polyalcohol, for example polyethylene glycol dimethacrylate, were incorporated into the knitted product K _1. The knitted products K ₀ to K_ were treated with the polymers according to the invention which contain methoxypolyoxyethylene glycol methacrylate and polyethylene glycol dimethacrylate. Fibers that had not been subjected to any antistatic treatment were processed for the product K ". ^

Table 2 shows that the static charge and the half-life of the knitted products K _p , K_, K. and K_ are smaller than those of the knitted products K and K _R and thus the first-mentioned products have increased antistatic properties. It is apparent that a copolymer containing polyethylene glycol dimethacrylate as a component has better antistatic properties and durability than a copolymer which does not contain this component.

Example 2

There was methoxy polyethylene glycol methacrylate prepared according to Example 1 mixed with seven different divinyl compounds according to Table 3. Each of the seven mixes M to M _ had a gelation concentration of 22; b.

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Table 3

Mix No. Divinyl compound M ₇ Ethylene glycol dimethacrylate ^M 8 Propylene glycol dimethacrylate ^M 9 Polyethylene glycol dimethacrylate ^M 1O Divinyl sulfone ^M ll Divinyl carbitol ^M 12 Divinyl ketone M ₁₅ Divinylbenzene

In the case of mixtures M_ to M ₁₁ , 90 parts by weight of the mixture and 10 parts by weight of acrylonitrile were dissolved in 900 deionized water.

Each copolymers A_ to A .. corresponding to the mixture Mjj was won by merger O ₈ 5 Gewictot-Stoil © ai persulfate and 0.1 weight Steep

Mixture prepared with stirring ₉ after which every hour at 4-0 C cbpolyiaerisiert iimardeo -

en M Ibis

five

In the case of the 'Mixtures M and M ₁ ', the 90 was GetsjicSatsteiX ©. the

Mixture and 10 parts by weight of acrylonitrile in. 8-3C3 Difsetisyledif021yd dissolved »To iodlsEäi dlojr P © XyESä © E * <3Si eatstandea aas the mixtures M ^ ₂ nmd M ₁ ^ ₃ ιια & ^ άοΐ & umt®T

0.3 parts by weight of azo-bis-isofeutylnitrile 3nag © £ tigt rast 35 StmmäW polymerized at 50 C. The MiseSraag M _Q ustter tjarde separately

009837

Use of dimethyl sulfoxide copolymerized in accordance with the cases M ₁₂ and M ₁ - in order to obtain the polymer A ₁ ^.

The copolymers A7 ^ is A ₁₁ formed a stable dispersion in water. However, the disperse solutions from A ₁₂ to A ₁ ^ were unstable.

The same acrylic fiber as in Example 1 was treated with an aqueous dispersion containing 0.8 percent by weight of each of the copolymers A_biSAA ₁₁ , or this fiber was treated with an aqueous dispersion containing 0.8 percent by weight of each of the copolymers A ₁₂ to Ar, with the addition of 10 percent by weight of Nonipole 7 $ (trademark of Sanyo Chemical Co.) based on the weight of the copolymer treated in the same manner as in Example 1. 8 treated fibers with a thread thickness of 3 denier were obtained.

8 fibers thus obtained were processed into 8 kinds of knitted products. These products were made as in Example 1 washed, and the static and half-life became the static charge of the product measured as in Example 1. The results are shown in Table 4.

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Table 4

knitted
Product No. Monomer
according to no. Solution
middle Static
Charging
(Volt) Half-life
aeit (see) K ₇ . H ₇ - " l800 5.2 ^K 8 M ₈ 1900 7.2 ^K 9 V water 1100 3.5 ^K 10 ^M 1O 45OO
47OO 34
53 ^K 12
^K 13 ^M 12 Dimethyl
sulfoxide 4200
43OO 42
39 ^K 14 ^M 14 2200 4.5 «B. - 83OO 300 <

From table 4 follows:

1. The knitted products K_ »Kg and K„ made with copolymers !! which diacrylate and deoxyethacrylate were treated as monomeric linking components have better antistatic properties than when other divine compounds are used as crosslinking components.

2. The knitted product &", treated with a copolymer en" which has been prepared in water as the solvent for the monomeric component, has a better antistatic property than the product K ₁ . ,. the Dimethylsv & lfoxydi as

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Solvent used.

3. The knitted products K ₁₂ to K ₁ /., Treated with aqueous dispersions of the polymers A ₄₀ to A. ,,, which were copolymerized using dimethyl sulfoxide as the solvent for the monomer components, are not very soft and difficult to handle.

Consequently, diacrylates and methacrylates of polyalcohols will be used as the monoic crosslinking component of the copolymer.
You can also use water as a solvent for the monomers *

Example 3

The mixtures M ₁₁ . to M ₁ ^ were according to the compilation
isa Table 5 »it Methoxypolyosyäthylenglykol-aaethacrylat produced as in example i, whereby the vinyl mosaosaere has a functional group, z. B. N-aaethyl alcohol acrylate (N-MAM) or
Glycidil methacrylate (GMA) ₈ nmu daa Katrimtas as the sulfonated styrene (SSS).

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Table 5

Mix No. component Composition'
(Percentages by weight) «15
^M l6
^M 17
^M 18 PEGM / N-MAM
PEGM / N-MAM / SSS.
PEGM / GMA-SSS
PEGM / PEGDM / AN 85/15
70/10/20
55/10/35
64/6/30

Also Μ. «Is a mixture of methoxy-polyoxyethylene glycol methacrylate, polyethylene glycol dimethacrylate and acrylonitrile (AN) as in Table 5 . dissolved hydrogen sulfite. The solution was copolymerized for k hours at 40 ° C. In the case of the M._ mixture, 1 percent by weight of glycerol monoleate, based on the weight of the mixture, was added to the solution as an emulsifier for glycidil methacrylate. _{The polymers A 1} - to A ₁ Q from the mixtures M were obtained by the method mentioned above
Copolymers A ₄ - and A ^ 5 weight percent potassium persulfate were used as the polymerization catalyst and in the case of copolymers A_ 5 weight percent dimethylaminome thylphenol was used as the catalyst.

received to M.g. In case of

The fiber of poly corresponding to the fiber of Example 1 Acrylonitrile type was made using a 0.8%

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aqueous dispersion of the polymers A ₁ , - to Ag treated according to the method of Example 1. A fiber with a thread size of 3 denier was obtained. Drying temperatures for the dipped fibers were 8o ° C and 15O ⁰ C and times each for 15 Minuren. Four knitted products K ₁₅ to K ₁ Q, which had been made from these fibers, were washed as in Example 1, and the dyeing power, the static charge and the half-life of the static charge of the knitted fabrics were measured. The results are shown in Table 6.

Table 6

fiber
No. Drying;
temperature »-Copoly-
* mer no. degree of
coloring
the be
acted
Fibers , Static
Charging
of the Gewa
shen
knitted
Product
(Volt) Half-life
time (see) ^F 15 A ₁₅ 7.5 3800 17th ^F l6 ^A l6 7.3 4000 20th ^F 17 80 ^Α ίψ 8.4 4200 24 ^F l8 ^A l8 6.8 I5OO 3.7 ^F B 6.2 83ΟΟ 300 ^F 15 ^A 15 17.8 3200 12th ^F l6 ^A l6 17.2 3400 15th ^F 17 150 ^A 17 19.2 28ΟΟ G m
Q / ^F l8 ^A l8 13.9 1800 4.2 ^F B - 13.5 8300 300 <

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The degree of coloration was measured in such a way that the treated fibers were carefully loosened at a thickness of 570 mju and 430 rough subjected to the ref lection measurement in the automatic spectrophotometer according to Shimazu. The difference between "the values" of the reflection measurement is a measure of the color. A greater degree of coloration means greater colorability, and this is consistent with the result which is noticeable to the naked eye.

From this experiment it follows:;

1. In the case of the copolymers A ₁ , - »A ₁ ^ and Α._, prepared by using a vinyl monomer which has a linking component as a copolymer component, it is necessary to treat the selected products at high temperatures, for. Post-treatment, e.g. at 150 ° C, in order to achieve satisfactory resistance to boiling water »washing and cleaning.

2. If the product is treated at such high temperatures, however, accelerate the copolymers ^ A ^ - to k * ~ äxe dyeing of the fibers, which is equivalent to the decomposition Polyäthylengruppe ₉ which is contained in the copolymer. ₃

f- 3 · The polyamide A ₁ Q according to the invention has excellent antistatic properties and resistance to boiling water, to washing and dry cleaning by drying at a relatively low temperature,

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ζ. B. 80 ° C. The reason for this is that the polymer A.Q represents a copolymer with a three-dimensional structure. Consequently, it is not necessary to post-treat at high temperature, so that there is no dyeing of the fiber or there is decomposition of the polyethylene group.

The 'aqueous dispersion of the polymer Ao according to the invention has a much greater stability than the polymers A ₁ to A ₁₇ . The stability of the dispersion is particularly important if one wants to obtain uniform treatment properties over a long period of time. Table 7 shows a comparison for the formation of agglomerates in the dispersion when a 0.1 percent by weight dispersion of the polymers A ₁ to Ag is pumped for 10 days.

Table 7

Copolyaer
No. Pumping over Agglomeration optical through
nonchalance (%) ,,, Λ5, -. ■ 'before
later not educated
educated 88.4
69.2 ^A l6 before
later not educated
educated 87.5
67.3 ^A 17 before
later not educated
educated 75.3
51.8 ^A l8 before
later not educated
not educated 89.2
85.3

The transmittance was determined by looking at light

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ORIQiNAL INSPECTED

of 400 μm , passed through a polymer dispersion (polymer gel 10% by weight), which was found in a 10 mm wide quartz cell'®- b © - and determined the permeability with a Hitachi Perkin-Ellmer 139 UT-VIS spectrophotometer. The smaller the value of the transmittance is ₈ the greater the agglomeration. In Table 8, the B © ~ relationship between the storage time of the above-mentioned dispersion of the polymer A is shown ₁ Q and the antistatic effect "

Table 8.

Storage time (days) Static charge (¥) Half-life
(lake) 0 1500 3 * 7 10 1400 ■ 4.1 " 30th 3 p.m. ^3, e. 100 1500 4.0

s A " ο, seta ·.

Table 8 shows that the dispersion of the is stable and that there is no change ± n in the effect even if the dispersion lagsor time,

B. 100 days long, wrd. -

Example 4

Acrylonitrile (AW), acrylic acid (AA) (AAm) as a copolymeric component

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glycol methacrylate and polyethylene glycol dimethacrylate of Example 1 were added. The mixing ratio is given in Table 9. The 7 mixtures produced are labeled _{M 1} Q to Μ _2ς.

Table 9

Mix No. Components Composition in
Weight percent ^M 19 PEGM / PEGDM 94/6 ^M 20 PEGM / PEGDM / AN 84.6 / 5.4 / 10 ^M 21 PEGM / PE6DM / AN 70.5 / 4.5 / 25 ^M 22 PEGM / PEGDM / AN 56.4 / 3.6 / 4.0 ^M 23 PEGM / PEGDM / AN 42.3 / 2.7 / 55 ^M 24 PEGM / PEGDM / AA 70.5 / 4.5 / 25 ^M 25 PEGM / PEGDM / AAm 70.5 / 4.5 / 25

There were 10 parts by weight of each of these mixtures was dissolved in 90 parts by weight of this solution desalinated water _f 0.3 parts by weight of potassium persulfate and 0.1 parts by weight of sodium hydrogen sulfite was added with stirring and then the solution copolymerized at 40 C for four hours. The result was the copolymers A. _Q to A _o _.

Among the obtained polymers, the particle size of the copolymer A ₂ - was large and its dispersion was unstable. The dispersions of all other copolymers were very stable.

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According to the method described below, fibers of the polyacrylonitrile type with a thread thickness of 3 denier were used. berge = provided. 24 parts by weight of a mixture of an acrylonitrile of 94.6% molar concentration _{s of} a methyl acrylate of 5 % ± ger molar concentration and a sodium aryl sulfonate (SAS) of 0.4% ± ger molar concentration, furthermore 1 weight steij. Water, 0 ₉ 05 parts by weight of dodecyliaerkaptan ₈ 0 _s 01 parts by weight of sulfuric acid and 0 ₅ parts by weight of azo-bis-disaethylvaleronitrile were added to 6 parts by weight of dimethyl sulfoxide and this solution was copolymerized at 50 ° C. for four hours in the recovered copolymer dispersion was 21.7 percent by weight. This copolymer dispersion was pressed through a spinneret with a diameter of 0.07 and coagulated in a 50 percent by weight aqueous solution of diethyl sulfoxide in fiber form. The koagulieri-^ M fiber was in a 30 percent by weight at 92 ° C Dimethylsulfoxydlösung stretched six times and 'then rinsed with water, the rinsed fibers VOES Folyacrylüitriltyp kill then Add. a 0.8% by weight dispersion of copolymers A ^ _Q to A _OK immersed ₉ by Abquetsehwalsen. to z ^ a 10 % liquid content based on the weight of the Fassir ₉ pressed and dried at 170 C for three minutes. The dried fibers were then immersed in an oil bath, crimped by means of a _{crimping machine, dried 9} at 50 ° C. and cut into staples F ₄₀ to F _o of 51 in length. 7 spun threads were made from the acrylic staple fibers F. _{Q to F} Y _4n to Y ₂ - made by 48 ^s . The slope of the staple fibers _s im

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Adhering to each other in the spinning process is shown in Table 10.

Table 10

Fiber no. Copolymer No. Breaking length of the fleece
due to his Ge
weight (cm) ^F 19
^F 20
^F 21
^F 22
^F 23
^F 24
P.
* 25 ^A 19
^A 20.
^A 21
^A 22
^A 23
^A 2k
^A 25 85
126
145
168
190
109
98 P. - 155

The breaking length of the fleece due to its © ewicfetes becomes such measured that a fleece © hue reinforcing Qewefoe 24 hours conditioned for a long time, spreads the kosditicmierte fleece on the floor, brings one end of the fleece between two plates and lifts off the ground in a vertical direction until eias ¥ 11es due its weight breaks off, the height @ from the ground surface up The end of the fleece is called the Brue & Xänge of the fleece.

Table 10 shows, that the. F.

20 ^s

21 '

F _OQ and F "_, the Bsit den ti & ej

and

Polymers A _o _. «A _n ^ uU 21

treated lower than that of the F fibers

_iq ,

00 9 8 37 / 20SS

- 28 -

ORIGINAL INSPECTED

F, and F_ is and that therefore the first-mentioned fibers

24t up

have better spinning properties.

The acrylic fibers were processed into 7 knitted products K to K ₂ _, treated with boiling water for 2 hours and then washed ten times as in Example 1. The antistatic properties of the washed knitted product are shown in Table 1.

Table 11

No. of ge
worked
Product To wash Static on
charge (V) Half-life
(lake) ^K 19 before
later 1500
38OO 2.7
, ^{22: K} 20 before
later 16ΟΟ
1900 3.1
3.9 ^K 21 before
later 1500
16 OO 3.5
3.9 ^K 22 before
nacjtiher 1900
2200 6.7
7.1 :: - · ■ ^K 23 before
later 37ΟΟ
3900 -ti f. - '· ■ - .. ■' ■ '-'
14 ■■ ^K 2k before
after ' I7OO
36ΟΟ -5.2 ..,.; '...
.. 21, -.-- T = -; αα ^K 25 before
later I6OO:
38ΟΟ . 3.9 _ _t .. before 6800 : ■ <

- 29 -

From Table 11 it follows:

1. Copolymers containing acrylonitrile have better stability towards boiling water and when washing as copolymers containing acrylic acid or acrylamide as a copolymer component.

2. The aqueous dispersion of the copolymer A _o _ obtained from a copolymerization system with 55 % acrylonitrile is unstable and its antistatic properties are poor. You should therefore keep the proportion of acrylonitrile below 45 %. Table 12 shows the properties of polyacrylonitrxl fibers F ₀ ", F ₀₁ and F ₀₀ , which are obtained with the inventive

copolymers

and from untreated fibers.

A ₀ , and A _{00 have been} dealt with

Table 12

Fiber no. F.
20th ^F 21 ^F 22 untreated
delt Thread size (d) 2.85 2.83 2.8I 2.83 Titock strength
( _S / d) 3.87 3.59 3.76 3.7I Elongation at break in
dry state (%) 29.2 3O.7 28.7 29.7 Knot enfe sti gke it
(g / d) 2.23 2.20 2.38 2.31 Knot strength
ratio (%) 76 61 63 62 Jfoung module (%) 45.9 45.5 45.6 45.7

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009837/2066

Table 12 clearly shows that the properties of fibers of the polyacrylonitrile type which have been treated with the copolymers according to the invention are almost the same as the properties of untreated fibers. The treated fibers Fpn '^ 21 ^ 22 * ^{unc were} ^ - ⁿ the same manner as the transparent untreated fibers and the dyeability of the treated fibers corresponded to that of the untreated fibers. The copolymers according to the invention accordingly give the fibers of the polyacrylonitrile type excellent antistatic properties and excellent spinnability without having to accept any disadvantage as a result.

Example 5
It became a 65% compound of the general formula

CH ₂ = CC- (OCH ₂ CH ₂ ) ₂₅ -R ₂
0

(wherein R ₁ and R are given in Table 13) with 5 weight percent polyethylene glycol dimethacrylate corresponding to Example 1 and mixed 30 weight percent acrylonitrile and 10 were prepared copolymers A ₂ ~ ^A ^ z = corresponding to Example 4. Fig.

009837/2066

Table 13 ^R l ' ^R 2 Copolymer H OCH ₃ No. radical CH ₃ OCH ₃ ^A 26 CH ₃ OC ₃ H ₇ ^A 27 CH ₃ ^SC 12 ^H 25 ^A 28 CH ₃ N (C ₂ H ₅ ) ₂ ^A 29 CH ₃ - ^o ~ 0 ^A 30 CH ₃ - ⁰ OO ^A 31 CH ₃ _G- ^ S- ^C 8 ^H 17 ^A 32 CH ₃ Cl ^A 33 C ₂ H ₅ OCH A ₃₄ ^A 35

Fibers of the polyacrylonitrile type in the form of the aquagels corresponding to the fibers of Example k were treated with a 10 percent by weight dispersion of these copolymers, and 10 knitted products Kg to K__ were produced. The antistatic properties of these knitted products after washing according to Example 1 are shown in Table 1 ^ t. All polymers A _p / - to A-- according to the invention have excellent antistatic properties.

0 0 9 8 3 7/2066

Table l4

No. of the knitted
Product Static
Charging
(V) Half-life
(sec) ^K 26 16OO 4.5 ^K 27 I5OO 4.3 ^K 28 I6OO 4.8 ^K 29 I7OO 5.6 ^K 3O I8OO 6.2 ^K 31 I7OO 5.8 ^K 32 I7OO 5.8 ^K 33 I8OO 6.3 ^K 34 I6OO 5.3 ^K 35 I6OO 5.6 ^K B 83OO 300

Example 6

8 polymers A _ / - to A., made from mixtures, those made from 5 percent by weight of polyethylene glycol dimeths crylate as in Example 1, 30 percent by weight Acrylonitrile and 65 percent by weight of a compound exist as in the following general Formula shown is:

CEL

= C-CO- (OCH CH ₀ ) - (0CH _Q CHCH_) -OCH,

- 33 -

009837/2 06 6

(The values for 1 and m are given in Table 5 are). Polyacrylonitrile type fibers in the aquagel form of Example 4 were treated as in Example 4 and made into 8 knitted products K "g bis

processed.

Table 15

Copolymer no. 1 m ^A 36 8th 0 ^A 37 15th 0 ^A 38 20th 0 A ₃₉ 50 0 ^A 40 90 0 ^A 4l 150 0 ^A 42 30th 10 ^A 43 30th 20th

Table 16 shows the antistatic properties of these knitted products after washing according to Example 1. It can be seen that the antistatic properties of the copolymers _{A 1 to A. n} are superior to those of the copolyraers A 1 -, - and A.

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009837/2066

Table l6

No. of the knitted fabric
th product Static
Charging
by
Friction (V) Half-life in sec. ^K 36 4000 28 ^K 37 2800 8.5 ^K 38 I6OO 3.5 ^K 39 I700 4.2 Ho 27OO 5-3 St. 3500 7-2 H2 I8OO 4.2 H ₃
^K B 23OO
83OO 5.9
300 <

Example 7

The concentration of a monomer mixture which has the same mixing ratio as A _0n in Example 4 was varied in the manner indicated in Table I7, so that the copolyraeren A

the specific viscosity M / C and the antistatic Property of the knitted product of the acrylic fiber according to Example 4, which is treated with the copolymers and washed became.

- 35 -

until A. _q emerged. Table I7 shows

009837/2066

- 35 Table 17

No. of ge
worked
Product Monomer
concentration
(Wt. %) 0.128 Static
Charging
(V) Half-life
(sec) Hk 3 0.218 48oo 53 H ₅ 5 0.246 3800 36 Ed 7th 0.332 2800 21 H ₇ 10 Ο.567 1800 4.8 Ha 12th I.873 1500 3.7 H ₉ 15th —— 1400 3.2 ^K B - - 8300 300 <

The antistatic property and the resistance of the copolymers A._ to A._ are clearly better than those of the copolymers Au to A./-, where the monomer concentration is below 10; o during the copolymerization. However that is practical value of the copolymer A ^, small because a solution this copolymer easily gelled and the treated acrylic fiber tends to get around the spinning drum frequently during the spinning process to wind up.

Example 8

This example shows the relationship between copolyrnei * en content the antistatic copolymer dispersion and the antistatic property of fibers made with this dispersion have been treated.

- 36 -

009837/2066

. 36 - 1 91741

Fibers were treated polyacrylonitrile type of the type used in Example 4 according to Example 4 with 6 dispersions L_ _o to l__ as indicated in Table l8. The fibers contained the same copolymer as the copolymer A ₂₁ used in Example 4. Table 18 shows the antistatic property of the knitted products and the amount of copolymers adhered to the treated fibers.

Table l8

Dispersion
No. Content of
Copolymers
in the Be
action
dispersion
(96) Adherent
lot
(96) Static
Charging
(V) Half
worth
Time
(sec) ^L 5O 0.1 0.09 4200 58 ^L 51 0.4 0.21 2400 12th ^L 52 0.8 0.32 15 00 3.5 ^L 53 1.5 0.6 1200 3.2 ^L 54 3.0 1.2 8oo 3.0 ^L 55 5.0 "2.6 6oo 2.8

It can be seen from Table 18 that the antistatic property of the knitted products, the greater the number of copolymers that adhere. .

The amount of carbon polymers retained on the fibers treated with the dispersions L _{1 and L was 1.2 and}

'■ * ■■ - ■''^{; ί} ' * - 37 -

3.7- / 2

2.6 percent by weight based on the weight of the fiber. If the antistatic properties and durability of the fibers were satisfactory, the spinnability was poor. The amount of copolymer A _{1 recorded} should be in the range between 0.25 and 1 percent by weight based on the weight of the fiber.

Example 9

Acrylic fibers were washed and dried as in Example 4 and with the dispersions L- to L- accordingly Example 8 treated. In Table 19 are the amount of copolymers adhered to the treated fibers and the antistatic property of the knitted products, which accordingly Example 1 made from the treated fibers

registered

and have been washed V The table shows that the antistatic property improves, as the amount of the copolymer Ap i adhered to the dried fiber increases. The held crowd should be over 0.25 percent by weight based on the weight of the fiber.

Table 19

Adhesive amount (%) Static charge
(V) Half-life
(sec) 0.12 4500 52 0.30 2300 12th 0.8 1400 3.2 1.2 1000 3.2 2.5 800 3.0

009837/2066

Example 10

20 parts by weight of a mixture M, prepared by adding methoxy-polyoxyethylene glycol methacrylate and polyethylene glycol dimethacrylate according to Example 1 and octyl acrylate in a ratio of 60: 5: 35, were dissolved in 90 parts by weight of water, the 0.15 part by weight of Sunmorine OT-70 (Trademark of Sanyo Chemical Co.) and 0.85 parts by weight of Nonipole 75 (trademark of Sanyo Chemical Co.). The gelation concentration of this mixture was 18 %. This solution was used as a polymerization catalyst 0.2? Parts by weight of KalMipersulfate and 0.1 parts by weight of sodium hydrogen sulfide were added. The polymerization system was kept at a temperature of 55 ° C. for 6 hours. The obtained dispersion of the copolymer A-. was very stable.

The optical transmittance of this copolymer was 80 %. The acrylonitrile type fibers in the form of an aquagel according to example 4 were treated according to this example with a 1% strength dispersion of this copolymer.

Table 20 gives the antistatic properties of the recognize treated acrylonitrile fibers.

-, 39 .-

0 0 9 837/2 0S6,

Table 20

Polymer Static Charging Half-life after ^A 50 before the after before the Dry ——— Dry Dry Dry cleaning fiber cleaning cleaning cleaning 4.2 ^F 5O 1800 1900 3-7 3 ^ 0 ^F B 8000 8100 320

For dry cleaning, the samples were subjected to the following 10 times Conditions cleaned. Approximately 2 grams of the knitted material was placed in a container of a testing machine (Laund-er-meter testing machine) given a capacity of over 450 ecm. 20 steel balls were added with a diameter of 0.64 mm and a mixture Made of 100 ecm perchlorethylene at a temperature of 30 - 2 C, a fraction of a non-ionic surface-active Agent, one gram of an anionic agent and 0.1 ecm of water. The container was tightly closed, attached to a rotating shaft and rotated at 42-2 revolutions per minute for 3 minutes. Then were the samples taken out, rinsed with 100 ecm perchlorethylene, the liquid removed and placed in a dryer dried at a temperature below 6o C.

As can be seen from Table 20, the copolymer A is excellent in antistatic property and durability during dry cleaning.

- 40 -

009837/2066

- ko -

Example 11

191741G

A spun yarn of kO was produced from a mixture of 65 percent by weight of a polyester fiber and 35 percent by weight of a cotton fiber. The mixed yarn was immersed in a dispersion which contained 1 percent by weight of copolymer A "according to Example 1. The humidity _w excess was removed in a way that 100 weight percent of the dispersion remained based on the weight of yarn in the yarn. The yarn was dried for 3 minutes at a t _e mperature of 170 ° C. The amount of copolymer A retained by the yarn was approximately 1 percent by weight based on the weight of the yarn. The static charge and the half-life of the treated and untreated yarn were measured. The results are recorded in Table 21.

Table 21

yarn Static charge
(V) Half-life
(sec) Treated yarn
Untreated yarn 45O
83O0 < 2.8
300 <*.

As can be seen from Table 21, the inventive Copolymers in polyester fibers have excellent antistatic properties Effect on.

- 41 -

009837/2066

Example 12

It was a nylon fabric in an aqueous dispersion with a content of 1 percent by weight of the copolymer A " immersed in accordance with Example 1, the moisture is removed to such an extent that 50 percent by weight of the dispersion is based to the weight of the fabric, left on the fabric and dried at 150 ° C for 10 minutes. The ones from the nylon fabric the amount of the copolymer A retained was 0.5 percent by weight, based on the weight of the fabric. There were static charges and the half-life of static Loads of treated and untreated fabric were measured and the results recorded in Table 22.

Table 22

tissue Static charge
(V) Half-life
(sec) Treated tissue
Untreated fabric 400
8300 3.0
300

From Table 22 it can be seen that the copolymer A_ a has excellent antistatic properties on nylon fabrics.

009 8 37/206 6

Claims (12)

69/8704 claims 1. Copolymeric product obtained by copolymerizing a mixture in water having the following composition has, is obtained: (I) monoester of the formula R 0 ¹ a
CH ₂ = CCO- (CH ₂ CH ₂ O ^ - (CH ₂ CHCH ₃ O) _1n -U ₂ in which R is H, CH “or C _Q II, R is an OH group, alkoxy radicals with not more than 18 carbon atoms, a halogen, alkyl sulfide radicals with not more than 18 carbon atoms, mono- and Di-alkylamines with no more than 18 carbon atoms, phenoxy radicals, naphtoxy radicals or their derivatives and 1 and m mean the formulas 10 <1 and 0 <m <1 are sufficient, and (II) Diacrylates or dimethacrylates of polyalcohols. - "2 - τ 009837/2066 2. Product according to claim 1, in which the Gelbildungskonzentration the mixture is 14 to 30 ° / o. 3. Product according to claim 1, in which the mixture as further Component contains acrylonitrile or vinyl esters of alkyl alcohols with more than 8 carbon atoms. 4. Product according to claim 3, in which the component makes up 5 to 45 percent by weight of acrylonitrile, based on the total weight Λ of the mixture. 5 · Product according to claim 3j in which the component 20 to 6θ weight percent vinyl ester, based on the total weight of the Mixture counts. 6. Product according to claim 4, in which the copolymer has a specific Has a viscosity of 0.3 to 1.0. 7 · Product according to claim 5 »in which a 0.25% dispersion of the copolyraeren has an optical transmission of over 45 % . 8. Electrostatic Reduction Process of hydrophobic synthetic fibers, characterized in that the fibers in a An aqueous liquid which contains at least one copolymer according to claim 1, dips the excess moisture from the The fiber is removed and the fiber dries. 009837/2066 - 5 - 9. The method according to claim 8, characterized by dipping a polyacrylonitrile fiber into the liquid. 10. The method according to claim 9 »characterized that the polyacrylonitrile fiber is used in the form of an aquagel. 11. The method according to claim 8, characterized in that that the fiber is steamed to over 90 C. 12. Hydrophobic synthetic fiber in which at least one copolymer according to claim 1 in an amount of 0.1 to 8.0 percent by weight, based on the weight of the fiber. 13 · Hydrophobic synthetic fiber according to claim 12, in which the copolymer in an amount of 0.2 to 2.0 percent by weight, based on the weight of the fiber. Ik . Hydrophobic synthetic fiber according to Claim 12, characterized in that it is a polyacrylonitrile fiber. 009837/2066