DE2242914A1 - DURABLE ANTISTATIC AGENT, METHOD FOR ITS MANUFACTURING AND APPLICATION FOR TREATMENT OF FIBERS - Google Patents

Description

Permanent antistatic agent, process for its manufacture and use for treatment of fibers

The invention "relates to a novel antistatic agent which is soluble in an organic solvent and with which one has permanent antistatic properties with high resistance Transferring washing and dry cleaning processes to hydrophobic fibers can made of polymers such as polyester, polyacrylic, polyamide, polyvinyl chloride, polyethylene and polypropylene polymers, exist, as well as on fiber structures, such as cloths and knitwear, which consist of such fibers, if these fibers or fiber structure an organic solvent system can be treated with it.

The invention also relates to hydrophobic lasers and Fa serge structures, which have a permanent antistatic property, as well as a method for the production of such fibers and Fa serge structure.

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Hydrophobic fibers and fiber structures made from the above-mentioned fibers have excellent properties in terms of their strength and chemical resistance. However, since they are hydrophobic, they have a large volume resistivity and therefore tend to be charged to a remarkably high level, even with the slightest jolt, which causes a wide variety of electrostatic disadvantages.

These disadvantages not only hinder normal operation when carrying out the process steps for the production of Textile goods made from textile fibers, e.g. for reeling and twisting, spinning, raising the warp, knitting and weaving, Sewing, etc., but also cause a decrease in quality of the end product and various disturbances such as stains on the end product due to dust absorption, and feeling uncomfortable for the human body.

Various methods have been proposed to overcome the electrostatic drawbacks of and from such fibers to fix existing fiber structures. So are for example Process known in which a material with antistatic properties is added to the fiber-forming polymeric substance so that it is copolymerized or mixed with the polymeric substance (e.g., Japanese Patent Publication No. 24143/1971), and processes in which a material with antistatic properties on the fibers or the fiber structure (for example, Japanese Patent Publication No. 9849/1964, Japanese Patent Publication No. 2292o / 1971 and U.S. Patent No. 2,729,577).

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The first method, however, has the disadvantage that the minor Dispersibility of the antistatic agent causes yarn breakage. There are knots during the lard spinning process or the quality is degraded to the extent that there is a decrease in strength and elasticity. In addition, due to the thermal deterioration that occurs in lard spinning, the dispersion in daa. Coagulating bath only very specific types of antistatic agents are used in wet spinning, etc.

On the other hand, the last procedure is just a temporary antistatic treatment method, in which the antistatic effect, since the antistatic agent is removed upon vashing, is gradually decreased or is completely lost, which is not only disadvantageous in that the feel of the Paser structure is worse but the antistatic effect also has no durability.

Furthermore, use conventional methods of antistatic treatment of fiber structures often emulsions more antistatic Means to which an emulsifier is added, so that here too, as already mentioned above, there is no lasting effect given is. Accordingly, they cannot be called permanent antistatic treatments. Finally could the same applies to conventional antistatic agents used in an aqueous medium or system

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with a relatively low HLB in a solvent system use because they are soluble in the solvent. But they were insufficient in terms of durability.

Recently, processes for the treatment of hydrophobic fiber structures, who use an organic solvent that is better than the conventional treatment methods in which water is used as a medium, attracts attention because it is more effective and brings economic benefit, and also because sewage pollution posed a social problem. Among the conventional anti-static However, no effective and permanent means can be found that is used in an organic solvent system can be.

The present invention is the result of intensive research in search of hydrophobic fibers and fiber structures, that have excellent, long-lasting antistatic properties and also feel good.

In the description and the claims, the term "fiber structure" stands for rayon, long threads, woven textiles, knitted textiles, nonwovens, wadding and the like.

The main object underlying the present invention is to provide an antistatic agent that is in one organic solvent is soluble and forms a stable solution and that has a high, high resistance against washing and dry cleaning if hydrophobic fibers or fiber structures are treated with them. ... / 5

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Another object of the invention is to create fibers and fiber structures that have permanent antistatic properties and also feel good.

Furthermore, the invention is intended to provide a process for the simple and, in an industrial context, economical production of JFibers and Ifaser fabric are created that are permanent antistatic Have properties and also feel good.

The problems outlined above can be avoided according to the invention solved that as the permanent antistatic agent used in an organic solvent system, a complex one Compound consisting of a polyvinyl derivative is used, which has a quaternary ammonium group in its side chain and which has a counter anion of a particular surface-active one Agent or an amphoteric surfactant, as described in more detail below, derived will. When a saser structure with a cationic polymer is treated as an antistatic agent, it is generally hard to the touch. In the antistatic agents according to the invention however, a desirable soft feel is imparted to the textile material. This is one of the most characteristic Features of the invention.

The permanent antistatic agent for the solvent system according to the invention contains a complex compound consisting of a polyvinyl derivative having a quaternary ammonium group exists in its side chain, the counteranion of which has been replaced by at least one surface-active compound consisting of anionic surfactants containing 2 to 8 ethylene oxide units contain, from ester-bonded sulfonates, alkyl

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amidocarboxylic acid salts or amphoteric surfactants of the carboxylic acid type.

Furthermore, with the invention, hydrophobic fibers and fibers - structures with a permanent antistatic property created, which contain 0.1 to 10 wt .- # of a complex compound, those made from a polyvinyl derivative with a quaternary ammonium group exists in its side chain, the counteranion having been replaced by at least one surface-active compound, those from anionic surface-active agents with a content of 2 to 8 ethylene oxide units, ester-linked sulfonates, Alkylamidocarboxylic acid salts or amphoteric surfactants of the carboxylic acid type.

Finally, the invention encompasses the treatment of a hydrophobic one fiber structure with an organic solvent solution, consisting of from 0.05 to 10% by weight of a complex compound consisting of a polyvinyl derivative with a quaternary ammonium group consists in its side chain, the counter-anion of which is formed by a surface-active compound of anionic surface-active agents with a content of 3 to 8 ethylene oxide units, ester-linked Sulfonates, alkylamidocarboxylic acid salts and / or amphoteric surfactants of the carboxylic acid type is, o, o5 to 2o wt .-? 6 alcohols and more than 70 wt .- ifr an organic solvent, consisting of hydrocarbons, halogenated hydrocarbons, ethers, ketones and / or esters, the weight ratio of the alcohols to the complex compounds being more than 0.2: 1.

The polyvinyl derivatives with quaternary ammonium groups in their Side chains which are used according to the invention are obtained

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"For example, through the following procedures:

(1) A method in which a vinyl monomer with at least a tertiary amine residue in the molecule is homopolymerized is or by this is copolymerized with another copolymerized vinyl monomer, whereupon the resulting polymers by a suitable quaternizing agent is quaternized, or

(2) a method in which a vinyl monomer with at least a quaternary ammonium group in the molecule is homopolymerized or by this being copolymerizable with another Vinyl monomers is copolymerized. '

The vinyl monomers with at least one tertiary mini residue in the molecule are represented by the following general formula :

CH-.

CH ₂

GOOCH ₂ GH IT

The vinyl monomers with at least one quaternary ammonium group in the molecule are represented by the following general formula:

OH ₂ = O

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in which R-, Hp and R, a methyl or ethyl group and X represent a halogen, methosulfate or ethosulfate.

The "other vinyl copolymerizable monomers" mentioned above are represented by the following general formula:

- C

^B 5

in which R. and R, - vinyl residues and, preferably, R ^ is hydrogen or methyl and R ₁ - represent CN or -O ₆ H ₅ - an alkoxycarbonyl group, alkoxy group, -COUH _2, -COOH,.

Particularly preferred copolymerizable vinyl monomers are Acrylic acid, acrylic esters, acrylonitrile, styrene and acrylamides.

In the method referred to in (1) above, conventional Quaternia agents such as dimethyl sulfate, diethyl sulfate, Methyl halides and ethyl halides for quaternizing the tertiary Amides can be used.

The molar ratio of the vinyl monomer with a tertiary amine residue or the vinyl monomer containing a quaternary ammonium group to the other copolymerizable vinyl monomers is expediently 1: 0-1.

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The complex "compound of the present invention includes the above mentioned polyvinyl derivative with quaternary ammonium groups in the side chains, but the counteranion by a particular anionic or amphoteric surfactant is replaced.

As a particular anionic surfactant, may be those with a content of 2 to 8 ethylene oxide units (preferably 3 to 5 ethylene oxide units), ester-linked sulfonates and / or alkylamidocarboxylic acid salts can be used.

Besides, the particular amphoteric surfactants are those of the carboxylic acid type.

As an example of these surface active agents the following compounds "can be mentioned; Natriumdioxyäthylendodecyläthersulfat, Natriumtrioxyäthylendodecyläthersulfat, Natriumtrioxyäthylen-n-nonylphenyläthersulf at, sodium p entaoxyäthylendodecyläthersulfat, Hatriumoctaoxyäthylen-n-nonylphenyläthersulf at, ITatriumtrioxyäthylendodecyläthermonophosphat, liatriumtrioxyäthyl en-n-nonylphenyläthermonopho sphat, Uatriumtrioxyäthylendodecyläthercarboxymethylat, Fatriumtrioxyäthylenn-nony ! phenyl ätherc _{arboxymethylat?} liatriumtri oxyäthyl en-nnonylphenyläther-ß-carboxyäthylat, ITatriumdioctylsuccinatmonosulfonat, Ii-methyl] Sr (sodium carboxymethyl) lauroamid _$ liatrium-Ii-lauroyl glutamate, sodium 2-0arboxyäthyldodecylamin _$ Natriumcarboxymethyidodecylamin ₉ di (natrinmcarboxymethyl) dodecylamine and di (sodium-2-carboxymethoxyeth2rl) dodecylamine.o

The antistatic agent of the present invention, namely the above mentioned complex connection, is applied to the textile material

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(upinn- or woven fabrics) in an amount of o, 1 to 1o wt .-%, preferably o, 2 to 3 wt .-%, most preferably ο, 3 to 1 _t oGew .-%, is applied. If the applied amount is less than o, 1 wt -.% By, the antistatic effect is insufficient, while if the amount 1o weight - exceeds%, the finished textile fabric feels noticeably worse, although the antistatic effect is further improved. .

The hydrophobic fibers that can be treated according to the invention include polyesters, polyacrylonitrile, polyamides, polyvinyl chloride, Polyethylene and polypropylene, although polyester and polyacrylonitrile are preferred. In addition, it can the fiber structures treated according to the invention (woven fabrics, Knitted fabrics, etc.) are rayon, endless threads, cloth, woven goods, knitted goods, nonwovens, wadding, etc. which have more than 5% by weight of the hydrophobic fibers mentioned.

Applying the antistatic agent (complex compound) on the fibers or fiber structure to be treated, should be carried out using an organic solvent as the medium will.

The concentration of the complex compound in the organic solvent solution should be in the range from 0.05 to 10% by weight, preferably 0.2 to 3% by weight. In particular, the range from 0.3 to 1.0% by weight is preferred. In the event that the concentration of the antistatic agent is less than o, o5 wt.% ™, it is impossible to apply the required amount of the complex compound uniformly on the textile material,

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while, moreover, the manufacturing efficiency increases worsened. On the other hand, when the concentration is 1o wt% exceeds, uniform application of the antistatic agent is impossible due to the increase in viscosity of the Solvents and sticky substances (called gums) that Adhere to the machines and the textile material, which means that both the product quality and the processability are noticeable be worsened.

Alcohols which can be used according to the invention are, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, Isoamyl alcohol, n-octyl alcohol, benzyl alcohol, o-chlorophenol, m-Gresol and n-Hexyl alcohol are possible. Ethyl alcohol and isopropyl alcohol are particularly suitable. The amount of alcohols present in the organic solvent solution should be in the range of 0.05 to 20% by weight, preferably 0.2 to 6% by weight and most preferably in the range from 0.3 to 2% by weight. Also, the crowd should of the alcohols used at least 0.2 parts by weight, based on 1 part by weight of the antistatic agent (complex Verbiodg.), be, but the amount is preferably 0.5 to 3 ° parts by weight and particularly preferably 1 to 20 parts by weight per part by weight of the complex connection. For the IPaIl that the alcohol concentration is less than 0.05 wt .-%, the Preparation of the solution of the antistatic agent difficult, while in the event that 20 wt .-% are exceeded, one Deterioration in product quality, in particular discoloration of the product, is caused. Eventually it will difficult to dissolve the antistatic agent in the solvent solution when the ratio of the amount of alcohol to that The amount of the complex compound is less than 0.2: 1.

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Hydrocarbons can be used as organic solvents such as η-hexane, cyclohexane, benzene and toluene, halogenated hydrocarbons such as methyl chloride, Methylene chloride, chloroform, carbon tetrachloride, methyl chloroform, dichloroethane, trichlorethylene, tetrachloroethane, perchlorethylene, Dichlorobenzene and trichlorobenzene; Ethers such as diethyl ether, methyl ethyl ether and ethyl propyl ether ketones such as acetone and Methyläthylketonj esters such as ethyl acetate, methyl acetate and Butyl acetate. Halogenated hydrocarbons, in particular methyl chloroform, trichlorethylene and perchlorethylene, are preferred. The organic solvent should be used in a concentration of at least 7% by weight, however the concentration is preferably in the range from 92 to 99 »6% by weight and particularly preferably in the range from 97 to 99.4% by weight. When the concentration of the organic solvent is less than 70% by weight, the alcohol concentration increases so strong that a deterioration in the product quality, in particular a discoloration of the product, can be caused.

The organic solvent solution of the antistatic agent (i.e. complex compound) can normally be prepared by swelling and dissolving the complex compound in a predetermined weight ratio of alcohols, whereupon then the solution thus obtained is dissolved in the organic solvent.

The organic solvent solution of the complex compound thus obtained can be applied to the fiber structure by any means conventional methods such as dipping, wetting, coating or spraying can be applied. Generally suitable wetting and covering for woven cloths while

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dipping, spraying and wetting is suitable for knitwear. Finally, threads and ropes are best immersed or sprayed o

The amount of organic applied to the fiber structure Solvent solution depends on the concentration of the solution, the type of material to be treated and the amount of material to be applied complex connection, but for example when a woven iDuch is treated by the immersion process is, the liquid is squeezed out, so that the solution 3o to 150% by weight, based on the luch before the treatment, by the organic solvent solution. The material to be treated should preferably be previously treated with the organic Solvent are washed out because such a pretreatment ensures uniform adhesion of the antistatic Means supports and the resistance of the antistatic properties is improved.

The fiber structure treated by the antistatic agent according to the invention can be used as it is as the end product, while it can, however, also be subjected to a further hardening treatment. In addition, if the fiber structure is to be treated with a melamine resin, the melamine resin can be used at the same time as the organic solvent solution according to the invention, which enables a special resin finishing treatment to be omitted. If concomitant melamine resin treatment is carried out _s Can Be increases the durability of the antistatic effect @ n, © that the antistatic property is reduced in © "

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The inventive method can be used to achieve an excellent Effect can be carried out at room temperature while however, in general, the durability can be further increased if the fiber structure is subjected to a heat treatment is after the organic solvent solution on the fiber structure applied and the solvent removed. The temperature of the heat treatment depends on the type is the fiber structure, but it is generally in the range. from 60 to 2I0 C, while the treatment duration 10 seconds to 2o minutes. In particular, the range from Ho to 19o G is preferable. The heat treatment is for example for polyesters at a temperature of 15o to 2oo ° 0 and at Polyacrylonitriles carried out at 11o to 16o ° C.

In the process to be treated according to the "method according to the invention" Fiber structure can be yarn-dyed or piece-dyed goods as well also trade cleaned and bleached goods. In addition, finished goods such as sweaters and blouses can also be treated.

In the method according to the invention, wetting agents or penetrants, Stabilizers and the like are used, such as dialkyl sulfosuccinates and alkyl phosphates are preferably used to increase the solvent stability of the organic solvent solution. aside from that Plasticizers and other types of antistatic agents can be used together if deemed necessary.

The fibers and fiber structure obtained in this way have an excellent antistatic effect and, in particular, remarkably improved durability, as compared with the commonly available products, which is why the anti-

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static effect of the obtained fibers or 3? aser structure not is reduced by washing. In addition, with a simultaneous Melamine resin treatment the resistance of the antistatic Effect in addition to the effect of the resin finish continues to increase. Finally, there will also be color fastness not diminished by rubbing, and the occurrence of water stains can be prevented.

The invention is to be explained in more detail below on the basis of exemplary embodiments.

example 1

Production of poly (2-methacryloyloxyäth.Yldimeth.Tläthylammoniumäthosulfat) (hereinafter referred to as "homopolymer A") In a 15 liter four-neck bottle, which is provided with a Dimroth condenser, a thermometer, a dropping funnel and an Auaäbrömleiter, 1o88 g ( 7 mol) of 2-dimethylaminoethyl methacrylate introduced. Then 1078 g (7 moles) of diethyl sulfate are added dropwise over a period of 1.5 hours, the heat generation being controlled so that the temperature is kept below 50 ° C. After the exothermic reaction has ended, the mixture becomes 30 minutes stirred at 50 ° in air to complete the quaternization reaction. Then 8191 g of water are added, whereupon the aqueous solution is obtained. After the air in the system has been completely replaced by nitrogen, a solution of 17.4 g of potassium persulfate in 500 g of water is added to the mixture, while the whole is allowed to react at 50 ° C. for 7 hours with stirring. The conversion was 96.3% while the viscosity of the solution obtained was 368 cp. was (2o% aqueous solution at 3o C).

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Example 2

Preparation of a complex compound from the in Example 1 obtained Homopol.ymeren A and sodium trioxyethylene-n-nonylphenyl ether sulfate

117 g sodium trioxyethylene-n-nonylphenyl ether sulfate (25% aqueous solution) were dropwise 100 g of an aqueous solution of the homopolymer A (20% solution) with vigorous Stir added. A precipitate forms immediately with the start of the addition, but regardless of the precipitate the addition and stirring are continued. When the additions are complete, the reaction is at room temperature continued an additional 30 to 60 minutes to complete the reaction. The precipitate is collected by filtration collected under a reduced pressure, rinsed with water, in an amount 2 to J times that of the precipitate makes up, washed several times and dried at 60 ° C under reduced pressure overnight, whereupon 39 g of one white, solid product is obtained (yield 98.3%).

Example 5

Manufacture; a complex compound of homopolymer A and sodium trioxyethylene dodecyl ether sulfate. 100 g of sodium trioxyethylene dodecyl ether sulfate (25% strength aqueous solution) are added dropwise to 100 g of a 20% strength aqueous solution of homopolymer A with vigorous stirring. When the addition begins, a precipitate forms. After the same treatment steps as in Example 8, 36 g of a matt, yellowish-brown, solid product are obtained (yield 96%).

Example 4

Production of a complex compound from homopolymer A and sodium pentaoxyethylene n-nonylphenyl ether monophosphonate

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"loo g of a 20% strength aqueous solution of homopolymer A were 137 6 • Sodium pentaoxyethylene n-nonylphenyl ether monophosphonate (25% aqueous solution) added dropwise with vigorous stirring. Following the same process steps as in Example 2 40 g of a white, solid product are obtained (yield

Example 5

Making a complex Compound from the homopolymer A

and sodium dioctyl succinate sulfonate

100 g of a 20% aqueous solution of homopolymer A were used 115 g sodium dioctyl succinate sulfonate (25% aqueous solution) added dropwise with vigorous stirring. Following the same process steps as in Example 2, 37 g of one are obtained light brown, resinous, solid product (yield 96.7%)

Example 6

Production of a copolymer from styrene and 2-methaoryloyloxyethyldimethylethylammonium ethosulfate (hereinafter referred to as "Copolymer B" is referred to)

In a 2 liter four-necked bottle equipped with a Dimroth condenser, a CD thermometer, a dropping funnel and a discharge line, 104 g (1 mol) of 2-dimethylamine ethyl methacrylate are dissolved in 559 g of dioxane. Replacing the air of the system with nitrogen , a solution of 1.3 g of azo-bis-isobutylnitrile in 50 g of dioxane was added. After a polymerization reaction of 5o ° for 1 hour, the mixture became a solution of 3 S azo-bis-isobutylnitrile in 50 g dioxane further added and polymerization was continued for 15 hours at 5o ° 0 continuing Hach the completion of the polymerization, the mixture 154- S (1 mol) of diethyl sulfate was added and the temperature was raised to 80 ⁰ G to cause the Quaternisierungsrealstion "It turned Precipitation occurred immediately and the Beaktioa continued for another hour o ο ο β / 18

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After the quaternization reaction was complete, the i) ioxane distilled off under a reduced pressure and the residue dissolved in water, whereupon 234-O 6 of a 17.7% viscous, milky, aqueous solution received.

Example 7

Preparation of a complex compound from the copolymer B obtained in Example 6 and sodium dioctyl succinate sulfonate 100 g of a 7.7% strength aqueous solution of the copolymer B were added dropwise to 76 g of a 25% strength aqueous sodium dioctyl succinate sulfonate solution with vigorous stirring at room temperature. After the addition was completed, stirring was continued at room temperature for an additional hour to complete the precipitate, after which the resulting precipitate was collected by filtration. The filtered precipitate was washed thoroughly with water and washed at 6 ° C. under a reduced pressure overnight, whereupon 27 g of a white solid were obtained (yield 89 _t %).

Example 8

Producing a complex compound of the copolymers B and Natriumpentaoxyäthylenn-nonylphenylätherphosphat 1oo grams of a 17t7 # »ig ^en aqueous solution of the copolymers B were 91 | 5 g of a 25% aqueous solution of Natriumpentaoxyäthylenn-nonylphenylätherphosphat dropwise with vigorous stirring at room temperature added. Following the same procedure as in Example 7, 33 g of a pale yellow, solid substance were obtained (yield 96.5%).

Example 9

Production of a complex compound from the copolymer n B

and sodium trioxyethylene n-nonylphenyl ether sulfate

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By adding Natriumtrioxyäthylen-n-nonylphenyläthersulfat to the aqueous copolymer B solution _s in the same manner as in Example 7 "was obtained a light yellow solid (yield 38%).

Example "Io

Preparation of a copolymer from acrylonitrile and 2-methacryloylpxyäthyldimethyläthylammoniumäthosulfat (hereinafter referred to as "Copolymer O" is designated)

In a 5-LItCr-S ¹ IaSChC, similar to that used in Example 6, 159 g (3 mol) of acrylonitrile and 311 g (1 mol) of 2-methacryloyloxyethyldimethylethylammonium ethosulfate are dissolved in 4073 g of water and the air within the reaction system is completely replaced by nitrogen . Then, a solution of 4.7 g of potassium persulfate in 1oo grams of water and subsequent thereto is added a solution of 1.8 g of sodium bisulfite in water 5o g of the mixture at 25 ⁰ G, and the mixture is stirred at 25 ° G for 13 hours to complete the polymerization. Part of the resulting polymer f degree of polymerization> 95%, viscosity of the solution = 7-4 cp. (10% aqueous solution at 30 ° C.) is taken, whereupon the water is removed thoroughly and the nitrogen content in the residue is determined by the Kjeldahl method. The nitrogen content is 5-69%. The result is believed that the ratio of the acrylonitrile monomer to the quaternary salt monomer in the copolymer is about 0.336 moles to the diol.

Example 11 Production of a copolymer from acrylonitrile and 2-methacryloyl

oxyäthyldimethyläthylainmoniumethosulfat (hereinafter referred to as

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"Copolymers * 3>" is called) and quaternization: des Copolymers D

159 g (3 mol) of acrylonitrile and 157 S (1 mol) of 2-dimethylamine ethyl methacrylate are dissolved in 274-2.4 g of dioxane and the air in the reaction system is thoroughly replaced by nitrogen. A solution of 0.316 g of azo-bis-isobutylnitrile in dioxane is then added to the mixture, and the polymerization is carried out at 50.degree. A solution of 0.316 g of azo-bis-isobutylnitrile in 20 g of dioxane is added every 10, 20, 30 and 4ό hours. The polymerization is complete after 50 hours. The conversion is 93.6% and 6] dioxane "°» ^ ⁸ * ^{A part of the} polymer thus obtained is removed, whereupon the water is removed thoroughly and the nitrogen content in the residue is determined by the Kjeldahl method

The nitrogen content is 10.77 ° / ° * From the result it is concluded that the ratio of acrylonitrile to 2-dimethylamine ethyl methacrylate in the copolymer is about 0.34-9 mol to 1 mol.

14-6 g of diethyl sulfate are added to 3 kg of the aqueous solution described above Solution of the polymer is added and the temperature is raised to 8o C to effect the quaternization. It educates a precipitate immediately. The reaction is continued at .80 O for 1 hour. Thereupon the dioxane is reduced Pressure is distilled off and the residue is dissolved in water, whereupon an aqueous solution of the quaternized Contains copolymers. The viscosity of the solution is 11.3 cp. (1o? 6 aqueous solution at 3o G).

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Example 12 Preparation of a complex compound from the in Example 1o

obtained copolymers Q and sodium trioxyäthrsrlendodecyläther-

sulfate

The quaternary ammonium group of the copolymer 0 is left with an equimolar amount of sodium trioxyethylendodecyl ether sulfate react in the same way as in Example 3, to which one

a solid product is obtained (yield 95%)

Example 13 Production of a complex connection from the according to the example

produced and quaternized copolymers D and sodium

trioxyethylene dodecyl ether sulfate

The reaction is carried out in the same manner as in Example 12, and a solid product is obtained (yield 90%).

example

Production of a complex compound from the homopolymer A _? Sodium dioctyl succinate sulfonate and sodium lauryl sulfate In the same manner as in Example 12, sodium dioctyl succinate sulfonate and sodium lauryl sulfate (molar ratio a 1 J 1) are allowed to react with the homopolymer A, whereupon a solid product is obtained (yield 100%).

Example 15

Production of a complex compound from homopolymer A.

and sodium lauroyl sarcosinate (O ₁₁ H OON (GH,) OH _g OOOira)

If the starting materials are allowed to react in the same manner as in Example 12, a solid product is obtained (Yield 95%).

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Example 16 Production of a complex compound from homopolymer A.

Dodecyldimethylamincarboxymethylbetain C ^C ₁ 2 ^H 2 S * ¹ and sodium "! Aurylsulf at

Wan leaves the homopolymer A with dodecyldimethylamine carboxymethyl betaine and sodium lauryl sulfate (molar ratio 1: 1) in react in the same manner as in Example 12 and obtain a solid product (yield 90%).

Example 17

Production of a complex compound from the homopolymer A _f

Sodium trioxyethylene dodecyl ether sulfate and potassium n-ootylsesqui-

phosphate

The homopolymer A is left with sodium trioxyethylene dodecyl ether sulfate and potassium n-octyl sesquiphosphate (molar ratio 1: 1) react in the same way as in Example 12 and

receives a solid product (yield 93%)

Example 18

A complex compound is obtained from the homopolymer A and C ₁₁ H ₂₅ CON (CH ^) CH ₂ CH ₂ COONa in the same manner as in Example 12.

Example 19

A complex compound is obtained from the homopolymer A and a compound represented by the following formula in the same manner as in example 12:

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Example 2o

A complex connection is obtained in the same way as in Example 3, with the exception that sodium dioxyethylene dodecyl ether sulfate is used.

Example 21

A complex compound is obtained in the same manner as in Example 3 with the exception that urodium octaoxyethylendo decyl ether sulfate is used.

Loading example 1

A complex compound from homopolymer A is obtained and sodium laurate in the same way as in Example 12 »

Reference example 2

A complex compound is obtained from homopolymer A and lauryl sulfate in the same manner as in Example 12.

Each of the compositions prepared in the above examples was dissolved in perchlorethylene, trichlorethylene or methyl chloroform, whereupon a solution having a solids content of 0.3% was obtained. A 100 ml aliquot of the solution was placed in a beaker as a treatment solution. In the treatment solution, pieces of cloth (20 × 20 cm) as samples of each nonwoven fabric of polyester (tropical: dyed in a dark color), nylon (tricot: not dyed) and acrylic (knitted fabric: not dyed) were immersed at room temperature for 10 seconds . They were pressed to 120% by weight with a mangle, air-dried and subjected to a 2-minute heat treatment at 160 ° C. The following property determinations were carried out:
1. Antistatic property:

Five test pieces of a round shape (diameter 5 cm) were made

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cut out of the treated cloth and stored for 24 hours at 25 ° 0 and a relative humidity of γοη 4o%. The insulation resistance (the surface electrical resistance) of the test pieces was measured with an ohmmeter (manufactured by Horikawa Denk Co.). The average of five values was determined as the antistatic property.

2. Resistance to washing (wet method)

Five test pieces that were given to those under Mr. 1 were placed in a container of a laundry analyzer, whereupon 100 ml of a 0.2% aqueous solution of a detergent ("New Wonderful" by Kao Soap Co., Ltd.) was added. The washing process took 20 minutes at 40 ° C. The same washing process was repeated ten times. Finally, the samples were each washed twice with 1 liter of warm "water, dehydrated and dried, was determined and then the antistatic property in the same manner as under no. · Λ.

3. Resistance to dry cleaning:

Five round samples (the same as No. 1) were placed in a washing machine and washed with too ml of a perchlorethylene solution with a 1 / fig content of a mixture of anionic and nonionic surfactants (, Lot Soap P from Kao Soap Co., Ltd. ) and 0.1 # water at 30 ⁰ C for 30 minutes. The sample pieces were finally rinsed twice with 100 ml perchlorethylene.

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309810/1038

4o color fastness to Heiben:

After 100 rubs with a friction tester under load of 2oo g the results were evaluated according to the specification JLS-L-Io48. The bigger the lobster, the better is the color fastness.

5 Hygroscopy:

A drop of water was applied to the sample using a burette and the time (in seconds) for penetration was determined.

6. Grip (by hand):

Essentially, softness was judged by touch.

If the untreated (raw) specimen is between O "^ Δ Q is softer than raw, A a little harder than raw and. X harder than raw.

The test erg ebrdags the properties of the samples, which after the The assessment or measurement methods described above are shown in Tables I to III below.

T, P and M in the following tables mean irichlorethylene, perchlorethylene and methylchloro form, respectively. The compositions of the reference examples are not dissolved in a solvent such as perchlorethylene or Ü3richloräthylen _xu eiaer stable solution. In addition, the composition of Reference Example 1 was much inferior in color fastness to rubbing.

One of the ingredients of each of the mixtures of the in the Examples i4 and 16 is the surfactant used the complex compound of the present invention, while the other component is not ο in use however, such a combination produces excellent results as shown in Tables I to III below will. «,« ./ 26

309810/1038

Table I. Polyester fabric, consisting of a yarn fabric and dyed in a dark color

O CD OO

CD CJ CO

At- treat solution T Before the Antistatic property (insulation resistance cm After washing wet dry iarbecht- He- Hygro Grippy - game ling middle P. Vaschen stand__Ohm / ash (OK times) 6.5x1ο 6.8x1o ^y Ness copy speed No. I. To! demW 8.2x1o ⁹ 4.1x1o ⁹ against ferocken Δ-Ο f P. (5 times) dry 7.9x1o ⁹ 4.4x1o ^y ben 4-5 Δ -O P. P. wet 3,6x1o ⁹ 1.1x1o ¹ ° 7.2x1o ^y wet 4-5 Δ-Ο 2 P. T S, 9x1o ⁷ 5.5x1o ⁹ 2.6x1o ⁹ 8.1x1o ⁹ 5.5xio ^y 3 4th 16 Δ ' 3 P. P. 7.5x1o ⁷ 4.2x1o ⁹ 2.2x1o2 7.7x1o ⁹ 5.6x1o ⁹ 3-4 4-5 81 Δ -Χ 4th P. 1.3x1o ⁸ 6.1x1o ⁹ 3.9x1o ⁹ - - 3 4-5 54 Δ 5 T 2.2x1o ⁸ 8.2x1o ⁹ 3.8x1o ⁹ - - 2-3 4th 32 Δ 7th 1.1x1o ⁸ 7.3x1o ⁹ 2.6x1o ⁹ - - 3-4 4th 52 Δ-Ο 8th 2.6x1o ⁸ 4,4x1o ⁹ 1.6x1o ⁹ - - 4th 4th 26th Δ- ο 9 3.3x1o ⁸ 6.2x1o ⁹ 2.1x1o ⁹ - - 4th 5 above
3min. O 12th 1.0x10 9.5x1o ⁹ 3.3x1o ⁹ - - 3-4 4-5 15o O 13th 1.5x1o ⁸ 1.1x1o ¹⁰ 1.6x1o ⁹ 4-5 4th 5 Δ 14th 2.5x1o ⁸ 8.1x1o ⁹ 3.8x1o ⁹ 4th 4th above
3min. 15th 1.6x1o ⁸ 7.6x1o ⁹ 1.6x1o ⁹ 3 4-5 15th 16 5.5x1o ⁷ 5.4x1 o ⁹ 1.9x1o ⁹ 2-3 above
. 3min. 17th
9
^ N
ΓΟ 6.5x1o ⁷ 3.1x1o ⁹ 3-4 2o "

SD

NI

KJ

NJ CO

■ 9

κν κν

KN LA

<ΐ

η η Φ-H KN VD : ρίΚΝ

KN

IA

KN

(Γι 4 KN KN

Κ \ IA

I I

JN ΤΟ S M

KN

ο Ο O τ T " ■ τ- O ο Η τ- T " Τ " M. Η M. ω τ- KN

σ *

, I.

CM

τ

O) -P • Η

τ- τ-

KN 4 "

“ON O

τ- τ-Η X

KN KN KN CU

σ »ο

CU

Τ

CVI

ΤΟ T "

σ »

^ on <OO τ-τ-τ-

O Τ-

LTN CO

ο οο

IA VO

οο

L> - OO

O

τ- τ-

PS rS

KN T "

& * ψ »

ON CU

egg

Ρ »

co

KN

CO 'O

(Q

τ-

I Φ

m ώ

00 Τ

ΟΝ O T-τ- CU CU

φ φ

η P ι φ ta τΐ.η O τν

IA

14 IA Φ

■ ω -

(Q

• η a

Φ

(Q 43

(Q CQ CQ

309810/1038

CU το

CU

^ o

T "

Table II

Polyacrylic C knitted fabric)

example

No.

Treatment solution with
tel

Antistatic property (.insulation resistance Ohm / cm)

Before washing

after washing (5 times) (wet / dry)

After washing

(1o times) (wet / dry)

Grip (softness)

CD CO OO

ο 5

9
12th

rv>

T
P.

T
P.

1.2x1o

6.2x1o ⁷

5.3x1o ⁷

7.6x1o ⁷ 6.4x1o ⁷

9.1x1o ⁷

2.1x1o ⁹ 5.5x1?

2.6x1o

¹⁰

i, 5xio 3.3xio

2.6x1o

2.5xio ^c

^{10 9}

¹ °

1.8x1o ⁹ 9.4x1o9

3.1x1o ⁹

4.2x1o

3.4x1o 4.6x1o '2.1x1o

¹ °

¹ °

8.5x1o 5.5xio-4.1x1o 6.6x1o 1.7x1o 5.5x1o ^:

3.4x1o 8.8x1o 9.1x1o

¹ °

1o

¹ °

1o

1o

8.8x1oJ ° 5 ^

Ο-Δ Δ Δ

Δ-

Δ-

ο -

X X

ο ■

οο

I O

O O O O OO

V CTn V-CTN V-CTn V-CT. V-V OO OO OO OO OO

SS MM

OO

£ 5 SS

• · «.«. ... »
IDKN 4 "KN KNLfN

COCTn V

• Η Φ CQ

OO O

VCO VCTN CTnCTn V CTn CTn OO OO OO ΟΟΟ VV VV VV VVV

-A 44 44 ⁸ Λ

TT VV CTNCvJ ν C \ J

V-CTn O

OLTNV

eh CO ν

[N CO O O ν ν M. ν IA

CN

. O

CTN

IA

LN. O

KN

co "

CTn O

cvi

ν O V

Bi Pi

Si

CQ CQ

CD

KN

IA

CN V

• rl pij

U Φ

CQ -P

CQ CQ CQ

> who

309810/1038

Table III Nylon (Irikot)

Example treatment no. solvent

Antistatic

Before washing property (insulation resistance

Ohm / cm)

After washing

;(5 times)

C wet / dry)

After washing

(OK times) (wet / dry)

Grip (softness)

• 2 co
O 3 CD OO 4th O > «. 5 O (O 7th co 8th 9 12th 13th 14th 15th

P P P P

'JJ α? ρ τ

P P

3.2x10 °

1.1χ1ο ^δ 9.6x10? 1.5x1ο ⁸

1.3x1o

1,0X1ο

2.2x1ο ⁸ 8.1x10-7 ^ 1.1χ1ο ^δ

3.1x1o

1.1x1 cV

8.2x10 ^
1.1X10 ^IO

6.5x1o; j
1.6x10 ^IO

8.8x10

3.5x1O
7, ox1o

4.4x1o
731

2.8x1o2 °
61 ⁷

3.6x1o
621

2.5x1

7.4x10- ^

ι, 3χΐοί ° 52 ^

8,1x10 ^ 2,1χ1ο ^ιο

2.7x10 ^Ι0

6.7x1Oq 8.6x1 ο ^ν

1.1χ1ο2 ° 6.2x10 ^

6,1χ1ο | 69 ⁹

5,
1,2χ1ο

1,2χ1ο

^ ^Ί0

9.6x1o

Δ O

Δ -

Δ Δ

O O

Δ - ο

(Continuation of Table III from page 30)

1ö

17th

Watery

ω system ο

cc sou

T P

water

6.2x1o 55

7.3x10 621

2.5x10 ^ 1.2x1o ^l0

12 Io ¹ ^

12th

Δ - .ο

χ
O - Δ

v> J

22A29U

In the following Examples 22 to 26, various were made Properties of the treated fabrics are determined according to the following methods:

To wash:

Haschine - washing machine from Toshiba VH-800 (4-35 revolutions per minute)

Detergent - high-performance detergent ("New

Wonderful "by Kao Soap Co., Ltd.)

Concentration 2 g / l

Badver- _. . _ς ratio ^Ί '? °

Washbasins _ _4q o _{c for} 5 minutes and Wasseraxngungen _ablution for 5 minutes

The above treatment constitutes a wash and the same process is repeated.

Electrification voltage:

Samples of 5 x 7 cm cut out of the treated fabric Size were measured for 24 hours at a temperature of 2o ° C and 5o% exposed to relative uncertainty. The electrification voltages the samples were collected by means of a static hot water storage device (Kyodai Kaken type, manufactured by K.oa Shokai) genier ;;; en. using calico # 3 cotton as a rubbing cloth and under a load of 500 g at 1/60 rpm. The average; of four values was assumed to be the electrification voltage.

Insulation resistance:

Five round specimens (diameter 5 οτα) were cut out of the specimen and exposed to a temperature of 20 ° G at 50% relative humidity. The insulation resistance of the specimens was measured with an electrometer (manufactured by Takeda Eiken Co., Ltd) . Es the average of five values was formed.

. . ./34-309810/1038

Grip (by hand)?

The appearance and feel of the sample cloth were evaluated by a panel of 10 people according to the following Assessment acala determines what the average is formed from became.

Excellent s 5

Excellent s 4-

Normal: 3

A little bad: 2

Bad ! 1

Processability ("gluing):

Mn endless search made of polyester tropical (75 d / 32 f / 2) of 40 cm Width was immersed in the treatment solution, squeezed out under a load of 2 kg / cm, and further dried at 8 ° C. This doorway was at a speed of 7 m / min. Repeated for 30 minutes, and the processability was determined according to the following rating scale

No sticking

Gluing the defect Δ

. Gluing the fabric X

Example 22

A fabric made of polyester tropical (75 d / 32 f / 2) (fabric density: 31.5 S 'threads per cm) was immersed in an organic solvent solution having the composition shown in (Table IV) at room temperature and at an extrusion ratio of 100 % _t, based on the weight of the substance, was then dried for one minute at 80 ° C. and heated for hardening for 2 minutes at 160 ° C. A complex compound of poly (2-methacryloyloxyethyldimethylethylammonium ethyl sulfate) and sodium trioxyethylendodecyl ether was found in labelleBF -

«../35

3098 10/1 038

sulfate, prepared according to Example 3, is used. The compositions the treatment solutions and the test results are summarized in Table IV.

3098 10/1038

Table IY

CD CO OO

at
spat]
No. complete
Connect
manure Iso-
propyl
alcohol Perchloric
ethylene 100 Amount of
broke up
th conn
manure
(%,based
ad weight
of the substance) Antistatic property
(top line: Elektrifi
voltage (V)
bottom line:
Resistance (-Ω-) after 1x
To wash after 5x
To wash grip Processing
bark it
(Gluing)
I. 1 0 0 0 99.9 0 in front of your
To wash - - - 2 0 0 99.8 0 y 2x1O ¹² - - '4.9 O 3 0.05 0 _f 05 99 ^ 5 5,800
y 2x1O ¹² 4,250
4.3X10 ¹⁰ 4.150
5o8x10 ¹⁰ Q 4th 0.1 0.1 640
8.6x1O ⁸ 2,200
3.1X10 ¹⁰ 2,400
2.3X10 ¹⁰ 4 * 5 Ö 5 O _f 25 0 _f 25 0.25 150
1.2x1O ⁸ 1,780
9.7x1O ⁹ 2.100
1 _e 8x10 ¹⁰ 4.3 0 65

O LA O O O 3b LA I. LA VD O 2242914 H LA X LA Si O O V- ω OJ O OJ V " V v- KN ω V- X O O O O O V
0 * O O KN VD KN ι O O O O O* V O" OJ LA O • V LA LA V- OO OO (N GO ω o ^ o CN KN O O 4 " X O O O O O V LA ON LA OJ V- LA V " O 4 "v LA [N V O CO X O O O ^ · O O oT CN X • oj x V v X OJ *> OJ vD V LN- V V OJ KN KN V LA [N X CN VD X LA • LA- ON O • LA • LA V O CO OJ ω O O V ON V CO V ON VD * • σ> ON KN V O OO V CO OJ O O VD CN CN ω ο ο OJ M ν * O O V O O V O V-
KN X O ON CN V OJ KN V CN V - co LA V O O KN X V V X X a V vD V KN CN KN OO OJ LA X O LA KN O 4 " V CN IN V- VD VD N
P. LA V- LA O M. O O Φ
CQ V- X CN KN V V V V ⁰⁰ Z -P vD O V M OJ X U vD O V OJ KN OJ O \? S V ON ω Ρή LA OJ φ
j - I
H , Ω cc!

30981 0/1 038

../38

Example 25

A polyester "] ersey (34-5 Gao was in an organic solvent solution obtained by dissolving o, 3 $ ew .-% of a complex compound in o, 3 wt .-% isopropyl alcohol, and then diluting with 99 _S 4- weight .-% of an organic solvent shown in lamelle V, immersed at room temperature, squeezed out by means of a mangle at an extrusion ratio of 160% and dried for 1 minute at 80 ° C. The complex compound was a copolymer of 2-methacryloyloxyethylmethylethylammonium ether sulfate and acrylamide (1ϊ1) and sodium dioctyl succinate monosulphate used »The results are summarized in! Table V.

Further, the electrification voltage of the raw sample was

12 62oo V and their insulation resistance was more than 2 χ 10 ohms. When water was used as a diluent instead of an organic solvent, the compound was complex Insoluble in water and therefore the experiment could not be carried out. The solubility in Table V was determined by observation of the solution is determined with the naked eye when it has stood for 5 hours after being sufficiently stirred.

The following criteria are used for assessment:

Solved

Loosened (swollen)

Insoluble X

.. ./39 3098 10/1038

Table V

O U> CO

Γ
Organic
Solution agent 1
I.
i Antistatic property
(top line: electrical
tension (Y)
bottom line:
Resistance (Sl) after 1x
To wash after 5x
To wash solubility grip at
game
No. TtI chloroethylene before the
To wash 1,800
7.2x10 ⁹ 2.100
1.2x10 ¹⁰ O 5.8 1 Methyl chloroform 60
8.4x1O ⁷ 1,450
5.2x10 ⁹ 1,700
8.3x10 ¹⁰ O 4.1 2 acetone 75
7.8x1O ⁷ 2.150
1.4X10 ¹⁰ 2,350
2.5x10 ¹ ° O 4.2 3 Cyclohexane 120
1.2x10 ⁹ 2,300
1.OxIO ¹⁰ 2,650
4.3X10 ¹⁰ O 5.7 4th Diethyl ether 85
9.8x1O ⁷ 1,800
9.8x1O ⁹ 2,800
ι, δχίο ¹⁰ ο 5.9 5 Ethyl acetate 145
2.5x10 ⁸ 2,200
1.2X10 ¹⁰ 2,450
3.2X10 ¹⁰ ο 5.2 6th 180
1.2x1O ⁸

Example 24

ils swatches acrylic jersey (I4o g / m) ₃ l \ fylontr ± feces (i35 g per m) were I / C blend (65/35) "and BauDrerolltueh used _s each cloth sample was immersed in an organic solvent solution which is received by ο "3 Gewo-% of a complex compound in o, 3 wt» - triggered% ethyl alcohol and those with 99 "4 wt -. diluted% perchlorethylene" the immersion was beiSaumtemperatur carried out, after which the samples with a Auspressverhältnis of I5o _5% based on the weight of the substance being _squeezed% and 1 minute were dried at 8ö ° 0 As complex compound such a Kopolyaerea of 2-Methacryloyloxyäthyldimethyläthylammoniumäthosulfat and acrylonitrile was ^(3: 1). Natriumpentaoxyäthylennonylphenyläthersulfat and used.

The results are summarized in Table VI ι

Table VI

No. btoffpro-
be Antistatic property
Top line! Electrification
voltage (V)
Lower line: Resistance
Ohm / cm Before the
Laundry To
1 wash After 5
To wash Grippy
speed 1 acrylic
shirt Raw ι
I. 11o _n
8.2x10 ^ 2.OOO η
9j1x1o ^ 2,425 _Λ
1.2x1o ^l0 4 _S 2 2 Nylon-
shirt 6.10Q ₉
> 2x1o ^nd 230 ₈
1.1x1o ° 1.95ο ο
8.7x1o ^ 2.15ο _Λ
2 ₉ 2χ1ο ^ηο 3.7 3 T / C-Ilisch-
tissue 4-Ö00
^ 2x1o ¹² 45 ₇
7.5x1o ' 1.28ο _Q
9.2x1o ^ ^{1 45} ° 1 o
1.2x1o ^lo ^, 3 4th Cotton
cloth 3.2ΟΟ _Λ
8.4x1o '' 185 ₈
3.5x1o ^ö 78o Q
4,4x1o ^ 65o Q
5.3x1o ^y 3.2 4o ₈
1.3x1o °

309810/1038

Example 25

A dyed polyester cashmere shawl (warp 15o d / 32 f / 1, Shot 1oo d / 48 f / l) was poured into an organic at room temperature Solvent solution shown in Table VII, immersed to an extrusion ratio of 160% by weight of the cloth, squeezed out and dried at 12o ° 0. The test results are shown in Table VII.

The coloring was made using Dianix Violet 5RSE ( by Mitsubishi Kasei Co., Ltd.) as a dye. It became a temperature and pressure inking analyzer (Oolorpet 12, manufactured by Japan Dyeing Machinery Go., Ltd.) at a concentration of 4% by weight based on weight of the substance, a temperature of 130 ° C and a duration of 60 minutes based on a bath ratio of 1: 3o used. The reducing washing treatment was carried out using the same equipment that was used for dyeing, with 2 g / l hydrosulfite, 2 g / l soda ash and 2 g / l Amylazine D (manufactured by Daiichi Kogyo Seijdcu Co., Ltd.) was used The treatment was carried out at 100 ° C. for 30 minutes and a bath ratio of 1: 5o became.

The color fading in Table VII was determined by the absorbance of each organic solvent solution after treatment was measured at the maximum absorption wavelength, below Using a Hitachi EPR-2 automatic recording spectrophotometer (manufactured by Hitachi Seisakusho) and below Use of a cell the size of 1 cm.

The solubility was determined by the same method as in Example 23.

Finally, a complex compound made from poly (2-methacryloyloxyethyldimethylethylammonium sulfate) and N-methyl

N- (sodium carboxymethyl) lauroamide is used.

... / 42

3098 10/1 038

Table VII

at
game
No. Complete
Connect
manure Ithyl -
alcohol
get Perchloric
ethylene Antistatic property
(top line: Elektrifi
voltage (V)
bottom line:
Resistance (Λ) laugh 1x
bags - after 5x
.To wash - solubility Parchment
(Absorbance) 1 0 0 100 before the i
To wash ' - 1,650
4.8x1O ⁷ - 2.100
1.2χ10 ¹ ° O <: 0.05 2 0.3 0 99.7 6,100
72XiO ¹² 1,750
6.5x1O ⁹ 1,850
9.7x1O ⁹ 'X <0.05 3 0.3 0.06 99.64 - 1.45O ₁
8.7x10 ⁹ ' 1,750
9.5x1O ⁹ Δ <Ο, 05 4th 0.3 0.15 99.55 60
7.2x10 ⁷ 1,700
7.5x1O ⁹ 2.050
9.3x1O ⁹ ο <; 0, Ό5 5 0.3 0.3 99.4 30 ·
5.3x1O ⁷ 1.6DG
8.1x1O ⁹ 1,800
7.5x1O ⁹ ο 0.05 6th 0.3 3 96.7 15th
6.8x1O ⁷ 1,800
7.1x1O ⁹ 1,950
8.7x1O ⁹ O 0.10 7th 0.3 6th -93.7 65 ·
5.9x1O ⁷ Ö 0.15 8th 0.3 15th 84.7 35
8.3x1O ⁷ O 0.30 20th
6.1x10 ⁷

22429U

Example 26

A polyester atlas (75 d / 32 f / l) would be in an organic solvent solution obtained by dissolving 0.5% by weight of a complex compound in 0.5% by weight of an alcohol shown in Table VIII and the whole thing is diluted with 99% by weight of perchlorethylene, immersed at tree temperature, squeezed out up to an extrusion ratio of 140 % _t based on the weight of the fabric, and dried for 1 minute at 100 ° C. The test results are summarized in Table VIII.

The electrification voltage of the raw swatch was

1 ? 68oo V and its insulation resistance more than 2x1ο Ohm.

A complex compound was made from poly (2-methacrylcyloxyethylenedimethylammonium sulfate) and sodium trioxyethylendodecyl ether monophosphate used.

Table VIII

No. alcohol Antistatic property
Top row: electrification Awake 1
Laundry After 5
Washes Grippy
speed 1 Lower line: Resistance
Ohm / cm 1.21ο Q 1,530 _1o
1,2χ1ο ^ΊΟ 2 Before the
Laundry 92o ₉ 1.o3o q
9.2x1o 3 methyl
alcohol 45 ₇ 87o ₉ 1,100 Q 4.2 4th ethyl
alcohol 1o ₉
5.8x1o ' 1.o2o Q 1,300 _1o 4, o 5 Iaopopyl-
alcohol 15 ₇
4,3x1o ^/ 1.25ο ₉ 1.43ο ₁
1,3χ1ο ^ίο 4.1 Propyl
alcohol 25 ο
5.1x10 ^ 4.3 Butyl
alcohol 4o ₇ 3.9

... / 44

30981 0/1038

Claims (1)

Claims 1. Permanent anti-static agent, characterized in that it consists essentially of a complex compound of a polyvinyl derivative having quaternary ammonium groups in its side chains, the counteranion being formed by an anionic surface-active agent with a content of 2 to 8 ethylene oxide units, ester-bonded sulfonates, ₉ alkylamidocarboxylic acid salts and / or amphoteric surfactants of the carboxylic acid type is substituted. 2. Antistatic agent according to claim 1, characterized in that that the polyvinyl derivative having a quaternary ammonium group in its side chain is a polymer obtained by making a vinyl polymer homopolymerized with at least one tertiary amine residue in the molecule or it initially with another copolymerized vinyl monomers and then the resulting polymer with a quaternizing agent quaternized. 3. Antistatic agent according to claim 1, characterized in that the quaternary ammonite groups in its Polyvinyl derivative having side chains is a polymer obtained by adding a vinyl monomer with at least one quaternary ammonium group in the molecule homopolymerizes or it is copolymerizable with another Copolymerized vinyl monomers » ..45 309810/1038 Antistatic agent according to Claim 2, characterized in that that the at least one tertiary amine residue in the molecule having vinyl monomers by the the following general formula is given: " _A .o , 0H ₂ M R, where R. and Rp independently of one another are methyl or Mean ethyl. 5. Antistatic agent according to claim 3, characterized in that that the vinyl monomer having at least one quaternary ammonium group in the molecule by the following general formula is shown: CH, ^ß 1 ₀ CH ₀ CH ₀ Ir- R _x X ^H 2 where R., R ₀ and R, independently of one another, represent methyl or ethyl and X denotes a halogen, methosulfate or ethosulfate. 6. Antistatic agent according to claim 4, characterized in that that the copolymerizable vinyl monomer through the following general formula is given: 309810/10 3 8 where R ₁ , water or methyl and Ej- represents alkoxycarbonyl groups, alkoxyl groups, -CONH ₂ , -COOH, -GN or -CgHt-. 7. Antistatic agent according to claim 5, characterized in that that the copolymerizable vinyl monomer through. the following general iOrmel is rendered: wherein R ₁ , hydrogen or methyl and R ₁ - alkoxycarbonyl groups, alkoxyl groups, -GOHH ₂ , -000H ₉ -CN or -CgH ₁ -. 8. The antistatic agent of claim 1 ₅ characterized in that the anionic surface active agent having 2 to 8 Äthylenoxydgruppen from Natriumdioxyäthylendodecyläthersulfat, Natriumtrioxyäthylendodecyläthersulfat, Natriumtrioxyäthylen-n-nonylphenyläthersulfat, liatriumpentaoxyäthylendodecyläthersulfat, Katriumoctaoxyäthyleii-n-nonylphenyläthersulfat, Hatriumfcrioxyathylendodecyläthermonophosphat, Natriumtrioxyäthylen-n-nonylphenyläthernionophosphat, Natriumtrioxyäthylendodecyläthercarboxymethylat, Hatriumtrioxyäthylen-n-nonylphenyläthercarboxymethylat or Liatriumtrioxyäthylen-n-nonylphenyläther-ß-carboxyätliylat consists. 9. Antistatic agent according to claim 1, characterized in that that the ester-bound sulfonate sodium diol «Is uccinate monosulfonate. ... / 4-7 30 9810/1038 22429U Ίο. Antistatic agent according to Claim 1, characterized in that that the alkylamidocarboxylic acid salt from N-methyl N- (sodium carboxymethyl) lauroamide or sodium .N-lauroyl glutainate consists. 11. Antistatic agent according to claim 1, characterized in that that the amphoteric surfactant of the carboxylic acid type from sodium 2-carboxyethyldodecylamine, Sodium carboxymethyldodecylamine, di (sodium carboxymethyl) dodecylamine or di (sodium-2-carboxymethoxyethyl) dodecylamine consists. 12. Antistatic agent according to claim 8, characterized in that that it is a complex compound which is derived from polyC 2-Mefchacryloyloxyäthyl dime fchyläthylanuaoniumtrioxyäthylen-n-nonylphenyläbhersulfat), Poly (2-methacryloyloxyäthyldimethyläthylammoniuintrioxyäthylendodecyläthersulfat), Poly (2-Methaci'yloyloxyäthyldimethyläthylammoniumpenbaoxyäthylen-n-nonylplienyläthermonophosphonat), PolyC2-Methacryloyloxyäthyldimethyläthylammoniumtrioxyäthylen-dodecyläthersulfat), PolyC2-MebhacryloyloxyäthyldimebhyläbhylammoniuiQdioxyäthylendodecyläthersulfafc), PolyC2-Mebhacryloyloxyäthyldimethyläthylammoniumoctaoxyäbhylen-dodecyläbhersulfat), PolyCStyrene-2-Methac c-yloyloxyäthyldime bhyläbhylammoniumtrioxyäthylenn-nonylphenyläthersulfat) odor PolyCacryMtril-2-methacryloyloxyä thyldime thyläbhylaiiimoniumtrioxyäthylendodecyläthersulfat). 13. Antistatic agent according to claim 9, characterized in that that it is a complex compound consisting of PolyC2-Methacryloyloxyäthyldimethyläthylammonium- 30981 0/1038 22429U dioctyl succinate sulfonate) or poly (styrene ~ 2methaeryloyl ~ oxyethyldimethylethylaiimoniumdioctylsuceinate sulfonate) consists. 14-. Antistatic agent after. Claim 1ο «, characterized in that that it is a complex compound consisting of poly (2-methacryloyloxyethyldimethylethylammo2iium lauroyl sarcosinate) or poly (2-methacryloyloxyäthyldimethyläthylainmoniura-ii-lauroyl-li-methyl-ß-aminopropionate) consists. 15 ° antistatic agent according to claim 11 _s, characterized in that it is a complex compound ₂ which consists of poly (2-methacryloy1 oxyäthyldimethylethylammoniumdodecyldimethylaminocarboxymethyIbetaine) or poly (2-ilethacryloyloxyäth.yldimethylethylethyl) -dimethylethylammonium-2-carboxyethyl-1-aoxyethylammonium-2-carboxyethyl-1-aoxyethylammonium 16. Application of the antistatic agent according to claims 1 to 15 for imparting water repellency to fibers and]? Asergefügen ₅ characterized in that the iTasern 1 enthaltenj to 1o wt .-% of a complex compound, the besteht- of a polyvinyl derivative, quaternary ammonium groups in its having oeitenketten, wherein the G-egeiianion _s included by anionic surfactants 2 to 8 Äthylenoxydgruppen, estergebundesSulfonate ,, Alkylamidocarbonsäuresalze or amphoteric surface active agents Gax'bonüäuretyps substituted. 17., application of the antistatic means according to claim 16 _S dadurcli characterized in that. the amount of force applied to the textile Mateidal complex compound o, 2 to 5 wt. is yo. . " 309810 / 103B. 22A29U 18. Application of the antistatic agent according to claim 16, characterized in that the amount of the on the textile material applied complex compound is o, 3 to 1, o wt .-%. 19. Use of the antistatic agent according to claim 16, characterized in that the fibers and fiber structure made of polyester, polyacrylonitrile, polyamide, polyvinyl chloride, Consist of polyethylene or polypropylene. That it is 20. Application of the antistatic agent according to claim 16, characterized in that the hydrophobic fiber structures to rayon staple, continuous filaments, woven fabrics, knitwear, non-woven fabrics or cotton that is more than 5o by weight - containing% fibers, made of polyester. Polyacrylonitrile, polyamide, polyvinyl chloride, polyethylene or polypropylene exist. 21. Application of the agent according to claims 1 to 15 for Production of hydrophobic fiber structures, characterized in that the fiber structure with an organic solvent solution are treated, which from 0.05 to 1o wt .-% of a complex compound of a polyvinyl derivative consists, which has quaternary ammonium groups in its side chains, the counteranion through anionic surfactants containing 2 to 8 ethylene oxide groups, ester-linked sulfonates, Alkylamidocarboxylic acid salts or amphoteric surfactants of the carboxylic acid type is replaced while the solution also o, o5 to 2o wt .-% of an alcohol and more than 70 wt .-% of an organic solvent, consisting of hydrocarbons, halogenated hydrocarbons, Ethers, ketones or esters, / where the .. ./5o / contains / 3098 10/1038 The weight ratio of the alcohol to the complex compound is more than 0.2 s 1. 22. The method according to claim 21, characterized in that the concentration of the complex compound in of the organic solvent solution ο, 2 to 3> o wt «.-? amounts to. 23 · The method according to claim 21, characterized in that that the concentration of the complex compound in the organic solvent solution is ο, 3 to 1, o wt .-%. 24. The method according to claim 21, characterized in that the alcohol is ethyl alcohol or isopropyl alcohol is. j 25 · Process according to Claim 21, characterized in that the concentration of the alcohol in the organic J solvent solution is ο, 2 to 6 wt .-%. ) 26. The method according to claim 21, characterized in that the concentration of the alcohol in the organic j solvent solution o _R 3 to 2 wt .-% by weight. 2 ?. Method according to claim 21, characterized in that that the weight ratio of the alcohol to the com-J plexing compound 0.5 to 3.0 parts alcohol per part of the complex connection. • · ./51 309810/1038 SO 28. The method according to claim 21, characterized in that the weight ratio of the alcohol to the complex Compound is 1 to 2o parts of alcohol per part of the complex compound. 29 · The method according to claim 21, characterized in that that the organic solvent is a halogenated hydrocarbon. 30. The method according to claim 29, characterized in that that the halogenated hydrocarbon methyl chloroform, Is trichlorethylene or perchlorethylene. 31. The method according to claim 21, characterized in that the concentration of the organic solvent in the organic solvent solution 92 to 99.6 wt .-? & Is. 32. The method according to claim 21, characterized in that cfe concentration of the organic solvent solution 97 to 99.4 wt% Sfc. 33 · Antistatic agent, characterized in that it consists of 0.05 to 10 wt amphoteric surfactants of the carboxylic acid type is replaced, o _f o5 to 2o wt .-% ... / 52 309810/1038 22429U of an alcohol and more than 7% by weight of an organic solvent j "consisting of hydrocarbons, halogenated hydrocarbons, ethers, ketones and / or esters, the weight ratio of the alcohol to the complex compound being more than o _s 2 ί 1 is O 34-. The antistatic agent of claim 31 'characterized in that the geweiligen concentrations of the complex compound of the alcohol and the organic solvent in the _s o of the composition is 2 to 3 John wt ° -%, o, 2 to 6 wt -Jo and 92 to 99. ₉ 6 wt .- $ "amount" Antistatic iüttel according to claim 31 »characterized in that the respective concentrations of the complex compound of the alcohol and the organic solvent ?? in the composition ο, 3 to 1 _s o wt .-%, 0.3 to 2 wt -.% and amount to 97-999 ^ Gewo-%. 3098 10/1038