DE3643334A1 - Addition for a granular detergent and cleaner - Google Patents

Abstract

An addition for a granular detergent and cleaner consists of (a) 50-99.8 % by weight of at least one quaternary ammonium salt which has two long-chain alkyl radicals and (b) 0.2-50 % by weight of at least one copolymer of an acrylamide monomer, a carboxyl-containing monomer and a sulphonyl-containing monomer of the formula <IMAGE> in which R<1>, R<4> and R<5>, which can be identical or different, are each a hydrogen atom or a methyl group, R<2> and R<3>, which can be identical or different, are each a hydrogen atom or an optionally hydroxyl- or oxyalkyl-substituted alkyl group; A is a direct linkage or an alkylene group with 1-5 carbon atom(s); B is an alkylene group with 1-5 carbon atom(s), a phenylene group which is optionally substituted by an alkyl radical having 1-5 carbon atom(s), or a unit of the formula <IMAGE> in which x and y, which can be identical or different, are each an integer from 0 to 5, or a unit of the formula <IMAGE> in which R<5> and A have the stated meaning; Y<1> and Y<2>, which can be identical or different, are each a hydrogen atom, an alkali metal or an alkaline earth metal, and l, m and n are molar monomer contents in the ratio 98.9 to 50 : 1 to 50 : 0.1 to 20. n

Description

The invention relates to an additive for granular washing and cleaning agents, especially for those with a anionic wetting agents.

If clothes are washed at home, they will after washing with common washing and cleaning agents and rinsing with a large amount of water treated with a plasticizer. Contain such plasticizers a cationic wetting agent, e.g. B. a quaternary ammonium salt. This separate treatment is necessary because the plasticizer is not together with the detergent and cleaning agent can be used. Cationic wetting agents, however, contain them own excellent softening and antistatic Properties when used together with washing and Detergents do not have a sufficient softening effect. This is due to the fact that home detergents in usually contain anionic wetting agents and consequently the cationic wetting agents incorporated into a washing system with those contained in the detergents and cleaning agents anionic wetting agents react. This reaction causes the ion properties the quaternary ammonium salts are lost and the the reaction formed stably dispersed in the washing system will. Hence the quaternaries Ammonium salts (in such systems) are no longer easy  be absorbed by the garment.

Separate washing and softening processes are labor intensive and time consuming, so by consumers Detergents and cleaning agents are desired with which Garments washed and softened at the same time can be.

Various attempts have already been made to make fabrics or garments in satisfactory Way to soften. These attempts passed in it, during the washing process the wash liquors are cationic Add wetting agents. For this purpose, have already been together with inorganic or organic salts or organic dispersion retarders granulated cationic Wetting agent developed (see JP-OS 36-8 927 (Kokoku), US-PS 40 73 735 and JP-OSen 55-86 895, 53-41 312 and 49-98 403 (Kokai).

Cationic wetting agents granulated with inorganic salts can be in terms of their plasticizing effect to improve synthetic fiber fabric, you However, the softening effect of cotton fabrics still leaves much to be desired.

To improve the softening effect on cotton fibers detergents and cleaning agents have already become acrylamide polymers incorporated (see JP-OS (Kokai) 61 7 397 and 61-7 398). These measures can reduce the amount of cationic absorbed by the fabrics after washing Increase wetting agents during washing However, dirt removed from the tissues settles again on the fabrics so that the washed fabrics or Garments still look dirty.  

From JP-OS 61-1 19 779 (Kokai) it is known by uniform Disperse a fine powdered acrylamide in one melted quaternary ammonium salt a plasticizer to manufacture. This makes it easy Way, d. H. by omitting a water evaporation stage ensure the desired uniform dispersion, nevertheless, the acrylamide polymer becomes by the shear force occurring during the mixing process significantly damaged. Hence, at lower Shear rate, for example 5-80 l / s, mixed will. This leads to partially coarse particles and operational problems (e.g. clogging the filter or sieves) occur.

The invention was based on the problem of not having one the possibility of the difficulties described to soften fabrics and garments create, d. H. one that is easy to manufacture fine-grained additive for granular detergents and cleaning agents to develop the fabrics or clothing, especially those made of cotton, an excellent one Softness and an excellent grip gives and the washed fabric or garment does not make it look dirty.

The invention thus relates to an additive for granular Detergent and cleaning agent, which from

• (a) 50-99.8% by weight of at least one two long chain Quaternary ammonium salt containing alkyl radicals and
• (b) 0.2-50% by weight of at least one copolymer from an acrylamide monomer, a carboxyl-containing monomer and a sulfonyl-containing monomer of the formula: in which mean:
  R ¹ , R ⁴ and R ⁵ , which may be the same or different, each have a hydrogen atom or a methyl group, R ² and R ³ , which may be the same or different, each have a hydrogen atom or an optionally hydroxyl or oxyalkyl (preferably with 1-4 carbon atom (s)) - substituted alkyl group preferably having 1-4 carbon atom (s);
  A is a direct bond or an alkylene group preferably having 1-5 carbon atoms;
  B is a direct bond or an alkylene group with preferably 1-5 carbon atoms or a phenylene group optionally substituted with an alkyl radical with preferably 1-5 carbon atoms, a unit of the formula: in which x and y , which may be the same or different, each represent an integer 0-5, or a unit of the formula: wherein R ⁵ and A have the meaning given;
  Y ¹ and Y ² , which may be the same or different, each represent a hydrogen atom, an alkali metal or an alkaline earth metal and
  l , m and n molar monomer proportions in a ratio of 98.9 to 50: 1 to 50: 0.1 to 20,

consists.

The invention further relates to a method for Production of such an addition, which is characterized is that one

• (a) the copolymer of formula (I) an average Particle size of 150 microns to one Melt at least one of two long chain alkyl residues having quaternary ammonium salt;
• (b) the copolymer in the quaternary ammonium salt melt with a shear rate of 50-150 l / s evenly dispersed and
• (c) the dispersion obtained to a powder Additive for a granular washing and cleaning agent powdered.

The di (long-chain alkyl) quaternary ammonium salts which can be used according to the invention as component (a) of the additive (hereinafter referred to as "quaternary ammonium salts containing two long-chain alkyl radicals") correspond, for example, to the formula: in which mean:
R ⁶ and R ⁷ , which may be the same or different, each represent an alkyl group having 12-26 carbon atoms;
R ⁸ and R ⁹ , which may be the same or different, each have an alkyl group with 1-4 carbon atoms, a benzyl group, a hydroxyalkyl group with 2-4 carbon atoms or a polyoxyalkylene group with 1-10 mol (s) of oxyalkylene units and

Typical examples of as component (a) in an inventive Additional usable cationic wetting agents are distearyldimethylammonium salts, dihydrogenated Tallow alkyl dimethyl ammonium salts, dihydrogenated tallow alkyl benzyl methyl ammonium salts, Distearylmethylbenzylammonium salts, Distearylmethylhydroxyethylammonium salts, Distearylmethylhydroxypropylammonium salts and distearyldihydroxyethylammonium salts. Typical counterions of the quaternary ammonium salts are chloride, bromide and Methosulfate.

The acrylamide monomers forming part of the copolymers used according to the invention as component (b) correspond to the formula: wherein R ¹ , R ² , R ³ and 1 have the meaning given. Examples include monomeric acrylamide (ie R ¹ = H) and monomeric methacrylamide (ie R ¹ = CH ₃ ). Typical examples of radicals R ² and R ³ in formula (I-1) are hydrogen, alkyl groups such as -CH ₃ , -C ₂ H ₅ , -CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , -C ₈ H ₁₇ and -C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₃ , hydroxyalkyl groups such as -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH and -CH (CH ₃ ) CH ₂ OH, and substituted alkyl groups, such as -CH ₂ OC ₄ H ₉ , -CH ₂ OC ₂ H ₄ (CH ₃ ) ₂ and -C (CH ₃ ) ₂ CH ₂ COCH ₃ -.

The carboxyl-containing monomers forming part of the copolymers which can be used as component (b) correspond to the formula: wherein R ⁴ , A, Y ¹ and m have the meaning given. Examples include acrylic acid (ie R ⁴ = H, A = O, Y ¹ = H), methacrylic acid (ie R ⁴ = CH ₃ , A = O, Y ¹ = H) and their salts.

The sulfonyl-containing monomers forming part of the copolymers that can be used as component (b) correspond to the formula: wherein R ⁵ , B, Y ² and n have the meaning given. Examples include ethylene sulfonic acid (ie R ⁵ = H,
B = O, Y ² = H), propenesulfonic acid (ie R ⁵ = CH ₃ ,
B = O, Y ² = H), methyl propenesulfonic acid (ie R ⁵ = CH ₃ ,
B = CH ₂ , Y ² = H), styrene sulfonic acid (ie R ⁵ = H, Y ² = H) or their salts.

The copolymerization molar ratio of the copolymer (b) should be 1 : m : n = 98.9-50: 1-50: 0.1-20, preferably 90-60: 10-30: 0.5-10. If the proportion of anionic monomers, ie the total proportion of carboxyl-containing monomers and sulfonyl-containing monomers, is greater than that of the acrylamide monomer, a considerable reaction takes place between the cationic wetting agent and the anionic monomer with deterioration in the plasticizing effect. If the proportion of the anionic monomer is not greater than that of the acrylamide monomer, the desired softening effect is not impaired by the reaction between the cationic wetting agent and the anionic monomer. On the other hand, if the proportion of carboxyl-containing and / or sulfonyl-containing monomers is too small, the redeposition (of dirt) cannot be prevented in a satisfactory manner. The degree of polymerization of the copolymer (b) should generally be 1000 or more, advantageously 10,000 or more, preferably 50,000 to 300,000.

The copolymers (b) which can be used according to the invention  is generally obtained by copolymerizing the Acrylamide monomers with the anionic monomers in the usual way known way. On the other hand you get the Copolymers (b) also by copolymerization of the acrylamide monomer with the sulfonyl group-containing Monomers and subsequent partial hydrolysis of the formed Copolymers.

The additive according to the invention contains 50-99.8, preferably 70-95% by weight of component (a) and 0.2-50, preferably 5-30% by weight of component (b). If the Amount of component (b) below the specified lower limit is the softening effect Cotton fabrics and the redeposition of Dirt preventing effect is not satisfactory Ensure way.

An additive according to the invention can be the most varied contain the usual ingredients, provided that these are the desired ones Softening effect and redeposition of Do not impair the dirt-preventing effect of the additive. Examples of such additives are nonionic Cellulose derivatives such as methyl cellulose and Hydroxyethyl cellulose, a wide variety of inorganic Compounds such as sodium sulfate, magnesium sulfate and calcium chloride, as well as various organic Connections, e.g. B. higher alcohols, fatty acids and non-ionic wetting agents.

An inventive additive for granular washing and Cleaning agents can be obtained by using the components (a) and (b) in a variety of ways, preferably united as evenly as possible. For example, the copolymer (b) can be in the form a solution or a powder to component (a)  be added. With the former method, however, one needs a large amount of solvent, such as water, to dissolve the copolymer (b). The consequence of this is that large plants are required to use the solvent to evaporate. In addition, the a redeposition of dirt preventing effect be affected. If the copolymer (b) added to component (a) in the form of a powder, this is preferably done in the form of a fine powder, expediently that of an average Particle size of 150 microns or less, preferably of 100 µm or less. Is the particle size of the component (b) too large, the desired softening effect deteriorates.

Polymers, e.g. B. the copolymers according to the invention (b) usually fall in the form of pellets Particle size of 0.5-2 mm (i.e. 500-2000 µm). It should be noted that almost all of these Polymers are commercially available in pellet form. According to the invention, these pellets can be pulverized be used. The pulverization takes place in the usual known manner, for example with With the help of a pre-cutter or a hammer mill Milling with, for example, a snail or by Jet powdering with a high speed air stream. The particle sizes of the powdered polymer are taken by suitable measures, for example with With the help of sieves or by air classification on the desired value. The softening effect against Cotton fabrics are improved when the particle size of the pulverized copolymer (b) drops. It it should be pointed out that if the Pulverize the molecular chains of the copolymer break open and the softening effect worse becomes.  

The desired finely powdered copolymer (b) can also be obtained without mechanical pulverization Polymerizing the monomeric components by reverse phase Suspension polymerization or reverse Emulsion polymerization. Leave with this procedure the desired copolymers of small particle size without an undesirable decrease in the degree of polymerization of the copolymer.

The finely divided obtained in the manner described Copolymers (b) are able to absorb moisture and contain 15-30 wt .-% water. The water intake takes place by absorption during grinding or pulverizing or during storage of the copolymers over time. Are copolymers (b) uses high water content, bake this and increase their particle size during mixing with the quaternary ammonium salts. These rough particles stick to fabrics or clothing while washing adhere at low temperature. To prevent a Formation of baked coarse particles of the copolymers (b) their water or moisture content suitably 10% by weight or less, preferably 7% by weight or less. The water or moisture content the copolymers (b) can be in usual devices, e.g. B. hot air dryers, vacuum dryers, Fluid bed dryers or freeze dryers, reduce.

The quaternary ammonium salt (a) and the copolymer (b) can be mixed evenly by using the finely powdered component (b) into the melted Component (a) and then the whole thoroughly mixed. The quaternary ammonium salts (a) are preferably to a temperature of 100 ° C to 130 ° C  warmed up and melted in the process. Is the temperature below 100 ° C the viscosity increases rapidly, so that the copolymers (b) no longer uniformly in the Allow the melt to disperse. If, on the other hand, the Temperature is above 130 ° C, the quaternary Ammonium salts decomposed with loss of the plasticizing effect. The desired uniform dispersion is achieved by mixing components (a) and (b) with a Shear rate of 50-150 l / s, preferably 80-130 l / s, stirred. If the shear rate is below 50 l / s, form during the dispersion coarse particles that clog the filters and sieves and complicate the operation. If, on the other hand, the The copolymers become shear force over 150 l / s (b) with loss of the desired plasticizing effect denatured. Is the shear rate 50-150 l / s, the desired uniform Ensure dispersion and the formation of coarse particles prevent, even if the water or Moisture content of the copolymers (b) is high.

The copolymers (b) are dispersed for example with the help of a paddle mixer or Propeller mixer. The uniform mixture obtained can by spraying with cooling or by Solidify by cooling and then grinding pulverize.

An addition according to the invention can be made according to the usual granulate known measures in a suitable manner. The average diameter is expediently the granules or the powder particles of the invention Additive 700 µm or less. Is the average diameter of the particles of the invention Addition too big, it prepares on the one hand  Difficulty in washing fabrics or clothing to soften evenly at all points, on the other hand can the particles themselves after the Place washing on the fabrics or clothing. Is the particle diameter of the additive according to the invention too small, for example less than 100 µm, the detergent and cleaning agent tends to cake. In such a case, the fine-particle additive can according to the invention in a suitable manner with a suitable inorganic coating agents, e.g. B. calcium carbonate, Silicon dioxide and zeolites or organic binders, such as non-ionic wetting agents and polyethylene glycol, be coarsened.

The granular washing and cleaning agent with the invention Plasticizers can be a surfactant, for example 5-35% by weight of a wetting agent, 10-70% by weight of one Builders and possibly other common additives contain.

An additive according to the invention can be any conventional granular one Detergents and cleaning agents are added. The additional amount (expressed as "cationic wetting agent) expediently 0.1-20, preferably 0.5-10% by weight, based on the amount of granular detergent and cleaning agent. Amount of additive (expressed as cationic wetting agent) is less than 0.1% by weight the softening effect is insufficient. On the other hand, the amount of additive according to the invention 20% by weight (expressed as a cationic wetting agent) the washing and cleaning power and the foaming power of the finished detergent and cleaning agent.

In granular detergents and cleaning agents according to the invention Usable wetting agents or surfactants are common  usable in such washing and cleaning agents Wetting agents or surfactants. examples for this are anionic wetting agents, such as linear alkylbenzenesulfonates, Olefin sulfonates, alkyl sulfates, alkyl ether sulfates, sulfo fatty acids or sulfofatty acid esters and soap. Further can also be non-ionic, ampholytic and / or zwitterionic wetting agents are used.

The builders which can be used in granular detergents and cleaning agents according to the invention are builders which can usually be used in such detergents and cleaning agents. Examples of such builders are wash builders such as sodium tripolyphosphate, tetrasodium pyrophosphate and zeolites, chelate builders such as sodium titratate, NTA and EDTA, alkaline builders such as sodium silicate, sodium carbonate and sodium bicarbonate, and other inorganic builders such as Na ₂ SO ₄ , NaCl and calcium carbonate.

Usually in the production of granular washing and Cleaning agents with (other) additives are preventing the redeposition of dirt Agents such as carboxymethyl cellulose (CMC) and polyethylene glycol (PEG), enzymes, bleach, optical brighteners, Colorants, pigments and perfumes.

A granular washing and cleaning agent according to the invention is obtained in the usual known manner. So be for example the named builders and the others any additives of a wetting agent-containing aqueous Slurry incorporated so that the dry weight of the Slurry is 30-60% by weight, for example. After that, the slurry comes out of a suitable nozzle under pressure in a drying chamber at one temperature sprayed from, for example, about 200 ° C. to about 500 ° C.  

An additive according to the invention comes in particular incorporation into granular detergents and cleaning agents, primarily those with anionic surfactants Agents or surfactants as the main ingredient. Nevertheless, an additive according to the invention can also alone and not only in combination with granular washing and cleaning agents are used.

Using an additive according to the invention components (a) and (b) in a given amount one can make garments or fabrics from both synthetic fibers as well as cotton in an excellent way give it a soft look and feel. In addition, when using an inventive Addition the unwanted redeposition of Dirt and a dirty or grubby look prevent washed fabrics or clothing.

It has an excellent softening effect additive according to the invention is obtained with a high degree of production without the formation of coarse powder particles uniform dispersion of the powdery copolymer particles in the melted quaternaries Ammonium salts.

The following examples are intended to illustrate the invention in more detail. Unless otherwise stated, mean all percentages "% by weight".

example 1

Powdered dihydrogenated tallow alkyl dimethyl ammonium chloride a purity of 94% and an average  Particle size of 70 microns with stirring melted at a temperature of 120 ° C. The agitated melted product are as component (b) Powdery copolymers listed in Table I. incorporated. After stirring for 30 minutes, the respective Allow the mixture to cool to room temperature.

The copolymer used in each case is after a aqueous solution polymerization process and pulverized using a jet mill. The received Powder particles have an average Size of 40 µm and a water content of 7%.

The cooled mixture obtained in the form of a block is ground, being a particulate material an average particle size of 50-100 microns is formed. The particulate material formed with the same amount of zeolite powder of a main particle size of 2 µm mixed, then the whole thing for baking with a 75% solution of a polyethylene glycol (MW = 400) is sprayed.

In this way you get various additives for granular detergents and cleaners of an average Particle size of 400-600 µm.

These additives are expressed in an amount of 4% ( as a quaternary ammonium salt) a granular washing and Detergent of the following composition is incorporated:

Granular detergent composition:% linear sodium alkylbenzenesulfonate
(C ₁₂ alkyl) 20 sodium silicate 10 sodium carbonate 10 zeolite (type A, average particle diameter: 0.7 µm) 15 carboxymethyl cellulose 0.6 soap (tallow fatty acid) 0.7 polyethylene glycol (MW = 6,000) 0.5 sodium citrate 0.8 fluorescent 0.5 perfume 0.2 sodium sulfate and residual water

The addition of Experiment No. 1 contains for comparison purposes only the dihydrogenated tallow alkyl ammonium chloride.

Evaluation of the plasticizer effect:
The softening effects of the various detergents and cleaning agents are investigated by washing tissue samples (with the detergents and cleaning agents in question). The following tissue samples are used:

Nylon jersey fabric (30 denier) 4 pieces of 30 g Acrylic jersey fabric, 2 pieces of 90 g each Cotton towel2 pieces of 80 g each bleached cotton cloth4 pieces of 50 g each 4 pieces of 85 g each

The contaminated tissue samples are first washed in tap water for 15 minutes at a temperature of 60 ° C. using the granular detergent and cleaning agent specified. The tissue samples are then rinsed three times with tap water at a temperature of 60 ° C. for 3 minutes each. The tissue samples pretreated in this way are then placed in an electric home washing machine of the jet type and washed in a wash liquor containing the specified granular detergent and cleaning agent and in each case an additive according to Table I and tap water for 10 minutes under the following conditions:
Bath temperature: 25 ° C
Detergent and cleaning agent concentration: 0.13%
Bath ratio (ratio of the volume of the wash liquor to the volume of the tissues): 30

After washing, the fabric is spun for 1 minute. The washed and spun tissue samples will be then with tap water at a temperature of 3 min Rinsed at 25 ° C and spun again for 1 min. The Whole thing is repeated twice. Eventually they will Tissue samples air dried for 24 hours. The air-dried Tissue samples are taken at a temperature of 25 ° C and a relative humidity of 65%.

Sample towels are produced from the various tissue samples and the softening effect of the additives listed in Table I is tested by five persons (impression when touched). The results are evaluated on average as follows:
The impression when touching the sample towel treated in a corresponding manner, but without the addition, is set to 0.

Impression when touching evaluation excellent softness5 very soft4  soft3 moderately soft 2 weakly soft 1

The test results can be found in Table I.

Assessment of dirt redeposition:
Seven undershirts worn for 2 days, 30 pieces of fabric, each measuring 25 cm x 8 cm, which had been sewn onto shirt collars to collect neck dirt, and as test items for the redeposition test, cotton fabric, nylon fabric, acrylic fabric and polyester fabric are placed in an electric home washing machine placed and washed in a wash liquor with the specified granular detergent and cleaning agent, one of the additives of Table I and tap water at 25 ° C, a detergent and cleaning agent concentration of 0.133% and a bath ratio of 30 for 10 minutes. The washed tissue samples are rinsed with tap water at a temperature of 25 ° C. for 3 minutes and then spun for 1 minute. This process is repeated twice.

The reflectance of the test tissue for the redeposition test is made using a commercially available Reflectivity meter measured. The degree of redeposition results from the difference ΔR between the Reflectance levels before and after washing. The redeposition can be determined visually when ΔR Is 1 or more. The one with the polyester fabric the highest level of redeposition results obtained are listed in Table I.  

Table I

Example 2

A melted mixture is prepared in accordance with Example 1, except that dihydrogenated tallow alkyl dimethylammonium methosulfate of 92% purity is used as component (a) and the copolymers listed in Table II are used as component (b). The melt obtained is cooled in a counter-air stream by spraying at a temperature of 15 ° C. under a delivery pressure of 3,924 kPa (40 kg / cm ² ), particles having an average particle size of 150-300 μm being obtained.

The particles obtained are used to make additives with zeolite powder (type A zeolite, average Particle size: 2 µm) in an amount of 3/4 of mixed by spraying cooled particles.

The various additives obtained are made accordingly Example 1 evaluated, with those given in Table II Test results can be obtained.  

Table II

Example 3

The copolymer is listed in Table III Conditions in the melted quaternary Dispersed ammonium salt using a propeller stirrer. Here you get an additive for a granular Detergents and cleaning agents of an average Particle size of 70 microns.

The abbreviations in Table III stand for the following copolymers (in which the copolymerization ratio is given in brackets) and quaternary ammonium salts:
A: acrylamide (80): sodium acrylate (10): sodium acrylamide-2-methylpropanesulfonic acid
B: acrylamide (60): sodium acrylate (10): sodium acrylamide-2-methylpropanesulfonic acid (30)
C: Dihydrogenated tallow alkyl dimethyl ammonium chloride
D: Distearyldimethylammonium chloride.

The dispersibility of the copolymer and the amount of coarse particles formed are evaluated as follows, the results are given in Table III:
Dispersibility of the copolymer:
The particles of the additive are observed on polar photomicrography and the dispersibility of the particles is assessed visually as follows:
○: good dispersibility
×: poor dispersibility
Amount of coarse particles:
The formation ratio of coarse copolymer particles results from the following formula: ○: 0.01% or less
×: more than 0.01%.

Table III

Claims (5)

1. Additive for a granular washing and cleaning agent, consisting of:

• (a) 50-99.8% by weight of at least one quaternary ammonium salt having two long-chain alkyl radicals and
• (b) 0.2-50% by weight of at least one copolymer from an acrylamide monomer, a carboxyl-containing monomer and a sulfonyl-containing monomer of the formula: in which mean:
  R ¹ , R ⁴ and R ⁵ , which may be the same or different, each have a hydrogen atom or a methyl group, R ² and R ³ , which may be the same or different, each have a hydrogen atom or an optionally hydroxyl- or oxyalkyl-substituted alkyl group;
  A is a direct bond or an alkylene group of up to 1-5 carbon atoms;
  B is an alkylene group with 1-5 carbon atoms, a phenylene group optionally substituted by an alkyl group with 1-5 carbon atoms, a unit of the formula: in which x and y , which may be the same or different, each represent an integer from 0-5, or a unit of the formula: wherein R ⁵ and A have the meaning given; Y ¹ and Y ² , which may be the same or different, each represent a hydrogen atom, an alkali metal or an alkaline earth metal and
  1 , m and n molar monomer proportions in a ratio of 98.9 to 50: 1 to 50: 0.1 to 20.

2. Additive according to claim 1, characterized in that the two long-chain alkyl radicals containing quaternary ammonium salt (a) consists of dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dihydrogenated tallow alkyl benzyl methyl ammonium chloride, dihydrogenated palm oil alkyl dimethyl ammonium chloride and / or the CH ₃ SO ₄ -alpha. 3. Additive according to claim 1, characterized in that the copolymer (b) has a degree of polymerization of 1000 or more. 4. A method for producing an additive according to claim 1, characterized in that

• (a) the copolymer of the formula (I) with an average particle size of 150 μm is added to a melt of at least one quaternary ammonium salt having two long-chain alkyl radicals;
• (b) the mixed polymer dispersed uniformly in the quaternary ammonium salt melt at a shear rate of 50-150 l / s and
• (c) the dispersion obtained is pulverized into a powdery additive for a granular washing and cleaning agent.

5. Granular washing and cleaning agent with an additive according to claim 1 as a plasticizer.