NL8601928A - TISSUE SOFTENING AND ANTI-STATIC DETERGENTS. - Google Patents

Description

iL * VO 8304

Fabric softening and anti-static detergents.

This invention relates to a detergent composition containing a clay softening and cationic anti-static agent. More particularly, this invention relates to a detergent powder containing a detergent surfactant, a clay softening agent and a water-soluble diammonium salt as an antistatic agent, to the method of preparing the composition or using it for washing textile materials. Detergent means the final product, composition or mixture in which all desired ingredients are present.

c. Powdered detergents containing a detergent surfactant (anionic, nonionic) with a clay softener and a cationic antistatic agent such as quaternary ammonium compounds, quaternary diammonium compounds, etc. are known. Representative patent literature in this field are U.S. patents 3862058, 3886055, 3915882, 3948790, and 4203851, as well as British patent application 1241152. Other patents pertaining to clay fabric treating compositions include U.S. patents 3594212 and 4062647.

The use of bentonites for fabric softening is known from British Pat. Nos. 401413 and 461221.

Although a satisfactory cleaning and softening effect has been achieved with the known clay softening detergents, it is generally difficult to reduce the static charge on washed fabrics so much that it is noticeable by the normal consumer.

Generally, the inclusion of an adequate amount of antistatic agent to provide an acceptable level of antistatic activity has led to the general reduction in cleaning, whitening and softening capacity.

This reduction in overall performance has been noted regardless of whether the cationic antistatic agent is added to the agent under conditions such that a surface modification of the clay softener results or under conditions such that only physical mixtures of the clay, the , cationic anti-static agent, the detergent and other components of the agent.

It is thus an object of this invention to provide a detergent with a clay softener containing a static charge-reducing compound.

It is another object of the invention to provide an antistatic detergent in the form of spray-dried granules incorporating a water-soluble diaramonium compound as an antistatic agent, the spray-dried granules being compatible with the mineral clay fabric softener as well as a method for preparing the spray dried granules.

It is another object of this invention to provide a powdered clay softener formulated laundry detergent having consumer appreciable anti-static properties without adversely affecting cleaning, whitening or softening effects of the agent.

Yet another object of the invention is to provide a powdered clay softening detergent wherein a water-soluble diammonium salt cationic antistatic agent can be added to the agent as a component of the spray-dried mixture wherein the antistatic agent can be uniform and homogeneous in the agent and the clay softening agent can be added to the spray dried granules or beads afterwards.

These and other objects of the invention which are further elucidated by the following detailed description as well as preferred embodiments thereof are achieved by mixing as an antistatic cationic compound in a clay softening detergent, and in particular as a component of spray dried beads or granules using the clay softening agent, a water-soluble diammonium salt of formula 1 of the formula sheet, wherein an aliphatic hydrocarbon is from about 12 to about 30 carbon atoms; R_, R_, R., R_ and R- each are independently selected 2j 4 5 o 35 from aliphatic hydrocarbon groups having 1-22 carbon atoms provided that the total number of carbon atoms in all aliphatic hydrocarbons is S 3 V 1 9 2 8 3 * * dust groups, including R ^, do not exceed about 75 and with the further proviso that no more than two of the R0-Rg groups contain more than 12 carbon atoms; and hydroxy groups of the formula (CH-CH-0) (CH (CH-) CH „0) H, where m and n are independently 0 or positive 2 2 IQ 3 μ Π 5 numbers such that the sum of m and n for all groups R -R- is at least 2 but not greater than 30; with the even further conditions

i O

that at least one of them is an alkanol group; R? a divalent linking group such as lower alkylene or substituted lower alkylene, k is a number from 1 to 20 and X is a water-soluble salt-10 anion.

Since the useful diammonium compounds of the formula ·· 1 are water-soluble and are also stable over a wide range of µ values and at elevated temperatures, they can be added directly to the softening mixture as an aqueous solution with the other softening wax active components, to be spray dried are added whereby the antistatic diammonium salt agents are uniformly and homogeneously incorporated into the spray dried beads or granules.

As a result of this homogeneous distribution, the desired level of anti-static performance can be achieved. Using low levels of the antistatic compound and without a negative effect on other detergent properties, including cleaning, whitening and softening properties.

As used herein, the term "water soluble" means that the antistatic diammonium compounds are soluble or form at least 25 stable dispersions in water of at least 5 wt% at 20 ° C. The preferred compounds of formula 1 are in water at ambient temperature for at least 10 wt% soluble Since the antistatic diammonium salts of formula 1 are available or can be prepared as organic solvent-free aqueous solutions or dispersions, they can be handled easily and safely in powder processing plants and easily mixed and spray dried as a component of a high performance granular or powdered detergent.

A typical detergent for very dirty laundry containing the spray dried granules containing the water-soluble antistatic agent of formula 1 may include the following ingredients.

Λ Λ j ', J' · * i Λ ft 1 * w / - »% 4 ____ Amount (wt%)

Ingredients Total Spray Dried _ composition granules_

Surfactant 1-95 10-60 5 Organic and Inorganic Detergents Builders 2-80 5-90 Softener 1-50 0 Antistatic Agent of Formula (1) 0.2-5 0.4-15 Fillers 0-25 0-10 10 bleaching agents and bleaching additives 0-25 0-5 optical brighteners, pigments and dyes 0-10 0-8 anti-foaming agents; foam suppressants, etc. 0-10 0-8 15 enzymes 0-5 0 pH adjusting agents, buffers, etc. 0-10 0-8 pH adjusting agents, buffers, etc. 0-5 0-3 anti-grazing agent, perfume, etc.

water rest 20. In a preferred method of preparing the potent granular or powder formulation softening detergents, the antistatic agent of formula 1 and the remaining pH-insensitive, heat stable ingredients are mixed in a crutcher and spray dried to form spray dried beads and beads, which beads become uniform mixed or sprayed with the detergent ingredients which are pH sensitive and / or heat sensitive or which may otherwise react with the cationic antistatic agent, anionic surfactant or other component of the spray dried granules or beads.

Examples of the subsequently added ingredients that are mixed with the spray dried granules are, for example, bleaches, clay softeners, enzymes, perfumes, non-ionic surfactants, etc.

Composition procedures are known in the art and those skilled in the art will be able to easily determine the optimal composition conditions.

5'v '; 1 0 0 £ 5

Synthetic organic detergent compounds

The detergents may contain one or more surfactants selected from anionic, nonionic, ampholitic and zwitterionic detergents. The synthetic organic detergents used in the invention may be any of a variety of such compounds which are well known and described in detail in the text of "Surface Active Agents and Detergents", Part II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, the relevant disclosure of which is incorporated herein by reference, The total amount of the surfactant detergent compound (s) may even be up to 95% by weight of the total detergent, although preferred amounts of about 1 to 70% by weight, in particular 5-50% by weight and especially 5-30% by weight, of the total detergent composition.

In the detergent compositions of the present invention, preferably one or more anionic detergent compounds are used as the major detergent compositions.

The anionic detergent can be optionally supplemented with another type of detergent, preferably a non-ionic gene detergent, especially when used in combination with a builder detergent salt.

Anionic surfactants

The anionic surfactants useful in the invention include those surfactants containing an organic hydrophobic group having about 8-26 carbon atoms and preferably about 10-18 carbon atoms in their molecular structure with at least one water solubilizing group selected from sulfonate, sulfate, carboxylate, phosphonate and phosphate, to form a water-soluble detergent.

Examples of suitable anionic detergents include soaps, such as the water-soluble salts (eg, the sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids, or resin salts, which contain about 8-20 carbon atoms and preferably 10-18 carbon atoms . Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, such as talc, fat, coconut oil and mixtures thereof.

Soi l 32? 6

Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and talc, for example, sodium coconut soap and potassium talc soap.

The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an aliphatic group, preferably an alkyl group containing about 8-26 and preferably about 12-22 carbon atoms. (The term alkyl includes the alkyl portion of the higher acyl groups). Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates, such as the higher alkyl benzene sulfonates containing about 10-16 carbon atoms in the higher alkyl group as straight or branched chain, for example the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.

Other suitable anionic detergents are the olefin sulfonates, including long olefin sulfonates, long hydroxyalkane sulfonates or mixtures of olefin sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergent compositions can be prepared in the conventional manner by reacting sulfur trioxide (SO2) with long olefins containing about 8-25 and preferably about 12-21 carbon atoms, such as olefins of the formula RCH = CHR *, wherein R is a higher alkyl group with about 6-23 carbon atoms and R * represents an alkyl group with about 1-17 carbon atoms or hydrogen, forming a mixture of sultones and olefin sulfonic acids, which is then treated to convert the sultones to sulfonates.

Other examples of sulfate or sulfonate detergents are paraffin sulfonates containing about 10-20 carbon atoms and preferably about 15-20 carbon atoms. The primary paraffin sulfonates are made by reacting long alpha olefins and bisulfite. Paraffin sulfonates, the sulfonate group of which is distributed along the paraffin chain, are described in U.S. Patent Nos. 2503280, 2507088, 3260741, 3372188, and German Patent No. 735096.

Other suitable anionic detergents are sulfated 35 ethoxylated higher fatty alcohols of the formula RO ^ H ^ O ^ SQ ^ M, where R represents a fatty alkyl group having 10-18 carbon atoms, m 2-6 380 1 82 8 7 (preferably with a value of about 1/5 to 1 of the number of carbon atoms in the R group) and M is a solubilizing salt-forming cation, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino or a higher alkylbenzene sulfonate, wherein the higher alkyl group is 10 -5 15 carbon atoms. The amount of ethylene oxide in the polyethoxylated higher alkanol sulfates is preferably 2-5 moles of ethylene oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higher alkanol is 11-15 carbon atoms. To maintain the desired hydrophilic-lipophilic balance, when the carbon content of the alkyl chain is in the lower portion of the 10-18 carbon atom range, the ethylene oxide content of the detergent can be decreased to about 2 moles per mole, while on the other hand, when the higher alkanol contains 16-18 carbon atoms in the higher part of the range, the number of ethylene oxide-15 groups can be increased to 4 or 5 and in some cases even 8 to 9. Also, the salt-forming cation can be modified to obtain the best solubility. It can be any suitable solubilizing metal or group, but most often it is an alkali metal, for example sodium or ammonium.

When lower alkylamine or alkanolamine groups are used, the alkyl groups and alkanols will usually contain 1-4 carbon atoms and the amines and alkanolamines can be mono-, di- and tri-substituted, such as a monoethanolamine, di-isopropanolamine and trimethylamine. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company under the trade name Neodol registered trade mark 25-3S.

The most preferred water-soluble anionic detergents are the ammonium and substituted ammonium (such as mono-, di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkylbenzene sulfonates, olefin sulfonates and higher alkyl sulfates. Most preferred among the above-mentioned anionics are the sodium linear alkylbenzene sulfonates (LABS), and especially those in which the alkyl group is a straight alkyl group of 12 or 13 carbon atoms.

The anionic surfactant will generally represent the main detergent component and may comprise about 30-100% of the total surfactant ingredients. Preferably the anionic substances take at least 50%, preferably at least 60%, especially preferably at least 70% and especially up to about 99%, preferably up to about 90% and especially preferably up to about 80% of the total surfactant ingredients.

The anionic surfactant is usually and preferably included as a component of the anti-static agent-containing spray dried granules and is added to the mixture as an aqueous solvent or dispersion and preferably as a highly concentrated aqueous suspension.

Non-ionic surfactants

The next class of preferred detergents are the nonionic synthetic organic detergents.

The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and organic hydrophilic group and they are typically produced by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature).

Practically any hydrophobic compound with a carboxy, hydroxy, amido-20 or amino group where a free hydrogen is attached to the nitrogen can be condensed with ethylene oxide or its polyhydration product, polyethylene glycol, to a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a poly-lower alkoxylated higher alkanol wherein the alkanol contains 8-22 carbon atoms, preferably 10-18 carbon atoms and the number of moles of lower alkylene oxide (or 2 or 3 carbon atoms) is 3-20. is. It is preferred to use such materials where the higher alkanol is a higher fatty alcohol of 11-15 carbon atoms and contains 5-13 lower alkoxy groups per mole.

The lower alkoxy group is preferably ethoxy, but in some cases it is desirable to mix it with propoxy, the latter, if present, usually being a minor component (less than 50%). Examples of such compounds are those in which the alkanol is 12-15

860 1 3 2 S

Contains 9 carbon atoms and contains about 7 ethylene oxide groups per mole. Examples are Neodol (registered trademark) 25-7 and Neodol 23-6.5, which products are manufactured by Shell Chemical Company, Inc. to be made. The former is a condensation product of a mixture of higher fatty alcohols having an average of about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the latter is a corresponding mixture in which the carbon atom number of the higher fatty alcohol is 12-13. number of ethylene oxide groups per mole is on average about 6.5. The higher alcohols are primary alkanols. Other examples of such detergent actives include Tergitol® (registered trademark) 15-2-7 and Tergitol 15-S-9, both of which are straight secondary alcohol ethoxylates made by Union Carbide Corporation. The former is a mixed ethoxylation product of a 11-15 carbon atoms of straight secondary alkanol with 7 moles of ethylene oxide, while the latter is a similar product with however 9 moles of ethylene oxide being converted.

Highly preferred nonionic detergents in the present compositions are the higher molecular weight nonionic detergents, such as Neodol 45-11, which represents similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol being 14- Contains 15 carbon atoms and the number of ethylene oxide groups per mole is about 11.

Such products are also made by Shell Chemical Company.

Of the total detergent surfactants in the detergent composition, the nonionic surfactant may be in amounts from up to about 70% by weight, preferably up to about 50%, most preferably up to about 40%, and especially up to about 15% are present. Typically, the nonionic surfactant will be present in use in amounts of at least 1%, preferably at least 10%, especially at least 30% of the combined weights of all surfactant surfactant ingredients. Expressed in the total softener detergent composition, the nonionic surfactant will usually be present in amounts within the range of about 0.1 to 20%, preferably 0.3-15%, especially 0.6-10% by weight. %.

Since the nonionic surfactant compounds are often only sparingly soluble in water or form viscous solutions or gels when added to fS A - \ 4, v »"> Λ 3 o - - 10, they are usually made available in the form of organic solvent solutions, for example in ethanol or isopropanol alone or together with water Thus, when the nonionic surfactant is obtained in the form of an organic solvent solution, it will not be used as part of the mixture to form the spray dried granules or beads, but are previously added to the already formed spray dried granules, even when the nonionic surfactant is in its pure liquid form (most 10 of the nonionic compounds are liquid at ambient temperatures) or as an aqueous solution it is still preferred to use the nonionic surfactant compound ng later to the spray dried granules.

Zwitterionic detergents such as the formula and sulfo formula. 2 of the formula sheet can also be used.

g

In this formula, R is an alkyl group having about 8-18 carbon atoms, R and R are each independently an alkyl or hydroxy alkyl group with about 1 to 4 carbon atoms, R is an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms while Y represents a carbon atom or an S: 0 group-20. The alkyl group may contain one or more intermediate linkages, such as amido, ether or polyether linkages or non-functional components, such as hydroxyl or halogen, which have virtually no influence on the hydrophobic character of the group. When Y represents a carbon atom, the detergent compound is called a betaine; and when Y represents an S: 0 group 25, the compound is called a sulfobetaine or sultaine.

Ampholytic detergent compounds are also suitable for the invention. Ampholytic compounds are well known, and many useful detergents of this group are described by Schwartz, Perry and Berch in the aforementioned "Surface Active Agents and Detergents". Examples of suitable amphoteric detergent compounds include: alkyl beta-amino dipropionates, RN (C 1 H H COOM) 1; alkyl beta-aminopropionates, RNCH 2 HCOOM; and long imidazole derivatives of the general formula 3 of the formula sheet, wherein in each of the above formulas R represents an acyclic hydrophobic group having about 8-18 carbon atoms and M 35 is a cation to neutralize the charge of the anion.

Specific useful amphoteric detergent compounds include the dimethyl cycloimidinium ethoxyethionic acid 2-ethionic acid, dead cycbeta-alanine and the internal salt of 2-trimethylaminoolauric acid.

The amounts of the zwitterionic synthetic organic detergent and the ampholytic synthetic organic detergent when present in the present compositions are not particularly critical and can be selected depending on the desired results. Generally, either or both of these classes of detergent compounds can be used to replace all or part of the anionic organic detergent compounds and / or nonionic organic detergent compounds within the above ranges.

As with the anionic and nonionic surfactants *, those skilled in the art will readily be able to determine whether he will incorporate the zwitterionic and ampholytic surfactant as a component of the mixture to form the spray dried granules or beads, or will add this compound to the spray dried beads afterwards to form the high performance final detergent intended for very dirty laundry.

Generally, when present as an aqueous solution, they are preferably added to the mixture and when available in organic solvents, they are added later to the spray dried granules. Clay softening compounds

The clay softener can be selected from any of the products known to impart softness to the fabrics to be washed. The pre-color clay products are smectite clay materials. Smectite-type clays useful in the invention are three-layer clays wherein the layered structure has the ability to increase its volume several times by swelling or expanding in the presence of water to form a thixotropic gelatinous substance. There are two classes of smectite-type clay products: in the first class, alumina is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. Atomic substitution by iron, magnesium, sodium, potassium, calcium and the like can take place within the crystal lattice of the smectite clay products. It is common to distinguish between clay products based on a predominantly cation. The sodium clay is, for example, a clay in which the cation is predominantly sodium.

S3ü1923 12

The smectite clay products used in the compositions are all commercially available. Such clay products include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite and vermiculite. These clays are available under different trade names, for example, Thixogel No. 1 (also "Thixo-Jel") and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay No. 325 from American Colloid Co., Skokie, Illinois. Clearly, such smectite-type minerals available under different trade names may comprise mixtures of different apar-10 mineral units. Such smectite mineral mixtures are also suitable for use.

In the detergent compositions of the invention, the most preferred clay softeners are aluminum silicates in which sodium is the predominant cation, such as, for example, bentonite clay. Among the bentonite clays, those from Wyoming (commonly referred to as Western or Wyoming bentonite) are particularly preferred.

Preferred swelling bentonites are marketed under the name Mineral Colloid, as industrial bentonites by Benton Clay Company, a sister company of Georgia Kaolin Co.

20 These materials which are the same as those previously sold under the trade name THIXO-JEL are selectively mined and enriched bentonites and those most suitable are available as Mineral Colloid Nos. 101 etc. corresponding to THIXO-Jel's 1, 2, 3 and 4. Such materials have a pH (6% concentration in water) in the range of 8-9.4, a maximum free moisture content of about 8%, and a specific gravity of about 2.6, while for powder quality at least about 85% (preferably 100%) passes through a sieve with 74 micrometer openings). More preferably, the bentonite is a bentonite in which essentially all particles (ie at least 90% thereof, preferably more than 95%) pass through a sieve with 44 micrometer openings. and most preferably, all particles pass through such a screen.

The swelling capacity of the bentonites in water is usually in the range of 3-15 ml / gram and its viscosity at a 6% concentration in water is usually about 8-30 centipoises.

Instead of Thixo-Jel or Mineral Colloid, one can use 85 0 1 32 ·? 13 tonites also use products as sold by American Colloid Company, Industrial Division, as general bentonite powder (325 mesh) of which at least 95% is less than 44 micrometers in diameter (wet particle size) and at least 96% is less than 74 micrometers in diameter (dry 5 particle size) ). Such an aqueous aluminum silicate mainly consists of montmorillonite (90% minimum), with small amounts of feldspar, biotite and selenite.

A typical analysis on an "anhydrous" basis is 63.05% silica, 21.5% alumina, 3.3% ferric iron (as Fe ^ O ^), 0.4% ferrous iron (as FeO), 2.7% 10 magnesium (as MgO), 2.6% sodium and potassium (as Na 2 O), 0.7% calcium (as CaO), 5.6% crystal water (as H 2 O) and 0.7% trace elements.

Although the Western bentonites are preferred, it is also possible to use other bentonites such as those made by treating Italian or similar bentonites containing relatively small amounts of exchangeable monovalent metals (sodium and potassium) with alkaline materials such as sodium carbons. to improve the cation exchange properties of such products. It is believed that the Na 2 O content of the bentonite should be at least about 0.5%, preferably at least 1%, and most preferably at least 2% for the clay to have satisfactory swelling properties and good softening and dispersion properties in a aqueous suspension.

Preferred swelling bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, for example Laviosa 25 AGB and Winkelmann G-13.

Of course, other clay minerals capable of imparting softness to textiles can also be used in the invention.

The preferred clay products used herein are "insensitive", that is, with a particle size that cannot be sensed by the senses. Intangible clays have particle sizes below about 5 microns; the clays used herein have a particle size traet from about 5 to about 50 microns.

The clay softeners are present in the detergent compositions in amounts from about 1 to about 50%, preferably about 2 - 30%, especially 4 - 20%, by weight, based on the 8 δ CJ 9 2 3 14 total composition.

In the present invention, it is highly preferred that the clay softening agent be subsequently added to the antistatic agents containing spray dried granules or beads to prevent any interaction, eg ion exchange, between mineral clay particles and the cationic antistatic diammonium compound. Since the diammonium compound is homogeneously present in and very finely divided by the spray-dried granules as a result of mixing and spray-drying, and since the ingredients added afterwards come into contact with the spray-dried beads under virtually anhydrous conditions, there is practically no ion exchange between the. clay softener and the cationic antistatic diammonium salt.

The clay softener is present in the detergent compositions of the invention in an amount sufficient to provide the desired softening effect when the composition is used in the amounts customary for detergent compositions, for example, about 1/8 to 1 cup of detergent per wash lot.

Builders The detergent compositions of the invention optionally contain, but preferably at least one detergent builder of the type commonly used in detergent compositions. Useful builders include any of the conventional inorganic water-soluble builder salts, such as, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, tripolyphosphates, silicates, carbonates, bicarbonates, borates, sulfates and the like.

The organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, amino polyacetates, carboxylates, polycarboxylates, succinates, phytates and the like. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates particularly include, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid.

Examples of these and other phosphorus builder compounds are described in U.S. Pat. Nos. 3213030, 2422021, 3422137, and 8 SO 1923 15 3400176.

Particularly preferred as water-soluble inorganic builders are penta-sodium tripolyphosphate and tetrasodium pyrophosphate.

Specific examples of non-phosphorus inorganic builders include water-soluble inorganic carbonate, bicarbonate and silicate salts.

The alkali metal, for example sodium and potassium, carbonates, bicarbonates and silicates are particularly preferred.

Water-soluble builders are also usable. For example, the al-10 potassium, ammonium and substituted ammonium acetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful builders for the invention. Specific examples of acetate and polycarboxylate builders include sodium, potassium, lithium, ammonium, substituted ammonium salts of ethylenediaminotetraacetic acid, nitrolotriacetic acid, benzene polycarboxylic acids (i.e., penta- and tetra), carboxyymoxy-tartaric acid and citric acid.

Other useful organic builder salts include the polycarboxylate materials as described in U.S. Patent No. 2264103, including the water-soluble alkali metal salts of mellic acid. The water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent No. 3308067 are also useful.

One can also use water insoluble builders, especially the complex silicates and more particularly the complex sodium aluminosilicates such as zeolites, eg zeolite 4A, a type of zeolite molecule where the univalent cation is sodium and the pore size is about $ 4.

The preparation of such types of zeolites is described in U.S. Patent 3,114,603. The zeolites can be known to be amorphous or crystalline and contain hydrate water.

Mixtures of organic and / or inorganic builders are also useful. Such a mixture is described in Canadian Patent No. 755038, for example, a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-1-35 hydroxy-1,1-diphosphonate. It is understood that while the alkali metal salts of the aforementioned inorganic and organic polyvalent anionic 31 9 2 2 16 and organic polyvalent anionic builder salts are preferred from an economic standpoint, the ammonium alkanolammonium, e.g. triethanolammonium, diethanol ammonium and the like water-soluble salts of any of the aforementioned builder anions are usable.

The builder salts, including both the inorganic and organic detergent builder salts, are suitably added to the crutcher mixture to be incorporated, along with the antistatic diammonium compounds, the anionic surfactant, etc., into the granules or beads spray dried according to the invention to provide about 5 - 90%, preferably about 15-65%, especially about 20-55% by weight of builder salts, based on the weight of the spray dried granules, leaving in the final composition, after mixing with subsequently added ingredients, about 2-80%, preferably 10-70%, and in particular 20-50% of detergent builder salts, based on the total composition, are present.

Diammonium compound anti-static agent

The antistatic agents used in the present invention are diammonium compounds characterized by their water solubility, ie they are able to form stable, clear solutions or dispersions in water at 25 ° C at least 5%, preferably at least 10% by weight of the diammonium compound.

The diammonium compounds useful herein to reduce static charge build-up are the water-soluble compounds of the following general formula 1 of the formula sheet, wherein is an aliphatic hydrocarbon of about 12 to 30 carbon atoms; , R ^, Rj, Rg and Rg are each independently selected from aliphatic hydrocarbon groups having 1-22 carbon atoms provided that the total number of carbon atoms in all aliphatic hydrocarbon groups, including R ^, does not exceed about 75 and with the further provided that no more than 3 of the 9 bars contain more 3 and 12 carbon atoms; as well as alkanol groups of the formula

CHL

I ^ (CH_CH_0) (CHCELO) H 2 2 m 2 n 35 of the formula sheet, where m and n are independently 0 or positive numbers, where the sum of m and n from all groups R ^ - Rg is at least 2 but not 8601928 17 is more than 30; on the further condition that at least one of

R 1 - is said alkanol group; R_ a divalent coupling group such as 2 o I.

a C 2 -C 5 alpha alkylene or substituted. C 2 -C 5 is lower alkylene, k is a number from 1 to 20 and 5 X is a water-soluble salt-forming anion.

The preferred compounds of formula (1) are those containing only 1 or 2, preferably only a single long carbon chain group, i.e. 12 or more carbon atoms. Accordingly, the preferred meanings for R ^ - Rg in Formula 1 are as follows: R ^ is an aliphatic hydrocarbon group which can be straight or branched chain as well as saturated or unsaturated (ie straight or branched chain alkyl, alkenyl or alkynyl), with 16-22 carbon atoms; R - R. are independently selected from alkyl or alkenyl 2 with 1 to 16, preferably 1 to 12, especially 1 to 6, carbon atoms, provided that the total number of carbon atoms in all aliphatic hydrocarbon radicals R. - R. is not greater than about 50, preferably 1 o no greater than about 35, and further provided that no more than 2, preferably no more than 1, and most preferably none of R- - R_ contains more than 12 carbon atoms; as well as alkanol groups of the 2 o 20 formula (CH_CHoO) (CH (CH-) CH-CH, O) - H i i m i i. in which m and n may be 0 or a positive number such that the sum of m and n in all alkanol groups R_-R ^ is at least 3 but not more than 2 b than 25, preferably not more than 15 among the still further conditions that at least 1, preferably at least 2 of R 1 -R 8 is said alkanol group; R7 is an alkylene of 2-4 carbon atoms, such as ethylene (-CI ^ CE ^ -), propylene (-CH2CH2CH2-}, isopropylene (-CH2CH (CH2) CH2-), butylene (-CH2CH2CH2CH2-}, etc.). or such an alkylene contains one or more such as one or two substituents such as hydroxyl, G 1 -C 1 lower alkyl, hydroxy bearing (C 1 -C 2) alkyl, etc. preferably -CH2CH2- or -CH2CH2CH2-most preferred -CH2CH2CH2-, k is 1 - 10, preferably 1 - 5, especially 1-3 and 35 X is a water-soluble salt-forming anion such as halide, for example bromide, chloride or iodide, sulfate, methosulfate,

»3 * 31 32S

* <· 18% ethosulfate, hydroxide, acetate, propionate or other similar inorganic or organic solubilizing monovalent anions.

Examples of preferred recall groups include stearyl, talc, hardened talc, eicosyl, soy and the like. Examples of preferred alkyl and alkenyl groups of R-R include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-butenyl, octyl, 1-octenyl, etc.

Especially preferred are methyl, ethyl, propyl and isopropyl. Most preferred are methyl and ethyl.

Examples of preferred alkanol groups for R 2 ~ R 6 10 include ethanol (n = 0, m = 1); propanol (m = 0, n = 1) and ethoxy, propoxy and mixed (ethoxy) (propoxy) ethanol and / or propanol, such as 1 1 (CH-CH-O) 1H, wherein m is 2-4; / CHCH 4 O \ n where n is 2-4; and 2 2 m I2! 1 V CH. / n 1J 1 (CH.CH-0) 1 (CH (CH,) CH „0) 1, where m and n are numbers 1-4 each and ^ ^ mj ** ix 15 m + n = 2 '- 6. In the mixed ethoxy-propoxyalkanol groups, the order of addition of the ethoxy and propoxy groups is not critical and it is clear that blocks of the ethoxy groups and blocks of the propoxy groups can be bonded to the N atom of the diammonium compound and that the ethoxy and propoxy groups can be statistically distributed. Thus, as is known in the art, the distribution of the ethoxy and propoxy groups will be determined by the order in which the ethylenediamine or propylene diamine compound is condensed with ethylene oxide (or its precursor) and propylene oxide (or its precursor).

Specific examples of compounds of formula 1 which are either commercially available or readily prepared by normal techniques include those of formulas 1 '- 5' of the formula sheet etc. and the corresponding ethosulfate, halide, acetate, etc. water-soluble salts.

The above-mentioned compound of formula 2 '(N-methyl-N- (2-hydroxyethyl) -N-tallowalkyl-N'-methyl-N'-bis (2-hydroxyethyl) propylene diammonium sulfate is particularly preferred. is commercially available as Rewoquat DQ35 from Rewo Chemicals Co. Germany and is a clear liquid solution with 35% solid dissolved therein Rewoquat DQ35 has a free amine content less than 2% by weight and a pH (1% solution) in water) in the range of 3.5-5. This compound can be prepared in the usual manner by reacting, for example, 1 mole of 860192 · 19 N-methyl-N-tallowalkyl-N'-methylpropylendiamine with 3 moles of ethylene oxide and quaternizing the resulting compound with methyl sulfate By ethoxylating with more than 3 moles of ethylene oxide, the corresponding higher ethoxylated compounds can be obtained.

It is a critical feature of the present invention that the antistatic diammonium salt has the specific degree of water solubility but is not so water soluble that it is only difficult to remove from the washing liquid during use of the detergent softening agent.

In general, a degree of solubility of up to about 50% by weight at 25 ° C is sufficient to impart the desired static charge reducing capacity to washed fabrics.

The aqueous (organic solvent free) solution (or dispersion) of the antistatic diammonium salt is added to the mixture along with the remaining pH insensitive and heat stable ingredients such as builders, fillers, anionic surfactants, pH adjusters, water, etc. and the mixture is spray dried according to conventional techniques. The amount of the antistatic agent in the mixture is such that the spray dried beads or beads are about 0.4-15%, preferably 1-12%, especially about 2-12% by weight of the beads, of contain the antistatic agent of formula 1. The antistatic agent is finely homogeneously finely distributed in the spray dried beads and can very effectively perform its antistatic function without interfering with the other functional ingredients.

The antistatic spray-dried beads are thoroughly mixed with the clay softener and the remaining ingredients, for example, nonionic surfactants, bleaches, enzymes, perfumes and other pH or heat sensitive and / or water insoluble ingredients to prepare the final composition with ver - emollient and anti-static agent. The amount of the spray dried beads and the subsequently added ingredients is such that the final composition contains the following amounts of the essential ingredients: r * r * 'J ί <Λ, * £ 0 1 sio 35

♦ Q

20

Ingredient Wide Amount wt% _ _ Intermediate range Preferred detergent 1-95 5-50 5-30

Builders 2-80 10-70 20-50 5 Clay Softener 1-50 2-30 4-20

Diammonium salt 0.2-5 0.4-3 0.5-2.5 (compound of formula (1)) additives, fillers 0-60 2-50 5-30 moisture 10 The rest of the composition can optionally be added with usual detergent additives, fillers and moisture. Optional components

The use of an inert, water-soluble filler salt is desirable in the detergent compositions according to the invention. A preferred filler salt 15 is an alkali metal sulfate, such as potassium or sodium sulfate, the latter being particularly preferred. The amount of filler will generally be up to about 5% by weight such as 0.1-2%, preferably 0.3-1%, on the composition.

Various auxiliary substances can be included in the detergent compositions 20 of the invention. Generally, these include perfumes, dyes such as pigments and colorants; bleaching agents such as sodium perborate, bleach activators, bleach stabilizers, anti-curing or soil suspending agents, such as alkali salts of carboxymethyl cellulose, optical brighteners such as anionic, cationic or nonionic brighteners; foam stabilizers such as alkanolamides, foaming promoters, germicides, anti-scaling agents, pH adjusters, enzymes and the like, all of which are well known in the art of washing for use in detergents. Flow enhancers commonly referred to as flow aids are also useful for maintaining the finely divided compositions as free-flowing granules or powders. Starch derivatives and special clays are commercially available as additives that improve the fluidity of otherwise tacky or pasty finely divided compositions, two such clay additives currently being commercially available under the tradenames "Satintone" 35 and "Microsil" . Bound water and free water in minor amounts may also be present therein without detrimental effect on the granular powdered compositions.

8601928 ♦ 21

The moisture amounts will normally be 1 - 15%, preferably 5 - 12%, usually 8 - 12% of the whole composition. Within these quantities a satisfactory liquid finely divided, granular or powdered product is formed, which does not have to be excersively dust-forming by adjusting the size of the particles and the moisture content.

Suitable ranges of detergent additives are: enzymes 0-2%, in particular 0.2-1%; corrosion inhibitors - * about 0 - 15% and preferably 2 - 8%; anti-foaming agents and suds suppressors - 0 - 15%. buttocks preferably 0-8%. bio example 0.1 - 5%; dirt sus-10 Soothing or anti-scarifying agents and anti-yellowing agents - 0 -10%, preferably 0.3 - 3%; dyes, perfumes, whiteners and bluebodies total weight 0 to about 2%, and preferably 0 to about 1%, such as 0.1-0.8%; pH modifiers and pH buffers 0-5%, preferably 0-2%; bleaching agents - 0 to about 40%, and preferably 0 to 15, about 25%, e.g., 2 - 20%, bleach stabilizers and bleaching agents, 0 to about 15%, preferably, 0 - 10%, e.g., 0.1-8%.

When selecting the auxiliary materials, care is taken to ensure that they are compatible with the main components of the detergent.

Whatever the form of the detergent, its use in the washing process is essentially the same. The finely divided composition is usually added to the wash water in an automatic washing machine such that its concentration in the wash water ranges from about 0.05 to 1.5%, usually 0.1-1.2%.

The water to which it is added preferably has a moderate or low hardness, preferably 30 to 120 dpra hardness, as calcium carbonate, but both soft and harder waters can be used.

The water temperature can be 20-100 ° C, but is preferably 60-100 ° C in those cases where the textile or laundry is able to withstand high temperatures without color matching or fading.

When it is desired to wash at low temperatures, the temperature can be kept at 20-40 ° C.

At the concentrations of the detergent compound as stated, the pH of the wash water will usually be on the alkaline side, for example 7-12, preferably 8-11 and especially 9-10.

The laundry: wash water weight ratio will usually be 1: 4 to 1:30, preferably 1:10 to 1:30.

1928 V v 22

The following examples illustrate the invention without limiting it. Unless otherwise indicated, all parts and percentages are by weight.

Example 1 The following composition was prepared by first forming the spray dried beads (A) and then adding the components (B).

11A "(Spray dried granules) Share

Tap water 6.8 ^ Hardened fish oil or tallow oil fatty acids 2.8

NaOH (35.7%) 1.3

Tap water 11.5

Sodium silicate (40%) Na »0: SiO“) 9.9 1 1 1

Anionic surfactant 16.0 2 15 Optical brightener 0.2

Sodium carboxymethyl cellulose 0.7

Pentasodium tripolyphosphate 36.4

Rewoquat DQ35 (30% diaromonium compound) 4.7

Sodium sulfate (anhydrous) · 0.7 20 Total: 91.0 ^ * linear dodecylbenzene sulfonate - as a thick aqueous suspension.

2

Stilbene whitener no. 4, high conc. grain.

^ 64.2 parts after drying.

25 Subsequently added ingredients (B) Share

Sodium perborate 15.0

Blue bentonite clay agglomeration 16.0

Enzyme 0.5

Magnesium Silicate / DTPA mixture No. 2 0.2 30 Potassium methylsiliconate (50%) 0.6

Non-ionic surfactant 3.0

Duet 787 (perfume) 0.5

Spray-dried granules (A) 64.2 C-C g fatty alcohol ethoxylated with 11 moles / ethylene oxide per mole.

. ”* -I Λ J Λ Λ ίΐ b o i kii 23

The concentration of Rewoquat DQ35 antistatic agent in the final agent was 1.63%.

For comparison, the same agent was prepared without using Rewoquat DQ 35.

Each of the compositions was tested for static charge-reducing capacity for four different types of fabric: acrylic; polyester; polyester / cotton blend and nylon.

Table A gives the results for electro-static values obtained according to the Bauman instrument method. Table B gives the results of an independent assessment of the static charge level (O = no charge up to 3 «strongly charged). All data was obtained after washing at 60 ° C and drying at full drying power in a Miele centrifuge for 40 minutes. The instrument readings were taken after conditioning at 20 ° C and 40 ° relative humidity. Also, Tables A and B indicate the results of a second series of tests comparing the agent of the invention with a commercially available emollient, detergent, anti-static powder composition (tallow trimethyl ammonium chloride-2%, dithmethylamine salt-4%).

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The evaluation of the softening, cleaning and whitening of the agent of the invention (A + B) showed that there was no negative effect on these capacity parameters compared to agent A + B without the Rewoquat DQ35.

Example II

In Example I, the same amount of Rewoquat DQ35 as used in component A was used instead of the subsequently added component B; the static load reducing capacity was lower.

Example III

Using the same general procedure as in Example I, the following composition was prepared:

Spray dried granules "* A" Wt%

Sodium tridecylbenzene sulfonate 15.0 15 Pentasodium tripolyphosphate 33.0

Sodium silicate (1Na 2 O: 2.4 SiO 2) 7.0

Sodium sulfate 4.0

Optical whitener (Tinopal 5BM) 0.2

Na-carboxymethyl cellulose 0.25 20 Rewoquat DQ35 1.8

NaOH (40%) 1.75

Subtotal 63.0

Added afterwards 11B "

Thixogel Nr. 1 clay 18.0 25 Sodium perborate 14.0

Enzyme 0.5

Potassium methyl silicate 0.6

Non-ionic surfactant1 3.0

Magnesium Silicate / DTPA Mixture No. 2 0.3 30 Duet 787 0.6

Subtotal 37.0

12-C14 fatty alcohol condensed with 9 moles of ethylene oxide per mole. Example IV

The following composition was prepared by following the general S 5 v 1 3 2 8 27 procedure of Example I:

Spray dried basic granules "A" Wt%

Anionic surfactant 16.6

Sodium tripolyphosphate 43.3 5 Sodium silicate 5.8

Sodium sulfate 10.0

Rewoquat DQ35 2.0

Na-carboxymethylcellulose 0.3

Subtotal 80.0 10 Added afterwards "B1 *

Non-ionic material 6.0

Optical whitener 0.2

Enzyme 0.6

Perfume 0.2 15 Gelwhite GP 13.0

Subtotal 20.0

Total 100.0 * 1.22: 1 ratio of sodium talkalkyl sulfate: sodium dodecylbenzene sulfonate 2 20 coconut alcohol ethoxylate (EO = 14: 1).

8601323

Claims (14)

An antistatic detergent in solid form compatible with a clay mineral fabric softener, which comprises spray dried granules composed of a homogeneous mixture of at least one pH and heat insensitive detergent compound selected from anionic synthetic detergents, nonionic synthetic detergents, seated ionic synthetic detergents, ampholytic synthetic detergents, and mixtures thereof; at least one pH and heat insensitive inorganic or organic detergent builder salt; An antistatic water-soluble diammonium compound selected from compounds of formula (1), wherein R 1 is an aliphatic hydrocarbon of about 12 to about 30 carbon atoms; R ^ / Rg and Rg are each independently selected from aliphatic hydrocarbon radicals having 1-22 carbon atoms provided that the total number of carbon atoms in all aliphatic hydrocarbon radicals including does not exceed about 75 and on the condition that no more than 3 of the E 1 -R 8 groups have more than 12 carbon atoms; and alkanol groups of the formula (CH-CH 2) (CH (CH.) - έ zm J CHoO) H, where m and n are independent 0 or positive numbers, 1 n 20 where the sum of m and n of all groups R2 ~ R6 is at least 2 but not more than 30; with the still further condition that at least one of R2-Rr is said alkanol group; O R 1 is a divalent linking group such as C 1 -C 1 lower alkylene or substituted C 1 -C 1 lower alkylene, 25. is a number from 1 to 20 and X is a water-soluble salt-forming anion; and optionally one or more pH and heat insensitive detergent additives, fillers and moisture. Antistatic detergent according to claim 1, characterized in that at least one detergent compound consists of an anionic synthetic detergent and at least one detergent builder salt comprises an inorganic polyphosphate builder salt. An anti-static detergent according to claim 1, characterized in that in formula 1, in formula 1 is a straight or branched chain alkyl, alkynyl or alkenyl group having 16-22 carbon atoms, R -R. are independently selected from alkyl or alkenyl 20 having from 1 to 16 carbon atoms provided that the total number of carbon atoms in all the aliphatic hydrocarbon groups R, -R- is not greater than about 6 and with the further condition that no more than 2 of R -R- contains more than 12 carbon atoms, and alkanol groups of the formula-2 mule (CH-CH 0) (CH (CH,) CH CH-0) H, 2. m J 2 2 n 10 where m and n are independently 0 or a positive number such that the sum of m + n of all the alkanol groups Rj-Rg is at least 3 but not more than 25, provided that at least one of the groups R 1 -Rg is said alkanol group, an alkylene of 2-4 carbon atoms or an alkyl-15 lene of 2-4 carbon atoms with a substituent selected from hydroxyl, C 1 -C 6 lower alkyl and hydroxy lower (C 1 -C 6) alkyl and k is a number from 1 to 10 is. Anti-static detergent according to claim 2, characterized in that R 1 -R. independently alkyl or alkenyl with 1-6 carbon atoms or said alkanol groups provided that the total number of carbon atoms in all aliphatic hydrocarbon groups R 1 -Rg is not greater than about 35 and the sum of m + n of all alkanol groups R 2 ~ R6 is not 9r ^ 15, R7 or -CH ^ CR ^ CH ^ - and k is 1. Antistatic detergent according to claim 1, characterized in that it consists of about 10 to about 60% by weight of said at least one detergent compound, about 5 to about 90% by weight of said at least one detergent builder salt, about 0.4 to about 15 weight percent of said anti-static agent and about 0 to about 50 weight percent of detergent additives, fillers and moisture. Antistatic detergent according to claim 4, characterized in that it consists by weight of about 15 to about 40% of a straight upper alkyl benzene sulfonate anionic synthetic detergent; £ 601923 about 5 to 55% of a zeolite builder; about 1 to 12% of said antistatic diammonium compound; and about 5-40% of at least one pH-insensitive and heat-stable detergent additive, filler, moisture or mixtures thereof. Antistatic detergent according to claim 4, characterized in that it comprises by weight about 15 to about 40% of a straight upper alkyl benzene sulfonate anionic synthetic detergent; About 15-65% of an inorganic polyphosphate detergent builder; about 1-12% of said anti-static diammonium compound and about 45% of at least one pH-insensitive and heat-stable detergent additive, filler, moisture or mixtures thereof. Antistatic detergent according to claim 7, characterized in that said straight upper alkyl benzene sulfonate is dodecyl benzene sulfonate, the polyphosphate detergent builder is pentasodium tripolyphosphate and the diammonium compound is a compound of formula 2 '. 9. Antistatic softening detergent comprising a clay softening agent mixed with the spray dried antistatic detergent according to claim 1. 10 R? a divalent linking group, such as lower alkylene or substituted C 2 -C 5 la alkylene, k is a number from 1-20, and X is a water-soluble salt-forming anion and 15 (E) 0 to about 50% of at least one wax active grout, filler and moisture. 10. Free-flowing powdered or granular detergent and softener and anti-static composition consisting of (A) about 1 to 95 weight percent of at least one detergent compound selected from anionic synthetic detergents, nonionic synthetic detergents, amphoteric synthetic detergents, zwitterionic synthetic detergents substances and mixtures thereof; (B) about 1 to about 50 weight percent of a mineral clay fabric softener; (C) about 2 to about 80 weight percent of at least one detergent builder and (D) about 0.2-5 weight percent of an antistatic diammonium compound of formula 1, wherein an aliphatic hydrocarbon is about 12 to 30 carbon atoms; each of R2, R3, R4, R5 and Rg are independently selected from aliphatic hydrocarbon groups having 1-22 carbon atoms provided that the total number of carbon atoms in all aliphatic hydrocarbon groups including R ^ is not greater is then about 75 and with the further proviso that no more than 3 of the poops 5 contain more than 12 carbon atoms; and alkanol groups of the formula (CH_CH_0) (CH (CH,) CH_0) H, where m and n are independently 0 or positive i 2 mj 2 n numbers, where the sum vein m and n are from all groups tenm * ns * -e 2 but is not more than 30; with the further proviso that at least one of 1 * 2 "Rg is said alkanol group; 11. Agent according to claim 10, characterized in that the diammonium compound of formula 1 is present in the agent as a component of a spray-dried granule composed of said diammonium compound; an anionic surfactant; a detergent builder salt and optionally pH insensitive and heat stable detergent additives, fillers and mixtures thereof, wherein said clay fabric softener is uniformly mixed with said spray dried granules. 12. Agent according to claim 10, characterized in that in formula 1 Rj is a straight or branched chain alkyl, alkenyl or alkynyl group having 16 to 22 carbon atoms; R2 ~ Rg are independently selected from alkyl or alkenyl 30 having 1-16 carbon atoms, provided that the total number of carbon atoms in all aliphatic hydrocarbon groups R ^ -R ^ does not exceed about 50, and further provided that no more than 2 of contain more than 12 carbon atoms and alkanol groups of the formula (CH-CH-O) (CH (CHJCH-CHLO) H 2 2 mj 2 2 n 35 where m and n are independently 0 or a positive number such that the sum of m + n of all alkanol groups R -R tenmin- 2 or μ Λ λ Λ Λ V Ö V 1 j ·>% ste 3 but not more than 25, provided that at least one of the groups R -R mentioned alkka- 2 ool group, R 1 is an alkylene of 2 to 4 carbon atoms or an alkylene of 2 to 4 carbon atoms with a substituent selected from hydroxyl, C 1 -C 20 lower alkyl and hydroxy bearing (C 1 -C 20) alkyl and k is a number from 1 - 10. 13. Agent according to claim 12, characterized in that R 1 -R 8 are independently alkyl or alkenyl of 1-6 carbon atoms or said alkanol groups provided that the total number of carbon atoms in all aliphatic hydrocarbon groups R, -R- is not greater than about 35 and the sum of m + n of all the alkanol groups R2_R6 is not greater than 15, -C ^ CH ^ - or -CH ^ H ^ CH. ^ - and k is 1. Agent according to claim 10, characterized in that the antistatic diammonium agent is a compound according to formula 2 '. 3301928 '4 κ- / R2 R4 Λ 0 RV 2 R1-N + - ^ R7) rN + -R5 r8-> N_r11_Y == o' v ,, \ J rfl- ° 3 Λ N ^ CH2 R— CN - CH2CH2OCH2COOM OH CH2COOM XV · 's ch3 ch2ch2oh talk - N® — CH2CH2CH2 - N ^ H3 · 2CH3S04-ch3 ch2ch2oh 2 * ch2ch2oh ch2ch2oh talk - N®-CH2CH2CH2 — N $ -CH3 2CH3S04' ch3 ch2ch2oh ^ f '3' η (CH2CH20) p (CH2CH20) qp stearyl— N & -CH2CH2CH2— N $ -CH3 2CH3S04 “ch3 ch3 J p + q» 2-10 fu '>> (CH2CH20) pH (CH2CH20) qH c16h37 - N®-CH2CH2— N®-CH2CH2OH 2CH3S04 - v CH 3 C 16 H 37> p + q. 2_10 r 5 '^ (CH (CH3) CH20) pH (CH (CH3) CH20) qH c26h37 - NO-CH2CH2CH2— N®-CH3 2CH3S04- C3H8 (CH (CH3) CH20) rH J p + q + r e 3_10 coO1S28