NO862985L - ANTISTATIC CLOTHING DRUGS MIXTURE. - Google Patents

Description

The invention relates to a laundry detergent mixture based on a clay softener and a cationic antistatic agent. The invention relates more particularly to a laundry detergent mixture in powder form containing surface-active cleaning agent, clay softener and a water-soluble diammonium salt as an antistatic agent, a method for producing the mixture, and use of the mixture for washing textile materials.

Powdered detergent mixtures containing

a surface-active cleaning agent (anionic, nonionic, etc.) together with a clay softener and a cationic antistatic agent, such as a quaternary ammonium compound, quaternary diammonium compound, etc., are known in the art. Representative of the patent literature in this area are

US Patents 3,862,058, 3,886,075, 3,915,882, 3,948,790 and 4,203,851 and British Patent Application 2,141,152A. Other prior patents relating to clay fabric treatment agents include US Patents 3,594,212 and 4,062,647. The use of bentonites for softening textiles is known from British Patents 401,413 and 461,221.

Although satisfactory cleaning and softening results have been achieved with the known clay softener-detergent mixtures, it is generally difficult to achieve a reduction of static charge on washed laundry to a sufficient extent that this will be noticed by the ordinary consumer.

In general, attempts to incorporate amounts of antistatic agent that will provide acceptable levels of antistatic action have led to an overall reduction in cleaning, whitening and softening action. This reduction in overall performance parameters has been observed regardless of whether the cationic antistatic agent is added to the mixture under such conditions as will result in surface modification of the clay softener, or under such conditions as will only result in mechanical mixing of the clay, the cationic antistatic agent, the surfactant and other components of the mixture.

The invention therefore aims to provide a clay softener-containing detergent mixture which contains a compound which reduces static charge.

The invention also aims to provide an antistatic fabric detergent mixture in the form of spray-dried beads containing a water-soluble diammonium compound as an antistatic agent and where the spray-dried beads are compatible with a fabric softener made of mineral clay, and a method for producing the spray-dried beads.

It is a further object of the invention to provide a built-up, clay softening agent-containing, powdery detergent mixture with antistatic properties that are noticed by consumers, without this affecting the cleaning, whitening or softening effect of the mixture.

The invention also aims to provide a clay softener-powder detergent mixture in which a cationic antistatic agent consisting of a water-soluble diammonium salt can be added to the mixture as a component of the slurry formed in the kneader to be spray-dried, whereby the antistatic agent evenly and homogeneously can be incorporated into the mixture and the clay softener subsequently added to the spray-dried beads or granules.

These and other objects of the invention which will be more easily understood from the following detailed description, and preferred embodiments are achieved by, as the antistatic cationic compound in a laundry detergent mixture containing clay softener, and especially as a component of spray-dried beads or granules to be mixed with the clay softener, to use a water-soluble diammonium salt of the formula (I):

in which R-^ is an aliphatic hydrocarbon with 12-30 carbon atoms R2, R^, R^, Rj. and Rg are independently selected from the group consisting of aliphatic hydrocarbon groups with 1-22 carbon atoms, with the proviso that the total number

of carbon atoms in all aliphatic hydrocarbon groups, including R^, is not more than 75, and with the further purpose that no more than two of the groups R2- R^ have more than 12 carbon atoms, and hydroxyl groups with the formula

in which m and n independently of each other are 0 or positive numbers, so that the sum of m and n for all groups R~-R, is at least 2, but not more than 30, and with the further proviso that at least one of R2-Rg is said alkanol group,

R_ is a divalent connecting radical, such as C~- Cr-

/2. Lower alkylene or substituted C~-C^-lower alkylene,

k is a number from 1 to 20,

and X is a water-soluble salt-forming anion.

Because the useful diammonium compounds of formula (I) are water-soluble and also stable over a wide range of pH values and at elevated temperatures, they can be added directly to the slurry in the kneader in the form of an aqueous solution together with the other components of the softener-detergent mixture which is to be spray-dried, thereby uniformly and homogeneously incorporating the antistatic diammonium salt agents into the spray-dried granules or beads. As a result of this homogeneous distribution, the desired level of antistatic effect can be achieved by using lower concentrations of the antistatic compound and without adversely affecting other detergent properties, including detergency, whitening and softening properties.

The term "water-soluble", as used in the description and in the patent claims, shall indicate that the antistatic diammonium compounds are soluble or at least form stable dispersions in water in a concentration of at least 5% by weight at 20° C. The preferred compounds with the formula (I) are soluble in water at ambient temperature in an amount of at least 10% by weight. Since the antistatic diammonium salt agents of formula (I) are available or can be prepared as organic solvent-free aqueous solutions or as dispersions, they can be easily and safely handled in powder processing plants and can be easily kneaded and spray-dried as a component of built granular or powder detergent mixtures.

A typically constructed detergent mixture containing the spray-dried beads which in turn contain the water-soluble antistatic agent of formula (I) may include the following ingredients:

According to a preferred method of preparing the built-up granular or powder softener-detergent mixture, the antistatic agent of formula (I) and the remaining pH-insensitive, heat-stable ingredients are mixed together in a kneader and spray-dried to form spray-dried beads, and these beads will be uniformly mixed or oversprayed with those ingredients according to the recipes which are pH sensitive and/or heat sensitive or which may otherwise react with cationic antistatic agents, anionic surfactants or other components of the spray dried beads or granules. As examples of the subsequently added components to be mixed with the spray-dried pearls, for example bleaches, clay softeners, enzymes, perfume or non-ionic surfactant etc. can be mentioned. Mixing preparation methods are well known in the relevant art, and the practicing expert will easily be able to determine the optimal mixing preparation conditions.

Synthetic, organic cleaning compounds

The laundry detergent compositions may contain one or more surfactants selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants. The synthetic organic surfactants used in accordance with the present invention may be any of a variety of such compounds which have become known and are extensively described in the textbook "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry and Merch, published in 1958 by Interscience Publishers. The total amount of the surface-active cleaning compound or cleaning compounds can be as much as 95% by weight of the total detergent mixture although the preferred amounts are within the range of 1-70, especially 5-50, and particularly preferably 5-30,% by weight of the overall detergent mixture.

The detergent mixture according to the invention preferably contains one or more anionic cleaning compounds as the primary surfactants. The anionic surfactant can, if desired, be supplemented with another type of surface-active agent, preferably a non-ionic surfactant, especially when used together with a surfactant-building salt.

Anionic surfactants

Among the anionic surfactants which can be used according to the present invention, such surfactant compounds which contain an organic hydrophobic group containing 8-26, preferably 10-18, carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group consisting of sulfonate, sulfate, carboxylate, phosphonate and phosphate, to form a water-soluble surfactant.

Examples of suitable anionic surfactants include soaps, such as the water-soluble salts (eg sodium, potassium, ammonium or alkanolammonium salts) of higher fatty acids or resin salts containing 8-20, preferably 10-18, carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, shortening, coconut oil or mixtures thereof. The sodium and potassium salts of the fatty acid mixtures obtained from coconut oil and tallow, such as sodium coconut soap and potassium tallow soap, are particularly useful.

The anionic group of surfactants also includes

the water-soluble sulfated and sulfonated surfactants with an aliphatic radical, preferably an alkyl radical, containing 8-26, preferably 12-22, carbon atoms (the term "alkyl" includes the alkyl portion of the higher acyl radicals). Examples of the sulfonated anionic surfactants are the higher alkyl aromatic sulfonates with one nucleus, such as the higher alkylbenzene sulfonates containing 10 - 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as e.g. the sodium, potassium or ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates or higher alkylphenolsulfonates.

Other suitable anionic surfactants are the olefin sulfonates which include long-chain alkenesulfonates, long-chain hydroxyalkanesulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates. The olefin sulfonate surfactants can be prepared in the usual way by reacting sulfur trioxide (SO^) with long-chain olefins containing 8-25, preferably 12-21, carbon atoms, such olefins having the formula RCH-CHR"'", in which R denotes a higher alkyl group with 6 -23 carbon atoms and R"<*>" an alkyl group of 1-17 carbon atoms, or hydrogen to form a mixture of sultones and alkenesulphonic acids which are then treated to convert the sultones into sulphonates. Other examples of sulfate or sulfonate surfactants are paraffin sulfonates containing 10-20, preferably 15-20, carbon atoms. The primary paraffin sulfonates are produced by reacting long-chain α-olefins and bisulfites. Paraffin sulfonates with sulfonate groups distributed along the paraffin chain are described in US patents 2,503,280, 2,507,088, 3,260,741 and 3,372,188 and in West German patent 735,096.

Other suitable surfactants are sulfated ethoxylated higher fatty alcohols of the formula RO(C~H.O) S0-.M, in which R

Z4 m 3

denotes a fatty alkyl group with 10 - 18 carbon atoms, m is 2-6, preferably from 1/5 to 1/2 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 in which the higher alkyl group has 10-15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated higher alkanol sulphate preferably has 2-5 mol ethylene oxide groups per moles of anionic surfactant, 3 moles being most preferred, especially when the higher alkanol has 11 - 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic balance when the carbon atom content in the alkyl chain is within the lower range of the range 10 - 18 carbon atoms, the ethylene oxide content in the surfactant can be reduced to 2 mol per molecule, while when the higher alkanol has 16 - 18 carbon atoms within the upper part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases to as many as 8 to 9. Similarly, the salt-forming cation can be changed to achieve the best resolution. It can be made up of any solubilizing metal or radical, but will most often be an alkali metal, e.g. sodium, or ammonium. If 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- or tri-substituted, as in monoethanolamine, diisopropanolamine and trimethylamine. A preferred surface-active polyethoxylated alcohol sulfate is marketed under the trademark Neodol 25-3S.

The most preferred water-soluble anionic surfactant compounds are the ammonium and the substituted ammonium (such as mono-, di- and tri-ethanolamine), alkali metal (such as sodium or potassium) and alkaline earth metal (such as calcium or magnesium) salts of higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates. Among the above-mentioned anionic compounds, the most preferred are linear sodium alkylbenzene sulphonates (LABS) and especially those in which the alkyl group is a straight-chain alkyl radical with 12 or 13 carbon atoms.

The anionic surface-active agent will generally constitute the main cleaning agent component and may constitute 3 - 100% of the total amount of surface-active components. Preferably, the anionic surfactant constitutes at least 50, preferably at least 60, particularly preferably at least 70, and up to 99, preferably up to 90, and particularly preferably up to 80,% of the total amount of surface-active cleaning ingredients.

The anionic surface-active compound will usually and preferably be included as a component of the spray-dried beads containing antistatic agent, and it will be added to the mixture in the kneader in the form of an aqueous solution or dispersion, and preferably as a highly concentrated aqueous slurry.

Non-ionic surfactants

The next most preferred group of surfactant ingredients are the nonionic, synthetic, organic surfactant compounds.

The non-ionic, synthetic, organic surfactants are characterized by the presence of an organic hydrophonic group and an organic hydrophilic group and are typically produced by condensation of an organic aliphatic or alkylaromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Virtually any hydrophobic compound with a carboxy, hydroxy, amide or amino group with a free hydrogen atom attached to the nitrogen atom can be condensed with ethylene oxide or with polyethylene glycol which is the polyhydrated product of ethylene oxide, forming a nonionic surfactant . The length of the hydrophilic chain or of the polyoxyethylene chain can be easily regulated to achieve the desired balance between the hydrophobic and hydrophilic groups.

The nonionic surfactant used is preferably a poly-lower alkylated-higher alkanol in which the alkanol has 8 - 22, preferably 10 - 18, carbon atoms and where the number of lower alkylene oxide molecules (with 2 or 3 carbon atoms) is 3 - 20. Among such materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol with 11-15 carbon atoms and which contains 5-13 lower alkoxy groups per molecule. The lower alkoxy group is preferably ethoxy, but in some cases it may be desirable for it to be mixed with propoxy, and the latter, if present, usually makes up a smaller proportion (below 50%). Examples of such compounds are those in which the alkanol has 12 - 15 carbon atoms and which contain approx. 7 ethylene oxide groups per molecule, e.g. Neodol 25-7 or Neodol 23-6.5. The first-mentioned is a condensation product of a mixture of higher fatty alcohols which, on average, have 12 - 15 carbon atoms, with approx. 7 mol ethylene oxide, and the latter is a corresponding mixture in which the carbon atom content for the higher fatty alcohol is 12 - 13 and the number of ethylene oxide groups per molecular average is approx. 6.5. The higher alcohols are primary alkanols. Other examples of such surfactants include Tergitol<®>15-2-7 and Tergitol<®>15-S-9 which are both linear secondary ethoxylates. The former is a mixed ethoxylation product of a linear-secondary alkanol of 11-15 carbon atoms, with 7 moles of ethylene oxide, and the latter is a similar product, but with 9 moles of ethylene oxide reacted.

The highly preferred nonionic surfactants which can be used in the present detergent compositions are the nonionic surfactants with higher molecular weight, such as Neodol 45-11,

which are similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol having 14 - 15 carbon atoms and the number of ethylene oxide groups per molecule is approx. 11.

Of the total surface-active surfactant components in the detergent mixture, the non-ionic surface-active agent can be present in an amount of up to 70, preferably up to 50, more preferably up to 40, and particularly preferably up to 15% by weight. As a rule, the non-ionic surfactant used will be present in an amount of at least 1, preferably 10, particularly preferably at least 30,% of the total weight amount of all the surface-active surfactant components. Expressed based on the overall active agent-detergent mixture, the non-ionic surfactant for binding will generally be present in an amount of 0.1 - 20, preferably 0.3 - 15, and particularly preferably 0.6 - 10, wt%.

Then the non-ionic surfactant compounds

are often only slightly soluble in water or form viscous solutions or gels when added to water, they are usually kept available as solutions in organic solvents, for example in ethanol or isopropanol, alone or together with water. Therefore, when the nonionic surfactant is obtained in the form of its solution in an organic solvent, it will not be included as part of the kneader slurry used to

form the spray-dried granules or beads, but rather it will be subsequently added to the already produced spray-dried beads. Even if the non-surfactant compound is used in its pure liquid form (most of the non-ionic surfactant compounds are liquid at ambient temperature) or as an aqueous solution, it is still preferred to subsequently add the non-ionic surfactant compound to the spray dried beads.

Zwitterionic surfactants, such as the betaines or sulfo-betaines of the following formula are also applicable:

wherein R g denotes an alkyl group containing 8-18 carbon-9 10 atoms, R and R both independently denote an alkyl or hydroxyalkyl group containing 1-4 carbon atoms, R"^ denotes an alkylene or hydroxyalkylene group containing 1- 4 carbon atoms, and Y denotes a carbon atom or an S:O group. The alkyl group may contain one or more intermediate bonds, such as amide, ether or polyether bonds, or non-functional substituents, such as hydroxyl or halogen, which are not substantially degree affects the hydrophobic nature of the group. When Y is a carbon atom, the surfactant is called a betaine, and when Y is an S:0 group, the surfactant is called a sulfobetaine or sultain. Ampholytic surfactants can also be used according to the invention. Ampholytic surfactants are well known in the art in question, and a number of useful surfactants within this group are described by Schwartz, Perry and Berch in the above-mentioned "Surface Active Agents and Detergents". Examples of suitable amphoteric surfactants include efatter alkyl-p-iminopropionates, RN(C^H^COOM)^ > alkyl-p-aminopropionates, RN(H) C^H^COOM, and long-chain imidazole derivatives of the general formula

wherein R in each of the above formulas denotes an acyclic hydrophobic group containing 8-18 carbon atoms, and M is a cation to neutralize the charge on the anion. Particular useful amphoteric surfactants include the disodium salt of undecylcycloimidinium-ethoxyethionic acid-2-ethionic acid, dodecyl-(3-alanine) and the inner salt of 2-trimethylaminolauric acid.

The amounts of the zwitterionic synthetic organic surfactant and of the ampholytic synthetic organic surfactant when present in the compositions according to the invention are not particularly critical and can be chosen depending on the desired results. One or both of these groups of surfactant components can generally be used to replace all or part of the anionic, organic, cleaning surfactant and/or the non-ionic, organic, cleaning surface-active agent within the areas indicated above.

In the same way as with the anionic and non-ionic surfactant compounds, the practitioner will easily be able to decide whether the zwitterionic and ampholytic surfactant should be included as a component of the kneader slurry used to form the spray-dried beads or granules or whether these compounds should be added afterwards to the spray-dried beads to produce the final constructed laundry detergent blend.

Briefly, it can be said that when they are available as aqueous solutions, they will preferably be added to the kneader slurry, and when they are available in organic solvents, they will be subsequently added to the spray-dried beads.

Softening clay compounds

Clay softeners can be made up of any of the clay softeners known in the relevant art in order for clothes washed with this to become soft. The preferred clays are smectite clay materials.

The clays of the smectite type which can be used according to the invention are three-layer clays which are characterized by the fact that the layered structure is able to increase its volume several times by swelling or expansion in the presence of water to form a thixotropic, gelatinous material . There are two distinct groups of smectite-type clays: In the first group, aluminum oxide is present in the silicate crystal lattice,

and in the second group magnesium oxide is present in the silicate crystal lattice. Atomic substitution with iron, magnesium, sodium, potassium, calcium or similar elements can occur in the crystal lattice of smectite clays. It is common to distinguish between clays on the basis of their dominant cation. For example, sodium clays are clays in which the cation is mainly sodium.

The smectite clays used in the present compositions are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite and vermiculite. These clays are available under various trade names, e.g. 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. It must be stated that such minerals of the smectite type which are available under the above trade names may comprise mixtures of the various separate mineral types. Such mixtures of the smectite minerals can be used according to the invention.

In the mixtures according to the invention, the most preferred among the clay softeners are the aluminum silicates in which sodium is the dominant cation, such as bentonite clays. Among the bentonite clays, those from Wyoming (commonly referred to as "western" or Wyoming bentonite) are particularly preferred.

Preferred swelling bentonites are sold under the trade name Mineral Collid, in the form of industrial bentonites, by the Benton Clay Company, a subsidiary of the Georgia Kaolin Co.

These materials are the same as those previously sold under the trade name THIXO-JEL, are selectively pit-mined and enriched bentonites, and those considered to be the most applicable are available as Mineral Collid No. 101 etc. corresponding to THIXO- JEL no. 1, 2, 3 and 4. Such materials have pH values (6% concentration in water) within the range 8 - 9.4, maximum free moisture content of approx. 8% and specific weights of approx. 2.6, and for the pulverized quality at least 85%, preferably 100%, passes through a sieve with a wash opening of 74 nm. The bentonite is preferably a bentonite in which substantially all the particles, i.e. at least 90% of these, preferably more than 95%, pass through a screen with a mesh opening of 44 µm, and it is most preferred that all of the particles pass through such a term. The swelling ability of the bentonites in water is usually in the range 3-15 ml/g, and their viscosity in a 6% concentration in water is usually 8-30 centipoise.

Instead of using THIXO-JEL or Mineral Colloid bentonites, such products as that sold by the American Colloid Company, Industrial Division, as General Purpose Bentonite Powder, 44 nm, having particles of which at least 95% are finer than one diameter can be used corresponding to 44 µm (wet particle size) and where at least 96% of the particles are more finely divided than corresponding to a diameter of 74 µm (dry particle size). Such a hydrated aluminum silicate consists mainly of montmorillonite (at least 90%) with smaller proportions of feldspar, biotite and selenite. A typical analysis on an "anhydrous" basis is 63.05% silica, 21.5% aluminum oxide, 3.3% trivalent iron ions

(as Fe2O^), 0.4% divalent iron (as FeO), 2.7% magnesium

(as MgO), 2.6% sodium and potassium (as Na^O), 0.7% calcium (as CaO), 5.6% crystal water (as H^O) and 0.7% trace elements.

Although the "western" bentonites are preferred, it is also possible to use other bentonites, such as those which can be prepared by treating Italian or similar bentonites containing relatively small proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials , such as sodium carbonate, to increase the cation exchange capacity of such products. It is considered that the Na20 content in the bentonite should be at least 0.5, preferably at least 1, and more preferably at least 2.%, so that the clay will swell satisfactorily with good softening and dispersing properties in aqueous suspension. Preferred swelling bentonites of the types described above are sold under the trade name Laviosa and Winkelmann, e.g. Laviosa AGB and Winkelmann G-13.

Of course, any clay minerals that adhere to and are capable of imparting "softness" to textile materials may be used in accordance with the present invention.

The clays used here that are preferred are "insensitive", i.e. they have such a particle size that they are not noticeable by feeling. Insensible clays have particle sizes below 50 µm, and the clays used here have a particle size range of 5 - 50 µm

The clay softening compounds are present in the detergent compositions in concentrations of 1 - 50, preferably 2 - 30, particularly preferably 4 - 20, % by weight, based on the total composition.

According to the present invention, it is strongly preferred that the clay softener is subsequently added to the spray-dried beads or granules containing antistatic agent, in order to avoid any mutual influence, e.g. ion exchange, between the clay mineral particles and the antistatic agent of cationic diammonium compound. Since the diammonium compound is homogeneously and very finely divided throughout all the spray-dried beads as a result of the kneading and spray-drying, and since the subsequently added components are in contact with the spray-dried beads under essentially anhydrous conditions, essentially no ion exchange will occur between the clay softener and the cationic diammonium salt antistatic agent.

The clay softener is present in the detergent mixtures according to the invention in a sufficient amount to

give the desired softening effect when the mixture is used in normal amounts for laundry detergent mixtures, e.g. 1/8 - 1.5 cup detergent mixture per washing charge.

Surfactant builders

The detergent mixtures according to the invention possibly, but preferably, contain at least one surfactant builder of the type that is commonly used in detergent mixtures. Useful builders include any of the usual inorganic water-soluble builder salts, such as water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, tripolyphosphates, silicates, carbonates, bicarbonates, borates or sulfates, etc. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, aminopolyacetates, carboxylates, polycarboxylates , succinates or phytates etc.

Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates more 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-containing builder compounds are described in US patents 3,213,030, 2,422,021, 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred water-soluble inorganic builders.

Specific examples of inorganic builders that do not contain phosphorus include water-soluble inorganic earbonate, bicarbonate, and silicate salts. Alkali metal, e.g. the sodium and potassium, -Carbonates, -bic:arbonates and

- the silicates are particularly useful here.

Water-soluble organic builders can also be used. For example, alkali metal, ammonium and the substituted ammonium acetates, -Qcarboxylates, -polyQcarboxylates or -polyhydroxysulfonates can be used as builders for the detergent mixtures according to the invention. Specific examples of acetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrile triacetic acid, benzene polycarboxylic acids (ie, penta or tetra acids), carboxy methoxy succinic acid or citric acid.

Further organic building salts that can be used here include the polycarboxylate materials described in US patent 2,263,103, including the water-soluble alkali metal salts of mellitic acid. The water-soluble salts of polycarboxylate polymers and copolymers, such as those described in US patent 3,308,067, can also be used here.

Water-insoluble builders can also be used, especially the complex silicates, and more especially the complex sodium-aluminosilicates, such as zeolites, e.g. zeolite 4A which is a type with a zeolite molecule in which the monovalent cation is sodium and the pore size is approx. 4 Å. The production of zeolite of such a type is described in US patent 3,114,603. The zeolites can be amorphous or crystalline and have water of hydration, as is well known in the relevant art.

Mixtures of organic and/or inorganic builders can be used according to the invention. Such a mixture of builders is described in Canadian patent 755 038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrile triacetate and trisodium ethane-1-hydroxy-1,1-diphosphonate. It will be understood that although the alkali metal salts of the above-mentioned inorganic and organic polyvalent anionic building salts are preferred for use according to the invention from an economic point of view, the water-soluble ammonium, alkanolammonium, e.g. triethanolammonium or diethanolammonium etc. salts of any of the above-mentioned building salts usable according to the invention.

The building salts, the inclusions as well as the inorganic ones

such as the organic surfactant builder salts, can conveniently be added to the kneader slurry to be included together with the antistatic diammonium compound as an antistatic agent, anionic surfactant, etc. in the spray-

dried pearls or granules according to the invention to give 5-90, preferably 15-65, particularly preferred 20-55, weight % building salts, based on the weight of the spray-dried pearls, so that in the finished mixture after mixing with the subsequently added components 2-80, preferably 10-70, and particularly preferably 20-50, % surfactant builder salt or salts are obtained, based on the overall mixture.

Antistatic agent of diammonium compounds

The antistatic compounds used according to the present invention are diammonium compounds which are characterized by their solubility in water, i.e. their ability to form stable, clear solutions or dispersions in water at 25° C and containing at least 5, preferably at least 10% by weight of the diammonium compound.

The diammonium compounds that can be used here to reduce the accumulation of static charge are the water-soluble compounds with the following general formula (I)

wherein is aliphatic hydrocarbon with 12 - 30 carbon atoms, each of R2, , R4, R^ and Rg is independent of each other and selected from the group consisting of aliphatic hydrocarbon groups with 1-22 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups, including R^, do not exceed 75, and with the further proviso that no more than 3 of the R2~Rg groups have more than 12 carbon atoms, and alkanol groups with the formula

wherein m and n independently of each other are 0 or positive numbers and such that the sum of m and n from all of the groups R2~R^ is at least 2, not more than 30, with the further precaution that at least one of R2~R^ is the said alkanol group,

R 7 is a divalent linking radical, such as C 2 -C 1 -lower alkylene or substituted C 1 -C 2 -lower alkylene, k is a number from 1 to 20, and X is a water-soluble salt-forming anion.

The preferred compounds of formula (I) are those which contain only 1 or 2, preferably only one single long carbon chain group, i.e. 12 or more carbon atoms. In formula (I), the preferred definitions for R,-R are therefore: 1 6

R^ is an aliphatic hydrocarbon group which can be a straight or branched chain and saturated or unsaturated

(ie linear or branched alkyl, alkenyl or alkynyl)

with 16-22 carbon atoms,

R2-Rg are independently selected from the group consisting of alkyl or alkenyl with 1-16, preferably 1-12, particularly preferably 1-6, carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R, - R, is not more than 50, not more than 35, and with the further proviso that no more than 2, preferably no more than 1, and most preferably none of R„-R^, have more than 12 carbon atoms, and alkanol groups of the formula

in which m and n can be 0 or a positive number, so that the sum of m plus n in all of the alkanol groups R,,-Rg is at least 3, but not more than 25, preferably not more than 15, and with the further proviso that at least one, preferably at least two, of R2~Rg is the mentioned alkanol group,

R^ is an alkylene with 2-4 carbon atoms, such as ethylene (-CH2CH2.-), propylene (-CH2CH2CH2-), isopropylene (-CH2CH(CH3)CH2-), butylene (-CH2CH2CH2CH2~) etc, or such an alkylene with one or more, such as one or two, substituents, such as hydroxyl, C^-C^-lower alkyl, hydroxyl lower (C1~C4)-alkyl etc, preferably -CH2CH2~ or -CH2CH2CH2-, most preferably -CH2CH2CH2-,

k is from 1 to 10, preferably 1-5, particularly preferably 1-3, and

X is a water-soluble salt-forming anion, such as e.g. halide, e.g. bromide, chloride or iodide, sulfate, methosulfate, ethosulfate, hydroxide, acetate, propionate or other similar inorganic or organic solubilizing monovalent anion.

Examples of preferred R 1 groups include stearyl, tallow, hydrogenated tallow, eicosyl, soy or the like.

Examples of preferred alkyl and alkenyl groups for R 2 - R 8 include methyl, ethyl, propyl, isopropyl, n-butyl, tert. butyl, n-butenyl, octyl or 1-octenyl etc. Methyl, ethyl, propyl and isopropyl are particularly preferred. Methyl and ethyl are most preferred.

Examples of preferred alkanol groups for R,,-Rg include ethanol (n=0, m=1), propanol (m=0, n=1) and ethoxy-propoxy- or mixed (ethoxy)(propoxy)-ethanol and/or -propanol, such as (CH„CH_0) 1H, where m"'" is from 2 to 4,

where n"^ is 2 to 4, and

(CH2CH20)mi(CH(CHj)CH20)ni' where m and n are both numbers from 1 to 4 and m + n =2 to 6. In the mixed ethoxy-propoxy-alkanol groups, the order of addition of the ethoxy and propoxy groups is not critical importance, and it will be understood that blocks of the ethoxy groups or blocks of the propoxy groups can be bonded to the N atom in the diammonium compound or that the ethoxy and propoxy groups can be arbitrarily distributed. As is well known in the relevant art, the distribution of the ethoxy and propoxy groups will thus be determined by the order in which the ethylenediamine or propylenediamine compound is condensed with ethylene oxide (or a starting material for this) and propylene oxide (or a starting -material for this).

Special examples of compounds with the formula

(I) which are commercially available or can be readily prepared by conventional methods, include

etc. and the corresponding water-soluble ethosulphate, halide or acetate salts etc.

The above compound (2) (N-methyl-N-(2-hydroxyethyl)-N-tallow alkyl-N'-methyl-N<1->bis(2-hydroxyethyl)-propylene diammonium methyl sulfate is particularly preferred. This compound is commercially available under the trade name Rewoquat DQ35 and is a clear liquid solution with 35% dissolved solids.Rewoquat DQ35 has a free amine content of 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 way, for example by reacting 1 mol of N-methyl-N-tallow alkyl-N'-methylpropylenediamine with 3 mol of ethylene oxide and then quaternizing the resulting compound with methyl sulfate. By ethoxylation with more than 3 mol of ethylene oxide, the corresponding higher ethoxylated compounds are prepared.

It is a critical feature of the present invention that the antistatic diaitvmonium salt agent has the specified degree of water solubility, but that it should not be so water soluble that it will only be possible to remove it from the washing liquid with difficulty when using the softener-detergent mixture. In general, a degree of solubility of up to 50% by weight at 25° C is sufficient to give washed laundry the necessary ability to reduce static charge.

The aqueous (organic solvent-free) solution (or dispersion) of the antistatic diammonium salt agent is added to the kneader slurry together with the other pH-insensitive and heat-stable ingredients, builder or builders, fillers, anionic surfactant, pH-adjusting agent or water etc, and the mixture is then spray-dried according to conventional methods. The quantity of the antistatic agent in the kneader slurry is such that the spray-dried beads or granules will contain 0.4 - 15, preferably 1 - 12, and particularly preferably 2 - 12% by weight, of the beads, of the antistatic compound of the formula (I) . The antistatic agent is finely distributed completely homogeneously in the spray-dried beads and can most effectively inhibit its antistatic function without adversely affecting the other functional components.

The spray-dried beads containing the antistatic agent were then intimately mixed with the clay softener and the other ingredients, e.g. nonionic surfactant, bleaching agent, enzymes, perfumes and other pH- or heat-sensitive and/or water-insoluble ingredients to produce the final mixture of softener-surfactant-antistatic agent. The quantity of the spray-dried beads and subsequently added components is such that the final mixture will contain the following quantities of the essential components:

Optional components

The use of an inert, water-soluble filler salt is desirable in the laundry detergent mixtures according to the invention. A preferred filler salt 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 5, such as 0.1 - 2, preferably 0.3 - 1, % by weight of the mixture.

Various auxiliary additives can be incorporated into the laundry detergent mixtures according to the invention. These generally include perfumes, dyes, e.g. pigments or dyes, bleaching agents such as sodium perborate, bleach activators, bleach stabilizers, antigen deposition or soil suspending agents, such as alkali metal salts of carboxymethylcellulose, optical brighteners such as anionic, cationic or non-ionic brighteners, foam stabilizers such as alkanolamides, foam drying agents, antimatting agents, pH -regulating agents, enzymes or similar auxiliary additives, all of which are well known in textile washing technology when used in detergent mixtures. Flowability-promoting agents, which are usually designated as flowability aids, can also be used to maintain the droplet-shaped mixtures as free-flowing beads or powders. Starch derivatives and special clays are commercially available as additives that enhance the flowability of otherwise sticky or pasty granular mixtures, and two such clay additives are currently marketed under the trade names Satintone<®> and Microsil. Bound water and free water in smaller quantities that do not adversely affect the fluidity of the granular or powdery mixtures may also be present in the detergent mixtures. The amount of moisture will normally be 1-15, preferably 5-12, most preferably 8-12, % of the entire mixture. Within these areas, a satisfactory flowable granular, powdery or granular product is obtained which, by regulating the particle size and moisture content, can be prevented from becoming too dusty.

Suitable ranges for the detergent additives are: enzymes =0-2, especially 0.2 - 1.%, corrosion inhibitors = 0-15, preferably 2 - 8.%, anti-foaming agents and suds-suppressing agents =0-15, preferably 0-8, e.g.

0.1 - 5.%, dirt suspending or antigen deposition agent

clays and anti-yellowing agents =0-10, preferably 0.3 - 3.%, dyes, perfumes, whitening agents and bluing agents, total weight =0-2, preferably 0-1, as 0.2 - 0.8, %, pH- modifiers and pH buffers =0-5, preferably 0-2,

%, bleach = 0 - 40, preferably 0 - 25, e.g. 2 - 20,

%, bleach stabilizers and bleach activators =0-15, preferably 0-10, e.g. 0.1 - 8.%. With the choices of the auxiliary additives, these will be chosen so that they are compatible with the main components of the detergent mixture.

Regardless of the form that the detergent mixture has, will

its use in the washing process be essentially the same. The doticle-shaped mixture is usually added to wash water in an automatic washing machine so that the concentration of this in the wash water would be from 0.05 to 1.5,

as a rule from 0.1 to 1.2%. The water to which it is added,

will preferably have medium or low hardness, e.g. hardness, calculated as calcium carbonate, of from 30 to 120 ppm, but both softer and harder water can be used. The water temperature can be 20 - 100° C and is preferably 60 - 100° C in such cases where the textile material or cloth is able to withstand high temperatures without deterioration or bleaching of dyes. When washing at a low temperature is desired, the temperature can be kept at 20 - 40° C.

At the mentioned concentrations of detergent mixture, the pH of the washing water will usually be on the alkaline side, for example from 7 to 12, preferably from 8 to 11, especially from 9 to 10. The weight ratio between laundry and washing water will usually be 1:4 - 1 :30, preferably 1:10 - 1:30.

The invention is further illustrated in the examples below. Unless otherwise stated, all parts and percentages are based on weight.

Example 1

The following mixture is prepared by first forming spray-dried beads (A) and then adding the components (B).

The concentration of the antistatic agent Rewoquat DQ3 5" in the final mixture was 1.63%.

For comparison, the same mixture was prepared, except that Rewoquat DQ35 was not used. Each of the compounds was tested to determine their ability to

to reduce static charge on four different types of textile materials, i.e. acrylic, polyester, polyester/cotton blend and nylon.

In Table 1 below, the results for electrostatic charge values obtained using Bauman's instrumental method are reproduced. In Table 2 below, the results of an independent expert to determine the degree of static charge (0 = no charge to 3 = strongly charged) are reproduced. All data is obtained after washing at 60° C and drying with full drying energy in a Miele dryer for 40 minutes. The instrument readings were taken after conditioning at 20° C and 40% relative humidity. The results from another series of tests are also reproduced in Tables 1 and 2, where the mixture according to the invention was compared with the commercially available powder mixture of softener-surfactant-antistatic agent (tallow trimethylammonium chloride-2%, tallow-methylamine salt-4%).

The softening, cleaning and whitening evaluation for the mixture (A + B) according to the invention showed that there was no negative effect on these usage parameters compared to the recipe A + B without Rewoquat DQ35 as an antistatic agent.

Example 2

When in Example 1 the same amount of Rewoquat DQ35 that was used in component A was instead used together with the subsequently added component B, the ability to reduce static charge was reduced.

Example 3

According to the same general method as described in Example 1, the following mixture is prepared:

Example 4

The following mixture is prepared by following the same general method as described in Example 1:

Claims (14)

i. Antistatic laundry detergent mixture in solid form and compatible with clay mineral fabric softener, characterized in that the mixture comprises spray-dried beads consisting of a homogeneous mixture of at least one pH- and heat-insensitive surfactant compound selected from the group consisting of anionic synthetic surfactants, non-ionic synthetic surfactants surfactants, zwitterionic synthetic surfactants, ampholytic synthetic surfactants and mixtures thereof, at least one pH- and heat-insensitive inorganic or organic surfactant builder salt, an antistatic agent of a water-soluble diamine compound selected from compounds of the general formula (I) wherein R^ is an aliphatic hydrocarbon with 12-30 carbon atoms, each of R2, R^, R4, R,, and Rg is independently selected from the group consisting of aliphatic hydrocarbon groups with 1-22 carbon atoms, with the proviso that the total the number of carbon atoms in all the aliphatic hydrocarbon groups, including R^, is not more than 75 and with the further proviso that no more than three of the R« - R^ groups have more than 12 carbon atoms, and alkanol groups with the formula in which m and n independently of each other are 0 or positive numbers and the sum of m and n from all the groups R2 - Rg is at least 2 but not more than 30, with the further proviso that at least one of R2 - Rg is the said alkanol group, R^ is a divalent connecting radical, such as C2 -C1 -lower alkylene or substituted C2 -C3 -lower alkylene, k 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. 2. Detergent mixture according to claim 1, characterized in that at least one surfactant compound comprises an anionic synthetic surfactant and that at least one surfactant builder salt comprises an inorganic polyphosphate builder salt. 3. Detergent mixture according to claim 1, characterized in that in formula (I) R is a linear or branched alkyl, alkenyl or alkynyl group with 16 - 22 carbon atoms, R2 _R6 is independently selected from the group consisting of alkyl or alkenyl with 1-16 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R-^-Rg is not more than 50 and with the further proviso that no more than 2 of the R„-R, groups have more than 12 carbon atoms, and alkanol groups with the formula wherein m and n independently of each other are .0 or a positive number such that the sum of m+n for all the alkanol groups R2 -R6 is at least 3, but not more than 25, with the proviso that at least one of the groups R2 -Rg is the aforementioned alkanol group, R^ is an alkylene of 2-4 carbon atoms or an alkylene of 2-4 carbon atoms with a substituent selected from the group consisting of hydroxyl, C-^ -C^ -lower alkyl and hydroxy-lower (C^ -C^ )-alkyl, and k is a number from 1 to 10. 4. Detergent mixture according to claim 2, characterized in that R2 -R^ independently of each other are alkyl or alkenyl with 1-6 carbon atoms or the aforementioned alkanol groups, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R-j^ Rg does not exceed 35 and that the sum of m+ n for all alkanol groups R2~ R^ is not more than 15, Ry is -CH2 CH2~ or -CH2 CH2 CH2 - and k is 1. 5. Detergent mixture according to claim 1, characterized in that it comprises 10-60% by weight of said at least one surfactant compound, 5-90% by weight of said at least one surfactant builder salt, 0.4-15% by weight of said antistatic agent and 0-50% by weight of detergent mixture additives, fillers and moisture. 6. Detergent mixture according to claim 4, characterized in that it comprises, on a weight basis, 15 - 40% of an anionic synthetic surfactant of a linear higher alkylbenzene sulfonate, 5 - 55% of a zeolite builder, 1 - 12% of the aforementioned diammonium compound as an antistatic agent and 5 - 40% of at least one member selected from the group consisting of pH insensitive and heat stable detergent blend additives, fillers, moisture and mixtures thereof. 7. Detergent mixture according to claim 4, characterized in that it comprises, on a weight basis, 15 - 40% of an anionic synthetic surfactant of a linear higher alkylbenzene sulfonate, 15 - 65% of an inorganic polyphosphate surfactant builder, 1 - 12% of the aforementioned diammonium compound as an antistatic agent and 5 - 40% of at least one member selected from the group consisting of pH insensitive and heat stable detergent composition additives, fillers, moisture and mixtures thereof. 8. Detergent mixture according to claim 7, characterized in that the linear higher alkylbenzenesulfonate is dodecylbenzenesulfonate, the polyphosphate surfactant builder is pentasodium tripolyphosphate and the diammonium compound is 9. Antistatic softening detergent mixture, characterized in that it comprises a clay softener in mixture with the spray-dried antistatic laundry detergent mixture according to claim 1. 10. Free-flowing, powdery or granular mixture for washing clothes and with softening and antistatic properties, characterized in that it comprises (A) 1-95% by weight of at least one surfactant compound selected from the group consisting of anionic synthetic surfactant, nonionic synthetic surfactant, amphoteric synthetic surfactant, zwitterionic synthetic surfactant and mixtures thereof, (B) 1-50% by weight of a clay mineral fabric softener, (C) 2-80% by weight of at least one surfactant builder and (D) 0.2-5% by weight of an antistatic agent of a diammonium compound of the formula (I) wherein R^ is an aliphatic hydrocarbon of 12-30 carbon atoms, each of R^ , R-^ , R^ / R5 0<3 Rg is independently selected from the group consisting of aliphatic hydrocarbon groups of 1-22 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups, including R^ , does not exceed 75, and with the further proviso that no more than three of the R-^-R^ groups have more than 12 carbon atoms, and alkanol groups with the formula wherein m and n independently of each other are 0 or positive numbers and where the sum of m and n for all groups R^-R^ is at least 2, but not more than 30, with the further proviso that at least one of R2~Rg is the aforementioned alkanol group, R^ is a divalent linking radical, such as C^-C^ -lower alkylene or substituted C2~C5 -lower alkylene, k is a number from 1 to 20, and X is a water-soluble salt-forming anion, and (E) 0 - 50% of at least one of detergent blend additives, fillers and moisture. 11. Mixture according to claim 10, characterized in that the diammonium compound with the formula (I) is present in the mixture as a component of a spray-dried bead consisting of the diammonium compound, an anionic surface-active agent, surfactant builder salt and possibly pH-insensitive and heat-stable detergent mixture additives, fillers and mixtures thereof, and that the fabric softening clay is mentioned mixed with the spray-dried beads. 12. Mixture according to claim 10, characterized in that in the formula (I) is a linear or branched alkyl, alkenyl or alkynyl group with 16 - 22 carbon atoms, R„-R, are independently selected from the group consisting of alkyl or alkenyl with 1-16 carbon atoms, with with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R-^ -Rg is not over 50, and with the further proviso that no more than 2 of the groups of R2~ Rg have more than 12 carbon atoms, and alkanol groups with the formula wherein m and n independently of each other are 0 or a positive number, so that the sum of m+n for all the alkanol groups R2~Rg is at least 3, but not more than 25, with the proviso that at least one of the groups R2~Rg is the aforementioned alkanol group, R7 is an alkylene of 2-4 carbon atoms or an alkylene of 2-4 carbon atoms with a substituent selected from the group consisting of hydroxyl, C-^ -C^ -lower alkyl and hydroxy-lower (C^ -C^ )- alkyl, and k is a number from 1 to 10. 13. Mixture according to claim 12, characterized in that R2~R5 independently of each other are alkyl or alkenyl with 1-6 carbon atoms or the aforementioned alkanol groups, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R-^-Rg does not exceed 35 and that the sum of m +n for all alkanol groups R2 _R6 is not over 15, R^ is -CH2 CH2~ or -CH2 CH2 CH2 - and k is 1. 14. Mixture according to claim 10, characterized in that the antistatic agent of the diammonium compound is