DE69019973T2 - Laundry treatment composition. - Google Patents

Description

Technical area

The present invention relates to fabric treatment preparations or compositions for treating laundry and in particular it relates to fabric treatment preparations containing fabric softening clays and fabric softening polysiloxanes and flocculants.

Background of the invention

The use of softening clays in fabric treatment preparations is well known to those skilled in the art and is widely used commercially. Clays have also been used in particular because of their application possibilities and the fact that the soft hand imparted to fabrics is different from that achieved with cationic softeners. Examples and descriptions of clay applications can be found in a wide variety of publications, for example U.S. 3,966,629 or U.K. 1,400,898 describe different types of clays and applications in fabric treatment preparations.

It has also been described that an improvement in the plasticization can be achieved by combining clay with plasticizing amines. Furthermore, DE-3 833 648 describes the improved agglomeration of plasticizing detergents containing clay. In addition, EP-A-313 146 teaches the use of a humectant to facilitate the improved wetting of the clay. EP-A-299 575 and EP-A-328 182 disclose clay and low levels of clay flocculants, but give no indication of the use of polysiloxanes.

Other agents known to give favorable results in tissue treatment are substituted polysiloxanes. They are described for use in low concentrations in, for example, EP-A-150 867 or EP-A-150 872. Relatively high concentrations of substituted Polysiloxanes are not uncommon in the textile industry and are described, for example, in EP-A-58 493 or US 4,247,592.

EP-A-354 856 describes the combination of siloxanes with cationic quaternary ammonium compounds.

EP-A-381 487 describes liquid detergent compositions which contain a clay component which has been pretreated with a siloxane in order to achieve phase and viscosity stability without impairing the cleaning effect.

It has now been shown that the fabric treatment effect of substituted polysiloxanes, softening clays and clay flocculants is significantly greater than the expected simple additive increase in performance. In particular, when intimate mixtures of softening clay and substituted polysiloxanes are used in the presence of clay flocculants, the softening effect achieved exceeds the expected additive softening effect of the compounds used.

It is an aim of the present invention to provide fabric treatment preparations which contain substituted polysiloxanes, softening clay and clay flocculants, preferably in the form of an intimate mixture. It is another object of the invention to provide detergent preparations, preferably granular detergent preparations, which soften the fabric during the washing process and which contain such fabric treatment preparations.

A further aim of the present invention is to provide such plasticizing preparations which show very good environmental compatibility in all application forms.

Summary of the invention

The present invention relates to fabric treatment compositions containing a softening clay, a clay flocculant and a substituted polysiloxane. The substituted polysiloxane is contained in the compositions in an amount of 0.1% to 50% of the softening clay, while the clay flocculant in an amount of 0.005% to 20% of the plasticizing clay.

The fabric treatment preparation can be applied in the form of liquid or granular products which can be used as such in the wash cycle or the rinse cycle of the washing process. According to a preferred embodiment of the present invention, the fabric treatment preparations are contained in detergent compositions which soften the fabric in the course of the washing process (softening-through-the-wash compositions) (STW). According to the invention, the STW detergent compositions contain at least one surfactant and 1% to 50%, preferably 1% to 20% and more preferably 5% to 15% of the fabric treatment preparations.

Even more preferred are particles comprising a coagglomerate of plasticizing clay and substituted polysiloxanes. Together with clay flocculants, these particles can be used in granular softening preparations or, preferably, in granular STW detergent compositions.

Definitions

Unless otherwise specified, the following definitions are used hereinafter:

- Percentages are percentages by weight

- Softening refers to a range of fabric treatment that is different from cleaning; in particular, this term includes softening, anti-wrinkle, anti-static and easy-iron treatments

- Clays are softening clays, which are described in more detail below

- Siloxanes are substituted polysiloxanes for tissue treatment, as described in more detail below

Detailed description of the invention The softening tone

An essential component of the present preparations consists of a clay.

According to the invention, any clay known and used for this purpose or mixtures thereof can be used.

Such clays include the various heat-treated kaolins and various multilayer smectites. As is known in the art, the preferred smectite clays have a cation exchange capacity of at least 50 meq. per 100 grams of the clay.

Also preferred are clays with a particle size in the range of 50 to 500 µm.

Further preferred smectite clays are hectorite clays of the general formula

Wherein y=0; or when y ≠ 0, MeIII represents Al, Fe or B; Mn+ represents a monovalent (n=1) or divalent (n=2) metal ion selected from, for example, Na, K, Mg, Ca or Sr. The value of (x+y) is the layer charge of the hectorite clay. The hectorite clays suitable for the detergent compositions of the invention have a layer charge distribution such that at least 50% is in the range of 0.23 to 0.31.

Preferred are hectorite clays of natural origin with a layer charge distribution such that at least 65% lies in the range of 0.23 to 0.31.

Specific examples of fabric softening smectite clay materials that do not limit the present invention are:

Sodium montmorillonite

Borck Volclay BC

Gelwhite GP

Thixo-Jel

Ben-A-Gel

Sodium hectorite

Veegum F

Laponite SP

Sodium Saponite

Barasym NAS 100

Calcium montmorillonite

Soft Clark

Gelwhite L

Invite K

Lithium hectorite

Barasym LIH 200

Clay flocculants

Clay flocculants are not normally used in fabric treatment preparations. On the contrary, one tends to use clay dispersants which serve to remove the clay stains from fabrics. Clay flocculants are, however, well known in other fields of technology, such as oil drilling or ore flotation in metallurgy. The majority of these materials are polymers and copolymers with relatively long chains derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone and ethyleneimine, with the exception of copolymers of acrylic acid and maleic acid. Gums such as guar gum are also suitable.

Preferred are polymers of ethylene oxide, acrylamide or acrylic acid. These polymers have been shown to dramatically enhance the deposition of a clay when their (weight average) molecular weights are in the range of 100,000 to 10,000,000. Preferred are polymers having a (weight average) molecular weight of 150,000 to 5,000,000, more preferably 150,000 to 800,000.

The most preferred polymer is poly(ethylene oxide). Molecular weight distributions can be readily determined by gel permeation chromatography against poly(ethylene oxide) standards with narrow molecular weight distribution.

The amount of clay flocculant, expressed as a percentage of the clay, ranges from 0.005% to 20%. For clay flocculants with a (weight average) molecular weight of less than 800,000, the preferred amount is 2% to 20% of the clay. For (weight average) molecular weights of above 800,000, the preferred amount is in the range of 0.005% to 2% of the clay.

The substituted polysiloxane

The amount of siloxane ranges from 0.1% to 50% by weight of the clay, preferably from 0.1% to 20%, and more preferably from 1.0% to 10%.

The siloxanes suitable for the present invention can be described as plasticizing, straight-chain or branched, organo-functional polydi-C₁₋₄-alkyl-siloxanes of the general formula:

wherein R is C₁₋₄alkyl;

R' R or a polyether of (C2-C3 oxides) 1-50 , with a terminating H or R end group;

R" is branched or straight chain C₁₋₄alkyl;

q�1 and q�2 are integers;

m and (q₁ + q₂) are integers with values from 4 to 1700;

n is an integer with a value from 0 to 6;

Y is a polyether of (C₂₋₃-oxides)k, wherein k has an average value of from 7 to 100, terminated by a H or C₁₋₄-alkyl end group;

wherein X and V are selected from -H; -C₁₋₃�0 alkyl, -C₅₋₆ aryl; -C₅₋₆ cycloalkyl; -C₁₋₆ NH₂; -COR; with the proviso that the nitrogen may be quaternized to give the following group

where W can be selected from X and V, or Y

wherein T and P are selected from -H, -COOH, -CO-O-C₁₋₂-alkyl or epoxy-C₅₋₆-cycloalkyl.

Preferred siloxanes of the above general formula are characterized in that

q₁+q₂ is an integer from 50 to 1,500 and

m represents an integer from 4 to 100.

The most preferred siloxanes of the general formula are characterized by compounds in which

- R, R' are methyl and R" are propyl and (q₁ + q₂) have the value 329, m has the value 21 and n has the value 1 and Y is a polyether consisting of 12 ethyl oxides and having an acetic acid end group, or

- R, R' are methyl and R" are propyl and (q₁ + q₂) have the value 485, m has the value 15 and n has the value 1 and Y is a polyether consisting of 12 ethylene oxides and having an acetic acid end group, or

- R, R' are methyl and R" are methyl-2-propyl, (q₁ + q₂) has a value of 1470, m has the value 30 and n has the value 1 and Y is (aminoethyl)amine.

Optional plasticizer components to be used

The present fabric treatment preparations may contain, in addition to the essential compounds, other useful known compounds. These compounds may be added in an amount of up to 85% of the fabric treatment preparation depending on application and manufacturing needs or other desires.

Suitable examples of these other softening compounds include the following softening amines of the formula R₁R₂R₃N, wherein R₁ is a hydrocarbon group having 6 to 20 carbon atoms, R₂ is a hydrocarbon group having 1 to 20 carbon atoms, and R₃ is a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. A preferred amine of this type is ditallowmethylamine.

Preferably, the softening amine is present in the form of a complex with a fatty acid of the formula RCOOH, where R is a C9-C20 alkyl or alkenyl group. It is desirable that the softening amine-fatty acid complex is in the form of microfine particles having a particle size in the range of 0.1 to 20 µm. These softening amine-fatty acid complexes are described in more detail in EP-A-133 804. Preferred are fabric treatment compositions containing 1% to 10% of the amine.

Also suitable are complexes of the above-described plasticizing amine and phosphate esters of the formulas:

Wherein R₈ and R₉ represent C₁-C₂�0 alkyl groups or ethoxylated alkyl groups of the general formula alkyl-(OCH₂CH₂) y , in which the alkyl substituent represents a C₁-C₂�0 alkyl group or preferably a C₈-C₁₆ alkyl group and Y represents an integer having a value of 1 to 15, more preferably 2 to 10 and most preferably 2 to 5. Complexes of a plasticizing amine and a phosphate ester of this type are described in more detail in EP-A-168 889.

Suitable additional plasticizer components to be used are also the plasticizing amines described in GB 2 173 827 and in particular the substituted cyclic amines. Suitable compounds for this are imidazolines of the general formula 1-(C₁₂₋₂₂-alkyl)-amide-(C₁₋₄-alkyl)-2-(C₁₂₋₂₂-alkyl)-imidazoline.

A preferred cyclic amine is di-tallowamidoethyl-2-tallowimidazoline. Preferred fabric treatment preparations contain 1% to 10% of the substituted cyclic amine.

Further examples of additional ingredients to be used include the plasticizing amides of the formula R₁₀R₁₁NCOR₁₂, wherein R₁₀ and R₁₁ are independently selected from C₁-C₂₂ alkyl, alkenyl, hydroxyalkyl, aryl and alkylaryl groups; R₁₂ is hydrogen or a C₁-C₂₂ alkyl or alkenyl group, an aryl or alkylaryl group. Preferred examples of these plasticizing amides are ditallow acetamide and ditallow benzamide. Good results are obtained when the plasticizing amides are present in the preparation in the form of a preparation with a fatty acid or a phosphate ester as described above with regard to the plasticizing amines.

The softening amides are preferably present in an amount of 1% to 10% in the fabric treatment preparation.

In addition, the present tissue treatment preparations can be used In addition to the ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product property benefits. Typical ingredients of this type include pH adjusters, humectants, which are described in more detail in EP-313 146, silicone/silica foam regulators, fragrances, colorants, hydrotropes and gel control agents, freeze-thaw stabilizers, bactericides and preservatives. Preferred fabric treatment preparations contain from 0.05% to 30% of these ingredients.

Technical application

The fabric treatment preparations according to the invention can be in liquid or granular form. They can be used in the rinse cycle or together with a detergent composition in the washing process. According to a preferred embodiment, the fabric treatment preparations are present in detergent compositions which soften the fabric in the course of the washing process (STW detergent compositions (softening-through-the-wash)).

According to a preferred embodiment, these fabric treatment preparations are in the form of particulate agglomerates and even more preferably these agglomerates are incorporated into particulate detergent compositions to form granular STW detergents.

Liquid and granular application forms

The fabric treatment preparations according to the invention can be in liquid form as an aqueous dispersion. When they are in the form of an aqueous dispersion, the fabric treatment preparation preferably contains a suspending agent or an anti-settling agent. According to the invention, the aqueous dispersion contains the clay of the fabric treatment preparation in an amount of 0.5% to 30% of the aqueous dispersion and siloxane and clay flocculants in corresponding amounts.

A suitable suspending agent must provide a fully activated carrier matrix to suspend the particles within the liquid preparations.

Particles in this sense are granules or droplets of suspendable size, with which the desired properties of the liquid preparation are achieved. In general, this particle size is below 200 µm. The individual particles can contain one or more of the essential or optionally used compounds of the fabric treatment preparations.

Finally, a suitable suspending agent must not affect the viscosity, elasticity or aesthetic appearance of the product.

These suspending agents or mixtures thereof are used in the preparations according to the invention in amounts of 0.25% to 5%.

Organophilic quaternized ammonium clay compounds, for example of the Benton family of clays and also pyrogenically produced silicas are examples of suspending agents that can be used in accordance with the invention. Benton type rheological aids are described as products of a clay comprising a negative layer lattice and an organic compound containing a cation and at least one alkyl group having at least 10 carbon atoms. Bentones have the ability to swell in certain organic liquids. Organophilic quaternized ammonium clay compounds are preferred suspending agents, as described in U.S. Patent 4,287,086.

Pyrogenic silicas also impart excellent anti-settling properties to the preparations of the invention. Pyrogenic silicas are generally defined as a colloidal form of silica prepared by burning silicon tetrachloride in a hydrogen-oxygen furnace. Normally, fumed silicas are used as thickeners, thixotropic agents and reinforcing agents in printing inks, resins, rubbers, paints and cosmetics. Fumed silicas of the CAB-O-SIL type are suitable as suspending agents in the invention.

Other suspension agents are cellulose suspending agents. For example, carboxyalkyl celluloses and preferably carboxymethyl celluloses are excellent suspending agents. In addition, other known suspending agents can also be used.

Mixtures of Benton clays, pyrogenic silicas or use cellulose suspending agents as suitable suspending agents.

The rheological properties of the resulting liquid preparations are very important for a commercially acceptable product. A liquid that is described as stringy (i.e., elastic), thick, or lumpy is undesirable. The suspending agents described above avoid these undesirable rheological properties while maintaining a pourable, homogeneous product with good consumer acceptance. A viscosity in the range of about 100 to about 1000 kg/(ms) is desirable.

It is also desirable that the liquid preparations have plastic rheological properties. Materials that have plastic flow properties only flow after an applied shear force has reached a critical minimum value.

The fabric treatment preparations according to the invention can also be in granular form. In the form of particulate preparations. Accordingly, the particulate preparations according to the invention contain the clay of the fabric treatment preparation in an amount of at least 15%, preferably more than 50% of the particulate preparation, and siloxane and clay flocculants in corresponding amounts.

To form the particulate preparations, the compounds of the fabric treatment preparation are preferably agglomerated. The typical agglomerate size suitable according to the invention is in the range of 0.2 to 1.2 millimeters on average, with the individual agglomerates having particle sizes of 0.05 mm to 2.5 mm.

According to a preferred embodiment of the invention, the clays, siloxanes and clay flocculants are agglomerated together from a slurry.

According to a further preferred embodiment, the agglomerates containing clay and siloxane are prepared separately from the agglomerates containing the clay flocculant and both types of agglomerates are then mixed according to the invention.

The agglomeration processes and the appropriate equipment include methods and equipment known per se. The agglomeration processes include the use of agglomeration aids such as sodium carbonate, sodium sulfate, potassium carbonate, potassium sulfate, magnesium sulfate, lithium sulfate, lithium carbonate, sodium citrate, sodium sesquicarbonate and water. Non-limiting examples of the equipment for agglomerating clay from smaller particles include the Dravo pan agglomerator, the Loedige Agglomerations KG/Schugi Beldner granulator, continuously operated vertical fluidized bed agglomerators with rotating knives, Niro fluidized bed agglomerators, Obrian mixer/agglomerators and Littleford mixers (Littleford Brothers, Inc., Florence, Kentucky. USA, eg. Model FM130D).

Other methods and devices that employ larger quantities of water, including the production of agglomerates directly from a slurry, include spray drying towers and prill towers.

On a laboratory scale, food processing equipment widely available to the consumer can be used to agglomerate agglomerates of smaller clay particles into agglomerates of the particle size ranges described.

Detergent compositions

When used together with detergent compositions, preferably as an integral part of STW detergent compositions, the fabric treatment preparation is present in amounts of from 1% to 50%, preferably from 1% to 20% and most preferably from 5% to 15% of the total composition.

The STW detergent compositions of the invention can be in liquid and granular form. To form liquid or granular STW detergent compositions, the detergent compounds can be prepared separately and then mixed with the aqueous suspension or granular agglomerates of the fabric treatment preparation, or the detergent compound and the fabric treatment preparation compounds can be prepared together in an integral process.

STW detergent compositions and preferably granular STW detergent compositions of the present invention are characterized in that they comprise at least one surface-active agent in addition to the fabric treatment preparations. They may also contain other conventional detergent compounds in amounts known per se.

The detergent surfactants which are particularly useful and which can be used in accordance with the invention include the well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical examples are the alkyl benzene sulfonates, alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters and the like, which are well known to those skilled in the art of detergents. In general, such detergent surfactants contain an alkyl group in the C9-C18 range; the anionic detergent surfactants can be used in the form of their sodium, potassium or triethylammonium salts; while the nonionic materials generally contain from about 5 to about 17 ethylene oxide groups. U.S. Patent 3,995,669 includes detailed listings of such typical surface-active detergents. In compositions of the present type, C11-C16 alkylbenzenesulfonates, C12-C18 paraffinsulfonates and alkylphenols are particularly preferred.

Water-soluble soaps are also suitable as surface-active agents, for example the well-known sodium and potassium, coconut or tallow soaps.

The detergent composition may contain as little as 1% of the surfactants, but preferably contains from 5% to 50% and more preferably from 10% to 30% surfactants or detergents. Mixtures of ethoxylated nonionic surfactants with anionic surfactants such as the alkylbenzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for removing a broad spectrum of soils and stains from fabrics in the wash cycle.

Detergent additives

The detergent compositions of the invention may contain further ingredients which assist in their cleaning action. For example, it is highly preferred that detergent compositions contain a detergent builder and/or a metal ion sequestering or chelating agent. Compounds classifiable as detergent builders and which are well known include the nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyro-phosphates, silicates and mixtures thereof. The metal ion sequestrants include all of the above materials plus materials such as ethylenediaminetetraacetate, amine polyphosphates (DEQUEST) and a wide variety of other polyfunctional organic acids and salts too numerous to be mentioned in detail here. U.S. Patent 3,579,454 describes typical examples of the use of such materials for various cleaning purposes. Generally, the builder/sequestrant component will comprise about 0.5% to 45% of the total composition. The zeolite builders (e.g., zeolite A) having a particle size of 1 to 10 µm described in German Patent 2,422,655 are particularly preferred for low phosphate compositions.

Particularly suitable phosphate-free builders are either carboxylate mixtures, which

a) 1% to 99% of the builder from a tartrate monosuccinate component of the formula:

wherein X is H or a salt-forming cation; and b 1% to 99% by weight of the builder of a tartrate disuccinate component of the formula:

wherein X is H or a salt-forming cation.

Builder systems of this type are described in more detail in U.S. Patent 4,663,071.

Typical detergent compositions suitable for use in the present invention contain 5% to 35% of this builder system.

The present detergent compositions further preferably contain enzymes or enzyme mixtures to improve their cleaning performance against a variety of soils and stains. Hydrolases and isomerases, such as amylase, lipase, cellulase and protease enzymes, suitable for use in detergents are well known to those skilled in the art and are contained in commercially available liquid and granular detergents. Typically, commercially available detergent enzymes (preferably a mixture of amylase, lipase, cellulase and protease) are used in amounts of 0.001% to 5.0% of the detergent compositions. Cellulase enzymes for detergents, which provide both a cleaning effect and a softening effect, especially against cotton fabrics, are particularly desirable for the compositions of the invention.

Furthermore, these detergent compositions can contain other ingredients that support their cleaning action. For example, the present compositions can contain a bleaching agent, in particular a peroxyacid bleaching agent. In the context of the present invention, the term "peroxyacid bleaching agent" refers both to peroxyacids as such and to systems that are suitable for producing peroxyacids in situ.

Peroxyacids per se also include their alkali metal and alkaline earth metal salts. Peroxyacids and diperoxyacids are commonly used. Examples of these are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.

Systems capable of producing peracids in situ consist of a peroxygen bleach and an activator for it.

The peroxygen bleaches are those that can yield hydrogen in aqueous solution; these compounds are well known and include hydrogen peroxide, alkali metal peroxides, organic peroxide bleaches such as urea peroxide, inorganic persalt bleaches such as alkali metal perborates, percarbonates, perphosphates and persillicates.

The released hydrogen peroxide reacts with the bleach activator to form the peroxyacid bleach. Classes of bleach activators include esters, imides, imidazoles, oximes and carbonates. Preferred materials in these classes include methyl o-acetoxybenzoates; sodium p-acetoxybenzenesulfonates, such as sodium 4-nonaoyloxybenzenesulfonate and sodium 4-decanoyloxybenzenesulfonate; bisphenol A diacetate; tetraacetylethylenediamine; tetraacetylhexamethylenediamine and tetraacetylmethylenediamine.

Other highly preferred peroxygen bleach activators described in U.S. Patents 4,483,778 and 4,539,130 are α-substituted alkyl or alkenyl esters such as sodium 4-(2-chlorooctanoyloxy)benzenesulfonate and sodium 4-(3,5,5-trimethylhexanoyloxy)benzenesulfonate. Suitable peroxyacids are also peroxygen bleach activators as described in EP-A-166 571, i.e. compounds of the general type RXAOOH and RXAL, where R is a hydrocarbon group, X is a heteroatom, A is a carbonyl bridging group and L is a leaving group, in particular the oxybenzenesulfonate group.

In addition, polymeric soil release agents are useful for the detergent compositions of the invention. They include cellulose derivatives such as hydroxyether cellulose polymers, copolymeric blocks of ethylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, cationic guar gums and the like.

The cellulose derivatives that act as soil release agents are commercially available and include hydroxy ethers of cellulose such as Methocel (Dow) and cationic cellulose ether derivatives such as Polymer JR-124, JR-400 and JR-30M (Union Carbide).

Other effective soil release agents are cationic guar gums, such as Jaguar Plau (Stein, Hall) and Gendrive 458 (General Mills).

Preferred cellulosic soil release agents that can be used in the present invention have a viscosity in aqueous solution at 20°C of 15 to 75,000 kg/(ms) and are selected from the group consisting of methylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, or mixtures thereof.

An even more preferred soil release agent is a random block copolymer of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers comprise repeating units of ethyl terephthalate and PEO terephthalate in a molar ratio of ethylene terephthalate units of about 25:75 to about 35:65, with the PEO terephthalate units containing polyethylene oxide having molecular weights of from 300 to 2,000. The molecular weight of these polymeric soil release agents ranges from 25,000 to 55,000. U.S. Patents 3,959,230 and 3,893,929 describe similar copolymers in widely varying forms. These polymeric soil release agents have previously been shown to provide more uniform distribution over a wider range of fabrics and therefore provide improved fabric protection properties.

Another preferred group of polymeric soil release agents comprises the crystallizable polyesters having repeating units of ethylene terephthalate units comprising from about 10% to 15% by weight ethylene terephthalate units together with from about 80% to about 90% by weight polyoxyethylene terephthalate units derived from a polyoxyethylene glycol having an average molecular weight of from 300 to 5,000 and wherein the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1. Examples of polymers of this type are the commercially available materials Zelcon 5126 (from Dupont) and Milease T (from ICI).

Preferred soil release polymers and processes for their preparation are described in EP-A-185 427.

When these soil release agents are used, they generally make up 0.05% to 5.0% of the detergent composition.

Examples:

The following examples illustrate preferred embodiments of the invention and facilitate its understanding.

Abbreviations for the individual components of the examples have the following meanings:

LAS : Sodium salt of linear dodecylbenzenesulfonate

TAS : Sodium salt of tallow alcohol sulfate

AOS : sodium salt of α-(C₁₂₋₁₈)-olefin sulfonate

TAE-11 : Tallow alcohol ethoxylated with approximately 11 moles of ethylene oxide

FA25E7 : Fatty alcohol (C₁₂₋₁₅) ethoxylated with 7 mole ethylene oxide

DTMA : Ditallowmethylamine

CFA : coconut fatty acid

HFA : hydrogenated C₁₆₋₂₂ fatty acid

Zeolite A : sodium salt of fully hydrated zeolite 4A (average particle size between 2 and 6um)

NTA : sodium salt of nitrilotriacetic acid

Copolymer : AA³⁻/MA⁻⁻ = Copolymer of 30 mol% acrylic acid and 70 mol% Maleic acid 50-70 mmol weight

CMC : sodium salt of carboxymethylcellulose

EDTA : sodium salt of ethylenediaminetetraacetic acid

Example I

For preparations A, B, A', B', the following is prepared: 500 grams of smectite clay with a cation exchange capacity of 70-80 meq/100g are mixed with 50 grams of polysiloxane (10% of the clay). The polysiloxane corresponds to the general formula given in which R is a methyl group, R' is a straight-chain propyl group, q is 329, m is 21 and n is 1 and Y is a polyether with 12 ethyl oxide groups, which has an acetic acid end group. Both compounds are mixed thoroughly and agglomerated using a Braun mixer (Multipractic-electronic-de-luxe-mixer). The agglomerating agent is water and the agglomerates are sieved to a particle size of 0.15 to 0.85 mm. In the same way, prepare a comparison product without siloxane.

Formulation A is prepared by dry blending the clay/siloxane granules with the detergent granules of Composition I of Table I so that the fabric softening detergent contains 10.5% of the smectite clay in the wash cycle. As a control material, composition B is prepared by dry blending the clay granules with the same detergent granules of Composition I of Table I so that the STW detergent also contains 10.5% of the smectite clay. Formulations A' and B' were prepared in the same manner as preparations A and B but using detergent composition II of Table I which contains a clay flocculant.

To facilitate comparison of the softness achieved by preparations A, B, A', B', the following test method was used: 3.5 kg of clean fabric loads are washed in a Miele 423 automatic drum washing machine at 60ºC for 1.5 hours. The water hardness is 3.0 mmol Ca²+ and Mg²+ per litre and the concentration of the preparation in the wash liquor is 1%. To assess the softness, sections of terry cloth softness test products are added. The softness test products are line dried before the softness is assessed. The comparative assessment of softness is carried out by trained panelists using a rating scale of 0 to 4 panel score units (PSU). On this scale, a rating of 0 represents no difference and a rating of 4 represents a maximum difference. Softness is assessed after one and after four wash cycles. Results of softness evaluation of composition A, B, A', B': Result Comparison of composition One wash cycle four wash cycles

Result 1 shows that no additive softening effect is achieved by adding siloxane to a clay-containing STW detergent. The effect according to the invention is illustrated by result 2, according to which the Combination of clay, flocculant and siloxane results in a surprisingly significant improvement in softness compared to the prior art composition containing clay and the flocculant.

Example II

The same compositions a, b, a', b' are prepared as in Example I, with the difference that 5 grams of polysiloxane are used, that is, one percent of the weight of the clay. The polysiloxane used in this Example II is Silwet L720 from Union Carbide. Result Comparison of composition One wash cycle four wash cycles

Examples III - XI

Other detergent compositions may be used in accordance with the invention together with the clay-siloxane agglomerates and the flocculant. Alternative granular detergent compositions are given in Table II.

Similar compositions in which the clay/siloxane granules are initially dry mixed with the granules containing the flocculant are also effective when added to granular detergent compositions.

Examples XII and XIII

These examples illustrate the use of the fabric treatment preparation in the form of an aqueous dispersion of the composition given below, which shows excellent softening properties when added in an appropriate amount to the last rinse of the washing process: Disperse 80 grams of smectite clay in 1 kg of water and add under vigorous Stir in 8 grams of the siloxane described in Example I or II. Add the flocculant and this mixture together to the last rinse of the wash cycle.

Example XIV

Prepare a stabilized aqueous dispersion of the fabric treatment composition using a propeller mixer operating at 100 to 1000 rpm and combine a liquid carrier material, plasticizing clay, siloxane and a suspending agent in the propeller mixer for about 30 minutes. The resulting mixture is then passed 4 to 10 times through a colloid mill (e.g., Model SD-40 from Tekmor Corp.) which exerts a shearing action of 10-40x10³ per second at a temperature of 20 to 40ºC. Then add the flocculant slowly while operating the propeller mixer for an additional 5 minutes.

The resulting mixture is stable, that is, it does not show any phase separation or settling of the clay when stored at ambient conditions for several weeks. Table I Composition of granular detergents. All values in percent by weight. Amount C₁₂-C₁₄-dimethyl-(hydroxyethyl)-ammonium chloride Zeolite A copolymer Diethylene-triamine-penta(-methylenephosphoric acid) Sodium perborate (1 xO) Tetraacetylethylenediamine Zn-phthalocyaninesulfonate Fragrance Enzyme (protease) Montmorillonite Clay Glycerol Polyethylene oxide (MW 300,000) Sodium carbonate Sodium silicate Silicone/silicon dioxide foam regulator Optical brightener Moisture and residual components in small quantities Table II Component Amounts (wt.%) C₁₄₋₁₅-alkyl sulfate (Na) Tallow-amino-C₁₋₄-alkyl glucosamide C₁₂-C₁₄-dimethyl-(hydroxyethyl)-ammonium chloride Sodium tripolyphosphate Zeolite A Polyethylene oxide (molar weight MM) Polyacrylate Polyacrylamide Sodium sulfate Sodium carbonate Continuation of Table II Component Amounts (wt.%) Sodium silicate Sodium perborate (H₂O) Polyacrylate (mol.wt.) Copolymer Enzymes (protease, amylase, lipase, cellulase) Optical brighteners Zn-phthalocyanine sulfonate (ppm) Ethylenediamine tetramethylene phosphoric acid Diethylenetriamine penta(methylene phosphoric acid) Tetraacetyl ethylenediamine iso-nonanoyloxy benzene sulfonate (Na) Silicone/silicon dioxide foam regulator Fragrance Montmorillonite clay Hectorite clay Moisture and residual components in small amounts up to

Claims (22)

1. Fabric treatment preparation containing a softening tone - 0.005% to 20% by weight, based on the plasticizing clay, of a clay flocculant having a weight average molecular weight in the range of 100,000 to 10 million, with the exception of a copolymer of acrylic acid and maleic acid as clay flocculant, and - 0.1%-50% by weight, based on the plasticizing clay, of a straight-chain or branched, substituted polysiloxane of the general formula wherein R is C₁₋₄alkyl; R' R or a polyether of (C2-C3 oxides) 1-50 , with a terminating H or R end group; R" is branched or straight chain C₁₋₄alkyl; q�1 and q�2 are integers; m and (q₁ + q₂) are integers with values from 4 to 1700; n is an integer with a value from 0 to 6; Y is a polyether of (C₂₋₃-oxides)k, where k has an average value of 7 to 100, terminated by an H or C₁₋₄-alkyl end group; or Y is a group of the formula wherein X and V are selected from -H; -C₁₋₃�0 alkyl, -C-aryl; -C₅₋₆ cycloalkyl; -C₁₋₆ NH₂; -COR; with the proviso that the nitrogen may be quaternized to give the following group where W can be selected from X and V, or Y wherein T and P are selected from -H, -COOH, -CO-O-C₁₋₂-alkyl or epoxy-C₅₋₆-cycloalkyl. 2. Fabric treatment preparation according to claim 1, characterized in that the softening clay is a smectite clay with a cation exchange capacity of at least 50 mEq/100 g of clay. 3. Fabric treatment preparation according to claims 1 or 2, characterized in that the clay flocculant has a weight average molecular weight of 800,000 to 5,000,000 and is present in an amount of 0.005% to 2%, based on the amount of softening clay. 4. Fabric treatment preparation according to claims 1 to 3, characterized in that the clay flocculant has a weight average molecular weight of 150,000 to 800,000 and is present in an amount of 2 to 20%, based on the amount of the softening clay. 5. Fabric treatment preparation according to one of the preceding claims, characterized in that the amount of substituted polysiloxane is in the range of 0.1 to 20%, based on the amount of plasticizing clay. 6. Fabric treatment preparation according to one of the preceding claims, characterized in that the amount of substituted polysiloxane is in the range of 1 to 10%, based on the amount of plasticizing clay. 7. Fabric treatment preparation according to one of the preceding claims, characterized in that the substituted polysiloxane of the general formula given in claim 1 has values of (q₁ + q₂) of 50 to 1,500 and the integer m has values of 4 to 100. 8. Fabric treatment preparation according to one of the preceding claims, characterized in that the substituted polysiloxane of the general formula given in claim 1 is selected from compounds in which either - R, R' are methyl and R" are propyl and (q₁ + q₂) have the value 329, m have the value 21 and n have the value 1 and Y is a polyether which consists of 12 ethyl oxides and has an acetic acid end group or - R, R' are methyl and R" are propyl and (q₁ + q₂) have the value 485, m have the value 15 and n have the value 1 and Y is a polyether which consists of 12 ethylene oxides and has an acetic acid end group, or - R, R' are methyl and R" are methyl-2-propyl, (q₁ + q₂) has a value of 1470, m has the value 30 and n has the value 1 and Y is (aminoethyl)amine. 9. Fabric treatment preparation according to one of the preceding claims, characterized in that it additionally contains softening amines in an amount of 1 to 10 wt.%, based on the fabric treatment preparation. 10. Fabric treatment preparation according to one of the preceding claims, characterized in that it additionally contains a humectant in an amount of 1 to 10 wt.%, based on the fabric treatment preparation. 11. Fabric treatment preparation according to one of the preceding claims, characterized in that it additionally contains silicone/silicon dioxide antifoaming agents in an amount of 1 to 30 wt.%, based on the fabric treatment preparation. 12. Fabric treatment preparation according to one of the preceding claims, characterized in that it is in the form of an aqueous dispersion and contains the softening clay in an amount of 0.5 to 30% by weight, based on the aqueous dispersion. 13. Aqueous dispersion according to claim 12, characterized in that it additionally contains a suspending agent in an amount of 0.25 to 5% by weight, based on the aqueous dispersion. 14. Fabric treatment preparation according to claims 1 to 11, characterized in that it is in the form of granular agglomerates with an average particle size in the range of 0.5 mm to 1.2 mm with individual agglomerates with a size in the range of 0.05 mm to 2.5 mm, and contains the softening clay in an amount of at least 15% by weight, based on the fabric treatment preparation. 15. Fabric treatment preparation according to claim 14, characterized in that it contains the softening clay in an amount of more than 50% by weight, based on the fabric treatment preparation. 16. Fabric detergent preparation containing at least one surfactant, characterized in that it additionally contains 1 to 50% by weight, based on the fabric detergent preparation, of the fabric treatment preparation according to one of the preceding claims. 17. Fabric detergent preparation according to claim 16, characterized in that the fabric treatment preparation is present in an amount of 1 to 20%, preferably 5 to 15% by weight, based on the fabric detergent preparation. 18. Fabric detergent preparation according to claims 16 and 17, characterized in that it additionally contains a detergent builder in an amount of 0.5 to 45% by weight, based on the fabric detergent preparation. 19. Fabric detergent preparation according to claims 16, 17 and 18, characterized in that it additionally contains amylase, lipase, cellulase or protease enzymes or mixtures thereof in an amount of 0.001 to 5% by weight, based on the fabric detergent preparation. 20. Fabric detergent preparation according to claims 16, 17 1, 18 and 19, characterized in that it additionally contains a bleaching agent or a soil release agent. 21. Fabric detergent preparation according to claims 16 to 20, characterized in that the fabric detergent preparation is liquid. 22. Fabric detergent preparation according to claims 16 to 20, characterized in that the fabric detergent preparation is in granular form.