CH678629A5 - - Google Patents

Description

CH 678 629 A5

description

The invention relates to non-aqueous, liquid textile treatment agents, in particular non-aqueous liquid textile detergents, which are stabilized against phase separation and gelling and are easy to pour.

5 and the use of the same for cleaning soiled textiles. ^

Liquid, non-aqueous heavy-duty detergents are well known. Compositions of this type r may contain, for example, a liquid nonionic surfactant with builder particles dispersed therein (e.g. U.S. Patents 4,316,812; 3,630,929; 4,254,466 and 4,661,280).

Liquid detergents are often perceived as more pleasant to use than dry, powdered "V

10 shaped or pond shaped products, which is why they have gained considerable favor. They are easy to measure, quickly dissolve in the wash water, can easily be applied in concentrated solutions or dispersions to soiled areas on collars to be washed, they do not dust and take up less storage space. In addition, it is possible to incorporate substances into the liquid detergents which drying measures would not survive without decomposition and which are frequently desired in the production of particulate detergents.

Although liquid detergents have numerous advantages over unitary or particulate solid products, they also often have certain disadvantages that must be eliminated in order to achieve economically acceptable products. Some products separate during storage, others during cooling and redispersion is not easy. In some cases the product viscosity changes and the product either becomes too thick to cast or so thin that it appears watery. Some clear products become cloudy, others gel when standing.

The applicant has dealt intensively with the rheological behavior of liquid nonionic surfactant systems with particulate substances suspended therein. She was particularly interested in non-aqueous, builder-containing liquid laundry detergents, as well as the problems of phase separation and settling of the suspended builder and other detergent additives. These phenomena have an influence, for example, on the pourability, dispersibility and stability of the product.

The theological behavior of non-aqueous, builder-containing liquid textile detergents can be compared to the behavior of paints, whereby the suspended iron particles correspond to the inorganic pigment and the non-ionic liquid surfactant corresponds to the non-aqueous color carrier.

It is known that one of the main problems of builder-containing liquid textile detergents is their physical stability. This problem arises from the fact that the density of the solid suspended particles is greater than the density of the liquid matrix. Therefore, the particles have a tendency to settle according to Stoke's law. There are basically two approaches to solving the sedimentation problem: the viscosity of the liquid matrix and the reduction in the size of the solid particles.

For example, the stabilization of such suspensions against settling is known by adding inorganic or organic thickeners and dispersants such as e.g. of inorganic materials with a very large surface area, e.g. finely divided silicon dioxide, clays, etc., from organic thickeners such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes etc.

Such increases in the suspension viscosity are naturally limited by the necessity that the liquid suspension must be easily pourable and flowable even at a low temperature. In addition, these additives do not contribute to the cleaning effect of the composition. US Pat. No. 4,661,280 discloses the use of aluminum stearate to increase the stability of suspensions of builder salts in liquid nonionic surfactants. The addition of small amounts of aluminum stearate increases the yield stress without increasing the plastic viscosity.

According to US Pat. No. 3,985,668, an aqueous body-simulating liquid scouring agent is produced from an aqueous liquid and a suitable colloid-forming material such as clay or an inorganic or organic thickening or suspending agent, especially smectite clays, and a relatively light, water-insoluble particulate filler, which, like the abrasive, is suspended in the body-simulating liquid phase. The light filler has particle size diameters in the range of 1 to 250 microns and a specific weight that is less than that of the body-simulating liquid phase. The patentee states that incorporating the relatively light, insoluble filler into the body-simulating liquid phase helps to minimize phase separation, i.e. minimizes the formation of a clear liquid layer above the body-simulating abrasive composition, firstly thanks to its buoyancy, which exerts an upward force on the structure of the colloid-forming agent in the body-simulating phase,

which counteracts the tendency of the heavy abrasive to compress the body-simulating structure and squeeze out the liquid. Second, the filler gives volume and replaces some of the water that would normally be used in the absence of the filler, with the result that less aqueous liquid is available to cause the formation of a clear layer and separation.

GB 2 168 377A discloses an aqueous dishwashing liquid detergent containing abrasives, colloidal clay thickener and particulate filler with particle sizes from about 65 liters to about 250 microns and densities from about 0.01 to about 0.5 g / cm3 in a concentration of about

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0.07 to about 1% by weight of the composition is used. The filler is said to improve stability by reducing the specific weight of the clay mass so that it hovers in the liquid phase of the composition. The type and amount of filler are chosen so that the specific weight of the finished composition matches that of the clear liquid 5 (i.e. the composition without clay or abrasive). The low density particulate fillers mentioned on page 4, lines 33 to 35 of the UK application can also be used as low density fillers in the compositions of the invention.

It is also known to incorporate an inorganic insoluble thickener or dispersant with a very large surface area, such as finely divided silicon dioxide with an extremely fine particle size of 10 (for example 5 to 100 millimeter diameter, for example sold as Aerosil) or other high-volume inorganic carrier materials, as described in US Pat. No. 3 630 929 are disclosed.

Milling to reduce the particle size as a measure to increase product stability offers the following advantages:

15 1. The specific surface area of the particles is increased and the particle wetting by the non-aqueous carrier (liquid nonionic surfactant) is accordingly improved.

2. The average distance between the “pigment” particles is reduced with a corresponding increase in the particle-particle interaction. Each of these effects contributes to increasing the resting gel strength and yield stress of the suspension, while the grinding significantly reduces the plastic viscosity.

The above mentioned U.S. Patent 4,316,812 describes the advantages of grinding solid particles, e.g. of builder and bleach to an average particle diameter below 10 microns. However, it has been shown that mere grinding to such small pond sizes does not as such confer sufficient long-term stability against phase separation.

There is therefore a need for further improvements in the stability of non-aqueous liquid textile treatment agents.

It is therefore an object of the invention to make liquid textile treatment agents available, which are suspensions of insoluble particles which can be used for textile treatment in a non-aqueous liquid which are stable in storage and transport, easy to pour and in cold, warm or hot water are dispersible.

Another object of the invention is to make available highly builder-containing, non-aqueous full-fabric detergents with liquid nonionic surfactant, in which the suspended solid particles do not settle and / or the liquid phase is not separated off.

35 A special object of the invention is to provide a non-vulting, stable, builder-containing, non-aqueous heavy-duty textile detergent with liquid nonionic surfactant which contains a nonionic surfactant in a non-aqueous liquid, solids which can be used for textile treatment and are suspended in the non-aqueous liquid, and one Contains an amount up to 10% by weight of a low density filler which is substantially sufficient to equalize the density of the continuous liquid phase and the density of the suspended particles or particle phase including the low density filler and other suspended particles such as builder particles.

The non-aqueous, liquid textile treatment agent based on a non-aqueous liquid is characterized by a content of

- liquid nonionic surfactant,

45 - solid textile treatment particles suspended in the non-aqueous liquid, and

Low density filler in an amount sufficient to substantially equalize the density of the continuous liquid phase and the density of the phase of the suspended particles comprising the low density filler and the solid particles for textile treatment, thereby inhibiting the separation or settling of the suspended particles becomes.

50 The solid textile treatment particles usually include builders, bleaches, antistatic agents, etc.

A preferred agent has a suspension of a builder salt in a liquid nonionic surfactant.

In another aspect, the invention provides a commercial process for cleaning soiled textiles outside the textile industry by contacting them with the non-aqueous liquid fabric treating agent described above in an aqueous wash bath. 55 The liquid phase of the non-aqueous liquid textile treatment agent of the invention contains predominantly or exclusively liquid organic synthetic nonionic surfactant. However, part of the liquid phase can be composed of organic solvents which can be incorporated into the composition as a solvent carrier or as a carrier for one or more of the particulate components, such as in enzyme slurries, perfumes and the like. Also, as described in detail below, 60 organic solvents such as alcohols and ethers can be added as viscosity-controlling and gel-preventing substances.

The nonionic surfactants used to practice the invention may belong to a variety of such compounds which are known and are extensively described, for example, in Surface Active Agents, Volume II, by Schwartz, Perry and Berch, published in Interscience Publishers, 1958, and in 65 McCutcheon's Detergents and Emulsifiers, Annual 1969. In general, the nio-

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surfactant poly (lower) alkoxylated lipophiles, the desired hydrophilic-lipophilic balance being obtained by adding a hydrophilic poly (lower) alkoxy group to a lipophilic residue. A preferred class of nonionic surfactants that can be used are the poly (lower) alkoxylated higher alkanols,

wherein the alkanol contains 10 to 22 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) is 3 to 20. Of these materials, preferred are those in which the higher alkanol is a higher fatty alcohol having 10 to 11 or 12 to 15 carbon atoms and the 5 to *

Have 18, preferably 6 to 14 lower alkoxy groups per mole. The lower alkoxy is often only ethoxy, but in some cases it may be desirably mixed with propoxy, the latter often being less (less than 50%) when present. Examples of v '

such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contains 7 ethylene oxide groups per mole, e.g. Neodol 25-7 and Neodol 23-6.5 (from Shell Chemical Company Inc.). The former is a condensation product of a mixture of a higher fatty alcohol with an average of 12 to 15 carbon atoms and 7 moles of ethylene oxide, the latter is a corresponding mixture, the carbon atom content of the higher fatty alcohol being 12 to 13 and the number of ethylene oxide groups being approximately 6.5 on average. The higher alcohols are primary alkanols. Other examples of such surfactants are Tergitol 15-S-7 and Tergitol 15-S-9, both ethoxylates of linear secondary alcohols from Union Carbide. The former is a mixed ethoxylation product of a 11 to 15 carbon atom linear secondary alkanol with 7 moles of ethylene oxide, the latter is a similar product but with 9 moles of ethylene oxide reacted.

Also applicable as nonionic surfactant components in the compositions according to the invention are nonionic surfactants with a higher molecular weight such as Neodol 45-11, which are similar ethylene oxide condensation products with higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of Ethylene oxide groups per mole 11. Such products are also manufactured by Shell Chemical Company. Another preferred class of nonionic surfactants are the commercial products which are the reaction product of a higher linear alcohol with a mixture of ethylene and propylene oxides, contain a mixed chain of ethylene oxide and propylene and are terminated by a hydroxide group. Examples include the nonionic surfactants marketed by BASF under the trade name "Plurafac", such as "Plurafac RA30", "Plurafac RA40" (a C13 to Ci5 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), and "Plurafac D25"

(a Ci3 to Ci5 fatty alcohol, condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide),

"Plurafac B26" and "Plurafac RA50" (a mixture of equal parts of "Plurafac D25" and "Plurafac RA40").

In general, the mixed ethylene oxide-propylene oxide-fatty alcohol condensation products of the general formula

R0 (C3H60) p (C2H40) qH

wherein R is a straight-chain or branched, primary or secondary aliphatic hydrocarbon radical, preferably alkyl or alkenyl, especially alkyl having 6 to 20, preferably 10 to 18, particularly preferably 12 to 18 carbon atoms, p is a number from 2 to 8, preferably 3 to 6 means and q is a number from 2 to 12, preferably 4 to 10, are advantageously used when low foaming is desired. In addition, these surfactants have the advantage of low gel temperatures.

Another group of liquid nonionic surfactants is available from Shell Chemical Company Inc. under the trade name “Dobanol”: “Dobanol 91-5” is an ethoxylated Cg to Cn fatty alcohol with an average of 5 moles of ethylene oxide; “Dobanol 25-7” is an ethoxylated C12 to cis fatty alcohol with an average of 7 moles of ethylene oxide; Etc.

In order to achieve the best balance between the hydrophilic and lipophilic moieties, in the preferred poly (lower) alkoxylated higher alkanols the number of lower alkoxy groups is usually 40 to 100% of the number of carbon atoms in the higher alcohol, for example 40 to 60% thereof, where the nonionic detergent often contains at least 50% of such preferred poly (lower) alkoxylated higher alkanols.

. Higher molecular weight alkanols as well as various other normally solid nonionic surfactants and surface-active substances can contribute to the gelation of the liquid detergent and are consequently preferably omitted or limited in the amount in the compositions according to the invention, although small amounts thereof can be used because of their cleaning properties etc. . For both the preferred and less preferred nonionic surfactants, the alkyl groups present are generally linear, although branching can be tolerated, for example, a carbon atom that is adjacent to, or away from, the straight chain terminal carbon atom the. * "Alkoxy chain is provided that such branched alkyl is no more than 3 carbon atoms long. Normally the proportion of carbon atoms in such a branched configuration will rarely exceed 20% of the total carbon atom content of the alkyl. In the same way, although linear alkyls, which are terminally connected to the alkylene oxide chains, are most preferred and are assumed

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that they have the best results in terms of the combination of cleaning power, biodegradability and non-gelling properties, medium or secondary linkages with the alkylene oxide in the chain possible. The proportion of these alkyls is usually only small, generally less than 20%, but, as in the case of the tergitols mentioned, can be larger. When propylene oxide is present in the lower 5 alkylene oxide chain, it usually makes up less than 20% thereof, preferably less than 10% thereof.

If larger amounts of non-terminally alkoxylated alkanols, propylene oxide-containing poly (lower) alkoxylated alkanols and less hydrophilic-lipophilic balanced nonionic surfactants than indicated above are used and if other nonionic surfactants are used instead of the preferred Nio-10 surfactants mentioned here, the resultant can be obtained The product has less good detergency, stability, viscosity and non-yellowing properties than the preferred compositions, but the use of the viscosity and gel-controlling compounds can also improve the properties of the detergents based on these nonionic surfactants. In some cases, such as when using a higher molecular weight poly (lower) alkoxylated higher alkanol (often because of its detergency), the amount thereof is adjusted or limited based on routine experiment results to achieve the desired detergency and still to obtain a non-gelling product with the desired viscosity. It has also been found that it is hardly necessary to use the non-ionic surfactants with a larger MG because of their cleaning properties, since the non-ionic surfactants described here are excellent cleaning agents and, moreover, allow the desired viscosity in the liquid detergents without gelling at low temperatures to reach. Mixtures of two or more of these liquid nonionic surfactants can also be used, in some cases the use of such mixtures can be advantageous.

Because of their low gel temperatures and low pour points, the secondary C12 to C13 fatty alcohols with relatively narrow ethylene oxide contents are in the range from 7 to 9 moles, in particular 8 mols / 25 moles, of ethylene oxide per molecule of the C9 to Cu, especially Cio, fatty alcohols about 6 moles of ethylene oxide is another preferred nonionic surfactant class.

In addition, it may be advantageous to incorporate in the compositions of the invention an organic solvent or diluent which acts as a viscosity controlling and gel inhibiting agent for the liquid non-ionic surfactants. Lower (Gi to 30 C6) aliphatic alcohols and glycols such as ethanol, isopropanol, ethylene glycol, hexylene glycol and the like have been used for this purpose. Polyethylene glycols such as PEG 400 are also useful diluents. Alkylene glycol ethers such as the compounds sold under the trade names "Carbopol" and "Carbitol" and which have relatively short hydrocarbon chains (C2 to Ca) and a low content of ethylene oxide (about 2 to 6 EO units per molecule) are special value-35 full viscosity control and gel-preventing solvents in the compositions of the invention. This application of the alkylene glycol ether is described in US-SN 687 815 (1984). Suitable glycol ethers can be represented by the following general formula

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R0 (CH2CH20) nH

in which R is a C2 to Cb, preferably C2 to Cs alkyl group, and n is a number from 1 to 6, preferably 1 to 4 on average.

Specific examples of suitable solvents include ethylene glycol monoethyl ether (C2H5-O-CH2CH2OH), diethylene glycol monobutyl ether (C4H9-0- (CH2CH20) nH), tetraethylene glycol monooctyl 45 ether (CsHi7-0- (CH2CH20) 4H), etc. Diethylene glycol is particularly preferred monobutyl ether.

Another gel-preventing substance that can be used, which may be present in the liquid phase as a component in a smaller amount, is an aliphatic linear or aliphatic monocyclic dicarboxylic acid, such as the C6- to Ci2-alkyl and alkenyl derivatives of succinic acid or maleic acid as well the corresponding anhydrides or an aliphatic monocyclic dicarboxylic acid compound. The use of these compounds as gel-preventing agents in non-aqueous liquid builder-containing heavy-duty textile detergents is described in US Pat. No. 756,334 (1985).

In short, the gel-preventing compounds are aliphatic linear or aliphatic monocyclic dicarboxylic acid compounds. The aliphatic part of the molecule can be saturated or ethylenically unsaturated, the aliphatic linear part can be straight-chain or branched. The aliphatic 55 monocyclic molecules can be saturated or have a single double bond in the ring. In addition, the aliphatic hydrocarbon ring may contain 5 or 6 carbon atoms in the ring, i.e. Cyclopentyl, cyclopentenyl, cyclohexyl or cyclohexenyl, where one carboxyl group is bonded directly to a ring carbon atom and the other carboxyl group is bonded to the ring via a linear alkyl or alkenyl group.

60 The aliphatic linear dicarboxylic acids have at least 6 carbon atoms in the aliphatic part, which can be alkyl or alkenyl with up to 14 carbon atoms, a preferred range being between 8 and 13, in particular 9 to 12, carbon atoms. One of the carboxylic acid groups (-COOH) is preferably bonded to the terminal (a) carbon atom of the aliphatic chain, the other carboxyl group is preferably bonded to the next adjacent (β) carbon atom

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the or may be 2 or 3 carbon atoms from the a position, i.e. on the y or A carbon atom. The preferred aliphatic dicarboxylic acids are the α, β-dicarboxylic acids and the corresponding anhydrides, particularly preferred are the derivatives of succinic acid or maleic acid which correspond to the general formula or

15 wherein R1 is an alkyl or alkenyl radical having 6 to 12, preferably 7 to 11 and particularly preferably 8 to 10 carbon atoms.

The alkyl or alkenyl group can be straight-chain or branched. The straight chain alkenyl groups are particularly preferred. It is not necessary that R1 be a single alkyl or alkenyl group, mixtures of different carbon chain lengths may be present, depending on the starting materials used to produce the dicarboxylic acids.

The aliphatic monocyclic dicarboxylic acid can contain either 5- or 6-membered carbon rings, one or two linear aliphatic groups being attached to ring carbon atoms. The linear aliphatic groups should contain at least 6, preferably at least 8, particularly preferably at least 10 carbons in total and up to 22, preferably up to 18, particularly preferably 25 to 15 carbon atoms. When two aliphatic carbon atoms are attached to the aliphatic ring, they are preferably in para position to one another. The preferred aliphatic cyclic dicarboxylic acid compounds can be represented by the following structural formula r2-cooh cooh, in which T is -CH2-, -CH =, -CH2-CH2- or -CH = CH-, R2 is an alkyl or alkenyl group with 3 is up to 12 carbon atoms; and R3 represents a hydrogen atom or an alkyl or alkenyl group having 1 to 12 carbon atoms, provided that the total number of 40 carbon atoms in R2 and R3 is about 6 to about 22.

The meaning of -T- is preferably -CH2-CH2- or -CH = CH-, in particular -CH = CH-,

R2 and R3 are each preferably aikyl groups having 3 to 10 carbon atoms, especially 4 to 9 carbon atoms, the total number of carbon atoms in R2 and R3 being 8 to 15. The alkyl or alkenyl groups can be straight-chain or branched, but straight chains are preferred. 45 The amount of non-ionic surfactant is generally in the range of 20 to 70%, e.g. 22 to 60%, and is e.g. 25%, 30%, 35% or 40% based on the weight of the composition. The amount of solvent or diluent optionally present is usually up to 20%, preferably up to 15%, for example 0.5 to 15, preferably 5.0 to 12%. The weight ratio of nonionic surfactant to alkylene glycol ether as a viscosity-controlling and gel-preventing agent (if the latter is present as in the preferred embodiment of the invention) is in the range from 100: 1 to 1: 1, preferably from 50: 1 to 2: 1 , e.g. at 10: 1, 8: 1, 6: 1.4: 1 or 3: 1.

The amount of dicarboxylic acid as a gel-preventing compound (if used) will depend on such factors as the type of liquid nonionic surfactant, e.g. whose gel temperature ,. the type of dicarboxylic acid, the other ingredients in the composition that can affect the gel temperature and the intended use (e.g. with hot or cold water, the climate, etc.). In general, it is possible to lower the gel temperature to a temperature not above 3 ° C., preferably not above 0 ° C., the amounts of dicarboxylic acid as a gel-preventing agent being in the range from 1 to about 30, preferably 1.5 to 15,% by weight .-%, based on the weight of the liquid nonionic surfactant, although in special cases the optimal amount can easily be determined by routine experimentation.

The preferred cleaning agents of the invention can also contain water-soluble and / or water-dispersible builder salts as an essential component. Typical suitable builder salts are, for example, those described in the aforementioned U.S. Patents 4,316,812, 4,264,466 and 3,630,929, and many others 65. Water-soluble inorganic alkaline builder salts, which alone with the surfactant or in

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Mixtures that can be used with other builders are the alkali carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium 5 tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate and potassium bicarbonate. Sodium tripolyphosphate (TPP) is particularly preferred, provided that phosphate-containing components are not prohibited for environmental reasons. The alkali silicates are valuable builders, which also make the composition anticorrosive to parts of the washing machine. Sodium silicates with Na20 / SiC> 2 ratios of 1.6 / 1 to 1 / 3.2, especially about 1/2 to 1 / 2.8, are preferred. Potassium silicates of the same proportions can be used.

Another class of builders are the water-insoluble aluminosilicates of both the crystalline and amorphous types. Various crystalline zeolites (i.e. aluminosilicates) are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477. An example of amorphous zeolites which can be used according to the invention can be found in Belgian PS 835 351. 15 The zeolites generally correspond to the formula

(M20) x (Al203) y- (Si02) zWH20,

wherein x is 1, y is 0.8 to 1.2 and preferably 1, z is 1.5 to 3.5 or more and preferably 2 is 20 to 3 and w is 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical Zeoli-th is of type A or a similar structure, with type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 meq / g or more, e.g. 400 meq / g.

Examples of organic alkaline sequestering builder salts that can be used alone with the surfactant or in admixture with other organic or inorganic builders are alkali, ammonium or substituted ammonium aminopolycarboxylates, e.g. Sodium and potassium ethylenediamine tetraacetate (EDTA), sodium and potassium nitrilodiacetate (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetate. Mixed salts of these polycarboxylates are also suitable.

Other suitable organic type builders include carboxymethyl succinates, tartronates and glycolates, as well as the polyacetal carboxylates. The polyacetal carboxylates and their use in detergents are described in U.S. Patents 4,144,226, 4,315,092 and 4,146,495. Other patents relating to similar builders include U.S. Patents 4,141,676; 4,169,934; 4,201,858; 4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,422; 4,233,423; 4,302,564 and 4,303,777. European patent applications numbers 0 015 024, 0 021 491 and 0 063 399 are also relevant.

The amount of suspended builders, based on the total composition, is usually in the range of 10 to 60% by weight, e.g. 20 to 50, e.g. 25 to 40% by weight of the composition.

According to the invention, the physical stability of the suspension of the builder or builders as well as any other suspended solid additive particles such as bleach, etc. in the liquid carrier is drastically improved by the presence of a low density filler in that the density 40 of the continuous liquid phase is approximately the same is like the density of the dispersed particulate phase including the low density filler.

The low density filler can be any inorganic or organic particulate that is insoluble in the liquid phase / solvents used in the composition and is compatible with the various components of the composition. In addition, the filler particles should have sufficient mechanical strength to withstand the shear forces that are expected to occur during the formulation, packaging, shipping and application of the product.

Within the above general criteria, suitable particulate fillers have effective densities in the range of about 0.01 to 0.50 g / cm3, especially about 0.01 to 0.20 g / cm3, especially 0.02 to 50 0.20 g / cm3, which is at room temperature, e.g. 23 ° C, and particle size diameters in the range from 1 to 300 micrometers, preferably 4 to 200 micrometers, the average particle size diameters being in the range from 20 to 100 micrometers, preferably 30 to 80 micrometers.

The types of inorganic and organic fillers that have these low bulk densities 55 are generally hollow microspheres or microballoons or at least highly porous solid particulate substances.

For example, either inorganic or organic microspheres such as various organic polymeric microspheres or glass beads are preferred. Specific non-limiting examples of organic polymeric materials in microsphere form include polyvinylidene chloride, polystyrene, 60 polyethylene, polypropylene, polyethylene terephthalate, polyurethanes, polycarbonates, polyamides and the like. In addition to the hollow microspheres, other low density inorganic filler materials can also be used, such as aluminosilicate zeolites, spray dried clays, etc.

According to a particularly preferred embodiment of the invention, however, the lightweight

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term filler formed from a water-soluble material. This has the advantage that when used to wash soiled textiles in an aqueous washing bath, the water-soluble particles dissolve and therefore do not settle on the textiles to be washed; in contrast, the water-insoluble filler particles can adhere more easily to the fibers or the surface of the washed textiles or be adsorbed.

As a special example of such light fillers which are insoluble in the non-aqueous liquid phase of the composition according to the invention but dissolve in water, sodium borosilicate glass may be mentioned, for example the hollow microspheres sold under the trade name “Q-Cell”, especially “ Q-Cell 400 »,« Q-Cell 200 »,« Q-Cell 500 »etc. are available. These materials have the additional advantage of providing silications in the wash water that are anti-corrosive.

Examples of water-soluble organic materials which are suitable for the production of hollow, low-density microsphere particles are, for example, starch, hydroxyethyl cellulose, polyvinyl alcohol and polyvinyl pyrrolidone, the latter also making functional properties available, for example by dissolving them in the aqueous washing bath act as a dirt carrier.

One of the critical features of the invention is that the amount of low density filler added to the non-aqueous liquid suspension is such that the average (average) statistically weighted densities of the suspended particles and the low density filler are the same as or not essential is different than the density of the liquid phase (including nonionic surfactant and other solvents, liquids and dissolved components). What this means in practice is that the density of the entire composition after addition of the low density filler is approximately the same or the same as the density of the liquid phase alone and also the density of the dispersed phase alone.

Therefore, the amount of the low-density filler to be added depends on the density of the filler, the density of the liquid phase alone, and the density of the whole composition except for the low-density filler. With all of the liquid dispersions used as starting materials, the required amount of low density filler will increase with the density of the filler and conversely, a smaller amount of the low density filler will be required to achieve a given decrease in the density of the finished composition when the density of the Filler is less.

The amount of the low density filler required to balance the densities of the liquid phase (known) and the dispersed phase can theoretically be calculated using the following equation, assuming ideal mixing of the low density filler and the non-aqueous one Dispersion is based on:

is added to the suspension to make the density of the final composition equal to the density of the liquid;

dms = the liquid displacement density of the low density filler;

diiq = density of the liquid phase of the suspension;

do = density of the starting composition (i.e. suspension before adding the filler);

Mf = mass of the finished composition (i.e. after adding the filler); and Mms = mass of the filler to be added.

In general, the amount of low density filler required to make the dispersed phase and liquid phase densities equal is in the range of 0.01 to 10, preferably 0.05 to 6.0% by weight the weight of the non-aqueous dispersion before the addition of the filler.

Although it is preferred to make the density of the liquid phase and that of the dispersed phase equal, i.e. diiq / dSf = 1.0, in order to achieve the highest degree of stability, small differences in densities, for example dnq / dSf = 0.90 to 1.10, especially 0.95 to 1.05 (where dsf is the final density of the dispersed phase after addition of the filler) still give stabilities which are acceptable in most cases, which is generally shown by the lack of phase separation, for example by the fact that no clear liquid phase appears for at least 3 to 6 months or more.

As just described, according to the invention it is necessary to add a sufficient amount of low density filler to the non-aqueous liquid suspension of finely divided textile treatment solids in order to ensure an average statistical density of the solid particles and filler particles which is equal to the density of the continuous liquid phase is. However, the fact in what

Mms

■ rrp— represents the mass fraction of the low density filler (e.g. microspheres) which

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however, the fact that there is a statistically weighted average density of the dispersed phase, which is the same as the density of the liquid phase, does not in itself explain how or why the low-density filler exerts its stabilizing influence, since the finished composition nevertheless has the relatively dense dispersed solid particles for textile treatment (eg phosphates), which should normally settle, and the fillers of low density, which should normally rise in the liquid phase.

Without wishing to be bound by any particular theory, it is believed (which seems to be confirmed by experimental data and microscopic observation) that the dispersed solid detergent additive particles such as builders, bleaches, etc. are actually attracted to and adhere to the low density filler particles to form a monolayer or poly layer of dispersed particles which surround the filler particles and form composite particles or composites which in fact act as unitary or single particles. These composite particles can be viewed as having a density that is close to a volume weighted average of the 15 densities of all the individual particles that make up the composite particles:

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^ cp =

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Vl vh where dcp = the density of the composite particle;

dH = the density of the dispersed phase (heavy particle);

di_ = the density of the filler (light particles);

30 Vh = total volume of the phase of the dispersed particles in the composite;

Vl = total volume of filler particles in the composite.

However, in order for the density of the composite particles to become equal to that of the liquid phase, it is necessary that a large number of the dispersed particles interact with each or each of the filler particles, for example, depending on the relative densities, 35 several Associate hundreds to several thousand dispersed (heavy) particles with or with each (each) filler particle of low density.

Accordingly, it is another preferred feature of the agent of the invention that the average particle size diameter of the low density filler is larger than the average particle size diameter of the dispersed phase particles such as detergent builder 40 etc. to accommodate the large number of dispersed particles on the surface of the filler particle. Regarding this, it has been found that the ratio of the average particle size diameter of the low density filler particle to the average particle size diameter of the dispersed particles is preferably at least 6: 1, for example 6: 1 to 30: 1, in particular 8: 1 to 20: 1 the best results are achieved at a ratio of 10: 1. With 45 diameter ratios smaller than 6: 1, generally unsatisfactory results are obtained, although some stabilization improvement can occur depending on the relative densities of the dispersed particles and filler particles and the density of the liquid phase.

Therefore, in the preferred range, the average particle size diameters of the low density filler particles should be 20 to 100 micrometers, in particular 30 to 80 micrometers, the 50 dispersed phase particles should have average particle size diameters of 1 to 18 micrometers, in particular 2 to 10 micrometers. These particle sizes can be prepared by suitable grinding as described below.

Since the compositions of the invention are generally highly concentrated and can therefore be used in relatively low doses, it is often desirable to supplement phosphate builders (such as sodium tripoly-55 phosphate) with an auxiliary builder, for example a polymeric carboxylic acid with a high calcium binding capacity, in order to incrustate to prevent, which can otherwise be caused by the formation of insoluble calcium phosphate. Such auxiliary builders are known. Mention should be made, for example, of “Sokolan GP5”, a copolymer of approximately the same number of moles of methacrylic acid and maleic anhydride, which is completely neutralized to form its sodium salt. The amount 60 of auxiliary agent is generally up to 6% by weight, preferably 1/4 to 4, e.g. 1, 2 or 3% based on the total weight of the composition. Of course, if required by environmental laws, the compositions of the invention can be made without any phosphate builder.

In addition to the builders, various other detergent additives or auxiliaries may be present in the detergent to give it additional desired functional or aesthetic properties

CH 678 629 A5

to give nature. For example, small amounts of dirt-bearing or re-precipitation substances, e.g. Incorporate polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydfoxypropyl methyl cellulose, usually in amounts up to about 10% by weight, for example 0.1 to 10, preferably 1 to 5%; optical brighteners, e.g. Cotton, polyamide and Po-5 polyester brighteners, e.g. Stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidine sulfone, etc., with stilbene and triazole combinations being most preferred. The amount of the optical brightener usually makes up up to about 2% by weight, preferably up to 1% by weight, for example 0.1 to 0.8% by weight can be used.

10 Bluing agents such as ultramarine blue can also be used; Enzymes, preferably proteolytic enzymes such as subtilisin, bromelin, papain, trypsin and pepsin, as well as enzymes of the amylase type and of the lipase type and mixtures thereof; Bactericides such as tetrachlorosalicylanilide, hexa-chlorophene; Fungicides; Dyes; Pigments (water dispersible); Protective substances; Ultraviolet absorber; anti-yellowing substances such as sodium carboxymethyl cellulose, a complex of C12 to 15 C22 alkyl alcohol with C12 to cis alkyl sulfate; pH modifiers and pH buffers; color-preserving bleaching agents; Fragrances and foam-preventing or foam-suppressing substances such as Silicon compounds.

The bleaches are roughly divided into chlorine bleach and oxygen bleach for convenience. Typical chlorine bleaches are sodium hypochlorite (NaOCl), potassium dichioroisocyanurate (59% 20 available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by per-compounds that release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates and per-phosphates and potassium monopersulfate. The perborates, especially sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in a mixture with an activator for the same. Suitable activators which can lower the actual temperature of action of the peroxide bleaching agent are described, for example, in US Pat. No. 4,264,466 or in column 1 of US Pat. No. 4,430,244. Polyacylated compounds are preferred activators. Of these, compounds such as tetraacetylethyl diamine (TEAD) and pentaacetyl glucose are particularly preferred.

30 Other useful activators are, for example, acetylsaiicylic acid derivatives, ethylidene benzoate acetate and the salts thereof, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU) and the derivatives thereof. Other useful classes of activators are disclosed, for example, in U.S. Patents 4,111,826, 4,422,950 and 3,661,789.

35 The bleach activator generally reacts with the peroxygen compound to form a peroxyacid bleach in the wash water. It is preferred to incorporate a high complexing sequestrant to inhibit any undesirable reaction between this peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred sequestering agents are able to form a complex with Cu2 + ions in such a way that the stability constant (40 pK) of the complex formation is equal to or greater than 6 at 25 ° C. in water with an ionic strength of 0.1 mol / l , where the pK is usually defined by the formula: pK = -log K, where K is the equilibrium constant. For example, the pK values for the complexation of copper ion with NTA or EDTA under the specified conditions are 12.7 and 18.8, respectively. Suitable sequestering agents in addition to those mentioned above are, for example, the compounds sold under the trade name "Dequest" 45, such as, for example, diethylenetriaminepentaacetic acid (DETPA); Diethylenetriaminepenta-methylenephosphoric acid (DTPMP); and ethylenediaminetetramethylene phosphoric acid (EDITEMPA).

To prevent loss of peroxide bending agent, e.g. To avoid sodium perborate, by enzyme induced (e.g. catalase) decomposition, the compositions may additionally contain an enzyme inhibiting compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of 50 peroxide bleaches. Suitable inhibitor compounds are described in U.S. Patent 3,606,990.

Hydroxylamine sulfate or other water-soluble hydroxylamine salts may be mentioned as a particularly interesting inhibitor compound. In the preferred non-aqueous compositions of the invention, suitable amounts of hydroxylamine salt inhibitors are as small as about 0.01 to 0.4%. In general, however, suitable amounts of enzyme inhibitors are up to about 15%, for example 0.1 to 10 55% by weight of the composition.

Although it is not necessary to achieve acceptable product stability, it is also within the scope of the invention to use other suspension stabilizers, theological additives and anti-gel agents. For example, the aluminum salts of higher fatty acids, especially aluminum stearate, as described in U.S. Patent 4,661,280, can be added to the composition in amounts of e.g. 60 0 to 3, preferably 0 to 1 wt .-%.

Another stabilizer potentially suitable for use in conjunction with the low density filler is an acidic organic phosphorus compound with an acidic POH group as described in US-SN 781 189. The acidic organic phosphorus compound may, for example, be a partial ester of phosphoric acid and an alcohol, e.g. an alkanol with an iipophilic character, for example more than 5 carbons, e.g. Has 8 to 20 carbon atoms. A specific example is

10th

CH 678 629 A5

a partial ester of phosphoric acid and a Ci6 to Cis alkanol. Marchon's "Empiphos 5632" is prepared from around 35% monoesters and 65% diesters. Amounts of phosphoric acid compound (if used) up to about 3%, preferably up to 1%, are sufficient.

As disclosed in U.S. Pat. No. 926,851 (1986), a nonionic surfactant which is partially converted with a free carboxy group, such as e.g. a partial ester of a nonionic surfactant and a polycarboxylic acid, are incorporated into the composition to further improve the rheological properties. For example, amounts of the acid-terminated nonionic surfactant of up to 1 part per part of the nonionic surfactant are sufficient.

Suitable ranges for these optional detergent additives are: 0 to 2, especially 0.1 to 1.3% En-10 enzymes; about 0 to 40%, preferably 5 to 30% corrosion inhibitors; 0 to 15, preferably 0 to 5, e.g. 0.1 to 3% anti-foam and anti-foam substances; 0 to 15, for example 0.1 to 10, preferably 1 to 5% thickening and dispersing agent; 0 to 10, preferably 0.5 to 5, dirt-bearing or re-precipitation-preventing and yellowing-preventing substances; a total of 0 to about 2 and preferably 0 to about 1% of dyes, perfumes, brighteners and bluing agents; 0 15 to 5, preferably 0 to 2% pH modifier and pH buffer; 0 to about 40 and preferably 0 to about 25, e.g. 2 to 20% bleach; 0 to about 15, preferably 0 to 10, e.g. 0.1 to 8% bleach stabilizers and bleach activators; 0 to 15, e.g. 0.01 to 15, preferably 0.1 to 10% enzyme inhibitors; up to about 5, preferably 1/4 to 3, for example about 1/2 to 2% sequestering agent with high complexing capacity. These auxiliaries are selected so that they are compatible with the main components of the detergent composition.

According to a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid components (in the other than the filler of low density) is subjected to grinding, for example with a sand or ball mill. Particularly useful are grater-type mills as sold by Wiener, Amsterdam or Netzsch, Germany, in which the particle size of the solid components is less than about 18 microns, e.g. be reduced to an average particle size of 2 to 10 microns or even less (e.g. one micron). Preferably less than about 10, especially less than about 5% of all suspended particles have larger particle sizes than 15 microns, preferably 10 microns. Because of the increasing costs due to energy consumption with decreasing particle size, it is often preferred that the average particle size is at least 3 micrometers, particularly approximately 4 micrometers. Compositions whose dispersed particles are of such small sizes have improved stability against separation or settling on storage. Other types of grinders such as a tooth mill, pin mill and the like can also be used.

When grinding, it is preferred that the proportion of solid components is sufficiently large, e.g. 35 at least about 40, e.g. about 50% that the solid particles are in contact with one another and not substantially shielded from one another by the liquid nonionic surfactant. Mills that use grinding balls (ball mills) or similar mobile grinding elements have achieved very good results. So you can use a discontinuously operating laboratory grinder with steatite grinding balls with a diameter of 8 mm.

40 For work on a larger scale, a continuously working mill can be used, in which grinding balls with a diameter of 1 or 1.5 mm work at a relatively high speed in a very narrow gap between a stator and a rotor (e.g. a CoBall mill); when using such a mill, it is desirable to first pass the mixture of nonionic surfactant and solids through a mill that does not grind as fine, e.g. a colloid mill to reduce the particle size to 45 less than 100 microns (e.g., about 40 microns) before grinding to an average particle diameter below about 18 or 15 microns of the continuous ball mill in the milling step.

Alternatively, the powdery solid particles can be finely ground, for example in a jet mill, to the desired particle size before they are mixed with the liquid matrix. The finished compositions of the invention are non-aqueous liquid suspensions which generally exhibit non-Newtonian flow properties. After the addition of the low density filler, the compositions are slightly thixotropic, namely they show reduced viscosity when pressure or shear is applied, and they behave rheologically essentially in accordance with the Cas-son equation. The finished compositions are characterized by a yield point between about 55 2.5 and 45 Pa, more often between 10 and 35 Pa, for example of 15, 20 or 25 Pa. Furthermore, the compositions have viscosities at room temperature in the range of 500 to 5000, usually about 800 to 3000 mPa.s, which was measured using an LVT-D viscometer with a number 4 spindle at 50 rpm. When shaking or applying pressure, for example by pushing it through a narrow opening in a squeeze tube, the product is easily flowable. Thus, the compositions of the invention can be conveniently packaged in conventional containers, for example in glass or plastic, rigid or flexible bottles, jugs or other containers, and from these directly into the aqueous washing bath, for example in an automatic washing machine, in conventional quantities, for example in quantities of 1/4 to 1 1/2 measuring cups, e.g. 1/2 measuring cup per wash load (from about 3 to 15 pounds e.g.) for each wash load, generally in 65 approx. 30.3 to 68.1 liters of water. The preferred compositions remain stable (no more than 1

11

CH 678 629 A5

or 2 mm separation of liquid phase) if left to stand for periods of 3 to 6 months or longer.

In the description, as in the appended claims, the term "non-aqueous" means the absence of water, however, small amounts of water, for example up to about 5%, preferably up to about 2%, in the compositions, particularly in the Use of water-insoluble filler of low density are tolerable; "Non-aqueous" compositions can therefore contain such small amounts of water, whether it is added directly or as a carrier or as a solvent for one of the other components of the composition.

The liquid textile treatment agents of the invention can be packed in conventional glass or plastic containers 10 and also in individual packs such as e.g. Dispensers and dispensing bags can be used.

The following example is intended to illustrate the invention, all quantities and percentages being based on weight, unless stated otherwise. Unless otherwise stated, the pressure is atmospheric pressure.

15 Example 1

A non-aqueous, liquid, builder-containing detergent composition of the invention was prepared by mixing the following ingredients, except for the Q-Cell filler, in about the following amounts, finely ground to about 4 microns, and then obtaining them Dispersion gave the Q-Ceii filler with stirring. To add the light filler, the milled dispersion was mixed with moderate shear with a blender using a paddle stirrer, at about 2000 to 5000 rpm, to create a “depression” or “cavity” (vortex) in the middle of the mixing vessel. The Q-Cell filler particles were added near the top of the vortex to evenly distribute them throughout the composition while minimizing the shear forces 25 that could cause the hollow microballoons to break.

30th

35

40

45

50

55

60

65

$

12

CH 678 629 A5

Quantity, weight%

45

50

55

60

65

5

I.

II (comparison)

Nonionic surfactant 1 /

34.6

36.6

10th

Diethylene glycol monobutyl ether

10.5

10.5

Sodium tripolyphosphate (hydrated)

27.5

29.5

Sokolan HC 9786 2 /

4.0

4.0

15

HGE 2817 4 /

2.0

2.0

Sodium perborate monchydrate

9.0

9.0

Tetraacetylethylenediamine

4.5

4.5

20th

DEQUEST 2066 3 /

1.0

1.0

Esperase 8 SL (enzyme)

1.0

1.0

Q-Cell 400 5 /

4.0

25th

Perfume, fragrance

0.5

0.5

Dye, the like

Remainder 100.0

Remainder 100.0

30th

Viscosity (mPa.s) 2000 900

1 / Mixed propylene oxide (4 moles) / ethylene oxide (7 moles) 35 condensation product of a fatty alcohol with 13 to 15

Carbon atoms (from BASF).

40 2 / copolymer of methacrylic acid and maleic anhydride

3 / diethylenetriaminepentamethylenephosphonic acid

4 / Cg derivative of maleic acid:

Co — C — COOII,

I.

C-COOH from American Hoechst.

5 / Sodium borosilicate hollow glass microspheres with a particle size in the range of 10 to 200 micrometers, average particle size of 75 micrometers and an effective density of 0.16 to 0.18 g / cm3.

13

CH 678 629 A5

The above composition I and a comparative composition II without the Q-cell filler were each filled in glass containers and left at room temperature (about 22 ° C). After 6 weeks, the amount of free liquid was measured on the upper part of each sample. The results are shown in the following table.

5

Physical stability after 6 weeks

Separated liquid (%)

Example! (with Q-Cell)

0

Comparative Example II (without Q-Cell)

9.5

15 This shows that the addition of small amounts of low density filler significantly improves the physical stability of the non-aqueous suspensions.

The above example was repeated with the exception that instead of the 4% Q-Cell 400 1% Ex-pancel (polyvinylidene chloride microspheres, particle size range 10 to 100 micrometers, average particle size 40 micrometers; density 0.03 g / cm3) was used, with similar results of 20 seconds. If you take the non-ionic surfactant through «Plurafac RA20», «Plurafac D25», «Plurafac RA50»,

"Dobanol 25-7" or "Neodoi 23-6.5" replaced, similar results were also obtained.

Claims (19)

Claims 25 1. Non-aqueous, liquid textile treatment agent based on a non-aqueous liquid, characterized by a content of liquid nonionic surfactant, solid particles suspended in the non-aqueous liquid for textile treatment, and Low density filler in an amount sufficient to substantially equalize the density of the continuous liquid phase and the phase density of the suspended particles comprising the low density filler and the solid particles for textile treatment, thereby separating or settling the suspended particles is inhibited. 2. Textile treatment agent according to claim 1, characterized in that the suspended particles for textile treatment have an average particle size of 15 micrometers or less. 35%, no more than 10% by weight of these particles have a particle size above 15 micrometers and that the low density filler has an average particle size in the range of 20 to 100 micrometers. 3. Textile treatment agent according to claim 1, characterized in that the suspended particles have an average particle size of 1 to 10 microns, not more than 10 wt .-% 40 of these particles have a particle size greater than 10 microns and the low density filler has an average particle size in the range of 20 to 80 microns. 4. Textile treatment agent according to claim 1, characterized in that the ratio of the average particle size diameter of the low density filler to the average particle size diameter of the suspended particles is at least 6: 1. 45 5. Textile treatment agent according to claim 1, characterized in that the low-density filler contains hollow spheres made of plastic with a density in the range from 0.01 to 0.5 g / cm 3. 6. Textile treatment agent according to claim 1, characterized in that the low-density filler contains hollow glass microspheres with a density in the range from 0.01 to 0.5 g / cm 3. 7. Textile treatment agent according to claim 6, characterized in that the filler contains lower 50 density water-soluble microspheres made of borosilicate glass. 8. Textile treatment agent according to claim 1, characterized in that the nonionic surfactant is an alkoxylated fatty alcohol of 10 to 22 carbon atoms. 9. Textile treatment agent according to claim 8, characterized in that the fatty alcohol is a C12 to Ci8 alcohol which is alkoxylated with up to 12 moles of ethylene oxide and up to 8 moles of propylene oxide. 55 10. Textile treatment agent according to claim 9, characterized in that the non-aqueous liquid also contains a diluent or organic solvent from the group consisting of lower alcohols having 1 to 6 carbon atoms and alkylene glycols having 2 to 6 carbon atoms. 11. Textile treatment agent according to claim 9, characterized in that the non-aqueous liquid also contains a viscosity-controlling and gel formation-preventing amount of an alkylene glycol 60 ether of the formula ^ R0 (CH2CH20) nH, wherein R is a C2 to Ca alkyl group and n is a number with an average value from 1 to 6, 65 contains. 14 CH 678 629 A5 12. Textile treatment agent according to claim 11, characterized in that the alkylene glycol ether is diethylene glycol monobutyl ether. 13. Textile treatment agent according to claim 1, characterized in that the non-aqueous liquid 30 to 70 wt .-% of the composition, and the suspended solid particles 70 to 30 Make up 5% by weight of the composition. 14. Textile treatment agent according to claim 13, characterized in that the non-aqueous liquid 40 to 65 wt .-%, and the suspended solid particles make up 60 to 35 wt .-% of the composition. 15. Textile treatment agent according to claim 1, characterized by a content, based on the 1 o weight of the agent - 30 to 50% alkoxylated fatty alcohol as nonionic surfactant; - 0 to 20% alkylene glycol ether as a viscosity-controlling and gel-preventing agent; -15 to 50% iron particles; - 0 to 50% in total of one or more of the following optional additives: enzymes, enzyme inhibitors, corrosion inhibitors, foam-preventing substances, foam dampers, dirt-carrying substances, yellowing-preventing substances, coloring substances, fragrances, optical brighteners, bluing agents, pH modifiers, pH Buffers, bleaches, bleach stabilizers and sequestering agents; and - 0.01 to 10% hollow microspheres as a low density filler. 20th 16. Builder-containing liquid, thickened, non-aqueous textile treatment agent according to claim 1, characterized by a content, based on the weight of the agent 30 to 40% of a mixed ethylene oxide / propylene oxide condensation product of a fatty alcohol with 12 to 18 carbon atoms as liquid nonionic surfactant; - 25 to 40% alkali phosphate as builder salt; 25 - 5 to 12% of an alkylene glycol ether solvent as a viscosity-controlling and gel-preventing agent; - 2 to 20% of a peroxide bleaching agent; - 0.1 to 8% of a bleach activator; - up to 2% enzymes; 30 - up to 10% dirt-suspending substances that prevent reprecipitation and yellowing; - up to 5% sequestering agent with high complexation capacity; and - about 2% of one or more dyes, perfumes and optical brighteners each; in which - The solid components of this composition 35 have average particle size in the range of 2 to 10 microns and no more than 10% of the particles have a particle size above 10 microns; and - 0.05 to 6% inorganic or organic filler particles with a density of 0.01 to 0.50 g / cm3 and an average particle size diameter of 20 to 80 micrometers are stably suspended in the liquid constituents of the composition; and the composition a viscous 40 did in the range of 500 to 5000 mPa.s. 17. Textile treatment agent according to claim 16, characterized in that the filler particles contain hollow microspheres made of sodium borosilicate glass. 18. Commercial process outside the textile industry for cleaning soiled textiles, characterized in that the soiled textiles are treated with the textile treatment agent after 45 contact 1 in an aqueous wash bath. 19. The method according to claim 18, characterized in that the contact takes place in an automatic washing machine. 50 55 v r ~ 60 65 15