CH678630A5 - - Google Patents

Description

CH 678 630 A5

description

The invention relates to a non-aqueous, liquid composition suitable for textile treatment. In particular, the invention relates to non-aqueous liquid laundry detergent compositions which are resistant to phase separation even at relatively low viscosities and which, above all, remain stable under both static and dynamic conditions and are easy to pour

are.

In addition, the invention relates to a commercial process for cleaning soiled textiles using the composition according to the invention. The procedure is preferred b

10 wise carried out in washing machines.

Liquid, non-aqueous heavy-duty detergents are well known. Compositions of this type 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 powder-15 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, substances can be incorporated into the liquid detergents that would not survive drying measures without decomposition, but which are often desirable for 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, 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 theological behavior of liquid nonionic surfactant systems with particulate matter suspended therein. She was particularly interested in non-aqueous buil-containing liquid textile 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.

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 under Stoke's 35 law. The non-aqueous liquid suspensions of the builder particles behave like e.g. the rheological polyphosphate builder, especially sodium tripolyphosphate (TPP), in non-ionic surfactant essentially according to the Casson equation:

a1 / 2 = ct01 / 2 + TI ° = 1/2 y1 / 2

40

where y = the shear rate;

c = the shear stress;

(To = the yield stress (or yield point); and ti ° o = is the "plastic viscosity" (apparent viscosity at an infinite shear rate). The yield stress is the minimum stress required to achieve plastic deformation (flow) Once the yield stress or yield point has been overcome, the network of suspended particles breaks at some points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much greater than the yield stress or yield point, the Partially shear-deflocculates and the apparent viscosity drops.

50 Finally, when the shear stress is much higher than the yield point, the particles are completely deflocculated and the apparent viscosity is very low, as if there were no particle interaction.

Therefore: the higher the yield stress or yield point of the suspension, the greater the apparent viscosity at low shear rate and the better the physical stability of the product.

There are basically two ways of solving the sedimentation problem: increasing the Vis- ^

viscosity of the liquid matrix and the reduction in the particle size of the solid particles.

Milling to reduce particle sizes as a measure to increase product stability provides the following advantages. 60 ^

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

2. The average distance between the particles is reduced, which is accompanied by a corresponding increase in the particle-particle interaction. Each of these effects contributes to that

65

2nd

CH 678 630 A5

To increase the resting gel strength and the yield point of the suspension, while at the same time significantly reducing the plastic viscosity.

U.S. Patent 4,316,812, mentioned above, mentions the advantages of solid particle milling, e.g. of 5 builders and bleaches, to an average particle diameter below 10 microns. However, it has been found that mere grinding to such small particle sizes does not in itself enable sufficiently long-lasting stability against phase separation.

You have e.g. found that such suspensions can be stabilized against settling by adding inorganic or organic thickeners or dispersants, such as inorganic materials with a very large surface area, e.g. finely divided silica, clays, etc., organic thickeners such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes etc. However, these increases in suspension viscosity are subject to natural limits due to the need for the liquid suspension to be easily pourable and flowable even at low temperatures got to. In addition, these additives do not contribute to the cleaning effect 15 of the composition. US Pat. No. 4,661,280 describes the use of aluminum stearate to increase the stability of suspensions of builder salts in liquid nonionic surfactant. The addition of small amounts of aluminum stearate increases the yield point without increasing the plastic viscosity.

According to US Pat. No. 3,985,668, an aqueous, body-simulating liquid abrasive composition is produced from an aqueous liquid and a suitable colloid former, such as clay or other inorganic or organic thickening or suspending substances, especially smectite clays, and a relatively light, water-insoluble particulate Filler material which, like the abrasive substance, is suspended in the body-simulating fluid phase. The light filler has particle size diameters from 1 to 250 micrometers and a specific weight that is smaller than that of the body-simulating liquid phase. The patent holders assume that the incorporation of the relatively light, insoluble filler into the body-pretending liquid phase (false body fluid phase) helps to minimize phase separation, i.e. minimize the formation of a clear layer of liquid over the body-pretending abrasive composition, firstly thanks to its buoyancy which exerts an upward force on the structure of the colloid-forming agent in the body-pretending phase which counteracts the tendency of the heavy abrasive 30 to compress and pretend the body-pretending structure Squeeze out liquid. Second, the filler material replaces a portion of the water that would normally be present in the absence of the filler material, resulting in less aqueous liquid being available that can form and separate a clear layer.

GB 2 168 377A discloses aqueous, liquid dishwashing detergent containing abrasive, col-35 loidal clay thickener and low density particulate filler having particle sizes from about 1 to 250 microns and densities from about 0.01 to about 0.5 g / cm3 at a concentration of about 0.07 to about 1% by weight of the composition. The filler is believed to improve stability by reducing the specific gravity of the clay mass so that it floats 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 (i.e. composition without clay or abrasive materials). The low density particulate fillers disclosed on page 4, lines 33-35 of the UK patent application can also be used as low density fillers in the compositions of the invention. According to this disclosure, the filler improves stability by reducing the specific weight of the clay-45 mass so that it floats in the aqueous liquid phase. The type and amount of filler are chosen so that the specific weight of the finished composition matches that of the clear liquid (without clay and polishing agent).

It is also known to incorporate an inorganic insoluble thickener or dispersant with a very large surface area, e.g. finely divided silica of extremely fine particles - 50 sizes (e.g. 5 to 100 millimicrometers in diameter, e.g. sold under the name Aerosil®) or the other high-volume inorganic carrier materials as disclosed in US Pat. No. 3,630,929.

It has also been known for a long time that aqueous, swelling colloidal clays such as bentonite and montmorillonite clays can be modified by replacing the metallic cation groups with organic groups, whereby the hydro-55-phile clays become organophilic clays. The use of such organophilic clays as gel-forming clays has been described in U.S. Patent 2,531,427. The improvements and modifications to the organophilic gel-forming clays are described, for example, in the following US Patents: 2,966,506; 4,105,578; 4,208,218; 4,287,086; 4,434,075; 4,343,076 (all patents from NL Industries, Inc., formerly National Lead Company). According to these NL patents, these organophilic clay gelling agents are useful for greases, oil-based slurries, oil-based sealing fluids (packer fluids), paints, paint strippers, varnishes and varnishes, adhesives, sealants, inks, polyester gel layers and the like. Use as a stabilizer in a non-aqueous liquid detergent composition for washing textiles has not yet been proposed.

65

3rd

CH 678 630 A5

The use of clays in combination with quaternary ammonium compounds (often referred to as “QA”) to achieve textile softening effects in detergents has also been described. See, for example, GB 2 141 152A and the many patents cited therein relating to fabric softening agents based on organophilic QA clays.

5 According to US Pat. No. 4,264,466 (mentioned above), the physical stability of a dispersion of particulate material, such as builders, in a non-aqueous liquid phase is improved by using, as the primary suspending agent, an imperceptible clay of the "chain structure type" such as sepiolite, Atta pulgite and polygorskite clays. The patent owners of the above U.S. patent state and the comparative examples in this patent show that other types of clay such as montmorillonite clay, e.g. Bentonite L, hectorite-10 ton (e.g. Veegum T) and kaolinite clay (e.g. Hydrite PX), even if they are used in conjunction with a suspension aid, including cationic surfactants, including QA compounds, are only bulky suspending agents. The patent holders also mention the use of other clays as suspension aids and refer, for example, to US Pat. Nos. 4,049,034, 4,005,027 (both aqueous systems); 4166,039,3259,574; 3,557,037; 3 549 542 and UK patent application 2 017 072. 15 Also proposed according to German patent application P 2 820 631 was the incorporation of up to about 1% by weight of an organophilic smectite clay which is quelible in water and modified with a cationic nitrogen-containing compound, which has at least one long-chain hydrocarbon group with 8 to 22 carbon atoms, in non-aqueous liquid textile treatment agents to form an elastic network or structure within the suspension and thereby increase the yield point 20 and the stability of the suspension.

Although the addition of organophilic clay improves the stability of the suspension, further improvements have been desired, particularly in the case of particulate suspensions with relatively low flow limits, in order to improve the spreadability and dispersibility in use.

German patent application P 3 824 252 describes the use of a filler of low density 25 for stabilizing liquid suspensions of finely divided solid substance in a liquid phase against phase separation by making the densities of the dispersed particle phase and the liquid phase equal. These modified liquid suspensions show excellent phase stabilization when left to stand for extended periods of time up to 6 months or longer or even when thrown down with moderate shaking. However, it has recently been observed that when the suspensions modified with low density filler 30 are subjected to strong vibrations as encountered during transportation by train, truck, etc., the homogeneity of the dispersion deteriorates when some of the low density filler is on the upper surface of the liquid suspension migrates.

Further improvements in the stability of non-aqueous liquid textile treatment compositions have therefore been desired. This was based on the inventors' finding that 35 by adding a small amount of up to 1% by weight of an organophilic clay to a liquid suspension of fine, functionally active suspended particles containing a small amount of low density filler the filler and the other functional suspended particles interact in such a way that essentially a suspension of composite particles was formed with a density which was substantially equal to the density of the continuous liquid phase, a stronger network structure was ensured which the The tendency of the suspended functional particles (e.g., builders, bleaches, antistatic agents, etc.) to counteract effectively, to settle and, conversely, to effectively inhibit the rise of the low density filler or the formation of a clear liquid phase when the composition was subjected to strong vibratory forces. German patent application P 3 824 252 therefore proposed a liquid textile treatment agent 45 which consisted of a suspension of functionally active particles in a liquid nonionic surfactant, the composition containing a suitable amount of low-density filler in order to increase the stability of the suspension , while at rest and when shaken, and an appropriate amount of an organophilic clay to improve the stability of the composition when subjected to strong vibratory forces.

50 However, although the stability of the non-aqueous suspension is significantly improved by the low density / organophilic clay filler system, certain disadvantages have been shown. First, it has been observed that the viscoelastic structure mediated by the organophilic clay loosens or weakens over time, this sagging being shown by a constant decrease in the yield point. As a result, there may be a point in time within the predetermined life of the product at which the yield point falls below a level required to maintain the stability of the low density filler, especially under strong vibration forces.

A second disadvantageous consequence of the older stabilization system is that the incorporation of the low density filler, e.g. of microspheres, increases the plastic viscosity of the product and consequently reduces its fluidity.

60 According to the invention, it has now been found that the problem of the increased viscosity of non-aqueous suspensions stabilized with low-density filler and the problem of changing the flow limit over time in the case of non-aqueous suspensions stabilized with organophilic clay can essentially be overcome in each case by that a small but effective amount of certain 65 phosphate esters is incorporated into the liquid composition stabilized with organophilic clay and / or low density filler. The addition of the phosphate ester compounds reduces the plastic Vis4

CH 678 630 A5

viscosity of the low density filler containing compositions and stabilizes the yield point during aging of compositions containing organophilic clay.

It is therefore an object of the invention to propose liquid textile treatment compositions which are suspensions of insoluble textile treatment parts in a non-aqueous liquid and which are persistently stable in storage, easy to pour and dispersible in cold, warm or hot water.

It is also an object of the invention to provide viscoelastic, non-aqueous suspensions of insoluble textile treatment parts which can maintain their theological properties even when subjected to strong vibratory forces.

A further object of the invention is to formulate heavy-duty, non-aqueous liquid nonionic surfactant textile detergents which are resistant to settling of the suspended solid particles or separation of the liquid phase and are easily flowable.

An object of the invention is to provide a stable, non-aqueous composition for textile treatment with liquid nonionic surfactant, which has a content of

15

a) a non-aqueous liquid which comprises nonionic surfactant,

b) functionally active solid textile detergent additive particles which are suspended in the non-aqueous liquid, at least one of components c) and d), namely c) low-density filler in a sufficient amount, preferably up to 10% by weight, around the 20th Density of the continuous liquid phase of the density of the «suspended particle phase», that is the

Equalize the phase comprising the low density filler and the suspended functionally active solid particles, thereby inhibiting settling of the suspended particles when the composition is at rest and / or d) an appropriate amount of organophilic clay to inhibit phase separation, preferably 25 to 1% by weight when the composition is subjected to strong vibratory forces, and e) a phosphate ester compound of the formula I or II

30th

35 \ H2 C-y O P — O — R (I)

to o

40

Red t

45 O "R3

HC O R2 O (II)

1 *

50 H2c O-p-o-R

55 in which

R represents a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, which is substituted by an amino group of the formula -NR4R5, where R4 and R5 are independently hydrogen or alkyl having 1 to 4 carbon atoms, or by a quaternized nitrogen of the formula -NR4R5R6 where R4 and R5 are as defined above and R6 is hydrogen or alkyl of 1 to 4 carbon atoms;

Ro is hydrogen or lower alkyl or lower alkenyl,

Ri is an acyl residue of a long chain fatty acid;

R2 is hydrogen or an acyl residue of a long chain fatty acid;

R3 is hydrogen or an acyl residue of a long chain fatty acid;

65 provided that R2 and R3 are not both hydrogen at the same time; and

5

CH 678 630 A5

where n is a number from 1 to 10 to reduce the viscosity and further stabilize the theological properties of the composition.

Component e) is preferably lecithin.

According to a further aspect, the invention provides a commercial method for cleaning soiled textiles by contacting the soiled textiles with the non-ionic textile detergent composition described above.

The viscosity-reducing and the yield point stabilizing phosphate ester compound, which is preferably used in the composition according to the invention, is lecithin. Pure lecithin is a fatty acid-substituted phosphatidylcholine of the general formula

10th

CH2OR

r ^ o-c-h o

15 T «©

ch2opoch2ch2n (ch3) 3

I.

O-

20th

In practice, however, lecithin is hardly available in pure form; Generally speaking, lecithin refers to a complex, namely a naturally occurring mixture of phosphatides, triglycerides, carbohydrates, sterols and other minor or minor components.

Lecithin is generally obtained from vegetable oil, with soybean oil as the main source. Other sources of lecithin include egg yolk, milk and animal brain matter. The phosphatides present in lecithin are the same or similar except that their proportions vary. In the same way, the other components of the lecithin present in smaller amounts vary depending on the specific occurrence.

Typical "fatty acid profiles" of commercially available lecithin are summarized in the following table;

Comparison of fatty acid profiles (% by weight)

Number of carbon atoms and double bonds

Soybean commercial lecithin

Oil-free commercial lecithin

Saturated

Ci6: o

9

15

19th

Eq 8: 8

5

5

5

total

14

20th

24th

Unsaturated

Ci8: 1

26

17th

10th

Ci8: 2

53

55

59

Ci8: 3

7

8th

7

total

86

80

76

50

A typical composition of soybean icithine, the most common commercially available product, is as follows.

Phosphatidylcholine (l)

20th

Phosphatidylethanolamine (II)

15

Phosphatidylinositide (III)

20th

Phosphate acids and other phosphatides

5

Hydrocarbons, sterols

5

Triglycerides

35

in which

65

6

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

ch 678 630 a5

O H2C-O-CO-RJ m 1

i »r2— co — ch o

»* (G h2c-o-p-o-ch2ch2n (ch3) 3

1

0-

o h 2c-o-co-rj

" 1

ii = r2— c— o — ch o

H2C-0-P-0-CH2CH2§H3

f

O-

0 h2c-o-co-r1 oh ho iii «r2-c-o-ch

• 'P

h2c-o-p o

«

o- oh oh where Ri, R2 = Ci6: 10, Ci8: 0. Ci8: 1, Ci8: 2, Ci8: 3-

Any of these naturally occurring forms of lecithin can be used in the composition according to the invention. Also, the lecithin need not be pure and any of the commercially available lecithin grades, which are generally mixtures of phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol (phosphatide) and triglycerides, regardless of their origin such as egg yolk, soybeans, etc. , can be used as a viscosity reducing stabilizer. In general, however, it is preferred to use a double bleached form of lecithin to minimize any base odors that may be present in the natural products.

Applicable phosphate ester compounds include phosphate esters of glycols, polyglycols and glycerols of the formulas I and II. Examples of glycols are ethylene glycol, propylene glycol, butylene glycol and glycol ethers, e.g. Called diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and the like. The polyglycols have 1 to 10 repeating oxyethylene or oxypropylene units. As glycerol compounds not only glycerol but also alkyl or alkenyl substituted glycerols may be mentioned, for example glycerols with up to about 20 carbon atoms, preferably up to about 10 carbon atoms, e.g. 1,2,3-butanetriol; 1,2,3-pentanetriol; 1,2,3-decanetriol; 1,2,3-hex-2-enetriol and the like. The non-phosphated hydroxyl group of the glycol compound and at least one of the non-phosphated hydroxyl groups of the glycerol compounds are esterified with a long-chain fatty acid.

The phosphate ester compounds including the preferred active phosphatidylcholine of lecithin are represented by the general formulas (I) and (II) above.

The term “lower alkyl” or “lower alkenyl” is intended to include alkyl or alkenyl having 1 to 5, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, propenyl and the like. The term “long-chain fatty acid” refers to saturated or unsaturated fatty carboxylic acids with 8 to 22, preferably 10 to 18, especially 12 to 18 carbon atoms,

including mixtures thereof. The acyl residue of the fatty acid has the formula -C-R.

II

O

The preferred phosphate ester compounds have structures similar to that of lecithin, especially phosphatidylcholine, namely the alkylamine, alkenylamine, alkylammonium or alkenylammonium phosphate ester of a glycol, polyglykois or glycerin with at least one long chain fatty acid ester group (ester group of a long chain fatty acid) in the molecule.

The viscosity reducing stabilizing additive is used in an appropriate amount which reduces the plastic viscosity of the composition to less than about 800 mPa.s, preferably less than about 600 mPa.s, for example to about 400 mPa.s. Generally amounts

7

CH 678 630 A5

from 0.1 to 3% by weight, based on the overall composition, viscosities within the desired range.

In the preferred embodiment, which is of particular interest here, the liquid phase of the composition of the invention consists predominantly or entirely of liquid synthetic organic surfactant. However, part of the liquid phase may consist of organic solvents which can enter the composition as a solvent carrier or media for one or more of the solid particulate components, such as in enzyme slurries, perfumes and the like. Also, as will be described in detail below, organic solvents such as alcohols and ethers can be added as viscosity-controlling and gel-preventing substances. 10 The nonionic synthetic organic surfactants contained in the composition according to the invention can be assigned to a large variety of such compounds which are sufficiently known and are described, for example, in detail in Surface Active Agents, Volume II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, and McCutcheon's Detergents and Emulsifiers, 1969 Annual. Usually the non-ionic surfactants are po-15 ly (lower) a! Koxylated lipophiles in which the desired hydrophilic-lipophilic balance is obtained by adding a hydrophilic poly (lower) -alkoxy group to a lipophilic part. A preferred class of nonionic surfactants used is that of the poly (lower) alkoxyated higher alkanols, the alkanol comprising 10 to 22 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) being 3 to 20. Of these materials, those in which the higher alkanol is a fatty alcohol having 10 to 11 or 12 to 15 carbon atoms and which have 5 to 18, preferably 6 to 14, lower alkoxy groups per mole are preferably used. The lower alkoxy is often only ethoxy, but may in some cases be desirably mixed with propoxy, the latter being often present in less amount (less than 50%) when present. Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms 25 and which have about 7 ethylene oxide groups per mole, e.g. Neodol 25-7 and Neodol 23-6.5, products manufactured by Shell Chemical Company Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 15 carbon atoms with about 7 moles of ethylene oxide, the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups is on average about 6.5 . The 30 higher alcohols are primary alkanols. Other examples of such surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both ethoxylates of Union Carbide Corp. linear secondary alcohols. The former is a mixed ethoxylation product of linear secondary alcohols with 11 to 15 carbon atoms with 7 moles of ethylene oxide, the latter is a similar product, but in which 9 moles of ethylene oxide are reacted.

35 Also suitable as nonionic surfactant component in the compositions according to the invention are nonionic surfactants with a higher molecular weight than Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is about 11. These products are also manufactured by Shell Chemical Company. Another preferred class of useful nonionic surfactants is represented by the commercially known class of nonionic surfactants which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides and which contain a mixed chain of ethylene oxide and propylene oxide terminated by a hydroxyl group becomes. Examples include the nonionic surfactants sold by BASF under the Plurafac® trade name, e.g. Plurafac RA30, Plurafac RA40 (a C13 to Ci5 fatty alcohol, condensed with 7 moles of propylene 45 and 4 moles of ethylene oxide), Plurafac D25 (a C13 to Cis 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

50

60

R0 (C3H60) p (C2H40) qH,

wherein R is a straight-chain or branched primary or secondary aliphatic hydrocarbon radical, preferably alkyl or alkenyl, particularly preferably alkyl having 6 to 20, preferably 55 from 10 to 18, particularly preferably 12 to 18 carbon atoms, p is a number from 2 to 8, preferably 3 to 6, and q is a number from 2 to 12, preferably 4 to 10, preferably used when the products are said to be low-foaming. 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 C9 to Cn fatty alcohol with an average of 5 moles of ethylene oxide; Dobanol 25-7 is an ethoxylated C12 to Ci5 fatty alcohol with an average of 7 moles of ethylene oxide; etc.

In the preferred poly (lower) alkoxylated higher alkanols, the number of lower Al-5 koxy groups makes for the best balance between the hydrophilic and lipophilic portions

8th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

CH 678 630 A5

usually from 40 to 100% of the number of carbon atoms in the higher alcohol, for example 40 to 60% of the same; the nonionic surfactant often contains at least 50% of such preferred poly (lower) alkoxylated higher alkanols.

Higher molecular weight alkanols as well as various other, normally solid, non-ionic surfactants and surface-active substances can contribute to the gel formation of the liquid detergent and are consequently preferably omitted or limited in their amount in the compositions according to the invention, although smaller amounts thereof due to their cleaning action, etc can be used. In 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 removes from, the straight chain terminal carbon atom of the alkoxy chain, provided that such branched alkyl is not more than 3 carbon atoms long. Typically, the proportion of carbon atoms in such a branched configuration will rarely exceed 20% of the total carbon atom content of the alkyl. Similarly, although linear alkyls that are terminally attached to the alkylene oxide chains are highly preferred and are believed to 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 are possible in the chain. These alkyls usually make up only a small proportion, generally less than 20%, which, however, as is the case with the tergitols mentioned, can be larger. Also, when present in the chain of lower alkylene oxides, propylene oxide usually makes up less than 20%, 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 nonionic surfactants mentioned here, the product obtained can be used have less good detergency, stability, viscosity and non-gelling properties than the preferred compositions, but the use of the viscosity and gel control compounds can also improve the properties of the detergents based on these nonionic surfactants. In some cases, such as when a higher molecular weight poly (lower) -aikoxylated higher alkanol is used (often because of its detergency), the amount thereof is adjusted or limited based on routine experimentation results to achieve the desired detergency and still not - Gelling product with the desired viscosity. It was also 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 to be achieved without gelling at low temperatures. Mixtures of 2 or more of these liquid nonionic surfactants can also be used, which may be advantageous in some cases.

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 7 to 9, in particular about 8 moles of ethylene oxide per molecule of the Cg to C11, especially Cio fatty alcohols, with about 6 moles 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 aliphatic (C1 to Cs) alcohols and glycols such as ethanol, isopropanol, ethylene glycol, hexylene glycol and the like have preferably been used for this purpose. Polyethylene glycols such as PEG 400 are also useful diluents. Alkylene glycol ethers such as the compounds which are sold under the trade names "Carbopol" ® and "Carbitol" ® and which have relatively short hydrocarbon chains (C2 to Cs) and a low content of ethylene oxide (about 2 to 6 EO units per molecule), are particularly valuable viscosity control and gel preventing solvents in the compositions of the invention. This application of the alkylene glycol ether is described in USSN 687 815 (1984). Suitable glycol ethers can be represented by the following general formula

R0 (CH2CH20) nH

in which R is a C2 to Cs, preferably G2 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 (C4Hg-0- (CH2CH20) 2H, tetraethylene glycol monooctyl ether CbHit-Ó- (CH2CH20) 4H), etc. Diethylene glycol monobutyl ether is particularly preferred.

Another gel-preventing substance that can be used, which can be contained in the liquid phase as a component in a small amount, is an aliphatic linear or aliphatic monocyclic dicarboxylic acid, such as the C6- to Gi2-alkyl and alkenyl derivatives of succinic acid and maleic acid and the corresponding ones Anhydrides or an aliphatic monocyclic dicarboxylic acid compound. The

9

CH 678 630 A5

Use of these compounds as gel-preventing agents in non-aqueous liquid builder-containing heavy duty textile detergents is described in US Pat. No. 4,744,916 dated May 17, 1988.

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 5 being between 8 and 13, especially 9 to 12, carbon atoms. One of the carboxylic acid groups (-COOH) is preferably attached to the terminal (alpha) carbon atom of the aliphatic chain, the other carboxyl group is preferably attached to the next adjacent (beta) carbon atom or can be 2 or 3 carbon atoms away from the alpha position, i.e. on the y- or a -carbon atoms, The preferred aliphatic dicarboxylic acids are the <x, β-dicarboxylic acids and corresponding anhydrides, particularly preferred are the derivatives of succinic acid or maleic acid which correspond to the general formula:

15

20th

^ 0,

Ri-C-C <^ RI-Ç-C ^

0h y \

i ^ -0 or |

c-c.

• oh wherein Rî 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 lengths may be present, depending on the starting materials used to make the dicarboxylic acid.

The aliphatic monocyclic dicarboxylic acid can contain either 5- or 6-membered carbon rings with one or two linear aliphatic groups attached to the carbon atoms. The linear aliphatic groups should contain at least 16, preferably at least 8, particularly preferably at least 10 carbon atoms in total and up to 22, preferably up to 18, particularly preferably up to 15 carbon atoms. When two aliphatic carbon atoms are attached to the aliphatic ring, they are preferably para to each other. For example, the preferred aliphatic cyclic dicarboxylic acid compounds can be represented by the following structure-35

40

are reproduced in which T stands for -CH2-, -CH =, -CH2-CH2- or -CH = CH-,

45 Rz is an alkyl or alkenyl group having 3 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 carbon atoms in R2 and R3 is about 6 to about 22.

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

50 R2 and R3 are each preferably alkyl groups of 3 to 10, 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 preferably straight-chain.

The amount of nonionic surfactant is generally in the range of 20 to about 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) is usually in the range of 100: 1 to 1: 1, preferably 50: 1 to 2: 1, e.g. at 10: 1, 8: 1, 6: 1.4: 1 or 3: 1. 60 The amount of dicarboxylic acid as a gel inhibiting compound (if used) will depend on factors such as the type of liquid nonionic surfactant, e.g. its gel temperature, the type of dicarboxylic acid, the other constituents in the composition that can influence 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 being used as a gel-preventing agent

10th

CH 678 630 A5

Agents usually range from 1 to 30, preferably 1.5 to 15% by weight based on the weight of the liquid nonionic surfactant, although in any case the optimal amount can be easily determined by routine experimentation.

The preferred cleaning agents of the invention can also contain, as an essential component, water-soluble and / or water-dispersible builder salts. Typical suitable builder salts are, for example, those described in the aforementioned U.S. Patents 4,316,812,4264,466, 3,630,929 and many others. Water-soluble inorganic alkaline builder salts which can be used alone with the surfactant or in a mixture with other builders are the alkali metal 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 arbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate and sodium monophosphate and sodium monophosphate and sodium monophosphate and sodium monophosphate and sodium monophosphate, Sodium tripolyphosphate (TPP) is particularly preferred, provided that phosphate-containing components are not prohibited for environmental reasons. The alkali silicates are valuable 15 builders, which also make the composition anticorrosive to parts of the washing machine. Sodium silicate with Na20 / SiO2 ratios of 1.6 / 1 to 1 / 3.2, especially 1/2 to 1 / 2.8, are preferred. Potassium silicates of the same proportions can also 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 No. 4,040,136 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.

The zeolites generally correspond to the formula

25th

(MêO) x. (Al203) y. (Si02) e.g. H20,

where 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 to 3 and w is 0 to 9, preferably 2.5 to 6 and M sodium is preferred. A typical zeolite 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 nitrilotriacetate (NTA) and triethanolammonium N- (2-hydroxy-ethyl) nitrilodiacetate. Mixed salts of these polycarboxylates are also suitable.

35 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 number 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, for example 20 to 50, e.g. 25 to 40% by weight of the composition.

In accordance with one embodiment of the invention, the physical stability of the suspension of 45 or the builders, as well as any other fine suspended solid additive particles such as bleach, pigment, etc., in the liquid carrier is dramatically improved by the presence of a low density filler in that the density of the continuous liquid Phase is approximately the same as 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 when the product is formulated, packaged, shipped and used.

Within the above general criteria, suitable particulate fillers have effective densities in the range of 0.01 to 0.50 g / cm3, preferably 0.02 to 0.50 g / cm3, especially up to 0.20 g / cm3 0.02 to 0.20 g / cm3, measured at room temperature, e.g. 23 ° C, and particle size diameters in the range of 1 to 300 microns, preferably 4 or 5 to 200 microns, 60 with the average particle size diameters in the range of 20 to 100 microns, preferably 30 to 80 microns.

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

65

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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, polyethylene, polypropylene, polyethylene terephthalate, polyurethanes, polycarbonates, polyamides and the like. In general, all of the low density particulate filler materials described in GB 2 168 377A above on page 4, lines 43 to 55 (including the patents cited therein) can be used in the non-aqueous compositions of the invention. In addition to the hollow microspheres, other low density inorganic filler materials can also be used, such as aluminosilicate zeolites, spray dried clays, and the like.

According to a particularly preferred embodiment of the invention, however, the lightweight filler is 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 15 water-insoluble filler particles can more easily adhere or adsorb to the fibers or the surface of the washed textiles.

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, under the trade name "Q-Cell" ®, especially 20 "Q-Cell 400", "Q-Cell 200", "Q-Cell 500" etc. are available. These materials have the additional advantage that they provide silications in the wash water that have an anti-corrosive effect.

Examples of water-soluble organic materials which are suitable for producing low-density hollow microparticles 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.

The amount of the low density filler added to the non-aqueous liquid suspension is such that the mean (average) statistically weighted densities of the suspended particles and the low density filler are the same or not significantly different from the liquid phase density (including nonionic surfactant) and other solvents, liquids and dissolved components). This practically means that the density of the entire composition after the 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 entire composition except for the low density filler. With all of the liquid dispersions used as feedstocks, the required amount of low density filler increases with the density of the filler, and conversely, a smaller amount of the low density filler is required to achieve a given decrease in the density of the finished composition when the density of the filler 40 decreases.

The amount of 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 an ideal mixture of low density and non-aqueous filler Dispersion is based on:

45

50

Mms = d d d,. ms. o- lxq

Mf d. d -d liq o ms where Mms represents the mass fraction of the low density filler (e.g. microspheres), wel-Mf

55 rather must be 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;

d0 = density of the starting composition (i.e. suspension before adding the filler); 60 Mf = mass of the finished composition (i.e. after adding the filler); and Mms = mass of the filler to be added.

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

12

CH 678 630 A5

Although it is preferred to make the density of the liquid phase and that of the dispersed phase equal, i.e. that diiq / dSf = 1.0 in order to achieve the highest degree of stability, small differences in densities, for example diiq / dSf = 0.90 to 1.10, especially 0.95 to 1.05 (where dSf is the final density the dispersed phase after addition of the filler) still give stabilities which are acceptable in the 5 most cases, which is generally shown by the absence 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, adding a sufficient amount of low density filler to the non-aqueous liquid suspension of fine, solid textile treatment particles to achieve an average statistically weighted density of the solid particles and filler particles equal to the density of the continuous phase effects the stabilization the suspension against phase separation. However, the mere fact that there is a statistically weighted average density of the dispersed phase which is equal to the density of the liquid phase would not in itself explain how or why the low density filler exerts its stabilizing influence since the finished composition composition still contains the relatively dense dispersed solid textile treatment parts (eg phosphates) which should normally settle, and the low-density filler which should normally rise in the liquid phase.

Without wishing to be bound by any particular theory, it is believed (experimental data and microscopic observations seem to confirm this) that the dispersed solid particulate detergent additives such as builders, bleaches, etc. are actually attracted to and adhere to the low density filler particles forming a monolayer or poly layer of dispersed particles which surround the low density filler particles and form composite particles or composites which in fact act as unitary or single particles. These composite particles can be considered to have a density that is closely approximated to a volume weighted average or volume weighted average of the densities of all of the individual particles that make up the composite particles:

30th

dcp

âh + vh dl

VL

35 1 + VH

where dCp = the density of the composite particle;

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

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

40 Vh = total volume of the phase of the dispersed particles in the assembled state; Vl = total volume of the filler particles in the composite particles.

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 of the filler particles, for example, depending on the relative densities, several hundreds should change to associate several thousand of the dispersed (heavy) particles with each low density filler particle.

Accordingly, in order to achieve the advantages of the invention, the average particle size diameter of the low density filler must be larger than the average particle size diameter of the dispersed phase particles such as detergent builders, etc., to accommodate the large number of 50 dispersed particles on the surface of the filler particle. As for 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 must be at least 6: 1, e.g. 6: 1 to 30: 1, especially 8: 1 to 20: 1, where the best results are achieved at a ratio of about 10: 1. With diameter ratios 55 less 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 60 dispersed phase particles should have average particle size diameters of approximately 1 to 18 micrometers, in particular 2 to 10 micrometers. These particle sizes can be prepared by suitable grinding as described below.

Although incorporation of the low density filler substantially reduces any tendency for the suspended or dispersed phase to settle or rise, or a clear liquid layer to form in the upper part of the composition, the filler causes lower

13

CH 678 630 A5

Density also an increase in the «plastic viscosity» (n ° ° C) of the suspension. Such an increase in viscosity is not necessarily disadvantageous; nonetheless, the ideas and wishes of consumers go so that the product is made easier to flow, i.e. that the plastic viscosity is reduced. However, the plastic viscosity should not be reduced at the expense of a reduction in the flow limit of the non-aqueous suspension, since this would otherwise impair physical stability.

According to the invention, the reduction in plastic viscosity is achieved without a significant reduction in the yield point by the installation of e.g. Lecithin or other phosphate ester additives achieved as described above. For example, in the absence of the viscosity reducing additive, the 10 non-aqueous suspensions containing low density filler have plastic viscosities in the range of about 500 to 5000 mPa.s. By adding lecithin or other phosphate ester, the viscosity can be reduced by or to 50% or more, for example to about 200 to 3000, preferably 250 to 1000, particularly preferably 300 to 600 mPa.s. The exact amount of additive required to reduce the plastic viscosity to a specific value cannot be exactly defined, but depends on such factors as the initial plastic viscosity, the special additive and the special components of the non- aqueous suspension. In general, amounts of viscosity-reducing additive of 0.1 to 3, preferably 0.3 to 2, particularly 0.5 to 1.5% by weight, based on the total composition, give the desired results.

The incorporation of organophilic clay into the non-aqueous suspension of fine textile treatment parts donated in liquid nonionic surfactant su-20 in accordance with the disclosure in German patent application P 3 826 631 creates a viscoelastic network which also improves the physical stability of the non-aqueous suspension. The incorporation of lecithin or other phosphate ester compound as defined above in the stated amounts creates a further improvement in the physical stability of the non-aqueous suspension.

According to the preferred embodiment of the invention, the non-aqueous suspension of the textile treatment additive contains both the low-density filler and organophilic clay. In this preferred embodiment, incorporation of lecithin or other phosphate ester compound within the above amount reduces plastic viscosity and helps maintain the viscoelastic network structure mediated by the organophilic clay.

Regarding this preferred embodiment, it has been found that under transportation (shipping) conditions where low density filler compositions are subject to strong and repeated vibratory forces normally encountered when transported by train or truck, the low density filler tends to occur increase the top of the composition, accompanied by a corresponding amount of settling of the 35 functionally active solid suspended particles to the bottom of the vessel in which the composition is stored.

Although the cause of the adverse effects of strong vibration forces has not been fully elucidated, it is believed that the vibration forces are strong enough to overcome the weak attraction between the low density filler and the functionally active suspended particles in the 40 composite particles described above. An alternative theory states that the strong vibratory forces may lead to localized disturbances in which the yield stress is greater than the yield point of the suspension, which triggers the destabilization.

However, by whatever mechanism the low density filler migrates to the top surface of the liquid suspension, the homogeneity of the liquid suspension composition can be maintained even when strong vibratory forces are applied if a low level is added to the composition before, during or after the introduction of the low density filler Amount, generally up to about 1% by weight of the composition, of an organophilic modified clay.

The applicable organophilic modified clays form a viscoelastic network structure in the composition, and although the applicant does not wish to be bound by any particular theory of action, it is believed that this elastic network structure is capable of absorbing the strong vibratory forces and thereby the suspensions even among them to stabilize adverse conditions. In particular, it is assumed that the organophilic clay additive increases the pour point of the suspensions in such a way that the yield stress resulting from the vibration does not exceed the 55 pour point.

All organophilically modified swelling clays with high gel activity, as described in German patent applications P 2 820 631 and P 3 824 253, can be used in the compositions according to the invention.

The organophilic modified clay can be based on any swelling clay modified to exert a strong gel effect in the organic liquid vehicle. Examples of such swelling clays which can be used (after appropriate modification as described below) are the smectite clays, in particular bentonite, e.g. Sodium and lithium bentonites; Montmo rillonite, e.g. Sodium and calcium montmorillonites; Saponites, e.g. Sodium saponite; and hectorite, e.g. Sodium hectorite. Other representative clays include beidellite and stevensite. Hectorite clays that have excellent swellability are particularly preferred.

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CH 678 630 A5

The smectite-type clays mentioned above are three-layer clays, which are distinguished by the ability of the layered structure to increase its volume several times by swelling or expanding in the presence of water, thereby forming a thixotropic gelatinous substance. There are two main classes of smectite type clays: in the first class aluminum oxide is present in the second 5 class magnesium oxide in the silicate crystal lattice. Atom substitution by iron, magnesium, sodium, potassium, calcium and the like can occur in the crystal lattice of the smectite clays. It is common to distinguish clays based on their predominant cation. For example, a sodium clay is one in which the cation is mainly sodium. Aluminum silicates in which sodium is the predominant cation are preferred, such as, for example, the bentonite clays. Of these bentonite tones, those from Wyoming (generally referred to as Western or Wyoming bentonite) are particularly preferred.

Preferred swelling bentonite clays are sold under the trade name "Mineral Colloid" ® as industrial bentonite by the Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials are the same as those previously sold under the trade name «THIXOJEL» ®. It is a selectively mined and enriched bentonite. The most valuable are considered to be mineral colloid numbers 101, etc. according to the previous THIXO-JELEN Nos. 1, 2, 3 and 4. These materials have pH values in the range at a concentration of 6% in water from 8 to 9.4, maximum free moisture levels of about 8% and specific weights of about 2.6. At least about 85% and preferably 100% of the powder quality passes through a 200 mesh sieve (US sieve series). Most preferably, the bentonite is one in which substantially all of the particles (i.e., at least 90%, preferably over 95% thereof) pass through a No. 325 sieve and it is most preferred that all particles pass through such a sieve. The swelling capacity of the bentonite in water is usually in the range of 2 to 15 ml / g; its viscosity at a concentration of 6% in water is usually around 8 to 30 cPs.

Instead of using the THIXO-JEL or mineral colloid bentonite, products such as those sold by American Colloid Company, Industriai Division, as general-purpose bentonite powder (325 mesh), at least 95% finer than 325 mesh or 44 microns in diameter, can be used (wet particle size) and at least 96% finer than 200 mesh or 74 micron diameter (dry particle size). Such a water-containing aluminum silicate consists mainly of montmorillonite (90% at least), although small amounts of feldspar, biotite and selenite can be present. A typical "anhydrous" analysis shows 63.0% silicon dioxide, 21.5% aluminum oxide, 3.3% ferric iron (as FeaOa), 0.4% ferrous iron (as FeO), 2.7% magnesium (as Mg) , 2.6% sodium and potassium (as Na20), 0.7% calcium (as CaO), 5.6% water of crystallization (as H2O) and 0.7% trace elements.

Although western bentonites are preferred, other bentonites can be used, such as those made by treating Italian or similar bentonites containing relatively small amounts of interchangeable monovalent metals (sodium and potassium) with alkaline materials such as sodium carbonate. to increase the cation exchange capacity of these products. It is assumed that the Na20 content of the bentonite should be at least about 0.5, preferably at least 1 and particularly preferably at least 2%, so that the clay swells sufficiently. Preferred swelling clays of the types described above are sold under the trade names "Laviosa" and "Winkelmann", e.g. "Laviosa AGB" and "Winkelmann G-13" sold. Other examples include "Veegum F" and "Laponite SP", both sodium hectorite, "Gelwhite L", a calcium montmorillonite, "Gelwhite GP", a sodium montmorillonite, "Barasym LIH 200", a lithium hectorite.

The smectite clay materials described above are hydrophilic, i.e. they show swelling behavior in aqueous media. Conversely, they are organophobic and do not swell in non-aqueous or predominantly non-aqueous systems.

The organophobic nature of smectite clay materials is therefore transformed into an organophilic nature. This is done by exchanging the metal cation, e.g. Na, K, Li, Ca, etc. of the clay by an organic cation, at least on the surface of the clay particles, for example by mixing the clay, organic cation and water together, preferably at a temperature in the range of 20 to 100 ° C , for a sufficient period of time that the organic cation is at least at the surface in the clay particles, then filtering, washing, drying and grinding. For further details, reference is made to one of the aforementioned U.S. Patents 2,531,427, 2,966,506, 4,105,578, 4,208,218, 4,287,086, 424,075 and 4,434,076.

The preferred organic cationic material is preferably a quaternary ammonium compound, especially one with surface-active properties, which is an indication of at least one long-chain hydrocarbon group (e.g. of at least 8 to 22 carbon atoms), although surface-active properties or other properties advantageous for textiles are not required nor is it essential that the cationic modifier be usable as such as a suspending agent. However, any of the cationic surfactants described in U.S. Patent 4,264,466, columns 23-29 above, as a valuable auxiliary suspending agent, can be used to modify the smectite material to make the latter organophilic. The organic cationic nitrogen compounds described in the aforementioned U.S. Patent 2,531,427

65

15

20th

25th

30th

35

40

45

50

55

60

15

5

10th

15

20th

25th

30th

35

40

45

50

55

60

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CH 678 630 A5

durigen or those mentioned in U.S. Patents 2,966,506 and 4,105,578, etc. may also be used to advantage.

The quaternary ammonium compounds of the formula [R1R2R3R4NPX-,

wherein R 1, R 2, R 3 and R 4 are each independently hydrogen or a hydrophobic organic alkyl,

Aryl, aralkyl, alkaryl or alkenyl radicals having 1 to 30, preferably 1 to 22, carbon atoms, at least two R groups preferably having 1 to 6 carbon atoms and at least one R & group, preferably at least two R groups 8 to 22 Have carbon atoms; X is an anion

which can be inorganic such as halide, e.g. Chloride or bromide, sulfate, phosphate, hydroxide or nitrate, or organic such as methyl sulfate, ethyl sulfate or a fatty acid residue, e.g. Acetate, propionate, laurate, myristate, palmitate, oleate or stearate.

Examples of preferred organophilic modifiers are the quaternary mono- and di-langketti-gene (e.g. Cs to Cis, especially C10 to Cis) alkyl compounds. Typical examples of the mono-long-chain quaternary ammonium surfactants include stearyl trimethyl ammonium chloride, tallow trimethyl ammonium chloride, benzyl stearyl dimethyl ammonium chloride, benzyl (hydrogenated) tallow dimethyl ammonium chloride, benyzl cetyl dimethyl ammonium chloride and the corresponding bromides, methosulfates, sulfides, sulfates

Acetates and other anions previously mentioned. Typical representative examples of quaternary di-iang-chain ammonium compounds include dimethyldistearylammonium chloride, dimethyldicetylammonium chloride, dimethylstearylcetylammonium chloride, dimethylditalgammonium chloride, dimethylmyristylcetylammonium chloride as well as the corresponding bromides, iodides, other sulfates, anions and methate sulfates. Other representative compounds include octadecylammonium chloride, hexadecylammonium acetates, etc. Dimethylalkylarylammoni salts are the most preferred QA compounds because of their high polarity.

In addition to the quaternary ammonium (QA) compounds, other quaternizable nitrogen-containing organic cations can also be used to form organophilic clay particles. Imidazoiinium compounds are mentioned as examples, e.g. 1- (2-hydroxyethyl) -2-dodecyl-1-benzyl-2-imidazolinium chloride, and compounds with a heterocyclic nitrogen ring, for example pyrrolidones, pyridines, morpholines and the like substituted with long chain hydrocarbon groups, e.g. N, N-octadecylmorpholinium chloride.

The amount of organic cation substitution only has to be sufficient to give the clay the necessary organophilic properties which ensure the desired increased stabilization. In general, depending on the nature of the organic substituent, this amount can be about 10 to 100, preferably 20 to 100, for example 30, 40, 50 or 60% of the available base exchange capacity of the clay material. Usually and preferably at least a sufficient amount of the organic compound is used to cover or coat the surface of the clay particles.

Suitable organophilic clays useful for the invention are commercially available, for example the products sold under the trade name "Bentone" by NL Industries, New York.

e.g. “Bentone 27”, a hectorite clay (magnesium montmorillonite) modified with benzyldimethyl (hydrogenated) tallow ammonium chloride, and “Bentone 38”, a hectorite clay modified with dimethyldioctadecylammonium chloride. Other suppliers of organophilic clays are, for example, Südchemie Munich, Germany; Laviosa, Livorno, Italy; Laporte, France; and Perchem, United Kingdom.

The organophilic clays are used only in small amounts, generally below 1.0, preferably below 0.7% by weight, based on the total composition. Amounts of at least 0.1, preferably 0.2% by weight, for example 0.25, 0.3, 0.35 or 0.4%, usually enable the production of stable, moderately thixotropic, non-aqueous liquid suspensions of finely divided builder or others water soluble or dispersible textile treatment agent.

The organophilic modified clay can either be incorporated directly into the non-aqueous liquid dispersion of the suspended particulate constituents as a powder or after it has first been incorporated into a part of the liquid carrier of the suspension, e.g. the liquid nonionic surfactant is predispersed, the latter method being preferred. In addition, the organophilic clay, whether added directly to the suspension as a powder or pre-gelled in part of the liquid carrier, can be added to the suspension before or after the suspension to an average particle size of not more than ^ 15, preferably not more than 10, especially 1 to 10, most preferably 4 to 8 microns.

According to a preferred embodiment, the organophilic clay is first either in a part of the liquid nonionic surfactant, which is the main liquid carrier, or in another- ^

ren nonionic surfactant or in a solvent or diluent as described above or in any suitable mixture of surfactant (s) and / or solvent (s) and / or diluent (s)

predispersed. The predispersed clay suspension can, if necessary, be subjected to grinding in a high shear mill to form an organophilic clay gel. Separately, the remaining solid particulate matter in the liquid nonionic surfactant and optionally

16

CH 678 630 A5

Diluent / solvent suspended and also subjected to a milling cycle. The clay gel and the suspension of the particulate substance can be ground to the final desired particle size before being mixed together; however, the pre-gel and the suspension can also be mixed with one another and then subjected to further grinding. In the latter case 5, the suspended particulate substance can further contribute to the "grinding" of the organophilic clay particles.

It is an advantage of this preferred embodiment of the invention, in which the organophilic clay is subjected to a milling step, that the incorporation of lecithin or other phosphate ester reduces the viscosity of the predispersed clay suspension, with or without another solid. Accordingly, the grinding step is largely facilitated and the use of processing aids or a heating step are not necessary.

In any of the foregoing embodiments in which the organophilic clay is ground to form an organophilic clay gel, the clay is added separately from the low density filler since the latter is not to be subjected to high shear or milling forces. In addition, it is preferred that the low density filler be added as the final component of the formulation under conditions that minimize the shear forces that act on the low density filler while still ensuring an even distribution of the filler throughout the composition should. In order to achieve this result, it has proven to be expedient to mix all constituents including the organophilic clay as previously described with the exception of the low-density filler and to form a thickened suspension, then the suspension under low shear with a mixing device having a paddle stirrer Mix at 2000 to 5000 rpm to create a "cavity" in the middle of the mixing vessel, and finally add the low density filler near the top of the cavity (vortex), which distributes the filler evenly throughout the composition.

25 In addition to its primary advantages as a viscosity-reducing agent and theological stabilizer, the use of lecithin in particular has several other advantages. For example, because of its amphoteric character, lecithin can interact with the nonionic surfactant, which forms the liquid phase, thereby increasing the washing power of the nonionic surfactant. Lecithin, which has two fatty acid residues and a quaternary ammonium group, can also impart advantageous softening to the textiles 30 treated with it. Lecithin can also serve as a sequestering agent for heavy metals and thus play the role of a bleach stabilizer.

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 all phosphate builders (such as sodium tripolyphosphate) with an auxiliary builder, for example a polymeric carboxylic acid with a high calcium binding capacity, in order to prevent incrustations which can otherwise be caused by the formation of insoluble calcium phosphate. Such auxiliary builders are known. Examples include Sokolan CP5, 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 of auxiliary builder 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, in the case of restrictive environmental laws, the compositions according to the invention can be produced without any phosphate builder.

In addition to the builders, various other detergent additives or adjuvants can be present in the detergent to give it additional functional or aesthetic properties. For example, small amounts of dirt-bearing substances or substances that prevent reprecipitation, e.g. Incorporate polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyimethyl cellulose, usually in amounts of up to 10, for example 0.1 to 10, preferably 1 to 5% by weight; optical brighteners, e.g. Cotton, polyamide and polyester brighteners, e.g. Stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted tri-50 azinylstilbene, 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 2, preferably up to 1, for example 0.1 to 0.8% by weight.

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 Amyla-55 set 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 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 Fertilize Silicverbin-60.

The bleaches can be divided into chlorine bleach and oxygen bleach. Typical chlorine bleaches are sodium hypochlorite (NaOCI), potassium dichloroisocyanurate (59% 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 perphosphates and potassium mono-

17th

CH 678 630 A5

persulfate. The perborates, especially sodium perborate monohydrate, are especially preferred.

The peroxygen compound is preferably used in admixture with an activator for the same. Suitable activators which can lower the actual temperature of action of the peroxide bleaching agent are e.g. in U.S. Patent 4,264,466 or column 1 of U.S. Patent 4,430,244. Po-5 lyacylated compounds are preferred activators; of these are compounds such as tetraacetyl-v,

ethylenediamine (TÂED) and pentaacetyiglucose are particularly preferred.

Other useful activators include, for example, acetylsaiicylic acid derivatives, ethylidene benzoate acetate and its salts, ethyldenocarboxylate acetate and its salts, alkyl and alkenylsuccinic anhydride, fetraacetyiglycouril (TAGU) and the derivatives thereof. Other applicable activator classes are e.g. in U.S. Patents 4,111,826, 4,422,950 and 3,661,789.

The bleach activator usually reacts with the peroxygen compound to form a peroxyacid bleach in the wash water. It is preferred to incorporate a high complexing sequestering agent to inhibit any undesirable reaction between this peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred Se-15 questing agents are able to form such a complex with copper 2+ ions that the stability constant (pK) of the complex is equal to or greater than 6 at 25 ° C. in water with an ionic strength of 0.1 mol / Liter, 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 sequestrants, for example, in addition to those mentioned above, are the compounds sold under the trade name "Dequest", such as diethylenetriaminepentaacetic acid (DETPA); Diethylenetriaminepentamethylenephosphonic acid (DTPMP) and ethylenediaminetetramethylenephosphonic acid (EDITEMPA).

To prevent loss of peroxide bleach e.g. To avoid sodium perborate by enzyme-induced (e.g., catalase-25) decomposition, the compositions may additionally contain an enzyme-inhibiting compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of peroxide bleach. Suitable inhibitor compounds are described in U.S. Patent 3,606,990.

Hydroxyiamine suifate 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%. Generally, however, suitable amounts of enzyme inhibitors are up to about 15%, for example 0.1 to 10%, based on the 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, rheological 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. 0 to 3, preferably 0 to 1% by weight.

Another stabilizer that is potentially suitable for use in conjunction with the low-density filler is an acidic organic phosphorus compound with an acidic POH group, as has also been proposed 40 (USSN 781 189, 1985). The acidic organic phosphorus compound may, for example, be a partial ester of phosphoric acid and an alcohol, e.g. an alkanol of lipophilic character, e.g. containing more than 5 carbon atoms, e.g. Has 8 to 20 carbon atoms. A specific example is a partial ester of phosphoric acid and a Ci6 to Cm alkanol.

Marchon's "Empiphos 5632" is prepared from around 35% monoesters and 65% diesters. Amounts of 45 phosphoric acid compound (if used) up to 3%, preferably up to 1%, are sufficient.

As also previously suggested (USSN 926 851, 1986), a nonionic surfactant which is partially modified with a free carboxyl group to convert a free hydroxyl group, e.g. a partial ester of a nonionic surfactant and a polycarboxylic acid can be incorporated into the composition to further improve the theological properties. For example, amounts of 50 acid-terminated nonionic surfactant of up to one part per part nonionic surfactant, for example 0.1 to 0.8 part, are sufficient.

Suitable ranges for these optional detergent additives are: 0 to 2, especially 0.1 to 1.3% enzymes; 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% of thickening and dispersing agents; 0 to 10, preferably 0.5 to 5% dirt-bearing substances or substances which prevent re-precipitation and yellowing; a total of 0 to about 2 and. '»Preferably 0 to 1% dyes, perfumes, brighteners and bluing agents; 0 to 5, preferably 0 to 2% pH modifier and pH buffer; 0 to 40 and preferably 0 to 25, e.g. 2 to 20% bleach; 0 to 15, preferably 0 to 10, e.g. 0.1 to 8% bleach stabilizers and activators; 0 to 15, e.g.

60 0.01 to 15, preferably 0.1 to 10% enzyme inhibitors; up to 5, preferably 1/4 to 3, e.g. 1/2 to 2% ^

Sequestering agent with great complexing ability. When selecting these auxiliaries, please note

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 constituents (other than the low density filler) is subjected to grinding, 65 for example with a sand or ball mill. Grater-type mills such as these are particularly useful

18th

CH 678 630 A5

from Wiener (Amsterdam) or Netzsch (Germany), in which the particle sizes of the solid components are less than about 18 microns, e.g. be reduced to an average particle size of 2 to 10 microns or even less (e.g. 1 micron). Preferably less than about 10, particularly less than about 5% of all suspended particles have a particle size larger than 15 micrometers, preferably 10 micrometers. 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 constituents is sufficiently large (for example at least 40, for example 50%), that the solid particles are in contact with one another and not substantially shielded from one another by the liquid nonionic surfactant. Mills with 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. 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 run the mixture of nonionic surfactant and solids through a less finely grinding mill, e.g. a colloid mill to reduce the particle size to less than 100 microns (e.g. to about 40 microns) before grinding to an average particle diameter below about 18 or 15 microns in the continuous ball mill in the milling step.

Alternatively, the powdery solid particles can be finely ground to the desired size before being mixed with the liquid matrix, for example in a jet mill.

The final compositions of the invention are non-aqueous liquid suspensions with generally non-Newtonian flow properties. After the addition of the low-density filler, the compositions are often slightly thixotropic, namely they show reduced viscosity when pressure or shear is applied and they behave rheologically essentially in accordance with the Cas-30 son equation. The finished compositions are characterized by a yield point between about 2.5 and 45 Pa, more often between 10 and 35 Pa, for example 15, 20 or 25 Pa. Furthermore, after the addition of lecithin or the phosphate ester compound, the compositions have viscosities at room temperature in the range from about 200 to 3000, usually from about 250 to 1000 mPa.s, which was measured using an LVT-D viscometer with a number 4 spindle at 50 rpm -35 en In addition, they are easy to flow and generally do not require the use of pressure or shaking. 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 amounts, e.g. in quantities of 1/4 to 1 1/2 measuring cups, e.g. 1/2 40 measuring cups per wash load (from about 1.36 to 6.8 kg, for example) for each wash load, generally in 30.3 to 68.1 l water. The preferred compositions remain stable (usually none and never more than 1 or 2 mm liquid phase separation) if left to stand for periods of 3 to 6 months or longer, even if shaken.

In the specification and claims, the term "non-aqueous" means the absence of water, although small amounts of water, for example up to about 5%, preferably up to about 2%, are tolerable in the compositions; "Non-aqueous" compositions can therefore contain such small amounts of water, be it that it is added directly or as a carrier or solvent for one or the other component of the composition.

The liquid textile treatment agents of the invention can be packaged in conventional glass or plastic containers 50 and can also be used in individual packs, for example in the metering devices according to German patent application P 2 820 631.

In the following examples which illustrate the invention, all quantities and percentages are based on weight, unless stated otherwise. Unless otherwise stated, the pressure is atmospheric pressure.

55

example

A non-aqueous, builder-containing liquid detergent composition according to the invention was obtained by mixing and finely grinding to about 4 microns of the following ingredients, with the exception of the Q-cell filler, in the approximate amounts below, and then adding the Q-Ceil filler to it Mixture prepared while stirring. To add the light filler, the ground dispersion was mixed under low shear using a propeller-type mixer with a paddle stirrer, which rotated at about 3500 rpm and produced a vortex in the middle of the mixing vessel. The Q-filler particles were added near the top of the cavity to effect an even distribution of the filler particles in the composition and

19th

5

10th

15

20th

25th

30th

35

40

45

50

55

CH 678 630 A5

at the same time minimize the shear forces that could cause the hollow spheres to break. This gave Composition I. By the same procedure except that the lecithin was omitted, Comparative Composition II was obtained. A second Comparative Composition 11-1 was prepared in the same manner as Comparative Composition II except that Bentone 27 the remaining ingredients were subsequently added in the same mixing vessel as the Q-cell filler particles. Comparative Composition III was prepared in the same manner as Composition I, except that the Q-Cell 400 and lecithin were removed.

Amount, wt% 1

II (comparison)

Nonionic surfactant 1

36.45

36.3

Diethylene glycol monobutyl ether

8.8

9.8

Sodium tripolyphosphate (hydrated)

28.70

29.1

Sokolan HC97862

2.0

1.9

Bentone 273

0.3

0.3

Sodium perborate monohydrate

10.5

10.6

Tetraacetylethylenediamine

4.5

4.3

Carboxylmethyl cellulose

1.0

1.0

Dequest 20664

1.0

1.0

Enzyme (mixture of preolytic enzyme

0.55

0.5

and amylase)

Q-Cell 4005

4.0

4.0

Perfume

0.5

0.5

T1O2 (rutile)

0.4

0.4

Optical brightener

0.3

0.3

Lecithin (soybeans)

1.0

-

Viscosity (mPa.s)

100.00 400

100.00 800

1) Condensation product of a C13 to cis fatty alcohol with a mixture of propylene oxide (4 moles) and ethylene oxide (7 moles) from BASF

2) Copolymer of methacrylic acid and maleic anhydride

3) Hectorite clay, modified with dimethylbenzyl (hydrogenated) tallow ammonium chloride, 35% cation exchange, from NL Industries

4) Diethylenetriaminepentamethylenephosphonic acid

5) Hollow microspheres made of sodium borosilicate glass, particle sizes in the range from 10 to 200 micrometers, average particle size 75 micrometers, effective density 0.16 to 0.18 g / cm3

Compositions I, II and 11-1 were stored in a clear plastic container overnight. At the end of the first day and after aging for 7 days, 15 days, 30 days and 60 days, the yield point and the plastic viscosity of each composition were determined. The results are summarized in Tables I and II.

Table I

Yield point (Pascal) after aging _

Composition of aging time (days)

1

7

15

30th

60

I.

11.3

12.2

12.2

12.7

-

II

8.9

7.8

7.0

5.4

4.2

11-1

10.8

9.4

7.6

6.2

-

20th

CH 678 630 A5

Table II

Plastic viscosity (mPa.s) according to the old

composition

Aging time (days)

1

7

15

30th

60

I.

390

400

400

420

-

II

750

800

800

830

870

11-1

600

600

650

700

-

III

200

230

250

270

270

From the above results it can be seen that the incorporation of 1% lecithin in the low-density / organophilic clay-stabilized non-aqueous suspension greatly stabilizes the aged composition 15 by maintaining and even slightly increasing its yield point and increasing its plastic viscosity decreased about 50%.

Without wishing to be bound by any specific theory of the mode of action, it is believed that the lecithin strongly strengthens or stabilizes the yield point of the composition by strengthening the hydrogen bond between bentone (organophilic clay) platelets by means of the phosphate group 20. In addition, the quaternary ammonium group (-N + (CH3) 3) of the phosphatidylcholine component is apparently substituted or bound to the Bentone platelets.

It can thus be seen that the addition of small amounts of lecithin or structurally similar phosphate ester compounds, in particular those compounds in which the phosphate ester comprises a terminal quaternary ammonium nitrogen atom which is bonded to the phosphate group via 1 or more, preferably 2 25 to 6, carbon atoms, to a non-aqueous suspension, which contains at least one of the components of low-density filler and organophilic clay, significantly improves the physical stability of the non-aqueous suspensions, even under strong vibratory forces, while the plastic viscosity is reduced, so that the suspension is easy to pour .

30 Repeating the example above, except that 1% Expancel (polyvinylidene chloride microspheres, particle size range 10 to 100 microns, average particle size 40 microns, density 0.03 g / cm2) was used instead of 4% Q-Cell 400 you get similar results. In the same way, replacement of the nonionic surfactant with Plurafac RA20, Plurafac D25, Plurafac RA50 or Dobanol 25-7 or Neodol 23-6.5 gave similar results. Repeating the above 35 example with the exception that instead of Bentone 27 Bentone 38 (hectorite clay, modified with dimethyldioctadecylammonium chloride) was used, similar results were obtained.

If the amount of lecithin in composition 1 was reduced to 0.3% by weight, the plastic viscosity rose to 500 mPa.s cPs, while it was still easy to pour.

Claims (19)

40 claims 1. A non-aqueous, liquid composition suitable for textile treatment comprising a) a non-aqueous liquid which comprises non-ionic surfactant, b) Functionally active solid textile detergent additive particles, which are donated in the non-aqueous liquid su-45, at least one of components c) and d), namely c) filler of low density in a sufficient amount to the density of the continuous liquid phase of density the "suspended particle phase", ie equalize the phase comprising the low density filler and the suspended functionally active solid particles, thereby inhibiting settling of the suspended particles when the composition is in ruin. 50 he, and / or d) a suitable amount of organophilic clay to inhibit phase separation when the composition is subjected to strong vibratory forces, and e) a phosphate ester compound of the formula I or II 55 60 65 21 CH 678 630 A5 10th (I) Ro 15 l hc o r3 I. hc o r2 o (ii) 20 * " h2c o p — o — r » O- 25th wherein R represents a linear or branched alkyl or alkenyl group with 1 to 8 carbon atoms, which is replaced by an amino group of the formula -NR4R5, where R4 and R5 independently represent hydrogen or alkyl 30 are 1 to 4 carbon atoms, or may be substituted by a quaternized nitrogen of the formula -NR4R5R6, where R4 and R5 are as defined above and R6 is hydrogen or alkyl of 1 to 4 carbon atoms; Ro is hydrogen or lower alkyl or lower alkenyl, Ri is an acyl residue of a long chain fatty acid; 35 R2 is hydrogen or an acyl residue of a long chain fatty acid; R3 is hydrogen or an acyl residue of a long chain fatty acid; provided that R2 and R3 are not both hydrogen at the same time; and wherein n represents a number from 1 to 10 to reduce the viscosity and further stabilize the theological properties of the composition. 40 2. Composition according to claim 1, characterized in that component e) is lecithin. 3. Composition according to claim 1, characterized in that component c) is present. 4. Composition according to claim 1, characterized in that component d) is present. 45 5. Composition according to claim 1, characterized in that the components c) and d) are both present. 6. The composition according to claim 1, characterized in that the amount of component e) is sufficient to reduce the plastic viscosity of the composition to a value within the range from 200 to 1000 mPa.s. 50 7. Composition according to claim 1, characterized in that the amount of component e) is sufficient to reduce the plastic viscosity of the composition to a value in the range from 300 to 600 mPa.s. 8. The composition according to claim 5, characterized in that the low density filler consists of hollow plastic or glass beads having a density in the range of 0.02 to 0.5 g / cm3. 55 9. The composition according to claim 8, characterized in that the low density filler consists of microspheres of water-soluble borosilicate glass. 10. The composition according to claim 5, characterized in that the organophilic clay comprises a swelling smectition which is modified with a nitrogen-containing compound which has at least one long-chain hydrocarbon radical having 8 to 22 carbon atoms. 60 11. The composition according to claim 10, characterized in that the nitrogen-containing compound is a quaternary ammonium compound. 12. The composition according to claim 11, characterized in that the quaternary ammonium compound is a compound of the formula 65 [RiR2R3R4N] + X- & 22 CH 678 630 A5 wherein R 1, R 2, R 3 and R 4 are each independently hydrogen or an alkyl, alkenyl, aryl, aralkyl or alkaryl group having 1-30, preferably having 1 to 22 carbon atoms, at least two of the Rr to R4 groups Have 1 to 6 carbon atoms and at most 2 of the R1 to R4 groups have 8 to 22 carbon atoms; and wherein X represents an inorganic or organic anion. 5 13. The composition according to claim 1, characterized in that the non-aqueous liquid 30 to 70 wt .-% of the composition, the suspended solid particles make up 70 to 30 wt .-% of the composition. 14. The composition according to claim 13, characterized in that the non-aqueous liquid 40 to 65 wt .-%, the suspended solid particles from 60 to 35 wt .-% of the composition Make 10. 15. The composition according to claim 1, characterized by a content, based on the weight of the composition 30 to 50% alkoxylated fatty alcohol as nonionic surfactant, - 0 to 20% alkylene glycol ether as a viscosity-controlling and gel-preventing agent; 15 -15 to 50% builder particles; - 0 to 50% in total of one or more of the optional detergent additives from the group consisting of 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 , Bleach, bleach 20 tel stabilizers and sequestrants; - up to 10% low density filler in the form of hollow microspheres; - 0.2 to 0.7% organophilic modified clay; and - 0.1 to 3% lecithin or an alkylamine, alkenylamine, alkylammonium or alkenylammonium phosphate ester of glycol, polyglycol or glycerol with at least one ester group of a long chain 25 fatty acid in the molecule of formula I or II. 16. Builder-containing, liquid, thickened, non-aqueous heavy duty textile detergent composition according to claim 1, characterized by a content, based on the weight of the composition 30 to 40% of a mixed ethylene oxide-propylene oxide condensation product of a fatty alcohol of 12 to 18 carbon atoms as a liquid nonionic surfactant; 30 - 25 to 40% alkali phosphate as builder salt; -5 to 12% alkylene glycol ether solvent as a viscosity-controlling and gel-preventing substance; - 2 to 20% of a peroxide bleaching agent; - 0.1 to 8% of a bleach activator; - up to 2% enzymes; 35 - up to 10% dirt-bearing substances that prevent re-precipitation and yellowing; - up to 5% sequestering agent with high complexation capacity; - up to 2% each of one or more dyes, fragrances and optical brighteners; - The solid components of the composition have an average particle size in the range of 2 to 10 microns, with no more than 10% of the particles having a particle size of 40 have more than 10 microns; - 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; - 0.2 to 0.7% of an organophilic modified smectite clay, wherein 10 to 100% of the available base exchange capacity of the smectite clay with an organic cationic nitrogen compound 45 at least one long chain, 8 to 22 carbon atom hydrocarbon residue are replaced; -0.1 to 3% lecithin, the viscosity of the composition being 200 to 1000.10-3 Pa.s. 17. The composition according to claim 16, characterized in that the filler particles consist of hollow sodium borosilicate glass beads. 50 18. Commercial process for cleaning soiled textiles, characterized in that the soiled textiles are brought into contact with the textile treatment composition of claim 1 in an aqueous washing bath. 19. The method according to claim 18, characterized in that the contacting takes place in an automatic washing machine. 55 65 23